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Ethylene/A Olefin/Non Conjugated Polyene Copolymer Production Method Therefor And Use Therefor

Abstract: Provided is a novel ethylene/a olefin/non conjugated polyene copolymer that has few long chain branches and that comprises a constituent unit that is derived from: ethylene (A); an a olefin (B) that has 3 20 carbon atoms; and a non conjugated polyene (C) that contains a total of two or more partial structures that are selected from the group consisting of formulas (I) and (II) in a molecule thereof. The present invention makes it possible to provide a novel ethylene/a olefin/non conjugated polyene copolymer that contains a non conjugated polyene such as VNB as a copolymer component that contains few long chain branches and that has excellent curing characteristics when cross linking is performed using a peroxide. The present invention also makes it possible to provide a production method for the ethylene/a olefin/non conjugated polyene copolymer and a use therefor.

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Patent Information

Application #
Filing Date
07 September 2016
Publication Number
54/2016
Publication Type
INA
Invention Field
POLYMER TECHNOLOGY
Status
Email
remfry-sagar@remfry.com
Parent Application
Patent Number
Legal Status
Grant Date
2020-03-20
Renewal Date

Applicants

MITSUI CHEMICALS INC.
5 2 Higashi Shimbashi 1 chome Minato ku Tokyo 1057117

Inventors

1. ICHINO Kotaro
c/o MITSUI CHEMICALS INC. 3 Chigusakaigan Ichihara shi Chiba 2990108
2. KIKUCHI Yoshiharu
c/o MITSUI CHEMICALS INC. 3 Chigusakaigan Ichihara shi Chiba 2990108
3. TOHI Yasushi
c/o MITSUI CHEMICALS INC. 5 2 Higashi Shimbashi 1 chome Minato ku Tokyo 1057117
4. MATSUGI Tomoaki
c/o MITSUI CHEMICALS INC. 580 32 Nagaura Sodegaura shi Chiba 2990265
5. YANAGIMOTO Yasushi
c/o MITSUI CHEMICALS INC. 580 32 Nagaura Sodegaura shi Chiba 2990265
6. ARINO Mitsunao
c/o MITSUI CHEMICALS INC. 3 Chigusakaigan Ichihara shi Chiba 2990108
7. SHISHIDO Keisuke
c/o MITSUI CHEMICALS INC. 3 Chigusakaigan Ichihara shi Chiba 2990108
8. HOSOYA Mikio
c/o MITSUI CHEMICALS INC. 3 Chigusakaigan Ichihara shi Chiba 2990108

Specification

DESCRIPTION ETHYLENE/a-OLEFIN/NON-CONJUGATED POLYENE COPOLYMER, AND PRODUCTION PROCESS AND USE THEREOF 5 FIELD OF THE INVENTION [0001] The present invention relates to an ethylene/a-olefin/non-conjugated polyene copolymer. Specifically, the invention relates to a novel 10 ethylene/a-olefin/non-conjugated polyene copolymer having a structural unit derived from a specific non-conjugated polyene such as 5-vinyl-2-norbornene (VNB) and exhibiting a rapid crosslinking rate and an excellent formability, and also relates to a production process and a use thereof. 15 [0002] The invention also relates to a crosslinked shaped article which is obtained by using the ethylene/a-olefin/non-conjugated polyene copolymer and suitably usable, for example, for tires, and also relates to a production process and a use thereof. 20 [0003] Further, the invention relates to a resin composition containing the ethylene/a-olefin/non-conjugated polyene copolymer and to a shaped article made from the resin composition. Specifically, the invention relates to a resin composition which SF-2923 2 contains the ethylene/ex-olefin/non-conjugated polyene copolymer and is suitable for producing anti-vibration shaped articles, and also relates to the shaped articles. BACKGROUND OF THE INVENTION 5 [0004] Since ethylene/ex-olefin rubbers represented by ethylene /propylene/non-conjugated diene copolymer rubber (EPDM) have no unsaturated bonds in the backbone of their molecular structure, they exhibits thermal resistance and weatherability superior to 10 those of generally used conjugation diene rubbers, and accordingly, they are widely used in automobile parts, materials for electrical wire, materials for construction and civil engineering, parts of industrial members, modifiers for various resins, and so on. [0005] 15 When ethylene/ex-olefin system rubbers are crosslinked by using peroxide, and in particular, when they c9ntain an non-conjugated polyene such as 5-vinyl-2-norbornene (hereinafter, also referred to as VNB) as a copolymerization component, they exhibit a rapid crosslinking rates. 20 [0006] However, ethylene/ex-olefin/VNB terpolymers produced by using existing catalysts have many long-chain branches derived from terminal vinyl groups of VNB. In this case, since many terminal vinyl groups of VNB in the copolymers have been consumed, SF-2923 3 improvement in crosslinking rate is not sufficient, and moreover, the long-chain branches may worsen the processability of the copolymers during their formation and their physical properties after the formation. Such long-chain branches may also be 5 generated by using vanadium-based catalysts, and the long-chain branch content was observed to have a tendency to increase especially when metallocene-based catalysts are used for polymerization. 