The present invention relates to a resin composition
containing an ethylene/a-olefin/non-conjugated polyene
copolymer and a use thereof.
[0002]
Specifically, the present invention relates to resin
compositions containing an ethylene/a-olefin/non-conjugated
polyene copolymer, including 1) a resin composition which enables
producing a crosslinked shaped article excellent in heat
resistance, 2) a resin composition which enables producing a
15 crosslinked shaped article excellent in sealing properties, 3)
a resin composition which enables producing a crosslinked shaped
article excellent in fatigue resistance and impact resilience,
and 4) a resin composition which enables producing a crosslinked
shaped article having excellent mechanical strength and heat aging
20 resistance by compounding a small amount of a crosslinking agent,
and also relates to a crosslinked shaped article using the above
resin compositions.
BACKGROUND ART
SF-3064
2
[0003]
In various apparatuses such as automobiles, a material
having elasticity and excellent heat resistance may be required,
such as a hose used under high thermal conditions.
5 [0004]
In recent years, engines for automobiles are increasingly
downsized and equipped with a turbocharger for improving fuel
efficiency. An engine with a turbocharger is configured so that
air compressed by a compressor wheel is cooled by a charge air
10 cooler and then sent to the engine, and the compressor wheel is
connected to the charge air cooler by a rubber hose. This
turbocharger hose is required to have high heat aging resistance
because air at high pressure and high temperature (about 180°C)
flows therethrough. It is also required to have fatigue
15 resistance to withstand continuous pressure oscillation caused
by the passage of the air. In such an application, a material
with high heat aging resistance such as acrylic rubber and silicone
elastomer is currently adopted.
20
[0005]
Patent Document 1 describes a composition containing an
ethylene/alkyl acrylate copolymer and a cured product of the
composition, which is a product of vulcanizate exhibiting improved
impact fatigue resistance and heat resistance in comparison with
conventional vulcanizates.
SF-3064
3
[0006]
Patent Document 2 proposes a tube-engagement structure
including an innermost rubber layer and an envelope rubber layer,
the innermost layer being made of a fluorocarbon rubber to exhibit
5 excellent heat resistance and fatigue resistance and protect the
inner layer of tubes from cracking, and the envelope layer being
made of a rubber such as silicone rubber, acrylic rubber, and
ethylene/acrylic rubber.
10
[0007]
Under such circumstances, a material excellent in not only
heat resistance but also fatigue resistance has been desired to
emerge.
[0008]
In addition to the above properties, lamps for automobiles
15 and motorbikes such as head lamps and fog lamps, and the display
part of meters are desirably not cloudy. For this reason,
materials for packing such as lamp seal packings (lamp seal rubber
packings) used for lamps of automobiles and motorbikes and meter
packings used for meters are required to have fogging resistance
20 so as not to cloud lamps and glass.
[0009]
Patent Document 3 proposes a sealing material for
automobiles, which includes a hollow sealing portion and a base
portion for attachment, both extrusion-molded integrally, the
SF-3064
4
sealing portion being configured by a shaped article of shape
memory rubber consisting of a vulcanizable rubber and a
particulate resin material dispersed and compounded therein, and
the document also describes the use of, as the resin material,
5 a crystalline resin such as a homopolymer and a copolymer of
a-olefin, and a resin such as polystyrene, ABS resin,
acrylonitrile, and AAS resin, and the use of an
ethylene/a-olefin/non-conjugated polyene copolymer rubber as the
vulcanizable rubber. However, Patent Document 3 neither
10 specifically describes a specific method of compounding and
preparing the rubber shaped article, nor recognizes a problem
involving fogging resistance.
[0010]
The fogging phenomenon which clouds lamps of automobiles
15 and motorcycles and glass in the display part of meters is caused
by the reduction of light transmittance owing to the
volatilization of a low volatile content compounded in rubber
packings and the adhesion thereof to the surface of such lamps
and glass. Examples of the causative substance of the fogging
20 phenomenon include a decomposition product from a softening agent,
a mold releasing agent, a vulcanizing agent, and a crosslinking
agent, and a low volatile content such as an activator, compounded
in a resin composition forming packings. Under a high temperature
condition caused by the lighting of the lamp or by a usage
SF-3064
5
environment of the meter, the fogging phenomenon is likely to occur
owing to the volatilization of a larger amount of the low volatile
content. The fogging phenomenon can be reduced unless a low
volatile content such as a softening agent is compounded, but in
5 this case, a problem may occur such as the deterioration of
moldability, namely, the deterioration of mold fluidity during
vulcanization molding and the difficulty in adjusting the hardness
of resultant packings.
10
[0011]
For this reason, a resin composition has been desired to
emerge which enables producing a packing excellent in moldabili ty
and fogging resistance.
[0012]
Patent Document 4 describes an article to be used for lamp
15 seals or packings for meters, which article is a rubber composition
crosslinked by organic peroxide, wherein the composition contains
an ethylene/a-olefin copolymer rubber or an
ethylene/a-olefin/non-conjugated polyene copolymer rubber, and
a copolymerized liquid rubber as a synthetic softening agent
20 containing no substance causative of fogging.
[0013]
In addition to the above properties, rubber shaped articles
used for wiper blades of vehicles, such as automobiles, motorbikes,
trains, aircrafts, and ships are required to be excellent in heat
SF-3064
6
aging resistance, weather resistance, and ozone resistance since
they are always exposed to sunlight, wind, and rain. Further,
they are required not to cause fatigue rupture under so-called
dynamic conditions, particularly with violent vibration, and to
5 have good reversibility (high impact resilience) for good wiping
performance.
[0014]
Patent Document 5 proposes a mechanical structure of a wiper
blade which is useful for smoothly reversing the blade rubber at
10 the turning points of the reciprocating wiper blade without
reducing the wiping performance of the wiper blade.
[0015]
However, the wiping performance and durability of wiper
blades is greatly affected by characteristics of their blade
15 rubber portion.
[0016]
Conventionally, a material, such as natural rubber (NR),
butadiene rubber (BR), and chloroprene rubber (CR) is used for
constituting the blade rubber portion of wiper blades. In recent
20 years, attempts have been made to use EPDM as a raw material for
blade rubber from the viewpoint of its environmental resistance,
but its fatigue resistance and impact resilience is insufficient
and it has not yet been put into practical use.
[0017]
5
SF-3064
7
Patent Document 6 describes that a rubber composition
containing a specific ethylene/a-olefin/non-conjugated polyene
copolymer rubber is suitable as a rubber composition for wiper
blades, and a resultant rubber shaped article for wiper blades
has a long service life time. Further, Patent Document 7
describes that a wiper blade including a polymer composition
applied thereto containing an ethylene polymer having a specific
particle size and a binder resin is excellent in both slidability
and wiping property, and moreover, durability.
10 [0018]
However, a wiper blade having more excellent fatigue
resistance and impact resilience has been required.
[0019]
Besides the above described wiper blade, various shaped
15 hoses such as automobile radiator hoses and air hoses tend to be
formed, in recent years, by using heat-resistant rubber materials,
and peroxides are often used as cross linking agents in many cases.
These shaped hoses are often curved tubes in order to be arranged
efficiently in an engine room.
20 [0020]
Such curved tubes are produced, for example, by using a
mandrel having a curved shape conformed to the shape of rubber
hoses to be produced. The material of conventionally used
mandrels has been exclusively metal (iron) (for example, Patent
SF-3064
8
Documents 8 and 9), but mandrels made of a heat-resistant resin,
especially mandrels made of TPX (polymethylpentene resin) (for
example, Patent Documents 10 and 11) are also used from the
viewpoint of weight reduction. Mandrels made of resin are not
5 discarded immediately after they were used for forming a bent tube,
and are used repeatedly.
DOCUMENTS OF RELATED ART
PATENT DOCUMENTS
10 [0021]
Patent Document 1: JP-T-2009-500473
Patent Document 2: JP-A-2013-221580
Patent Document 3: JP-A-2001-151038
Patent Document 4: JP-A-2000-239465
15 Patent Document 5: JP-A-2008-254697
Patent Document 6: JP-A-2004-256803
Patent Document 7 : JP-A-2012-131959
Patent Document 8: JP-A-2005-319775
Patent Document 9: JP-A-09-207143
20 Patent Document 10: JP-A-10-237241
Patent Document 11: JP-A-10-100161
SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
SF-3064
9
[0022]
An object of the present invention is to provide a resin
composition which enables producing a crosslinked rubber
excellent in not only heat aging resistance, but also fatigue
5 resistance, and a crosslinked shaped article and a hose which are
obtained by using the resin composition.
[0023]
Another object of the present invention is to provide a resin
composition which enables producing a packing excellent in
10 formability and anti-fogging property, a sealing material using
the resin composition, and a lamp seal packing or a packing for
meters which are excellent in heat aging resistance and fogging
15
resistance.
[0024]
Still another object of the present invention is to provide
a resin composition which enables producing a crosslinked shaped
article excellent in fatigue resistance and impact resilience,
a crosslinked shaped article obtained by using the resin
composition, and a sliding member and a wiper blade which are
20 excellent in fatigue resistance and impact resilience.
[0025]
Conventionally used crosslinking agents, which are
contained in non-crosslinked rubbers are mainly reactive
organic-peroxide-based compounds. Therefore, a resin mandrel in
SF-3064
10
repeated contacts with the non-crosslinked rubber causes the
roughness (owing to oxidation deterioration) of its surface which
is attributed to the migration of the crosslinking agent among
others, necessitating frequent replacement of the mandrel.
5 Accordingly, a crosslinked shaped article has been desired to
emerge which enables reducing the oxidative deterioration of the
mandrel surface and the frequency of replacing the mandrel, and
can be suitably crosslinked by a small amount of a crosslinking
agent so as to reduce resource consumption and waste generation,
10 and which is excellent in mechanical strength and heat resistance.
[0026]
The present invention has been made to solve such
conventional problems and an object of the present invention is
to provide a resin composition which enables producing suitably
15 a crosslinked shaped article excellent in mechanical strength and
heat aging resistance by compounding a small amount of a
crosslinking agent, and to provide a crosslinked shaped article
and rubber hoses which are obtained by using the resin composition.
20 MEANS FOR SOLVING THE PROBLEM
[0027]
As a result of intensive studies under such circumstances,
the present inventors have found that when a resin composition
containing a specific ethylene/a-olefin/non-conjugated polyene
SF-30 64
11
copolymer is used, a crosslinked shaped article can be produced
which has a heat aging resistance comparable to that of acrylic
rubber and exhibits fatigue resistance higher than that of the
acrylic rubber, and that even when a small amount of a crosslinking
5 agent and a crosslinking aid are used or when no crosslinking aid
is used, a crosslinked shaped article can be obtained which is
more excellent in mechanical strength and heat aging resistance
than ethylene/propylene copolymer conventionally used as a
packing material, enabling a significant suppression of a fogging
10 phenomenon caused by such as the crosslinking agent or the
cross linking aid, and further, that even when cross linking
densities are comparable, a crosslinked shaped article can be
produced which is more excellent in fatigue resistance and impact
resilience than that produced by using a resin composition
15 containing a conventional ethylene/propylene terpolymer (EFT)
obtained by using 5-ethylidene-2-norbornene (ENB) as a
non-conjugated polyene (EFT), and still further, that even when
a small amount of a crosslinking agent is compounded, a crosslinked
shaped article can be suitably obtained which is superior to a
20 crosslinked shaped article such as a rubber hose containing a
conventional ethylene/a-olefin/non-conjugated polyene copolymer
in terms of mechanical strength and heat aging resistance, and
even still further, that when a crosslinked shaped article such
as a rubber hose (in particular, a curved tube) is produced by
SF-3064
12
using a resin mandrel, the resin composition of the present
invention requires a small amount of crosslinking agent to be
compounded, and therefore, the oxidation deterioration of the
resin mandrel is small, enabling reducing the frequency of
5 replacing the mandrel and reducing largely its environmental load,
and thus, the present invention has been completed.
10
[0028]
In other words, the present invention relates to the
following items [1] to [41].
[ 1] A resin composition comprising
(A) 100 parts by mass of an ethylene/a-olefin/non-conjugated
polyene copolymer and
(B) 0.1 to 5 parts by mass of organic peroxide,
wherein the ethylene/a-olefin/non-conjugated polyene copolymer
15 (A) comprisesstructural units derived from ethylene (al), an
a-olefin (a2) having 3 to 20 carbon atoms, and a non-conjugated
polyene (a3) comprising intramolecularly two or more partial
structures in total selected from the group consisting of
structures represented by the following general formulae (I) and
20 (II) ,
[0029]
[Chern. 1]
~c-c~ .. (I)
,
SF-3064
13
and satisfies the following requirements (i) to (v):
(i) a molar ratio of ethylene/ex-olefin is from 40/60 to
99.9/0.1;
(ii) a weight fraction of the structural unit derived from the
5 non-conjugated polyene (a3) is from 0.07% by weight to 10% by
weight in 100% by weight of the ethylene/ex-olefin/non-conjugated
polyene copolymer;
(iii) a weight-average molecular weight (Mw) of the
ethylene/ex-olefin/non-conjugated polyene copolymer, a weight
10 fraction of the structural unit derived from the non-conjugated
polyene (a3) (weight fraction of (a3)), and a molecular weight
of the non-conjugated polyene (a3) (molecular weight of (a3))
satisfy the following Formula (1),
[0030]
15 4. 5 :0: Mw x weight fraction of (a3) I 100 I (molecular weight
of (a3) :0: 40; Formula (1)
( i v) a ratio P of a complex viscosity I)* lw ~ 0 .11 ( Pa ·sec) at a
frequency of w = 0. 1 rad/ s to a complex viscosity I)* lw ~ 1001 ( Pa
· sec) at a frequency of w
20 viscoelastic measurement
100 rad/s, both obtained by linear
by using a rheometer,
represented by (I)* lw ~ 0 . 11 !I)* lw ~ 1001 ), an intrinsic viscosity [I)],
and the weight fraction (weight fraction of (a3)) of the structural
unit derived from the conjugated polyene ( a3) satisfy the
following Formula (2),
SF-3064
14
[0031]
p I ( [IJ] 2
·
9
) ~ weight fraction of (a3) x 6; Formula (2)
and
(v) a number of long-chain branches per 1000 carbon atoms
5 (LCB1ooocl and a natural logarithmic number of the weight-average
molecular weight (Mw) represented by [Ln (Mw) ], obtained using
30-GPC, satisfy the following Formula (3),
10
[0032]
LCB1oooc ~ 1 - 0. 07 x Ln (Mw) . Formula (3)
[ 2] The resin composition according to [1], wherein the
ethylene/a-olefin/non-conjugated polyene copolymer (A) has an
intrinsic viscosity [IJ] of 1.0 to 4.0 dl/g which is measured in
decalin at 135°C.
[3] The resin composition according to [1] or [2], wherein
15 the non-conjugated polyene (a3) comprises 5-vinyl-2-norbornene
20
(VNB) .
[0033]
[ 4] The resin composition according any one of [ 1] to [ 3],
cmprising
(c) 10 to 300 parts by mass of carbon black, and
(D) 0.5 to 5 parts by mass of antioxidant,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0034]
SF-3064
15
[ 5] The resin composition according to any one of [ 1] to
[4], comprising
(E) a softening agent in an amount of less than 20 parts by mass,
with respect to 100 parts by mass of the
5 ethylene/a-olefin/non-conjugated polyene copolymer (A).
[6] The resin composition according to any one of [1] to
[5], comprising
(F) a crosslinking aid in an amount of 0 to 4 parts by mass,
with respect to 100 parts by mass of the
10 ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0035]
[ 7] A crosslinked shaped article obtained by cross linking
the resin composition according to any one of [1] to [6].
[8] A process for producing a crosslinked shaped article
15 comprising a step of crosslinking the resin composition according
to any one of [1] to [6].
20
[0036]
[ 9] A hose comprising a layer formed by crosslinking the
resin composition according to any one of [1] to [6].
[10] The hose according to [9], which is used in any one
of applications for an automobile, a motorbike, industrial
machinery, construction machinery, and agricultural machinery.
[0037]
[11] The hose according to [9], which is used for a
SF-3064
16
turbocharger hose for an automobile.
[ 12] A process for producing a hose, comprising a step of
shaping and crosslinking the resin composition according to any
one of [1] to [6] to form a layer of a crosslinked shaped article.
5 [0038]
[13] The resin composition according to [1] to [3],
comprising
(G) 10 to 250 parts by mass of a white filler, except for silica,
with respect to 100 parts by mass of the
10 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
[14] The resin composition according to [13], comprising
(E) 0 to 40 parts by mass of a softening agent,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
15 [0039]
[15] The resin composition according to any one of [13]
or [14], comprising:
(D) 0 to 5 parts by mass of an antioxidant; and
(F) 0 to 4 parts by mass of a crosslinking aid,
20 with respect to 100 parts by mass of
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0040]
the
[16] A crosslinked shaped article obtained by crosslinking
the resin composition according to any one of [13] to [15].
SF-30 64
17
[17] A process for producing a crosslinked shaped article,
comprising a step of crosslinking the resin composition according
to any one of [13] to [15].
[0041]
5 [18] A sealing material using the crosslinked shaped
article according to [16].
[19] The sealing material according to [18], which is used
in any one of applications for an automobile, a motorbike,
industrial machinery, construction machinery, and agricultural
10 machinery.
[0042]
[20] The sealing material according to [18] or [19], which
is used for a lamp seal packing or a packing for a meter.
[21] The resin composition according to any one of [1] to
15 [3], comprising:
(C) 10 to 300 parts by mass of a carbon black;
(E) 5 to 50 parts by mass of a softening agent; and
(F) 0.1 to 4 parts by mass of a crosslinking aid,
with respect to 100 parts by mass of
20 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
[0043]
the
[22] The resin composition according to [21], containing
(D) 0 to 5 parts by mass of an antioxidant,
with respect to 100 parts by mass of the
SF-30 64
18
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[23] A crosslinked shaped article obtained by cross linking
the resin composition according to [21] or [22].
[0044]
5 [24] A process for producing a crosslinked shaped article,
comprising a step of crosslinking the resin composition according
to any one of [21] to [23].
[25] A sliding member using the crosslinked shaped article
according to [23].
10 [0045]
15
20
[26] The sliding member according to [25], which is used
in any one of applications for an automobile, a motorbike,
industrial machinery, construction machinery, and agricultural
machinery.
[27] A wiper blade using the crosslinked shaped article
according to [23] .
[0046]
[28] The resin composition according to any one of [1] to
[3], which comprises
(H) 0.1 to 10 parts by mass of magnesium oxide,
with respect to (A) 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A),
wherein the resin composition is substantially free from zinc
oxide (I).
