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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Notices, Deadlines & Correspondence
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
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;;
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