10 [0007] Patent document l and Patent document 2 describe ethylene copolymers which are polymerized by using metallocene-based catalysts and contain structural units derived from ethylene, an a-olefin, and VNB, and Patent document l describes that the copolymer is suitable for foam shaping, and Patent document 2 15 describes that a rubber shaped article can be formed which has an excellent surface appea:rance, strength property,, heat a.ging resistance, and light resistance, and a small compression set. However, ethylene copolymers obtained by these techniques have a large long-chain branch content. 20 [ 0 0 0 8] Patent document 3 describes a process for producing a polymer containing monomer units of ethylene, an a-olefin, VNB, and 5-ethylidene-2-norbornene (ENB) by using a Group 4 metal compound having a single cyclopentadienyl ligand and a SF-2923 4 monosubstituted nitrogen ligand, aluminoxane and a catalyst-activating agent as a catalyst system, and also describes the production of an EPDM polymer having a high VNB content and a low degree of branching. However, the EPDM polymer described 5 in Patent document 3 has a problem that it is unsuitable to obtain a shaped article having an enough heat aging resistance because of too many dienes per molecule of the copolymer. [0009] In this situation, a novel ethylene/a-olefin-based rubber 10 has been required which contains, with a small long-chain branch content, a non-conjugated polyene such as VNB as a copolymerization component. [0010] Styrene-butadiene rubber (SBR) is conventionally widely 15 used for tires, for example, for automobile uses. Diene rubbers such as styrene-::butadiene rubber singly have insufficient ' 11 weatherability, and when they are used for a long outdoor use such ),i il ~-:I (:II ·J •.·1 II l 20 ll as for a tire use, an amine-based rubber antioxidant or a paraffin-based wax are usually added to improve weatherability. However, diene-rubber products in which the amine-based '·,'1 II antioxidant or the paraffin-based wax are blended may undergo the bleed out of these components and discoloration on the surface thereof with time. Appearance worsening, such as discoloration and blooming due to the bleeding out during storage in shops may SF-2923 5 also cause lowering their commercial value. For these reasons, weatherability improvement by rubber components themselves has been required. [0011] 5 Although improving weatherability by blending ethylene-propylene-diene rubber (EPDM) to styrene-butadiene rubber has been studied in order to solve these problems, another problem occurs that styrene-butadiene rubber and EPDM tend to cause phase separation during heat crosslinking, resulting in 10 insufficient fatigue-resistance. [0012] The present applicants have proposed a rubber composition containing not only a random copolymer rubber consisting of structural units derived from ethylene, an a-olefin, and a 15 specific triene compound, but also a diene rubber, carbon black, and a vulcanizer (See Patent document 4) . This rubber composition . . is suitable for a tire sidewall use since the ethylene/a-olefin/triene random copolymer rubber shows fast vulcanization rate comparative to that of the diene rubber and 20 consequently it is unlikely to cause phase separation from the diene rubber with no damage of the excellent mechanical strength intrinsically possessed by diene rubbers. [0013] The present applicants have also found and proposed a rubber SF-2923 6 composition obtained by mixing a composition containing a non-conjugate polyene copolymer containing structural units derived from an a-olefin and from a non-conjugate polyene and a softening agent, and a diene rubber, and the rubber composition 5 is sui table for forming a tire excellent in braking performance and fuel economy performance (See Patent documents 5 and 6). [0014] Recently in tire production, there is mainly adopted a process including steps of forming an uncrosslinked composition 10 mainly composed of a diene rubber such as styrene/butadiene rubber and natural rubber, for example, into a sheet-like shape, subsequently crosslinking only the surface of the shaped composition by electron beam to prevent sagging, and then assembling into a tire shape, followed by sulphur-crosslinking. 15 [0015] Further, diene rubbers such as natural rubber (NR), styrene-butadiene rubber (SBR), and butadiene rubber (BR) are known as a rubber excellent in dynamic fatigue resistance and dynamical properties, and are used as a raw material rubber for 20 car tires and for anti-vibration rubbers. However nowadays, environmental conditions under which these rubber products are used have been greatly changed, and improvement in thermal resistance and weatherability of the rubber products has been required. For car tires, tread and tire sidewall are particularly SF-2923 7 required to have weatherability. However, there is so far no rubber having not only excellent mechanical properties, fatigue-resistance, and dynamical property, all being possessed by current diene rubbers, but also good weatherability. 