SF-3064
19
[29] The resin composition according to [28], comprising
the antioxidant (D) in an amount of 5 parts by mass or less, with
respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
5 [0047]
10
[30] The resin composition according to [28] or [29],
comprising the softening agent (E) in an amount of 80 parts by
mass or less with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[31] The resin composition according to any one of [28]
to [30], comprising the crosslinking aid (F) in an amount of 4
parts by mass or less with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0048]
15 [ 32] A crosslinked shaped article obtained by crosslinking
the resin composition according to any one of [28] to [31].
[33] A process for producing a crosslinked shaped article,
comprising a step of crosslinking the resin composition according
to any one of [28] to [31].
20 [0049]
[ 34] A rubber hose including a layer formed by cross linking
the resin composition according to any one of [28] to [31] by using
a resin mandrel.
[35] The rubber hose according to [34], wherein a resin
SF-3064
20
constituting the resin mandrel is a 4-methyl-1-pentene-based
polymer.
[0050]
[36] A process for producing a rubber hose comprising a
5 step of crosslinking and shaping the resin composition according
to any one of [28] to [31] by using a resin mandrel.
[37] The process for producing a hose according to [36],
wherein a resin constituting the resin mandrel is a
4-methyl-1-pentene-based polymer.
10 [0051]
15
[38] The crosslinked shaped article according to [32],
which is used in any one of applications for an automobile, a
motorbike, industrial machinery, construction machinery, and
agricultural machinery.
[39] The crosslinked shaped article according to [32],
which is used for a water hose for an automobile.
[0052]
[40] The rubber hose according to [34] or [35], which is
used in any one of applications for an automobile, a motorbike,
20 industrial machinery, construction machinery, and agricultural
machinery.
[41] The rubber hose according to [34] or [35], which is
used for a water hose for an automobile.
SF-3064
EFFECT OF THE INVENTION
[0053]
21
The resin composition of the present invention is excellent
in crosslinking properties.
5 [0054]
According to the resin composition of the present invention,
a crosslinked shaped article excellent in heat aging resistance
and fatigue resistance can be produced. The crosslinked shaped
article of the present invention exhibits excellent heat aging
10 resistance and fatigue resistance and can be suitably used in
applications at high temperature, and therefore, it can be
suitably used in applications such as hoses for automobiles,
motorbikes, industrial machinery, construction machinery,
agricultural machinery, and in particular, turbocharger hoses
15 among others.
[0055]
According to the present invention, the inclusion of a
specific ethylene/a-olefin/non-conjugated polyene copolymer
also can provide a resin composition which enables producing a
20 crosslinked shaped article excellent in crosslinking properties
and thermal aging resistance even when the content of a
crosslinking agent is small. The crosslinked shaped article of
the present invention is octained by a resin composition which
comprises a specific ethylene/a-olefin/non-conjugated polyene
SF-3064
22
copolymer and is obtained from a resin composition containing
small contents of a crosslinking agent and a crosslinking aid,
and therefore, the article is excellent in heat aging resistance,
releases a small amount of volatile even when used under high
5 temperature conditions, and is excellent in not only mechanical
properties for use in packings, but also fogging resistance,
allowing a sui table use thereof as a lamp seal packing or a packing
for meters. Further, according to the present invention, it can
provide lamp seal packings or packings for meters which are
10 excellent in heat aging resistance and fogging resistance.
[0056]
According to the resin composition of the present invention,
a crosslinked shaped article excellent not only in fatigue
resistance and impact resilience, but also in abrasion resistance
15 also can be produced. Since the crosslinked shaped article of
the present invention exhibits excellent fatigue resistance and
impact resilience and is excellent in abrasion resistance, it can
be suitably used for various sliding members for automobiles,
motorbikes, industrial machinery, construction machinery, and
20 agricultural machinery, and in particular, suitably used for wiper
blades of vehicles such as automobiles, motorbikes, trains,
aircrafts, and ships. Sliding members and wiper blades of the
present invention are not only excellent in fatigue resistance
and impact resilience, but also excellent in abrasion resistance.
SF-3064
23
[0057]
According to the resin composition of the present invention,
a crosslinked shaped article excellent in mechanical strength and
heat aging resistance also can be produced, even with a small
5 amount of crosslinking agent compounded. Further, according to
the resin composition of the present invention, even when a resin
mandrel is used in producing a crosslinked shaped article, the
oxidative deterioration of the resin mandrel is small and the
frequency of replacing the mandrel can be reduced, resulting in
10 a greatly reduced environmental load.
[0058]
Since the crosslinked shaped article of the present
invention exhibits excellent mechanical strength and heat aging
resistance, it is also suitable in application for hoses, such
15 as hoses for automobiles, motorbikes, industrial machinery,
construction machinery, and agricultural machinery, and in
particular, sui table in an application for water hoses for
automobiles among others.
20 BRIEF DESCRIPTION OF THE DRAWINGS
[0059]
[FIG. 1] FIG. 1 is a graph indicating a relation between
the number of repeated contacts with a resin composition and values
of MFR of TPX at the measurement in a TPX durability test.
5
SF-3064
24
[FIG. 2] FIG. 2 is a graph indicating the relation
between the number of repeated contacts with the resin composition
and hue values b of TPX at the measurement in the TPX durability
test.
DETAILED DESCRIPTION OF THE INVENTION
[0060]
Hereinafter, the present invention will be described in
detail.
10 Resin composition
The resin composition of the present invention contains (A)
an ethylene/a-olefin/non-conjugated polyene copolymer and (B) an
organic peroxide as essential components, and as necessary, may
further contain one or more selected from the group consisting
15 of (C) carbon black, (D) an antioxidant, (E) a softener, (F) a
crosslinking aid, (G) a white filler, and (H) magnesium oxide,
and as necessary, (J) other components.
20
[0061]

(A) Ethylene/a-olefin/non-conjugated polyene copolymer
The ethylene/ a-olefin/non-conjugated polyene copolymer
(A) according to the present invention contains structural units
derived from ethylene ( al) , an a-olefin ( a2) having 3 to 20 carbon
atoms, and a non-conjugated polyene (a3) containing
SF-3064
25
intramolecularly two or more of partial structures selected from
the group consisting of structures represented by the following
general formulae (I) and (II),
[0062]
5 [Chern. 2]
10
15
.. (!)
The ethylene/a-olefin/non-conjugated polyene copolymer (A)
according to the present invention may further contain, in
addition to the structural units derived from the above components
( al) , (a2), and (a3), a structural unit derived from a
non-conjugated polyene ( a4) containing intramolecularly only one
partial structure selected from the group consisting of structures
represented by the above general formulae (I) and (II).
[0063]
Examples of the a-olefin (a2) having 3 to 20 carbon atoms
include, for example, 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 them,
a-olefins having 3 to 8 carbon atoms are preferable, such as
20 propylene, 1-butene, 1-hexene, and 1-octene, and in particular,
propylene is preferable. Such a-olefins are preferable because
they are relatively inexpensive in raw material cost, and provide
not only an ethylene/a-olefin/non-conjugated polyene copolymer
5
SF-3064
26
excellent in mechanical properties but also a shaped article
exhibiting rubber elasticity. These ex-ole fins may be used singly
or in combination of the two or more kinds.
[0064]
In other words, the ethylene/ex-olefin/non-conjugated
polyene copolymer (A) according to the present invention contains
a structural unit derived from at least one kind of ex-olefin ( a2)
having 3 to 20 carbon atoms, and may contain a structural unit
derived from two or more kinds of ex-olefins (a2) having 3 to 20
10 carbon atoms.
[0065]
Examples of the non-conjugated polyene (a3) containing
intramolecularly two or more partial structures in total selected
from the group consisting of the structures represented by the
15 above general formulae (I) and (II) includes 5-vinyl-2-norbornene
(VNB), norbornadiene, 1,4-hexadiene, dicyclopentadiene, and the
like. The non-conjugated polyene (a3) contains preferably VNB,
and more preferably, is VNB because VNB, among them, is easily
available and excellent in crosslinking reactivity with organic
20 peroxide during its crosslinking reaction after polymerization,
enabling easy improvement in the thermal resistance of its
polymerized composition. The non-conjugated polyene (a3) may be
used singly or in combination of the two or more kinds.
[0066]
SF-3064
27
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the invention may contain a structural unit
derived from the non-conjugated polyene (a4) containing
intramolecularly only one partial structure selected from the
5 group consisting of the structures represented by the above
general formulae (I) and (II), as well as the structural units
derived from ethylene (al), the ex-olefin (a2) having 3 to 20 carbon
atoms, and the non-conjugated polyene (a3). Examples of such
non-conjugated polyene (a4) include 5-ethylidene-2-norbornene
10 (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,
15 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,
20 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,
I
SF-3064
28
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 because it is easily available,
5 highly reactive with sulphur and vulcanization enhancers during
its crosslinking reaction after polymerization, easily
controllable in its crosslinking rate, and easy to yield
sufficient mechanical physical properties. The non-conjugated
polyene (a4) can be used singly or in combination of the two or
10 more kinds thereof. When the ethylene/a-olefin/non-conjugated
polyene copolymer of the invention contains a structural unit
derived from the non-conjugated polyene (a4) containing
intramolecularly only one partial structure selected from the
group consisting of the structures represented by the above
15 general formulae (I) and (II), the unit is usually contained in
a weight fraction of from about 0 to about 20% by weight, preferably
from about 0 to about 8% by weight, and more preferably from about
0.01 to about 8% (with the proviso that the sum of the weight
fractions of (a1), (a2), (a3), and (a4) isl00%byweight) although
20 the fraction of the unit is not especially limited so long as the
purposes of the present invention are not harmed.
[ 0 0 67]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the invention is, as described above, a copolymer
SF-3064
29
containing structural units derived from ethylene ( a1) , an
a-olefin (a2) having 3 to 20 carbon atoms, the above-described
non-conjugated polyene (a3), and as necessary, the above
non-conjugated polyene (a4), and satisfies the following
5 requirements (i) to (v):
10
(i) the molar ratio of ethylene I a-olefin is from 40/60 to
99.9/0.1;
( ii) the weight fraction of the structural unit derived from the
non-conjugated polyene (a3) is 0.07% by weight to 10% by weight;
(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 (a3) (weight fraction of (a3) (% by weight)), and the
molecular weight of the non-conjugated polyene (a3) (molecular
15 weight of (a3)) satisfy the following Formula (1),
[0068]
4. 5 :": Mw x weight fraction of (a3) I 100 I molecular weight
of (a3) :": 40; Formula (1)
( i v) the ratio of a complex viscosity I)* 10 ~ 0 . 11 ( Pa ·sec) at a
20 frequency of w = 0. 1 rad/ s to a complex viscosity I)* 1w ~ 1001 ( Pa ·sec)
at a frequency of w = 100 rad/s, both obtained by linear
viscoelastic measurement by using a rheometer,
represented by P (I)* lw ~ 0 • 11 I I)* 1w ~ 1001 ), an intrinsic viscosity
represented by [IJ], and the weight fraction of the structural unit
SF-3064
30
derived from the non-conjugated polyene (a3) (weight fraction of
(a3)) satisfy the following Formula (2),
[0069]
P I ( [1]] 2
'
9
) ~ weight fraction of (a3) x 6; Formula (2)
5 (v) the number of long-chain branches per 1000 carbon atoms
represented by (LCB1oooc) and the natural logarithmic number of the
weight-average molecular weight (Mw) represented by [Ln(Mw)],
obtained by using 3D-GPC, satisfy the following Formula (3),
10
[0070]
LCB1oooc ~ 1 - 0. 07 x Ln (Mw) . Formula (3)
In this specification, the above requirements (i) to (v)
are also described as Requirements (i) to (v). In the present
specification, "a-olefin having 3 to 20 carbon atoms" is also
simply described as "a-olefin."
15 (Requirement (i))
Requirement (i) specifies that the molar ratio of
ethylene/ a-olefin in the ethylene/a-olefin/non-conjugated
polyene copolymer (A) according to the invention falls within a
range from 4 0 I 60 to 99. 9/0. 1, and this molar ratio preferably falls
20 within a range from 50/50 to 90/10, more preferably from 55/45
to 85/15, and still preferably from 55/45 to 78/22.
Such an ethylene/a-olefin/non-conjugated polyene copolymer of
the invention is preferable because when it is used as a raw
material for crosslinked shaped articles, resultant crosslinked
SF-3064
31
shaped articles not only exhibits excellent rubber elasticity,
but also is excellent in mechanical strength and flexibility.
[ 0 071]
The amount of ethylene (content of a structural unit derived
5 from the ethylene (al)) and the amount of a-olefin (content of
a structural unit derived from the a-olefin (a2)) in the
ethylene/a-olefin/non-conjugated polyene copolymer can be
determined by using 13C-NMR.
10
(Requirement (ii))
Requirement (ii) specifies that in the
ethylene/a-olefin/non-conjugated polyene copolymer (A)
according to the invention, the weight fraction of the structural
unit derived from the non-conjugated polyene (a3) is within a range
from 0.07% by weight to 10% by weight in 100% by weight of the
15 ethylene/a-olefin/non-conjugated polyene copolymer (i.e. 100% by
weight in total of the weight fractions of all the structural
units). This weight fraction of the structural unit derived from
the non-conjugated polyene ( a3) is preferably from 0. 1% by weight
to 8. 0% by weight, and more preferably from 0. 5% by weight to 5. 0%
20 by weight.
[0072]
It is preferable that the ethylene/a-olefin/non-conjugated
polyene copolymer (A) according to the invention satisfies
Requirement (ii) not only because it has sufficient hardness and
SF-3064
32
exhibits excellent mechanical properties, but also because the
ethylene/~-olefin/non-conjugated polyene copolymer (A)
according to the invention is sui table for producing crosslinked
shaped articles owing to its rapid crosslinking rate when
5 crosslinked by using organic peroxide.
[0073]
The amount of the non-conjugated polyene (a3) (content of
the structural unit derived from the non-conjugated polyene (a3))
in the ethylene/a-olefin/non-conjugated polyene copolymer can be
10 obtained by using 13C-NMR.
[0074]
(Requirement (iii))
Requirement (iii) specifies
ethylene/a-olefin/non-conjugated polyene
that in the
copolymer (A)
15 according to the invention, 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 (a3) in the copolymer (weight fraction of
(a3) in % by weight), and the molecular weight of the
20 non-conjugated polyene (a3) (molecular weight of (a3)) satisfy
the following Formula (1),
[0075]
4. 5 ~ Mw x weight fraction of (a3) I 100 I molecular weight
of (a3) ~ 40. Formula (1)
SF-3064
33
It is preferable that the ethylene/a-olefin/non-conjugated
polyene copolymer (A) according to the invention satisfies
Requirement (iii) not only because the copolymer has an
appropriate content of the structural unit derived from the
5 non-conjugated polyene (a3) such as VNB and exhibits sufficient
cross linking performance, but also because when the
ethylene/a-olefin/non-conjugated polyene copolymer of the
invention is used to produce a crosslinked shaped article, it is
excellent in crosslinking rate, resulting in the crosslinked
10 shaped article excellent in mechanical properties after
crosslinking.
[0076]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the invention more preferably satisfies the
15 following Formula ( 1' ) ,
[0077]
4. 5 ~ Mw x weight fraction of (a3) I 100 I molecular weight
of (a3) ~ 35. Formula ( 1' )
The weight-average molecular weight (Mw) of the
20 ethylene/a-olefin/non-conjugated polyene copolymer can be
obtained as a numerical value in terms of polystyrene by using
Gel Permeation Chromatography (GPC) .
[0078]
When "Mw x weight fraction of (a3) I 100 I (molecular weight
SF-3064
34
of ( a3) ) " satisfies the Formula ( 1) or ( 1 I ) f the
ethylene/a-olefin/non-conjugated polyene copolymer (A)
according to the invention has an appropriate degree of
crosslinking, enabling producing shaped articles well-balanced
5 between their mechanical physical properties and heat aging
resistance. When "Mw x weight fraction of (a3) I 100 I molecular
weight of (a3)" is too low, the crosslinkability may be
insufficient, causing a slow crosslinking rate, and when it is
too high, excessive crosslink may occur, causing worsened the
10 mechanical physical properties.
[0079]
(Requirement (iv))
Requirement (iv) specifies that the ratio of a complex
viscosity I)* 1 w~o. 11 (Pa·sec) at a frequency of w = 0.1 rad/s to
15 a complex viscosity 17* 1w ~ 1001 ( Pa ·sec) at a frequency of w = 100
rad/s, both obtained by linear viscoelastic measurement (190°C)
by using a rheometer, represented by P (I)* lw ~ 0 . 11 I I)* lw ~ 1oo 1), and
the intrinsic viscosity [I)], of the
ethylene/a-olefin/non-conjugated polyene copolymer (A)
20 according to the invention, and the weight fraction of the
structural unit derived from the non-conjugated polyene (a3)
(weight fraction of (a3) in % by weight) satisfy the following
Formula ( 2) ,
[0080]
SF-30 64
35
P I ( [r)] 2
"
9
) :>: weight fraction of (a3) x 6, Formula (2)
where the ratio of the complex viscosity I)* 1"" 0 . 11 at the frequency
w 0. l rad/ s to the complex viscosity I)* 1"" 1001 at the frequency
w 100 rad/s, represented by P(I)* 1"" 0 . 11 /I)* 1"" 1001 ), represents
5 a frequency dependence of the viscosity, and P I ( [I)] 2
"
9
) which
corresponds to the left side of the Formula (2) tends to be higher
with increase in the number of long-chain branches although
depending on quantities such as short-chain branching and the
molecular weight. In general, ethylene/ a-olefin/non-conjugated
10 polyene copolymers containing a larger amount of structural unit
derived from non-conjugated polyene tend to contain a larger
number of long-chain branches, but the
ethylene/a-olefin/non-conjugated polyene copolymer of the
invention is thought to be able to satisfy the above Formula (2)
15 owing to its fewer long-chain branches than those of conventional
well-known ethylene/ a-olefin/non-conjugated polyene copolymers.
In the present invention, the P value is a ratio (I)* ratio)
calculated from complex viscosities at 0.1 rad/s and 100 rad/s
obtained by using a viscoelastic measurement apparatus Ares (from
20 Rheometric Scientific) under a measurement condition of 190 °C and
1.0% of distortion at the different frequencies.
[0081]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the present invention preferably satisfies the
5
SF-3064
36
following Formula (2'),
[0082]
p I ( [[j] 2
·
9
) S: weight fraction of (a3) x 5. 7,
Formula ( 2' )
The intrinsic viscosity [IJ] means a value measured in
decalin at 135°C.
