DESCRIPTION
TITLE OF INVENTION:
ETHYLENE COPOLYMER, COMPOSITION INCLUDING THE COPOLYMER, AND
SHAPED ARTICLE AND FILM OR SHEET FORMED FROM THE ETHYLENE
5 COPOLYMER OR THE COMPOSITION
TECHNICAL FIELD
[OOOl]
The present invention relates to ethylene copolymers
which have excellent rubber elasticity even without being
10 crosslinked and exhibit excellent shaping processability and
mechanical characteristics even when combined with large
amounts of inorganic fillers and plasticizers such as process
oils, as well as to compositions including the copolymers, and
shaped articles and films or sheets formed from the ethylene
15 copolymers or the compositions.
BACKGROUND ART
[0002]
Because of the absence of unsaturated bonds in the main
chain, ethy1ene.a-olefin copolymers and
20 ethy1ene.a-olefin.non-conjugated diene copolymers outperform
diene rubbers in terms of weather resistance, heat resistance
and ozone resistance and are therefore widely used in products
such as automobile industrial parts, industrial rubber
products, electrical insulating materials, civil engineering
and building articles, and rubber products including
rubber-coated fabrics.
[0003]
In particular, ethy1ene.a-olefin.non-conjugated
5 polyene copolymers have found a wide use because of the fact
that the double bonds derived fromthe non-conjugated polyenes
can participate in crosslinking reactions and the copolymers,
byundergoingthe crosslinkingreactions, canachieve a further
increase in strength and rubber elasticity of rubber products.
10 [0004]
The production of rubber products using
ethy1ene.a-olefin,non-conjugated diene copolymers usually
involves the addition of large amounts of inorganic fillers
such as carbon blacks, calcium carbonate and talcs and
15 plasticizers such as process oils.
[0005]
However, the addition of large amounts of inorganic
fillers such as carbon blacks, calcium carbonate and talcs and
plasticizers such as process oils results in a marked decrease
20 in shaping processability such as rolling processability and
extrusion processability as well as in a marked deterioration
in mechanical characteristics and rubber elasticity of rubber
products obtained by crosslinking.
[0006]
For example, one approachrihichhas b e e n p r o p o s e d i n o r d e r
t o obtain ethy1ene.a-olefin.non-conjugated diene copolymers
with e x c e l l e n t f i l l a b i l i t y is t o use an
ethy1ene.a-olefin.non-conjugateddiene copolymerwhich has an
5 i n t r i n s i c v i s c o s i t y [q] measured a t 135'C i n d e c a l i n solvent
of 3.7 t o 4 . 1 d l / g (Patent L i t e r a t u r e 1: JP-A-H06-1893), or
t o use an ethy1ene.a-olefin.non-conjugated diene copolymer
having high molecular weight such as a copolymer (A) which
includes ethylene, an a - o l e f i n of 6 t o 12 carbon atoms and a
10 c y c l i c non-conjugated diene and has a polystyrene equivalent
mass average molecular weight (Mw) i n the range of 450,000 t o
3,000,000 oracopolymer (B) whichincludes e t h y l e n e , propylene,
an a - o l e f i n of 6 t o 12 carbon atoms and a c y c l i c non-conjugated
diene and has a s i m i l a r molecular weight (Patent L i t e r a t u r e
15 2: JP-A-H09-151283).
[0007]
However, even t h e use of t h e
ethylene~a-olefin~non-conjugateddienecopolymerdisclosedin
Patent L i t e r a t u r e 1 or Patent L i t e r a t u r e 2 (with an i n t r i n s i c
20 v i s c o s i t y [q] of about4 d l / g ) does not a l l o w t h e d e s i r e d r u b b e r
e l a s t i c i t y t o be e x h i b i t e d without c r o s s l i n k i n g and thus it
is d i f f i c u l t f o r such a copolymer t o be used i n a p p l i c a t i o n s
where the copolymer is f i l l e d w i t h s i g n i f i c a n t l y l a r g e amounts
of a d d i t i v e s .
[0008]
Although Patent L i t e r a t u r e 2 does not d i s c l o s e any
i n t r i n s i c v i s c o s i t y [q] values, EP98A, product name,
manufactured by JSR Corporation t h a t is described i n
5 Comparative Example 3 [an
ethylene/propylene/5-ethylidene-2-norbornen random
copolymer having e t h y l e n e c o n t e n t : 75.9 mol%, propylene
content: 22.6 mol%, ENB content: 1.16 mol%, Mw 1,179,000 and
Mw/Mn 4.4, a n d c o n t a i n i n g 7 5 p a r t s bymass of a p a r a f f i n p r o c e s s
10 o i l as anextender o i l ] was obtainedandtheintrinsicviscosity
[q] of t h e random copolymer was measured a f t e r the removal of
the extender o i l , t h e measurement r e s u l t i n g i n 4.45 d l / g .
[0009]
In one shaping method, a f i l m or sheet having a constant
15 thickness is continuously formed by r o l l i n g a thermoplastic
polymer through two or more r o l l s (a calendering method).
[OOlO]
The calendering method achieves a h i g h e r output than by
a u s u a l e x t r u s i o n method and thus allows films or s h e e t s t o
20 be produced a t low c o s t . Conventionally, the calendering
method most o f t e n i n v o l v e s p o l y v i n y l c h l o r i d e containing
v a r i o u s p l a s t i c i z e r s , a n d i s u s e d i n m a s s productionof a r t i c l e s
such as l e a t h e r s , s h e e t s and f i l m s . In r e c e n t years, due t o
t h e VOC problem a s s o c i a t e d w i t h p o l y v i n y l c h l o r i d e and a l s o
because the i n c i n e r a t i o n of wastes c a u s e s p r o b l e m a t i c
generation of gas, t h e r e has been a demand t h a t the m a t e r i a l
be replaced by a l t e r n a t i v e s .
[OOll]
M a t e r i a l s i n c l u d i n g o l e f i n polymers have been regarded
as promising a l t e r n a t i v e s t o polyvinyl c h l o r i d e . However,
highly c r y s t a l l i n e m a t e r i a l s such as high-density
polyethylenes and polypropylenes have problems i n f l e x i b i l i t y
a n d a l s o exhibitadrasticchangeinviscositywhenbeingmolten.
10 Thus, t h e s e m a t e r i a l s have problems such a s t h a t t h e s u i t a b l e
range i n which calendering is f e a s i b l e is l i m i t e d , t h a t t h e
m a t e r i a l s e x h i b i t poor r e l e a s a b i l i t y from t h e calender r o l l s ,
and t h a t t h e calendered products have low s u r f a c e smoothness
and tend t o be nonuniform i n t h i c k n e s s .
15 [0012]
On t h e other hand, a - o l e f i n copolymers, which a r e low
c r y s t a l l i n e o l e f i n m a t e r i a l s , have very low calendering
p r o p e r t i e s due t o such problems as poor r e l e a s e and engagement
f a i l u r e . The term poor r e l e a s e means t h a t t h e r e s i n is not
20 separated f r o m t h e r o l l s and becomes t w i s t e d around t h e r o l l s .
The term engagement f a i l u r e means t h a t t h e r e s i n is not engaged
between the r o l l s and t h e bank continues t o i n c r e a s e i t s s i z e .
These problems tend t o be worsened when t h e m a t e r i a l s a r e
formulated t o become more f l e x i b l e by the a d d i t i o n of
p l a s t i c i z e r s such a s o i l s .
[0013]
Many s o l u t i o n s t o t h e above problems have been proposed.
For example, Patent L i t e r a t u r e 3 d i s c l o s e s a blend s u i t e d f o r
5 calendering which includes a broad molecular weight
d i s t r i b u t i o n polypropylene. Patent L i t e r a t u r e 4 d i s c l o s e s a
calendering method which involves a composition including a
propylene/ethylene random copolymer and a propylene/ethylene
block copolymer. Patent L i t e r a t u r e 5 proposes a s o f t
10 s y n d i o t a c t i c p o l y p r o p y l e n e compositionbased on a s y n d i o t a c t i c
propylene polymer and i n c l u d i n g a s y n d i o t a c t i c s t r u c t u r e
propylene.ethylene copolymer, an amorphous a - o l e f i n copolymer,
an e t h y 1 e n e . a - o l e f i n copolymer and an i s o t a c t i c propylene
polymer.
15 [0014]
I n o r d e r t o improve t h e r e l e a s a b i l i t y f r o m c a l e n d e r r o l l s ,
Patent L i t e r a t u r e 6 d i s c l o s e s a composition including a
polypropylene r e s i n composition and an a l i p h a t i c
monocarboxylic acid metal s a l t . However, no f i l m s with
20 s u f f i c i e n t performance have been obtained.
CITATION LIST
PATENT LITERATURE
[0015]
Patent L i t e r a t u r e 1: JP-A-H06-1893
Patent Literature 2: JP-A-H09-151283
Patent Literature 3: JP-A-H08-67778
Patent Literature 4: JP-A-S53-119946
Patent Literature 5: JP-A-2001-172448
Patent Literature 6: JP-A-H08-319382
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0016]
Objects of the present invention are to obtain ethylene
10 copolymers which have excellent rubber elasticity even without
being crosslinked and maintain sufficient shaping
processability even when filled with significantly large
amounts of additives, to provide crosslinked products having
good mechanical properties, to provide films or sheets having
15 flexibility and high stretchability, and to provide methods
capable of producing with good productivity films or sheets
having flexibility and high stretchability.
SOLUTION TO PROBLEM
[0017]
The present invention is directed to an ethylene
copolymer (X) that has the characteristics (1) to (3) described
below and includes structural units derived from a component
[A], a component [B] and a component [C] which are ethylene
[A], ana-olefinof 3to 20 carbonatoms [B] andapolyene and/or
a c y c l i c o l e f i n [C], a s w e l l a s d i r e c t e d t o a n e t h y l e n e c o p o l y m e r
composition including t h e copolymer (X), a f i l m or sheet
i n c l u d i n g t h e copolymer (X), and a f i l m or s h e e t formed from
t h e composition.
(1) The content of s t r u c t u r a l u n i t s derived from t h e
ethylene [A] is i n t h e range of 50 t o 90 mol% i n 100 mol% of
a l l t h e s t r u c t u r a l u n i t s i n t h e copolymer (X);
(2) t h e content of s t r u c t u r a l u n i t s derived f r o m a t l e a s t
one polyene and/or t h e c y c l i c o l e f i n [C] is i n t h e range of
10 1.0 t o 5.0 mol% i n 100 mol% of a l l t h e s t r u c t u r a l u n i t s i n t h e
copolymer (X) ; and
(3) t h e i n t r i n s i c v i s c o s i t y [q] o f t h e e t h y l e n e copolymer
(X) a s measured a t 135°C i n a d e c a l i n s o l u t i o n is i n t h e range
of 7.8 t o 13.0 d l / g .
15 [0018]
In t e r m s of f l e x i b i l i t y and s t r e t c h a b i l i t y , it is
p r e f e r a b l e t h a t t h e durometer type A hardness of t h e f i l m or
sheet measured by a method s p e c i f i e d i n JIS K 6253 be 10 t o
80.
20 [0019]
In o r d e r t o reduce t h e r e s i d u a l s t r a i n a f t e r s t r e t c h i n g ,
it is p r e f e r a b l e t h a t a t l e a s t p a r t of t h e f i l m o r sheet have
been c r o s s l i n k e d , i n p a r t i c u l a r , c r o s s l i n k e d by e l e c t r o n beam
i r r a d i a t i o n .
[0020]
In t e r m s of c r o s s l i n k i n g r e a c t i v i t y , it is p r e f e r a b l e
t h a t t h e component [C] be 5-ethylidene-2-norbornene (ENB).
[0021]
In t e r m s o f m e c h a n i c a l c h a r a c t e r i s t i c s and shaping
p r o c e s s a b i l i t y , it is p r e f e r a b l e t h a t t h e component [B] be
propylene o r 1-butene.
[00221
The p r e s e n t i n v e n t i o n is a l s o directed t o an e t h y l e n e
10 copolymer composition i n c l u d i n g 100 p a r t s by mass of t h e
e t h y l e n e copolymer ( X ) and 100 t o 500 p a r t s by mass of a
p l a s t i c i z e r ( Y ) .
[0023]
In terms o f r u b b e r e l a s t i c i t y i n a n u n c r o s s l i n k e d state,
15 it is p r e f e r a b l e t h a t t h e e t h y l e n e copolymer composition have
a l o s s t a n g e n t ( t a n 6) at 190°C and 0.01 rad/sec of 0 . 1 t o 1 . 0 .
ADVANTAGEOUS EFFECTS OF INVENTION
[0024]
The e t h y l e n e copolymer (X) according t o t h e i n v e n t i o n h a s
20 e x c e l l e n t mechanical c h a r a c t e r i s t i c s by i t s e l f r e g a r d l e s s of
whether o r not t h e copolymer is c r o s s l i n k e d . F u r t h e r , t h e
i n v e n t i v e e t h y l e n e copolymer ( X ) can be combined with l a r g e
amounts of p l a s t i c i z e r s and o t h e r a d d i t i v e s p e r 100 p a r t s by
mass o f t h e e t h y l e n e copolymer ( X ) . Even i n t h e casewhere such
a d d i t i v e s a r e added i n s i g n i f i c a n t l y l a r g e amounts exceeding
700 p a r t s by mass i n t o t a l , t h e r e s u l t a n t composition shows
good shaping p r o c e s s a b i l i t y and can e x h i b i t e x c e l l e n t
mechanical c h a r a c t e r i s t i c s and rubber e l a s t i c i t y r e g a r d l e s s
5 of whether o r not it is c r o s s l i n k e d . Thus, t h e i n v e n t i o n can
p r o v i d e novel m a t e r i a l s .
[0025]
The f i l m o r s h e e t produced using t h e i n v e n t i v e e t h y l e n e
copolymer ( X ) has f l e x i b i l i t y and high s t r e t c h a b i l i t y .
10 [0026]
In p a r t i c u l a r , f i l m s or s h e e t s o b t a i n e d by e l e c t r o n beam
c r o s s l i n k i n g e x h i b i t a markedly small r e s i d u a l s t r a i n a f t e r
t h e f i l m s o r s h e e t s a r e s t r e t c h e d .
[0027]
F u r t h e r , t h e i n v e n t i v e e t h y l e n e copolymer (X) and t h e
e t h y l e n e copolymer composition i n c l u d i n g t h e e t h y l e n e
copolymer ( X ) can be produced i n t o f i l m s o r s h e e t s by
c a l e n d e r i n g , and show good shaping p r o p e r t i e s during t h e
p r o d u c t i o n .
20 BRIEF DESCRIPTION OF DRAWING
[0028]
LFig.11 Fig. 1 i s a v i e w i l l u s t r a t i n g a r o l l c o n f i g u r a t i o n
of complex s i x c a l e n d e r r o l l s used i n Examples.
DESCRIPTION OF EMBODIMENTS
[0029]
[ E t h y l e n e copolymers ( X ) ]
An e t h y l e n e copolymer ( X ) a c c o r d i n g t o t h e i n v e n t i o n
i n c l u d e s s t r u c t u r a l u n i t s d e r i v e d from a component [A], a
5 component [B] and a component [C] which a r e e t h y l e n e [A], an
a - o l e f i n of 3 t o 20 carbon atoms [B] and a polyene a n d / o r a
c y c l i c o l e f i n [C]. The e t h y l e n e copolymer ( X ) is a n e t h y l e n e
copolymer c h a r a c t e r i z e d i n t h a t :
(1) t h e c o n t e n t o f s t r u c t u r a l u n i t s d e r i v e d from t h e
10 e t h y l e n e [A] is i n t h e range of 50 t o 90 mol%, p r e f e r a b l y 55
t o 85 mol%, and more p r e f e r a b l y 55 t o 83 mol% i n 100 mol% of
a l l t h e s t r u c t u r a l u n i t s i n t h e copolymer ( X ) ;
( 2 ) t h e c o n t e n t of s t r u c t u r a l u n i t s d e r i v e d from a t l e a s t
one p o l y e n e a n d / o r t h e c y c l i c o l e f i n [C] is i n t h e range of
15 l . O t o 5.0mol%, p r e f e r a b l y l . O t o 4.0mol%, andmore p r e f e r a b l y
1 . 0 t o 3 . 5 mol% i n 100 mol% of a l l t h e s t r u c t u r a l u n i t s i n t h e
copolymer ( X ) ; and
( 3 ) t h e i n t r i n s i c v i s c o s i t y [q] o f t h e e t h y l e n e copolymer
(X) a s measured a t 135'C i n a d e c a l i n s o l u t i o n is i n t h e range
20 o f 7 . 8 t 0 1 3 . O d l / g , preferably8.Oto13.Odl/g, m o r e p r e f e r a b l y
8.0 t o 12.0 d l / g , and s t i l l more p r e f e r a b l y 8 . 5 t o 12.0 d l / g .