5 [0016] For this reason, there are studied various blended rubber compositions of a diene rubber and an ethylene/a-olefin of 3 to 20 carbons/non-conjugate polyene copolymer such as ethylene/propylene/non-conjugate diene copolymer rubber (EPDM), 10 the diene rubber being excellent in mechanical properties, dynamic fatigue resistance, and dynamical properties, and the copolymer being excellent in thermal resistance and weatherability. However, because the dynamical properties of the ethylene/a-olefin of 3 to 20 carbons/non-conjugate polyene 15 copolymer and those of the diene rubber are at different levels, no blend-based rubber composition exhibiting uniform physical properties has been achieved. Note that the dynamical properties in car tires are used only to estimate whether a subject material worsens fuel economy or not, and the index of the properties is 20 tan i5 (loss tangent), a lower value of which means better dynamical properties. [0017] On the other hand, anti-vibration rubber products for cars based on natural rubber which is a currently used diene rubber SF-2923 8 have been made difficult to provide a fatigue resistance sufficient to practical use due to increase in temperature in engine rooms. Accordingly, a novel rubber material is required which is excellent in thermal resistance, and exhibits mechanical 5 properties, dynamical properties, and fatigue-resistance which are equal to or better than those of diene rubbers. [0018] In general, in order to improve the dynamical properties, crosslinking density must be high. However in existing 10 techniques, in order to make the dynamical properties of ethylene/a-olefin of 3 to 20 carbons/non-conjugated polyene copolymers be comparative to those of diene rubbers such as NR, the crosslinking density becomes too high, resulting in degradation of mechanical properties such as tensile break 15 elongation and causing incompatibility between the dynamical properties and the physical properties. [0019] In this situation, the applicants propose; an anti-vibration rubber composition containing a specific 20 ethylene/a-olefin/polyene amorphous copolymer, a crosslinking agent, and a filler, which composition is able to reduce the used amount of the organic peroxide crosslinking agent and has an excellent thermal resistance, a durability equal to or larger than that of natural rubber, and also exhibits an excellent ::-·: ;-:: i ~_-_j SF-2923 9 dynamic-to-static modulus ratio (See Patent document 7); a rubber composition containing an ethylene/a-olefin/non-conjugated polyene copolymer, a powdered silica, a metal unsaturated carboxylate, and an organic peroxide, which composition not only 5 is excellent in dynamical properties and mechanical strength, but also has an improved heat aging resistance (See Patent document 8) ; and an anti -vibration rubber composition containing a specific ethylene/a-olefin/non-conjugated polyene copolymer having a small B value and containing a powdered silica, a metal unsaturated 10 carboxylate, and an organic peroxide, which composition is not only excellent in thermal resistance and fatigue resistance, but also well-balanced between dynamical properties and mechanical strength (See Patent document 9). [ 0 02 0 l 15 In anti-vibration rubbers made from ethylene/a-olefin/non-conjugated polyene copolymers, in ord,' Patent document 8 : JP-A-2003-82174 Patent document 9: JP-A-2006-348095 DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION SF-2923 11 [0023] An object of the present invention is to provide a novel ethylene/a-olefin/non-conjugated polyene copolymer which contains a specific non-conjugated polyene such as VNB as a 5 copolymerization component, and which has a small long-chain branch content and is excellent in curing properties in the case of crosslinking by using peroxide, a production process, and a use thereof. [0024] 10 Another object of the invention is to provide a crosslinked shaped article without phase separation during its production, the crosslinked shaped article being excellent in weatherability and prevented from worsening of its appearance due to the improved weatherability of rubber components such as styrene/butadiene 15 rubber and natural rubber. [0025] Still another object of the invention is to provide a resin composition suitable for producing anti-vibration rubber products and the anti-vibration rubber products, the resin 20 composition having a crosslinking density easy to be increased, excellent anti-vibration properties, an elongation property unlikely to deteriorate even with increased crosslinking density, a sufficient strength even with its molecular weight within a range for easy kneading, and an excellent thermal resistance. ~: [-, ),> t~ i II SF-2 92 3 12 MEANS FOR SOLVING THE PROBLEMS [0026] The present inventors have earnestly studied