(Requirement (v))
Requirement (v) specifies that the number of long-chain
branching per 1000 carbon atoms (LCB1oooc) and the natural
10 logarithmic number of the weight-average molecular weight (Mw)
15
20
represented by [Ln (Mw)], obtained by using 30-GPC, of the
ethylene/a-olefin/non-conjugated polyene copolymer satisfy the
following Formula (3),
[0083]
LCB1oooc S: 1 - 0. 07 x Ln (Mw), Formula (3)
The Formula ( 3) specifies the upper limit of the long-chain
branch content per carbon of
ethylene/a-olefin/non-conjugated polyene copolymer.
[0084]
Such an ethylene/a-olefin/non-conjugated
the
polyene
copolymer is preferable not only because it is excellent in curing
properties owing to its small fraction of the number of long-chain
branches when crosslinked by organic peroxide, but also because
shaped articles obtained from the copolymer are excellent in heat
SF-3064
37
aging resistance.
[0085]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the invention preferably satisfies the following
5 Formula (3'),
[0086]
LCB1oooc :S 1 - 0. 071 x Ln (Mw), Formula ( 3' )
where Mw and the number of long-chain branches per 1000 carbon
atoms (LCB1oooc) can be obtained by a structural analysis using
10 3D-GPC. In this specification, they were specifically obtained
as follows.
[0087]
Absolute molecular weight distribution was obtained by
using 3D-high temperature GPC apparatus, Model PL-GPC220 (from
15 Polymer Laboratories Ltd.), and intrinsic viscosity was also
obtained by a viscometer. Main measurement conditions are as
follows.
20
[0088]
Detector: refractive index detector/incorporated GPC apparatus
Two-angle light scattering detector,
(manufactured by Precision Detectors Inc.)
Model PD2 04 0
Bridge viscometer, Model PL-BV400 (manufactured by Polymer
Laboratories Ltd.)
Columns: TSKgel GMHHR-H(S)HT x 2 + TSKgel GMHHR-M(S) x 1
SF-3064
38
(each 7.8 mm ~in internal diameter x 300mm in length)
Temperature: 140°C
Mobile phase: 1,2,4-trichlorobenzene (containing 0.025% of BHT)
Loaded quantity: 0.5 mL
5 Sample concentration: ca 1. 5 mg I mL
Sample filtration: filtration by a sintered filter with pore
diameter of 1.0 ~m
Values of dn/dc necessary for determining absolute molecular
weights were determined for respective samples by using a dn/dc
10 value of 0. 053 of a polystyrene standard (molecular weight
190, 000) and a response intensity of the refractive index detector
per unit loaded mass.
[0089]
Based on a relation between the intrinsic viscosity obtained
15 by the viscometer and the absolute molecular weight obtained by
20
the light scattering detector, a long-chain branch parameter g'i
for each eluted component was calculated by using Formula (v-1),
[0090]
[Exp. 1]
[n]i.br
[ 71 J I, lin
g ' ··-(v-1)
[ n] i.br :measured intrinsic viscocity of i-th sliced component
[ 71 J i, I in :intrinsic viscosity under the assumption that the i-th sliced
component does not have a long-chain branching structure and has
only a short-chain branching structure
5
SF-3064
39
where a relation [D] KMv with v 0.725 was used.
[0091]
Respective average values represented by the following
parameters, g' s, were calculated by using Formulae (v-2} , (v-3} ,
and (v-4} . A trend line based on an assumption that only
short-chain branches were contained was determined for each
sample.
[0092]
[Exp. 2]
number
long-chain
parameter
average , :E(Ci/Mixg'i)
branching g n=--{·C-Ci/Mi) --·(v-2)
weight
long-chain
parameter
l:(Cixg'i)
average g'~= "·(v- 3 )
branching
:E Ci
z-average long-chain
branching parameter g' '=
2:: {Ci x Mi 2
x g' i)
-···-· ··-----
2::(CiXMi2)
... ( v- 4)
concentration for respective eluted components
absolute molecular weight for respective eluted components
The parameter g'w, was also used to calculate the number
of branching sites per molecular chain BrNo, the number of
long-chain branches per 1000 carbon atoms LCB1000c, and the degree
of branching per unit molecular weight A. The Zimm-Stockmayer
15 Formula (v-5} was used to calculate BrNo, and the Formulae (v-6}
and (v-7} were used to calculate LCB1oooc and/\. The parameter g
is a long-chain branching parameter determined from the radius
SF-3064
40
of the gyration Rg, and is supposed to have the following simple
correlation with g' determined from intrinsic viscosity. Various
values are proposed for E taken into account in the equation,
depending on the shape of the molecule. Herein, E = 1 (i.e. g'
5 = g) was assumed for calculation.
[0093]
[Exp. 3]
g ' w JJ 1 + BrNo / 7
A = BrNo / M
10 LCB10ooc =Ax 14,000
1
+ 4 x BrNo/9 TC
(v - 6)
(v - 7)
(v - 5)
*In the Formula (v-7), the value of 14,000 indicates a
molecular weight of 1,000 methylene (CH2 ) units.
[0094]
The ethylene/a-olefin/non-conjugated polyene copolymer
15 (A) according to the present invention has an intrinsic viscosity
[I]] within a range preferably from 0.1 to 5 dL/g, more preferably
from 0. 5 to 5. 0 dL/g, still more preferably from 0. 9 to 4. 0 dL/g.
[0095]
The ethylene/a-olefin/non-conjugated polyene copolymer
20 (A) according to the present invention also has a weight-average
molecular weight (Mw) within a range preferably from 10,000 to
600,000, more preferably from 30,000 to 500,000, and still more
SF-3064
41
preferably from 50,000 to 400,000.
[0096]
In the present invention, an
ethylene/a-olefin/non-conjugated polyene copolymer having
5 sui table characteristics depending on its use can be selected to
be used as the component (A) of the resin composition, within a
scope satisfying the above-mentioned requirements.
[0097]
For example, in an application for a heat-resistant hose,
10 such as a turbocharger hose for automobiles, having a layer formed
by crosslinking the resin composition of the present invention,
an ethylene/a-olefin/non-conjugated polyene copolymer having a
relatively high molecular weight can be suitably used, and
specifically, an ethylene/a-olefin/non-conjugated polyene
15 copolymer having a weight-average molecular weight (Mw) of 2 00, 0 00
to 600,000 can be suitably used.
[0098]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the invention preferably satisfies the above
20 intrinsic viscosity [~] and the above weight-average molecular
weight (Mw) simultaneously.
[0099]
For the ethylene/a-olefin/non-conjugated polyene
copolymer of the present invention, the non-conjugated polyene
SF-3064
42
(a3) preferably contains VNB, and more preferably is VNB. In
other words, in the Formulae (l) and (2), and a Formula (4)
described later, the "weight fraction of (a3)" is preferably the
"weight fraction of VNB" (% by weight).
5 [0100]
As described above, the ethylene/a-olefin/non-conjugated
polyene copolymer (A) according to the present invention also
preferably contains, in addition to the structural units derived
from (al), (a2), and (a3), the structural unit derived from the
10 non-conjugated polyene ( a4) containing intramolecularly only one
partial structure selected from the group consisting of the
structures represented by the general formulae (I) and (II), in
a weight fraction within a range from 0% by weight to 20% by weight
(with the proviso that the sum of the weight fractions of (al),
15 (a2), (a3), and (a4) is 100%byweight). Inthiscase, Requirement
(vi) below is preferably satisfied.
(Requirement (vi))
The weight-average molecular weight (Mw) of the
ethylene/a-olefin/non-conjugated polyene copolymer, the weight
20 fraction of the structural unit derived from the non-conjugated
polyene (a3) (the weight fraction of (a3) (% by weight)), the
weight fraction of the structural unit derived from the
non-conjugated polyene (a4) (weight fraction of (a4) (% by
weight)), the molecular weight of the non-conjugated polyene (a3)
.I
! I
5
SF-3064
43
(molecular weight of (a3)), and the molecular weight of the
non-conjugated polyene (a4) (molecular weight of (a4)) satisfy
the following Formula (4),
[0101]
4. 5 ~ Mw x { (weight fraction of (a3) I 100 I molecular weight
of (a3)) + (weight fraction of (a4) I 100 I molecular weight of
(a4))} ~ 45. Formula (4)
The Formula (4) specifies the content of the non-conjugated
polyene in one molecule of the copolymer (sum of (a3) and (a4)).
10 [0102]
It is preferable that the ethylene/a-olefin/non-conjugated
polyene copolymer containing the structure unit derived from the
above (a4) satisfies the Formula (4), because shaped articles
obtained from the ethylene/a-olefin/non-conjugated polyene
15 copolymer are excellent in mechanical physical properties and heat
aging resistance.
[0103]
When Requirement (vi) is not satisfied and "Mw x { (weight
fraction of (a3) I 100 I molecular weight of (a3)) + (weight
20 fraction of (a4) I 100 I molecular weight of (a4)) } " is too small
in the Formula (4), in other words, when the content of the
non-conjugated diene is too small, crosslinking may not be enough
to obtain sufficient mechanical physical properties, and in
contrast, when the content of the non-conjugated diene is too large,
SF-3064
44
crosslinking may be excessive, causing worsening of not only the
mechanical physical properties but also heat aging resistance.
(Requirement (vii))
The ethylene/ ex-olefin/non-conjugated polyene copolymer
5 (A) according to the present invention preferably does not have
any particular limitation, but it is preferable that a complex
viscosity I)* 1w" 0 . 011 (Pa·sec) at a frequency of w = 0.01 rad/s and
a complex viscosity I)* (W"lOI ( Pa ·sec) at a frequency of w = 10 rad/ s,
obtained by linear viscoelastic measurement (190°C) by using a
10 rheometer, and an apparent iodine value derived from the
non-conjugated polyene (a3) satisfy the following Formula (5),
Log{I)*(w" o.o1d I Log{I)* 1w" 10}! :<:: 0.0753 x {apparent iodine
value originated from non-conjugated polyene (a3)) + 1.42.
15
Formula (5)
In this Formula, the complex viscosity I)* 1W"0 . 011 and the
complex viscosity I)* lw " 101 are obtained in the same manner as in
the case of the complex viscosity I)* iw" 0 . 11 and the complex viscosity
I)* lw " 1001 in Requirement (vi) except for the measurement
frequencies.
20 [0104]
The apparent iodine value derived from the non-conjugated
polyene (a3) is obtained from the following formula,
[0105]
Apparent iodine value derived from (a3) weight fraction
SF-3064
45
of (a3) x 253.81 I molecular weight of (a3).
In the above Formula (5), the left side represents shear
speed dependence, which is an index of the amount of long-chain
branch, and the right side represents an index of the content of
5 the non-conjugated polyene ( a3) which is not consumed as a
long-chain branch during polymerization. Requirement (vii) and
the Formula (5) are preferably satisfied because the degree of
long-chain branching is not too high. In contrast, when the
Formula ( 5) is not satisfied, it is easily understood that a large
10 fraction of the copolymerized non-conjugated polyene (a3) was
consumed for the formation of long-chain branches.
[0106]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) of the present invention also preferably contains a sufficient
15 amount of the structural unit derived from the non-conjugated
polyene (a3), and the weight fraction of the structural unit
derived from the non-conjugated polyene (a3) in the copolymer
(weight fraction of (a3) (% by weight)) and the weight-average
molecular weight (Mw) of the copolymer preferably satisfy the
20 following Formula (6),
[0107]
6 - 0.45 x Ln(Mw) ~weight fraction of (a3) ~ 10.
Formula (6)
Further, the ethylene/a-olefin/non-conjugated polyene
SF-3064
46
copolymer (A) according to the present invention has a number of
the structural units derived from the non-conjugated polyene ( a3)
per weight-average molecular weight (Mw), represented by (nc),
which is preferably 6 or more, more preferably 6 or more and 40
5 or less, still more preferably 7 or more and 39 or less, and still
more preferably 10 or more and 38 or less.
[0108]
Such an ethylene/a-olefin/non-conjugated polyene
copolymer of the prevent invention contains a sufficient number
10 of structural units derived from a non-conjugated polyene (a3)
such as VNB and a small content of long-chain branch, and is
excellent not only in curing properties when crosslinked by using
organic peroxide but also in formability, and moreover, it is well
balanced between physical properties such as mechanical
15 properties, and is excellent particularly in heat aging
resistance.
[0109]
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the present invention also has a number of the
20 structural units derived from the non-conjugated polyene (a4) per
weight-average molecular weight (Mw), represented by (nn), which
is preferably 29 or less, more preferably 10 or less, still more
preferably less than one.
[0110]
SF-3064
47
Such an ethylene/a-olefin/non-conjugated polyene
copolymer (A) according to the present invention is preferable
not only because the number of the structural units derived from
a non-conjugated polyene (a4) such as ENB is controlled within
5 a range unharmful to the purpose of the invention but also because
the copolymer is unlikely to cause post-crosslinking and
sufficient in heat aging resistance.
[0111]
The number of structural units derived from the
10 non-conjugated polyene (a3), represented by (nc), or the number
of structural units derived from the non-conjugated polyene (a4) ,
represented by (n0 ), per weight-average molecular weight (Mw) of
the ethylene/a-olefin/non-conjugated polyene copolymer can be
obtained from the molecular weight of the non-conjugated polyene
15 (a3) or (a4), the weight fraction (%by weight) of the structural
unit derived from the non-conjugated polyene (a3) or (a4) in the
copolymer (weight fraction of (a3) or (a4)), and the
weight-average molecular weight (Mw) of the copolymer, by using
the following formulae,
20 [ 0112]
(nc) = (Mw) x {weight fraction of (a3) I 100} I molecular
weight of non-conjugated polyene (a3), and
(n0 ) = (Mw) x {weight fraction of (a4) I 100} I molecular
weight of non-conjugated polyene (a4).
SF-3064
48
When the numbers of the structural units (nc) and (n0 ) per
weight-average molecular weight (Mw) derived from the
non-conjugated polyenes (a3) and (a4) both satisfy the above
described ranges, the ethylene/~-olefin/non-conjugated polyene
5 copolymer (A) according to the present invention is preferable
not only because it has a small content of long-chain branch, with
excellent curing properties when crosslinked by using organic
peroxide and good formability, but also because it is well balanced
between physical properties such as mechanical properties,
10 unlikely to cause post-crosslinking, and particularly excellent
in heat aging resistance.
15
[ 0113]

of ethylene/a-olefin/non-conjugated polyene
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the present invention is a copolymer obtained
by copolymerizing monomers consisting of ethylene (al), an
a-olefin (a2) having 3 to 20 carbon atoms, anon-conjugated polyene
(a3) containing intramolecularly two or more partial structures
20 in total selected from the group consisting of the structures
represented by the aforementioned general formulae (I) and (II) ,
and as necessary, a non-conjugated polyene (a4) containing
intramolecularly only one partial structure selected from the
group consisting of the structures represented by the
SF-3064
49
aforementioned general formulae (I) and (II).
[0114]
Although the ethylene/a-olefin/non-conjugated polyene
copolymer of the present invention may be prepared by any process
5 so long as aforementioned Requirements (i) to (v) are satisfied,
it is preferably a copolymer obtained by copolymerizing monomers
in the presence of a metallocene compound, more preferably a
copolymer obtained by copolymerizing monomers in the presence of
a catalyst system containing a metallocene compound.
10 [0115]
Metallocene compound
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the present invention is desirably a copolymer
obtained by copolymerizing monomers in the presence of at least
15 one kind of metallocene compound selected from compounds
represented by the following general formula [All. The
copolymerization of monomers carried out by using a catalyst
system containing such a metallocene compound yields a copolymer
20
containing
preparing
suppressed long-chain branching, facilitating
the ethylene/a-olefin/non-conjugated polyene
copolymer (A) according to the present invention satisfying the
above requirements.
[0116]
[Chern. 3]
SF-3064
50
... [A 1]
In the above formula [Al] , R1
, R2
, R3
, R4
, R5
, R8
, R9
, and R12 are
each independently a hydrogen atom, a hydrocarbon group, a
silicon-containing group, or a heteroatom-containing group other
5 than any silicon-containing group, and among R1 to R4 adjacent two
groups may together form a ring.
[0117]
The hydrocarbon group is preferably a hydrocarbon group
having 1 to 20 carbon atoms, and specific examples thereof include
10 an alkyl group having 1 to 20 carbon atoms, an arylalkyl group
having 7 to 20 carbon atoms, an aryl group or substituted aryl
group having 6 to 20 carbon atoms, and the like. For example,
they include methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl,
iso-butyl, sec-butyl, t-butyl, amyl, n-pentyl, neopentyl,
15 n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decanyl, 3-methylpentyl,
1,1-diethylpropyl, 1,1-dimethylbutyl, 1-methyl-1-propyl butyl,
1,1-propyl butyl, 1,1-dimethyl-2-methyl propyl,
1-methyl-1-isopropyl-2-methyl propyl, cyclopentyl, cyclohexyl,
SF-3064
51
cycloheptyl, cyclooctyl, norbornyl, adamantyl, phenyl, o-tolyl,
m-tolyl, p-tolyl, xylyl, isopropylphenyl, t-butylphenyl,
naphthyl, biphenyl, terphenyl, phenanthryl, anthracenyl, benzyl,
and cumyl groups, and also include oxygen-containing groups, such
5 as methoxy, ethoxy, and phenoxy groups, nitrogen-containing
groups, such as nitro, cyano, N-methylamino, N,N-dimethylamino,
and N-phenylamino groups, boron-containing groups, such as
boranetriyl, and diboranyl groups, sulfur-containing groups,
such as sulfonyl, and sulphenyl groups.
10 [0118]
The above hydrocarbon groups may have a hydrogen atom
substituted by a halogen atom, and examples thereof include
trifluoromethyl, trifluoromethylphenyl, pentafluorophenyl, and
chlorophenyl groups.
15 [ 0119]
20
Examples of the silicon-containing group include silyl,
siloxy, hydrocarbon-substituted silyl, and
hydrocarbon-substituted siloxy groups. For example, they
include methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl,
diethylsilyl,
triphenylsilyl,
triethylsilyl,
dimethylphenylsilyl,
diphenylmethylsilyl,
dimethyl-t-butylsilyl,
dimethyl(pentafluorophenyl)silyl groups, and the like.
[0120]
R6 and R11 are the same atom or the same group selected from
SF-3064
52
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
group selected from a hydrogen atom, a hydrocarbon group, a
5 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. However,
all of R6
, R7
, R10
, and R11 are not a hydrogen atom simultaneously.
[0121]
10 R13 and R14 each independently represent an aryl group.
[0122]
M1 represents a zirconium atom.