[00301
The above (1) t o ( 3 ) w i l l be d e s c r i b e d i n d e t a i l
h e r e i n b e l o w .
[00311
( ( 1 ) [A] Ethylene)
S t r u c t u r a l u n i t s d e r i v e d from e t h y l e n e [A] ( h e r e i n a f t e r ,
a l s o r e f e r r e d t o simply a s "component [A]") give
5 low-temperature impact r e s i s t a n c e and e x c e l l e n t mechanical
s t r e n g t h t o rubber shaped a r t i c l e s o b t a i n e d by shaping and
c r o s s l i n k i n g a n e t h y l e n e copolymer composition i n c l u d i n g t h e
i n v e n t i v e e t h y l e n e copolymer (X) ( h e r e i n a f t e r , sometimes
r e f e r r e d t o simply as "copolymer ( X ) " ) .
10 [00321
The p r o p o r t i o n of t h e s t r u c t u r a l u n i t s d e r i v e d from
e t h y l e n e [A] i n a l l t h e s t r u c t u r a l u n i t s i n t h e i n v e n t i v e
copolymer (X) may be measured by any of v a r i o u s known methods.
For example, t h e p r o p o r t i o n may be determined by measuring a
15 'H-NMR spectrum.
[00331
{[B] a - O l e f i n s of 3 t o 20 carbon atoms)
S t r u c t u r a l u n i t s d e r i v e d from an a - o l e f i n of 3 t o 20
carbon atoms [B] ( h e r e i n a f t e r , a l s o r e f e r r e d t o simply a s
20 "component [B] " ) g i v e f l e x i b i l i t y (low c r y s t a l l i n i t y ) t o t h e
e t h y l e n e copolymer (X) of t h e i n v e n t i o n .
[0034]
From t h e viewpoints of m a t e r i a l c o s t s , mechanical
c h a r a c t e r i s t i c s of t h e i n v e n t i v e copolymer (X), and rubber
e l a s t i c i t y of shaped a r t i c l e s obtained from a composition
described l a t e r which i n c l u d e s t h e copolymer, the number of
carbon atoms i n t h e component [B] is p r e f e r a b l y 3 t o 20.
Preferably, t h e a - o l e f i n has 3 t o 8 carbon atoms, and is more
5 p r e f e r a b l y propylene or 1-butene, and p a r t i c u l a r l y p r e f e r a b l y
propylene.
[0035]
Examples of t h e components [Bl include propylene,
1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene,
10 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene
and 1-eicosene. Of these, propylene, 1-butene, 1-hexene and
1-octene a r e p r e f e r a b l e , propylene and 1-butene a r e more
p r e f e r a b l e , and propylene is p a r t i c u l a r l y p r e f e r a b l e .
[0036]
Thecomponents [B] m a y b e u s e d s i n g l y , or twoormore kinds
may be used i n combination.
[0037]
In terms of f l e x i b i l i t y of t h e inventive copolymer ( X )
and low-temperature impact r e s i s t a n c e of inventive rubber
20 shaped a r t i c l e s , t h e content of t h e s t r u c t u r a l u n i t s derived
from t h e component [B] is u s u a l l y 9 t o 49 mol%, and p r e f e r a b l y
1 4 t o 44 mol% i n 100 mol% of a l l the s t r u c t u r a l u n i t s i n the
i n v e n t i v e copolymer ( X ) .
[0038 ]
The p r o p o r t i o n of t h e s t r u c t u r a l u n i t s d e r i v e d from t h e
component [B] i n a l l t h e s t r u c t u r a l u n i t s i n t h e i n v e n t i v e
copolymer may be measured by any of v a r i o u s known methods. For
example, t h e p r o p o r t i o n m a y b e d e t e r m i n e d b y measuring ~ ~ H - N M R
5 spectrum.
[0039]
( ( 2 ) [C] A t l e a s t one p o l y e n e a n d / o r c y c l i c o l e f i n )
S t r u c t u r a l u n i t s d e r i v e d f r o m a t l e a s t o n e p o l y e n e and/or
t h e c y c l i c o l e f i n [C] ( h e r e i n a f t e r , a l s o r e f e r r e d t o simply
10 a s "component [C]") g i v e c r o s s l i n k i n g r e a c t i v i t y t o t h e
i n v e n t i v e e t h y l e n e copolymer ( X ) .
[0040]
The a t l e a s t one polyene [C-l] ( h e r e i n a f t e r , a l s o
r e f e r r e d t o simply a s "component [ C - I ] " ) , which is one of t h e
15 components [C] i n t h e i n v e n t i o n , is not p a r t i c u l a r l y l i m i t e d
a s long a s t h e compound has two o r more ( u s u a l l y f o u r o r less)
doublebonds and t h e double bonds a r e not c o n j u g a t e d . F r o m t h e
viewpoint of c o s t s , however, non-conjugated d i e n e s of 5 t o 20
carbon atoms a r e p r e f e r a b l e , and non-conjugated d i e n e s of 5
20 t o 15 carbon atoms a r e more p r e f e r a b l e .
[0041]
Examples of t h e non-conjugated d i e n e s i n c l u d e c y c l i c
non-conjugated d i e n e s such a s 5-ethylidene-2-norbornene ( E N B ) ,
d i c y c l o p e n t a d i e n e , 5-vinyl-2-norbornene ( V N B ) , norbornadiene
and methyltetrahydroindene, and chain non-conjugated dienes
such as 1,4-hexadiene and 7-methyl-1,6-octadiene.
[0042]
Of these, 5-ethylidene-2-norbornene (ENB),
5 dicyclopentadiene and 5-vinyl-2-norbornene (VNB) are
preferably used, and 5-ethylidene-2-norbornene (ENB) is
particular1 y preferably used.
[0043]
The cyclic olefin [C-21, which is one of the components
10 [C] in the invention, is an unsaturated monocyclic hydrocarbon
having one carbon-carbon double bond in the ring. Specific
examples of the cyclic olefins include cyclopentene,
cycloheptene, cyclohexene, norbornene, 5-methyl-2-norbornene,
tetracyclododecene and
15 2-methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene.
[0044]
The components [C] in the invention may be used singly,
or two or more kinds may be used in combination.
20 [0045]
The proportion of the structural units derived from the
at least one polyene and/or the cyclic olefin [C] in all the
structural units in the inventive copolymer may be measured
by any of various known methods. For example, the proportion
may be determined by measuring a 'H-NMR spectrum.
[ 0 0 4 6 ]
In t h e e t h y l e n e copolymer (X) of t h e i n v e n t i o n , it is
p r e f e r a b l e t h a t t h e component [C] be a non-conjugated polyene;
5 i n p a r t i c u l a r , a non-conjugated diene is p r e f e r a b l e , and ENB
is p a r t i c u l a r l y p r e f e r a b l e .
[ 0 0 4 7 ]
( ( 3 ) I n t r i n s i c v i s c o s i t y [ q ] )
The e t h y l e n e copolymer (X) of t h e invention has an
1 0 i n t r i n s i c v i s c o s i t y [ q ] intheaforementionedrange asmeasured
a t 135'C i n a d e c a l i n s o l u t i o n . This ensures t h a t e x c e l l e n t
rubber e l a s t i c i t y is e x h i b i t e d even without c r o s s l i n k i n g .
[ 0 0 4 8 ]
An e t h y l e n e copolymer with an i n t r i n s i c v i s c o s i t y [ q ]
15 less than t h e aforementioned range may be p l a s t i c a l l y deformed
when it c o n t a i n s a l a r g e amount of a p l a s t i c i z e r . On t h e o t h e r
hand, an e t h y l e n e copolymer having an i n t r i n s i c v i s c o s i t y [ q ]
exceeding t h e aforementioned range may cause problems during
production.
20 [ 0 0 4 9 ]
The e t h y l e n e copolymer (X) of t h e invention p r e f e r a b l y
has (i) a value B of 0 . 9 t o 1 . 0 , t h e value B being obtained
from a spectrum based on t h e following equation:
Value B = [ P O E ] / ( ~ ' [ P E. [I P O I )
( i n t h e equation, [ P E ] i s t h e m o l a r f r a c t i o n o f t h e c o n t e n t
of t h e u n i t s derived from e t h y l e n e ( a ) i n t h e random copolymer,
[Po] is t h e molar f r a c t i o n of t h e content of t h e u n i t s d e r i v e d
from t h e a - o l e f i n (b) i n t h e random copolymer, and [PoE] is t h e
5 p r o p o r t i o n of t h e number of a - o l e f i n . e t h y l e n e c h a i n s r e l a t i v e
t o t h e number of a l l t h e dyad chains i n t h e random copolymer);
and
(ii) a l o s s tangent value, t a n 6, o f n o t more than 0 . 1
a s determined by dynamic v i s c o e l a s t i c i t y measurement a t -lO°C
10 and 1 Hz.
[0050]
The value B is an i n d i c a t o r of t h e d i s t r i b u t i o n s t a t e of
e t h y l e n e and t h e a - o l e f i n i n t h e ethylene copolymer ( X ) , and
may be determined based on t h e r e p o r t s by J. C. Randall
15 (Macromolecules, 15, 353 (1982)) and J. Ray (Macromolecules,
1 0 , 773 (1977) ) .
[0051]
The ethylene copolymer s a t i s f y i n g t h e above (i) and (ii)
achieves e x c e l l e n t rubber c h a r a c t e r i s t i c s a t a l o w t e m p e r a t u r e
20 r e g i o n .
[0052]
[Methods f o r producing e t h y l e n e copolymers ( X ) ]
The e t h y l e n e copolymers (X) according t o t h e i n v e n t i o n
may be produced u s i n g m e t a l l o c e n e c a t a l y s t s . In d e t a i l , t h e
copolymers can be produced by t h e following methods.
( C a t a l y s t Example 1)
Examples o f t h e m e t a l l o c e n e c a t a l y s t s include t r a n s i t i o n
5 metal compounds represented by General Formula [I] or [ I I ]
below.
[Chem. 11
.R2. g: RT4 --. MQj
R"
RQ R8 . -
10 [0055]
[Chem. 21
100561
In General Formulae [ I ] and [ I I ] , Y is a s i l i c o n atom o r
a carbon atom.
[0057]
In General Formulae [ I ] and [ 1 1 ] , R1, R2, R3, R4, R5, R6,
R7, R8, R9, R", R", R", R13 and R14 may be t h e s a m e o r d i f f e r e n t
from one a n o t h e r and a r e each selected from a hydrogen atom,
a halogen atom, an o p t i o n a l l y halogenated hydrocarbon group
of 1 t o 20 carbon atoms and a s i l i c o n - c o n t a i n i n g group, and
10 a d j a c e n t s u b s t i t u e n t s of R1 t o R14 may be l i n k e d t o each o t h e r
t o form a r i n g .
[0058]
Examples of t h e halogen atoms i n c l u d e f l u o r i n e atom,
c h l o r i n e atom, bromine atom and i o d i n e atom.
15 [0059]
Examples o f t h e hydrocarbongroups o f l t o 20 carbonatoms
i n c l u d e a l k y l groups of 1 t o 20 carbon atoms, a r y l a l k y l groups
of 7 t o 20 carbon atoms, and a r y l groups and s u b s t i t u t e d a r y l
g r o u p s o f 6 t o 20 carbon atoms.
20 [0060]
S p e c i f i c examples i n c l u d e methyl group, e t h y l group,
n-propyl group, i s o p r o p y l group, a l l y 1 group, n-butyl group,
i s o b u t y l group, s e c - b u t y l group, t - b u t y l group, amyl group,
n - p e n t y l g r o u p , n e o p e n t y l g r o u p , n-hexylgroup, n - h e p t y l g r o u p ,
n-octyl group, n-nonyl group, n-decanyl group, 3-methylpentyl
group, 1 , l - d i e t h y l p r o p y l group, 1 , l - d i m e t h y l b u t y l group,
1-methyl-1-propylbutyl group, 1 , l - p r o p y l b u t y l group,
1,l-dimethyl-2-methylpropyl group,
5 1-methyl-1-isopropyl-2-methylpropyl group, c y c l o p e n t y l g r o u p ,
cyclohexyl group, cycloheptyl group, c y c l o o c t y l group,
norbornylgroup, adamantylgroup, phenylgroup, o - t o l y l g r o u p ,
m-tolyl group, p - t o l y l group, x y l y l group, isopropylphenyl
group, t-butylphenyl group, naphthyl group, biphenyl group,
10 t e r p h e n y l g r o u p , p h e n a n t h r y l g r o u p , a n t h r a c e n y l group, benzyl
group and cumyl group. Examples of t h e hydrocarbon groups
f u r t h e r i n c l u d e t h o s e c o n t a i n i n g o x y g e n - c o n t a i n i n g g r o u p s such
a s methoxy group, ethoxy group and phenoxy group,
n i t r o g e n - c o n t a i n i n g groups such a s n i t r o group, cyano group,
15 N-methylamino group, N,N-dimethylamino group and
N-phenylamino group, boron-containing groups such a s
b o r a n e t r i y l group and diboranyl group, and s u l f u r - c o n t a i n i n g
groups such a s s u l f o n y l group and s u l f e n y l group.
[0061]
Any hydrogen atoms of t h e above hydrocarbon groups may
be s u b s t i t u t e d by halogen atoms. Examples of such halogenated
hydrocarbon groups i n c l u d e t r i f l u o r o m e t h y l group,
t r i f l u o r o m e t h y l p h e n y l group, pentafluorophenyl group and
chlorophenyl group.
[0062]
Examples of the silicon-containing groups include silyl
groups, siloxy groups, hydrocarbon-substituted silyl groups
andhydrocarbon-substituted siloxy groups. Specificexamples
5 include methylsilyl group, dimethylsilyl group,
trimethylsilyl group, ethylsilyl group, diethylsilyl group,
triethylsilyl group, diphenylmethylsilyl group,
triphenylsilyl group, dimethylphenylsilyl group,
dimethyl-t-butylsilyl group and
10 dimethyl (pentafluorophenyl) silyl group.
[0063]
Examples of the cyclopentadienyl groups with R1 to R4 in
General Formulae [I] and [II] include but are not limited to
unsubstituted cyclopentadienyl group in which R1 to R~ are
15 hydrogen atoms; 3-monosubstituted cyclopentadienyl groups
such as 3-t-butylcyclopentadienyl group,
3-methylcyclopentadienyl group,
3-trimethylsilylcyclopentadienyl group,
3-phenylcyclopentadienyl group, 3-adamantylcyclopentadienyl
20 group, 3-amylcyclopentadienyl group and
3-cyclohexylcyclopentadienyl group; and 3,5-disubstituted
cyclopentadienyl groups such as
3-t-butyl-5-methylcyclopentadienyl group,
3-t-butyl-5-ethylcyclopentadienyl group,
3-phenyl-5-methylcyclopentadienyl group,
3,5-di-t-butylcyclopentadienyl group,
3,5-dimethylcyclopentadienyl group,
3-phenyl-5-methylcyclopentadienyl group and
5 3-trimethylsilyl-5-methylcyclopentadienyl group.
[0064]
The unsubstituted (R1 to R4 being hydrogen atoms)
cyclopentadienylgroupis preferable because of easy synthesis
of the transition metal compounds, production costs, and
10 performance in the copolymerization of the non-conjugated
polyenes [C] .