to achieve the above-mentioned objects, and found that a novel 5 ethylene/ex-olefin/non-conjugated polyene copolymer specified by the following requirements from (i) to (v) contains a structural unit derived from a specific non-conjugated polyene such as VNB, and that the copolymer has a small long-chain branch content and is crosslinkable by peroxides at a rapid rate, and moreover, 10 excellent in properties after crosslinking, and thus the invention has been completed. [0027] The inventor have also found that a crosslinked shaped article obtained by crosslinking a composition which contains the 15 specific ethylene/ex-olefin/non-conjugated polyene copolymer and a rubber component such as diene rubber is not accompanied by phase separation during its production, particularly during cross linking, and in addition, it is excellent in weatherability, and thus the invention has been completed. 20 [0028] The invention relates to the following items. [1] An ethylene/a-olefin/non-conjugated polyene copolymer comprising structural units derived from ethylene (A) , an ex-olefin (B) of 3 to 20 carbon atoms, and a non-conjugated polyene (C) j I SF-2923 13 containing intramolecularly two or more partial structures in total selected from the group consisting of structures represented by Formulae (I) and (II), and satisfying the following requirements of from (i) to (v): 5 [0029] [Chern. 1] .. (I) [cH2=cHj-- [0030] (i) the molar ratio of the ethylene/a-olefin is from 40/60 to 10 99.9/0.1; (ii) the weight fraction of the structural unit derived from the non-conjugated polyene (C) is from 0. 07% by weight to 10% by weight in 100% by weight of the ethylene/a-olefin/non-conjugated polyene copolymer; 15 (iii) the weight-average molecular weight (Mw) of the ethylene/a-olefin/non-conjugated polyene copolymer, the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C) (%by weight)), and a molecular weight of the non-conjugated polyene (C) (molecular weight of (C)) 20 satisfy Formula (1), [0031] 4.5 ~ Mw x weight fraction of (C) I 100 I molecular weight SF-2923 14 of (C) 5: 40 Formula (1); (iv) the ratio of a complex viscosity ll*(w ~ 0.11 (Pa·sec) at a frequency of w = 0. 1 rad/ s to a complex viscosity ll* (w~ 1001 ( Pa ·sec) at a frequency of w = 100 rad/s, both obtained by linear 5 viscoelastic measurement (190°C) by using a rheometer, represented by P(ll*(w ~ 0.11 I ll*(w ~ 1001 ), an intrinsicviscosity represented by [Ill, and a weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C)) satisfy Formula (2), 10 [0032l PI ( [!ll 2 ' 9 ) :<;weight fraction of (C) x 6 Formula (2); and (v) the number of long-chain branches per 1000 carbon atoms represented by (LCB1ooocl and the natural logarithmic number of the weight-average molecular weight (Mw) represented by [Ln(Mw)l, 15 obtained by using 30-GPC, satisfy Formula (3), [0033l LCB1oooc :<; 1 - 0. 07 x Ln (Mw) Formula ( 3) . [2l The ethylene/a-olefin/non-conjugated polyene copolymer according to [ ll , wherein the intrinsic viscosity [Ill is from 0. 1 20 to 5 dL/g, and the weight-average molecular weight (Mw) is from 10000 to 600000. [3l The ethylene/a-olefin/non-conjugated polyene copolymer according to [ll or [2l, wherein the non-conjugated polyene (C) is 5-vinyl-2-norbornene (VNB) . SF-2923 15 [4) The ethylene/a-olefin/non-conjugated polyene copolymer according to any one of [1) to [3), further comprising a structural unit derived from a non-conjugated polyene (D) containing intramolecularly only one partial structure selected from the 5 group consisting of structures represented by Formulae (I) and (II), at a weight fraction of from 0% by weight to 20% by weight (with the proviso that the sum of the weight fractions of (A), (B), (C), and (D) is 100% by weight), and satisfying the following requirement (vi); 10 (vi) the weight-average molecular weight (Mw) of the ethylene/a-olefin/non-conjugated polyene copolymer, the weight fraction of the structural unit derived from the non-conjugated polyene (C) (weight fraction of (C) (% by weight)), the weight fraction of the structural unit derived from the conjugated 15 polyene (D) (weight fraction of (D) (% by weight) ) , the molecular weight of the non-conjugated polyene (C) (molecular weight of (C)), and a molecular weight of the conjugated polyene (D) (molecular weight of (D)) satisfy Formula (4), ~:] M [oo34J E'.l H il 20 4. 5 ~ Mw x [(weight fraction of (C) I 100 I molecular weight l[ 1 of (C)) + (weight fraction of (D) I 100 I molecular weight of (D))) i .I ~ 45 Formula ( 4) . [5) The ethylene/a-olefin/non-conjugated polyene copolymer according to [4), wherein the non-conjugated polyene (D) is SF-2923 16 5-ethylidene-2-norbornene (ENB). [6] The ethylene/~-olefin/non-conjugated polyene copolymer according to any one of [1] to [5], obtained by copolymerizing monomers in the presence of at least one kind of metallocene 5 compound represented by Formula [Al], [0035] [Chern. 