[0123]
Y1 represents a carbon atom or a silicon atom.
15 [0124]
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, and a neutral
ligand coordinatable by an anionic ligand or a lone pair, and j
20 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.
[ 012 5]
Examples of the halogen atom include a fluorine atom, a
SF-3064
53
chlorine atom, a bromine atom, and an iodine atom, and the chlorine
atom is preferable.
[0126]
The hydrocarbon groups are preferably those having 1 to 10
5 carbon atoms, and specific examples thereof include methyl, ethyl,
n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl,
2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl,
1,1,2,2-tetramethylpropyl, sec-butyl,
1,1-dimethylbutyl, 1,1,3-trimethylbutyl,
t-butyl,
neopentyl,
10 cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl, benzyl
groups, and the like, and methyl, ethyl, and benzyl groups are
preferable.
[0127]
The neutral conjugated or non-conjugated diene having 4 to
15 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- or s-trans-04-1,3-butadiene, s-cis- or
s-trans-04-1,4-diphenyl-1,3-butadiene, s-cis- or
s-cis- or
s-cis- or
20 s-trans-04-3-methyl-1,3-pentadiene,
s-trans-04-1,4-dibenzyl-1,3-butadiene,
s-trans-04-2,4-hexadiene, s-cis- or s-trans-04-1,3-pentadiene,
s-cis- or s-trans-04-1,4-ditoryl-1,3-butadiene, s-cis- or
s-trans-04-l, 4 -bis (trimethylsilyl) -1, 3-butadiene, and the like.
SF-3064
54
[0128]
Specific examples of the anionic ligand include alkoxy
groups, such as methoxy, t-butoxy, and phenoxy groups, carboxylate
groups, such as acetate and benzoate groups, and sulfonate groups,
5 such as mesylate and tosylate groups, and the like.
[ 012 9 J
Specific examples of the neutral ligand coordinatable by
a lone pair include organic phosphorus compounds, such as
trimethylphosphine, triethylphosphine, triphenylphosphine, and
10 diphenylmethylphosphine, or ethers, such as tetrahydrofuran,
diethylether, dioxane, and 1,2-dimethoxyethane.
[0130]
Examples of the cyclopentadienyl group having substituents
from R1 to R4 in the formula [All include, but are not limited to,
15 non-substitutedcyclopentadienylgroupshavingsubstituents from
R1 to R4 which are a hydrogen atom, cyclopentadienyl groups
monosubstituted at position 3, such as 3- t-butylcyclopentadienyl,
3-methylcyclopentadienyl,
3-phenylcyclopentadienyl,
3-trimethylsilylcyclopentadienyl,
3-adamantylcyclopentadienyl,
20 3-amylcyclopentadienyl, and 3-cyclohexylcyclopentadienyl groups,
and cyclopentadienyl groups disubstituted at positions 3 and 5,
such as 3-t-butyl-5-methylcyclopentadienyl,
3-t-butyl-5-ethylcyclopentadienyl,
3-phenyl-5-methylcyclopentadienyl,
SF-3064
55
3,5-di-t-butylcyclopentadienyl, 3,5-dimethylcyclopentadienyl,
3-phenyl-5-methylcyclopentadienyl,
3-trimethylsilyl-5-methylcyclopentadienyl groups.
and
The non-substituted cyclopentadienyl groups (R1 to R4 are a
5 hydrogen atom) are preferable from the view point of easiness to
synthesize metallocene compounds, and their production cost and
copolymerization ability for non-conjugated polyenes.
[0131]
Examples of a fluorenyl group having the substituents from
10 R5 to R12 in the formula [All include, but are not limited to,
non-substituted fluorenyl groups having substituents from R5 to
R12 which are a hydrogen atom,
fluorenyl groups monosubstituted at position 2, such as
2-methylfluorenyl, 2-t-butylfluorenyl, and 2-phenylfluorenyl
15 groups,
fluorenyl groups monosubstituted at position 4, such as
4-methylfluorenyl, 4-t-butylfluorenyl, and 4-phenylfluorenyl
groups, and
fluorenyl groups disubstituted at positions 2 and 7 or 3 and 6,
20 such as 2, 7-di- t-butylfluorenyl, and 3, 6-di- t-butylfluorenyl
groups,
fluorenyl groups tetrasubstituted at positions 2, 3, 6, and 7,
such as 2,7-dimethyl-3,6-di-t-butylfluorenyl, and
2,7-diphenyl-3,6-di-t-butylfluorenyl groups, and
SF-3064
56
fluorenyl groups tetrasubstituted at positions 2, 3, 6, and 7 in
which R6 together with R7 and R10 together with R11 each form a ring,
as represented by the formulae [V-I] and [V-II].
[0132]
5 [Chern. 4]
R' . . . [V-I]
[0133]
[Chern. 5]
R"
R'
"'
R' Rh R'
· • • [V-II]
10 In the formulae [V-I] and [V-II], R5
, R8
, R9
, and R12 are the same
as the definitions in the formula [A1],
Ra, Rb, Rc, Rd, Re, Rf, Rg, and Rh are each independently a hydrogen
atom or an alkyl group having 1 to 5 carbon atoms, and each may
bond to an adjacent substituent to form together a ring.
15 The alkyl groups are specifically exemplified by methyl, ethyl,
n-propyl, isopropyl, n-butyl, t-butyl, amyl, and n-pentyl groups.
In the formula [V-I], Rx and RY are each independently a hydrocarbon
group having 1 to 3 carbon atoms which may have an unsaturated
bond, Rx may form a double-bond together with a carbon atom to
20 which Ra or Rc bonds, RY may form a double-bond together with a
5
SF-3064
57
carbon atom to which Re or Rg bonds, and Rx and RY are both preferably
a saturated or unsaturated hydrocarbon group having one or two
carbon atoms.
[0134]
Specific examples of the compounds represented by the
formula [V-I] or [V-II] include
octamethyloctahydrodibenzofluorenyl group represented by the
formula [V-III], tetramethyldodecahydrodibenzofluorenyl group
represented by the formula [V-IV],
10 octamethyl tetrahydrodicyclopentafluorenyl group represented by
the formula [V-V], hexamethyldihydrodicyclopentafluorenyl group
represented by the formula [V-VI] , and b, h-dibenzofluorenyl group
represented by the formula [V-VII] .
[0135]
15 [Chern. 6]
[0136]
[Chern. 7]
20 [0137]
· · • [V-lll]
. . . [V-IV]
5
SF-3064
[Chern. 8]
[0138]
[Chern. 9]
[0139]
[Chern. 10]
58
• • • [V-V]
• • • [V-VI]
• • • [\f-VH]
A meta11ocene compound containing any of these fluorenyl
10 groups and represented by the general formula [All is excellent
in copolymerization ability for non-conjugated polyene, and when
Y1 is a silicon atom, transition metal compounds are particularly
excellent which have any of a fluorenyl group disubstituted at
positions 2 and 7, a fluorenyl group disubstituted at positions
15 3 and 6, a fluorenyl group tetrasubstituted at positions 2, 3,
6, and 7, and a fluorenyl group tetrasubstituted at positions 2,
3, 6, and 7 represented by the above general formula [V-I].
When Y is a carbon atom, metallocene compounds are particularly
excellent which have any of a non-substituted fluorenyl group in
SF-3064
59
which R5 to R12 are a hydrogen atom, a fluorenyl group disubsti tuted
at positions 3 and 6, a fluorenyl group tetrasubstituted at
positions 2, 3, 6, and 7, and a fluorenyl group tetrasubstituted
at position 2, 3, 6, and 7 represented by the above general formula
5 [V-I].
[0140]
In the present invention, in a metallocene compound
represented by the general formula [All , when Y1 is a silicon atom,
with all substi tuents from R5 to R12 being a hydrogen atom, R13 and
10 R14 are preferably selected from groups other than methyl, butyl,
phenyl, silicon-substituted phenyl, cyclohexyl, and benzyl
groups;
when Y1 is a silicon atom, with both R6 and R11 being t-butyl group,
and R5
, R7
, R8
, R9
, R10
, and R12 not being t-butyl group, R13 and
15 R14 are preferably selected from groups other than benzyl group,
and silicon-substituted phenyl group;
when Y1 is a carbon atom, with all substituents from R5 to R12 being
a hydrogen atom, R13 and R14 are preferably selected from groups
other than methyl, isopropyl, t-butyl, isobutyl, phenyl,
20 p-t-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl,
4-biphenyl, p-tolyl, naphthyl, benzyl, cyclopentyl, cyclohexyl,
and xylyl groups;
when Y1 is a carbon atom, with R6 and R11 being the same group
selected from t-butyl, methyl, and phenyl groups, and being a
SF-3064
60
different group or atom from R5
, R7
, R8
, R9
, R10
, and R12
, R13 and
R14 are preferably selected from groups other than methyl, phenyl,
p-t-butylphenyl, p-n-butylphenyl, silicon-substituted phenyl,
and benzyl groups;
5 when Y1 is a carbon atom, with R6 being dimethylamino, methoxy,
or methyl group, and R5
, R7
, R8
, R9
, R10
, R11
, and R12 being a different
group or atom from R6
, R13 and R14 are preferably selected from groups
other than methyl and phenyl groups; and
when Y1 is a carbon atom, with sites constituted by a fluorenyl
10 group and substi tuents from R5 to R12 being b, h-dibenzofluorenyl
or a, i -dibenzofluorenyl groups, R13 and R14 are preferably selected
from groups other than methyl and phenyl groups.
[01411
Although specific examples of the metallocene compound
15 represented by the formula [All in the present invention will be
described below, the scope of the invention is not particularly
limited thereby.
[01421
Specific examples of the metallocene compound represented
20 by the formula [All in the invention include,
when Y is a silicon atom,
diphenylsilylene(cyclopentadienyl) (2,7-di-t-butylfluorenyl)zi
rconium dichloride,
diphenylsilylene(cyclopentadienyl) (3,6-di-t-butylfluorenyl)zi
SF-3064
61
rconium dichloride,
diphenylsilylene(cyclopentadienyl) (2,7-dimethyl-3,6-di-t-buty
lfluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-buty
5 1 fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl) (octamethyloctahydrodibenzo
fluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl) (tetramethyldodecahydrobenz
ofluorenyl)zirconium dichloride,
10 diphenylsilylene(cyclopentadienyl) (octamethyltetrahydrodicycl
opentafluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl) (hexamethyldihydrodicyclope
ntafluorenyl)zirconium dichloride,
diphenylsilylene(cyclopentadienyl) (b,h-dibenzofluorenyl)zirco
15 nium dichloride
di(p-tolyl)silylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (2,7-di-t-butylfluorenyl
)zirconium dichloride,
20 di(p-tolyl)silylene(cyclopentadienyl) (3,6-di-t-butylfluorenyl
)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (2,7-dimethyl-3,6-di-t-b
utylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-b
SF-3064
62
utylfluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (octamethyloctahydrodibe
nzofluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (tetramethyldodecahydrob
5 enzofluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (octamethyltetrahydrodic
yclopentafluorenyl)zirconium dichloride,
di(p-tolyl)silylene(cyclopentadienyl) (hexamethyldihydrodicycl
opentafluorenyl)zirconium dichloride,
10 di(p-tolyl)silylene(cyclopentadienyl) (b,h-dibenzofluorenyl)zi
rconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (2,7-di-t-butylfluorenyl
15 ) zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (3,6-di-t-butyl
fluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (2,7-dimethyl-3,6-di-t-b
utylfluorenyl)zirconium dichloride,
20 di(m-tolyl)silylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-b
utylfluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (octamethyloctahydrodibe
nzofluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (tetramethyldodecahydrob
SF-3064
63
enzofluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (octamethyltetrahydrodic
yclopentafluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (hexamethyldihydrodicycl
5 opentafluorenyl)zirconium dichloride,
di(m-tolyl)silylene(cyclopentadienyl) (b,h-dibenzofluorenyl)zi
rconium dichloride, and the like.
[0143]
When Y is a carbon atom, they include
10 diphenylmethylene(cyclopentadienyl) (3,6-di-t-butylfluorenyl)z
irconium dichloride,
diphenylmethylene(cyclopentadienyl) (2,7-dimethyl-3,6-di-t-but
ylfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-but
15 ylfluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (octamethyloctahydrodibenz
ofluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (tetramethyldodecahydrodib
enzofluorenyl)zirconium dichloride,
20 diphenylmethylene(cyclopentadienyl) (octamethyltetrahydrodicyc
lopentafluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (hexamethyldihydrodicyclop
entafluorenyl)zirconium dichloride,
diphenylmethylene(cyclopentadienyl) (b,h-dibenzofluorenyl)zirc
SF-3064
64
onium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (2,7-di-t-butylfluoreny
l)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (3,6-di-t-butylfluoreny
5 l)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (2,7-dimethyl-3,6-di-tbutylfluorenyl)
zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-tbutylfluorenyl)
zirconium dichloride,
10 di(p-tolyl)methylene(cyclopentadienyl) (octamethyloctahydrodib
enzofluorenyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (tetramethyldodecahydro
dibenzofluorenyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (octamethyltetrahydrodi
15 cyclopentafluorenyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (hexamethyldihydrodicyc
lopentafluorenyl)zirconium dichloride,
di(p-tolyl)methylene(cyclopentadienyl) (b,h-dibenzofluorenyl)z
irconium dichloride,
20 di(m-tolyl)methylene(cyclopentadienyl) (fluorenyl)zirconium
dichloride,
di(m-tolyl)methylene(cyclopentadienyl) (2,7-di-t-butylfluoreny
l)zirconium dichloride,
di(m-tolyl)methylene(cyclopentadienyl) (3,6-di-t-butylfluoreny
SF-3064
65
l)zirconiurn dichloride,
di(m-tolyl)rnethylene(cyclopentadienyl) (2,7-dirnethyl-3,6-di-tbutylfluorenyl)
zirconium dichloride,
di(m-tolyl)rnethylene(cyclopentadienyl) (2,7-diphenyl-3,6-di-t-
5 butylfluorenyl)zirconiurn dichloride,
di(m-tolyl)rnethylene(cyclopentadienyl) (octarnethyloctahydrodib
enzofluorenyl)zirconiurn dichloride,
di(m-tolyl)rnethylene(cyclopentadienyl) (tetramethyldodecahydro
benzofluorenyl)zirconium dichloride,
10 di(m-tolyl)rnethylene(cyclopentadienyl) (octarnethyltetrahydrodi
cyclopentafluorenyl)zirconiurn dichloride,
di(m-tolyl)rnethylene(cyclopentadienyl) (hexamethyldihydrodicyc
lopentafluorenyl)zirconium dichloride,
di(m-tolyl)methylene(cyclopentadienyl) (b,h-dibenzofluorenyl)z
15 irconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (3,6-di-t-butyl
fluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (2,7-dimethyl-3
,6-di-t-butylfluorenyl)zirconiurn dichloride,
20 di(p-t-butylphenyl)methylene(cyclopentadienyl) (2, 7-diphenyl-3
,6-di-t-butylfluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (octamethylocta
hydrodibenzofluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (tetrarnethyldod
SF-3064
66
ecahydrodibenzofluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (octamethyltetr
ahydrodicyclopentafluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (hexamethyldihy
5 drodicyclopentafluorenyl)zirconium dichloride,
di(p-t-butylphenyl)methylene(cyclopentadienyl) (b,h-dibenzoflu
orenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (2,7-di-t-butylfluor
enyl)zirconium dichloride,
10 di(4-biphenyl)methylene(cyclopentadienyl) (3,6-di-t-butylfluor
enyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (2,7-dimethyl-3,6-di
-t-butylfluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,6-di
15 -t-butylfluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (octamethyloctahydro
dibenzofluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (tetramethyldodecahy
drodibenzofluorenyl)zirconium dichloride,
20 di(4-biphenyl)methylene(cyclopentadienyl) (octamethyltetrahydr
odicyclopentafluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (hexamethyldihydrodi
cyclopentafluorenyl)zirconium dichloride,
di(4-biphenyl)methylene(cyclopentadienyl) (b,h-dibenzofluoreny
SF-3064
67
l)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (fluorenyl)zirco
nium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (2,7-di-t-butylf
5 luorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (3,6-di-t-butylf
luorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (2,7-dimethyl-3,
6-di-t-butylfluorenyl)zirconium dichloride,
10 di(p-chlorophenyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,
6-di-t-butylfluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (octamethyloctah
ydrodibenzofluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (tetramethyldode
15 cahydrodibenzofluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (octamethyltetra
hydrodicyclopentafluorenyl)zirconium dichloride,
di(p-chlorophenyl)methylene(cyclopentadienyl) (hexamethyldihyd
rodicyclopentafluorenyl)zirconium dichloride,
20 di(p-chlorophenyl)methylene(cyclopentadienyl) (b,h-dibenzofluo
renyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (fluorenyl)zirco
nium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (2,7-di-t-butylf
SF-3064
68
luorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (3,6-di-t-butylf
luorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (2,7-dimethyl-3,
5 6-di-t-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,
6-di-t-butylfluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (octamethyloctah
ydrodibenzofluorenyl)zirconium dichloride,
10 di(m-chlorophenyl)methylene(cyclopentadienyl) (tetramethyldode
cahydrodibenzofluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (octamethyltetra
hydrodicyclopentafluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (hexamethyldihyd
15 rodicyclopentafluorenyl)zirconium dichloride,
di(m-chlorophenyl)methylene(cyclopentadienyl) (b,h-dibenzofluo
renyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (fluore
nyl)zirconium dichloride,
20 di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (2,7-di
-t-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (3,6-di
-t-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (2,7-di
SF-3064
69
methyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (2,7-di
phenyl-3,6-di-t-butylfluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (octame
5 thyloctahydrodibenzofluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (tetram
ethyldodecahydrodibenzofluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (octame
thyltetrahydrodicyclopentafluorenyl)zirconium dichloride,
10 di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (hexame
thyldihydrodicyclopentafluorenyl)zirconium dichloride,
di(m-trifluoromethylphenyl)methylene(cyclopentadienyl) (b,h-di
benzofluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (2,7-di-t-butylfluor
15 enyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (3,6-di-t-butylfluor
enyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (2,7-dimethyl-3,6-di
-t-butylfluorenyl)zirconium dichloride,
20 di(2-naphthyl)methylene(cyclopentadienyl) (2,7-diphenyl-3,6-di
-t-butylfluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (octamethyloctahydro
dibenzofluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (tetramethyldodecahy
SF-3064
70
drodibenzofluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (octamethyltetrahydr
odicyclopentafluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (hexamethyldihydrodi
5 cyclopentafluorenyl)zirconium dichloride,
di(2-naphthyl)methylene(cyclopentadienyl) (b,h-dibenzofluoreny
l)zirconium dichloride, and the like.