[0065]
Examples of the fluorenyl groups with R5 to R12 in General
Formulae [I] and [II] include but are not limited to
15 unsubstituted fluorenyl group in which R5 to R12 are hydrogen
atoms; 2-monosubstituted fluorenyl groups such as
2-methylfluorenyl group, 2-t-butylfluorenyl group and
2-phenylfluorenyl group; 4-monosubstituted fluorenyl groups
such as 4-methylfluorenyl group, 4-t-butylfluorenyl group and
20 4-phenylfluorenyl group; 2,7- or 3,6-disubstituted f luorenyl
groups such as 2,7-di-t-butylfluorenyl group and
3,6-di-t-butylfluorenyl group; 2,3,6,7-tetrasubstituted
fluorenylgroups suchas 2,7-dimethyl-3,6-di-t-butylfluorenyl
group and 2,7-diphenyl-3,6-di-t-butylfluorenyl group; and
2,3,6,7-tetrasubstituted f l u o r e n y l groups represented by
General Formulae [ V - I ] and [V-111 below wherein R6 and R' a r e
linked t o g e t h e r t o form a ring and R1° and R~~ a r e linked t o g e t h e r
t o form a ring
5 [0066]
[Chem. 31
[0067]
[Chem. 41
. . . CV- 113
[0068]
In General Formulae [ V - I ] and [V-111 , R5, Re, R9 and R1'
a r e t h e same as defined i n General Formula [ I ] or [II]; and
Ra, Rb, RC, Rd, Re, R ~ ,Rg and Rh a r e each independently
15 a hydrogen atom or an a l k y l group of 1 t o 5 carbon atoms, and
may be linked t o a d j a c e n t s u b s t i t u e n t s t o form a r i n g .
[0069]
S p e c i f i c examples of t h e a l k y l groups i n c l u d e methyl
group, e t h y l group, n-propyl group, isopropyl group, n-butyl
group, t - b u t y l group, amyl group and n-pentyl group.
[0070]
In General Formula [ V - I ] , RX and RY a r e each independently
a hydrocarbon group of 1 t o 3 carbon atoms which may have an
u n s a t u r a t e d bond; RX may form a double bond with t h e carbon atom
t o which R~ o r RC is bonded; RY may form a double bond with t h e
carbon atom t o which Re or Rg is bonded; and RX and RY a r e
10 p r e f e r a b l y both s a t u r a t e d or u n s a t u r a t e d hydrocarbon groups
of 1 or 2 carbon atoms.
[0071]
Specificexamples ofthecompounds representedbyGenera1
Formula [V-I] or [V-111 i n c l u d e
15 octamethyloctahydrodibenzofluorenyl group of Formula [V-1111
below, t e t r a m e t h y l d o d e c a h y d r o d i b e n y l group of
Formula [V-IV] below,
octamethyltetrahydrodicyclopentafluorenyl group of Formula
[V-V] below, hexamethyldihydrodicyclopentaf1uorenyl group of
20 Formula [ V - V I ] b e l o w a n d b , h - d i b e n z o f l u o r e n y l g r o u p o f Formula
[V-VII] below.
[0072]
[Chem. 51
[0073]
[Chem. 63
5 [0074]
[Chem. 71
[0075]
[Chem. 83
10
[0076]
[Chem. 91
[0077]
The transition metal compounds of General Formula [I] or
[II] containing these fluorenyl groups each shows an excellent
5 performance in the copolymerization ofthe atleastonepolyene
and/or the cyclic olefin [C]. When Y is a silicon atom, the
transition metal compounds that have a 2,7-disubstituted
fluorenyl group, a 3,6-disubstituted fluorenyl group, a
2,3,6,7-tetrasubstituted fluorenyl group or a
10 2,3,6,7-tetrasubstituted fluorenyl group of General Formula
[V-I] show particularly excellent performance. When Y is a
carbon atom, the transition metal compounds that have an
unsubstituted fluorenyl group with R5 to R12 being hydrogen
atoms, a 3,6-disubstituted fluorenyl group, a
15 2,3,6,7-tetrasubstituted fluorenyl group or a
2,3,6,7-tetrasubstituted fluorenyl group of General Formula
[V-I] show a particularly excellent performance in the
copolymerization of the non-conjugated polyenes [C].
[0078]
2 0 In both cases in which Y is a silicon atom or a carbon
atom, particularly excellent polymerization activity is
achieved by t h e t r a n s i t i o n m e t a l compounds of General Formulae
[ I ] and [11] which have a 2 , 7 - d i s u b s t i t u t e d f l u o r e n y l group,
a 3 , 6 - d i s u b s t i t u t e d f l u o r e n y l group, a
2,3,6,7-tetrasubstituted f l u o r e n y l group or a
5 2,3,6,7-tetrasubstituted f l u o r e n y l group of General Formula
[ V - I ] .
[0079]
In General Formula [ I ] , R13 and R1* may be t h e same or
d i f f e r e n t from each o t h e r . A s a l r e a d y mentioned, R13 and R14
10 may be hydrocarbon groups. Of t h e hydrocarbon groups, methyl
group, e t h y l group, n-propyl group, isopropyl group, n-butyl
group, i s o b u t y l group, t - b u t y l group, cyclopentyl group,
cyclohexyl group, cycloheptyl group, phenyl group, m-tolyl
group, p - t o l y l group, 4-t-butylphenyl group, p-chlorophenyl
15 group, 4-biphenyl group, 2-naphthylgroup, x y l y l g r o u p , benzyl
group and m-trifluoromethylphenyl group a r e p r e f e r a b l e .
[00801
In t h e t r a n s i t i o n m e t a l compounds r e p r e s e n t e d by General
Formula [ I I ] , A is a d i v a l e n t and s a t u r a t e d or u n s a t u r a t e d
20 hydrocarbon group of 2 t o 20 carbon atoms which may i n c l u d e
an aromatic r i n g , and Y and A a r e l i n k e d t o g e t h e r t o form, f o r
example, a s t r u c t u r e such a s a c y c l o a l k y l i d e n e group such a s
cyclohexylidene group r e p r e s e n t e d by Formula [ V I - I ] below or
a cyclomethylenesilylene group such a s
cyclotetramethylenesilylene group (1-silacyclopentylidene
group) represented by Formula [VI-111 below.
[0081]
[Chem. 101
[0082]
(In Formulae [VI-I] and [VI-111, the black dots
represent bonding points with the (substituted)
cyclopentadienyl group and the (substituted) fluorenyl group
10 in General Formula [II].)
In General Formula [II], the group A may contain two or
more ring structures including the ring it forms with Y.
[0083]
Specific examples of the ring structures formed by the
15 bonding of Y with A, other than the cyclohexylidene group
represented by Formula [VI-I] above, include cyclopropylidene
group, cyclobutylidene group, cyclopentylidene group,
cycloheptylidene group, cyclooctylidene group,
bicyclo[3.3.1]nonylidene group, norbornylidene group,
20 adamantylidene group, tetrahydronaphthylidene group and
dihydroindanylidene group.
[0084]
Similarly, specific examples of the ring structures
formed by the bonding of Y with A, other than the
5 cyclotetramethylenesilylene group (1-silacyclopentylidene
group) represented by Formula [VI-111 above, include
cyclodimethylenesilylene group, cyclotrimethylenesilylene
group, cyclopentamethylenesilylene group,
cyclohexamethylenesilylene group and
10 cycloheptamethylenesilylene group.
[0085]
In General Formulae [I] and [II], M is a titanium atom,
a zirconiumatomorahafniumatom, andis preferablyatitanium
atom or a hafnium atom.
15 [00861
In General Formulae [I] and [II], Q is selected from
halogen atoms, hydrocarbon groups of 1 to 10 carbon atoms,
neutral and conjugated or non-conjugated dienes of 10 or less
carbon atoms, anionic ligands, and neutral ligands capable of
20 coordination by lone pair electrons.
roo871
Specific examples of the halogen atoms include fluorine
atom, chlorineatom, bromineatomandiodineatom, withchlorine
atom being preferable.
100881
Specific examples of the hydrocarbon groups of 1 to 10
carbonatoms includemethyl group, ethyl group, n-propyl group,
isopropyl group, 2-methylpropyl group, 1,l-dimethylpropyl
5 group, 2,2-dimethylpropyl group, 1,l-diethylpropyl group,
1-ethyl-1-methylpropyl group, 1,1,2,2-tetramethylpropyl
group, sec-butylgroup, t-butylgroup, 1,l-dimethylbutylgroup,
1,1,3-trimethylbutylgroup, neopentylgroup, cyclohexylmethyl
group, cyclohexyl group, 1-methyl-1-cyclohexyl group and
10 benzyl group, with methyl group, ethyl group and benzyl group
being preferable.
[0089]
Specific examples of the neutral and conjugated or
non-conjugateddienes of10 or less carbonatomsinclude s-cis-
15 or s-trans-q4-1, 3-butadiene, s-cis- or
s-trans-q4-1, 4-diphenyl-1,3-butadiene, s-cis- or
s-trans-q4-3-methyl-1,3-pentadiene, s-cis- or
s-trans-q4-1,4-dibenzyl-1,3-butadiene, s-cis- or
s-trans-q4-2,4-hexadiene, s-cis-or s-trans-q4-1,3-pentadiene,
20 s-cis- or s-trans-q4-1, 4-ditolyl-1,3-butadiene, and s-cis- or
s-trans-q4-1, 4-bis (trimethylsilyl) -1,3-butadiene.
[0090]
Specific examples of the anionic ligands include alkoxy
groups such as methoxy, t-butoxy and phenoxy, carboxylate
groups such as acetate and benzoate, and sulfonate groups such
as mesylate and tosylate.
[00911
Specific examples of the neutral ligands capable of
5 coordination by lone electron pairs include organophosphorus
compounds such as trimethylphosphine, triethylphosphine,
triphenylphosphine and diphenylmethylphosphine, and ethers
such as tetrahydrofuran, diethyl ether, dioxane and
1,2-dimethoxyethane.
10 [0092]
Lastly, j in General Formulae [I] and [11] is an integer
of 1 to 4. When j is 2 or greater, the plurality of Q may be
the same or different from one another.
[0093]
Examples of the transition metal compounds discussed
above are described in JP-A-H2011-1497.
[00941
The transition metal compounds may be produced by known
methods, and the production methods are not particularly
20 limited. Exemplary production methods are described in J.
Organomet. Chem., 63, 509 (1996) andWO2006-123759,WO01/27124,
JP-A-2004-168744, JP-A-2004-175759andJP-A-2000-212194 filed
by the present applicant.
[0095]
(Catalyst Example 2)
Examples of the metallocene catalysts which may be used
in the production of the inventive ethylene copolymers (X)
further include compounds represented by General Formula (X)
5 below.
[00961
[Chem. 111
R'
[0097]
In Formula (X), R' and R" are each independently a
hydrogen atom or a hydrocarbyl group of 1 to 20 carbon atoms,
M is titanium, Y is -NR*-, Z* is -siR12-, the two R*S are each
independently a hydrogen atom or a hydrocarbyl group of 1 to
20 carbon atoms, p and q are such that one is 0 and the other
15 is 1,
when p is 0 and q is 1, M is in the +2 oxidized state and
X' is 1,4-diphenyl-1,3-butadiene or 1,3-pentadiene, and
when p is 1 and q is 0, M is in the +3 oxidized state and
X is 2-(N,N-dimethy1amino)benzyl.
[0098]
Fromthevieripointthatthe obtainable ethylene copolymer
is suppressed from the occurrence of fogging and stickiness
due to ultralow-molecular weight components, a particularly
5 preferred compound having a structure represented by General
Formula (X) is (t-butylamido) dimethyl
(q5-2-methyl-s-indacen-1-yl)silanetitanium (11)
1,3-pentadiene (alias: (t-butylamido)d imethyl
(q5-2-methyl-s-indacen-1-yl)s ilanetitanium (11)
10 1,3-pentadiene) (a compound having a structure represented by
Formula (XI) below). For example, the compound having a
structure of Formula (XI) below may be obtained by a method
described in JP-A-2001-522398.
[0099]
15 [Chem. 121
[OlOO]
The compounds having a structure of General Formula (X)
provide excellentpolymerizability ofthe at least one polyene
and/orthe cyclic olefin [C]. Further, the ethylene copolymer
(X) of the invention synthesized with such a metallocene
catalysthas anarrowmolecularweightdistributionandanarrow
5 composition distribution as well as a uniform molecular
structure. Thus, copolymer compositions including the
inventive copolymer (X) and shaped articles obtained from the
compositions tend to achieve an excellent surface appearance.
[OlOl]
10 (Cocatalysts)
For example, the ethylene copolymer (X) of the invention
may be synthesized using the above metallocene catalyst as a
main catalyst and a boron compound and/or an organoaluminum
compound such as a trialkylaluminum as a cocatalyst.
15 [0102]
Examples of the boron compounds include
trityltetrakis(pentafluoropheny1) borate,
trimethylammoniumtetrakis(pentaf1u0r0phenyl) borate,
di (hydrogenated tallow alkyl)
20 methylammoniumtetrakis(pentafluorophenyl) borate,
triethylammoniumtetrakis(pentafluorophenyl) borate,
tripropylammoniumtetrakis (pentafluoropheny) borate,
tri (n-butyl) ammoniumtetrakis (pentafluoropheny borate,
tri (s-butyl) ammoniumtetrakis (pentaf luoropheny borate,
N,N-dimethylaniliniumtetrakis(pentafluorophenyl) borate,
N,N-dimethylanilinium-n-butyltris(pentafluorophenyl) borate,
N,N-dimethylaniliniumbenzyltris(pentafluorophenyl) borate,
N, N-dimethylaniliniumtetrakis
5 (4-(t-butyldimethylsilyl)-2,3,5,6-tetrafluorophenyl) borate,
N,N-dimethylaniliniumtetrakis
(4- (triisopropylsilyl) -2,3,5,6-tetrafluorophenyl) borate,
N,N-dimethylaniliniumpentaf1~oropheno~ytris
(pentafluorophenyl) borate,
10 N,N-diethylaniliniumtetrakis(pentafluorophenyl) borate,
N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis
(pentafluorophenyl) borate,
trimethylammoniumtetrakis (2,3,4,6-tetrafluorophenyl borate,
triethylammoniumtetrakis(2,3,4,6-tetrafluorophenyl) borate,
15 tripropylammoniumtetrakis(2,3,4,6-tetrafluorophenyl) borate,
N,N-dimethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl)
borate,
N,N-diethylaniliniumtetrakis(2,3,4,6-tetrafluorophenyl)
borate and N,N-dimethyl-2,4,6-trimethylaniliniumtetrakis
20 (2,3,4,6-tetrafluorophenyl) borate;
dialkylammonium salts such as
di(isopropyl)ammoniumtetrakis(pentafluorophenyl) borate,
tri (n-butyl) ammoniumtetrakis (2,3,4,6-tetrafluorophenyl)
borate, dimethyl(t-buty1)ammoniumtetrakis
(2,3,4,6-tetrafluorophenyl) borate and
dicyclohexylammoniumtetrakis(pentafluoropheny1) borate;
trisubstituted phosphonium salts such as
triphenylphosphoniumtetrakis(pentafluoropheny1) borate,
5 tri(o-tolyl)phosphoniumtetrakis(pentafluorophenyl) borate
and tri(2,6-dimethylphenyl)phosphoniumtetrakis
(pentafluorophenyl) borate;
disubstituted oxonium salts such as
diphenyloxoniumtetrakis(pentaf1uorophenyl) borate,
10 di(o-tolyl)oxoniumtetrakis(pentafluorophenyl) borate and
di(2,6-dimethylphenyl)oxoniumtetrakis(pentafluorophenyl)
borate; and
disubstituted sulfonium salts such as
diphenylsulfoniumtetrakis(pentafluoropheny1) borate,
15 di(o-tolyl)sulfoniumtetrakis(pentafluorophenyl) borate and
bis(2,6-dimethylphenyl)sulfoniumtetrakis
(pentafluorophenyl) borate.
[0103]
Examples of the organoaluminum compounds include
20 trialkylaluminums suchas trimethylaluminum, triethylaluminum,
triisobutylaluminum and tri-n-octylaluminum,
tricycloalkylaluminums, isobutylaluminum dichloride,
diethylaluminum chloride, ethylaluminum dichloride,
ethylaluminum sesquichloride, methylaluminum dichloride,
dimethylaluminum chloride, diisobutylaluminum hydride,
LiA1 (C2H5)4 , LiA1 (C7H154), and organoaluminumoxy compounds.
[0104]
The organoaluminumoxy compounds may be conventionally
5 known aluminoxanes or may be benzene-insoluble
organoaluminumoxy compounds such as those described in
JP-A-H02-78687.