2] ··· [A 1] [0036] independently represent a hydrogen atom, a hydrocarbon group, a silicon-containing group, or a heteroatom-containing group other than any silicon-containing group, and adjacent two groups among R1 to R4 may together form a ring; 15 [0037] R6 and R11 are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a SF-2923 17 silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R7 and R10 are the same atom or the same group selected from the group consisting of a hydrogen atom, a hydrocarbon group, a silicon-containing group, 5 and a heteroatom-containing group other than any silicon-containing group, R6 and R7 may together form a ring, and R10 and R11 may together form a ring, with the proviso that all of R6 , R7 , R10 , and R11 are not a hydrogen atom simultaneously; [0038] 10 R13 and R14 each independently represent an aryl group; [0039] M1 represents a zirconium atom; [0040] Y1 represents a carbon atom or a silicon atom; 15 [0041] Q represents a halogen atom, .a hydrocarbon group, a. halogenated hydrocarbon group, a neutral conjugated or. non-conjugated diene of 4 to 20 carbon atoms, or a neutral ligand coordinatable by an anionic ligand or a lone pair, and j represents 20 an integer from 1 to 4, and when j is an integer from 2 or more, a plurality of Qs may be the same or different from each other.] [7] A process for producing an ethylene/ex-olefin/non-conjugated polyene copolymer, the process including performing copolymerization in the presence of at least SF-2923 18 one kind of metallocene compound represented by Formula [Al] to produce the ethylene/a-olefin/non-conjugated polyene copolymer according to any one of [1] to [5]. [0042] 5 [Chern. 3] R1 R4 R 14---._ 1 1Q. R 13 ,/'f, J 5 R11 R6 ""----- R1D Rg R8 R7 ··· [A 1] [0043] [In Formula [Al], R1 , R2 , R3 , R4 , R5 , R8 , R9 , and R12 each independently represent a hydrogen. atom, .a hydrocarbon group, a 10 silicon-containing group, or a heteroatom-containing group other than any silicon-containing group, and adjacent two groups among R1 to R4 may together form a ring; [0044] R6 and R11 are the same atom or the same group selected from 15. a hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R7 and R10 are the same atom or the same SF-2923 19 group selected from hydrogen atom, a hydrocarbon group, a silicon-containing group, and a heteroatom-containing group other than any silicon-containing group, R6 and R7 may together form a ring, and R10 and R11 may together form a ring, with the 5 proviso that all of R6 , R\ R10 , and R11 are not a hydrogen atom simultaneously; [0045] R13 and R14 each independently represent an aryl group; [0046] 10 M1 represents a zirconium atom; [0047] Y1 represents a carbon atom or a silicon atom; [0048] Q represents a halogen atom, a hydrocarbon group, a 15 halogenated hydrocarbon group, a neutral conjugated or non-conjugated diene of 4 to 20 carbon atoms, or a neutral ligand coordinatable by an anionic ligand or a lone pair, and j represents an integer from 1 to 4, and when j is an integer of 2 or more, a plurality of Qs may be the same or different from each other.] 20 [ 8] The process for producing an ethylene/Ci-olefin/non-conjugated polyene copolymer according to i ' I [7], wherein the process includes continuously feeding to a reactor and copolymerizing ethylene (A), an Ci-olefin (B) of 3 to 20 carbon atoms, a non-conjugated polyene (C) containing ' ; SF-2923 20 intramolecularly two or more partial structures in total selected from the group consisting of structures represented by Formulae (I) and(II), and as necessary, a non-conjugated polyene (D) containing intramolecularly only one partial structure selected 5 from the group consisting of structures represented by Formulae (I) and (II) , [0049] [Chern. 4] .. (I) .. (II) 10 [0050] [ 9] The process for producing an ethylene/a-olefin/non-conjugated polyene copolymer according to [8], wherein the non-conjugated polyene (C) is 5-vinyl-2-norbornene (VNB), and the non-conjugated polyene (D) is 5-ethylidene-2-norbornene (ENB) . [10] A thermoplastic resin composition comprising the ethylene/a-olefin/non-conjugated polyene copolymer according to any one of [1] to [6]. [11] A thermoplastic resin composition comprising the ethylene/ a-o1efin/non-conj ugated polyene copolymer according to any one of [1] to [6] and an organic peroxide, wherein the content (mol) of the organic peroxide satisfies SF-2923 21 Formula ( 7) , [0051] content (mol) of organic peroxide x number of oxygen-oxygen bonds per molecule in organic peroxide ~ weight fraction of (C) 5 I molecular weight of (C) x 100 Formula ( 7) . (In formula ( 7) , the weight fraction of (C) represents the weight fraction (% by weight) of the structural unit derived from the non-conjugated polyene (C) in the ethylene/a-olefin/non-conjugated polyene copolymer, and the 10 molecular weight of (C) represents the molecular weight of the non-conjugated polyene (C).) [12) A rubber composition comprising the ethylene/a-olefin/non-conjugated polyene copolymer according to any one of [1) to [6). 