[0144]
The following exemplary structural formulae of these metallocene
10 compounds depict
di(p-tolyl)methylene(cyclopentadienyl) (octamethyloctahydrodib
enzofluorenyl) zirconium dichloride (in the following formula
(Al-l)) and
di(p-chlorophenyl)methylene(cyclopentadienyl) (octamethyloctah
15 ydrodibenzofluorenyl) zirconium dichloride (in the following
20
formula (Al-2)).
[0145]
[Chern. 11]
.. l>\I-1), ... (Al-2)
The above compounds may be used singly or in combination
of the two or more kinds.
[0146]
SF-3064
71
The metallocene compound represented by the formula [All
which can be suitably used for preparing the
ethylene/a-olefin/non-conjugated polyene copolymer of the
invention can be produced by any process without any special
5 limitation. Specifically, it can be produced, for example, in
accordance with processes described in J. Organomet. Chern., 63,
50 9 ( 1996) , and WO 2 005/100410, WO 2 00 6/1237 59, WO 01/27124,
JP-A-2004-168744, JP-A-2004-175759, and JP-A-2000-212194, which
are documents according to the applications by the present
10 applicants.
[01471
Catalyst containing metallocene compound
Examples of polymerization catalysts which can be suitably
used for producing the ethylene/a-olefin/non-conjugated polyene
15 copolymer of the present invention include catalysts which contain
the metallocene compound represented by the aforementioned
formula [All and are capable of copolymerizing monomers.
20
[01481
Preferably, they include catalysts consisting of:
(a) a metallocene compound represented by the aforementioned
formula [All;
(b) at least one compound selected from (b-1) an organometallic
compound, (b-2) an organoaluminum oxycompound, and (b-3) a
compound reacting with the metallocene compound (a) to form an
5
SF-3064
72
ion pair;
and as necessary,
(c) a particulate carrier.
[0149]
Each of the components will be specifically explained below.
(b-1) Organometallic compound
The organometallic compound (b-1) to be used in this
invention is an organometallic compound of Groups 1, 2 and 12,
13 specifically represented by the following general formulae from
10 [VII] to [IX].
(b-1a) Organoaluminum compound represented by a general
[VII]
(In the formula [VII], Ra and Rb may be the same or different from
each other, and represent a hydrocarbon group having 1 to 15 carbon
15 atoms, and preferably 1 to 4 carbon atoms, X represents a halogen
atom, m is a number of 0 < m ~3, n is a number of 0 ~ n < 3, p
is a number of 0 ~ p < 3, q is a number of 0 ~ q < 3, and m + n
20
+p+q=3.)
[0150]
Such compounds can be exemplified by trialkylaluminums,
such as trimethylaluminum, triethylaluminum,
triisobutylaluminum, tri-n-octylaluminum,
tricycloalkylaluminums,
diethylaluminum chloride,
and
isobutylaluminum
ethylaluminum
dichloride,
dichloride,
SF-3064
73
ethylaluminum sesquichloride, methylaluminum dichloride,
dimethylaluminum chloride, and diisobutylaluminum hydride.
(b-lb) Complex alkylated product of Group 1 metal and
aluminum, represented by a general formula of M2AlRa4 [VIII]
5 (In the formula [VIII], M2 represents Li, Na, or K, Ra is a
hydrocarbon group having 1 to 15 carbon atoms, and preferably 1
to 4 carbon atoms.)
10
Such compounds can be exemplified by LiAl (C2H5 ) 4 ,
LiAl (C7H1sl ,, and the like.
(b-lc) Dialkyl compound having Group 2 or 12 metal,
represented by a general formula of RaRbM3 [IX]
(In the formula [IX] , Ra and Rb may be the same or different from
each other, and represent a hydrocarbon group having 1 to 15 carbon
atoms, and preferably 1 to 4 carbon atoms, and M3 is Mg, Zn, or
15 Cd. )
[0151]
Among the above organometallic compounds (b-1)'
organoaluminum compounds, such as triethylaluminum,
triisobutylaluminum, and tri-n-octylaluminum are preferable.
20 Such organometallic compounds (b-1) can be used singly or in
combination with the two or more kinds.
(b-2) Organoaluminum oxy-compound
Organoaluminum oxycompounds (b-2) to be used in the
invention may be conventionally well-known aluminoxanes, or
i
SF-3064
74
organoaluminum oxycompounds insoluble into benzene as described
in JP-A-H2-78687.
[0152]
Conventionally known aluminoxanes can be produced, for
5 example, by the following processes, and usually obtained as a
solution with a hydrocarbon solvent.
(1) A process in which an organoaluminum compound such as
a trialkylaluminum is added to a hydrocarbon solution suspending
a compound containing adsorbed water or a salt containing
10 crystallization water, such as magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate,
and cerous chloride hydrate, to make the adsorbed water or the
crystallization water react with the organoaluminum compound.
15
[0153]
(2) A process in which water, ice, or water vapor is directly
applied to an organoaluminum compound such as a trialkylaluminum
in a medium such as benzene, toluene, ethyl ether, and
tetrahydrofuran.
( 3) A process in which an organo-tin oxide such as
20 dimethyltin oxide and dibutyltin oxide is made react with an
organoaluminum compound such as a trialkylaluminum in a medium,
such as decane, benzene, and toluene.
[0154]
The aluminoxanes may contain a small amount of an organic
SF-3064
75
metal component. Furthermore, al uminoxane in the above recovered
aluminoxane solution may be separated by distillation from the
solvent or the non-reacted organoaluminum compound, to be
dissolved again into a solvent or suspended into a poor solvent
5 for aluminoxane.
[0155]
Specific examples of organoaluminum compounds used for
preparing the aluminoxane include those which are the same as
organoaluminum compounds exemplified by (b-la).
10 [0156]
15
Among them, trialkylaluminums and tricycloalkylaluminums
are preferable, and trimethylaluminum and triisobutylaluminum
are particularly preferable.
[0157]
The organoaluminum compounds as described above can be used
singly or in combination of the two or more kinds.
[0158]
A benzene-insoluble organoaluminum oxycompound which is one
aspect of the organoaluminum oxycompound (b-2) used in the present
20 invention is preferably a compound in which the Al component
soluble into benzene at 60°C is usually 10% or less by weight in
terms of Al atom with respect to 100% by weight of benzene,
preferably 5% or less by weight, and especially preferably 2% or
less by weight, and in other words, the organoaluminum
SF-3064
76
oxycompounds are preferably insoluble or poorly soluble into
benzene.
[0159]
Examples of the organoaluminum oxycompound (b-2) to be used
5 in the invention can include those which contain boron and are
represented by the following general formula [X]
[0160]
[Chern. 12]
• • • [X]
10 [In the formula [X], R1 represents a hydrocarbon group having 1
to 10 carbon atoms, and substituents from R2 to R5 may be the same
or different from each other and represent a hydrogen atom, a
halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms.]
Organoaluminum oxycompounds containing boron, represented by the
15 above general formula [X] can be produced by reacting an
alkylboronic acid represented by the following general formula
[XI] ,
[XI]
(In the formula [XI], R1 represents the same group as R1 in the
20 above general formula [X].) with an organoaluminum compound in
an inert solvent under an inert gas atmosphere at a temperature
within the range from -80°C to room temperature for 1 minute to
SF-30 64
77
24 hours.
[0161]
Specific examples of the alkylboronic acid represented by
the above general formula [XI] include methylboronic acid,
5 ethylboronic acid, isopropylboronic acid, n-propylboronic acid,
n-butylboronic acid, isobutylboronic acid, n-hexyl boronic acid,
cyclohexylboronic acid, phenylboronic acid,
3,5-difluorophenylboronic acid, pentafluorophenylboronic acid,
and 3,5-bis(trifluoromethyl)phenylboronic acid, and the like.
10 [0162]
Among them, methylboronic acid, n-butylboronic acid,
isobutylboronic acid, 3,5-difluorophenylboronic acid, and
pentafluorophenylboronic acid are preferable. These are used
singly or in combination of the two or more kinds.
15 [0163]
Specific examples of organoaluminum compounds to be reacted
with these alkylboronic acids include those which are the same
as an organoaluminum compound exemplified by the above compound
represented by (b-la).
20 [ 0 164]
Among them, trialkylaluminums and tricycloalkylaluminums
are preferable, and trimethylaluminum, triethylaluminum, and
triisobutylaluminum are particularly preferable. These are used
singly or in combination with the two or more kinds. The above
5
SF-3064
78
organoaluminum oxycompound (b-2) is used singly or in combination
with the two or more kinds.
(b-3) Compound to be reacted with transition metal compound (A)
to form an ion pair
Examples of the compound (b-3) to be reacted with a
crosslinked metallocene compound (A) used in the present invention,
to form an ion pair (hereinafter referred to as "ionized ionic
compounds") includes Lewis acids, ionic compounds, borane
compounds, and carborane compounds described in, for example,
10 JP-A-Hl-501950, JP-A-Hl-502036, JP-A-H3-179005, JP-A-H3-179006,
JP-A-H3-207703, JP-A-H3-207704, USP-5321106, and the like.
Further, they can include heteropolycompounds and
isopolycompounds. The ionized ionic compound (b-3) is used
singly or in combination with the two or more kinds.
15 [0165]
20
Specific examples of the Lewis acids includes compounds
represented by BR3 (R is fluorine or a phenyl group which may have
a substituent, such as fluorine, methyl, and trifluoromethyl
groups), and includes, for example, trifluoroboron,
triphenylboron, tris(4-fluorophenyl)boron,
tris(3,5-difluorophenyl)boron,
tris(4-fluoromethylphenyl)boron, tris(pentafluorophenyl)boron,
tris(p-tolyl)boron, tris(o-tolyl)boron, and
tris(3,5-dimethylphenyl)boron.
SF-3064
79
[0166]
Examples of the ionic compound include, for example,
compounds represented by following general formula [XII],
[ 0 167]
5 [Chern. 13]
R2
R1G RL~G R5
14
R [XII)
(In the formula [XII] , examples of Rl+ include H+, carbonium cations,
oxonium cations, ammonium cations, phosphonium cations,
cycloheptyltrienyl cations, and ferrocenium cations having a
10 transition metal. Substi tuents from R2 to R5 may be the same or
different from each other, and are an organic group, preferably
an aryl or substituted aryl group.) Specific examples of the
carbonium cation include trisubstituted carbonium cations such
as triphenyl carbonium cation, tri (methylphenyl) carbonium cation,
15 tri(dimethylphenyl)carbonium cation, and the like.
[0168]
Specific examples of the ammonium cations include
trialkylammonium cations, such as trimethylammonium cation,
triethylammonium cation, tripropylammonium cation,
20 tributylammonium cation, and tri(n-butyl)ammonium cation;
N,N-dialkylanilinium cations, such as N,N-dimethylanilinium
cation, N,N-diethylanilinium cation, and
5
10
15
20
SF-3064
80
N,N,2,4,6-pentamethylanilinium cation; and
dialkylammonium cations, such as di(isopropyl)ammonium cation
and dicyclohexyl ammonium cation.
[0169]
Specific examples of the phosphonium cation include
triarylphosphonium cations, such as triphenylsulfonium cation,
tri(methylphenyl)phosphonium
tri(dimethylphenyl)phosphonium cation.
[0170]
cation, and
Examples of Rl+ are preferably carbonium cations or ammonium
cations, and triphenylcarbonium cation, N,N-dimethylanilinium
cation, and N,N-diethylanilinium cation are particularly
preferable.
[0171]
Examples of the ionic compound can also include, for example,
trialkyl-substi tuted ammonium salts, N, N-dialkylanilinium salts,
dia1kylammonium salts, and triarylphosphonium salts.
[0172]
Specific examples of the trialkyl-substituted ammonium
salts include triethylammonium
tripropylammonium tetra(phenyl)boron,
tetra(phenyl)boron, trimethylammonium
trimethylammonium tetra(o-tolyl)boron,
tetra(pentafluorophenyl)boron,
tetra(phenyl)boron,
tri(n-butyl)ammonium
tetra(p-tolyl)boron,
tri(n-butyl)ammonium
tripropylammonium
SF-3064
81
tetra(o,p-dimethylphenyl)boron, tri(n-butyl)ammonium
tetra(N,N-dimethylphenyl)boron, tri(n-butyl)ammonium
tetra(p-trifluoromethylphenyl)boron, tri(n-butyl)ammonium
tetra(3,5-ditrifluoromethylphenyl)boron, tri(n-butyl)ammonium
5 tetra(o-tolyl)boron, and the like.
[0173]
Specific examples of theN, N-dialkylanilinium salts include
N,N-dimethylanilinium tetra(phenyl)boron, N,N-diethylanilinium
tetra(phenyl)boron, N,N,2,4,6-pentamethylanilinium
10 tetra(phenyl)boron, and the like.
[0174]
Specific examples of the dialkylammonium salts include
di(l-propyl)ammonium tetra(pentafluorophenyl)boron,
dicyclohexylammonium tetra(phenyl)boron, and the like.
15 [0175]
Examples of the ionic compounds also can include
triphenylcarbenium
N,N-dimethylanilinium
tetrakis(pentafluorophenyl)borate,
tetrakis(pentafluorophenyl)borate,
ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium
20 pentaphenylcyclopentadienyl
pentaphenylcyclopentadienyl
complex,
complex,
N,N-diethylanilinium
boron compounds
represented by the following general formula [XIII] or [XIV], and
the like. In the formulae, Et represents an ethyl group.
[0176]
SF-3064
82
[Chern. 14]
• • • [XIII]
[0177]
[Chern. 15]
5 • • • [XIV]
Specific examples of the borane compounds include:
decaborane;
anionic salts, such as bis[tri(n-butyl)ammonium]nonaborate,
bis[tri(n-butyl)ammonium]decaborate,
10 bis[tri(n-butyl)ammonium]undecaborate,
bis[tri(n-butyl)ammonium]dodecaborate,
bis[tri(n-butyl)ammonium]decachlorodecaborate, and
bis[tri(n-butyl)ammonium]dodecachlorododecaborate;
salts of metal borane anion, such as tri(n-butyl)ammonium
15 bis(dodecahydridedodecaborate)cobaltate (III),
bis[tri(n-butyl)ammonium]bis(dodecahydridedodecaborate)nickel
ate (III), and the like.
[0178]
Specific examples of the carborane compounds include
20 anionic salts, such as 4-carbanonaborane, 1, 3-dicarbanonaborane,
5
SF-3064
83
6,9-dicarbadecaborane,
dodecahydride-1-phenyl-1,3-dicarbanonaborane,
dodecahydride-1-methyl-1,3-dicarbanonaborane,
undecahydride-1,3-dimethy1-1,3-dicarbanonaborane,
7,8-dicarbaundecaborane, 2,7-dicarbaundecaborane,
undecahydride-7,8-dimethyl-7,8-dicarbaundecaborane,
dodecahydride-11-methyl-2,7-dicarbaundecaborane,
tri(n-butyl)ammonium
tri(n-butyl)ammonium-1-carbaundecaborate,
1-carbadecaborate,
10 tri(n-butyl)ammonium-1-carbadodecaborate,
tri(n-butyl)ammonium-1-trimethylsilyl-1-carbadecaborate,
tri(n-butyl)ammonium bromo-1-carbadodecaborate,
tri(n-butyl)ammonium-6-carbadecaborate,
tri(n-butyl)ammonium-7-carbaundecaborate,
15 tri(n-butyl)ammonium-7,8-dicarbaundecaborate,
tri(n-butyl)ammonium-2,9-dicarbaundecaborate,
tri(n-butyl)ammonium
dodecahydride-8-methyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium
20 undecahydride-8-ethyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium
undecahydride-8-butyl-7,9-dicarbaundecaborate,
tri(n-butyl)ammonium
undecahydride-8-allyl-7,9-dicarbaundecaborate,
SF-3064
84
tri(n-butyl)ammonium
undecahydride-9-trimethylsilyl-7,8-dicarbaundecaborate, and
tri(n-butyl)ammonium
undecahydride-4,6-dibromo-7-carbaundecaborate; and
5 salts of metal carborane anion, such as tri (n-butyl) ammonium
bis(nonahydride-1,3-dicarbanonaborate)cobaltate
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)ferrate
tri(n-butyl)ammonium
10 bis(undecahydride-7,8-dicarbaundecaborate)cobaltate
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)nickelate
tri(n-butyl)ammonium
bis(undecahydride-7,8-dicarbaundecaborate)cuprate
15 tri(n-butyl)ammonium
(III),
(III),
(III),
(III),
(III),
bis(undecahydride-7,8-dicarbaundecaborate)aurate (III),
tri(n-butyl)ammonium
bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)ferrate
(III), tri(n-butyl)ammonium
20 bis(nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate)chromate
(III), tri(n-butyl)ammonium
bis(tribromooctahydride-7,8-dicarbaundecaborate)cobaltate
(III),
tris[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecabora
5
SF-3064
85
te)chromate (III),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborat
e)manganate (IV),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborat
e)cobaltate (III),
bis[tri(n-butyl)ammonium]bis(undecahydride-7-carbaundecaborat
e)nickelate (IV), and the like.
[0179]
The heteropolycompounds consist of an atom selected from
10 silicon, phosphorus, titanium, germanium, arsenic, and tin, and
one or more kinds of atoms selected from vanadium, niobium,
molybdenum, and tungsten. Specifically, those which can be used
include, but are not limited to, phosphovanadic acid,
germanovanadic acid, arsenovanadic acid, phosphoniobic acid,
15 germanoniobic acid, siliconomolybdic acid, phosphomolybdic acid,
titanomolibdic acid, germanomolybdic acid arsenomolybic acid,
tin molybdic acid, phosphotungstic acid, germanotungstic acid,
20
tin tungstic acid,
phosphotungstovanadic
phosphomolybdotungsto
acid,
phosphomolybdovanadic
germanotungstovanadic
vanadic
acid,
acid,
acid,
germanomolybdotungstovanadic acid, phosphomolybdotungstic acid,
phosphomolybdoniobic acid, and salts of these acids, for example,
salts with Group 1 or Group 2 metals, specifically, with lithium,
sodium, potassium, rubidium, cesium, beryllium, magnesium,
SF-3064
86
calcium, strontium, and barium, and organic salts such as
triphenylethyl salt.
[0180]
Among the ionized ionic compounds (b-3), the above ionic
5 compounds are preferable, and especially triphenylcarbenium
tetrakis(pentafluorophenyl)borate and N,N-dimethylanilinium
tetrakis (pentafluorophenyl) borate are more preferable. The
ionized ionic compounds (b-3) are used singly or in combination
of the two or more kinds.