[0105]
(Polymerization conditions)
The reaction temperature in the synthesis of the
inventive ethylene copolymer ( X ) is usually -20 to 200°C, and
preferably 0 to 150'~. The polymerization pressure is usually
from above 0 MPa to not more than 8 MPa (gauge pressure), and
preferably from above 0 MPa to not more than 5 MPa (gauge
15 pressure).
[0106]
The reaction time (the average residence time in the case
of continuous copolymerization) may vary depending on
conditions such as the catalyst concentration and the
20 polymerization temperature, but it is usually 0.5 minutes to
5 hours, and preferably 10 minutes to 3 hours. Further,
molecular weight modifiers such as hydrogen may be used.
[0107]
When the olefins are polymerized with use of the above
metallocene catalysts, the transition metal compounds
represented by General Formulae [I], [II] and [XI are usually
used in 10-12 to lo-' mol, and preferably 10-lo to lo-' mol per
1 liter of the reaction volume.
5 [0108]
The cocatalyst used in combination with the transition
metalcompoundisusuallyusedinamolarratioofthecocatalyst
to the total of transition metal atoms (M) in the transition
metal compound [cocatalyst/M] of O.1/1 to 1000/1, and
10 preferably 1/1 to 500/1.
[01091
In the invention, the ethylene copolymer may be produced
by any of liquid phase polymerization methods such as solution
(dissolution) polymerization and suspension polymerization,
15 or gas phase polymerization methods. Although the
polymerization method is not particularly limited, it is
preferable that the method include a step of obtaining a
polymerization reaction liquid described below.
[OllO]
2 0 The step of obtaining a polymerization reaction liquid
is a step in which the ethylene [A], the component [B], the
atleastonepolyene and/orthecyclicolefin [C] andoptionally
other monomers are copolymerized in the presence of the
metallocene catalyst and the cocatalyst using an aliphatic
hydrocarbon as the polymerization solvent to form a
polymerization reaction liquid containing a copolymer of the
ethylene [A], the component [B] , and the at least one polyene
and/or the cyclic olefin [C] (and other monomers).
5 [Olll]
Examples of the polymerization solvents include
aliphatic hydrocarbons and aromatic hydrocarbons. Specific
examples include aliphatic hydrocarbons such as propane,
butane, pentane, hexane, heptane, octane, decane, dodecane and
10 kerosine, alicyclic hydrocarbons such as cyclopentane,
cyclohexane and methylcyclopentane, aromatic hydrocarbons
such as benzene, toluene and xylene, and halogenated
hydrocarbons such as ethylene chloride, chlorobenzene and
dichloromethane.
15 [0112]
These may be used singly, or trio or more kinds may be used
in combination. The a-olefin itself subjected to
polymerization may be used as the polymerization solvent.
[0113]
20 Of the polymerization solvents described above, hexane
is preferable from the viewpoints of separation and
purification of the ethylene copolymer obtained.
[01141
The polymerization reactionmaybe carried out batchwise,
semi-continuously or continuously. F u r t h e r , t h e
polymerization may be c a r r i e d out i n two or more s t a g e s under
d i f f e r e n t r e a c t i o n c o n d i t i o n s .
[0115]
For example, t h e polymerizationreactionmaybeperformed
a s d e s c r i b e d above and may be terminated by t h e a d d i t i o n of
an a c i d i c a l c o h o l such a s methanol t o t h e r e a c t i o n system.
[01161
The molecular weight o f t h e ethylene polymer obtained by
10 t h e polymerization r e a c t i o n may be c o n t r o l l e d by allowing
hydrogen t o be p r e s e n t i n t h e polymerization system or by
c h a n g i n g t h e p o l y m e r i z a t i o n t e m p e r a t u r e . In d e t a i l , reducing
theamount of h y d r o g e n i n t h e p o l y m e r i z a t i o n s y s t e m c a n i n c r e a s e
t h e molecular weight of t h e o b t a i n a b l e ethylene copolymer and
15 consequently r e s u l t s i n an e t h y l e n e copolymer having an
intrinsicviscosityintheinventiverange. B y m a i n t a i n i n g t h e
p o l y m e r i z a t i o n t e m p e r a t u r e a t a moderate temperature and t h e
c a t a l y t i c a c t i v i t y a t a high l e v e l , t h e molecular weight of
t h e o b t a i n a b l e e t h y l e n e copolymer can be s i g n i f i c a n t l y
20 i n c r e a s e d , t h e r e b y a c h i e v i n g an i n t r i n s i c v i s c o s i t y i n t h e
aforementioned range.
[01171
F u r t h e r , t h e molecular weight of t h e e t h y l e n e copolymer
can be a d j u s t e d by c o n t r o l l i n g t h e amount of t h e c o c a t a l y s t
used.
[01181
[ E t h y l e n e copolymer c o m p o s i t i o n s ]
I n t h e p r e s e n t i n v e n t i o n , t h e t e r m e t h y l e n e copolymer
5 composition means a composition o b t a i n e d by adding v a r i o u s
known a d d i t i v e s t o t h e e t h y l e n e copolymer ( X ) . I n terms of
s h a p i n g p r o c e s s a b i l i t y and f l e x i b i l i t y , a composition
i n c l u d i n g 100 t o 1000 p a r t s by mass of a p l a s t i c i z e r ( Y ) w i t h
r e s p e c t t o 100 p a r t s by mass of t h e e t h y l e n e copolymer ( X ) is
10 p r e f e r a b l e . Needless t o mention, t h e composition may c o n t a i n
any o f v a r i o u s known a d d i t i v e s o t h e r t h a n p l a s t i c i z e r s .
[a1191
The e t h y l e n e copolymer c o m p o s i t i o n o f t h e i n v e n t i o n
p r e f e r a b l y i n c l u d e s t h e p l a s t i c i z e r ( Y ) i n an amount of n o t
15 less t h a n 130 p a r t s by mass, more p r e f e r a b l y not less t h a n 150
p a r t s by mass, s t i l l more p r e f e r a b l y not less t h a n 180 p a r t s
by mass, p a r t i c u l a r l y p r e f e r a b l y n o t less t h a n 200 p a r t s by
mass, and most p r e f e r a b l y n o t less t h a n 250 p a r t s by mass with
r e s p e c t t o 100 p a r t s by mass of t h e e t h y l e n e copolymer ( X ) .
20 [0120]
On t h e o t h e r hand, t h e upper l i m i t of t h e p l a s t i c i z e r ( Y )
is p r e f e r a b l y n o t more t h a n 700 p a r t s by mass, more p r e f e r a b l y
n o t more t h a n 500 p a r t s by mass, and p a r t i c u l a r l y p r e f e r a b l y
n o t more t h a n 400 p a r t s by mass. In an embodiment, it is a l s o
preferable that the amount of the plasticizer be not less than
700 parts by mass, and preferably not less than 701 parts by
mass.
[01211
As compared with conventional ethylene copolymer
compositions, the inventiveethylene copolymer compositionhas
a lower risk that the plasticizer (Y) will exudate from the
composition even when the composition contains as much as 1000
parts by mass or less of the plasticizer (Y). Thus, the
10 inventive compositions can be extended by large volumes of
extender oils.
[0122]
In terms of rubber elasticity in an uncrosslinked state,
it is preferable that the ethylene copolymer composition of
15 the invention have a loss tangent (tan 6) at 190°C and 0.01
rad/sec of 0.1 to 1.0, and more preferably 0.3 to 1.0.
[01231
The ethylene copolymer composition of the invention
preferably satisfies Equation [I] below:
20 [0124]
q+max > 10000 x (q+@10s) "0.47 . . Equation [I]
(in the equation, q+max is the maximum viscosity reached
in the measurement of extensional viscosity at 190°C and 0.01
[l/s], and q+@lOs is the viscosity after 10 seconds after the
start of the measurement).
The ethylene copolymer composition satisfying Equation
[I] exhibits high viscosity when it is elongated in a molten
state and thus achieves excellent calendering properties to
5 allow for the calendering of thin, flat and smooth films.
[0125]
In an example of the ethylene copolymer compositions of
the invention, a crosslinking agent is added to the ethylene
copolymer to give a copolymer composition, which is then shaped
10 and crosslinked to produce desired rubber shaped articles.
[0126]
In terms of shaping processability and flexibility, the
ethylene copolymer ofthe invention is preferably used singly,
namely, the inventive ethylene copolymer composition does not
15 substantially contain any other polymer components. However,
other polymer components may be contained while ensuring that
characteristics are not deteriorated.
[0127]
The ethylene copolymer composition of the invention
20 containing various components described above is excellent in
shaping processability and thus can be shaped into desired
rubber shaped articles. Methods for crosslinking such rubber
shaped articles according to the invention will be described
later.
[0128l
Specifically, the ethylene copolymer composition of the
invention can be processed by roll kneading without sticking
to the rolls or causing bugs even when the composition has been
5 filled kith significantly large amounts of additives, and the
composition exhibits excellent handling properties during
extrusion and molding and can be shaped easily.
[01291
The Mooney viscosity [ML (1+4) 125"C)I of the ethylene
10 copolymer composition measured at 125'C in accordance with JIS
K6300withaMooneyviscometer (SMV202manufacturedbyShimadzu
Corporation) is usually 20 to 80, and preferably 25 to 70.
[01301
The term "polymer components" indicates compounds
15 obtained by reactingmonomers having polymerizable functional
groups (forexample, combinationsofethylenicallyunsaturated
bonds, carboxyl groups and amino groups).
[01311
Next, the phrase "does not substantially contain" means
20 that in the ethylene copolymer composition of the invention,
the content of polymer components other than the inventive
ethylene copolymer is not more than 1 mass% in 100 mass% of
the composition.
[01321
Examples of the crosslinking agents include vulcanizing
agents, vulcanization accelerators and vulcanization aids.
[0133]
(Vulcanizing agents)
Examples of the vulcanizing agents include sulfur
compounds, organic peroxides, phenolic resins and oxime
compounds.
101341
Preferredexamples ofthe sulfurcompoundsinclude sulfur,
10 sulfur chloride, sulfur dichloride, morpholine disulfide,
alkylphenol disulfide, tetramethylthiuram disulfide and
selenium dithiocarbamate. Of these, for example, sulfur and
tetramethylthiuram disulfide are more preferred.
[0135]
The amount of the sulfur compounds added is usually 0.1
to 10 parts by mass with respect to 100 parts by mass of the
inventive ethylene copolymer (X). This amount advantageously
ensures that the obtainable crosslinked products show
excellent mechanical properties.
20 [0136]
Preferred examples of the organic peroxides include
dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane,
2,5-dimethyl-2,5-di (benzoylperoxy)h exane,
2,5-dimethyl-2,5-di (t-butylperoxy)h exyne-, di-t-butyl
peroxide, di-t-butylperoxy-3,3,5-trirnethylcyclohexane and
t-dibutyl hydroperoxide. Of these, for example, dicumyl
peroxide, di-t-butyl peroxide and
di-t-butylperoxy-3,3,5-trirnethylcyclohexane are more
5 preferred.
[0137]
The amountoftheorganicperoxidesaddedisusually0.001
to 0.05 mol with respect to 100 g of the inventive ethylene
copolymer (X). This amount of the organic peroxides added
10 advantageously ensures that the obtainable crosslinked
products show excellent mechanical properties.
[OX381
Thevulcanizing agents describedabovemaybeused singly,
or two or more kinds may be used in combination.
15 [01391
(Vulcanization accelerators)
When the sulfur compounds are used as the vulcanizing
agents, vulcanization accelerators are preferably used in
combination therewith.
20 [0140]
Examples of the vulcanization accelerators include
thiazole compounds such as
N-cyclohexylbenzothiazole-2-sulphenarnide (for example:
"Sanceler CM" (product name, manufactured by SANSHIN CHEMICAL
INDUSTRY CO., LTD.)), N-oxydiethylene-2-benzothiazole
sulphenamide, N,Nf-diisopropyl-2-benzothiazole sulphenamide,
2-mercaptobenzothiazole (for example: "Sanceler M" (product
name, manufactured by SANSHIN CHEMICAL INDUSTRY CO. , LTD. ) ) ,
5 2-(4-morpholinodithio)benzothiazole (for example: "Nocceler
MDB-P" (product name, manufactured by SANSHIN CHEMICAL
INDUSTRY CO. , LTD. ) ) ,
2-(2,4-dinitrophenyl)mercaptobenzothiazole,
2-(2,6-diethyl-4-morpholinothio)benzothiazole,
10 dibenzothiazyl disulfide, and cyclohexylamine salt of
2-mercaptobenzothiazole (for example: "Sanceler HM" (product
name, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.));
guanidine compounds such as diphenylguanidine,
triphenylguanidine and diorthotolylguanidine; aldehyde amine
15 compounds such as acetaldehyde-aniline condensate and
butylaldehyde-aniline condensate; imidazoline compounds such
as 2-mercaptoimidazoline; thiourea compounds such as
diethylthiourea and dibutylthiourea;
thiuramcompounds suchastetramethylthiurammonosulfide
20 (for example: "Nocceler TS" (product name, manufactured by
OUCH1 SHINKO CHEMICAL INDUSTRIAL CO., LTD.)),
tetramethylthiuram disulfide (for example: "Sanceler TT"
(product name, manufactured by SANSHIN CHEMICAL INDUSTRY CO.,
LTD.)), tetraethylthiuram disulfide (for example: "Sanceler
TET" (product name, manufactured by SANSHIN CHEMICAL INDUSTRY
CO., LTD.)), dipentamethylenethiuram tetrasulfide (for
example: "Sanceler TRA" (product name, manufacturedby SANSHIN
CHEMICAL INDUSTRY CO., LTD.)), and
5 tetrakis(2-ethylhexy1)thiuram disulfide (for example:
"Nocceler TOT" (product name, manufactured by OUCHI SHINKO
CHEMICAL INDUSTRIAL CO., LTD.));
dithioate salt compounds such as zinc
dimethyldithiocarbamate (for example: "Sanceler PZ" (product
10 name, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)),
zincdiethyldithiocarbamate, zincdibutyldithiocarbamate (for
example: "Sanceler BZ" (product name, manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD.)), tellurium
diethyldithiocarbamate (for example: "Sanceler TE" (product
15 name, manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.)),
and zinc dibenzyldithiocarbamate (for example: "Nocceler ZTC"
(product name, manufactured by OUCHI SHINKO CHEMICAL
INDUSTRIAL CO., LTD.));
thiourea compounds such as ethylenethiourea (for
20 example: "Sanceler 22-C" (product name, manufactured by
SANSHINCHEMICAL INDUSTRYCO., LTD.)) andN,N1-diethylthiourea
(for example: "Sanceler BUR" (product name, manufactured by
SANSHINCHEMICAL INDUSTRYCO., LTD.)); xanthate compounds such
as zinc dibutylxanthate; and
others such as Chinese white (for example, META-Z102
(product name, manufacturedby Inoue Calcium Corporation, zinc
oxide) ) .
[0141]
The amount of the vulcanization accelerators added is
usually 0.1 to 20 parts by mass with respect to 100 parts by
mass of the inventive ethylene copolymer ( X ) . The
vulcanization accelerators may be used singly, or two or more
kinds may be used in combination.
10 [0142]
The amounts of the vulcanizing agents and the
vulcanization accelerators in the above ranges advantageously
ensure that the obtainable crosslinkedproducts show excellent
mechanical properties.
15 [0143]
(Vulcanization aids)
Examples of the vulcanization aids as examples of the
crosslinking agents include quinone dioximevulcanizationaids
such as p-quinone dioxime; acrylic vulcanization aids such as
20 ethylene glycol dimethacrylate and trimethylolpropane
trimethacrylate; ally1 vulcanization aids such as diallyl
phthalate and triallyl isocyanurate (for example, M-60
(product name, manufactured by Nippon Kasei Chemical Co.,
Ltd.)); other maleimide vulcanization aids; divinylbenzene;
zinc oxide, and magnesium oxide/Chinese white (for example,
META-2102 (product name, manufactured by Inoue Calcium
Corporation, zincoxide)). Appropriatevulcanization aids may
be selected in accordance with purposes.
5 [0144]
The vulcanization aids may be used singly, or two or more
kinds may be used in combination.