15 [ 13) A vulcanized rubber shaped article obtained by cross linking the rubber composj_tion according to [12). [14) A hose for an automobile use obtained by crosslinking the rubber composition according to [12). [15) A turbocharger hose obtained by crosslinking the rubber 20 composition according to [12). [16) A muffler hanger obtained by crosslinking the rubber composition according to [12). [17) An engine mount obtained by crosslinking the rubber composition according to [12). SF-2923 22 [18] A conveyance belt obtained by crosslinking the rubber composition according to [12]. [19] A material for a wire cover obtained by crosslinking the rubber composition according to [12]. 5 [20] A crosslinked shaped article obtained by crosslinking a rubber composition (X) comprising the ethylene/a-olefin/non-conjugated polyene copolymer (S) according to [l] and a rubber component (T) selected from the group consisting of diene rubber, butyl rubber, and halogenated butyl 10 rubber, in a mass ratio of (S) I (T) = 5/95-50/50. [21] The crosslinked shaped article according to [20] obtained by crosslinking the rubber compositions (X) by irradiation with electron beam. [22] The crosslinked shaped article according [20] or [21], 15 wherein the conjugated polyene (C) comprises 5-vinyl-2-norbornene (VNB) . [23] The crosslinked shaped article according to any oneof [20] to [22], wherein the rubber component (T) comprises one or more kinds selected from the group consisting of natural rubber, 20 isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, and halogenated butyl rubber. [24] The crosslinked shaped article according to [20] to [23], wherein the rubber component (T) comprises styrene-butadiene copolymer rubber. SF-2923 23 [25] A process for producing a crosslinked shaped article comprising the step of crosslinking a rubber composition (X) comprising the ethylene/a-olefin/non-conjugated polyene copolymer (S) according to [1] and a rubber component (T) selected 5 from the group consisting of diene rubber, butyl rubber, and halogenated butyl rubber, in a mass ratio of (S) I (T) = 5/95-50/50. [26] A process for producing a crosslinked shaped article according to [25], wherein the crosslinking step is performed by · irradiation with electron beam. 10 [27] A tire member using the crosslinked shaped article according to any one of [20] to [24]. [28] A tire tread using the crosslinked shaped article according to any one of [20] to [24]. [29] A tire sidewall using the crosslinked shaped article 15 according to any one of [20] to [24]. [30] A tire comprising one or more kinds of tire. members sele.cted from the group consisting of a tire inner liner, a tire inner tube, a tire flap, a tire shoulder, a tire bead, a tire tread, and a tire sidewall, the members being composed of the crosslinked 20 shaped article according to any one of [20] to [24]. [31] A resin composition comprising: (S) 100 parts by weight of the ethylene/a-olefin/non-conjugated polyene copolymer according to [ 1] ; :i !] ;; 0 f,·j II , I : i SF-2923 24 (E) 5-90 parts by weight of a powdered silica and/or a powdered silicate salt having a specific surface area within the range of 5-500 m2/g; and, as crosslinking agents, 5 (G) 0.1-15 parts by weight of an organic peroxide; and/or (H) 0.1-100 parts by weight of a SiH group-containing compound comprising at least two SiH groups per molecule. [32] The resin composition according to [31], wherein the ethylene/a-olefin/non-conjugated polyene copolymer (S) has an 10 intrinsic viscosity [~] of 1.0-4.0 dl/g measured in decalin at [33] The resin composition according to [31] or [32], comprising 0.1-20 parts by weight of (F) an metal a, ~-unsaturated carboxylate with respect to 100 parts by weight of the 15 ethylene/a-olefin/non-conjugated polyene copolymer (S). [34] The resin composition,according to [33], where.in the Il)etal a,~-unsaturated carboxylate (F) comprises at least one. kind selected from the group consisting ofmetal methacrylate and metal maleate. 20 [35] The resin composition according to any one of [31] to [34], comprising (J) a compound comprising at least one unsaturated hydrocarbon group and at least one hydrolysable silyl group, in an amount of less than Bxl0-6 per 1 m2 of the surface area of the powdered silica and/or the powdered silicate salt (E) having the SF-2923 25 specific surface area within the range of 5-500 m2/g. [36] A crosslinked shaped article made of the resin composition according to any one of [31] to [35]. [37] An anti-vibration rubber product obtained by crosslinking 5 the resin composition according to any one of [31] to [35]. [38] An anti-vibration rubber product according to [37] which is an anti-vibration rubber for an automobile use. [39] An anti-vibration rubber product according to [37] which is a muffler hanger for an automobile use. 10 [ 4 0 l An anti-vibration rubber product according