10 [0181]
In the invention, when a metallocene catalyst containing
the metallocene compound (a) represented by the above general
formula [Al] , an organometallic compound (b-1) such as
triisobutylaluminum, an organoaluminum oxycompound (b-2) such as
15 rnethylaluminoxane, and an ionized ionic compound (b-3) such as
triphenylcarbenium tetrakis (pentafluorophenyl) borate is used as
a catalyst, it can exhibit very high polymerization activity in
the production of the ethylene/a-olefin/non-conjugated polyene
copolymer.
20 [0182]
The metallocene catalyst used for the present invention can
utilize the above metallocene compound (a) and at least one kind
of compound (b) selected from the organometallic compound (b-1),
the organoaluminum oxycompound (b-2), and the ionized ionic
SF-3064
87
compound (b-3), and as necessary, it can also utilize a carrier
(c) .
(c) Carrier
The carrier (c) used as necessary in the present invention
5 (microparticulate carrier) is an inorganic or organic compound,
which is a granular or microparticulate solid.
[0183]
Examples of the inorganic compound are preferably porous
oxides, inorganic halides, clays, clay minerals, or
10 ion-exchangeable layered compounds.
[0184]
Specific examples of the porous oxides which can be used
include Si02 , Al20 3 , MgO, ZrO, Ti02 , B20 3 , CaO, ZnO, BaO, Th02 , and
the like, or composites or mixtures containing any of them, for
15 example, natural or synthesized zeolite, SiOz-MgO, Si02-Al20 3 ,
Si02-Ti02 , Si0z-V205 , Si0z-Cr20 3 , SiOz-TiOz-MgO, and the like.
Among them, those mainly composed of Si02 and/ or Al20 3 are
preferable. Although these porous oxides are different in nature
depending on their kinds and production processes, the carrier
20 preferably used in the present invention desirably has a particle
diameter within a range from 10 to 300 rm, preferably from 20 to
200 rm, a specific surface area within a range from 50 to 1,000
m2 /g, preferably 100 to 700 m2 /g, and a pore volume within a range
from 0. 3 to 3. 0 cm3 /g. Such a carrier is used, as necessary, after
I
SF-30 64
88
calcination at a temperature with in a range from 100 to 1, 000°C,
preferably from 150 to 700°C.
[0185]
Examples of the inorganic halides to be used are MgCl2 , MgBr2 ,
5 MnCl2 , MnBr2 , and the like. The inorganic halides may be used as-is, i_
I
or after trituration by ball milling or vibration milling.
Alternatively, they can also be used in a microparticulate form
which is obtained by precipitating, using a precipitating agent,
inorganic halide dissolved into a solvent such as alcohol.
10 [0186]
The clays to be used in the present invention are usually
composed mainly of clay minerals. The ion-exchangeable layered
compounds to be used in the present invention are compounds which
have a structure in which planes formed by, for example, ionic
15 bonds are piled in parallel on each other by a weak bonding force,
and are compounds containing exchangeable ions. Most clay
minerals are ion-exchangeable layered compounds. These clays,
clay minerals, and ion-exchangeable layered compounds are not
limited to natural materials, and synthesized ones can also be
20 used.
[0187]
The clays, clay minerals, and ion-exchangeable layered
compounds can be exemplified by clays, clay minerals, or ionic
crystal compounds having a layered crystalline structure, such
SF-3064
89
as the hexagonal close-packed structure, the antimony structure,
the CdC12 structure, and the Cdi2 structure. Examples of the clays
andclaymineralsincludekaolin, bentonite, kibushiclay, gairome
clay, allophane, hisingerite, pyrophyllite, mica group,
5 montmorilonite group, vermiculite, chlorite group, palygorskite,
kaolinite, nakhlite, dickite, halloysite, and the like, and
examples of the ion-exchangeable layered compound include
10
crystalline acidic salts of multivalent metal, such as
a-Zr(HAs04) 2 ·H20,
a-Ti(HAs04) 2 ·H20,
[0188]
a-Ti (HP04) 2,
y-Ti (HP04) 2,
Such clays and clay minerals, or ion-exchangeable layered
compounds have a pore volume preferably of 0.1 cc/g or more, and
15 particularly preferably of from 0.3 to 5 cc/g, as measured for
pores of 20 A or more in radius by using a mercury intrusion method.
The pore volume is measured for pores of 20 to 30,000 A in a radius
by a mercury intrusion method using a mercury porosimeter.
20
[0189]
When a carrier is used which has a pore volume of less than
0. 1 cc/ g as measured for pores of 20 A or more in radius, it tends
to be difficult to yield high polymerization activity.
[0190]
Clay and clay mineral used in the present invention are also
SF-3064
90
preferably chemically treated. Any chemical treatment can be
used such as a treatment for removing impurity attached to the
surface of the materials and a treatment affecting the crystalline
structure of the clay. Specific examples of the chemical
5 treatment include acid treatments, basic treatments, treatments
with salts, and treatments with organics. The acid treatments
not only remove impurities on the surface of the materials, but
also increase their surface area by eluting cations, such as Al,
Fe, and Mg. The basic treatments destroy the crystalline
10 structure of the clay, resulting in a change in its structure.
15
The treatments with salts or organics can create ionic complexes,
molecular composites, organic derivatives, and the like, to change
the surface area or the interlayer distance of the materials.
[0191]
Ion-exchangeable layered compounds to be used in the present
invention may be those having an increased interlayer distance
owing to the replacement of exchangeable ions between the layers
with other bulkier ions by using their ion-exchangeability.
Such bulky ions play a role of poles supporting the layered
20 structure and are usually called ''pillars." Inserting another
substance between the layers of a layered compound is called
"intercalation." Examples of the intercalated guest compound
include cationic inorganic compounds such as TiCl4 and ZrCl4 , metal
alkoxides, such as Ti(OR) 4 , Zr(OR) 4 , PO(OR) 3 , and B(OR) 3 (R is,
SF-3064
91
for example, a hydrocarbon group), metal hydroxide ions, such as
[Al1304(0H)24l 7+, [Zr4(0H)14] 2+, and [Fe30(0COCH3)6]+, and the like.
These compounds are used singly or in combination of the two or
more kinds. These compounds can be intercalated in the presence
5 of polymers obtained through hydrolysis of metal alkoxides, such
as Si (OR) 4, Al (OR) 3, and Ge (OR) 4 (R is, for example, a hydrocarbon
group), colloidal inorganic compounds such as Si02 , and the like.
Examples of the pillars include an oxide produced by thermal
dehydration of the above intercalated metal hydroxide ion.
10 [0192]
The clay, clay mineral, and ion-exchangeable layered
compound to be used in the present invention can be used as-is
or after treated by, for example, ball milling or sieving. They
can also be used after fresh adsorption of water or thermal
15 dehydration. Further, they can be used singly or in combination
of the two or more kinds.
[0193]
Among them, preferable are clays or clay minerals, and
particularly preferable are montmorilonite, vermiculite,
20 hectorite, taeniolite, and synthesized mica.
[0194]
Examples of the organic compound include granular or
microparticu1ate solids ranging from 10 to 300 rm in particle
diameter. Specifically, they can be exemplified by polymers or
SF-3064
92
copolymers mainly composed of an a-olefin having 2 to 14 carbon
atoms, such as ethylene, propylene, 1-butene, and
4-methyl-1-pentene, polymers or copolymers mainly composed of
vinylcyclohexane or styrene, and modified products thereof.
5 [0195]
The metallocene catalyst to be used in the present invention
contains not only the metallocene compound (a), at least one kind
of compound (b) selected from the organometallic compound (b-1),
the organoaluminum oxycompound (b-2), the ionized ionic compound
lO (b-3), and the carrier (c) used as necessary, but also the
following specific organic compound component (d) , as necessary.
(d) Organic compound component
In the present invention, the organic compound component
(d) is used, as necessary, in order to improve polymerization
15 performance and the physical properties of the produced polymer.
Examples of such organic compound include, but are not limited
to, alcohols, phenol compounds, carboxylic acids, phosphorus
compounds, and sulfonate salts.
[0196]
20 Process for producing ethylene/a-olefin/non-conjugated polyene
copolymer (A)
The ethylene/a-olefin/non-conjugated polyene copolymer
(A) according to the present invention can be produced by
copolymerizing monomers consisting of ethylene (al), an a-olefin
5
SF-3064
93
(a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3)
containing intramolecularly two or more partial structures in
total selected from the group consisting of the structures
represented by the following general formulae (I) and (II), and
as necessary, a non-conjugated polyene (a4) containing
intramolecularly only one partial structure selected from the
group consisting of the structure represented by the following
general formulae (I) and (II),
[0197]
10 [Chern. 16]
.. (I)
When such monomers are copolymerized, processes of how to
use respective components composing the above polymerization
catalyst and the order of adding the components are arbitrarily
15 selected, and some exemplary processes are given below:
20
(1) A process in which the metallocene compound (a) alone is
added to a polymerizer.
(2) A process in which the meta1locene compound (a) and the
compound (b) are added to the polymerizer in an arbitrary order.
( 3) A process in which a catalyst component including the
carrier (c) and the metallocene compound (a) supported on the
carrier, and the compound (b) are added to the polymerizer in an
arbitrary order.
5
SF-3064
94
(4) A process in which a catalyst component including the
carrier (c) and the compound (b) supported on the carrier, and
the metallocene compound (a) are added to the polymerizer in an
arbitrary order.
( 5) A process in which a catalyst component including the
carrier (c) and metallocene compound (a) and the compound (b) both
supported on the carrier is added to the polymerizer.
[0198]
In each of the above methods (2) to (5), at least two of
10 the metallocene compound (a), the compound (b), and the carrier
(c) may be contacted with each other in advance.
[0199]
In each of the above processes (4) and (5) in which the
compound (b) is supported on the carrier, an additional
15 unsupported compound (b) may be added in an arbitrary order as
necessary. In this case, the additional compound (b) may be the
same as or different from the compound (b) supported on the carrier
20
(c) .
[0200]
The solid catalyst component including the above carrier
(c) and the metallocene compound (a) supported on the carrier and
the solid catalyst component including the carrier (c) and the
metallocene compound (a) and the compound (b) both supported on
the carrier may be prepolymerized with olefin, and an additional
SF-3064
95
catalyst component may be supported on the prepolymerized solid
catalyst component.
[0201]
In the invention, the ethylene/a-olefin/non-conjugated
5 polyene copolymer can be suitably obtained by copolymerizing
monomers in the presence of the metallocene catalyst as described
above.
[0202]
When the olefin is polymerized by using the metallocene
10 catalyst as described above, the metallocene compound (a) is used
usually in an amount with in a range from 10-12 to 10-2 mol,
preferably from 10-10 to 10-8 mol per one liter of the reaction
volume.
15
[0203]
The compound (b-1) is used in an amount such that the molar
ratio of the compound (b-1) to all atoms of the transition metal
(M) in the metallocene compound (a), represented by [(b-1)/M],
is usually within a range from 0.01 to 50,000, preferably from
0. 05 to 10, 000. The compound (b-2) is used in an amount such that
20 the molar ratio of aluminum atoms of the compound (b-2) to all
atoms of the transition metal (M) in the metallocene compound (a),
represented by [(b-2)/M], is usually within a range from 10 to
50,000, preferablyfrom20to10,000. The compound (b-3) is used
in an amount such that the molar ratio of the compound (b-3) to
5
SF-3064
96
all atoms of the transition metal (M) in the metallocene compound
(a), represented by [(b-3)/M], is usually within a range from 1
to 20, preferably 1 from 15.
[0204]
In the present invention, the
ethylene/a-olefin/non-conjugated polyene copolymer can be
produced in either liquid phase polymerization processes such as
solution (dissolution) polymerization, suspension
polymerization, or vapor phase polymerization processes, and the
10 processes preferably include, but are not especially limited to,
the following steps of obtaining a polymerization-reaction
solution.
[0205]
The step of obtaining a polymerization-reaction solution
15 is a step to obtain a polymerization-reaction solution of the
ethylene/a-olefin/non-conjugated polyene copolymer by
polymerizing monomers consisting of ethylene (al), an a-olefin
(a2) having 3 to 20 carbon atoms, a non-conjugated polyene (a3),
and as necessary, a non-conjugated polyene (a4), by using an
20 aliphatic hydrocarbon as a polymerization solvent, in the presence
of a metallocene catalyst according to the present invention, the
metallocene catalyst containing a transition metal compound
wherein R13 and R14 bonding to Y1 in the aforementioned general
formula [All are preferably a phenyl group, or a phenyl group
SF-3064
97
substituted by an alkyl or halogen group, and R7 and R10 preferably
contain an alkyl substituent.
[0206]
When the concentration of the
5 ethylene/a-olefin/non-conjugated polyene copolymer in the
polymerization solvent exceeds the above range, the viscosity of
the polymerization solution too high to be stirred uniformly may
cause a difficulty in the polymerization reaction.
10
[0207]
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
15 methyl cyclopentane, aromatic hydrocarbons, such as benzene,
toluene, and xylene, halogenated hydrocarbons, such as ethylene
chloride, chlorobenzene, and dicloromethane, and they can be used
singly or in combination of the two or more kinds. Ole fins
themselves can also be used as a solvent. Among them, hexane is
20 preferable from the view point of the separation and purification
of the obtained ethylene/a-olefin/non-conjugated polyene
copolymer.
[0208]
Polymerization temperature is usually within a range from
SF-3064
98
-50 to +200°C, preferably from 0 to +200°C, more preferably from
+80 to +200°C, and a higher temperature (+80°C or more) is
preferable from the viewpoint of catalyst activity,
copolymerization ability, and productivity, although depending
5 on a molecular weight to be achieved and the polymerization
activity of a metallocene catalyst system to be used.
[0209]
Polymerization pressure is generally within a range from
atmospheric pressure to 10 MPa gauge pressure, preferably from
10 atmospheric pressure to 5 MPa gauge pressure, and polymerization
reaction can be carried out by any one of batchwise,
semi -continuous, and continuous methods. The polymerization can
also be carried out in two or more steps under different reaction
conditions. In the present invention, it is preferable to adopt,
15 among them, a step of carrying out copolymerization by feeding
monomers continuously into a reactor.
[0210]
Reaction time (average residence time in the case that
copolymerization is carried out continuously) varies depending
20 on conditions such as catalyst concentration and polymerization
temperature, but it is usually within a range from 0.5 minutes
to 5 hours, preferably 5 minutes to 3 hours.
[0211]
The molecular weight of the obtained
SF-3064
99
ethylene/a-olefin/non-conjugated polyene copolymer can also be
controlled by adding hydrogen in the polymerization system or by
changing the polymerization temperature. It can also be
controlled by the amount of the compound (b) to be used.
5 Specific examples of the compound include triisobutylaluminum,
methylaluminoxane, and diethyl zinc. When hydrogen is added, its
amount is suitably with in a range from about 0.001 to about 100
NL per 1 kg of olefin.
10
[0212]
The charged molar ratio of ethylene ( al) to the above
ex-olefin (a2), (ethylene (al) I a-olefin (a2)), is preferably with
in a range from 40/60 to 99.9/0.1, more preferably from 50/50 to
90/10, still more preferably from 55/45 to 85/15, and most
preferably from 55/45 to 78/22.
15 [0213]
The charged amount of the non-conjugated polyene (a3) is
usually within a range from 0. 07 to 10% by weight, preferably from
0.1% by weight to 8.0% by weight, more preferably from 0.5% by
weight to 5.0% by weight, with respect to 100% by weight of the
20 sum of ethylene (al), a-olefin (a2), and non-conjugated polyene
(a3) (amount of the total charged monomers).
(B) Organic peroxide
The resin composition of the present invention includes
organic peroxide (B) .
SF-3064
100
[0214]
Any organic peroxide that can act as a crosslinking agent
for the ethylene/a-olefin/non-conjugated polyene copolymer (A)
can be suitably used as the organic peroxide (B).
5 [0215]
Specific examples of the organic peroxide (B) include
dicumyl peroxide, di-tert-butyl
2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
peroxide,
10 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,
1,3-bis(tert-butylperoxyisopropyl)benzene,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis(tert-butylperoxy)valerate, peroxybenzoate,
p-chloroperoxybenzoate, 2,4-dichloroperoxybenzoate,
15 tert-butylperoxybenzoate, tert-butylperoxyisopropylcarbonate,
diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide,
and the like.
20
[0216]
From the view point of their reactivity, odor, and scorch
stability, bi-functional organic peroxides having two
intramolecular peroxide bonds ( -0-0-) are preferable among them,
such as 2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane,
2,5-dimethyl-2,5-di-(tert-butylperoxy)hexyne-3,
SF-3064
101
1,3-bis(tert-butylperoxyisopropyl)benzene,
1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,
n-butyl-4,4-bis(tert-butylperoxy)valerate, and in particular,
2,5-di-(tert-butylperoxy)hexane and
5 2,5-dimethyl-2,5-di-(tert-butylperoxy)hexane are most
preferable.
[0217]
The organic peroxide (B) can be used singly or in combination
of two or more kinds.
10 [0218]
The organic peroxide (B) is used preferably in an amount
with in a range of 0.1 to 5 parts by mass, preferably 0.5 to 5
parts by mass, and more preferably 0.5 to 4 parts by mass, with
respect to 100 parts by mass of the
15 ethylene/ cx-olefin/non-conj ugated polyene copolymer (A) . The
compounded amount of the organic peroxide (B) within the above
range is suitable because shaped articles and crosslinked shaped
articles obtained from the resin composition have no bloom on the
surface thereof and the rubber shaped articles exhibit excellent
20 crosslinking characteristics.
(C) Carbon black
The resin composition of the present invention may include
carbon black (C), as necessary. Examples of the carbon black (C)
include various carbon blacks such as SRF, GPF, FEF, MAF, HAF,
5
10
SF-3064
102
ISAF, SAF, FT, and MT, and surface treated carbon blacks which
are these carbon blacks surface-treated with an agent such as a
silane coupling agent.
[0219]
The compounded amount of the carbon black (C) in the resin
composition is not particularly limited as long as it is effective
in the present invention, but is preferably 10 to 300 parts by
mass, preferably 10 to 200 parts by mass, more preferably 10 to
120 parts by mass, still more preferably 10 to 100 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0220]
The resin composition of the present invention containing
such an amount of carbon black (C) is preferable because it can
15 provide crosslinked shaped articles having improved mechanical
properties such as tensile strength and abrasion resistance,
increase the hardness thereof without impairing other physical
properties thereof, and reduce the production cost thereof.