[0145]
The amount of the vulcanization aids added is usually 1
10 to 50 parts by mass with respect to 100 parts by mass of the
inventive ethylene copolymer (X).
[0146]
The ethylene copolymer composition of the invention may
contain other components as required in addition to the
15 inventive copolymer (X) and the crosslinking agents.
[0147]
(Plasticizers (Y))
Examples ofthe plasticizers (Y) in the invention include
petroleumplasticizers such asprocess oils (for example, Diana
20 Process Oil PW-380, Diana Process Oil PW-100 (product name,
manufactured by Idemitsu Kosan Co., Ltd.) and Diana Process
Oil PS-430 (product name, manufactured by Idemitsu Kosan Co.,
Ltd.)), lubricating oils, paraffin oils, liquid paraffins,
petroleum asphalts and vaselines; coal tar plasticizers such
a s coal t a r s and coal t a r p i t c h e s ; f a t t y o i l p l a s t i c i z e r s such
a s c a s t o r o i l , l i n s e e d o i l , rapeseed o i l , soybean o i l and
coconut o i l ; waxes such a s bees wax, carnauba wax and l a n o l i n ;
f a t t y a c i d s and s a l t s thereof s u c h a s r i c i n o l e i c a c i d , p a l m i t i c
5 a c i d , s t e a r i c a c i d , barium s t e a r a t e , calcium s t e a r a t e and z i n c
l a u r a t e ; naphthenic a c i d , p i n e o i l , r o s i n and d e r i v a t i v e s
t h e r e o f ; s y n t h e t i c polymer substances such as t e r p e n e r e s i n s ,
petroleum r e s i n s , a t a c t i c polypropylenes and coumarone indene
r e s i n s ; ester p l a s t i c i z e r s such as d i o c t y l p h t h a l a t e , d i o c t y l
10 a d i p a t e and d i o c t y l s e b a c a t e ; and o t h e r s such a s
m i c r o c r y s t a l l i n e waxes, l i q u i d polybutadienes, modified
l i q u i d polybutadienes, l i q u i d t h i o k o l s , hydrocarbon-based
s y n t h e t i c l u b r i c a t i n g o i l s , t a l l o i l s and rubber s u b s t i t u t e s
( f a c t i c e s ) .
15 [0148]
Of t h e s e , petroleum p l a s t i c i z e r s a r e p a r t i c u l a r l y
p r e f e r a b l e . The p l a s t i c i z e r s ( Y ) i n t h e invention may be used
s i n g l y , o r two or more kinds may be used i n combination.
[01491
2 0 In t h e case where rubber shaped a r t i c l e s obtained from
t h e i n v e n t i v e e t h y l e n e copolymer composition a r e used i n
automobile p a r t a p p l i c a t i o n s , it is p r e f e r a b l e t h a t t h e use
o f t h e p e t r o l e u m p l a s t i c i z e r s beminimally suppressed i n o r d e r
t o avoid e x t r a c t i o n of o i l s .
(Other components)
Examples of other components include foaming agents,
foaming aids, reinforcing agents, inorganic fillers,
5 anti-aging agents (stabilizers), processing aids, activating
agents and moisture absorbers. These components may be added
to the composition in accordance with, for example, the
applications and purposes of the inventive copolymer
composition.
10 [0151]
Examples of the foaming agents include inorganic foaming
agents such as sodium bicarbonate and sodium carbonate; and
organic foaming agents, including nitroso compounds such as
N,N1-dinitrosopentamethylenetetramine and
15 N,N1-dinitrosoterephthalamide; azo compounds such as
azodicarbonamide and azobisisobutyronitrile; hydrazide
compounds such as benzenesulfonylhydrazide and
4,4'-oxybis(benzenesulfony1hydrazide); and azide compounds
such as calcium azide and 4,4'-diphenyldisulfonyl azide.
20 [0152]
Examples of commercially available such products include
VINYFORAC-2F (productname,manufacturedbyEIWACHEMICAL IND.
CO., LTD. ) , VINYFOR AC#LQ (product name, manufactured by EIWA
CHEMICAL IND. CO., LTD., azodicarbonamide (abbreviated to
ADCA)), NEOCELLBORN N#1000SW (product name, manufactured by
EIWA CHEMICAL IND. CO., LTD.,
4,4'-oxybis(benzenesulfony1hydrazide (abbreviated to OBSH))
and CELLULAR D (product name, manufactured by EIWA CHEMICAL
5 IND. CO., LTD., N,N1-dinitrosopentamethylenetetramine
(abbreviated to DPT) ) .
[0153]
The amount of the foaming agents added is usually 1 to
70 parts by mass with respect to 100 parts by mass of the
10 inventive ethylene copolymer ( X ) .
[0154]
The foaming aids have effects such as lowering the
decomposition temperature or facilitating the decomposition
of the foaming agent, and making cells uniform. Examples of
15 the foaming aids include organic acids and salts thereof such
as salicylic acid, phthalic acid, stearic acid, oxalic acid
and citric acid; urea and derivatives thereof.
[0155]
Examples of commercially available such products include
20 CELLPASTE K5 (product name, manufactured by EIWA CHEMICAL IND.
CO., LTD., urea) and FE-507 (product name, manufactured by EIWA
CHEMICAL IND. CO., LTD., sodium bicarbonate) .
101561
The amount of the foaming aids added is usually 0.1 to
5 p a r t s b y m a s s w i t h r e s p e c t t o 1 0 0 p a r t s bymass o f t h e inventive
ethylene copolymer (X) .
[0157]
In order t o improve t h e mechanical p r o p e r t i e s of rubber
5 shaped a r t i c l e s obtained from the composition such a s t e n s i l e
s t r e n g t h , t e a r s t r e n g t h and abrasion r e s i s t a n c e , r e i n f o r c i n g
agents or inorganic f i l l e r s may be added t o t h e ethylene
copolymer composition of the i n v e n t i o n .
[0158]
Examples of t h e r e i n f o r c i n g agents include ASAHI #55G,
ASAHI #50HGandASAHI #6OG (productnames,manufacturedbyASAHI
CARBON CO., LTD.) and carbon black SEAST s e r i e s (such as SRF,
GPF, FEF, MAF, HAF, ISAF, SAF, FT and MT) (manufactured by Tokai
Carbon Co., L t d . ) ; products obtainedby s u r f a c e - t r e a t i n g t h e s e
15 carbon blacks with agents such as s i l a n e - c o u p l i n g a g e n t s ;
s i l i c a ; a c t i v a t e d calcium carbonate; f i n e l y powderedtalc and
f i n e l y powdered s i l i c i c a c i d .
[0159]
Of these, p r e f e r r e d a g e n t s i n c l u d e ASAHI #55G, ASAHI
20 #50HG, ASAHI #60G and SEAST FEF.
[0160]
Examples of t h e inorganic f i l l e r s include l i g h t calcium
carbonates, heavy calcium carbonates, t a l c s and c l a y s , with
t a l c s being p a r t i c u l a r l y p r e f e r a b l e . Examples of t h e talcs
include commercially available MISTRON VAPOR (manufactured by
NIHON MISTRON CO., LTD. ) .
[0161]
The amount of the reinforcing agents or the inorganic
5 fillers added is usually 150 to 800 parts by mass with respect
to 100 parts by mass of the inventive ethylene copolymer ( X ) .
[0162]
Whentheamountofthereinforcingagents orthe inorganic
fillers added is in the above range, the ethylene copolymer
10 composition of the invention exhibits excellent kneading
processability and gives rubber shaped articles (crosslinked
shaped articles) excellent in mechanical properties such as
strength and flexibility as well as in permanent compression
set.
15 [0163]
Similarly to usual rubber compositions, the ethylene
copolymer composition of the invention may be extended in
product life by the use of anti-aging agents.
[0164]
2 0 Examples of the anti-aging agents include known
anti-aging agents such as amine anti-aging agents, phenolic
anti-aging agents and sulfur anti-aging agents. Specific
examples include aromatic secondary amine anti-aging agents
such as phenylbutylamine and
N,Nr-di-2-naphthyl-p-phenylenediamine; phenolic anti-aging
agents such as dibutylhydroxytoluene and
tetrakis[methylene(3,5-di-t-butyl-4-hydroxy)
hydrocinnamato]methane; thioether anti-aging agents such as
5 bis[2-methyl-4-(3-n-alkylthiopropionyloxy)-5-t-butylphenyllsulfide;
dithiocarbamate salt anti-aging agents such
as nickel dibutyldithiocarbamate; zinc salts of
2-mercaptobenzoylimidazole and 2-mercaptobenzimidazole; and
sulfur anti-agingagents such as dilaurylthiodipropionate and
10 distearyl thiodipropionate. These anti-aging agents may be
used singly, or two or more kinds may be used in combination.
[0165]
The amount of the anti-aging agents added is usually 0.3
to 10 parts by mass with respect to 100 parts by mass of the
15 inventive ethylene copolymer (X). This amount of the
anti-aging agents added advantageously ensures that the
obtainable ethylene copolymer composition is free from
blooming on the surface as well as that vulcanization is not
inhibited.
20 [0166]
The processing aids may be any of processing aids
generally added to rubbers. Specific examples include
ricinolic acid, palmitic acid, lauric acid, stearic acid,
stearate esters, barium stearate, zinc stearate and calcium
s t e a r a t e , with s t e a r i c a c i d being p r e f e r a b l e .
[0167]
The amount of t h e processing a i d s added is u s u a l l y 10 p a r t s
bymassor less w i t h r e s p e c t t o 1 0 O p a r t s b y m a s s o f t h e i n v e n t i v e
5 e t h y l e n e copolymer ( X ) . This amount of t h e processing a i d s
added advantageously ensures t h a t t h e o b t a i n a b l e e t h y l e n e
copolymer composition is f r e e from blooming on t h e s u r f a c e a s
w e l l a s t h a t v u l c a n i z a t i o n is not i n h i b i t e d .
[0168]
Examples of t h e a c t i v a t i n g a g e n t s i n c l u d e amines such a s
di-n-butylamine, dicyclohexylamine, monoethanolamine, Acting
B (product name, manufactured by Yoshitomi Seiyaku K.K.) and
Acting SL (product name, manufactured by Yoshitomi Seiyaku
K . K . ) ;
a c t i v a t o r s such as d i e t h y l e n e g l y c o l , polyethylene
g l y c o l ( f o r example, PEG #4000 (product name, manufactured by
Lion Corporation) ) , l e c i t h i n , t r i a l l y l t r i m e l l i t a t e and zinc
compounds of a l i p h a t i c and aromatic c a r b o x y l i c a c i d s ( f o r
example, S t r u k t o l a c t i v a t o r 73, S t r u k t o l I B 531 and S t r u k t o l
20 FA 541 (product names, manufactured by S c i l l & S e i l a c h e r ) ) ;
z i n c p e r o x i d e m a s t e r b a t c h e s such a s ZEONET ZP (product name,
manufacturedby ZEONCORPORATION); octadecyltrimethylammonium
bromide; s y n t h e t i c h y d r o t a l c i t e ; and s p e c i a l quaternary
ammonium compounds ( f o r example, Arquad 2HT-F (product name,
manufactured by LION AKZO Co., L t d . ) ) .
[0169]
Of t h e s e , p o l y e t h y l e n e g l y c o l ( f o r example, PEG #4000
( p r o d u c t name, manufactured by Lion C o r p o r a t i o n ) ) and Arquad
5 2HT-F a r e p r e f e r a b l e .
[0170]
These a c t i v a t i n g a g e n t s m a y b e used s i n g l y , o r two ormore
kinds may be used i n combination.
The amount of t h e a c t i v a t i n g a g e n t s added is u s u a l l y 0.2
10 t o 10 p a r t s by mass with r e s p e c t t o 100 p a r t s by mass of t h e
i n v e n t i v e e t h y l e n e copolymer ( X ) .
[0171]
Examples o f t h e m o i s t u r e a b s o r b e r s i n c l u d e calcium oxide
( f o r example, VESTA-18 ( p r o d u c t name, manufactured by INOUE
15 SEKKAI KOGYO K . K . ) , s i l i c a g e l , sodium s u l f a t e , molecular
s i e v e s , z e o l i t e s and white carbon. Of t h e s e , calcium oxide is
p r e f e r a b l e .
[0172]
A p p r o p r i a t e m o i s t u r e a b s o r b e r s may be s e l e c t e d i n
20 accordance with p u r p o s e s . The m o i s t u r e a b s o r b e r s may be used
s i n g l y , o r two o r more kinds may be used i n combination. The
amount of t h e m o i s t u r e a b s o r b e r s added is u s u a l l y 0 . 5 t o 15
p a r t s bymass with r e s p e c t t o 1 0 0 p a r t s by mass o f t h e i n v e n t i v e
e t h y l e n e copolymer (X) .
[OX731
(Methods for producing ethylene copolymer compositions)
The ethylene copolymer compositions of the invention may
be produced by any methods riithout limitation. Various known
5 methods may be adopted in which the ethylene copolymer ( X ) is
mixed together with the additives.
[0174]
Exemplary production methods include a method in which
the components forthe ethylene copolymercompositionaremixed
10 together with, for example, a conventional kneading apparatus
suchasamixer, a kneader or rolls and further wit ha continuous
kneading apparatus such as a twin-screw extruder, and a method
in which the components for the ethylene copolymer composition
are dissolved or dispersed and the solvent is removed from the
15 solution.
[01751
[Crosslinked rubber shaped articles]
Crosslinked rubber shaped articles can be obtained by
shapingandcrosslinkingthe aforementionedinventive ethylene
20 copolymer composition simultaneously (production method 1) or
by shaping and thereafter crosslinking the composition
(production method 2).
[0176]
In the invention, the term "shaped articles" refers to
shaped a r t i c l e s other than f i l m s or s h e e t s with a t h i c k n e s s
of not more than 1.5 mm.
[0177]
In an example of t h e production method 1, t h e inventive
5 ethylene copolymer composition is p r e l i m i n a r i l y shaped, while
performing heating c o n c u r r e n t l y w i t h t h e preliminary shaping,
i n t o a d e s i r e d shape by any of various shaping methods which
involve a h e a t e r such as a h e a t i n g tank with a h e a t i n g
c o n f i g u r a t i o n such as e x t r u d e r , p r e s s , i n j e c t i o n molding
10 apparatus, t r a n s f e r molding apparatus, hot a i r , g l a s s bead
f l u i d i z e d bed, UHF ( u l t r a high frequency wave), steam or LCM
(molten s a l t b a t h ) .
[01781
In t h i s method, t h e aforementioned v u l c a n i z i n g a g e n t is
15 used, o p t i o n a l l y together with the v u l c a n i z a t i o n a c c e l e r a t o r
and/or t h e v u l c a n i z a t i o n a i d . The h e a t i n g c o n d i t i o n s a r e
g e n e r a l l y 140 t o 300°C, p r e f e r a b l y 150 t o 270°C and u s u a l l y
0.5 t o 30 minutes, p r e f e r a b l y 0.5 t o 20 minutes. This heating
induces a crosslinkingreactiontoallowtheinventive ethylene
20 copolymer t o form a high-order network s t r u c t u r e and thereby
t o give rubber shaped a r t i c l e s having high s t r e n g t h and
e x c e l l e n t rubber e l a s t i c i t y .
[0179]
The shaping and c r o s s l i n k i n g of t h e i n v e n t i v e e t h y l e n e
copolymer composition may be performed with o r without a mold.
Without a mold, t h e i n v e n t i v e copolymer composition is u s u a l l y
shaped and c r o s s l i n k e d c o n t i n u o u s l y .
[0180]
In an example of t h e p r o d u c t i o n method 2, t h e e t h y l e n e
copolymer composition is p r e l i m i n a r i l y shaped by t h e
a f o r e m e n t i o n e d s h a p i n g method and t h e shaped a r t i c l e is
i n t r o d u c e d and heated i n a v u l c a n i z a t i o n tank o r t h e shaped
a r t i c l e is i r r a d i a t e d with e l e c t r o n beams.
10 [0181]
When t h e shaped a r t i c l e is i n t r o d u c e d and h e a t e d i n a
v u l c a n i z a t i o n tank, t h e h e a t i n g c o n d i t i o n s may be s i m i l a r t o
t h o s e i n t h e method i n which t h e composition is heated
c o n c u r r e n t l y w i t h t h e p r e l i m i n a r y shaping.