to [37] which is an anti-vibration rubber for railroad use. [ 41] An anti-vibration rubber product according to [37] which is an anti-vibration rubber for use in an industrial machine. [ 4 2] An anti-vibration rubber product according to [37] which 15 is a quake-absorbing rubber for construction. ADVANTAGEOUS EFFECT OF THE INVENTION [0052] The present invention can provide a novel ethylene/olefin/non-conjugated polyene copolymer which contains 20 a specific non-conjugated polyene such as VNB as a copolymerization component, and which has a small long-chain branch content and is excellent in curing properties in the case of crosslinking by using peroxide, and the invention can also provide a production process and a use thereof. SF-2923 26 [0053] In addition, the ethylene/a-olefin/non-conjugated polyene copolymer according to the invention is excellent in formability, crosslinking properties, and curing properties, yielding a shaped 5 article well-balanced in physical properties such as mechanical properties and particularly excellent in heat aging resistance. [0054] The invention can also provide a crosslinked shaped article exhibiting no phase separation, excellent weatherability even 10 when used in situations exposed to environmental atmosphere and daylight for a long period of time, and no worsening of appearance due to bleeding out, for example, of an additive, and can provide a production process thereof. In addition, according to the process for producing the shaped article of the invention, which 15 uses compositions with extremely excellent crosslinking properties, the crosslinking using only electron-beam is made li if possible, so that crosslinking at high temperature for a long !'; li i[ I period of time can be avoided, and phase separation can be H II prevented in the crosslinked shaped article. The resultant I 20 article, which exhibits not only excellent mechanical properties il t[ and surface properties but also excellent weatherability, can be ' i I suitably used for applications requiring weatherability, such as tire members and materials for wire cover. [0055] SF-2923 27 Still further, the invention can provide a shaped article having a crosslinking density easy to be increased, an elongation property unlikely to deteriorate even with the increased crosslinking density, and a sufficient strength and thermal 5 resistance even with a molecular weight within the range for easy kneading, and the invention can also provide a resin composition sui table for producing anti -vibration rubber products. In other words, the invention can provide an excellent resin composition and an anti-vibration rubber product which have a striking effect 10 capable of achieving not only anti-vibration properties but also heat aging resistance and which are well-balanced between kneadability and mechanical properties such as anti-vibration properties and elongation. In addition, anti-vibration rubber products of the invention have good rubber properties and exhibit 15 excellent anti-vibration properties and an excellent thermal resistance, enabling suitable applications which require ~igh thermal resistance such as anti-vibration rubber products for an automobile use, particularly for muffler hanger. DETAILED DESCRIPTION OF THE INVENTION 20 [0056] The present invention will be hereinafter explained specifically. [0057] SF-2923 28 The ethylene/a-olefin/non-conjugated polyene copolymer according to the invention (ethylene/a-olefin/non-conjugated polyene copolymer (S)) has structural units derived from ethylene (A), an a-olefin (B) of 3 to 20 carbon atoms, and a non-conjugated 5 polyene (C) containing intramolecularly two or more partial structures in total selected from the group consisting of structures represented by Formulae (I) and (II), 10 [0058] [Chern. 5] [0059] .. (I) [cH2=CHt- The ethylene/a-olefin/non-conjugated polyene copolymer of the invention may have, in addition to the structure units derived from the above-mentioned (A), (B), and (C), a structural unit 15 derived from a non-conjugated polyene (D) containing intramolecularly only one partial structure selected from the group consisting of the structures of Formulae (I) and (II). [0060] Examples of the a-olefin (B) of 3 to 20 carbon atoms include 20 propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-l-pentene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, and so on. Among them, a-olefins of SF-2923 29 3 to 8 carbon atoms are preferable, such as propylene, 1-butene, 1-hexene, 1-octene, and particularly propylene is preferable. Such a-olefins are preferable because they are relatively inexpensive in raw material cost, and provide not only an 5 ethylene/a-olefin/non-conjugated polyene copolymer excellent in mechanical properties but also a shaped article exhibiting rubber elasticity. These a-olefins may be used singly or in combination of the two or more kinds. [0061] 10 In other words, the ethylene/a-olefin/non-conjugated polyene copolymer of the invention contains a structural unit derived from at least one kind of a-olefin (B) of 3 to 20 carbon atoms, and may contain structural units derived from two or more kinds of a-olefins (B) of 3 to 20 carbon atoms. 