阅读说明：本技术 乙烯-α-烯烃-非共轭多烯共聚物、其制造方法及用途 (Ethylene-alpha-olefin-nonconjugated polyene copolymer, process for producing the same, and use thereof ) 是由 市野光太郎 菊地义治 宍户启介 田中润平 有野恭巨 于 2018-03-20 设计创作，主要内容包括：本发明的课题在于提供含有VNB等特定的非共轭多烯作为共聚成分,并且长链支链含量少,使用过氧化物进行交联的情况下的固化特性优异,加工性良好的新型乙烯-α-烯烃-非共轭多烯共聚物。本发明涉及的乙烯-α-烯烃-非共轭多烯共聚物的特征在于,具有来源于乙烯(A)、碳原子数3～20的α-烯烃(B)和非共轭多烯(C)的结构单元,且满足特定的要件,所述非共轭多烯(C)在分子中合计包含2个以上选自由下述通式(I)和(II)所组成的组中的部分结构。<Image he="113" wi="700" file="DDA0002678526700000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>(The present invention addresses the problem of providing a novel ethylene-alpha-olefin-nonconjugated polyene copolymer which contains a specific nonconjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, has excellent curing properties when crosslinked with a peroxide, and has good processability. The ethylene-alpha-olefin-nonconjugated polyene copolymer is characterized by having structural units derived from ethylene (A), an alpha-olefin (B) having 3 to 20 carbon atoms, and a nonconjugated polyene (C) containing 2 or more partial structures selected from the group consisting of the following general formulae (I) and (II) in total in the molecule, and satisfying specific requirements.)

1. An ethylene-alpha-olefin-nonconjugated polyene copolymer which has structural units derived from ethylene (A), an alpha-olefin (B) having 3 to 20 carbon atoms, and a nonconjugated polyene (C) comprising a total of 2 or more partial structures selected from the group consisting of the following general formulae (I) and (II) in a molecule, and satisfies the following requirements (I) to (vii),

[ solution 1]

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

(ii) the weight fraction of the structural unit derived from the nonconjugated polyene (C) is from 0.07 to 10% by weight in 100% by weight of the ethylene-alpha-olefin-nonconjugated polyene copolymer;

(iii) the weight average molecular weight (Mw) of the ethylene-alpha-olefin-nonconjugated polyene copolymer, the weight fraction (wt%) of (C) which is the weight fraction of structural units derived from the nonconjugated polyene (C), and the molecular weight of (C) which is the molecular weight of the nonconjugated polyene (C) satisfy the following formula (1);

4.5. ltoreq. Mw x (C)/100/(C) molecular weight. ltoreq.40 40 … formula (1)

(iv) Complex viscosity η at a frequency ω of 0.1rad/s obtained by linear viscoelasticity measurement (190 ℃) using a rheometer^* ₍ω_＝0.1)(Pa sec) and a complex viscosity η at a frequency ω of 100rad/s^* ₍ω_＝100)(Pa sec) ratio P, i.e.. eta ^* ₍ω_＝0.1)/η^* ₍ω_＝100)Intrinsic viscosity [ eta ]]And a weight fraction of structural units derived from the non-conjugated polyene (C), that is, a weight fraction of (C) satisfies the following formula (2);

P/([η]^2.9) Weight fraction of not more than (C). times.6 6 … formula (2)

(v) A ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn), which is measured by Gel Permeation Chromatography (GPC), i.e., a molecular weight distribution Mw/Mn, is in a range of 8 to 30;

(vi) the number average molecular weight (Mn) is 30,000 or less;

(vii) the pattern obtained by GPC measurement shows 2 or more peaks, and the area of the peak appearing on the side of the smallest molecular weight is in the range of 1 to 20% of the total peak area.

2. The ethylene- α -olefin-nonconjugated polyene copolymer according to claim 1, wherein the intrinsic viscosity [ η ] is 0.1 to 5dL/g, and the weight average molecular weight (Mw) is 10,000 to 600,000.

3. The ethylene- α -olefin-nonconjugated polyene copolymer according to claim 1 or 2, wherein the nonconjugated polyene (C) is 5-vinyl-2-norbornene (VNB).

4. The ethylene-alpha-olefin-nonconjugated polyene copolymer according to any one of claims 1 to 3, further comprising a structural unit derived from a nonconjugated polyene (D) in a weight fraction of 0 to 20% by weight, wherein the total of the weight fractions of (A), (B), (C) and (D) is 100% by weight, and the following requirement (viii) is satisfied, the nonconjugated polyene (D) comprising only 1 partial structure selected from the group consisting of the general formulae (I) and (II) in the molecule,

(viii) The weight average molecular weight (Mw), the weight fraction (weight%) of (C) which is the weight fraction of the structural unit derived from the non-conjugated polyene (C), the weight fraction (weight%) of (D) which is the weight fraction of the structural unit derived from the conjugated polyene (D), the molecular weight of (C) which is the molecular weight of the non-conjugated polyene (C), and the molecular weight of (D) which is the molecular weight of the conjugated polyene (D) satisfy the following formula (4),

4.5. ltoreq. Mw × { ((weight fraction of (C)/100/(molecular weight of C) + ((weight fraction of (D)/100/(molecular weight of D) } 45 … formula (4).

5. The ethylene- α -olefin-nonconjugated polyene copolymer according to claim 4, wherein the nonconjugated polyene (D) is 5-ethylidene-2-norbornene (ENB).

6. A process for producing an ethylene- α -olefin-nonconjugated polyene copolymer, which comprises the steps of:

a step (1) of copolymerizing in the presence of a polymerization catalyst containing at least 1 metallocene compound represented by the following general formula [ A1 ]; and

a step (2) of adding an alcohol as a catalyst deactivator to deactivate the polymerization catalyst,

[ solution 2]

Formula [ A1]In, R¹、R²、R³、R⁴、R⁵、R⁸、R⁹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, R¹～R⁴Wherein adjacent two groups may be bonded to each other to form a ring,

R⁶and R¹¹Is the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than the silicon-containing group, R⁷And R¹⁰Is the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than the silicon-containing group, R⁶And R⁷May combine with each other to form a ring, R¹⁰And R¹¹May be bonded to each other to form a ring wherein R⁶、R⁷、R¹⁰And R¹¹Not all of them being hydrogen atoms,

R¹³and R¹⁴Each independently represents an aryl group, or a salt thereof,

M¹represents a group of atoms of zirconium,

Y¹represents 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 having 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or more, the Q may be the same or different.

7. The process for producing an ethylene- α -olefin-nonconjugated polyene copolymer according to claim 6, wherein,

The copolymerization in the step (1) is carried out in the presence of a polymerization catalyst comprising (a), (b) and, if necessary, (c),

(a) the metallocene compound represented by the general formula [ A1],

(b) at least 1 compound selected from (b-1) an organometallic compound, (b-2) an organoaluminum oxy-compound, and (b-3) a compound which reacts with the metallocene compound (a) to form an ion pair,

(c) a particulate carrier, which is a mixture of a particulate carrier,

the polymerization catalyst contains at least the organometallic compound (b-1) as the compound (b).

8. The process for producing an ethylene- α -olefin-nonconjugated polyene copolymer according to claim 6 or 7, wherein ethylene (A), an α -olefin (B) having 3 to 20 carbon atoms, a nonconjugated polyene (C) having a partial structure selected from the group consisting of the following general formulae (I) and (II) in total of 2 or more in a molecule, and if necessary, a nonconjugated polyene (D) having a partial structure selected from the group consisting of the following general formulae (I) and (II) in only 1 in a molecule are continuously supplied to a reactor to be copolymerized,

[ solution 3]

9. The process for producing an ethylene- α -olefin-nonconjugated polyene copolymer according to claim 8, wherein the nonconjugated polyene (C) is 5-vinyl-2-norbornene (VNB), and the nonconjugated polyene (D) is 5-ethylidene-2-norbornene (ENB).

10. The method for producing an ethylene- α -olefin-nonconjugated polyene copolymer according to any one of claims 6 to 9, wherein the catalyst deactivator is methanol or ethanol, and the organometallic compound (b-1) is trimethylaluminum or triisobutylaluminum.

11. A thermoplastic resin composition comprising the ethylene- α -olefin-nonconjugated polyene copolymer according to any one of claims 1 to 5.

12. The thermoplastic resin composition according to claim 11, further comprising an organic peroxide, wherein the content (mole) of the organic peroxide satisfies the following formula (7),

content (mol) of organic peroxide x number of oxygen-oxygen bonds in organic peroxide 1 molecule

(ii) weight fraction/(C) of ≤ (C) × 100 … formula (7)

In the formula (7), the weight fraction of (C) represents the weight fraction (% by weight) of the structural unit derived from the nonconjugated polyene (C) in the ethylene- α -olefin-nonconjugated polyene copolymer, and the molecular weight of (C) represents the molecular weight of the nonconjugated polyene (C).

13. A rubber composition comprising the ethylene- α -olefin-nonconjugated polyene copolymer according to any one of claims 1 to 5.

14. The rubber composition according to claim 13, further comprising a rubber component (T) selected from the group consisting of diene rubbers, butyl rubbers and halogenated butyl rubbers, and a content ratio of the ethylene- α -olefin-nonconjugated polyene copolymer (S) to the rubber component (T), i.e., a mass ratio (S)/(T), is in a range of 5/95 to 50/50.

15. The rubber composition according to claim 14, wherein the rubber component (T) comprises a styrene-butadiene rubber.

16. A crosslinked molded article comprising a crosslinked product of the rubber composition according to any one of claims 13 to 15.

17. A hose for an automobile, comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

18. A turbocharger hose comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

19. A muffler hanger comprising the crosslinked body of the rubber composition according to any one of claims 13 to 15.

20. An engine mount characterized by comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

21. A conveyor belt comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

22. An electric wire coating material comprising a crosslinked product of the rubber composition according to any one of claims 13 to 15.

23. A tire member comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

24. A tire tread comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

25. A tire side wall comprising a crosslinked body of the rubber composition according to any one of claims 13 to 15.

26. A tire characterized in that 1 or more tire members selected from the group consisting of a tire inner liner, a tire inner tube, a tire rim, a tire shoulder, a tire bead, a tire tread, and a tire side wall comprise a crosslinked body of the rubber composition according to any one of claims 13 to 15.

27. A process for producing a crosslinked molded article, which comprises a step of crosslinking a rubber composition (X) comprising the ethylene- α -olefin-nonconjugated polyene copolymer (S) according to any one of claims 1 to 5 and a rubber component (T) selected from the group consisting of diene rubbers, butyl rubbers and halogenated butyl rubbers in a mass ratio of (S)/(T) of 5/95 to 50/50.

28. The method of producing a crosslinked molded article according to claim 27, wherein the step of crosslinking is performed by electron beam crosslinking.

29. A resin composition characterized by comprising:

(S) 100 parts by weight of the ethylene-alpha-olefin-nonconjugated polyene copolymer described in any one of claims 1 to 5,

(E) the specific surface area is 5-500 m²(ii) 5 to 90 parts by weight of finely powdered silicic acid and/or finely powdered silicate per gram, and

as a crosslinking agent,

(G) 0.1 to 15 parts by weight of an organic peroxide, and/or

(H) 0.1 to 100 parts by weight of a SiH group-containing compound having at least 2 SiH groups in 1 molecule.

30. The resin composition according to claim 29, further comprising (F) 0.1 to 20 parts by weight of an α, β -unsaturated carboxylic acid metal salt.

31. The resin composition according to claim 30, wherein the metal salt of α, β -unsaturated carboxylic acid (F) contains at least 1 selected from the group consisting of a metal salt of methacrylic acid and a metal salt of maleic acid.

32. The resin composition according to any one of claims 29 to 31, wherein the amount of the crosslinking agent is 1m per unit²The surface area of the component (E) is less than 8X 10 ^-6The molar amount further comprises (J) a compound containing at least 1 unsaturated hydrocarbon group and at least 1 hydrolyzable silyl group.

33. A crosslinked molded article comprising a crosslinked product of the resin composition according to any one of claims 29 to 32.

34. A vibration-isolating rubber product comprising a crosslinked product of the resin composition according to any one of claims 29 to 32.

35. The vibration-isolating rubber product according to claim 34, which is a vibration-isolating rubber for automobiles.

36. Vibration-isolating rubber product according to claim 34, which is a muffler suspension rubber for automobiles.

37. The vibration-proof rubber product according to claim 34, which is a railway vibration-proof rubber.

38. The vibration-proof rubber product according to claim 34 is a vibration-proof rubber for industrial machinery.

39. The vibration-isolating rubber product according to claim 34, which is a vibration-isolating rubber for construction.

Technical Field

The present invention relates to a novel ethylene- α -olefin-nonconjugated polyene copolymer, a production process therefor, and use thereof.

Background

Ethylene- α -olefin rubbers represented by ethylene-propylene-non-conjugated diene copolymer rubbers (EPDM) have no unsaturated bond in the main chain of the molecular structure thereof, and therefore have excellent heat resistance and weather resistance as compared with general-purpose conjugated diene rubbers, and are therefore widely used in applications such as automobile parts, electric wire materials, building and civil engineering materials, industrial material parts, and modified materials for various resins.

It is known that when an ethylene- α -olefin rubber is crosslinked using a peroxide, the crosslinking rate is high particularly when a nonconjugated polyene such as 5-vinyl-2-norbornene (hereinafter also referred to as "VNB") is contained as a copolymerization component.

However, ethylene- α -olefin-VNB terpolymers made using previous catalysts have many long chain branches resulting from the terminal vinyl groups of VNB. In this case, most of the terminal vinyl groups of VNB in the copolymer are consumed, the effect of improving the crosslinking rate is insufficient, and the long-chain branch may deteriorate the processability at the time of molding and the physical properties after processing. Such long chain branches are also generated when a vanadium-based catalyst is used, and particularly, the long chain branch content tends to be large when polymerization is performed using a metallocene-based catalyst.

Patent documents 1 and 2 describe ethylene copolymers containing structural units derived from ethylene, α -olefin and VNB polymerized using a metallocene catalyst, patent document 1 describes that the copolymers are suitable for foam molding, and patent document 2 describes that a rubber molded article having excellent surface appearance, strength characteristics, heat aging resistance and light resistance and small compression set can be molded. However, the ethylene copolymers obtained by these techniques have a large content of long-chain branches.

Patent document 3 describes a method for producing a polymer containing monomer units of ethylene, α -olefin, VNB, and 5-ethylidene-2-norbornene (ENB) using a group 4 metal compound having a single cyclopentadienyl ligand and a monosubstituted nitrogen ligand, aluminoxane, and a catalyst activator as a catalyst system, and describes that an EPDM polymer having a high VNB content and a low branching degree is produced. However, the EPDM polymer described in patent document 3 has a problem that the number of dienes per 1 molecule of the copolymer is too large, and therefore a molded product obtained using the copolymer does not have sufficient heat aging resistance.

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

Conventionally, styrene-butadiene rubber (SBR) has been widely used for tires for automobiles and the like. Since diene rubbers such as styrene-butadiene rubber have insufficient weather resistance when used alone, in the case of being used for outdoor use for a long time such as tires, an amine antioxidant, paraffin wax, or the like is generally added and used to improve weather resistance. However, diene rubber products containing an amine antioxidant, paraffin wax, or the like sometimes bleed out these components on the surface thereof over time, and discolor the surface. In addition, discoloration due to bleeding, dusting, and other appearance deterioration may occur during storage on a counter or the like, resulting in a reduction in the commercial value. Therefore, improvement in weather resistance due to the rubber component itself is desired.

In order to solve such problems, it has been studied to improve weather resistance by blending ethylene-propylene-diene rubber (EPDM) with styrene-butadiene rubber, but there is a problem that phase separation is likely to occur when styrene-butadiene rubber and EPDM are thermally crosslinked, and sufficient fatigue resistance cannot be obtained.

The applicant proposes a rubber composition comprising: a random copolymer rubber composed of structural units derived from ethylene, an α -olefin and a specific triene compound, a diene rubber, carbon black and a vulcanizing agent (see patent document 4). The ethylene- α -olefin-triene random copolymer rubber in the rubber composition exhibits a high vulcanization rate substantially equivalent to that of a diene rubber, and therefore, is less likely to undergo phase separation from the diene rubber, does not impair excellent mechanical strength characteristics inherent in diene rubbers, and is suitable for tire side applications.

Further, the present applicant has found that a rubber composition containing a non-conjugated polyene copolymer containing a structural unit derived from an α -olefin and a structural unit derived from a non-conjugated polyene and a diene rubber and a softening agent are mixed and suitable for forming a tire excellent in braking performance and fuel efficiency (see patent documents 5 and 6).

Currently, in the manufacture of tires, the following processes are mainly employed: an uncrosslinked composition containing a diene rubber such as styrene-butadiene rubber or natural rubber as a main component is molded into a sheet or the like, and only the surface is crosslinked with an electron beam to prevent sagging, and then assembled into a tire shape, followed by vulcanization crosslinking.

Further, diene rubbers such as Natural Rubber (NR), styrene-butadiene rubber (SBR), and Butadiene Rubber (BR) are known to be rubbers excellent in dynamic fatigue resistance and dynamic characteristics, and are used as raw material rubbers for automobile tires and vibration-proof rubbers. Recently, however, the environment in which these rubber products are used has changed greatly, and improvement in heat resistance and weather resistance of the rubber products has been demanded. For example, for treads and tire sidewalls for automobile tires, weatherability is particularly desired. However, there has not been a rubber having good weather resistance while maintaining excellent mechanical properties, fatigue resistance and dynamic properties of conventional diene rubbers.

Therefore, various blended rubber compositions of diene rubbers having excellent mechanical properties, dynamic fatigue resistance, and dynamic properties and ethylene-propylene-nonconjugated diene copolymer rubbers (EPDM) having excellent heat resistance and weather resistance and other ethylene- α -olefin-nonconjugated polyene copolymers having 3 to 20 carbon atoms have been studied. However, since the level of dynamic properties of an ethylene- α -olefin-nonconjugated polyene copolymer having 3 to 20 carbon atoms is different from that of a diene rubber, a blended rubber composition having uniform physical properties has not been obtained in the past. The dynamic characteristics of automobile tires are subject to whether or not the fuel consumption is not deteriorated, and the index thereof is tan (loss tangent) value, and the lower the tan value, the more excellent the dynamic characteristics.