15 [01821
Next, i n t h e m e t h o d w i t h t h e applicationofelectronbeams,
t h e p r e l i m i n a r i l y shaped a r t i c l e may be i r r a d i a t e d with 0 . 1
t o 10 MeV e l e c t r o n beams such t h a t t h e a b s o r b e d d o s e w i l l be,
f o r example, 0 . 5 t o 35 Mrad, and p r e f e r a b l y 0.5 t o 20 Mrad.
20 In t h i s manner, s i m i l a r l y a s d e s c r i b e d above, a c r o s s l i n k i n g
r e a c t i o n is induced which allows t h e i n v e n t i v e e t h y l e n e
copolymer composition t o forma c r o s s l i n k e d p o l y m e r a n d t o g i v e
rubber shaped a r t i c l e s having high s t r e n g t h .
[0183]
For example, t h e rubber shaped a r t i c l e s produced by the
aforementioned methods may be used i n various f i e l d s . I n
d e t a i l , t h e shaped a r t i c l e s may be s u i t a b l y manufactured as
products such a s automobile p a r t s , marine v e s s e l p a r t s , c i v i l
5 engineering and b u i l d i n g p a r t s , medical p a r t s , e l e c t r i c and
e l e c t r o n i c appliance p a r t s , t r a n s p o r t machine p a r t s , l e i s u r e
goods, hoses (such as r a d i a t o r hoses and h e a t e r h o s e s ) ,
vibration-proof r u b b e r s , s h e e t s , various b e l t s , various
packings, s e a l i n g m a t e r i a l s , p o t t i n g m a t e r i a l s and coating
10 m a t e r i a l s .
[0184]
Examples of t h e automobile p a r t s include g l a s s run
channels, weather s t r i p sponges, door opening t r i m s , s e a l
members, grommets, automobile engine gaskets, s e a l i n g
15 m a t e r i a l s f o r e l e c t r i c a l components o r o i l f i l t e r s ; p o t t i n g
m a t e r i a l s f o r i g n i t e r H I C s or automobile hybrid I C s ; coating
m a t e r i a l s f o r automobile bodies, automobile window g l a s s e s and
engine c o n t r o l boards; gaskets f o r p a r t s such a s o i l pans or
timing b e l t covers, and adhesives f o r moles, head lamp l e n s e s ,
20 sun roof s e a l s and mirrors.
[0185]
Examples of t h e weather s t r i p sponges include door
w e a t h e r s t r i p s , trunk w e a t h e r s t r i p s , luggage w e a t h e r s t r i p s ,
roof s i d e r a i l w e a t h e r s t r i p s , s l i d e door w e a t h e r s t r i p s ,
v e n t i l a t o r w e a t h e r s t r i p s , s l i d i n g roof w e a t h e r s t r i p s , f r o n t
window w e a t h e r s t r i p s , r e a r window w e a t h e r s t r i p s , q u a r t e r
window w e a t h e r s t r i p s , l o c k p i l l a r w e a t h e r s t r i p s , door g l a s s
o u t e r w e a t h e r s t r i p s and door g l a s s i n n e r w e a t h e r s t r i p s .
5 [0186]
Examples of t h e marine v e s s e l p a r t s include s e a l i n g
m a t e r i a l s f o r wire connection and branching boxes, e l e c t r i c a l
systempartsorelectricwires; a n d a d h e s i v e s f o r e l e c t r i c w i r e s
or g l a s s e s .
10 [0187]
Examples of t h e c i v i l engineering and b u i l d i n g p a r t s
i n c l u d e b u i l d i n g s e a l a n t s u s e d f o r b u t t j o i n t s i n a g l a s s screen
method f o r commercial b u i l d i n g s , j o i n t s of g l a s s f r i n g e s and
sashes, i n t e r i o r j o i n t s in t o i l e t f a c i l i t i e s , l a v a t o r i e s , show
15 cases or t h e l i k e , j o i n t s i n b a t h t u b circumferences, outer wall
expansion j o i n t s i n p r e f a b r i c a t i o n h o u s e s , a n d j o i n t s o f s i d i n g
boards; s e a l i n g m a t e r i a l s f o r double g l a s s e s ; c i v i l
engineering s e a l a n t s used i n road r e p a i r i n g ; coatings and
adhesives f o r metals, g l a s s e s , s t o n e m a t e r i a l s , s l a t e s ,
20 concretes or t i l e s ; and p r e s s u r e - s e n s i t i v e adhesive s h e e t s ,
waterproof s h e e t s or vibration-proof s h e e t s .
[0188]
Examples of t h e medical p a r t s include medical rubber
s t o p p e r s , s y r i n g e g a s k e t s and rubber stoppers f o r pressure
r e d u c t i o n v e s s e l s .
[0189]
Examples of t h e electric and e l e c t r o n i c a p p l i a n c e p a r t s
i n c l u d e s e a l i n g m a t e r i a l s , p o t t i n g m a t e r i a l s , c o a t i n g
5 m a t e r i a l s o r adhesives f o r heavy electric machinery p a r t s ,
l i g h t electric machinery p a r t s , and c i r c u i t s and boards f o r
electric and e l e c t r o n i c a p p l i a n c e s ; r e p a i r i n g m a t e r i a l s f o r
electric w i r e c o a t i n g s ; i n s u l a t i n g s e a l i n g m a t e r i a l s f o r
electric w i r e j o i n t s ; OA appliance r o l l s ; v i b r a t i o n absorbing
10 m a t e r i a l s ; grommets; o r g e l s or c a p a c i t o r s e a l i n g m a t e r i a l s .
[0190]
Examples of t h e t r a n s p o r t machine p a r t s i n c l u d e
automobiles, marine v e s s e l s , a i r p l a n e s and railway v e h i c l e s .
[0191]
Examples oftheleisuregoodsinclude swimming gears such
a s swimming caps, diving masks and earplugs; and g e l b u f f e r i n g
members f o r i t e m s such a s s p o r t shoes and b a s e b a l l gloves.
[01921
Examples of t h e v i b r a t i o n - p r o o f rubbers i n c l u d e
20 automobilevibration-proof rubbers (enginemounts, l i q u i d s e a l
engine mounts, damper p u l l e y s , chain dampers, c a r b u r e t o r
mounts, t o r s i o n a l dampers, s t r u t mounts, rubber bushes, bumper
rubbers, h e l p e r rubbers, s p r i n g s e a t s , shock a b s o r b e r s , a i r
s p r i n g s , body mounts, bumper guards, muffler s u p p o r t s , rubber
couplings, c e n t e r bearing s u p p o r t s , c l u t c h rubbers, deaf
mounts, suspension bushes, s l i d e bushes, cushion s t r u t b a r s ,
s t o p p e r s , handle dampers, r a d i a t o r s u p p o r t e r s o r muffler
h a n g e r s ) , railway v i b r a t i o n - p r o o f r u b b e r s ( s l a b mats, b a l l a s t
5 mats o r t r a c k mats) and i n d u s t r i a l machinery v i b r a t i o n - p r o o f
rubbers (expansion j o i n t s , f l e x i b l e j o i n t s , bushes and
mounts) .
[0193]
Examples of t h e s h e e t s i n c l u d e roofing s h e e t s and
10 waterproof s h e e t s .
[0194]
Examples of t h e v a r i o u s b e l t s i n c l u d e t r a n s m i s s i o n b e l t s
(V b e l t s , f l a t b e l t s , toothed b e l t s and timing b e l t s ) and
c o n v e y o r b e l t s ( l i g h t c o n v e y o r b e l t s , c y l i n d r i c a l b e l t s , rough
15 t o p b e l t s , f l a n g e d c o n v e y o r b e l t s , U-typeguidedconveyorbelts
and V-type guided conveyor b e l t s ) .
[01951
For example, t h e above s e a l i n g m a t e r i a l s a r e s u i t a b l y
u s e d a s s e a l i n g m a t e r i a l s f o r r e f r i g e r a t o r s , f r e e z e r s , washing
20 machines, gas meters, microwave ovens, steam i r o n s and leakage
b r e a k e r s . The t e r m s e a l i n g m a t e r i a l s r e f e r s t o m a t e r i a l s which
s e a l ( e n c a p s u l a t e o r t i g h t l y c l o s e ) o b j e c t s . I n a b r o a d s e n s e ,
thesealingmaterialsincludematerialswhichareusedtoobtain
water or a i r t i g h t n e s s a t j o i n t s o r c o n t a c t s i n v a r i o u s
i n d u s t r i e s such as machinery, e l e c t r i c i t y and chemistry.
[0196]
For example, the p o t t i n g m a t e r i a l s a r e s u i t a b l y used f o r
t h e p o t t i n g of transformer high-voltage c i r c u i t s , p r i n t e d
5 boards, high voltage t r a n s f o r m e r s w i t h v a r i a b l e r e s i s t o r s ,
e l e c t r i c a l i n s u l a t i n g p a r t s , semiconductive p a r t s and
conductive p a r t s .
[0197]
For example, the coating m a t e r i a l s a r e s u i t a b l y used f o r
10 t h e coating of various c i r c u i t elements such as high voltage
t h i c k f i l m r e s i s t o r s or hybrid I C s ; H I C s , e l e c t r i c a l i n s u l a t i n g
p a r t s ; semiconductive p a r t s ; conductive p a r t s ; modules;
p r i n t e d c i r c u i t s ; ceramicboards; b u f f e r m a t e r i a l s f o r diodes,
t r a n s i s t o r s or bonding wires; semiconductor elements; or
15 o p t i c a l f i b e r s f o r o p t i c a l communication.
[0198]
I n a d d i t i o n t o the aforementioned a r t i c l e s , t h e rubber
shaped a r t i c l e s of the invention may be s u i t a b l y manufactured
as automobile c u p / s e a l m a t e r i a l s (master cylinder p i s t o n cups,
20 wheel c y l i n d e r p i s t o n c u p s , c o n s t a n t - v e l o c i t y j o i n t b o o t s , pin
boots, dust covers, p i s t o n s e a l s , packings, O-rings,
diaphragms, damwindow s h i e l d s , d o o r m i r r o r b r a c k e t s , s e a l head
lamps and s e a l cowl t o p s ) , i n d u s t r i a l s e a l i n g m a t e r i a l s
( c a p a c i t o r packings, O-rings and packings), foams
(hose-protecting sponges, cushioning sponges, heat i n s u l a t i n g
sponges and i n s u l a t i o n p i p e s ) , e l e c t r i c wire coverings,
e l e c t r i c wire j o i n t s , e l e c t r i c a l i n s u l a t i n g p a r t s ,
semiconductive r u b b e r p a r t s , OAappliance r o l l s ( c h a r g e d r o l l s ,
5 t r a n s f e r r o l l s , development r o l l s and paper feed r o l l s ) ,
i n d u s t r i a l r o l l s (iron-making r o l l s , paper-making r o l l s and
p r i n t i n g e l e c t r i c wire r o l l s ) , anode caps, plug caps, i g n i t i o n
cables, lamp socket covers, terminal covers, wiper blades,
v a r i o u s t u b e s (vacuum tubes and t i r e t u b e s ) , a i r s p r i n g s , shoe
10 s o l e s , shoe h e e l s , t i r e s i d e walls and f a b r i c c o a t i n g s .
[01991
[Films or s h e e t s ]
I n a p r e f e r r e d embodiment, films or s h e e t s ( h e r e i n a f t e r ,
sometimes c o l l e c t i v e l y r e f e r r e d t o as f i l m s ) t h a t include the
15 i n v e n t i v e ethylene copolymer ( X ) contain t h e ethylene
copolymer ( X ) a s t h e p r i n c i p a l r e s i n component.
[02001
The f i l m s of t h e invention may contain r e s i n s o t h e r than
t h e copolymer ( X ) as long as t h e i r performance is not
20 d e t e r i o r a t e d . S p e c i f i c examples of such r e s i n s include LDPE
and LLDPE.
[02011
The thickness of t h e inventive f i l m s may be determined
i n accordance with a p p l i c a t i o n s , but is u s u a l l y i n t h e range
of 10 t o 1500 pm, and p r e f e r a b l y 20 t o 1500 pm.
[0202]
The f i l m s of t h e i n v e n t i o n may c o n t a i n a p l a s t i c i z e r ( Y )
i n t h e r a n g e o f 100 t o 1000 p a r t s by mass, p r e f e r a b l y 130 t o
5 700 p a r t s by mass, and more p r e f e r a b l y 150 t o 500 p a r t s by m a s s
with r e s p e c t t o 100 p a r t s by mass of t h e e t h y l e n e copolymer
( X ) .
[0203]
By c o n t a i n i n g t h e p l a s t i c i z e r ( Y ) i n t h e above amount,
10 t h e o b t a i n a b l e f i l m s become advantageously s o f t e n e d t o e x h i b i t
f l e x i b i l i t y (low h a r d n e s s ) and high s t r e t c h a b i l i t y . F u r t h e r ,
such f i l m s can be calendered a s w i l l be d e s c r i b e d l a t e r .
[02041
The p l a s t i c i z e r s ( Y ) i n t h e i n v e n t i o n may be s e l e c t e d
15 a p p r o p r i a t e l y i n accordance with p u r p o s e s . A s i n g l e
p l a s t i c i z e r o r a mixture of two o r more kinds of p l a s t i c i z e r s
may be used. Examples of t h e p l a s t i c i z e r s i n c l u d e petroleum
p l a s t i c i z e r s such as p r o c e s s o i l s ( f o r example: "Diana Process
O i l PW-380" (product name, manufactured by Idemitsu Kosan Co.,
20 L t d . ) , "Diana Process O i l PW-100" (product name, manufactured
by Idemitsu Kosan Co., L t d . ) and "Diana Process O i l PS-430"
(product name, manufactured by Idemitsu Kosan Co., Ltd. ) ) ,
l u b r i c a t i n g o i l s , p a r a f f i n o i l s , l i q u i d p a r a f f i n s , petroleum
a s p h a l t s a n d v a s e l i n e s ; c o a l t a r p l a s t i c i z e r s such as c o a l tars
and coal tar pitches; fatty oil plasticizers such as castor
oil, linseed oil, rapeseed oil, soybean oil and coconut oil;
waxes such as bees wax, carnauba wax and lanolin; fatty acids
and salts thereof such as ricinoleic acid, palmitic acid,
5 stearic acid, barium stearate, calcium stearate and zinc
laurate; naphthenic acid, pine oil, rosin and derivatives
thereof; synthetic polymer substances such as terpene resins,
petroleum resins and coumarone indene resins; ester
plasticizers such as dioctyl phthalate, dioctyl adipate and
10 dioctyl sebacate; and others such as microcrystalline waxes,
liquidthiokols, hydrocarbon-based synthetic lubricating oils,
tall oils and rubber substitutes (factices). Of these,
petroleum plasticizers are preferable, and process oils are
particularly preferable.
15 [0205]
In terms of flexibility and stretchability, the hardness
(the durometer type A hardness measured by a method specified
in JIS K 6253) of the inventive films or sheets is preferably
in the range of 10 to 80, and more preferably 10 to 60.
20 [0206]
Further, the films or sheets of the invention have
sufficient strength and high elongation.
[0207]
The ethylene copolymer (X) contained in the inventive
f i l m or sheet may be p a r t i a l l y c r o s s l i n k e d . Crosslinking
produces an e f f e c t t h a t the r e s i d u a l s t r a i n a f t e r s t r e t c h i n g
is reduced.
[0208]
Any c r o s s l i n k i n g methods may be used without l i m i t a t i o n .
Exemplary methods include a method using c r o s s l i n k i n g agents
such as s u l f u r and peroxides, and a method i n which e l e c t r o n
beams a r e a p p l i e d . Any e l e c t r o n beams may be used without
l i m i t a t i o n a s long as t h e electronbeams cancause t h e ethylene
10 copolymer (X) t o be c r o s s l i n k e d .
[02091
I n g e n e r a 1 , t h e c r o s s l i n k i n g i s performedinsuchamanner
t h a t the films formed a r e i r r a d i a t e d with e l e c t r o n beams i n
t h e range of 10 t o 200 kGy. The dose of t h e e l e c t r o n beams is
15 a d j u s t e d i n accordance with t h e a p p l i c a t i o n s of the f i l m s . In
general, t h e degree of c r o s s l i n k i n g tends t o be increased with
i n c r e a s i n g dose.