(D) Antioxidant
20 The resin composition of the present invention can contain
an antioxidant (D as necessary. When the resin composition of
the present invention contains an antioxidant (D), it can prolong
the life-time of products obtained therefrom. Antioxidants (D)
which may be used are conventionally well-known antioxidants, for
SF-30 64
103
example, amine-based antioxidants, phenol-based antioxidants,
and sulfur-based antioxidants.
[0221]
Specific examples of the antioxidant (D) include
5 aromatic-secondary-amine-based antioxidants such as
phenylbutylamine and N,N-di-2-naphthyl-p-phenylenediamine, and
4,4'-bis ( Oi, a-dimethylbenzyl)diphenylamine, amine-based
antioxidants such as 2,2,4-trimethyl-1,2-dihydroquinoline
polymer, phenol-based antioxidants such as dibutylhydroxytoluene
10 and
tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)hydrocinnamate]me
thane; thioether antioxidants such as
bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]su
lfide; dithiocarbamate-based antioxidants such as nickel
15 dibutyldithiocarbamate; zinc salts of
20
2-mercaptobenzoylimidazole and 2-mercaptobenzoimidazole;
sulfur-based antioxidants such as dilaurylthiodipropionate and
distearylthiodipropionate, and the like.
[0222]
These antioxidants (D) can be used singly or in combination
of two or more kinds.
[0223]
The compounded amount of the antioxidant (D) in the resin
composition of the present invention can be usually 5 parts by
SF-3064
104
mass or less, preferably 0. 5 to 5. 0 parts by mass, more preferably
0.5 to 4.5 parts by mass, still more preferably about 0.5 to 4.0
parts by mass, with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
5 [0224]
Specifically, in a second resin composition described later
which is suitably used for applications such as a turbocharger
hose, the compounded amount of the antioxidant (D) is, for example,
0.5 to 5.0 parts by mass, preferably 0.5 to 4.5 parts by mass,
10 more preferably 0. 5 to 4. 0 parts by mass, with respect to 100 parts
by mass of the ethylene/a-olefin/non-conjugated polyene
copolymer (A) .
[0225]
In a third resin composition described later which is
15 suitably used for applications such as sealing materials and lamp
seal packings, the content of the antioxidant (D) is usually 0
to 5 parts by mass, preferably 0.5 to 5.0 parts by mass, more
preferably 0.5 to 4.5 parts by mass, still more preferably 0.5
to 4.0 parts by mass, with respect to 100 parts by mass of the
20 ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0226]
In a fourth resin composition described later which is
suitably used for applications such as sliding members and wiper
blades, the compounded amount of the antioxidant (D) is usually
SF-3064
105
0 to 5 parts by mass, preferably 0.5 to 5.0 parts by mass, more
preferably 0.5 to 4.5 parts by mass, still more preferably 0.5
to 4.0 parts by mass, with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
5 [0227]
In a fifth resin composition described later which is
suitably used for applications such as water hoses, the compounded
amount of the antioxidant (D) is, although not particularly
limited as long as it is effective in the present invention, 5
10 parts by weight or less, preferably 0.5 to 5.0 parts by weight,
more preferably 0. 5 to 4. 5 parts by weight, still more preferably
0.5 to 4.0 parts by weight, with respect to 100 parts by mass of
ethylene/a-olefin/non-conjugated polyene copolymer (A).
15
[0228]
The above ranges are preferable because shaped articles and
crosslinked articles obtained from the resin composition of the
invention have excellent heat aging resistance.
(E) Softening agent
The resin composition of the present invention may contain
20 a softening agent (E), as necessary. Agents known as components
conventionally compounded in rubber, such as softening agents and
processing aids can be widely used as the softening agent (E) .
[0229]
Specific examples of the agent include:
5
10
SF-3064
106
petroleum-based softening agents such as paraffin-based
processed oils, naphthene-based processed oils, and aromatic
processed oils;
softening materials based on synthesized oils;
cooligomer of ethylene and a-olefin;
paraffin wax;
liquid paraffin;
white oil;
petrolatum;
softening agents based on coal tar such as coal tar and coal
tar pitch;
softening agents based on vegetable oils, such as castor
oil, cotton oil, linseed oil, canola oil, coconut oil, palm oil,
soya oil, groundnut oil, Japan wax, rosin, pine oil, dipentene,
15 pine tar, and tall oil;
substitutes (factices), such as black substitute, white
substitute, and candy substitute;
waxes, such as beeswax, carnauba wax, and lanolin;
fatty acids, fatty acid salts and esters, such as ricinoleic acid,
20 palmitic acid, stearic acid, linoleic acid, lauric acid, myristic
acid, barium stearate, calcium stearate, magnesium stearate, zinc
stearate, and zinc laurate;
ester-based plasticizers, such as dioctyl phthalate,
dioctyl adipate, and dioctyl sebacate;
5
SF-3064
107
coumarone-indene resin;
phenol-formaldehyde resin;
terpene-phenol resin;
polyterpene resin;
petroleum-based hydrocarbon resins, such as synthesized
polyterpene resins, aromatic hydrocarbon resins, aliphatic
hydrocarbon resins,
aliphatic/alicyclic
aliphatic
petroleum
ring hydrocarbon resins,
resins, aliphatic/aromatic
petroleum resins, hydrogenated modified alicyclic hydrocarbon
10 resins, hydrogenated hydrocarbon resins, liquid polybutene,
liquid polybutadiene, atactic polypropylene, and the like.
15
[0230]
Among them, petroleum-based softening agents,
phenol-formaldehyde resin, petroleum-based hydrocarbon resins
are preferable, and petroleum-based softening agents,
petroleum-based hydrocarbon resins are more preferable, and
petroleum-based softening agents are particularly preferable.
[0231]
Among the petroleum-based softening agents, preferable are
20 petroleum-based processed oils, among which paraffin-based
processed oils, naphthene-based processed oils, aromatic
processed oils are more preferable, and paraffin-based processed
oils are particularly preferable. Among the petroleum-based
hydrocarbon resins, aliphatic ring hydrocarbon resins are
SF-3064
108
preferable.
[0232]
Among these softening agents, paraffin-based processed oils
are particularly preferable.
5 [0233]
These softening agents can be used singly or in combination
of the two or more kinds.
[0234]
In the resin composition of the present invention, the
10 compounded amount of the softening agent (E) is not particularly
limited as long as it achieves a desired hardness, but it can be
usually less than 100 parts by mass and can be preferably 0 to
80 parts by mass, with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
15 [0235]
Specifically, for example in a second resin composition
described later which is suitably used for applications such as
a turbocharger hose, the content of the softening agent (E) is
preferably less than 20 parts by mass, more preferably 0 to 19
20 parts by mass, still more preferably 0 to 10 parts by mass, still
more preferably 0 to 5 parts by mass, and particularlypreferably
0.1 to 5 parts by mass, with respect to 100 parts by mass of
ethylene/a-olefin/non-conjugated polyene copolymer (A) .
[0236]
SF-3064
109 ' I'
In a third resin composition described later which is
suitably used for applications such as sealing materials and a
lamp seal packings, the content of the softening agent (E) is
usually within a range from 0 to 40 parts by mass, and is preferably
5 0 to 20 parts by mass, more preferably 0 to 10 parts by mass, still
more preferably 0 to 5 parts by mass, and particularly preferably
0.1 to 5 parts by mass, with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0237]
10 In a fourth resin composition described later which is
suitably used for applications such as sliding members and wiper
blades, the content of the softening agent (E) is usually within
a range from 5 to 50 parts by mass, and is preferably 10 to 50
parts by mass, more preferably 10 to 40 parts by mass, still
15 preferably 10 to 30 parts, with respect to 100 parts by mass of
the ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0238]
In a fifth resin composition described later which is
suitably used for applications such as water hoses, the compounded
20 softening agent (E) is usually in an amount of 80 parts by mass
or less, preferably 0 to 80 parts by mass, more preferably 0 to
70 parts by mass, still more preferably 0 to 50 parts by mass,
particularly preferably 0.1 to 50 parts by mass, with respect to
100 parts by mass of the ethylene/a-olefin/non-conjugated polyene
SF-3064
110
I
I
'
copolymer (A) .
[0239]
(F) Crosslinking aid
The resin composition of the present invention may contain
5 a crosslinking aid (F), as necessary. In the resin composition
of the present invention, the compounded amount of the
crosslinking aid (F) is not particularly limited, but it is usually
0 to 4. 0 parts by mass, and is preferably 0. 1 to 4. 0 parts by mass,
more preferably 0 to 3.5 parts by mass, more preferably 0 to 3.0
10 parts by mass, still more preferably 0.1 to 3.0 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
It is also desirable that the compounded amount of the crosslinking
aid (F) is preferably with in a range from 0.5 to 2 mols, more
15 preferably approximately equimolar, with respect to 1 mol of the
organic peroxide (B) .
[0240]
When a crosslinked shaped article is produced using a fifth
resin composition described later using a mandrel made of a resin,
20 a small amount of the crosslinking aid is preferably included in
consideration of suppression of the oxidative deterioration of
the resin mandrel and improvement of the mechanical properties
the article. In this case, the compounded amount of the (F)
crosslinking aid is usually 0 to 4.0 parts by mass, preferably
SF-3064
111
0.1 to 3.0 parts by mass in the fifth resin composition, with
respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0241]
5 Examples of the crosslinking aid (F) include: sulfur;
quinonedioxime compounds such as p-quinonedioxime; (met h)
acrylate compounds, such as polyfunctional monomers, such as
trimethylolpropane triacrylate and polyethylene glycol
dimethacrylate; allyl compounds such as diallylphthalate and
10 triallyl cyanurate; male imide compounds such as m-phenylene
bismaleimide; divinylbenzene, andthelike. Thecrosslinkingaid
(F) may be used singly or in combination of two or more kinds.
[0242]
(G) White filler
15 The resin composition of the present invention may include
a white filler (G), as necessary. White fillers except for silica
can be used as the white filler (G), and those conventionally known
as fillers can be used without any particular limitation, except
for a black filler such as carbon black and silica. Examples of
20 the white filler (G) include inorganic fillers such as activated
calcium carbonate, light calcium carbonate, heavy calcium
carbonate, fine powdered talc, talc, fine powdered silicic acid,
and clay. The white filler (G) may be used singly or in combination
of two or more kinds. The white filler (G) is suitably compounded
5
SF-3064
112
in a third resin composition described later which is suitably
used for applications such as sealing materials or lamp seal
packings.
[0243]
When contained in the resin composition, the white filler
(G) is used in an amount within a range from 10 to 250 parts by
mass, preferably 20 to 200 parts by mass, more preferably from
30 to 150 parts by mass, with respect to 100 parts by mass of the
ethylene/ex-olefin/non-conjugated polyene copolymer (A). The
10 white filler (G), when in a compounded amount within the above
range, is preferable because a shaped article and a crosslinked
shaped article obtained from the resin composition have excellent
mechanical strength and heat resistance, and a sealing material
obtained from the resin composition not only exhibits suitable
15 mechanical properties as packings, but also is excellent in
appearance and can be colored arbitrarily, as necessary. In
addition, adjusting the type and compounded amount of the white
filler (G) enables not only providing desired mechanical
properties such as tensile strength, tear strength, and hardness,
20 but also lowering the production cost of the crosslinked shaped
article.
[0244]
(H) Magnesium oxide
The resin composition of the present invention contains (H)
SF-3064
113
magnesium oxide, as necessary. When the resin composition of the
present invention contains magnesium oxide, a crosslinked shaped
article excellent in mechanical strength and heat aging resistance
can be produced. In addition, the copolymer (A) according to the
5 present invention is excellent in compatibility with magnesium
oxide, and therefore, a crosslinked shaped article containing
magnesium oxide can be suitably produced with a small amount of
a crosslinking agent.
10
[0245]
Examples of the magnesium oxide include, for example,
powdered magnesium oxide used for industrial use. Examples of
the magnesium oxide which can also be used include those
surface-treated with a fatty acid (for example, stearic acid,
hydroxystearic acid, higher fatty acid, alkali metal salt thereof),
15 resin acid (for example, abietic acid), fatty acid amide, ester
of fatty acid.
[0246]
Examples of the magnesium oxide include KYOWAMAG® 150,
KYOWAMAG® 30, MAGSARAT® 30 (surface treated product), from Kyowa
20 Chemical Industry Co., Ltd.
[0247]
The magnesium oxide (H) in the resin composition does not
have any particular limitation in its compounded amount as long
as it exerts the effect of the present invention, but it is
SF-3064
114
preferably compounded in a material such as a fifth resin
composition described later which is suitably used for
applications such as water hoses, and the compounding amount
thereof is usually 0.1 to 10 parts by mass, preferably 0.5 to 8
5 parts by mass, more preferably 1 to 8 parts by mass, with respect
to 100 parts by mass of the ethylene/a-olefin/non-conjugated
polyene copolymer (A) . When the compounded amount of magnesium
oxide is within this range, a crosslinked shaped article
particularly excellent in mechanical strength and heat aging
10 resistance can be produced.
[0248]
(I) Zinc oxide
The resin composition of the present invention may contain
zinc oxide (I) as a filler, but when it contains magnesium oxide
15 (H), it desirably is substantially free from zinc oxide (I), and
in particular in a fifth resin composition described later, it
is preferably substantially free from zinc oxide (I). When a
crosslinked shaped article, particularly a heat-resistant hose,
is produced through cross linking using an organic peroxide, with
20 zinc oxide included in the composition, the zinc oxide becomes
a zinc salt and will react with acid in cooling water flowing
through the hose, to form an insoluble component, potentially
causing clogging of the radiator.
[0249]
SF-3064
115
In the present invention, the amount of zinc oxide can be
measured as the total amount of zinc contained in the resin
composition in accordance with the Rubber products-Determination
of zinc contents-EDTA titrimetric method of JIS K 6232 (1998}.
5 The expression "is substantially free from zinc oxide" means that
when the total amount of zinc (total zinc amount} in the resin
composition of the present invention detected by the above JIS
method is converted to the amount of zinc oxide, the content of
the zinc oxide is less than 0.01 parts by mass with respect to
10 10 0 parts by mass of the ethylene/ cx-olefin/non-conj ugated polyene
copolymer (A} .
[0250]
Similarly, the amount of zinc oxide in the crosslinked
article can also be measured as the total amount of zinc contained
15 in the crosslinked product in accordance with the Rubber
products-Determination of zinc contents-EDTA titrimetric method
of JIS K 6232 (1998}. In the present invention, it is preferable
that the crosslinked article is substantially free from zinc
component derived from zinc oxide among others. The amount of
20 zinc in the crosslinked article detected by the above JIS method
is usually less than 0. 01 parts by mass with respect to 100 parts
by mass of the crosslinked article.
[0251]
In the present invention, "zinc oxide" refers to a solid
5
10
SF-3064
116
solution of metallic zinc and zinc oxide in a ratio of 1:1, and
zinc contained in rubber compositions or crosslinked articles is
usually attributed to that compounded as zinc oxide.
(J) Additional component
The resin composition of the present invention may contain
an additional component (J) depending on its desired properties
within the scope not to impair the object of the present invention.
[0252]
Examples of the additional component (J) include various
additive components conventionally added to the rubber
composition such as a filler, a foaming agent, an antioxidant,
a processing aid, surfactants, and a weathering agent. The resin
composition of the present invention may contain a resin component
other than the ethylene/a-olefin/non-conjugated polyene
15 copolymer (A) as the additional component (J), as necessary.
[0253]
Examples of the filler include inorganic fillers such as
silica, activated calcium carbonate, light calcium carbonate,
heavy calcium carbonate, fine powdered talc, talc, fine powder
20 silicic acid, and clay. These fillers can be in an amount of not
more than 300 parts by mass, preferably from 10 to 300 parts by
mass, more preferably from about 10 to 200 parts by mass, with
respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A). When
SF-30 64
117
the resin composition of the present invention contains such a
filler, a crosslinked shaped article can be obtained which has
improved mechanical properties, such as tensile strength, tear
strength, and abrasion resistance, and increased hardness without
5 impairing its other physical properties, and which enables
reducing its manufacturing cost.
10
15
[0254]
The resin composition according to the present invention
preferably contains an antioxidant from the viewpoint of
capability to prolong its material life.
antioxidant include:
Examples of the
stabilizing agents based on aromatic secondary amines, such as
phenylnaphthylamine, 4,4'-(a,a-dimethylbenzyl)diphenylamine,
N,N'-di-2-naphthyl-p-phenylenediamine;
stabilizing agents based on phenol, such as
2,6-di-t-butyl-4-methylphenol,
tetrakis-[methylene-3-(3',5'-di-t-butyl-4'-hydroxyphenyl)prop
ionate]methane;
stabilizing agent based on thioether such as
20 bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyl]su
lfide;
stabilizing agent based on benzoimidazole such as
2-mercaptobenzoimidazole;
stabilizing agent based on di thiocrabamates such as nickel
SF-3064
118
dibutyldithiocarbamate;
stabilizing agent based on quinoline such as a polymerized product
of 2,2,4-trimethyl-1,2-dihydroquinoline,
and the like. These may be used alone or in combination of two
5 or more kinds.
[0255]
The antioxidant can be used in an amount of, for example,
5 parts by mass or less, preferably 3 parts by mass or less, with
respect to 100 parts by mass of the
10 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
[0256]
The resin composition according to the present invention
also can appropriately contain, if necessary, various additives
that can be compounded in known rubber compositions.
15 [0257]
20
The resin composition according to the present invention
may contain a surfactant. Examples of the surfactant include
amines, such as di-n-butylamine, dicyclohexylamine,
monoethanolamine, triethanolamine, " Acting B" (manufactured by
YOSHITOMI PHARMACEUTICAL INDUSTRIES, LTD.) , "Acting SL"
(manufactured by YOSHITOMI PHARMACEUTICAL INDUSTRIES, LTD.),
polyethylene glycol, diethylene glycol, lecithin,
triallyltrimellitate, and compounds of zinc aliphatic or aromatic
carboxylate (example; "Struktol activator 73", "Struktol IB 531",
SF-3064
119
and "Struktol FA 541", manufactured by Schill+Seilacher GmbH),
"ZEONET ZP" (manufactured by ZEON CORPORATION),
octadecyltrimethylammonium bromide, synthesized hydrotalcite,
and special quaternary ammonium compounds (example; "Arquad 2HF"
5 (manufactured by LION AKZO Co., Ltd.), and the like.