On the other hand, in the case of vibration-proof rubber products for automobiles, fatigue resistance that can withstand practical use cannot be obtained in vibration-proof rubber products based on conventional natural rubber, which is a diene rubber, as the temperature in the engine compartment increases. Therefore, a new rubber material having excellent heat resistance and having mechanical properties, dynamic properties, and fatigue resistance equal to or higher than those of diene rubbers is desired.

Generally, in order to improve dynamic characteristics, it is necessary to increase the crosslinking density. However, in the conventional techniques, if an attempt is made to make the dynamic properties of an ethylene- α -olefin-nonconjugated polyene copolymer having 3 to 20 carbon atoms equal to those of a diene rubber such as NR, the crosslink density becomes excessively high, and as a result, mechanical properties such as tensile elongation at break become poor, and dynamic properties and physical properties cannot be simultaneously achieved.

In addition, in order to improve vibration-proof characteristics, that is, to reduce dynamic magnification, in a vibration-proof rubber containing an ethylene- α -olefin-nonconjugated polyene copolymer, it is considered effective to use a copolymer having a high molecular weight and to increase the crosslinking density by suppressing the amount of a filler, and various studies have been made on this method.

However, the ethylene- α -olefin-nonconjugated polyene copolymer having a high molecular weight has a problem that kneading is difficult because the viscosity of the polymer itself is high. Further, in order to improve the vibration damping characteristics, it is necessary to further improve the crosslinking density as described above, but there is a problem that mechanical properties such as elongation are lowered by this. In addition, in vibration-proof rubber products, high heat resistance is particularly required in applications such as vibration-proof rubber for automobiles, particularly muffler suspension rubber.

Under such circumstances, the present applicant has proposed: an ethylene- α -olefin-nonconjugated polyene copolymer which contains a specific nonconjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, and is excellent in curing properties when crosslinked with a peroxide; a crosslinked molded article which comprises the copolymer, does not cause phase separation during production, has improved weather resistance of rubber components such as styrene-butadiene rubber and natural rubber, is prevented from deterioration in appearance, and has excellent weather resistance; and a resin composition which comprises the copolymer, is easily improved in crosslinking density, has excellent vibration-proof properties, is less likely to decrease in elongation even when the crosslinking density is increased, has sufficient strength even when the molecular weight is in a range in which kneading is easy, and has excellent heat resistance, and is suitable for producing a vibration-proof rubber product (see patent document 7).

However, the ethylene- α -olefin-nonconjugated polyene copolymer obtained in patent document 7 has a molecular weight distribution (Mw/Mn) as narrow as about 2, and thus the processability and the like are not necessarily sufficient. The conventional EPDM polymers containing a large amount of low-molecular weight components have a problem of reduced crosslinking density and stickiness.

Disclosure of Invention

Problems to be solved by the invention

The present invention addresses the problem of providing a novel ethylene- α -olefin-nonconjugated polyene copolymer which contains a specific nonconjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, has excellent curing properties when crosslinked with a peroxide, and has good processability, and a method for producing the ethylene- α -olefin-nonconjugated polyene copolymer and use of the ethylene- α -olefin-nonconjugated polyene copolymer.

Further, another object of the present invention is to provide a crosslinked molded article which does not cause phase separation during production, improves weather resistance of rubber components such as styrene-butadiene rubber and natural rubber, prevents deterioration in appearance, and has excellent weather resistance.

Further, another object of the present invention is to provide a resin composition suitable for producing a vibration-damping rubber product, which is easily improved in crosslinking density, has excellent vibration-damping characteristics, is less likely to decrease in elongation even when the crosslinking density is increased, can obtain sufficient strength even when the crosslinking density is in a range in which kneading is easy, and has excellent heat resistance, and a vibration-damping rubber product.

Means for solving the problems

The present inventors have made extensive studies to achieve the above object, and as a result, have found that: an ethylene- α -olefin-nonconjugated polyene copolymer obtained by copolymerization under specific conditions using a specific catalyst has a broad molecular weight distribution showing bimodality, contains a structural unit derived from a specific nonconjugated polyene such as VNB, has a small content of long-chain branches, can be peroxide-crosslinked at a high speed, is excellent in processability, and is excellent in properties after crosslinking, and thus the present invention has been completed.

The present inventors have also found that a crosslinked molded article obtained by crosslinking a composition containing the ethylene- α -olefin-nonconjugated polyene copolymer and a rubber component such as a diene rubber can be obtained without phase separation particularly at the time of crosslinking in the production, and is excellent in weather resistance, and thus have completed the present invention.

The ethylene-alpha-olefin-nonconjugated polyene copolymer is characterized by having structural units derived from ethylene (A), an alpha-olefin (B) having 3 to 20 carbon atoms, and a nonconjugated polyene (C) containing 2 or more partial structures selected from the group consisting of the following general formulae (I) and (II) in total in the molecule, and satisfying the following requirements (I) to (vii).

[ solution 1]

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

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

(iii) The weight average molecular weight (Mw) of the ethylene- α -olefin-nonconjugated polyene copolymer, the weight fraction of structural units derived from the nonconjugated polyene (C) ((weight fraction (wt%) of C)), and the molecular weight of the nonconjugated polyene (C) ((molecular weight of C)) satisfy the following formula (1).

4.5. ltoreq. Mw x (C)/100/(C) molecular weight. ltoreq.40 40 … formula (1)

(iv) Complex viscosity η at a frequency ω of 0.1rad/s obtained by linear viscoelasticity measurement (190 ℃) using a rheometer^* ₍ω_＝0.1)(Pa sec) and a complex viscosity η at a frequency ω of 100rad/s^* ₍ω_＝100)(Pa sec) ratio P (. eta.)^* ₍ω_＝0.1)/η^* ₍ω_＝100)) Intrinsic viscosity [ eta ]]And the weight fraction of the structural units derived from the non-conjugated polyene (C) (the weight fraction of (C)) satisfies the following formula (2).

P/([η]^2.9) Weight fraction of not more than (C). times.6 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) as measured by Gel Permeation Chromatography (GPC) is in the range of 8 to 30.

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

(vii) The pattern obtained by GPC measurement showed 2 or more peaks, and the area of the peak appearing on the side of the smallest molecular weight was 20% or less of the total peak area.

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, it is possible to provide a novel ethylene- α -olefin-nonconjugated polyene copolymer which contains a specific nonconjugated polyene such as VNB as a copolymerization component, has a small content of long-chain branches, and is excellent in curing characteristics when crosslinked with a peroxide, a method for producing the ethylene- α -olefin-nonconjugated polyene copolymer, and use thereof.

The ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention is excellent in moldability, crosslinking characteristics, curing characteristics and processability, and the molded article obtained therefrom is excellent in balance of physical properties such as mechanical properties and is excellent in heat aging resistance. In particular, the ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention exhibits an unexpected special effect of high crosslink density after crosslinking, although the processability becomes good by containing a low-molecular-weight component.

Further, according to the present invention, it is possible to provide a crosslinked molded article which does not cause phase separation, exhibits excellent weather resistance even when used for applications such as exposure to outdoor air or sunlight for a long period of time, and does not cause appearance deterioration or the like due to bleeding of additives or the like, and a method for producing the same. Further, according to the method for producing a crosslinked molded article of the present invention, crosslinking is performed using a composition having extremely excellent crosslinkability, whereby crosslinking or the like can be performed even by crosslinking only with electron beams, crosslinking at high temperature and for a long time can be avoided, phase separation inside the crosslinked molded article can be prevented, and the obtained crosslinked molded article is excellent in mechanical properties and surface properties, is excellent in weather resistance, and can be suitably used for applications requiring weather resistance, such as tire member applications and electric wire coating material applications.

Further, according to the present invention, it is possible to provide a resin composition which is easily improved in crosslinking density, hardly decreases in elongation even when the crosslinking density is increased, and can obtain a molded article having sufficient strength and heat resistance even if the molecular weight is in a range in which kneading is easy, and which is suitable for producing a vibration-damping rubber product. That is, according to the present invention, it is possible to provide a resin composition and a vibration-proof rubber product which have a remarkable effect of achieving both vibration-proof characteristics and heat aging resistance and which are excellent in balance between kneading properties and mechanical characteristics such as vibration-proof characteristics and elongation. The vibration-proof rubber product of the present invention has good rubber properties, excellent vibration-proof properties, and excellent heat resistance, and can be suitably used for applications requiring high heat resistance, such as vibration-proof rubber products for automobiles, particularly muffler suspension rubber.

Drawings

FIG. 1 is a schematic view of a continuous polymerization apparatus used in examples.

Detailed Description

The present invention will be described in detail below.

[ ethylene-alpha-olefin-nonconjugated polyene copolymer ]

The ethylene-alpha-olefin-nonconjugated polyene copolymer (S)) has structural units derived from ethylene (A), an alpha-olefin (B) having 3 to 20 carbon atoms, and a nonconjugated polyene (C) containing 2 or more partial structures selected from the group consisting of the following general formula (I) and general formula (II) in total in the molecule.

[ solution 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, and 1-eicosene. Among these, preferred are alpha-olefins having 3 to 8 carbon atoms such as propylene, 1-butene, 1-hexene, 1-octene, and the like, and particularly preferred is propylene. Such an α -olefin is preferable because the raw material cost is relatively low, and the obtained ethylene- α -olefin-nonconjugated polyene copolymer exhibits excellent mechanical properties, and further a molded article having rubber elasticity can be obtained. These alpha-olefins may be used singly or in combination of two or more.

That is, the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention may contain a structural unit derived from at least 1 kind of α -olefin (B) having 3 to 20 carbon atoms, or may contain a structural unit derived from 2 or more kinds of α -olefins (B) having 3 to 20 carbon atoms.

Examples of the nonconjugated polyene (C) containing 2 or more partial structures selected from the group consisting of the general formula (I) and the general formula (II) in total in the molecule include 5-vinyl-2-norbornene (VNB), norbornadiene, 1, 4-hexadiene, and dicyclopentadiene. Among these, the non-conjugated polyene (C) is preferably VNB, and more preferably VNB, from the viewpoint of high availability, good reactivity with a peroxide at the crosslinking reaction after polymerization, and easy improvement in heat resistance of the polymer composition. One species of the nonconjugated polyene (C) may be used alone, or two or more species may be used.

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention may further include a structural unit derived from a nonconjugated polyene (D) containing only 1 partial structure selected from the group consisting of the above general formulae (I) and (II) in the molecule, in addition to the structural units derived from ethylene (a), an alpha-olefin (B) having 3 to 20 carbon atoms, and the above nonconjugated polyene (C). One species of the nonconjugated polyene (D) may be used alone, or two or more species may be used.

Examples of the non-conjugated polyene (D) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5- (2-propenyl) -2-norbornene, 5- (3-butenyl) -2-norbornene, 5- (1-methyl-2-propenyl) -2-norbornene, 5- (4-pentenyl) -2-norbornene, 5- (1-methyl-3-butenyl) -2-norbornene, 5- (5-hexenyl) -2-norbornene, 5- (1-methyl-4-pentenyl) -2-norbornene, 5- (2, 3-dimethyl-3-butenyl) -2-norbornene, 5- (2-ethyl-3-butenyl) -2-norbornene, 5- (6-heptenyl) -2-norbornene, 5- (3-methyl-5-hexenyl) -2-norbornene, 5- (3, 4-dimethyl-4-pentenyl) -2-norbornene, 5- (3-ethyl-4-pentenyl) -2-norbornene, 5- (7-octenyl) -2-norbornene, 5- (2-methyl-6-heptenyl) -2-norbornene, and pharmaceutical compositions comprising the same, 5- (1, 2-dimethyl-5-hexenyl) -2-norbornene, 5- (5-ethyl-5-hexenyl) -2-norbornene, 5- (1,2, 3-trimethyl-4-pentenyl) -2-norbornene and the like. Among them, ENB is preferable in terms of high availability, high reactivity with sulfur and a vulcanization accelerator at the time of crosslinking reaction after polymerization, easy control of crosslinking rate, and easy obtainment of good mechanical properties.

When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention contains a structural unit derived from a nonconjugated polyene (D) having only 1 partial structure selected from the group consisting of the general formula (I) and the general formula (II) in the molecule, the proportion thereof is not particularly limited within a range not impairing the object of the present invention, and is usually contained in a weight fraction of 0 to 20% by weight, preferably 0 to 8% by weight, more preferably about 0.01 to 8% by weight (wherein the total of the weight fractions of (a), (B), (C), and (D) is 100% by weight).

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention is a copolymer having structural units derived from ethylene (a), an alpha-olefin (B) having 3 to 20 carbon atoms, the nonconjugated polyene (C), and, if necessary, the nonconjugated polyene (D), and satisfies the following requirements (i) to (vii).

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

(ii) The weight fraction of the structural units derived from the nonconjugated polyene (C) is 0.07 to 10% by weight.

(iii) The weight average molecular weight (Mw) of the ethylene- α -olefin-nonconjugated polyene copolymer, the weight fraction of structural units derived from the nonconjugated polyene (C) ((weight fraction (wt%) of C)), and the molecular weight of the nonconjugated polyene (C) ((molecular weight of C)) satisfy the following formula (1).

4.5. ltoreq. Mw x (C)/100/(C) molecular weight. ltoreq.40 40 … formula (1)

(iv) Complex viscosity η at a frequency ω of 0.1rad/s obtained by linear viscoelasticity measurement (190 ℃) using a rheometer^*(ω_＝0.1) (Pa sec) and a complex viscosity η at a frequency ω of 100rad/s^*(ω_＝100) (Pa sec) ratio P (. eta.)^*(ω_＝0.1)/η^*(ω_＝100) Eta, intrinsic viscosity [. eta. ]), and]and the weight fraction of the structural units derived from the non-conjugated polyene (C) (the weight fraction of (C)) satisfies the following formula (2).

P/([η]^2.9) Weight fraction of not more than (C). times.6 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) as measured by Gel Permeation Chromatography (GPC) is in the range of 8 to 30.

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

(vii) The pattern obtained by GPC measurement showed 2 or more peaks, and the area of the peak appearing on the side of the smallest molecular weight was 20% or less of the total peak area.

In the present specification, "an α -olefin having 3 to 20 carbon atoms" will be simply referred to as "an α -olefin".

< requirement (i) >

The requirements (i) define: the ethylene/alpha-olefin molar ratio in the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention satisfies 40/60 to 99.9/0.1, and is preferably 50/50 to 90/10, more preferably 55/45 to 85/15, and even more preferably 55/45 to 78/22. When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is used as a raw material for a crosslinked molded article, the resulting crosslinked molded article exhibits excellent rubber elasticity and is excellent in mechanical strength and flexibility.

The ethylene content (the content of the structural unit derived from the ethylene (A)) and the α -olefin content (the content of the structural unit derived from the α -olefin (B)) in the ethylene- α -olefin-nonconjugated polyene copolymer can be determined by¹³C-NMR was obtained.

< requirement (ii) >

The requirement (ii) defines: in the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, the weight fraction of the structural unit derived from the nonconjugated polyene (C) is in the range of 0.07 to 10% by weight in 100% by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (i.e., in total 100% by weight of the weight fractions of all the structural units). The weight fraction of the structural unit derived from the nonconjugated polyene (C) is preferably from 0.1 to 8.0% by weight, more preferably from 0.5 to 5.0% by weight.

Since the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention has sufficient hardness and excellent mechanical properties if the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfies requirement (ii), it is preferable that the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention exhibits a high crosslinking rate when crosslinked with a peroxide, so that the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is suitable for the production of a crosslinked molded product.

The amount of the nonconjugated polyene (C) (the content of the structural unit derived from the nonconjugated polyene (C)) in the ethylene- α -olefin-nonconjugated polyene copolymer can be determined by¹³C-NMR was obtained.

< requirement (iii) >

Requirement (iii) defines: in the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, the weight average molecular weight (Mw) of the ethylene- α -olefin-nonconjugated polyene copolymer, the weight fraction of the structural unit derived from the nonconjugated polyene (C) in the copolymer ((weight fraction of C): weight%) and the molecular weight of the nonconjugated polyene (C) ((molecular weight of C)) satisfy the following relational expression (1).

4.5. ltoreq. Mw x (C)/100/(C) molecular weight. ltoreq.40 40 … formula (1)

When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfies the requirement (iii), the ethylene- α -olefin-nonconjugated polyene copolymer is preferable because the content of the structural unit derived from the nonconjugated polyene (C) such as VNB is appropriate, sufficient crosslinking performance is exhibited, and when a crosslinked molded product is produced using the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, the crosslinking speed is excellent, and the crosslinked molded product exhibits excellent mechanical properties.

It is desirable that the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention more preferably satisfies the following relational formula (1').

4.5. ltoreq. Mw x (C) weight fraction/100/(C) molecular weight. ltoreq.35 35 … formula (1')

The weight average molecular weight (Mw) of the ethylene- α -olefin-nonconjugated polyene copolymer can be determined as a polystyrene-equivalent value measured by Gel Permeation Chromatography (GPC).

When the "weight fraction of Mw × (C)/molecular weight of 100/(C)" satisfies the above formula (1) or (1'), the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention can be suitably crosslinked, and by using the copolymer, a molded article having an excellent balance between mechanical properties and heat aging resistance can be produced. If the "weight fraction of Mw × (C)/molecular weight of 100/(C)" is too small, the crosslinking property may be insufficient and the crosslinking rate may be slow, and if too large, excessive crosslinking may occur and the mechanical properties may be deteriorated.

< requirement (iv) >

The requirement (iv) defines: the complex viscosity η at a frequency ω of 0.1rad/s obtained by measuring linear viscoelasticity (190 ℃) using a rheometer for the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention^*(ω_＝0.1) (Pa sec) and a complex viscosity η at a frequency ω of 100rad/s^*(ω_＝100) (Pa sec) ratio P (. eta.)^*(ω_＝0.1)/η^*(ω_＝100) Eta, intrinsic viscosity [. eta. ]), and]and the weight fraction of the structural units derived from the non-conjugated polyene (C) (weight fraction of C: weight%) satisfies the following formula (2).