[0210]
Films formed by shaping a n e t h y l e n e copolymer with an
20 i n t r i n s i c v i s c o s i t y [q] of l e s s than 7.8 d l / g u s u a l l y tend t o
be o r i e n t e d i n t h e m a c h i n e d i r e c t i o n (MD) when t h e m o l t e n f i l m s
a r e drawn. Thus, such films or s h e e t s tend t o e x h i b i t higher
s t r e n g t h i n the machine d i r e c t i o n (MD) than i n the t r a n s v e r s e
d i r e c t i o n (TD) perpendicular t h e r e t o .
[0211]
I n c o n t r a s t , t h e f i l m s o r s h e e t s formed f r o m t h e i n v e n t i v e
e t h y l e n e copolymer ( X ) t e n d t o show h i g h e r s t r e n g t h i n t h e TD
t h a n i n t h e MD.
5 [0212]
Although t h e r e a s o n f o r t h i s is u n c l e a r , it is p r o b a b l e
t h a t t h e mechanism by which t h e f i l m s o r s h e e t s formed from
t h e i n v e n t i v e e t h y l e n e copolymer ( X ) e x h i b i t high s t r e n g t h be
mainly a s c r i b e d t o t h e d i f f e r e n c e of entanglement s t r e n g t h of
10 polymer m o l e c u l e s . I n t h i s c a s e , it is c o n s i d e r e d t h a t t h e
polymer m o l e c u l e s a r e d i s e n t a n g l e d by s t r e t c h i n g and
c o n s e q u e n t l y t h e number of i n t e r l o c k s becomes s m a l l e r i n t h e
MD a s compared with t h e TD of t h e f i l m s , and t h e consequent
s t r e n g t h - l o w e r i n g e f f e c t s u r p a s s e s t h e s t r e n g t h - i n c r e a s i n g
15 e f f e c t by t h e c r y s t a l l i z a t i o n of t h e polymer by s t r e t c h i n g .
T h i s is p r o b a b l y t h e reason why t h e s t r e n g t h i n t h e TD becomes
h i g h e r t h a n i n t h e MD.
[0213]
While i n a p r e f e r r e d embodiment t h e i n v e n t i v e e t h y l e n e
20 polymer (X) is produced with use of t h e a f o r e m e n t i o n e d
m e t a l l o c e n e c a t a l y s t , such a p o l y m e r t e n d s t o h a v e a l o w e r v a l u e
B t h a n polymers o b t a i n e d u s i n g c o n v e n t i o n a l Z i e g l e r c a t a l y s t s .
This f a c t i n d i c a t e s t h a t t h e polymer has high b l o c k
c h a r a c t e r i s t i c s . Provided t h a t polymers a r e amorphous, it is
g e n e r a l l y reasonable t o t h i n k t h a t apolymer w i t h a l o r i e r value
B has higher c o m p a t i b i l i t y with o i l s ( i n p a r t i c u l a r , p a r a f f i n
o i l s ) . Thus, it is assumed t h a t a s compared with
Z i e g l e r - c a t a l y z e d polymers, t h e polymers c a t a l y z e d by t h e
5 aforementioned metallocene c a t a l y s t s have more uniform
entanglement, p a r t i c u l a r l y i n t h e TD, which is e f f e c t i v e f o r
t h e i n c r e a s e of s t r e n g t h i n t h e TD, and consequently t h e
d i f f e r e n c e i n s t r e n g t h between t h e MD and t h e TD is f u r t h e r
i n c r e a s e d .
10 [02141
P r e f e r a b l y , t h e f i l m s or s h e e t s formed f r o m t h e i n v e n t i v e
e t h y l e n e copolymer ( X ) have a STD/SMD r a t i o of not less than
1.1, andpreferablynotlessthan1.5 wherein S T D i s t h e t e n s i l e
break s t r e n g t h i n t h e TD and SMD is t h e t e n s i l e break s t r e n g t h
15 i n t h e MD obtained by c a r r y i n g o u t a t e n s i l e test ( J I S K 6251)
d e s c r i b e d l a t e r . Althoughthe upper l i m i t is not p a r t i c u l a r l y
l i m i t e d , t h e r a t i o is u s u a l l y not more than 3.0.
102151
The f i l m s or s h e e t s formed from t h e i n v e n t i v e e t h y l e n e
20 copolymer ( X ) u s u a l l y have a t h i c k n e s s of about 100 pm t o 1000
pm; and t h e s t r e n g t h thereof is u s u a l l y 2 MPa t o 15 MPa i n an
uncrosslinked s t a t e and is u s u a l l y 2 MPa t o 15 MPa a f t e r
c r o s s l i n k e d . However, t h e s e p r o p e r t i e s a r e n o t l i m i t e d t o t h e
above ranges.
[0216]
The films or s h e e t s formed from the inventive ethylene
copolymer ( X ) have e x c e l l e n t s t r e t c h a b i l i t y , p a r t i c u l a r l y i n
the t r a n s v e r s e d i r e c t i o n , and thus achieve e x c e l l e n t
5 a p p l i c a t i o n p r o p e r t i e s . Forexample, usual f i l m s o r s h e e t s a r e
e a s i l y broken by being s t r e t c h e d i n the t r a n s v e r s e d i r e c t i o n
when they a r e used t o wrap o b j e c t s l a r g e r than t h e width of
t h e films o r s h e e t s . Because of t h i s , wrapping frequently
e n t a i l s t h e a p p l i c a t i o n two times. The f i l m s or s h e e t s formed
10 from the i n v e n t i v e e t h y l e n e copolymer ( X ) a r e r e s i s t a n t t o
c u t t i n g o r breakage even when they a r e applied t o wrap o b j e c t s
while being s t r e t c h e d i n the t r a n s v e r s e d i r e c t i o n . Thus,
wrapping can be completed i n one a p p l i c a t i o n .
[0217]
15 [Film production methods]
The f i l m s of the invention may be formed by various known
production methods, f o r example, by melt e x t r u s i o n methods
(T-die methods and blown-film extrusion methods), s o l u t i o n
methods ( s o l u t i o n c a s t i n g methods and wet castingmethods) and
20 calendering methods. In p a r t i c u l a r , calendering methods a r e
p r e f e r a b l e from t h e viewpoint of p r o d u c t i v i t y .
[0218]
[Applications of f i l m s ]
The films of the invention may be used i n a p p l i c a t i o n s
where c o n v e n t i o n a l f i l m s such a s v i n y l c h l o r i d e f i l m s and
s i l i c o n f i l m s have been u t i l i z e d .
EXAMPLES
[0219]
Next, t h e p r e s e n t i n v e n t i o n w i l l be d e s c r i b e d i n f u r t h e r
d e t a i l by p r e s e n t i n g examples without l i m i t i n g t h e scope of
t h e i n v e n t i o n .
[02201
P r o p e r t i e s of e t h y l e n e copolymers o b t a i n e d i n examples
10 and comparative examples were measured i n accordance with t h e
f o l l o w i n g methods.
[0221]
[Molar amount of s t r u c t u r a l u n i t s d e r i v e d from e t h y l e n e [A]]
The amount was determinedbymeasuringtheintensitywith
15 a 'H-NMR s p e c t r o m e t e r .
[0222]
[Molar amount of s t r u c t u r a l u n i t s d e r i v e d from non-conjugated
polyene [Cl I
The amount was determinedbymeasuringtheintensitywith
20 a 'H-NMR s p e c t r o m e t e r .
[0223]
[ I n t r i n s i c v i s c o s i t y [q] : d l / g ]
The i n t r i n s i c v i s c o s i t y [ql was measured a t t e m p e r a t u r e :
135°C i n measurement s o l v e n t : d e c a l i n using a f u l l y automatic
i n t r i n s i c viscometer manufactured by RIG0 CO., LTD.
[0224]
[Loss tangent ( t a n 6) ]
The l o s s tangent ( t a n 6) was measured using a
5 v i s c o e l a s t i c i t y t e s t e r (model: ARES) manufactured by TA
Instruments. In d e t a i l , a 25mmin diameter x 2 mminthickness
disk-shaped specimen sampled from a 2 mm t h i c k sheet obtained
b y p r e s s i n g a t l 9 O 0 C r i a s t e s t e d u n d e r t h e following c o n d i t i o n s .
RSI Orchestrator (manufactured by TA Instruments) was used as
10 the data p r o c e s s i n g s o f t w a r e .
[0225]
Geometry: p a r a l l e l p l a t e
Measurement temperature: -10°C
Frequency: 1 Hz
15 [0226]
[Example 1: Ethylene copolymer-11
In a 300-L volume polymerizer equipped with a s t i r r i n g
blade, a polymerization r e a c t i o n was continuously c a r r i e d out
a t 60°C t o produce a terpolymer i n c l u d i n g a component [ A ] :
20 ethylene, a component [B]: propylene and a component [C]:
5-ethylidene-2 -norbornene (ENB) .
[0227]
To the polymerizer were continuously fed hexane as a
polymerization solvent ( f e e d r a t e : 4 4 kg/h), ethylene a t a feed
rate of 4.5 kg/h, propylene at a feed rate of 2.9 kg/h, ENB
at a feed rate of 0.55 kg/h, and hydrogen at 0.4 NL/h. While
maintaining the polymerization pressure at 1.6 MPa,
(t-butylamido)-dimethyl(q5-2-methyl-s-indacen-l-yl)
5 silanetitanium (11) 1,3-pentadiene having a structure
represented by aforementioned Formula (VIII) was continuously
fed as a main catalyst to the polymerizer at 0.04 mmol/h.
Further, cocatalysts, namely,
trityltetrakis (pentaf luorophenyl) borate [ (CsH5) 3CB(CsFs) 41
10 and triisobutylaluminum (hereinafter, also referred to as
"TIBA") as an organoaluminum compound were continuously fed
to the polymerizer at 0.2lmmol/h and 13 mrnol/h, respectively.
[0228]
In the abovemanner, a polymerization liquidwas obtained
15 which contained 2.1 mass% of a copolymer including ethylene,
propylene and ENB. The main catalyst had been obtained by
synthesis i n a c c o r d a n c e w i t h a m e t h o d d e s c r i b e d i n W 0 98/49212.
The polymerization reaction was terminated by the addition of
a small amount of methanol to the polymerization liquid
20 withdrawn from the lower portion of the polymerizer. The
polymer was separated from the solvent by steam stripping
treatment and was thereafter dried at 80°C and a reduced
pressure for all day and night. The properties ofthe obtained
ethylene copolymer-1 are described in Table 1.
[02291
[Example 2: Ethylene copolymer-21
Polymerization was performed under t h e same conditions
as i n Example 1, except t h a t t h e feed r a t e s f o r ethylene,
5 propylene, ENB and hydrogen were changed. The p r o p e r t i e s of
the obtained ethylene copolymer-2 a r e described i n Table 1.
[02301
[Example 3: Ethylene copolymer-31
Polymerization was performed under the same conditions
10 as i n Example 1, except t h a t t h e feed r a t e s f o r ethylene,
propylene, ENB and hydrogen were changed. The p r o p e r t i e s of
the obtained ethylene copolymer-3 a r e described i n Table 1.
[0231]
[Example 4 : Ethylene copolymer-41
Polymerization was performed under t h e same conditions
a s i n Example 1, except t h a t t h e feed r a t e s f o r ethylene,
propylene, ENB and hydrogen were changed. The p r o p e r t i e s of
t h e obtained ethylene copolymer-4 a r e described i n Table 1.
[02321
20 [Comparative Example 1: Ethylene copolymer-51
Polymerization was performed under t h e same conditions
as i n Example 1, except t h a t t h e feed r a t e s f o r ethylene,
propylene, ENB and hydrogen were changed. The p r o p e r t i e s of
the obtained ethylene copolymer-5 a r e described i n Table 1.
[0233]
[Comparative Example 2: Ethylene copolymer-61
Polymerization was performed under the same conditions
as in Example 1, except that the feed rates for ethylene,
5 propylene, ENB and hydrogen were changed. The properties of
the obtained ethylene copolymer-6 are described in Table 1.
[0234]
[Comparative Example 31
EP98 (product name, manufactured by JSR Corporation,
10 amount of extender oil: 75 parts by mass) was subjected to
Soxhlet extraction using boiling methyl ethyl ketone (MEK).
The residue was obtained as an
ethylene.propylene.5-ethylidene-2-norbornen terpolymer
(three-component polymer). The properties of the obtained
15 copolymer are described in Table 1.
[0235]
[Comparative Example 4: Ethylene copolymer-71
[Production example of
ethylene.propylene.5-ethylidene-2-norbornen (ENB)]
Ethylene, propylene and 5-ethylidene-2-norbornene (ENB)
were continuously copolymerized in a 15-L volume polymerizer
equipped with a stirring blade. From the upper portion of the
polymerizer, hexane as a polymerization solvent was
continuously fed at a rate of 5 L per hour. On the other hand,
the polymerization liquid was continuously withdrawn fromthe
lower portion of the polymerizer such that the volume of the
polymerization liquid in the polymerizer was constantly 5 L.
The catalysts used were VOC13 and A1 (C2H5)1 .5C11.5.I n detail,
5 VOc13 and A1 (C2H5)1 .5C11.w5e re continuously fed to the
polymerizer such that the vanadium atom concentration and the
aluminum atom concentration in the polymerizer would be 0.55
mmol/L and 3.3 mmol/L, respectively.
102361
Ethylene and propylene monomers were continuously fed at
rates of 200 L/h and 60 L/h, respectively. Further, ENB was
continuously fedsuchthat its concentrationinthepolymerizer
would be 4 g/L. Hydrogen was used as a molecular weight
modifier and was fed such that the hydrogen concentration in
15 the gas phase in the polymerizer would be 5 mol%. The
copolymerization reaction was performed at a temperature of
40°C while circulating cooling water through a jacket on the
exterior of the polymerizer.
102371
The copolymerization reaction under the above conditions
afforded a uniform solution of an ethylene,propylene,ENB
copolymer. The polymerization reaction was terminated by the
addition of a small amount of methanol to the polymerization
liquid withdrawn from the lower portion of the polymerizer.
The polymer was separated from the solvent by steam stripping
treatment and was thereafter dried at 80°C and a reduced
pressure for all day and night. Through the above procedures,
the ethylene.propylene.ENB copolymer was obtained at a rate
5 of 265 g per hour.
[0238]
The obtained ethylene copolymer-7 had an
ethylene/propylene molar ratio of 77/23, an intrinsic
viscosity [q] of 4.5 dl/g, and an ENB content of 1.3 mol%. The
10 properties of the obtained copolymer are described in Table
[Table 11
Table 1
15 102401
The permanent compression set of ethylene copolymers
obtained in Comparative Example 5 and Reference Example 1
described below was measured i n accordance with t h e following
method.
[0241]
[Permanent compression s e t ]
Specimens f o r the measurement of permanent compression
s e t were prepared as follows.
[0242]
With a 1 . 7 L Banbury mixer, t h e r e were kneaded 220 p a r t s
by mass of an ethylene copolymer composition (ethylene
10 copolymer: 100 p a r t s by mass, p l a s t i c i z e r : 120 p a r t s by mass),
5 p a r t s by mass of Chinese white No. 3 as a v u l c a n i z a t i o n a i d ,
1 p a r t by mass of s t e a r i c acid a s a processing a i d , 1 p a r t by
mass of "PEG #400OW (product name, polyethylene glycol,
manufactured by Lion Corporation) as an a c t i v a t i n g agent, 50
15 p a r t s by mass of carbon black: "ASAHI #50GW (product name,
manufacturedbyASAH1 CARBONCO., LTD.) as a r e i n f o r c i n g a g e n t ,
40 p a r t s by mass of calcium bicarbonate: "WHITON SB" (product
name, manufactured by SHIRAISHI CALCIUM KAISHA, LTD.) and 30
p a r t s by mass of s u r f a c e - t r e a t e d calcium carbonate "HAKUENKA
20 CC" (product name, manufactured by SHIRAISHI CALCIUM KAISHA,
LTD.) as inorganic f i l l e r s , and 50 p a r t s by mass of "Diana
Process O i l PW-380" (product name, manufactured by Idemitsu
Kosan Co., L t d . ) a s a p l a s t i c i z e r .