15 [0062] Examples of the non-conjugated polyene (C) containi~g intramolecularly two or more partial structures in total selected from the group consisting of the structures of Formulae (I) and (II) include 5-vinyl-2-norbornene (VNB), norbornadiene, 20 1,4-hexadiene, dicyclopentadiene, and so on. Among them, the non-conjugated polyene (C) preferably contains VNB, and the non-conjugated polyene (C) is more preferably VNB because of its easy availability and its good crosslinking reactivity with peroxide during crosslinking after polymerization, and easy SF-2923 30 improvement in thermal resistance of its polymerized composition. The non-conjugated polyene (C) may be used singly or in combination of the two or more kinds. [0063] 5 The ethylene/ex-olefin/non-conjugated polyene copolymer of the invention may contain, in addition to the structural units derived from ethylene (A), the ex-olefin (B) of 3 to 20 carbon atoms, and the non-conjugated polyene (C), a structural unit derived from a non-conjugated polyene (D) containing intramolecularly only one 10 partial structure selected from the group consisting of the structures of Formulae (I) and (II). Examples of the non-conjugated polyene (D) include 5-ethylidene-2-norbornene (ENB), 5-methylene-2-norbornene, 5-(2-propenyl)-2-norbornene, :: I 5-(3-butenyl)-2-norbornene, 15 5-(l-methyl-2-propenyl)-2-norbornene, 5-(4-pentenyl)-2-norbornene, i' r: H [;!, 5-(l-methyl-3-butenyl)-2~norbornene, '[ 5-(5-hexenyl)-2-norbornene, ij I ['! 20 ·-i II 1,-: 5-(l-methyl-4-pentenyl)-2-norbornene, 5-(2,3-dimethyl-3-butenyl)-2-norbornene, 5-(2-ethyl-3-butenyl)-2-norbornene, l 5-(6-heptenyl)-2-norbornene, i I 5-(3-methyl-5-hexenyl)-2-norbornene, 5-(3,4-dimethyl-4-pentenyl)-2-norbornene, SF-2923 31 5-(3-ethyl-4-pentenyl)-2-norbornene, 5-(7-octenyl)-2-norbornene, 5-(2-methyl-6-heptenyl)-2-norbornene, 5-(1,2-dimethyl-5-hexenyl)-2-norbornene, 5 5-(5-ethyl-5-hexenyl)-2-norbornene, 5-(1,2,3-trimethyl-4-pentenyl)-2-norbornene, and so on. Among them, ENB is preferable because of its easy availability and its high reactivity with sulphur and a vulcanization enhancer during crosslinking reaction after polymerization, easy controllability 10 of its crosslinking rate, easiness to obtain its good mechanical physical properties. The non-conjugated polyene (D) can be used singly or in combination of the two or more kinds. When the ethylene/a-olefin/non-conjugated polyene copolymer of the invention contains a structural unit derived from the 15 non-conjugated polyene (D) containing intramolecularly only one partial structure sel

Documents

Application Documents

# Name Date
1 Priority Document [07-09-2016(online)].pdf 2016-09-07
2 Power of Attorney [07-09-2016(online)].pdf 2016-09-07
3 Form 5 [07-09-2016(online)].pdf 2016-09-07
4 Form 3 [07-09-2016(online)].pdf 2016-09-07
5 Form 18 [07-09-2016(online)].pdf_1.pdf 2016-09-07
6 Form 18 [07-09-2016(online)].pdf 2016-09-07
7 Form 1 [07-09-2016(online)].pdf 2016-09-07
8 Description(Complete) [07-09-2016(online)].pdf 2016-09-07
9 Other Patent Document [14-09-2016(online)].pdf 2016-09-14
10 201617030514-OTHERS-150916.pdf 2016-09-17
11 201617030514-Correspondence-150916.pdf 2016-09-17
12 201617030514.pdf 2016-09-21
13 abstract.jpg 2016-10-04
14 Marked Copy [17-10-2016(online)].pdf 2016-10-17
15 Form 13 [17-10-2016(online)].pdf 2016-10-17
16 Description(Complete) [17-10-2016(online)].pdf 2016-10-17
17 Form 3 [03-11-2016(online)].pdf 2016-11-03
18 201617030514-FORM 3 [03-05-2018(online)].pdf 2018-05-03
19 201617030514-FORM 3 [15-04-2019(online)].pdf 2019-04-15
20 201617030514-FORM 3 [17-04-2019(online)].pdf 2019-04-17
21 201617030514-FER.pdf 2019-09-25
22 201617030514-OTHERS [05-02-2020(online)].pdf 2020-02-05
23 201617030514-FORM 3 [05-02-2020(online)].pdf 2020-02-05
24 201617030514-FER_SER_REPLY [05-02-2020(online)].pdf 2020-02-05
25 201617030514-COMPLETE SPECIFICATION [05-02-2020(online)].pdf 2020-02-05
26 201617030514-CLAIMS [05-02-2020(online)].pdf 2020-02-05
27 201617030514-ABSTRACT [05-02-2020(online)].pdf 2020-02-05
28 201617030514-PatentCertificate20-03-2020.pdf 2020-03-20
29 201617030514-IntimationOfGrant20-03-2020.pdf 2020-03-20
30 201617030514-Response to office action [01-06-2020(online)].pdf 2020-06-01
31 201617030514-RELEVANT DOCUMENTS [08-09-2021(online)].pdf 2021-09-08
32 201617030514-FORM-26 [28-10-2021(online)].pdf 2021-10-28
33 201617030514-RELEVANT DOCUMENTS [21-09-2022(online)].pdf 2022-09-21
34 201617030514-RELEVANT DOCUMENTS [08-09-2023(online)].pdf 2023-09-08
35 201617030514-PROOF OF ALTERATION [07-11-2023(online)].pdf 2023-11-07

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1 2019-09-2311-14-22_23-09-2019.pdf

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