P/([η]^2.9) Weight fraction of not more than (C). times.6 6 … formula (2)

Here, the complex viscosity η at a frequency ω of 0.1rad/s^*(ω_＝0.1) Complex viscosity eta with frequency omega of 100rad/s^*(ω_＝100) Ratio P (η)^*(ω_＝0.1)/η^*(ω_＝100) P/([ eta. ] eta.) to the left of formula (2) represents the frequency dependence of viscosity]^2.9) Although there are effects of short chain branching, molecular weight, etc., inWhen the number of long-chain branches is large, the value tends to be high. It is considered that the ethylene- α -olefin-nonconjugated polyene copolymer tends to contain more long-chain branches as the number of structural units derived from the nonconjugated polyene increases, but the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention has less long-chain branches than conventionally known ethylene- α -olefin-nonconjugated polyene copolymers, and can satisfy the above formula (2). In the present invention, the P value is a ratio (. eta.^*Ratio) of the two components.

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

P/([η]^2.9) Weight fraction of not more than (C). times.5.7 5.7 … formula (2')

The intrinsic viscosity [. eta. ] means a value measured in decalin at 135 ℃.

< requirement (v) >

The requirement (v) defines: the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention has a ratio (molecular weight distribution; Mw/Mn) of a weight average molecular weight (Mw) to a number average molecular weight (Mn) as measured by Gel Permeation Chromatography (GPC) within a range of 8 to 30. The molecular weight distribution (Mw/Mn) is preferably in the range of 9 to 28, more preferably 10 to 26.

When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfies the requirement (v), processability is improved because a low-molecular-weight component is contained in an appropriate amount.

The weight average molecular weight (Mw) and the number average molecular weight of the ethylene- α -olefin-nonconjugated polyene copolymer can be determined as polystyrene-equivalent values measured by Gel Permeation Chromatography (GPC).

< requirement (vi) >

The requirement (vi) defines: the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention has a number average molecular weight (Mn) of 30,000 or less. The number average molecular weight (Mn) is preferably in the range of 3,000 to 26,000, more preferably 6,000 to 23,000.

When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfies the requirement (vi), processability is improved because a low-molecular-weight component is contained in an appropriate amount.

< requirement (vii) >

Element (vii) defines: the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention shows 2 or more peaks in a pattern measured by GPC, and the area of the peak appearing on the side having the smallest molecular weight is 20% or less of the entire peak area. The area of the peak appearing on the side of the smallest molecular weight is preferably 2 to 18%, more preferably 3 to 16%, relative to the total peak area.

When the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfies the requirement (vii), the molecular weight distribution of the copolymer shows multimodality such as bimodality, and processability becomes good by containing a high molecular weight component and a low molecular weight component in an appropriate ratio.

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is preferably: number of Long chain branches per 1000 carbon atoms (LCB) obtained by 3D-GPC_1000C) And the natural number of weight average molecular weight (Mw) [ Ln (Mw)]Satisfies the following formula (3).

LCB_1000CLess than or equal to 1-0.07 XLn (Mw) … formula (3)

The upper limit of the content of the long-chain branch per unit number of carbon atoms of the ethylene- α -olefin-nonconjugated polyene copolymer is defined by the above formula (3).

Such an ethylene- α -olefin-unconjugated polyene copolymer is preferable because the proportion of long-chain branches contained is small, the curing properties in the case of crosslinking with a peroxide are excellent, and the heat aging resistance of a molded article obtained using the copolymer is excellent.

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention more preferably satisfies the following formula (3').

LCB_1000C1-0.071 XLn (Mw) … formula (3')

Here, Mw and the number of long-chain branches per 1000 carbon atoms (LCB)_1000C) Can be used forThe molecular weight was determined by a structure analysis method using 3D-GPC. In the present specification, the following is specifically found.

The absolute molecular weight distribution was determined using a 3D-high temperature GPC apparatus PL-GPC220 type (Polymer Laboratories, Inc.), and the intrinsic viscosity was determined using a viscometer. The main measurement conditions are as follows.

A detector: differential refractometer/GPC apparatus built-in

Two-angle light scattering photometer PD2040 model (Precison Detectors Co., Ltd.)

Bridge viscometer PL-BV400 type (Polymer Laboratories, Inc.)

Column: TSKgel GMHHR-H (S) HT × 2 roots + TSKgel GMHHR-M (S) × 1 roots

(each 1 root is)

Temperature: 140 deg.C

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

Sample introduction amount: 0.5mL

Sample concentration: ca 1.5mg/mL

And (3) filtering a sample: filtering with sintered filter with pore size of 1.0 μm

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

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

[ number 1]

[η]^i,br: measured intrinsic viscosity of the ith slice component

[η]^i,lin: it is assumed that the ith slice component has no long-chain branched structure and exhibits only a short lengthIntrinsic viscosity in the case of chain branched structure

Here, [ eta ] is applied]＝KM^v(ii) a And v is 0.725. This formula is called Mark-Houwink-Sakutan formula, K represents the solvent constant, and M represents the average molecular weight.

Further, as g', the average values were calculated from the following formulae (v-2), (v-3) and (v-4). Note that Trendline assumed to have only short-chain branches was identified for each sample.

[ number 2]

CⁱConcentration of each dissolved component

MⁱAbsolute molecular weight of each dissolved component

Further, using g' w, the number of branches per chain BrNo and the number of long chain branches per 1000 carbons LCB were calculated_1000CThe degree of branching λ per unit molecular weight. BrNo was calculated using the formula (v-5) of Zimm-Stockmayer, and LCB_1000CAnd λ are calculated by using the formulae (v-6) and (v-7). g is a long chain branch parameter determined from the radius of gyration Rg, and has the following simple correlation with g' determined from the intrinsic viscosity.

g＝g’^{(1/ )}

(structural factor) ═ 0.5 to 1.5 (usually 0.75)

Various values are proposed according to the form of the molecule in the formula, and the calculation is assumed to be 1 (that is, g ═ g).

[ number 3]

λ＝BrNo/M…(V-6)

LCB_1000C＝λ×14000…(V-7)

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

The intrinsic viscosity [ eta ] of the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention is preferably 0.1 to 5dL/g, more preferably 0.5 to 5.0dL/g, and still more preferably 0.9 to 4.0 dL/g.

The weight average molecular weight (Mw) of the ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention is preferably 10,000 to 600,000, more preferably 30,000 to 500,000, and still more preferably 50,000 to 400,000.

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention preferably satisfies both the above intrinsic viscosity [ eta ] and weight average molecular weight (Mw).

With respect to the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, the nonconjugated polyene (C) preferably comprises VNB, more preferably VNB. That is, in the above formulas (1), (2), and (4) and the like, the "(C) weight fraction" is preferably "VNB weight fraction" (wt%).

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention preferably contains the structural unit derived from the nonconjugated polyene (D) in a weight fraction of 0 to 20% by weight (wherein the total of the weight fractions of (a), (B), (C), and (D) is 100% by weight) in addition to the structural units derived from the above (a), (B), and (C) as described above. In this case, the following requirement (viii) is preferably satisfied.

< requirement (viii) >

The weight average molecular weight (Mw) of the ethylene- α -olefin-non-conjugated polyene copolymer, the weight fraction of the structural unit derived from the non-conjugated polyene (C) ((weight) of C), the weight fraction of the structural unit derived from the conjugated polyene (D) ((weight) of D)), the molecular weight of the non-conjugated polyene (C) ((molecular weight of C)) and the molecular weight of the conjugated polyene (D) ((molecular weight of D)) satisfy the following formula (4).

4.5. ltoreq. Mw × { ((weight fraction of (C)/100/(molecular weight of C)) + ((weight fraction of (D)/100/(molecular weight of D) } 45 or less 45 … formula (4)

In the formula (4), the content of the non-conjugated diene (the total of (C) and (D)) in the molecule of the copolymer 1 is defined.

In the case where the ethylene- α -olefin-nonconjugated polyene copolymer containing the structural unit derived from the above (D) satisfies the formula (4), a molded body obtained from the ethylene- α -olefin-nonconjugated polyene copolymer exhibits excellent mechanical properties and heat aging resistance, and is therefore preferable.

If the requirement (viii) is not satisfied and "Mw × { ((weight fraction of (C)/100/(C) molecular weight) + ((weight fraction of) 100/(D)) }" in formula (4) is too small, that is, if the content of the non-conjugated diene is too small, adequate crosslinking may not be achieved and appropriate mechanical properties may not be obtained, and if too much, crosslinking may become excessive and mechanical properties may deteriorate and heat aging resistance may deteriorate.

< essential part (ix) >

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is not particularly limited, but it is obtained by measuring the linear viscoelasticity (190 ℃) using a rheometer and has a complex viscosity η at a frequency ω of 0.01rad/s^*(ω_＝0.01) (Pa sec) and a complex viscosity η at a frequency ω of 10rad/s^*(ω_＝10) The apparent iodine values of (Pa sec) and the non-conjugated polyene (C) preferably satisfy the following formula (5).

Log{η^*(ω_＝0.01)}/Log{η^*(ω_＝10) 0.0753 x { apparent iodine value derived from a nonconjugated polyene (C) } +1.42 … formula (5)

Here, the complex viscosity η in the requirement (iv) is determined in addition to the frequency^*(ω_＝0.1) And complex viscosity η^*(ω_＝100) Similarly, the complex viscosity η is determined^*(ω_＝0.01) And complex viscosity η^*(ω_＝10)。

The apparent iodine value derived from the nonconjugated polyene (C) is determined by the following equation.

The apparent iodine value derived from (C) is the weight fraction of (C) x 253.81/(C) molecular weight

In the above formula (5), the left side indicates the shear rate dependency as an index of the amount of long-chain branches, and the right side indicates an index of the content of the nonconjugated polyene (C) which is not consumed as long-chain branches at the time of polymerization. When the requirement (ix) is satisfied and the formula (5) is satisfied, the degree of long-chain branching is not excessively high, and therefore, it is preferable. On the other hand, when the formula (5) is not satisfied, it is found that the non-conjugated polyene (C) after copolymerization is consumed in a large proportion at the time of formation of a long-chain branch.

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

A weight fraction of 6-0.45 XLn (Mw) not more than 10 … formula (6)

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention has the number of structural units derived from the nonconjugated polyene (C) (n) per weight average molecular weight (Mw)_C) Preferably 6 or more, more preferably 6 or more and 40 or less, still more preferably 7 or more and 39 or less, and particularly preferably 10 or more and 38 or less.

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention as described above contains a sufficient amount of structural units derived from a nonconjugated polyene (C) such as VNB, has a small content of long-chain branches, is excellent in curing characteristics when crosslinked with a peroxide, is good in moldability and processability, is excellent in a balance of physical properties such as mechanical properties, and is particularly excellent in heat aging resistance. In particular, the ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention exhibits an unexpected special effect of high crosslink density after crosslinking, although processability becomes good by containing a low-molecular-weight component. In general, when the low-molecular weight component is contained in a large amount, the crosslinking density tends to decrease, but in the case of the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, it is presumed that the low-molecular weight component is also crosslinked, and therefore such unexpected special effect is obtained. This also achieves the effect of avoiding the problems such as stickiness, which are common to conventional EPDM containing a large amount of low-molecular weight components.

It is further desirable that the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention has the number of structural units derived from the nonconjugated polyene (D) (n) per weight average molecular weight (Mw)_D) Preferably 29 or less, more preferably 10 or less, and still more preferably less than 1.

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is preferably such that the content of the structural unit derived from a nonconjugated polyene (D) such as ENB is suppressed within a range not to impair the object of the present invention, post-crosslinking is less likely to occur, and sufficient heat aging resistance is obtained.

Here, the number of structural units derived from the nonconjugated polyene (C) (n) per weight average molecular weight (Mw) of the ethylene-alpha-olefin-nonconjugated polyene copolymer_C) Or the number of structural units (n) derived from the nonconjugated polyene (D)_D) The molecular weight of the nonconjugated polyene (C) or (D), the weight fraction of the structural units derived from the nonconjugated polyene (C) or (D) in the copolymer ((weight fraction (wt%) of the nonconjugated polyene (C) or (D)), and the weight average molecular weight (Mw) of the copolymer can be determined by the following formula.

(n_C) (Mw) x { (C) weight fraction/100 }/molecular weight of the nonconjugated polyene (C)

(n_D) (Mw) x { (D) weight fraction/100 }/molecular weight of the nonconjugated polyene (D)

The ethylene-alpha-olefin-nonconjugated polyene copolymer in the present invention has an average molecular weight (Mw) per weight due to the number (n) of the respective structural units derived from the nonconjugated polyenes (C) and (D) _C) And (n)_D) When the content of the long-chain branch of the ethylene- α -olefin-unconjugated polyene copolymer is within the above range, the ethylene- α -olefin-unconjugated polyene copolymer is preferably small, the curing property in the case of crosslinking with a peroxide is excellent, the moldability and processability are good, the physical property balance such as mechanical properties is excellent, the post-crosslinking is less likely to occur, and the heat aging resistance is particularly excellent.

[ production of ethylene-alpha-olefin-nonconjugated polyene copolymer ]

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention is a copolymer obtained by copolymerizing monomers including ethylene (a), an alpha-olefin (B) having 3 to 20 carbon atoms, the nonconjugated polyene (C), and, if necessary, the nonconjugated polyene (D).

The ethylene- α -olefin-nonconjugated polyene copolymer of the present invention can be prepared by any method as long as the above requirements (i) to (vii) are satisfied, and can be obtained by copolymerizing monomers preferably in the presence of a metallocene compound, more preferably in the presence of a polymerization catalyst system containing a metallocene compound, and further preferably by a method comprising the steps of: a step (1) of carrying out copolymerization in the presence of a polymerization catalyst containing a specific metallocene compound, and a step (2) of adding an alcohol as a catalyst deactivator to deactivate the polymerization catalyst.

< metallocene Compound >

It is desirable that the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention is obtained by copolymerizing monomers in the presence of a polymerization catalyst system containing at least 1 metallocene compound selected from the compounds represented by the following general formula [ A1 ]. When the copolymerization of the monomers is carried out using a polymerization catalyst system containing such a metallocene compound, the long-chain branches contained in the resulting copolymer can be suppressed, and the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention satisfying the above requirements can be easily prepared.

[ solution 3]

The above formula [ A1]In, R¹、R²、R³、R⁴、R⁵、R⁸、R⁹And R¹²Each independently represents a hydrogen atom, a hydrocarbon group, a silicon-containing group or a hetero atom-containing group other than a silicon-containing group, R¹～R⁴Wherein adjacent two groups may be bonded to each other to form a ring.

The hydrocarbyl group is preferably a hydrocarbyl group having 1 to 20 carbon atoms, and specific examples thereof include an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group (aryl) having 6 to 20 carbon atoms, a substituted aryl group (aryl), and the like. Examples thereof include methyl group, ethyl group, n-propyl group, isopropyl group, allyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, 3-methylpentyl group, 1-diethylpropyl group, 1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, isopropylphenyl group, tert-butylphenyl group, naphthyl group, biphenyl group, terphenyl group, Phenanthryl, anthryl, benzyl, cumyl, and also include oxygen-containing groups such as methoxy, ethoxy, and phenoxy groups; nitrogen-containing groups such as nitro, cyano, N-methylamino, N-dimethylamino, and N-phenylamino groups; boron-containing groups such as borane triyl and diborane groups; sulfonyl, sulfinyl, and the like sulfur-containing groups as the hydrocarbon group.

The hydrogen atom of the hydrocarbon group may be substituted with a halogen atom, and examples thereof include a trifluoromethyl group, a trifluoromethylphenyl group, a pentafluorophenyl group, and a chlorophenyl group.

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

R⁶And R¹¹Is the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than the silicon-containing group, R⁷And R¹⁰Is the same atom or the same group selected from hydrogen atom, hydrocarbon group, silicon-containing group and hetero atom-containing group other than the silicon-containing group, R⁶And R⁷May combine with each other to form a ring, R¹⁰And R¹¹Can be mutually combinedAnd then combined to form a ring. Wherein R is⁶、R⁷、R¹⁰And R¹¹Not all hydrogen atoms.

R¹³And R¹⁴Each independently represents an aryl group.

M¹Represents a zirconium atom.

Y¹Represents 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 having 4 to 20 carbon atoms, an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair, j represents an integer of 1 to 4, and when j is an integer of 2 or more, the Q may be the same or different.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

The hydrocarbon group is preferably a hydrocarbon group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a 2-methylpropyl group, a 1, 1-dimethylpropyl group, a 2, 2-dimethylpropyl group, a 1, 1-diethylpropyl group, a 1-ethyl-1-methylpropyl group, a 1,1,2, 2-tetramethylpropyl group, a sec-butyl group, a tert-butyl group, a 1, 1-dimethylbutyl group, a 1,1, 3-trimethylbutyl group, a neopentyl group, a cyclohexylmethyl group, a cyclohexyl group, a 1-methyl-1-cyclohexyl group, and a benzyl group, and preferably a methyl group, an ethyl group, and a benzyl group.

The neutral conjugated or non-conjugated diene having 4 to 20 carbon atoms is preferably a neutral conjugated or non-conjugated diene having 4 to 10 carbon atoms. Specific examples of the neutral conjugated or non-conjugated diene include s-cis-and s-trans-. eta.⁴-1, 3-butadiene, s-cis-or s-trans-eta⁴-1, 4-diphenyl-1, 3-butadiene, s-cis-or s-trans-eta⁴-3-methyl-1, 3-pentadiene, s-cis-or s-trans-eta⁴-1, 4-dibenzyl-1, 3-butadiene, s-cis-or s-trans-eta⁴-2, 4-hexadiene, s-cis-or s-trans-eta⁴-1, 3-pentadiene, s-cis-or s-trans-eta ⁴-1, 4-xylyl-1, 3-butadiene, s-cis-or s-trans-eta⁴1, 4-bis (trimethylsilyl) -1, 3-butadiene and the like.

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

Specific examples of the neutral ligand capable of coordinating with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine and diphenylmethylphosphine, and tetrahydrofuran, diethyl ether and di-n-butyl ether

And ethers such as alkane and 1, 2-dimethoxyethane.

As the above formula [ A1]With a substituent R in (1)¹～R⁴Examples of the cyclopentadienyl group of (1) include R¹～R⁴3-position monosubstituted cyclopentadienyl such as unsubstituted cyclopentadienyl, 3-tert-butylcyclopentadienyl, 3-methylcyclopentadienyl, 3-trimethylsilylcyclopentadienyl, 3-phenylcyclopentadienyl, 3-adamantylcyclopentadienyl, 3-pentylcyclopentadienyl, 3-cyclohexylcyclopentadienyl, etc., 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., which are hydrogen atoms, a 5-disubstituted cyclopentadienyl group, and the like, but is not limited thereto. From the viewpoints of ease of synthesis of the metallocene compound, production cost, and copolymerization ability of the nonconjugated polyene, the unsubstituted (R) is preferred ¹～R⁴Hydrogen atom).