[0258]
When the resin composition of the present invention contains
a surfactant, the compounded amount of the surfactant is, for
example, about 0.2 to 10 parts by mass, preferably about 0.3 to
10 5 parts by mass, more preferably about 0.5 to 4 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A). The
surfactant can be appropriately selected depending on its use,
and it can be used singly or in combination of the two or more
15 kinds.
[0259]
The resin composition of the present invention may contain
a pseudo-gel inhibitor. Examples of the pseudo-gel inhibitor
include, for example, "NHM-007" (manufactured by Mitsui Chemicals,
20 Inc.).
[0260]
When the resin composition of the present invention contains
a pseudo-gel inhibitor, the compounded amount thereof is within
a range usually from 0.1 to 15 parts by mass, and preferably from
5
SF-3064
120
0. 5 to 12 parts by mass, more preferably 1. 0 to 10 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
[0261]
The resin composition of the present invention may further
contain an additional additive, as necessary. Examples of the
additional additive include agents such as heat stabilizers,
weathering stabilizers, antistatic agents, colorants, lubricants,
and thickeners.
10 [0262]
The resin composition of the present invention may contain
an additional resin component other than the
ethylene/a-olefin/non-conjugated polyene copolymer (A), as
necessary. Examples of the additional resin component include,
15 but are not particularly limited to, polyolefin resins.
[0263]
The resin composition of the present invention containing
a polyolefin resin enables controlling the hardness of products
from the composition and decreasing its compound viscosity at
20 processing temperature, resulting in further improvement of its
processabili ty. It is also preferable because it can be treated
as a thermoplastic elastomer, resulting in its easier handling
property and more choices of kneading methodology.
[0264]
5
SF-3064
121
The polyolefin resin having a number-average molecular
weight, as measured by GPC, of 10,000 or more in terms of
polystyrene standard is suitably used.
[0265]
Examples of the polyolefin resin include an a-olefin
homopolymer and an a-olefin copolymer. Examples of the a-olefin
homopolymer include polyethylene, polypropylene, and the like,
and examples of the a-olefin copolymer include a copolymer of
ethylene/ a-olefin having 3 to 20 carbon atoms and a copolymer of
10 ethylene/a-olefin having 3 to 20 carbon atoms/non-conjugated
polyene (which is, however, different from the
ethylene/a-olefin/non-conjugated polyene copolymer according to
the present invention) . Examples of the copolymer of
ethylene/a-olefin having 3 to 20 carbon atoms include
15 ethylene-propylene rubber (EPR), propylene-ethylene rubber (PER),
ethylene-butene rubber (EBR), ethylene-octene rubber (EOR), and
the like.
[0266]
Examples of the copolymer of ethylene/ a-olefin having 3 to
20 20 carbon atoms/non-conjugated polyene (which is, however,
different from the ethylene/a-olefin/non-conjugated polyene
copolymer according to the invention) include ethylene-propylene
terpolymer (EPT), ethylene-butene terpolymer (EBT), and the like.
[0267]
SF-3064
122
Among these polyolefin resins, polyethylene,
ethylene/a-olefin copolymer, and polypropylene are preferable.
[0268]
The polyolefin resins can be used singly or in combination
5 of the two or more kinds.
[0269]
When the resin composition of the present invention contains
the polyolefin resin, the content of the polyolefin resin is within
a range, for example, from 1 to 100 parts by mass, preferably from
10 5 to 80 parts by mass, more preferably from 10 to 50 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A) . The
resin composition within the above ranges enables controlling the
hardness of products from the composition and decreasing its
15 compound viscosity at processing temperature, resulting in
further improvement of its processabili ty. It is also preferable
because it can be treated as a thermoplastic elastomer, resulting
in its easier handling property and more choices of kneading
methodology.
20 [ 02 7 0 l

The resin composition of the present invention can be
prepared by compounding the respective components of the
above-mentioned resin composition, that is, the
SF-3064
123
ethylene/a-olefin/non-conjugated polyene copolymer (A) and the
organic peroxide (B), both of which are essential components, and
as necessary, one or more selected from the group consisting of
the carbon black (C), the antioxidant (D), the softener (E), the
5 cross linking aid (F), the white filler (G), and the magnesium oxide
(H), and an additional component (J).
[0271]
Methods of preparing the resin composition include, but are
not particularly limited to, a method, such as a method of mixing
10 each component contained in the resin composition by using a
conventionally known kneading machine such as a mixer, a kneader,
and a roll, and a method of preparing a solution in which each
component contained in the resin composition is dissolved or
dispersed, followed by removing the solvent.
15 [0272]

A first resin composition of the present invention contains
100 parts by mass of the ethylene/a-olefin/non-conjugated polyene
copolymer (A) and 0. 1 to 5 parts by mass of the organic peroxide
20 (B). The content of the organic peroxide (B) which is preferable
for the ethylene/a-olefin/non-conjugated polyene copolymer (A)
is as described above in the description on the organic peroxide
(B) •
[0273]
SF-3064
124
It is preferable that the first resin composition of the
present invention contains an ethylene/a-olefin/non-conjugated
polyene copolymer (A) which preferably has an intrinsic viscosity
[~] of 1.0 to 4.0 dl/g measured in decalin at 135'C. It is also
5 preferable that the nonconjugated polyene (a3) constituting the
ethylene/a-olefin/non-conjugated polyene copolymer (A) contains
5-vinyl-2-norbornene (VNB).
[0274]
The first resin composition of the present invention
10 exhibits excellent crosslinking properties owing to containing
the above-mentioned ethylene/a-olefin/non-conjugated polyene
copolymer (A) and the organic peroxide (B), and it can be suitably
used for producing a crosslinked shaped article which can be used
for various applications.
15 [ 02 7 5 J
The first resin composition of the present invention may
contain a component other than the
ethylene/a-olefin/non-conjugated polyene copolymer (A) and the
organic peroxide (B) without any limitation, depending on the
20 desired properties of the resin composition.
[0276]
Examples of the component other than the
ethylene/a-olefin/non-conjugated polyene copolymer (A) and the
organic peroxide (B) include the respective above-mentioned
5
SF-3064
125
components, and the preferable compounded amounts of which are
as in the description on the respective components.
[0277]
Production of crosslinked shaped article
The crosslinked shaped article composed of the first resin
composition of the present invention can be obtained through
shaping as necessary, and cross linking the first resin composition.
The crosslinking may or may not use molds. When molds are not
used, the first resin composition is normally shaped and
10 crosslinked continuously.
[0278]
Processes of crosslinking the resin composition include,
for example: (a) a process of preforming the resin composition
into a desired shape by a molding method such as extrusion molding,
15 press molding, and injection molding, and by roll processing, and
heating the composition simultaneously with preforming it or after
introducing it into a crosslinking tub; and (b) a process of
preforming the resin composition in the same manner as described
above and then irradiating it with a radiation such as an electron
20 beam.
[0279]
In the process (a), heating triggers a cross linking reaction
by the crosslinking agent (organic peroxide) in the resin
composition, which reaction yields a crosslinked product. In the
SF-3064
126
process (b), the electron beam triggers a crosslinking reaction,
which yields a crosslinked product. In the process (b), the
preformed resin composition is usually irradiated with an electron
beam having an energy of 0.1 to 10 MeV so that the dose absorbed
5 into the resin composition may be usually 0. 5 to 36 Mrads,
preferably 0.5 to 20 Mrads, and more preferably 1 to 10 Mrads.
[0280]
Application
The first resin composition of the present invention and
10 crosslinked shaped articles obtained from the resin composition
can be used for various applications, and are used, without any
limitation, in conventional applications as a composition or
crosslinked shaped article having rubber properties.
[0281]
15
20
A second resin composition of the present invention contains,
among the above-mentioned components:
(A) 100 parts by mass of the ethylene/a-olefin/non-conjugated
polyene copolymer;
(B) 0.1 to 5 parts by mass of the organic peroxide,
(C) 10 to 300 parts by mass of the carbon black; and
(D) 0.5 to 5 parts by mass of the antioxidant.
[0282]
In other words, the second resin composition of the present
SF-3064
127
invention is a first resin composition, which further contains:
(C) 10 to 300 parts by mass of the carbon black; and
(D) 0.5 to 5 parts by mass of the antioxidant,
with respect to 100 parts by mass of
5 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
[0283]
the
Such a second resin composition of the present invention
preferably contains a softening agent (E) in an amount of less
than 20 parts by mass with respect to 100 parts by mass of the
10 ethylene/a-olefin/non-conjugated polyene copolymer (A), and also
preferably contains 0 to 4 parts by mass of a crosslinking aid
(F) ' with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A). The
softening agent (E) and the crosslinking aid (F) may be used singly,
15 or in a combination thereof.
[0284]
The second resin composition of the present invention also
can be prepared through compounding, according to its desired
properties, the ethylene/a-olefin/non-conjugated polyene
20 copolymer (A), the organic peroxide (B), carbon black (C), and
the antioxidant (D), and components to be compounded as necessary,
that is, the softener (E), the crosslinking aid (F), and the
additional component described above. The compounded amount of
these components is as described above in the description on the
SF-3064
128
respective components.
[0285]
Crosslinked shaped articles composed of the second resin
composition can be produced through crosslinking and shaping in
5 the same manner as in the first resin composition described above.
[0286]
Application
The second resin composition of the present invention is
a resin composition suitable for producing crosslinked shaped
10 articles.
[0287]
The second resin composition of the present invention
enables producing crosslinked shaped articles excellent in heat
aging resistance and fatigue resistance. Crosslinked shaped
15 articles obtained by shaping and crosslinking the second resin
composition of the present invention exhibit excellent heat aging
resistance and fatigue resistance and can be suitably used also
for use at high temperatures, and for example, as horses for
motorbikes, industrial machinery, construction machinery,
20 agricultural machinery, and particularly as turbocharger hoses
among others.
[0288]
The second resin composition and its crosslinked shaped
article of the present invention are suitably used for automotive
SF-3064
129
interior and exterior parts and applications requiring heat
resistance, and for example, hoses requiring heat resistance such
as turbocharger hoses, brake reservoir hoses, and radiator hoses.
Although the hose of the present invention does not have any
5 particular limitation in its use, it is preferably a hose used
in any one of applications for automobiles, motorbikes, industrial
machinery, construction machinery, and agricultural machinery,
and is more preferably a hose used as a turbocharger hose for
automobiles.

CLAIMS
1. A resin composition comprising
(A) 100 parts by mass of an ethylene/~-olefin/non-conjugated
polyene copolymer and
(B) 0.1 to 5 parts by mass of an organic peroxide,
wherein the ethylene/~-olefin/non-conjugated polyene copolymer
(A) comprises structural units derived from ethylene (al), an
a-olefin (a2) having 3 to 20 carbon atoms, and a non-conjugated
polyene ( a3) comprising intramolecularly two or more partial
10 structures in total selected from the group consisting of
structures represented by the following general formulae (I) and
(II) ,
[Chern. 1]
.. (!)
15 and satisfies the following requirements from (i) to (v) :
(i) a molar ratio of ethylene/a-olefin is from 40/60 to 99.9
I 0.1;
(ii) a weight fraction of the structural unit derived from the
non-conjugated polyene (a3) is from 0.07% by weight to 10% by
20 weight in 100% by weight of the ethylene/~-olefin/non-conjugated
polyene copolymer;
(iii) a weight-average molecular weight (Mw) of the
ethylene/a-olefin/non-conjugated polyene copolymer, a weight
5
SF-30 64
191
fraction of the structural unit derived from the non-conjugated
polyene (a3) (weight fraction of (a3) ), and a molecular weight
of the non-conjugated polyene (a3) (molecular weight of (a3))
satisfy the following Formula (1),
4.5 ~ Mw x weight fraction of (a3) I 100 I molecular weight
of (a3) ~ 40; Formula (1)
( i v) a ratio of a complex viscosity I)* 10 " 0. 11 ( Pa ·sec) at a
frequency of w= 0.1 rad/s to a complex viscosity !)* 10 " 1001 (Pa·sec)
at a frequency of w = 100 rad/s, both obtained by linear
10 viscoelastic measurement (190°C) by using a rheometer,
15
represented by P (I)* lo" 0. 11 /I)* 10 " 1001 ), an intrinsic viscosity
represented by [I)], and the weight fraction of the structural unit
derived from the non-conjugated polyene (a3) (weight fraction of
(a3)) satisfy the following Formula (2),
P I ( [!)] 2
•
9
) ~ weight fraction of (a3) x 6; Formula (2)
and
(v) a number of long-chain branches per 1000 carbon atoms
(LCB1ooocl and a natural logarithmic number of the weight-average
molecular weight (Mw) represented by [Ln (Mw) ] , obtained by using
20 30-GPC, satisfy the following Formula (3),
LCB1oooc ~ 1 - 0. 07 x Ln (Mw) . Formula (3)
2. The resin composition according to claim 1, wherein the
ethylene/a-olefin/non-conjugated polyene copolymer (A) has an
SF-3064
192
intrinsic viscosity [~] of 1.0 to 4.0 d1/g which is measured in
decalin at 135°C.
3. The resin composition according to claim 1 or 2, wherein
5 the non-conjugated polyene (a3) comprises 5-vinyl-2-norbornene
(VNB).
4. The resin composition according to any one of claims 1 to
3, comprising
10 (C) 10 to 300 parts by mass of carbon black, and
(D) 0.5 to 5 parts by mass of antioxidant,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
15 5. The resin composition according to any one of claims 1 to
4, comprising
(E) a softening agent in an amount of less than 20 parts by mass,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
20
6. The resin composition according to any one of claims 1 to
5, comprising
(F) a crosslinking aid in an amount of 0 to 4 parts by mass,
with respect to 100 parts by mass of the
5
10
SF-3064
193
ethylene/a-olefin/non-conjugated polyene copolymer (A).
7. A crosslinked shaped article obtained by crosslinking the
resin composition according to any one of claims 1 to 6.
8. A process for producing a crosslinked shaped article
comprising a step of crosslinking the resin composition according
to any one of claims 1 to 6.
9. A hose comprising a layer formed by crosslinking the resin
composition according to any one of claims 1 to 6.
10. The hose according to claim 9, which is used in any one of
applications for an automobile, a motorbike, industrial machinery,
15 construction machinery, and agricultural machinery.
20
11. The hose according to claim 9, which is used for a
turbocharger hose for an automobile.
12. A process for producing a hose, comprising a step of shaping
and crosslinking the resin composition according to any one of
claims 1 to 6 to form a layer of a crosslinked shaped article.
13. The resin composition according to any one of claims 1 to
5
10
SF-3064
194
3, comprising
(G) 10 to 250 parts by mass of a white filler, except for silica,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
14. The resin composition according to claim 13, comprising
(E) 0 to 40 parts by mass of a softening agent,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
15. The resin composition according to claim 13 or 14,
comprising
(D) 0 to 5 parts by mass of an antioxidant, and
(F) 0 to 4 parts by mass of a crosslinking aid,
15 with respect to 100 parts by mass of the
20
ethylene/a-olefin/non-conjugated polyene copolymer (A).
16. A crosslinked shaped article obtained by crosslinking the
resin composition according to any one of claims 13 to 15.
17. A process for producing a crosslinked shaped article,
comprising a step of crosslinking the resin composition according
to any one of claims 13 to 15.
SF-3064
195
18. A sealing material using the crosslinked shaped article
according to claim 16.
19. The sealing material according to claim 18, which is used
5 in any one of applications for an automobile, a motorbike,
industrial machinery, construction machinery, and agricultural
machinery.
20. The sealing material according to claim 18 or 19, which is
10 used for a lamp seal packing or a packing for a meter.
15
20
21. The resin composition according to any one of claims 1 to
3, comprising:
(C) 10 to 300 parts by mass of carbon black;
(E) 5 to 50 parts by mass of a softening agent; and
(F) 0.1 to 4 parts by mass of a crosslinking aid,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A) .
22. The resin composition according to claim 21, comprising:
(D) 0 to 5 parts by mass of an antioxidant,
with respect to 100 parts by mass of the
ethylene/a-olefin/non-conjugated polyene copolymer (A).
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23. A crosslinked shaped article obtained by crosslinking the
resin composition according to claim 21 or 22.
24. A process for producing a crosslinked shaped article,
5 comprising a step of crosslinking the resin composition according
to any one of claims 21 to 23.
10
15
20
25. A sliding member using the crosslinked shaped article
according to claim 23.
26. A sliding member according to claim 25, which is used in
any one of applications for an automobile, a motorbike, industrial
machinery, construction machinery, and agricultural machinery.
27. A wiper blade using the crosslinked shaped article according
to claim 23.
28. The resin composition according to any one of claims 1 to
3, which comprises
(H) 0.1 to 10 parts by mass of magnesium oxide, with respect
to 100 parts by mass of the ethylene/a-olefin/non-conjugated
polyene copolymer (A),
wherein the resin composition is substantially free from zinc
oxide (I).
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29. The resin composition according to claim 28, comprising the
antioxidant (D) in an amount of 5 parts by mass or less, with
respect to 100 parts by mass of the
5 ethylene/a-olefin/nonconjugated polyene copolymer (A).
30. The resin composition according to claim 28 or 29,
comprising the softening agent (E) in an amount of 80 parts by
mass or less with respect to 100 parts by mass of the
10 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
31. The resin composition according to any one of claims 28 to
30, comprising the crosslinking aid (F) in an amount of 4 parts
by mass or less with respect to 100 parts by mass of the
15 ethylene/a-olefin/non-conjugated polyene copolymer (A) .
20
32. A crosslinked shaped article obtained by crosslinking the
resin composition according to any one of claims 28 to 31.
33. A process for producing a crosslinked shaped article,
comprising a step of crosslinking the resin composition according
to any one of claims 28 to 31.
34. A rubber hose comprising a layer formed by cross linking the
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resin composition according to any one of claims 28 to 31 by using
a resin mandrel.
35. The rubber hose according to claim 34, wherein the resin
5 constituting the resin mandrel is a 4-methyl-1-pentene polymer.
10
15
20
3 6. A process for producing a rubber hose comprising a step of
crosslinking and shaping the resin composition according to any
one of claims 28 to 31 by using a resin mandrel.
37. The process for producing a rubber hose according to claim
36, wherein a resin constituting the resin mandrel is a
4-methyl-1-pentene polymer.
38. The crosslinked shaped article according to claim 32, which
is used in any one of applications for an automobile, a motorbike,
industrial machinery, construction machinery, and agricultural
machinery.
39. The crosslinked shaped article according to claim 32, which
is used in an application for a water hose for an automobile.
40. The rubber hose according to claim 34 or 35, which is used
in any one of applications for an automobile, a motorbike,
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industrial machinery, construction machinery, and agricultural
machinery.
41. The rubber hose according to claim 34 or 35, which is used
5 for a water hose for an automobile.