As formula [ A1]With a substituent R in (1)⁵～R¹²Examples of the fluorenyl group include:

R⁵～R¹²an unsubstituted fluorenyl group which is a hydrogen atom,

2-position monosubstituted fluorenyl groups such as 2-methylfluorenyl group, 2-t-butylfluorenyl group, 2-phenylfluorenyl group and the like,

4-position mono-substituted fluorenyl groups such as 4-methylfluorenyl group, 4-t-butylfluorenyl group, 4-phenylfluorenyl group and the like,

or a 2, 7-or 3, 6-disubstituted fluorenyl group such as a 2, 7-di-t-butylfluorenyl group or a 3, 6-di-t-butylfluorenyl group,

2,3,6, 7-tetrasubstituted fluorenyl group such as 2, 7-dimethyl-3, 6-di-t-butylfluorenyl group and 2, 7-diphenyl-3, 6-di-t-butylfluorenyl group,

or the following general formula [ V-I]、[V-II]R as shown⁶And R⁷Combine with each other to form a ring, R¹⁰And R¹¹And 2,3,6, 7-tetrasubstituted fluorenyl group and the like which are bonded to each other to form a ring, but are not limited thereto.

[ solution 4]

[ solution 5]

Formula [ V-I]、[V-II]In, R⁵、R⁸、R⁹、R¹²And the above general formula [ A1 ]]The same applies to the definition in (1),

R^a、R^b、R^c、R^d、R^e、R^f、R^gand R^hEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and may form a ring by bonding to each other an adjacent substituent. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, a pentyl group, and an n-pentyl group. Furthermore, formula [ V-I]In, R^xAnd R^yEach independently a hydrocarbon group having 1 to 3 carbon atoms which may have an unsaturated bond, R ^xCan be reacted with R^aOr R^cThe bound carbons together form a double bond, R^yCan be reacted with R^eOr R^gThe bound carbons together form a double bond, R^xAnd R^yPreferably, they are each a saturated or unsaturated hydrocarbon group having 1 or 2 carbon atoms.

Specific examples of the compound represented by the general formula [ V-I ] or [ V-II ] include octamethyloctahydrodibenzofluorenyl group represented by the formula [ V-III ], tetramethyldodecadihydrodibenzofluorenyl group represented by the formula [ V-IV ], octamethyltetrahydrodicyclopentadienofluorenyl group represented by the formula [ V-V ], hexamethyldihydrodicyclopentadienofluorenyl group represented by the formula [ V-VI ] and b, h-dibenzofluorenyl group represented by the formula [ V-VII ].

[ solution 6]

[ solution 7]

[ solution 8]

[ solution 9]

[ solution 10]

Containing these fluorenyl groups is represented by the general formula [ A1]The metallocene compounds shown therein all have excellent copolymerization ability with respect to unconjugated polyenes, and Y is¹When it is a silicon atom, it has a 2, 7-disubstituted fluorenyl group, a 3, 6-disubstituted fluorenyl group, a 2,3,6, 7-tetrasubstituted fluorenyl group, the above general formula [ V-I ]]The transition metal compound represented by the 2,3,6, 7-tetrasubstituted fluorenyl group is particularly excellent. When Y is a carbon atom, has R⁵～R¹²Unsubstituted fluorenyl group which is a hydrogen atom, disubstituted fluorenyl group at the 3, 6-position, tetrasubstituted fluorenyl group at the 2,3,6, 7-position, the above general formula [ V-I]The metallocene compound having a 2,3,6, 7-tetrasubstituted fluorenyl group is particularly excellent.

In the present invention, the general formula [ A1 ] is]In the metallocene compound shown, in Y¹Is a silicon atom, and R⁵～R¹²In the case where all are hydrogen atoms, R¹³And R¹⁴Preferably selected from the group consisting of methyl, butyl, phenyl, silicon-substituted phenyl, cyclohexyl, benzyl;

at Y¹Is a silicon atom, R⁶And R¹¹Is also tert-butyl, and R⁵、R⁷、R⁸、R⁹、R¹⁰、R¹²In the case where R is not tert-butyl¹³And R¹⁴Preferably selected from groups other than benzyl and silicon-substituted phenyl;

at Y¹Is a carbon atom, and R⁵～R¹²In the case where all are hydrogen atoms, R¹³And R¹⁴Preferably selected from the group consisting of groups other than methyl, isopropyl, tert-butyl, isobutyl, phenyl, p-tert-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl, 4-biphenyl, p-tolyl, naphthyl, benzyl, cyclopentyl, cyclohexyl and xylyl;

at Y¹Is a carbon atom, R⁶And R¹¹Is the same group selected from tert-butyl, methyl or phenyl, and is the same as R⁵、R⁷、R⁸、R⁹、R¹⁰And R¹²In the case of different radicals or atoms, R¹³And R¹⁴Preferably selected from the group consisting of groups other than methyl, phenyl, p-tert-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl and benzyl;

at Y¹Is a carbon atom, R⁶Is dimethylamino, methoxy or methyl, and R⁵、R⁷、R⁸、R⁹、R¹⁰、R¹¹And R¹²Is a reaction with R ⁶In the case of different radicals or atoms, R¹³And R¹⁴Preferably selected from groups other than methyl and phenyl;

at Y¹Is a carbon atom, and fluorenyl and R⁵～R¹²When the moiety is b, h-dibenzofluorenyl or a, i-dibenzofluorenyl, R is¹³And R¹⁴Preferably selected from groups other than methyl and phenyl.

Specific examples of the metallocene compound represented by the above general formula [ A1] in the present invention will be described below, but the scope of the present invention is not particularly limited thereto.

Specific examples of the metallocene compound represented by the above general formula [ A1] in the present invention,

when Y is a silicon atom, there may be mentioned:

diphenylsilylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Diphenylsilylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (p-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (m-tolyl) silylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

And the like.

When Y is a carbon atom, there may be mentioned:

Diphenylmethylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Diphenylmethylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (p-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene fluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (m-tolyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienofluorenyl) zirconium dichloride,

Bis (p-tert-butylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (4-biphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-t-butylfluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (p-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-t-butylfluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-t-butylfluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (m-chlorophenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (m-trifluoromethylphenyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (2, 7-di-tert-butylfluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (2, 7-dimethyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (2, 7-diphenyl-3, 6-di-tert-butylfluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (tetramethyldodecahydrodibenzofluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentadiene-fluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (hexamethyldihydrodicyclopentadienylfluorenyl) zirconium dichloride,

Bis (2-naphthyl) methylene (cyclopentadienyl) (b, h-dibenzofluorenyl) zirconium dichloride

And the like.

As examples of the structural formula of the metallocene compound represented by the above general formula [ a1], structural formulas of bis (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (a)) and bis (p-chlorophenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride (the following (B)) are shown below.

[ solution 11]

The metallocene compound may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The metallocene compound represented by the above formula [ a1], which can be suitably used for preparing the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention, is not particularly limited, and can be produced by any method. Specifically, the compound can be produced by the methods described in, for example, J.organomet.chem.,63,509(1996), WO2005/100410, WO2006/123759, WO01/27124, Japanese patent application laid-open No. 2004-168744, Japanese patent application laid-open No. 2004-175759, and Japanese patent application laid-open No. 2000-212194.

< polymerization catalyst containing metallocene Compound >

Examples of the polymerization catalyst which can be suitably used for producing the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention include those which contain the metallocene compound [ a1] and can copolymerize a monomer.

Preferably, a polymerization catalyst comprising (a), (b) and, if necessary, (c),

(a) a metallocene compound represented by the general formula [ A1],

(b) At least 1 compound selected from the group consisting of (b-1) an organometallic compound, (b-2) an organoaluminum oxy-compound and (b-3) a compound which reacts with the metallocene compound (a) to form an ion pair (hereinafter, also referred to as "ionizing ionic compound"), and

(c) a particulate carrier. Hereinafter, each component will be specifically described.

Compound (b)

The compound (b) is at least 1 compound selected from the group consisting of (b-1) an organometallic compound, (b-2) an organoaluminum oxy-compound and (b-3) an ionizing ionic compound, and preferably at least the organometallic compound (b-1) is contained.

(b-1) organometallic Compound

As the organometallic compound (b-1), for example, organometallic compounds of groups 1 and 2 and groups 12 and 13 of the periodic Table of the elements such as the following general formulae [ VII ] to [ IX ] can be used.

(b-1a) an organoaluminum compound represented by the general formula [ VII ].

A compound of the general formula: r^a _mAl(OR^b)_nH_pX_q…[VII]

(formula [ VII ]]In, R^aAnd R^bThe alkyl group may be the same or different from each other and has 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X represents a halogen atom, m is 0 < m < 3, n is 0 < n < 3, p is 0 < p < 3, q is a number of 0 < q < 3, and m + n + p + q is 3. )

Examples of such a compound include trialkylaluminums such as trimethylaluminum, triethylaluminum, triisobutylaluminum and tri-n-octylaluminum, tricycloalkylaluminum, isobutylaluminum dichloride, diethylaluminum chloride, ethylaluminum dichloride, ethylaluminum sesquiethylaluminum chloride, methylaluminum dichloride, dimethylaluminum chloride and diisobutylaluminum hydride.

(b-1b) a complex alkylate of a metal of group 1 of the periodic Table of the elements represented by the general formula [ VIII ] with aluminum.

A compound of the general formula: m²AlR^a ₄…[VIII]

(formula [ VIII)]In, M²Represents Li, Na or K, R^aIs a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. )

Examples of such a compound include LiAl (C)₂H₅)₄、LiAl(C₇H₁₅)₄And the like.

(b-1c) a dialkyl compound of a metal of group 2 or group 12 of the periodic Table of the elements represented by the general formula [ IX ].

A compound of the general formula: r^aR^bM³…[IX]

(formula [ IX [)]In, R^aAnd R^bThe same or different alkyl groups each represent a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M represents ³Is Mg, Zn or Cd. )

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

(b-2) organoaluminum oxy-compound

The organoaluminum oxy-compound (b-2) may be a conventionally known aluminoxane or a benzene-insoluble organoaluminum oxy-compound such as that exemplified in Japanese patent application laid-open No. 2-78687.

Conventionally known aluminoxanes can be produced by the following method, for example, and are usually obtained as a solution in a hydrocarbon solvent.

(1) A method in which an organoaluminum compound such as trialkylaluminum is added to a hydrocarbon medium suspension of a compound containing adsorbed water or a salt containing water of crystallization, for example, magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, cerium chloride hydrate or the like, and the adsorbed water or the water of crystallization is reacted with the organoaluminum compound. (2) A method in which water, ice or water vapor is allowed to directly act on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, diethyl ether or tetrahydrofuran.

(3) A method of reacting an organotin oxide such as dimethyltin oxide or dibutyltin oxide with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene or toluene.

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

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

Among them, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum and triisobutylaluminum are particularly preferable.

The above-mentioned organoaluminum compounds may be used singly or in combination of 1 or more.

In addition, as for the benzene-insoluble organoaluminum oxy-compound which is one form of the organoaluminum oxy-compound (b-2) used in the present invention, it is preferable that the Al component of benzene dissolved at 60 ℃ is usually 10% by weight or less, preferably 5% by weight or less, particularly preferably 2% by weight or less, in terms of Al atom, based on 100% by weight of benzene, that is, it is preferable that the organoaluminum oxy-compound shows insolubility or insolubility to benzene.

The organoaluminum oxy-compound (b-2) used in the present invention includes an organoaluminum oxy-compound containing boron represented by the following general formula [ X ].

[ solution 12]

Formula [ X ]]In, R¹Represents a hydrocarbon group having 1 to 10 carbon atoms, R²～R⁵The alkyl groups may be the same or different and each represents a hydrogen atom, a halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.

The organoaluminum oxy-compound containing boron represented by the general formula [ X ] can be produced by reacting an alkylboronic acid represented by the general formula [ XI ] with an organoaluminum compound in an inert solvent in an inert gas atmosphere at a temperature of-80 ℃ to room temperature for 1 minute to 24 hours.

A compound of the general formula: r¹-B(OH)₂…[XI]

(formula [ XI ]]In, R¹Is represented by the general formula [ X ] above]R in (1)¹The same groups. )

Examples of the alkylboronic acid represented by the above general formula [ XI ] include methylboronic acid, ethylboronic acid, isopropylboronic acid, n-propylboronic acid, n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid, cyclohexylboronic acid, phenylboronic acid, 3, 5-difluorophenylboronic acid, pentafluorophenylboronic acid, 3, 5-bis (trifluoromethyl) phenylboronic acid and the like.

Among them, methylboronic acid, n-butylboronic acid, isobutylboronic acid, 3, 5-difluorophenylboronic acid and pentafluorophenylboronic acid are preferable. These can be used alone in 1 or a combination of 2 or more.

Examples of the organoaluminum compound to be reacted with such an alkylboronic acid include the same organoaluminum compounds as exemplified as the organoaluminum compounds belonging to the above-mentioned (b-1 a). Among them, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum and triisobutylaluminum are particularly preferable.

The organoaluminum oxy-compounds (b-2) mentioned above may be used singly in 1 kind or in combination in 2 or more kinds.

(b-3) ionizing Ionic Compound

Examples of the ionizing ionic compound (b-3) include Lewis acids, ionic compounds, borane compounds, carborane compounds, and the like described in, for example, Japanese patent application laid-open Nos. H1-501950, 1-502036, 3-179005, 3-179006, 3-207703, 3-207704, and 5321106. Further, heteropoly compounds and isopoly compounds can be mentioned. Such ionizing ionic compounds (b-3) may be used alone in 1 kind or in combination of 2 or more kinds.

Specifically, as the Lewis acid, BR can be mentioned₃(R is a phenyl group or a fluorine group which may have a substituent such as a fluorine group, a methyl group or a trifluoromethyl group), examples of the compound include trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3, 5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-tolyl) boron, tris (o-tolyl) boron and tris (3, 5-dimethylphenyl) boron.

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

[ solution 13]

Formula [ XII]In (1) as R¹⁺Examples thereof include H⁺Carbon, carbonCation, oxygen

A cation, an ammonium cation,

Cation, cycloheptatrienyl cation, ferrocene with transition metalCations, and the like. R²～R⁵Which may be the same or different from each other, are organic groups, preferably aryl or substituted aryl groups.

As the above carbon

The cation may specifically be a triphenylcarbonCationic, tri (methylphenyl) carbons

Cationic, tri (dimethylphenyl) carbonsTri-substituted carbons such as cationsCations, and the like.

Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri (n-butyl) ammonium cation;

n, N-dialkylanilinium cations such as N, N-dimethylanilinium cation, N-diethylanilinium cation, and N, N,2,4, 6-pentamethylanilinium cation;

and dialkylammonium cations such as di (isopropyl) ammonium cation and dicyclohexylammonium cation.

As mentioned aboveThe cation includes, specifically, triphenylCationic, tris (methylphenyl)Cationic, tris (dimethylphenyl)

Triaryl radicals such as cationsCations, and the like.

As R ¹⁺Preferably carbonCation, ammonium cation, etc., particularly preferably triphenylcarbonCation, N-dimethylanilinium cation, N-diethylanilinium cation.

Further, examples of the ionic compound include trialkyl-substituted ammonium salts, N-dialkylanilinium salts, dialkylammonium salts, and triaryl saltsSalts and the like.

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

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

Specific examples of the dialkyl ammonium salt include bis (1-propyl) ammonium tetrakis (pentafluorophenyl) boron, dicyclohexylammonium tetrakis (phenyl) boron and the like.

Further, examples of the ionic compound include a triphenyl carbonTetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, ferroceneTetrakis (pentafluorophenyl) borate, triphenylcarbenesA pentaphenylcyclopentadienyl complex, an N, N-diethylanilinium pentaphenylcyclopentadienyl complex, a pentaphenylcyclopentadienyl complex represented by the formula [ XIII]Or [ XIV ]]Boron compounds shown below, and the like. In the following formula, Et represents an ethyl group.

[ solution 14]

[ solution 15]

Specific examples of the borane compound include

Decaborane;

salts of anions such as bis [ tri (n-butyl) ammonium ] nonaborate, bis [ tri (n-butyl) ammonium ] decaborate, bis [ tri (n-butyl) ammonium ] undecaborate, bis [ tri (n-butyl) ammonium ] dodecaborate, bis [ tri (n-butyl) ammonium ] decachlorodecaborate, bis [ tri (n-butyl) ammonium ] dodecachlorododecaborate, and the like;

and salts of metal borane anions such as tris (n-butyl) ammonium bis (dodecahydrododecaborate) cobaltate (III) and bis [ tri (n-butyl) ammonium ] bis (dodecahydrododecaborate) nickelate (III).

Specific examples of the carborane compound include 4-carbanonaborane, 1, 3-dicarbanonaborane, 6, 9-dicarbadecaborane, dodecahydro-1-phenyl-1, 3-dicarbanonaborane, dodecahydro-1-methyl-1, 3-dicarbanonaborane, undecahydro-1, 3-dimethyl-1, 3-dicarbanonaborane, 7, 8-dicarbaundecaborane, 2, 7-dicarbaundecaborane, undecahydro-7, 8-dimethyl-7, 8-dicarbaundecaborane, dodecahydro-11-methyl-2, 7-dicarbaundecaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaundecaborate, and the like, Tri (n-butyl) ammonium-1-carbadodecaborate, tri (n-butyl) ammonium-1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromide-1-carbadodecaborate, tri (n-butyl) ammonium-6-carbadecaborate, tri (n-butyl) ammonium-7-carbaundecaborate, tri (n-butyl) ammonium-7, 8-dicarbaundecaborate, tri (n-butyl) ammonium-2, 9-dicarbaundecaborate, tri (n-butyl) ammonium dodecahydro-8-methyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydro-8-ethyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydro-8-butyl-7, anion salts such as 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydrido-8-allyl-7, 9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydrido-9-trimethylsilyl-7, 8-dicarbaundecaborate, tri (n-butyl) ammonium undecahydrido-4, 6-dibromo-7-carbaundecaborate;

Tri (n-butyl) ammonium bis (nonahydro-1, 3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydro-7, 8-dicarbaundecaborate) ferrite (III), tri (n-butyl) ammonium bis (undecahydro-7, 8-dicarbaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydro-7, 8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydro-7, 8-dicarbaundecaborate) cuprate (III), tri (n-butyl) ammonium bis (undecahydro-7, 8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydro-7, 8-dimethyl-7, 8-dicarbaundecaborate) ferrite (III), And metal carborane anion salts such as tri (n-butyl) ammonium bis (nonahydro-7, 8-dimethyl-7, 8-dicaundecaborate) chromate (III), tri (n-butyl) ammonium bis (tribromooctahydro-7, 8-dicaundecaborate) cobaltate (III), tri (n-butyl) ammonium bis (undecahydrido-7-carbaundecaborate) chromate (III), bis (tri (n-butyl) ammonium) bis (undecahydrido-7-carbaundecaborate) manganate (IV), bis (tri (n-butyl) ammonium) bis (undecahydrido-7-carbaundecaborate) cobaltate (III), and bis (tri (n-butyl) ammonium) bis (undecahydrido-7-carbaundecaborate) nickelate (IV).

The heteropoly compound is formed of an atom selected from the group consisting of silicon, phosphorus, titanium, germanium, arsenic and tin and 1 or more than 2 atoms selected from the group consisting of vanadium, niobium, molybdenum and tungsten. Specifically, phosphovanadic acid, germanomovanadic acid, arseniovanadic acid, phosphoniobic acid, germanomoniobic acid, silicomolybdic acid, phosphomolybdic acid, titanolybdic acid, germanomolybdic acid, arsenomolybdic acid, stannomolybdic acid, phosphotungstic acid, germanotungstic acid, stannotungstic acid, phosphomolybdovanadic acid, phosphotungstovanadic acid, germanotungstovanadic acid, phosphomolybdotungstovanadic acid, germanomotungstovanadic acid, phosphomolybdotungstovanadic acid, phosphomolybdotungstic acid, phosphomolybdoni; salts with, for example, metals of group 1 or group 2 of the periodic table, specifically, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, and the like; organic salts such as triphenylethyl salt, but not limited thereto.

Among the ionizing ionic compounds (b-3), the above-mentioned ionic compounds are preferred, and among them, triphenylcarbon is more preferred

Tetrakis (pentafluorophenyl) borate, N-dimethylanilinium tetrakis (pentafluorophenyl) borate.

In the present invention, as the polymerization catalyst, those containing the above-mentioned general formula [ A1 ] are used]The metallocene compound (a), an organometallic compound (b-1) such as triisobutylaluminum, an organoaluminum oxy-compound (b-2) such as methylaluminoxane, and a triphenylcarbon The metallocene catalyst of the ionizing compound (b-3) such as tetrakis (pentafluorophenyl) borate can exhibit a very high polymerization activity in the production of an ethylene- α -olefin-nonconjugated polyene copolymer.

(c) Particulate carrier

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

The inorganic compound is preferably a porous oxide, an inorganic halide, a clay mineral, or an ion-exchange layered compound. Specific examples thereof include inorganic compounds described in WO 2015/122495.

The clay, clay mineral, and ion-exchange layered compound used in the present invention may be used as they are, or may be used after being subjected to treatment such as ball milling or sieving. Further, it may be used after adding water again to adsorb it or after heat dehydration treatment. Further, these may be used alone or in combination of 2 or more.

Among them, preferred are clays or clay minerals, and particularly preferred are montmorillonite, vermiculite, hectorite, taeniolite and synthetic mica.

Examples of the organic compound include a granular or particulate solid having a particle diameter in the range of 10 to 300 μm. Specifically, a (co) polymer mainly composed of an α -olefin having 2 to 14 carbon atoms such as ethylene, propylene, 1-butene, 4-methyl-1-pentene, a (co) polymer mainly composed of vinylcyclohexane and styrene, and modified products thereof are exemplified.

The metallocene catalyst used in the present invention may further contain a specific organic compound component (d) as required, in addition to the metallocene compound (a), at least 1 compound (b) selected from the group consisting of the organometallic compound (b-1), the organoaluminum oxy-compound (b-2) and the ionizing ionic compound (b-3), and the carrier (c) as required.

(d) Organic compound component

In the present invention, the organic compound component (d) is used as needed 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.

< production method and conditions >

The ethylene- α -olefin-nonconjugated polyene copolymer (hereinafter, sometimes referred to as "ethylene- α -olefin-nonconjugated polyene copolymer (S)") according to the present invention can be produced by copolymerizing monomers including ethylene (a), an α -olefin (B) having 3 to 20 carbon atoms, the nonconjugated polyene (C), and, if necessary, the nonconjugated polyene (D).

In the case of copolymerizing a monomer, the method of using each component constituting the above polymerization catalyst and the order of addition may be arbitrarily selected, and the following methods can be exemplified.

(1) A method in which the metallocene compound (a) is added separately to a polymerizer.

(2) A method in which the metallocene compound (a) and the compound (b) are added to a polymerization vessel in an arbitrary order.

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

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

(5) A method of adding a catalyst component comprising a metallocene compound (a) and a compound (b) supported on a carrier (c) to a polymerization reactor.

In each of the above-mentioned methods (2) to (5), at least 2 of the metallocene compound (a), the compound (b) and the support (c) may be contacted in advance.

In each of the above-mentioned methods (4) and (5) in which the compound (b) is supported, the unsupported compound (b) may be added in an arbitrary order as required. In this case, the compound (b) may be the same as or different from the compound (b) supported by the carrier (c).

The solid catalyst component having the metallocene compound (a) supported on the carrier (c) and the solid catalyst component having the metallocene compound (a) and the compound (b) supported on the carrier (c) may be polymerized with an olefin in advance, or the catalyst component may be further supported on the solid catalyst component polymerized in advance.

In the present invention, the ethylene- α -olefin-nonconjugated polyene copolymer can be suitably obtained by copolymerizing monomers in the presence of the metallocene catalyst as described above.

When the monomer is copolymerized using the metallocene catalyst as described above, the metallocene compound (a) is usually used in an amount of 10 per 1 liter of the reaction volume^-12～10^-2Molar, preferably 10^-10～10^-8In such an amount that the amount is in molarity.

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

In the present invention, the method for producing the ethylene- α -olefin-nonconjugated polyene copolymer is not particularly limited, and can be carried out by any of liquid-phase polymerization methods such as solution (solution) polymerization and suspension polymerization, and gas-phase polymerization methods.

The step of obtaining a polymerization reaction solution is to add a fatThe group hydrocarbon is preferably used as a polymerization solvent in the presence of the metallocene catalyst of the present invention in the presence of the above-mentioned general formula [ A1 ]]And Y in¹Bound R¹³And R¹⁴Is phenyl or phenyl substituted by alkyl or halogen groups, and R⁷、R¹⁰And (B) copolymerizing monomers comprising ethylene (A), an alpha-olefin having 3 to 20 carbon atoms (B), a nonconjugated polyene (C), and, if necessary, a nonconjugated polyene (D) in the presence of a metallocene catalyst comprising a transition metal compound having an alkyl substituent to obtain a polymerization reaction solution of an ethylene-alpha-olefin-nonconjugated polyene copolymer.

Examples of the polymerization solvent include aliphatic hydrocarbons and aromatic hydrocarbons. Specific examples thereof include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane and kerosene, alicyclic hydrocarbons such as cyclopentane, cyclohexane and methylcyclopentane, aromatic hydrocarbons such as benzene, toluene and xylene, and halogenated hydrocarbons such as vinyl chloride, chlorobenzene and dichloromethane, and 1 kind or more thereof may be used alone or in combination. In addition, the olefin itself can also be used as a solvent. Among these, hexane is preferable from the viewpoint of separation and purification from the obtained ethylene- α -olefin-nonconjugated polyene copolymer.

The polymerization temperature is usually in the range of-50 to +200 ℃, preferably 0 to +150 ℃, and more preferably +70 to +110 ℃, and is desirably higher than (+70 ℃ or higher) from the viewpoints of catalytic activity, copolymerizability, and productivity, although it depends on the final molecular weight of the metallocene catalyst system used and the polymerization activity.

The polymerization reaction can be carried out according to any one of a batch type, a semi-continuous type and a continuous type under the condition that the polymerization pressure is usually normal pressure to 10MPa gauge, preferably 1.1 to 5MPa gauge, and more preferably 1.2 to 2.0MPa gauge. Further, the polymerization can be carried out in 2 or more stages with different reaction conditions. In the present invention, among them, a method of continuously supplying a monomer to a reactor to carry out copolymerization is preferably employed.

The reaction time (average residence time in the case of copolymerization by a continuous method) varies depending on the conditions such as catalyst concentration and polymerization temperature, but is usually 0.5 minutes to 5 hours, preferably 5 minutes to 3 hours, and more preferably 10 minutes to 2 hours.

The molecular weight of the ethylene- α -olefin-nonconjugated polyene copolymer obtained can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature. Further, it can also be adjusted by the amount of the compound (b) used. Specifically, triisobutylaluminum, methylaluminoxane, diethyl zinc, and the like can be given. In the case where hydrogen is added, the amount of hydrogen is suitably about 0.001 to 100NL per 1kg of olefin.

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

The amount of the non-conjugated polyene (C) to be added is usually 0.07 to 10% by weight, preferably 0.1 to 8.0% by weight, and more preferably 0.5 to 5.0% by weight, based on 100% by weight of the total amount (the amount of all monomers to be added) of the ethylene (A), the α -olefin (B), and the non-conjugated polyene (C).

In the present invention, it is preferable that the step (1) of carrying out copolymerization in the presence of the polymerization catalyst is followed by a step (2) of adding a catalyst deactivator to deactivate the polymerization catalyst.

As the catalyst deactivator, an alcohol, preferably methanol or ethanol, and particularly preferably ethanol, can be used.

[ thermoplastic resin composition ]

The thermoplastic resin composition of the present invention is characterized by containing the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention.

The thermoplastic resin composition of the present invention may contain, as appropriate, various additives and fillers which can be blended in the resin composition, and the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention.

The thermoplastic resin composition of the present invention can be crosslinked to be suitably used for various purposes, and a crosslinking agent is preferably contained in the thermoplastic resin composition. As the crosslinking agent, known crosslinking agents can be used without particular limitation, and among them, organic peroxides are preferable.

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

Content (mol) of organic peroxide x number of oxygen-oxygen bonds in organic peroxide 1 molecule

(ii) weight fraction/(C) of ≤ (C) × 100 … formula (7)

In the formula (7), the weight fraction of (C) represents the weight fraction (% by weight) of the structural unit derived from the nonconjugated polyene (C) in the ethylene- α -olefin-nonconjugated polyene copolymer, and the molecular weight of (C) represents the molecular weight of the nonconjugated polyene (C).

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

[ rubber composition ]

The ethylene-alpha-olefin-nonconjugated polyene copolymer of the present invention exhibits excellent rubber properties and is suitable as a raw material for a rubber composition.

The rubber composition of the present invention is characterized by containing the ethylene- α -olefin-nonconjugated polyene copolymer (S) of the present invention. In addition, a preferred embodiment of the rubber composition according to the present invention (hereinafter also referred to as "rubber composition (X)") further contains a rubber component (T) selected from the group consisting of diene rubbers, butyl rubbers, and halogenated butyl rubbers, and the content ratio (mass ratio: (S)/(T)) of the ethylene- α -olefin-nonconjugated polyene copolymer (S) to the rubber component (T) is in a 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 a double bond in the main chain can be used without limitation, and 1 kind thereof may be used alone, or 2 or more kinds thereof may be used in combination. 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 rubber also includes Natural Rubber (NR) and hydrogenated rubber. As the rubber component (T), an uncrosslinked one can be usually used, and the iodine value is desirably 100 or more, preferably 200 or more, and more preferably 250 or more.

Examples of such a rubber component (T) include diene rubbers such as Natural Rubber (NR), Isoprene Rubber (IR), styrene-butadiene rubber (SBR), Butadiene Rubber (BR), Chloroprene Rubber (CR), acrylonitrile-butadiene rubber (NBR), acrylonitrile-butadiene rubber, and hydrogenated acrylonitrile-butadiene rubber, butyl rubber, and halogenated butyl rubber.

Butyl rubber and halogenated butyl rubber are generally classified as non-diene rubbers, but since they have unsaturated carbon bonds in the main chain as in diene rubbers, they have the same problem as diene rubbers, such as poor weather resistance, as compared with other non-diene rubbers such as ethylene-propylene rubbers. In the present invention, even when butyl rubber or halobutyl rubber is used as the rubber component (T), the weather resistance can be improved as in the case of diene rubber.

In the present invention, as the rubber component (T), diene rubbers are preferable, and among them, Natural Rubber (NR), Isoprene Rubber (IR), styrene-butadiene rubber (SBR), and Butadiene Rubber (BR) are more preferable, and styrene-butadiene rubber (SBR) is particularly preferable. These rubber components (T) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

As the Natural Rubber (NR), a natural rubber standardized by a green book (international quality packaging standard for various grades of natural rubber) can be used. The Isoprene Rubber (IR) preferably has a specific gravity of 0.91 to 0.94 and a Mooney viscosity [ ML ]₁₊₄(100 ℃ C.), JIS K6300 is 30 to 120.

The styrene-butadiene rubber (SBR) preferably has a specific gravity of 0.91 to 0.98 and a Mooney viscosity [ ML ]₁₊₄(100 ℃ C.), JIS K6300 is 20 to 120. The Butadiene Rubber (BR) preferably has a specific gravity of 0.90 to 0.95 and a Mooney viscosity [ ML ]₁₊₄(100 ℃ C.), JIS K6300 is 20 to 120.

The rubber composition (X) according to the present invention contains the ethylene- α -olefin-nonconjugated polyene copolymer (S) and the rubber component (T) as essential components, and these components are contained in an amount such that the mass ratio [ (S)/(T) ] of the ethylene- α -olefin-nonconjugated polyene copolymer (S) to the rubber component (T) satisfies 5/95 to 50/50, preferably 15/85 to 45/55, and more preferably 20/80 to 40/60.

The total content of the ethylene- α -olefin-nonconjugated polyene copolymer (S) and the rubber component (T) in the rubber composition (X) according to the present invention is 3 mass% or more, preferably 5 mass% or more, and there is no particular upper limit, but it is desirable that the content is 90 mass% or less. The rubber composition of the present invention is also excellent in rubber elasticity, weather resistance and ozone resistance, and particularly excellent in mechanical properties, weather resistance and fatigue resistance. Further, the rubber composition is also excellent in wear resistance. Therefore, if the rubber composition according to the present invention is applied, excellent braking performance and excellent fuel economy can be achieved at the same time, and a tire having excellent rubber elasticity, weather resistance, and ozone resistance, and particularly excellent mechanical properties and fatigue resistance can be obtained. Further, a tire excellent in wear resistance can be obtained.

< optional component >

The rubber composition according to the present invention (including the rubber composition (X). the same applies hereinafter) may further contain any optional component such as a softener, a filler, other resin components, a crosslinking agent, a foaming agent, an antioxidant (stabilizer), a weather resistant agent, a plasticizer, a coloring agent, and various additives blended in conventionally known rubber compositions, as appropriate depending on the application, within a range not impairing the object of the present invention.

Softening agent

As the softener, a softener conventionally blended with rubber is widely used.

Specifically, there may be mentioned:

petroleum softeners such as paraffin-based process oils, naphthenic-based process oils, and aromatic-based process oils;

a synthetic oil-based softening material;

co-oligomers of ethylene and alpha-olefins;

paraffin wax;

liquid paraffin;

white oil (White oil);

petrolatum;

coal tar softeners such as coal tar and coal tar pitch;

vegetable oil-based softeners such as castor oil, cottonseed oil, linseed oil, rapeseed oil, coconut oil, palm oil, soybean oil, peanut oil, wood wax, rosin, pine oil, dipentene, pine tar, tall oil, and the like;

oil gels (ointments) such as black oil gel, white oil gel, and sugar oil gel (candy face);

waxes such as beeswax, carnauba wax, and lanolin;

fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, myristic acid, barium stearate, calcium stearate, magnesium stearate, zinc stearate, and zinc laurate;

ester plasticizers such as dioctyl phthalate, dioctyl adipate and dioctyl sebacate;

coumarone-indene resin;

a phenol-formaldehyde resin;

terpene-phenolic resins;

a polyterpene resin;

synthetic polyterpene resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic-alicyclic petroleum resins, aliphatic-aromatic petroleum resins, hydrogenated and modified alicyclic hydrocarbon resins, hydrogenated hydrocarbon resins, liquid polybutene, liquid polybutadiene, atactic polypropylene and other petroleum hydrocarbon resins.

Among them, petroleum-based softeners, phenol-formaldehyde resins, and petroleum-based hydrocarbon resins are preferable, petroleum-based softeners and petroleum-based hydrocarbon resins are more preferable, and petroleum-based softeners are particularly preferable.

Among the petroleum softening agents, petroleum processing oils are preferable, and among them, paraffin processing oils, naphthene processing oils, aromatic processing oils, and the like are more preferable, and paraffin processing oils are particularly preferable. Among the petroleum hydrocarbon resins, aliphatic cyclic hydrocarbon resins are preferred.

Among these softening agents, paraffin-based process oil is particularly preferable.

One kind of the softening agent 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, and more preferably 5 to 200 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. When the content is within the above range, the rubber composition is preferable because the rubber composition is excellent in moldability such as extrusion moldability, press moldability, and roll processability such as injection moldability.

Filler

The filler is not particularly limited, and is preferably an inorganic filler because it improves the mechanical strength of the rubber composition, such as tensile strength, tear strength, and abrasion resistance.

Examples of the inorganic filler include carbon blacks such as SRF, GPF, FEF, MAF, HAF, ISAF, SAF, FT, and MT; surface-treated carbon black obtained by surface-treating these carbon blacks with a silane coupling agent or the like; silica, activated calcium carbonate, light calcium carbonate, heavy calcium carbonate, fine talc, fine silicic acid, clay, and the like.

One filler may be used alone, or two or more fillers may be used.

The content of the filler in the rubber composition of the present invention is 1 to 300 parts by weight, preferably 5 to 250 parts by weight, and more preferably 10 to 200 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer of the present invention. Within the above range, the rubber composition is preferable because it is excellent in kneading property and processability, and the rubber molded product is excellent in mechanical properties and compression set. Further, a crosslinked molded article having improved mechanical properties such as tensile strength, tear strength, and abrasion resistance can be obtained, and the hardness can be improved without impairing other physical properties of the crosslinked molded article, and the production cost of the crosslinked molded article can be further reduced.

Other resin component

The rubber composition of the present invention may contain a resin component other than the ethylene- α -olefin-nonconjugated polyene copolymer as required. The other resin component is not particularly limited, and is preferably a polyolefin resin.

When the rubber composition of the present invention contains a polyolefin resin, the compound viscosity at the processing temperature can be reduced while adjusting the product hardness, and therefore the processability can be further improved. Further, it is preferable because it can be handled as a thermoplastic elastomer and the range of workability and kneading method is widened.

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

Examples of the polyolefin resin include an α -olefin homopolymer and an α -olefin copolymer. Examples of the α -olefin homopolymer include polyethylene and polypropylene, and examples of the α -olefin copolymer include an ethylene- α -olefin copolymer having 3 to 20 carbon atoms and an ethylene- α -olefin-nonconjugated polyene copolymer having 3 to 20 carbon atoms (however, the α -olefin-nonconjugated polyene copolymer is different from the ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention). Examples of the ethylene- α -olefin copolymer having 3 to 20 carbon atoms include ethylene-propylene rubber (EPR), propylene-ethylene rubber (PER), ethylene-butene rubber (EBR), ethylene-octene rubber (EOR), and the like.

Examples of the ethylene- α -olefin-nonconjugated polyene copolymer having 3 to 20 carbon atoms (which is different from the ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention) include an ethylene-propylene terpolymer (EPT) and an ethylene-butene terpolymer (EBT).

Among the polyolefin resins, polyethylene, ethylene- α -olefin copolymer, and polypropylene are preferable.

The polyolefin resin may be used alone or in combination of two or more.

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, preferably 5 to 80 parts by weight, and more preferably 10 to 50 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. When the amount is within the above range, the hardness of the molded article formed of the rubber composition can be adjusted, and the compound viscosity at the processing temperature can be reduced, so that the processability can be further improved. Further, it is preferable because it can be handled as a thermoplastic elastomer and the range of workability and kneading method is widened.

Crosslinking agent

The rubber composition according to the present invention is a crosslinkable composition, and a crosslinked molded article according to the present invention described later can be produced by crosslinking the crosslinkable composition. The crosslinking can be performed by heating or the like using a crosslinking agent, and can also be performed by radiation crosslinking in which crosslinking is performed by irradiation with radiation such as electron rays, X-rays, γ -rays, α -rays, and β -rays. Among the radiation crosslinking, electron beam crosslinking is preferable.

The crosslinked molded article according to the present invention is preferably produced by crosslinking through radiation crosslinking, particularly electron beam crosslinking, and in this case, the rubber composition may contain no crosslinking agent.

Further, in the case where the rubber composition is crosslinked by heating, the rubber composition preferably contains a crosslinking agent.

Examples of the crosslinking agent include crosslinking agents generally used for crosslinking rubbers, such as sulfur compounds, organic peroxides, phenol resins, hydrosilicon compounds, amino resins, quinones or derivatives thereof, amine compounds, azo compounds, epoxy compounds, and isocyanates. Among these crosslinking agents, sulfur compounds, organic peroxides, and phenol resins are preferable. The ethylene- α -olefin-nonconjugated polyene copolymer according to the present invention can realize particularly excellent crosslinking characteristics when crosslinked by using an organic peroxide, and therefore the rubber composition of the present invention particularly preferably contains an organic peroxide as a crosslinking agent.

When the crosslinking agent is an organic peroxide, specific examples thereof include dicumyl peroxide, di-t-butyl peroxide, 2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, n-butyl-4, 4-bis (t-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2, 4-dichlorobenzoyl peroxide, t-butylperoxybenzoate, t-butylperoxyisopropyl carbonate, di-t-butylperoxy isopropyl carbonate, di-t-butyl peroxide, n-butyl peroxy-hexyl carbonate, di-t-butyl peroxy-hexyl carbonate, di-butyl peroxy-isopropyl, Diacetyl peroxide, lauroyl peroxide, t-butylcumyl peroxide, and the like.

Among them, 2-functional organic peroxides having 2 peroxide bonds (-O-O-) in 1 molecule, such as 2, 5-di (t-butylperoxy) hexane, 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexyne-3, 1, 3-bis (t-butylperoxyisopropyl) benzene, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane and n-butyl-4, 4-bis (t-butylperoxy) valerate, are preferable from the viewpoints of reactivity, odor property and scorch stability, and among them, 2, 5-di (t-butylperoxy) hexane and 2, 5-dimethyl-2 are most preferable, 5-di (t-butylperoxy) hexane.

When the crosslinking agent is an organic peroxide, the amount of the organic peroxide is 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-unconjugated polyene copolymer. When the amount of the organic peroxide is within the above range, the surface of the resulting rubber molded article does not bloom and the rubber molded article exhibits excellent crosslinking characteristics, and therefore, the organic peroxide is suitable.

In the case of using an organic peroxide 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, examples of the crosslinking assistant preferably contained in the rubber composition include, for example, a quinone dioxime-based crosslinking assistant such as sulfur and p-quinone dioxime; acrylic crosslinking aids such as ethylene glycol dimethacrylate and trimethylolpropane trimethacrylate; allyl crosslinking aids such as diallyl phthalate and triallyl isocyanurate; other maleimide-based crosslinking assistants; divinylbenzene, and the like. The amount of the crosslinking assistant to be blended is usually 0.5 to 10 mol, preferably 0.5 to 7 mol, and more preferably 1 to 5 mol based on 1 mol of the organic peroxide. The amount of the crosslinking assistant to be blended is preferably 0.5 to 2 mol, more preferably 0.5 to 1.5 mol, and still more preferably substantially equimolar with respect to 1 mol of the organic peroxide.

In the rubber composition of the present invention, the amount of the organic peroxide to be blended is preferably an amount contained in the thermoplastic resin composition of the present invention, that is, an amount in which the content (mole) of the organic peroxide satisfies the following formula (7).

Content (mol) of organic peroxide x number of oxygen-oxygen bonds in organic peroxide 1 molecule

(ii) weight fraction/(C) of ≤ (C) × 100 … formula (7)

In the formula (7), the weight fraction of (C) represents the weight fraction (% by weight) of the structural unit derived from the nonconjugated polyene (C) in the ethylene- α -olefin-nonconjugated polyene copolymer, and the molecular weight of (C) represents the molecular weight of the nonconjugated polyene (C).

One crosslinking agent may be used alone, or two or more crosslinking agents may be used.

When the crosslinking agent is a sulfur-based compound, specific examples thereof include sulfur, sulfur monochloride, sulfur dichloride, dithiomorpholine, alkylphenol disulfide, tetramethylthiuram disulfide, selenium dithiocarbamate, and the like.

When the crosslinking agent is a sulfur-based compound, the amount of the sulfur-based compound is usually 0.3 to 10 parts by weight, preferably 0.5 to 7.0 parts by weight, and more preferably 0.7 to 5.0 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-unconjugated polyene copolymer. When the blending amount of the sulfur-based compound is within the above range, the surface of the obtained rubber molded article is not bloomed, and the rubber composition exhibits excellent crosslinking characteristics, and therefore, the sulfur-based compound is suitable.

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

When a sulfur-based compound is used as the crosslinking agent, examples of the crosslinking aid preferably contained in the rubber composition include zinc oxide, zinc white, and the like. The amount of the crosslinking assistant is usually 1 to 20 parts by weight per 100 parts by weight of the ethylene-olefin-nonconjugated polyene copolymer.

When a sulfur-based compound is used as the crosslinking agent, it is desirable to use sulfur and a vulcanization accelerator in combination.

Specific examples of the vulcanization accelerator include N-cyclohexyl-2-benzothiazolesulfenamide (CBS) (for example, "NOCCELER NS" (trade name; manufactured by shin-chan-sho Co., Ltd.)), N-oxydiethylene-2-benzothiazolesulfenamide, N' -diisopropyl-2-benzothiazolesulfenamide, 2-mercaptobenzothiazole (for example, "SANCELER M" (trade name; manufactured by shin-chan-Kagaku Co., Ltd.)), 2- (4-morpholinodithio) benzothiazole (for example, "NOCCELER MDB-P" (trade name; manufactured by shin-chan-cham-sho Co., Ltd.)), 2- (2, 4-dinitrophenyl) mercaptobenzothiazole, 2- (2, 6-diethyl-4-morpholinothio) benzothiazole, Thiazole-based compounds such as dibenzothiazyl disulfide; guanidine-based compounds such as diphenylguanidine, triphenylguanidine and di-o-tolylguanidine; acetaldehyde-aniline condensate, butylaldehyde-aniline condensate, and aldehyde amine; imidazoline systems such as 2-mercaptoimidazoline; thiourea systems such as diethyl thiourea and dibutyl thiourea; thiuram systems such as Tetramethylthiuram Monosulfide and Tetramethylthiuram Disulfide (TMTD) (for example, "NOCCELER TT" (trade name; manufactured by Okawa Kagaku Co., Ltd.)); dithioates such as zinc dimethyldithiocarbamate, zinc diethyldithiocarbamate, zinc dibutyldithiocarbamate (ZnBDC) (e.g., "SANCELER Bz" (trade name; manufactured by Sanxin chemical industries Co., Ltd.), tellurium diethyldithiocarbamate, etc.; thiourea systems such as ethylenethiourea, N '-diethylthiourea and N, N' -dibutylthiourea; xanthate systems such as zinc dibutylxanthate; and other zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Okinawa Kaisha) and the like).

The amount of the vulcanization accelerator is usually 0.1 to 20 parts by weight, preferably 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. When the compounding amount of the vulcanization accelerator is within the above range, the resulting rubber molded article does not bloom on the surface and exhibits excellent crosslinking characteristics, and therefore, the vulcanization accelerator is suitable.

The vulcanization aids may be appropriately selected depending on the use, and may be used alone or in combination of 2 or more. Specific examples of the vulcanization aid include magnesium oxide, zinc white (for example, zinc oxide such as "META-Z102" (trade name; manufactured by Okinawa Kaisha) and the like). The amount of the ethylene-alpha-olefin-nonconjugated polyene copolymer is usually 1 to 20 parts by weight per 100 parts by weight of the ethylene-alpha-olefin-nonconjugated polyene copolymer.

Foaming agent

The rubber composition of the present invention may contain a foaming agent. When the rubber composition of the present invention contains a foaming agent, the crosslinking agent is usually 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; nitroso compounds such as N, N '-dinitrosopentamethylenetetramine and N, N' -dinitrosoterephthalamide; azo compounds such as azodicarbonamide (ADCA) and azobisisobutyronitrile; hydrazide compounds such as benzenesulfonyl hydrazide and p, p' -oxybis (benzenesulfonyl hydrazide) (OBSH); and an azide compound such as calcium azide and 4, 4' -diphenyldisulfonylazide. Preferred blowing agents are ADCA and OBSH. One or more kinds of the blowing agents may be used alone.

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

Foaming aid

When the rubber composition of the present invention contains a foaming agent, a foaming aid may be further contained as needed. The foaming auxiliary agent has the functions of reducing the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles and the like.

Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, oxalic acid, and citric acid, salts thereof, urea, and derivatives thereof.

When the rubber composition of the present invention contains a foaming auxiliary, the amount of the foaming auxiliary is usually 0.2 to 30 parts by weight, preferably 0.5 to 25 parts by weight, and more preferably 0.5 to 20 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer.

Antioxidant agent

The rubber composition of the present invention preferably further contains an antioxidant, from the viewpoint of extending the life of the material. Examples of such antioxidants include:

aromatic secondary amine stabilizers such as phenylnaphthylamine, 4 '- (α, α -dimethylbenzyl) diphenylamine and N, N' -di (2-naphthyl) p-phenylenediamine;

phenol stabilizers such as 2, 6-di-tert-butyl-4-methylphenol and tetrakis [ methylene-3- (3 ', 5 ' -di-tert-butyl-4 ' -hydroxyphenyl) propionate ] methane;

thioether stabilizers such as bis [ 2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl ] sulfide; benzimidazole stabilizers such as 2-mercaptobenzimidazole;

dithiocarbamate stabilizers such as nickel dibutyldithiocarbamate;

quinoline stabilizers such as polymers of 2,2, 4-trimethyl-1, 2-dihydroquinoline. These can be used alone, or in combination of 2 or more.

Processing aid

The rubber composition of the present invention may contain a processing aid. As the processing aid, those generally blended in rubber as a processing aid 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 them, stearic acid is preferable.

When the rubber composition of the present invention contains a processing aid, the amount of the processing aid is usually 0.1 to 10 parts by weight, preferably 0.5 to 8 parts by weight, and more preferably 1 to 6 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. When the amount is within the above range, the surface of the resulting rubber composition is not frosted, and further, when the rubber composition is crosslinked, crosslinking inhibition does not occur, and therefore, the amount is preferable. Further, the rubber composition containing a processing aid is preferable because it is excellent in moldability such as extrusion moldability, press moldability and injection moldability and roll processability.

Surface active agent

The rubber composition of the present invention may contain a surfactant. Examples of the surfactant include amines such as di-n-butylamine, dicyclohexylamine, monoethanolamine, triethanolamine, "activating B" (manufactured by Gekko pharmaceutical Co., Ltd.), "activating SL" (manufactured by Gekko pharmaceutical Co., Ltd.), polyethylene glycol, diethylene glycol, polyethylene glycol, lecithin, triallyl trimellitate, zinc compounds of aliphatic and aromatic carboxylic acids (e.g., "Struktol activator 73", "Struktol IB 531", "Struktol FA 541" (manufactured by Schill & Seilacher Co., Ltd.), "ZEONET ZP" (manufactured by Nippon Rasuzu Co., Ltd.), octadecyl trimethyl ammonium bromide, synthetic hydrotalcite, and special quaternary ammonium compounds (e.g., "ARQUAD 2 HF" (manufactured by LION AKZO Co., Ltd.).

When the rubber composition of the present invention contains a surfactant, the amount of the surfactant is usually 0.2 to 10 parts by weight, preferably 0.3 to 5 parts by weight, and more preferably 0.5 to 4 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. The surfactant can be appropriately selected depending on the use, and can be used alone or in combination of 2 or more.

Anti-aging agent

The rubber composition of the present invention may contain an antioxidant. If the rubber composition of the present invention contains an antioxidant, the life of the product obtained from the composition can be prolonged. As the antioxidant, conventionally known antioxidants can be used, for example, amine antioxidants, phenol antioxidants, sulfur antioxidants, and the like.

Specific examples of the antioxidant include aromatic secondary amine antioxidants such as phenylbutylamine and N, N-bis (2-naphthyl) p-phenylenediamine, and phenolic antioxidants such as dibutylhydroxytoluene and tetrakis [ methylene (3, 5-di-tert-butyl-4-hydroxy) hydrocinnamate ] methane; thioether-based antioxidants such as bis [ 2-methyl-4- (3-n-alkylthiopropionyloxy) -5-tert-butylphenyl ] sulfide; dithiocarbamate-based antioxidants such as nickel dibutyldithiocarbamate; and sulfur-based antioxidants such as 2-mercaptobenzoylimidazole, zinc salts of 2-mercaptobenzimidazole, dilauryl thiodipropionate, distearyl thiodipropionate, and the like.

When the rubber composition of the present invention contains an antioxidant, the amount of the antioxidant to be blended is usually 0.01 to 10 parts by weight, preferably 0.02 to 7 parts by weight, and more preferably 0.03 to 5 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer. Within the above range, the molded article obtained from the rubber composition of the present invention is excellent in heat aging resistance, and therefore, it is preferable.

Pseudo-gel inhibitor (pseudo Anti-Gelation Agent)

The rubber composition of the present invention may contain a pseudo-gelation inhibitor. Examples of the pseudo-gelation inhibitor include "NHM-007" (manufactured by Mitsui chemical Co., Ltd.).

When the rubber composition of the present invention contains the pseudo-gelation inhibitor, the amount of the pseudo-gelation inhibitor is usually 0.1 to 15 parts by weight, preferably 0.5 to 12 parts by weight, and more preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer.

Other additives

The rubber composition of the present invention may further contain other additives. Examples of the other additives include a heat-resistant stabilizer, a weather-resistant stabilizer, an antistatic agent, a colorant, a lubricant, and a thickener.

The rubber composition (X) according to the present invention can contain various arbitrary components without particular limitation as described above, the ethylene- α -olefin-nonconjugated polyene copolymer (S) and the rubber component (T) constituting the rubber composition (X) have good compatibility, and if the rubber composition (X) containing these components is used, a crosslinked molded product can be produced without phase separation, and the ethylene- α -olefin-nonconjugated polyene copolymer (S) can impart excellent weather resistance to the resulting crosslinked molded product, so that a crosslinked molded product having excellent weather resistance can be easily obtained even when the content of a weather resistance agent, an antioxidant and the like in the rubber composition (X) is suppressed. Therefore, the content of additives such as weather resistance agents and antioxidants can be appropriately suppressed, cost can be reduced, and the quality of the crosslinked molded article can be prevented from being deteriorated due to bleeding.

< method for producing rubber composition >

The rubber composition of the present invention is a rubber composition containing the ethylene- α -olefin-nonconjugated polyene copolymer, and preferably contains a softener, a filler, a crosslinking agent, and the like. For example, the rubber composition may contain 0.1 to 300 parts by weight of a softening agent and 1 to 300 parts by weight of a filler per 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer, but the method for preparing the same is not particularly limited.

Examples of the method for preparing the rubber composition include the following methods: a method of mixing the components contained in the rubber composition using a conventionally known kneading machine such as a mixer, a kneader, or a roll, or a continuous kneading machine such as a twin-screw extruder; a method of preparing a solution in which each component contained in the rubber composition is dissolved or dispersed, and removing the solvent.

The rubber composition (X) according to the present invention can be prepared by blending the ethylene- α -olefin-nonconjugated polyene copolymer (S), the rubber component (T), and, if necessary, any of the components in a simultaneous or sequential manner.

The method for preparing the rubber composition (X) is not particularly limited, and a general method for preparing a rubber compound can be used without particular limitation. For example, when the rubber composition (X) of the present invention contains an arbitrary component, at least a part of the arbitrary component may be blended with the ethylene- α -olefin-nonconjugated polyene copolymer (S) or the rubber component (T) in advance, or the arbitrary component may be added to the ethylene- α -olefin-nonconjugated polyene copolymer (S) and the rubber component (T) to blend them.

For example, the modulation can be performed by: the ethylene- α -olefin-nonconjugated polyene copolymer (S), the rubber component (T) and other components blended as needed are kneaded at a temperature of 80 to 170 ℃ for 3 to 10 minutes using a closed mixer such as a banbury mixer, a kneader or an internal mixer, then a crosslinking agent and further a crosslinking accelerator, a crosslinking aid, a foaming agent and the like are added as needed, and then a roll or a kneader such as an open roll is used to knead at a roll temperature of 40 to 80 ℃ for 5 to 30 minutes and then tabletted. In this manner, a rubber composition (X) in a tape or sheet form can be obtained. When the kneading temperature in the internal mixers is low, the crosslinking agent, the crosslinking accelerator, the foaming agent, and the like can be kneaded at the same time.

< crosslinked shaped article >

The crosslinked molded article of the present invention is obtained by crosslinking the rubber composition of the present invention. In the crosslinking, a mold may be used or may not be used. The rubber composition is usually continuously molded and crosslinked without using a mold.

Examples of the method for crosslinking the rubber composition include the following methods: (a) a method of preforming a rubber composition containing a crosslinking agent into a desired shape by a molding method such as ordinary extrusion molding, pressure molding, injection molding, or roll processing, and heating the preformed rubber composition simultaneously with molding or introducing the molded rubber composition into a crosslinking vessel and heating the molded rubber composition; (b) a method in which a rubber composition containing a crosslinking agent is preformed by the same method as that of the method (a), and then irradiated with an electron beam.

In the method (a), a crosslinked material can be obtained by causing a crosslinking reaction by a crosslinking agent in the rubber composition by heating. In the method (b), a crosslinking reaction is caused by an electron beam, and a crosslinked material can be obtained. In the method (b), the preformed rubber composition is generally irradiated with electron beams having an energy of 0.1 to 10MeV so that the amount of radiation absorbed by the rubber composition is generally 0.5 to 36Mrad, preferably 0.5 to 20Mrad, and more preferably 1 to 10 Mrad.

The crosslinking of the rubber composition (X) can be carried out by preforming an uncrosslinked rubber composition (X) into a desired shape by various molding methods usually using a molding machine such as an extrusion molding machine, a calender roll, a press, an injection molding machine, or a transfer molding machine, heating the rubber composition (X) simultaneously with molding, introducing the molded article into a crosslinking vessel, and heating the rubber composition (X), or crosslinking the rubber composition (X) by radiation such as irradiation of electron rays, X rays, γ rays, α rays, and β rays. As the molding or preforming method, a known molding method for molding into a desired shape by extrusion molding, injection molding, inflation molding, blow molding, extrusion blow molding, pressure molding, vacuum molding, calender molding, foam molding, or the like can be suitably used. In addition, when the crosslinked molded article is a foam, the crosslinked rubber composition can be produced by foam molding an uncrosslinked rubber composition containing a foaming agent and then crosslinking the composition by electron beam irradiation or heating, or crosslinking the composition simultaneously with foam molding. Further, in the step of crosslinking the rubber composition (X), crosslinking by heating and electron beam crosslinking may be carried out in combination.

When the rubber composition (X) is crosslinked by heating, it is generally preferable to heat the rubber composition (X) containing a crosslinking agent such as sulfur, a sulfur-based compound, or a peroxide at a temperature of 150 to 270 ℃ for 1 to 30 minutes using a crosslinking bath in a heating form such as hot air, a glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, or LCM (hot melt salt bath). Sulfur crosslinking or peroxide crosslinking has an advantage that no special equipment is required in the crosslinking step, and thus has been widely used in the crosslinking step of rubber compositions.

In addition, in the case of crosslinking by electron beam crosslinking in which crosslinking is performed by electron beam irradiation, it is generally preferable to produce a crosslinked molded article by irradiating a rubber composition (X) after preforming with an electron beam using a rubber composition (X) containing no crosslinking agent. Crosslinking by electron beam irradiation can be performed without using a crosslinking agent, and there is an advantage that generation of volatile matter in the crosslinking step is small.

Specifically, the production of a crosslinked molded article with a crosslinking step by electron beam irradiation can be performed, for example, as follows. First, the ethylene- α -olefin-nonconjugated polyene copolymer (S), the rubber component (T), and, if necessary, various additives and crosslinking aids are kneaded at a temperature of 80 to 170 ℃ for 3 to 10 minutes by using a mixer such as a banbury mixer, and then kneaded at a roll temperature of 40 to 80 ℃ for 5 to 30 minutes by using rolls such as open rolls, and then the kneaded product is tableted to prepare a rubber composition (X) in a band or sheet form, or the components are blended in a container or the like to prepare a rubber composition (X). The rubber composition (X) prepared in this way is irradiated with an electron beam directly while maintaining a sheet shape or the like, or is formed into a desired shape by an extrusion molding machine, a calender roll, an injection molding machine or a press machine and then irradiated with an electron beam, or is extruded into a strand shape by an extruder, pulverized into pellets by a cutter or the like, and then irradiated with an electron beam. Alternatively, a crosslinked product of the rubber composition (X) can be prepared by directly irradiating a powder of the ethylene- α -olefin-nonconjugated polyene copolymer (S) impregnated with a compound such as a crosslinking assistant and the rubber component (T) with an electron beam. Regarding the irradiation of the electron beam, the electron beam having an energy of 0.1 to 10MeV (MeV), preferably 0.3 to 5MeV, is irradiated so that the absorbed dose is usually 0.5 to 100kGy (kilogray), preferably 0.5 to 70 kGy.

The gamma irradiation has a higher transmittance for the rubber composition (X) than the electron irradiation, and in particular, when an object having a particle shape of the rubber composition (X) is irradiated, the rubber composition (X) can be sufficiently crosslinked into the particle interior by only a small amount of direct irradiation. The irradiation with the gamma ray can be performed on the rubber composition (X) so that the irradiation dose with the gamma ray is usually 0.1 to 50kGy, preferably 0.3 to 50 kGy.

In the present invention, the step of crosslinking the rubber composition (X) is preferably performed by a step including electron beam crosslinking, and more preferably performed by electron beam crosslinking. Conventionally, electron beam crosslinking by electron beam irradiation has been used for crosslinking the surface of an uncrosslinked molded article, but in the present invention, since the ethylene- α -olefin-nonconjugated polyene copolymer (S) constituting the rubber composition (X) has high crosslinking properties and the crosslinking properties of the rubber composition (X) are excellent, even in the case of crosslinking the rubber composition (X) into the inside by electron beam crosslinking, crosslinking can be uniformly performed without phase separation or the like, and a crosslinked molded article can be suitably produced.

The degree of crosslinking of the crosslinked molded article can be expressed as a gel fraction. Generally, the gel fraction of the crosslinked material is 1 to 80%. However, the crosslinked molded article of the present invention is not limited to this range in the degree of crosslinking, and even a crosslinked article having a low degree of crosslinking and exhibiting a gel fraction of less than 10%, particularly a gel fraction of less than 0.5%, can obtain an effect of excellent appearance surface, as in the crosslinked molded article of the present invention having a high degree of crosslinking.

The crosslinked molded article according to the present invention can be used for various products having rubber characteristics without limitation. The crosslinked molded article according to the present invention may be one that constitutes at least a part of a product, and is preferably composed entirely of the crosslinked molded article according to the present invention, and is also preferably a laminate or a composite in which the crosslinked molded article according to the present invention constitutes at least a part of a product. The laminate may be a multilayer laminate having 2 or more layers, and at least 1 layer of the laminate is a crosslinked molded product according to the present invention, and examples thereof include multilayer films and sheets, multilayer containers, multilayer tubes, multilayer coating laminates contained as one component of an aqueous coating material, and the like.

The crosslinked molded article according to the present invention is particularly excellent in weather resistance, and therefore can be suitably used for applications in which the article is used outdoors for a long period of time, such as a tire and a wire coating material, and particularly can be suitably used for tire members constituting at least a part of various tires.

Examples of the tire member include a tire inner liner, a tire inner tube, a tire rim, a tire shoulder, a tire bead, a tire tread, and a tire side wall. Among them, the rubber composition can be suitably used for a tire tread and a tire sidewall.

The crosslinked molded article of the present invention is homogeneous, has excellent weather resistance, and exhibits excellent dynamic mechanical strength, because it retains excellent mechanical strength inherent in diene rubbers and the rubber composition (X) exhibits excellent co-crosslinking properties. The crosslinked molded article of the present invention is used for a tire member such as a tire tread or a tire side wall, which is excellent in weather resistance and dynamic fatigue resistance.

< foam >

The foam of the present invention is obtained by crosslinking and foaming the rubber composition of the present invention containing the above foaming agent.

Since the rubber composition contains the foaming agent, the foaming agent is decomposed to generate carbon dioxide and nitrogen gas while the crosslinking reaction by the crosslinking agent is carried out by heating the rubber composition. Thus, a foam having a cell structure can be obtained.

< use >)

The rubber composition of the present invention is excellent in moldability such as low-temperature characteristics, mechanical characteristics, extrusion moldability, pressure moldability and injection moldability, and roll processability, and thus a molded article excellent in low-temperature characteristics (flexibility at low temperature, rubber elasticity, etc.) and mechanical characteristics can be suitably obtained from the rubber composition of the present invention.

Further, the rubber composition of the present invention can produce a crosslinked material having excellent processability, moldability and crosslinking characteristics and excellent heat resistance stability by using the ethylene- α -olefin-nonconjugated polyene copolymer, and therefore the crosslinked material obtained from the rubber composition of the present invention can be suitably used also for applications expected to be used at high temperatures for a long period of time.

The rubber composition of the present invention and a molded article obtained from the composition, for example, a crosslinked product, a foam, and the like can be used for various applications. Specifically, the rubber composition is suitably used for hoses such as rubber for tires, O-rings, industrial rollers, gaskets (e.g., condenser gaskets), gaskets, conveyor belts (e.g., heat-insulating conveyor belts, copier conveyor belts, conveyor belts), and hoses for automobiles (e.g., turbocharger hoses, water hoses, brake fluid reservoir hoses, radiator hoses, air hoses), vibration-proof rubber, vibration-proof materials, or vibration-proof materials (e.g., engine mounts and motor mounts), a muffler hanger, a sponge (e.g., a sealing strip sponge, a heat insulating sponge, a protective sponge, a micro-foam sponge), a cable (an ignition cable, a rubber insulated cable, a high voltage cable), a wire coating material (a high voltage wire coating material, a low voltage wire coating material, a wire coating material for a ship), a glass run channel sealing strip (glass run channel), a color skin material, a paper feed roller, a ceiling plate, and the like. Among them, the resin composition is suitably used for applications requiring heat resistance for automobile interior and exterior parts, and is suitably used for hose applications such as brake fluid reservoir hoses and radiator hoses for automobile interior parts.

In the present invention, the ethylene- α -olefin-nonconjugated polyene copolymer having appropriate characteristics can be selected and used within a range satisfying the above requirements in accordance with the use thereof. For example, in the application of the muffler ceiling rubber, an ethylene- α -olefin-nonconjugated polyene copolymer having a relatively high molecular weight can be suitably used, and specifically, an ethylene- α -olefin-nonconjugated polyene copolymer having a weight average molecular weight (Mw) of 200,000 to 600,000 can be preferably used.

[ resin composition ]

The resin composition of the present invention comprises (S) the ethylene- α -olefin-nonconjugated polyene copolymer, (E) fine powder silicic acid and/or fine powder silicate, and (G) an organic peroxide and/or (H) a crosslinking agent which is a compound having at least 2 SiH groups in the molecule and contains (F) a metal salt of an α, β -unsaturated carboxylic acid as the crosslinking agent.

< (E) micropowder silicic acid/micropowder silicate

The specific surface area of the fine powder silicic acid and/or the fine powder silicate (E) is 5 to 500m²(BET adsorption amount: ISO5794/1, Annex D), preferably 10 to 400m²(ii) in terms of/g. Examples of the fine silicic acid powder and the fine silicate powder (E) include dry silica, wet silica, and synthetic silicate-based silica. Examples of the silicate include magnesium silicate. In the present invention, it is also possible to use finely powdered silicic acid and/or finely powdered silicate each independently (E) Further, they can be used in combination. In the present invention, the fine powder is not particularly limited, and means a fine powder having an average particle diameter of about 10 to 50 μmm.

In the resin composition of the present invention, the fine silicic acid powder and/or the fine silicate powder (E) is used in an amount of usually 5 to 90 parts by weight, preferably 20 to 80 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S), based on the total amount of the fine silicic acid powder and the fine silicate powder. When the resin composition of the present invention is used for a vibration damping rubber product, the dynamic characteristics of the vibration damping effect according to the application of the vibration damping rubber product are required to be exhibited, and therefore the mixing ratio of the fine powder silicic acid and/or the silicate (E) can be adjusted and used according to the application purpose.

< metal salt of alpha, beta-unsaturated carboxylic acid >

The metal salt of α, β -unsaturated carboxylic acid (F) preferably includes at least 1 compound selected from the group consisting of a metal acrylate, a metal methacrylate, and a metal maleate.

Examples of the metal acrylate, metal methacrylate and metal maleate include alkali metal salts (e.g., lithium salt, sodium salt, potassium salt), alkaline earth metal salts (e.g., magnesium salt, calcium salt), heavy metal salts (e.g., zinc salt) and aluminum salts of acrylic acid, methacrylic acid and maleic acid, and specific examples thereof include lithium acrylate, sodium acrylate, potassium acrylate, magnesium diacrylate, calcium diacrylate, zinc diacrylate, aluminum triacrylate, lithium methacrylate, sodium methacrylate, potassium methacrylate, zinc methacrylate, magnesium dimethacrylate, calcium dimethacrylate, zinc dimethacrylate, aluminum trimethacrylate, lithium maleate, sodium maleate, potassium maleate, magnesium maleate, zinc maleate and aluminum maleate. The metal salt of an α, β -unsaturated carboxylic acid is particularly preferably zinc methacrylate or zinc dimethacrylate, and most preferably zinc methacrylate. The metal salts of α, β -unsaturated carboxylic acid may be used alone or in combination of 2 or more.

The α, β -unsaturated carboxylic acid metal salt (F) is contained in the resin composition of the present invention as needed, and is usually used in a proportion of 20 parts by weight or less, preferably 0.1 to 20 parts by weight, more preferably 0.2 to 10 parts by weight, based on the total amount of all α, β -unsaturated carboxylic acid metal salts, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). By using the metal salt of α, β -unsaturated carboxylic acid, the interaction between the ethylene- α -olefin-nonconjugated polyene copolymer (S) as a polymer and the fine powder silicic acid and/or the fine powder silicate (E) is improved, and a crosslinked rubber product excellent in dynamic characteristics and mechanical properties can be obtained. In particular, when the resin composition of the present invention contains an organic peroxide (G) described later as a crosslinking agent, if the metal salt of α, β -unsaturated carboxylic acid (F) is contained, the interaction between the fine powder silicic acid and/or the fine powder silicate (E) and the metal salt of α, β -unsaturated carboxylic acid (F) becomes particularly excellent, and therefore, it is preferable.

(G) organic peroxide

When the resin composition of the present invention contains the organic peroxide (G) as the crosslinking agent, conventionally known organic peroxides generally used for crosslinking rubbers can be used as the organic peroxide (G). Specific examples of the organic peroxide include the same organic peroxides as those exemplified for the rubber composition. These organic peroxides may be used alone or in combination of 2 or more.

The organic peroxide (G) is used in an amount of 0.1 to 15 parts by weight, preferably 0.5 to 12 parts by weight, based on 100 parts by weight of the total amount of all organic peroxides, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S), from the viewpoints of obtaining desired physical properties by sufficient crosslinking and preventing adverse effects due to excessive decomposition products, and also from the viewpoint of cost.

When the resin composition of the present invention contains the organic peroxide (G) as a crosslinking agent, the resin composition may contain a crosslinking assistant as an optional component. Specific examples of the crosslinking assistant include sulfur; quinone dioxime compounds such as p-quinone dioxime; methacrylate compounds such as polyethylene glycol dimethacrylate; allyl compounds such as diallyl phthalate and triallyl cyanurate; a maleimide compound; divinylbenzene, and the like. Such a crosslinking assistant is used in an amount of 0.5 to 2 mol, preferably substantially equimolar amount, based on 1 mol of the organic peroxide to be used.

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

In the case where the resin composition of the present invention contains (H)1 an SiH group-containing compound having at least 2 SiH groups in the molecule (hereinafter, also simply referred to as "SiH group-containing compound (H)") as a crosslinking agent, the SiH group-containing compound (H) functions as a crosslinking agent by reacting with the ethylene- α -olefin-nonconjugated polyene copolymer (S). The molecular structure of the SiH group-containing compound (H) is not particularly limited, and conventionally produced resins having, for example, a linear, cyclic, branched or three-dimensional network structure can be used, but it is necessary to contain SiH groups, which are hydrogen atoms directly bonded to silicon atoms, in at least 2, preferably 3 or more, in 1 molecule.

As such an SiH group-containing compound (H), a compound represented by the following general formula can be generally used.

R⁴ _bH_cSiO_(4-b-c)/2

In the above formula, R⁴Is a substituted or unsubstituted 1-valent hydrocarbon group having 1 to 10 carbon atoms, particularly 1 to 8 carbon atoms, excluding an aliphatic unsaturated bond, and the 1-valent hydrocarbon group is not limited to the above R¹Examples of the alkyl group in (1) include phenyl and a halogen-substituted alkyl group such as trifluoropropyl. Among them, methyl, ethyl, propyl, phenyl and trifluoropropyl are preferable, and methyl and phenyl are particularly preferable.

Furthermore, b is 0. ltoreq. b < 3, preferably 0.6. ltoreq. b < 2.2, particularly preferably 1.5. ltoreq. b.ltoreq.2, c is 0. ltoreq. c.ltoreq.3, preferably 0.002. ltoreq. c < 2, particularly preferably 0.01. ltoreq. c.ltoreq.1, and b + c is 0. ltoreq. b + c.ltoreq.3, preferably 1.5. ltoreq. b + c.ltoreq.2.7.

The SiH group-containing compound (H) is preferably 2 to 1000, particularly preferably 2 to eAn organohydrogenpolysiloxane of 300, most preferably 4 to 200, and specific examples thereof include siloxane oligomers such as 1,1,3, 3-tetramethyldisiloxane, 1,3,5, 7-tetramethyltetracyclosiloxane, and 1,3,5,7, 8-pentamethylpentacyclosiloxane; trimethylsiloxy-terminated methylhydrogenpolysiloxane at two ends of a molecular chain, trimethylsiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at two ends of a molecular chain, silanol-terminated methylhydrogenpolysiloxane at two ends of a molecular chain, silanol-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at two ends of a molecular chain, dimethylhydrogensiloxy-terminated dimethylpolysiloxane at two ends of a molecular chain, dimethylhydrogensiloxy-terminated methylhydrogensiloxane at two ends of a molecular chain, dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at two ends of a molecular chain, a compound containing R ⁴ ₂(H)SiO_1/2Unit and SiO_4/2Unit and may optionally contain R⁴ ₃SiO_1/2Unit, R⁴ ₂SiO_2/2Unit, R⁴(H)SiO_2/2Unit, (H) SiO_3/2Or R⁴SiO_3/2Silicone resins of units, and the like.

Examples of the trimethylsiloxy-terminated methylhydrogenpolysiloxane at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl, propyl, phenyl, trifluoropropyl, etc.

(CH₃)₃SiO-(-SiH(CH₃)-O-)_d-Si(CH₃)₃

[ wherein d is an integer of 2 or more. ]

Examples of the trimethylsiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups, and the like.

(CH₃)₃SiO-(-Si(CH₃)₂-O-)_e-(-SiH(CH₃)-O-)_f-Si(CH₃)₃

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

Examples of the silanol group-blocked methylhydrogenpolysiloxane having both terminal silanol groups in the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl, propyl, phenyl, trifluoropropyl, or the like.

HOSi(CH₃)₂O-(-SiH(CH₃)-O-)₂-Si(CH₃)₂OH

Examples of the dimethylsiloxane-methylhydrogensiloxane copolymer having silanol groups blocked at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups, and the like.

HOSi(CH₃)₂O-(-Si(CH₃)₂-O-)_e-(-SiH(CH₃)-O-)_f-Si(CH₃)₂OH

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

Examples of the dimethylhydrogensiloxy-terminated dimethylpolysiloxane at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl, propyl, phenyl, trifluoropropyl, or the like.

HSi(CH₃)₂O-(-Si(CH₃)₂-O-)_e-Si(CH₃)₂H

[ wherein e is an integer of 1 or more. ]

Examples of the dimethylhydrogensiloxy group-blocked methylhydrogenpolysiloxane at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl, propyl, phenyl, trifluoropropyl, etc.

HSi(CH₃)₂O-(-SiH(CH₃)-O-)_e-Si(CH₃)₂H

[ wherein e is an integer of 1 or more. ]

Examples of the dimethylhydrogensiloxy-terminated dimethylsiloxane-methylhydrogensiloxane copolymer at both ends of the molecular chain include compounds represented by the following formula, and further include compounds in which some or all of the methyl groups in the following formula are substituted with ethyl groups, propyl groups, phenyl groups, trifluoropropyl groups, and the like.

HSi(CH₃)₂O-(-Si(CH₃)₂-O-)_e-(-SiH(CH₃)-O-)_h-Si(CH₃)₂H

[ wherein e and h are each an integer of 1 or more. ]

Such a compound can be produced by a known method, and can be easily obtained by, for example, equilibrating a triorganosilyl group-or diorganohydrogensiloxy group-containing compound such as octamethylcyclotetrasiloxane and/or tetramethylcyclotetrasiloxane with hexamethyldisiloxane or 1, 3-dihydro-1, 1,3, 3-tetramethyldisiloxane which can be terminal groups, in the presence of a catalyst such as sulfuric acid, trifluoromethanesulfonic acid or methanesulfonic acid at a temperature of about-10 ℃ to +40 ℃.

The SiH group-containing compound (H) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The SiH group-containing compound (H) is used in the resin composition of the present invention in a proportion of usually 0.1 to 15 parts by weight, preferably 0.5 to 10 parts by weight, based on the total amount of the SiH group-containing compounds (H), based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). When the SiH group-containing compound (H) is used in a proportion within the above range, a resin composition capable of forming a crosslinked rubber molded product having excellent compression set resistance, moderate crosslinking density, and excellent strength characteristics and elongation characteristics is obtained. If the SiH group-containing compound (H) is used in an amount exceeding 15 parts by weight, it may be disadvantageous in terms of cost.

< catalyst for addition reaction >

When the resin composition of the present invention contains the SiH group-containing compound (H), the resin composition may contain, as an optional component, an addition reaction catalyst having an action of promoting an addition reaction (hydrosilylation reaction of an olefin) of an alkenyl group of the ethylene- α -olefin-nonconjugated polyene copolymer (S) with an SiH group of the SiH group-containing compound (H).

The addition reaction catalyst is not particularly limited as long as it is a substance that promotes such an addition reaction, and examples thereof include an addition reaction catalyst containing a platinum group element such as a platinum group catalyst, a palladium group catalyst, or a rhodium group catalyst (a group 8 metal-based catalyst such as a group 8 metal, a group 8 metal complex, or a group 8 metal compound of the periodic table), and among them, a platinum group catalyst is preferable.

The platinum-based catalyst may be a known platinum-based catalyst generally used for addition curing, and examples thereof include a fine powder metal platinum catalyst described in U.S. Pat. No. 2,970,150, a chloroplatinic acid catalyst described in U.S. Pat. No. 2,823,218, a complex compound of platinum and a hydrocarbon described in U.S. Pat. No. 3,159,601 and U.S. Pat. No. 159,662, a complex compound of chloroplatinic acid and an olefin described in U.S. Pat. No. 3,516,946, and a complex compound of platinum and a vinyl siloxane described in U.S. Pat. No. 3,775,452 and U.S. Pat. No. 3,814,780. More specifically, the catalyst includes simple substance platinum (platinum black), chloroplatinic acid, a platinum-olefin complex, a platinum-alcohol complex, a carrier of platinum supported on a carrier such as alumina or silica, and the like.

The palladium-based catalyst includes palladium, a palladium compound, chloropalladic acid, and the like, and the rhodium-based catalyst includes rhodium, a rhodium compound, chloropalladic acid, and the like.

Examples of the catalyst for addition reaction other than the above-mentioned catalysts include Lewis acids and cobalt carbonyls. The addition reaction catalyst is used in a proportion of 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, particularly preferably 5 to 1,000 ppm by weight, based on the ethylene- α -olefin-nonconjugated polyene copolymer (S).

When the addition reaction catalyst is used in a proportion within the above range, a rubber composition capable of forming a crosslinked rubber molded product having an appropriate crosslinking density and excellent strength characteristics and elongation characteristics can be obtained. If the addition reaction catalyst is used in a proportion exceeding 100,000 ppm by weight, it is not preferable because it may be disadvantageous in terms of cost.

In the present invention, a crosslinked rubber molded product can also be obtained by irradiating an uncrosslinked rubber molded product of a rubber composition containing no addition reaction catalyst with light, gamma rays, electron rays, or the like.

< reaction inhibitor >

The resin composition of the present invention may contain a reaction inhibitor as an optional component in addition to the addition reaction catalyst. Examples of the reaction inhibitor include benzotriazole, an ethynyl group-containing alcohol (e.g., ethynylcyclohexanol), acrylonitrile, amide compounds (e.g., N-diallylacetamide, N-diallylbenzamide, N ' -tetraallyl-phthalic diamide, N ' -tetraallyl-isophthalic diamide, N ' -tetraallyl-terephthalic diamide, etc.), sulfur, phosphorus, nitrogen, an amine compound, a sulfur compound, a phosphorus compound, tin, a tin compound, tetramethyltetravinylcyclotetrasiloxane, and organic peroxides such as hydrogen peroxide.

The reaction inhibitor is used in a proportion of 0 to 50 parts by weight, usually 0.0001 to 50 parts by weight, preferably 0.0001 to 30 parts by weight, more preferably 0.0001 to 20 parts by weight, further preferably 0.0001 to 10 parts by weight, particularly preferably 0.0001 to 5 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). When the reaction inhibitor is used in an amount of 50 parts by weight or less, a rubber composition having a high crosslinking rate and excellent productivity of a crosslinked rubber molded product can be obtained. If the reaction inhibitor is used in a proportion of more than 50 parts by weight, the cost becomes unfavorable, and therefore, it is not preferable.

In the resin composition of the present invention, the crosslinking agent may be one of the organic peroxide (G) and the SiH group-containing compound (H), or both of them may be contained.

< (J) A compound having at least 1 unsaturated hydrocarbon group and at least 1 hydrolyzable silyl group

The resin composition of the present invention may contain, as an optional component, a compound (J) containing at least 1 unsaturated hydrocarbon group and at least 1 hydrolyzable silyl group. Examples of such a compound (J) include silane coupling agents having an unsaturated hydrocarbon group, and specific examples thereof include γ -methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, vinyl-tris (. beta. -methoxyethoxy) silane, vinyltriethoxysilane, γ -methacryloxypropylmethyldimethoxysilane, and the like.

Since such a compound (J) also functions as a crosslinking agent, the total surface area of the fine powder silicic acid and/or the silicate (E) is 1m per 1m in terms of obtaining an appropriate crosslinking density and securing sufficient elongation²The content in the resin composition is preferably less than 8X 10^-6mol, more preferably less than 8X 10^-7mol。

< other silane coupling agent >

The resin composition of the present invention may contain, as an optional component, a bis [3- (triethoxysilyl) propyl ] silane coupling agent other than the component (J)]And silane coupling agents having no unsaturated hydrocarbon group such as tetrasulfide. Since such a silane coupling agent does not act as a crosslinking agent, it is generally possible to coat the surface area of the fine powder silicic acid and/or silicate (E) with 1m per surface area²Is less than 1 × 10^-3mixing the mol ratio.

< anti-aging agent >

The resin composition of the present invention may contain an antioxidant.

In the present invention, when an antioxidant is used, at least 1 kind selected from the group consisting of a sulfur-based antioxidant, a phenol-based antioxidant and an amine-based antioxidant can be used, and as the sulfur-based antioxidant, a sulfur-based antioxidant usually used in rubber is used. Specific examples of the antioxidant include those described in WO2015/122495 and the like.

In the present invention, the sulfur-based antioxidant, the phenol-based antioxidant and the amine-based antioxidant may be used alone, but it is preferable to use 2 or more in combination from the viewpoint of maintaining the heat aging resistance at high temperatures for a long period of time. In the present invention, the sulfur-based antioxidant is used in a proportion of usually 0.2 to 10 parts by weight, preferably 0.2 to 8 parts by weight, and more preferably 0.2 to 6 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). The sulfur-based antioxidant is preferably used in such a proportion that the effect of improving heat aging resistance is large and that the crosslinking of the resin composition of the present invention is not inhibited.

The phenol-based antioxidant is used in an amount of usually 0.2 to 5 parts by weight, preferably 0.5 to 4 parts by weight, and more preferably 0.5 to 3 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). The use of the phenol-based antioxidant in the above-mentioned proportion is preferable because the effect of improving the heat aging resistance is large and the crosslinking of the resin composition of the present invention is not inhibited.

The amine antioxidant is used in an amount of usually 0.05 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). It is preferable to use the amine-based antioxidant in such a proportion because the effect of improving the heat aging resistance is large and the crosslinking of the copolymer rubber is not inhibited.

< processing aid >

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

As the processing aid, a compound used in processing of general rubbers can be used. Specific examples thereof 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, and calcium stearate; esters of higher fatty acids such as ricinoleic acid, stearic acid, palmitic acid, and lauric acid.

Such a processing aid is used in a proportion of usually 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S), and it is desirable to appropriately determine an optimum amount in accordance with the desired physical property values.

< softening agent >

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

As the softener, a known softener used in general rubber can be used. Specific examples thereof include petroleum softeners such as process oil, lubricating oil, liquid paraffin, petroleum asphalt, and vaseline; coal tar softeners such as coal tar and coal tar pitch; fatty oil softeners such as castor oil, linseed oil, rapeseed oil, soybean oil, coconut oil and the like; tall oil; oil gels (ointments); waxes such as beeswax, carnauba wax, and lanolin; fatty acids and fatty acid salts such as ricinoleic acid, palmitic acid, stearic acid, barium stearate, calcium stearate, and zinc laurate; synthetic high molecular substances such as petroleum resin, atactic polypropylene, coumarone indene resin and the like. Among them, petroleum-based softeners are preferably used, and processing oil is particularly preferably used.

The softening agent may be used singly or in combination of 2 or more. The amount thereof may be 0 to 100 parts by weight, preferably 2 to 80 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S).

< blowing agent >

The resin composition of the present invention may contain a foaming agent as an optional component in a range not impairing the object of the present invention depending on the use.

Specific examples of the foaming agent include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate and ammonium nitrite; nitroso compounds such as N, N ' -dimethyl-N, N ' -dinitrosoterephthalamide and N, N ' -dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, and barium azodicarboxylate; sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p '-oxybis (benzenesulfonyl hydrazide), diphenyl sulfone-3, 3' -disulfonyl hydrazide and the like; azide compounds such as calcium azide, 4-diphenyldisulfonylazide and p-toluenesulfonylazide, and the like.

These blowing agents can be used in an amount of 0.5 to 30 parts by weight, preferably 1 to 20 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S). When the foaming agent is used in the above-mentioned proportion, the specific gravity of the composition can be 0.03 to 0.8g/cm ³The amount of the foam is preferably determined as appropriate in accordance with the desired physical property values.

Further, if necessary, a foaming aid may be used in combination with the foaming agent. The foaming auxiliary agent has the functions of reducing the decomposition temperature of the foaming agent, promoting decomposition, homogenizing bubbles and the like. Examples of such a foaming aid include organic acids such as salicylic acid, phthalic acid, stearic acid, and oxalic acid, urea, or derivatives thereof.

The foaming aid is used in an amount of 0.01 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the ethylene- α -olefin-nonconjugated polyene copolymer (S), and the optimum amount is preferably determined according to the desired physical property values.

< optional component >

The resin composition of the present invention may contain, in addition to the above components, various optional components such as various additives, fillers, and other resin components that may be added to the rubber composition as needed, within a range that does not impair the object of the present invention.

< production of resin composition and crosslinked molded article >

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

The resin composition of the present invention can be used even in an uncrosslinked state, but when used as a crosslinked product such as a crosslinked molded article or a crosslinked foamed molded article, the properties thereof are most exhibited.

In the production of the crosslinked molded article such as the resin composition and the vibration-proof rubber product of the present invention, an uncrosslinked resin composition may be prepared first, and then the rubber composition may be crosslinked after being molded into a desired shape, as in the case of crosslinking a known rubber composition. The preparation, molding and crosslinking of the resin composition may be carried out separately or continuously.

The uncrosslinked resin composition of the present invention can be prepared as follows: for example, the ethylene- α -olefin-nonconjugated polyene copolymer (S), the finely powdered silicic acid and/or the finely powdered silicate (E), and other inorganic fillers and softeners are kneaded at a temperature of 80 to 190 ℃, preferably 80 to 170 ℃ for 2 to 20 minutes, preferably 3 to 10 minutes by means of a closed mixer such as a Banbury mixer, a kneader, or an internal mixer, and then (F) the metal salt of an α, β -unsaturated carboxylic acid, the organic peroxide (G) as a crosslinking agent and/or the SiH group-containing compound (H) having at least 2 SiH groups in the molecule, and, if necessary, various additives such as an addition reaction catalyst, a reaction inhibitor, a crosslinking accelerator, a crosslinking assistant, a foaming agent, an anti-aging agent, a colorant, a dispersant, a flame retardant, and the like are additionally mixed by using a roll or a kneader such as an open roll, kneading the mixture at a roll temperature of 40 to 60 ℃ for 3 to 30 minutes, and extruding and sheeting the kneaded mixture to prepare a resin composition in the form of a tape or sheet.

When the kneading temperature in the internal mixer is low, the resin composition can be prepared by kneading the crosslinking agent and various additives together with (S) the ethylene- α -olefin-unconjugated polyene copolymer, (E) the fine powder silicic acid and/or the fine powder silicate, and if necessary, the inorganic filler, the softener, and the like.

The resin composition of the present invention prepared as described above can be molded into a desired shape by various molding methods using an extrusion molding machine, a calender roll, a press, an injection molding machine, a transfer molding machine, or the like, and the molded product can be crosslinked simultaneously with molding or by introducing the molded product into a crosslinking tank. The crosslinking can be performed by heating at 100 to 270 ℃ for 1 to 30 minutes or by irradiating with radiation such as light, gamma rays, or electron rays. In addition, crosslinking can also be performed at normal temperature.

The resin composition of the present invention contains (G) an organic peroxide and/or (H)1 an SiH group-containing compound having at least 2 SiH groups in a molecule as a crosslinking agent, and thus can be crosslinked by heating, or by irradiation with radiation such as light, gamma ray, or electron beam, or by a method combining these.

Such crosslinking may be performed using a mold, or may be performed without using a mold. The molding and crosslinking steps are usually performed continuously without using a mold. As a heating method in the crosslinking tank, a heating tank of hot air, a glass bead fluidized bed, UHF (ultra high frequency electromagnetic wave), steam, or the like can be used.

The resin composition of the present invention has a high crosslinking speed and excellent productivity, can be crosslinked by hot air such as HAV (hot air vulcanization tank) or UHF (ultra high frequency electromagnetic wave), and the crosslinked molded product of the present invention obtained from the resin composition of the present invention has excellent appearance of the product, is excellent in compression set resistance and thermal aging resistance, and is environmentally friendly because the crosslinking agent does not bleed out of the surface of the product, and does not emit a nitrosoamine compound or the like suspected of being a so-called carcinogenic substance. The crosslinked molded article of the present invention is excellent in vibration-proof performance and can be suitably used as a vibration-proof rubber product, and specifically can be suitably used for applications such as vibration-proof rubber for automobiles, muffler suspension rubber for automobiles, vibration-proof rubber for railways, vibration-proof rubber for industrial machines, vibration-proof rubber for buildings, engine mounts, gaskets, bushes, cushions, washers, air springs, ring mounts, stoppers for bumpers, fenders, flexible joints, and dynamic dampers.

According to the present invention, such a resin composition, a crosslinked molded article, and a vibration-damping rubber product can be produced at low cost.