102431
The resultant kneadate was supplied to 14-inch rolls
(front roll temperature/rear roll temperature = 50"~/50"a~n)d
was kneaded together with vulcanization accelerators: 2.0
parts by weight of "Sanceler BZ" manufactured by SANSHIN
5 CHEMICAL INDUSTRY CO., LTD.: name of compound: zinc
di-n-butyl.dithiocarbamate, 1.0 part by weight of "Sanceler
M" manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.: name
of compound: 2-mercaptobenzothiazole, 0.5 parts by weight of
"Sanceler TT" manufactured by SANSHIN CHEMICAL INDUSTRY CO.,
10 LTD. : name of compound: tetramethylthiuram disulf ide, and 0.5
parts by weight of "Sanceler TRA" manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD.: name of compound:
dipentamethylenethiuram tetrasulfide, and with 1.2 parts by
weight of sulfur. Thus, a compounded rubber (a rubber
15 composition) was obtained.
[0244]
Next, the rubber composition was treated in accordance
with JIS K 6250-8.5 (vulcanization at 170"~f or 15 minutes)
into a vulcanized sample, and the permanent compression set
20 a f t e r t r e a t m e n t a t - 1 0 o ~ f o r 2 2 h o u r s w a s m e a s u r e d i n a c c o r d a n c e
with JIS K 6262 (1997).
102451
[Comparative Example 51
Polymerization was performed under the same conditions
as in Comparative Example 4, except that the feed rates for
ethylene, propylene, ENB and hydrogen were changed. The
properties ofthe obtained ethylene copolymer-7 are described
in Table 2.
5 [0246]
[Reference Example 11
Polymerization was performed under the same conditions
as in Example 1, except that the feed rates for ethylene,
propylene, ENB and hydrogen were changed. The properties of
10 the obtained ethylene copolymer-r are described in Table 2.
[0247]
[Table 21
Table 2
[0248]
[Ethylene copolymer compositions]
Properties of ethylene copolymer compositions obtained
in examples and comparative examples were measured in
accordance with the following methods.
[Loss tangent (tan 6) 1
The loss tangent (tan 6) was measured using a
viscoelasticity tester (model: ARES) manufactured by TA
Instruments. In detail, a 25 mmin diameter x 2 mminthickness
5 disk-shaped specimen sampled from a 2 mm thick sheet obtained
b y p r e s s i n g a t 1 9 O 0 C w a s t e s t e d u n d e r t h e following conditions.
RSI Orchestrator (manufactured by TA Instruments) was used as
the data processing software.
[0250]
Geometry: parallel plate
Measurement temperature: 190°C
Frequency: 0.01 rad/sec
Strain: 1.0%
[0251]
15 [Permanent elongation]
A 2 mm thick sheet obtained by pressing at 190'~ was used
as a test specimen, which was held at room temperature (23'~)
under 100% elongation for 24 hours andwas thereafter released.
The permanent elongation was determined by measuring the
20 residual strain after 1 hour.
[0252]
[Example 111
(Production of ethylene copolymer composition)
With an MS pressure kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 100 parts by mass
ofthe ethylene copolymer-1 fromExample 1 was kneadedtogether
with 200 parts by mass of process oil "PW-380" (product name,
manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer.
5 [0253]
The kneading conditions were such that the rotor
rotational speed tias 50 rpm, the floating weight pressure was
3 kg/cmz, the kneading time was 20 minutes, and the kneadate
discharge temperature was 150'~.
10 [0254]
The properties of the obtained ethylene copolymer
composition are described in Table 3.
[02551
[Example 121
An ethylene copolymer composition was obtained in the
same manner as in Example 11, except that the ethylene
copolymer-1 used in Example 11 was replaced by the ethylene
copolymer-2 from Example 2.
[0256]
The properties of the obtained ethylene copolymer
composition are described in Table 3.
[0257]
[Example 131
An ethylene copolymer composition was obtained in the
same manner a s i n Example 11, except t h a t t h e ethylene
copolymer-1 used i n Example 11 was replaced by t h e ethylene
copolymer-3 from Example 3.
102581
The p r o p e r t i e s of the obtained ethylene copolymer
composition a r e described i n Table 3.
[0259]
[Comparative Example 111
An ethylene copolymer composition was obtained i n t h e
10 same manner as i n Example 11, except t h a t t h e ethylene
copolymer-1 used i n Example 11 was replaced by the ethylene
copolymer-5 from Comparative Example 1.
[0260]
The p r o p e r t i e s of t h e obtained ethylene copolymer
15 composition a r e described i n Table 3.
[0261]
[Comparative Example 121
An ethylene copolymer composition was obtained i n t h e
same manner as i n Example 11, except t h a t t h e ethylene
20 copolymer-1 used i n Example 11 was replaced by the ethylene
copolymer-6 from Comparative Example 2.
[0262]
The p r o p e r t i e s of t h e obtained ethylene copolymer
composition a r e described i n Table 3.
[Comparative Example 131
With an MS p r e s s u r e kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 175 p a r t s by mass
5 of EF98 (ethylene copolymer: 100 p a r t s by mass + extender o i l :
7 5 p a r t s b y m a s s ) describedinComparativeExample 3was kneaded
together with 125 p a r t s by mass of process o i l : "PW-380"
( ~ r o d u c tn ame, manufactured by Idemitsu Kosan Co., L t d . ) as
a p l a s t i c i z e r .
The kneading conditions were such t h a t t h e r o t o r
r o t a t i o n a l speed tias 50 rpm, t h e f l o a t i n g weight pressure was
3 kg/cmz, t h e kneading time was 20 minutes, and t h e kneadate
discharge temperature was 142°C. The p r o p e r t i e s of t h e
15 obtained ethylene copolymer composition a r e d e s c r i b e d i n Table
[Table 31
Table 3
Rubber p r o p e r t i e s of copolymer + p a r a f f i n o i l (200 p h r )
compositions I Permanent e l o n g a t i o n a t
t a n 6 (0 . O 1 r a d / s ) a t 190 "C _230C.(1~~-~..elonngdtLp?L-.
P
E x . 11
E x . 12
R x . 17
Comp. Ex. 11 1 1 . 8 2 I 25.5
Comp. Ex. 12 1 3.20 38.1
0.58
0 . 5 1
Comp. Ex. 13 / 2. 68
"
6 . 1
5 7
40.8
Properties of ethylene copolymers and compositions
thereof obtained in the following examples and comparative
examples were measured in accordance with the aforementioned
methods and also the following method.
5 [0267]
[Extensional viscosity]
The extensional viscosity was measured with a
viscoelasticity tester (a rheometer (model: MCR301)
manufacturedbyAnton Paar) equippedr.rithamonoaxialextension
10 jig (Sentmanat Extensional Rheometer).
[0268]
The ethylene copolymer composition was pressed at 210°C
to form a 2 mm thick sheet, and the sheet was cut to give an
extensional viscosity measurement specimen having a width of
15 10 mm and a length of 20 mm. The sample was subjected to
extensional viscosity measurement at 190°C and a strain rate
of 0.01sec-l, thus measuringthemaximumviscosityreached and
the viscosity after 10 seconds after the start of the
measurement.
20 [0269]
[Example 211
(Production of ethylene copolymer)
An ethylene copolymer-21 was obtained by polymerization
under the same conditions as in Example 1, except that the feed
rates for ethylene, propylene, ENB and hydrogen were changed.
The properties of the obtained ethylene copolymer-21 are
described in Table 4.
[02701
5 (Production of ethylene copolymer composition)
With an MS pressure kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 100 parts by mass
of the ethylene copolymer-21 from Example 21 was kneaded
together with 150 parts by mass of process oil "PW-380" (product
10 name, manufactured by Idemitsu Kosan Co., Ltd.) as a
plasticizer.
[0271]
The kneading conditions were such that the rotor
rotational speed was 50 rpm, the floating weight pressure was
15 3 kg/cm2, the kneading time was 20 minutes, and the kneadate
discharge temperature was 150°C.
[0272]
The value of extensional viscosity of the obtained
ethylene copolymer composition is described in Table 4.
20 [0273]
[Example 221
(Production of ethylene copolymer)
An ethylene copolymer-22 was obtained by polymerization
under the same conditions as in Example 1, except that the feed
r a t e s f o r ethylene, propylene, ENB and hydrogen were changed.
The p r o p e r t i e s of the obtained ethylene copolymer-22 a r e
described i n Table 4 .
[0274]
5 (Production of ethylene copolymer composition)
With an MS pressure kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
of t h e ethylene copolymer-22 from Example 22 was kneaded
t o g e t h e r w i t h 1 5 0 p a r t s b y m a s s o f p r o c e s s o i l " P W - 3 8 0 " (product
10 name, manufactured by Idemitsu Kosan Co., L t d . ) as a
p l a s t i c i z e r .
[0275]
The kneading conditions were such t h a t t h e r o t o r
r o t a t i o n a l speed was 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
15 3 kg/cmz, t h e kneading time was 20 minutes, and t h e kneadate
discharge temperature was 150°C.
[02761
The value of extensional v i s c o s i t y of the obtained
ethylene copolymer composition is described i n Table 4 .
20 [02771
[Example 231
(Production of ethylene copolymer)
An ethylene copolymer-23 was obtained by polymerization
under the same conditions as i n Example 1, except t h a t t h e feed
r a t e s f o r e t h y l e n e , propylene, ENB and hydrogen were changed.
The p r o p e r t i e s of t h e o b t a i n e d e t h y l e n e copolymer-23 a r e
d e s c r i b e d i n Table 4 .
[0278]
5 (Production o f e t h y l e n e copolymer composition)
With an MS p r e s s u r e kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
of t h e e t h y l e n e copolymer-23 from Example 23 was kneaded
t o g e t h e r w i t h 1 5 0 p a r t s b y m a s s ofprocessoi1"PW-380" ( p r o d u c t
10 name, manufactured by Idemitsu Kosan Co., L t d . ) a s a
p l a s t i c i z e r .
[02791
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
r o t a t i o n a l speed was 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
15 3 kg/cmz, t h e kneading t i m e was 20 m i n u t e s , a n d t h e kneadate
d i s c h a r g e t e m p e r a t u r e was 1 5 0 ' ~ .
[02801
The v a l u e of e x t e n s i o n a l v i s c o s i t y of t h e o b t a i n e d
e t h y l e n e copolymer composition is d e s c r i b e d i n Table 4 .
20 [0281]
[Example 241
(Production o f e t h y l e n e copolymer composition)
With an MS p r e s s u r e kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
of t h e e t h y l e n e copolymer-21 from Example 21 was kneaded
t o g e t h e r w i t h 2 5 O p a r t s b y m a s s o f p r o c e s s oilVPW-380" ( p r o d u c t
name, manufactured by Idemitsu Kosan Co., L t d . ) a s a
p l a s t i c i z e r .
5 [0282]
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
r o t a t i o n a l speed was 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cm2, t h e kneading t i m e was 20 m i n u t e s , and t h e kneadate
d i s c h a r g e t e m p e r a t u r e was 150°C.
10 LO2831
The v a l u e o f e x t e n s i o n a l v i s c o s i t y of t h e o b t a i n e d
e t h y l e n e copolymer composition is d e s c r i b e d i n Table 4 .
102841
[Example 251
15 (Production o f e t h y l e n e copolymer composition)
With an MS p r e s s u r e kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3 . 0 L ) , 100 p a r t s by mass
of t h e e t h y l e n e copolymer-23 from Example 23 was kneaded
t o g e t h e r w i t h 2 5 0 p a r t s b y m a s s o f p r o c e s s oilmPW-380" ( p r o d u c t
20 name, manufactured by Idemitsu Kosan Co., L t d . ) as a
p l a s t i c i z e r .
LO2851
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
r o t a t i o n a l speed was 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cmz, the kneading time was 20 minutes, and the kneadate
discharge temperature was 150°C.
102861
The value of extensional viscosity of the obtained
5 ethylene copolymer composition is described in Table 4.
[0287]
[Example 261
(Production of ethylene copolymer composition)
With an MS pressure kneader (manufactured by MORIYAMA
10 COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 100 parts by mass
of the ethylene copolymer-23 from Example 23 was kneaded
together with 400 parts by mass of process oil "PW-380" (product
name, manufactured by Idemitsu Kosan Co., Ltd.) as a
plasticizer.
15 [0288]
The kneading conditions were such that the rotor
rotational speed was 50 rpm, the floating weight pressure was
3 kg/cm2, the kneading time was 20 minutes, and the kneadate
discharge temperature was 150°C.
20 [02891
The value of extensional viscosity of the obtained
ethylene copolymer composition is described in Table 4.
[0290]
[Comparative Example 211
(Production o f ethylene copolymer)
An ethylene copolymer-24 was obtained by polymerization
under t h e same conditions as i n Example 1, except t h a t t h e feed
r a t e s f o r ethylene, propylene, ENB and hydrogen were changed.
5 The p r o p e r t i e s of the obtained ethylene copolymer-24 a r e
described i n Table 4 .
[0291]
(Production of ethylene copolymer composition)
With an MS pressure kneader (manufactured by MORIYAMA
10 COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
of t h e ethylene copolymer-24 from Example 21 was kneaded
t o g e t h e r w i t h 1 5 0 p a r t s b y m a s s ofprocessoi1"PW-380" (product
name, manufactured by Idemitsu Kosan Co., L t d . ) as a
p l a s t i c i z e r .
15 [0292]
The kneading conditions were such t h a t t h e r o t o r
r o t a t i o n a l speed was 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cm2, t h e kneading time was 20 minutes, and t h e kneadate
discharge temperature was 150°C.
20 [0293]
The value of extensional v i s c o s i t y of t h e obtained
ethylene copolymer composition is described i n Table 4 .
[0294]
[Comparative Example 221
( P r o d u c t i o n of e t h y l e n e copolymer)
An e t h y l e n e copolymer-25 w a s o b t a i n e d b y p o l y m e r i z a t i o n
under t h e s a m e c o n d i t i o n s a s i n Example 1, e x c e p t t h a t t h e f e e d
rates f o r e t h y l e n e , p r o p y l e n e , ENB and hydrogen were changed.
5 The p r o p e r t i e s of t h e o b t a i n e d e t h y l e n e copolymer-25 a r e
d e s c r i b e d i n Table 4 .
[02951
( P r o d u c t i o n o f e t h y l e n e copolymer composition)
With an MS p r e s s u r e k n e a d e r ( m a n u f a c t u r e d b y MORIYAMA
10 COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
of t h e e t h y l e n e copolymer-25 from Example 21 was kneaded
t o g e t h e r w i t h 1 5 0 p a r t s bymass ofprocessoi1"PW-380" ( p r o d u c t
name, manufactured by Idemitsu Kosan Co., L t d . ) as a
p l a s t i c i z e r .
15 [02961
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
r o t a t i o n a l speed w a s 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cmz, t h e kneading t i m e was 20 m i n u t e s , and t h e kneadate
d i s c h a r g e t e m p e r a t u r e w a s 150°C.
20 [0297]
The v a l u e of e x t e n s i o n a l v i s c o s i t y of t h e o b t a i n e d
e t h y l e n e copolymer composition is d e s c r i b e d i n Table 4 .
[0298]
[Table 41
Table 4
10000 x
[0299]
P r o p e r t i e s of rubber compositions and crosslinked
products obtained i n the following examples and comparative
examples were measured i n accordance with t h e following
5 methods.
[0300]
[ P r o p e r t i e s of rubber compositions: minimum v i s c o s i t y (Vm) and
scorch time ( t 5 , min) 1
P r o p e r t i e s of rubber compositions were t e s t e d i n
10 accordance with JIS K 6300. In d e t a i l , changes i n Mooney
v i s c o s i t y were measured a t 125°C using a Mooney viscometer
(SMV202 manufactured by Shimadzu Corporation) and, from t h e
s t a r t of t h e measurement, the minimum v i s c o s i t y (Vm) was
determined and f u r t h e r t h e time required f o r t h e v i s c o s i t y t o
15 i n c r e a s e by 5 p o i n t s from t h e minimum v i s c o s i t y Vm was
determined a s t h e scorch time ( t 5 , min).
[0301]
[Evaluation of r o l l i n g p r o c e s s a b i l i t y of compounds]
To e v a l u a t e r o l l i n g p r o c e s s a b i l i t y , f i r s t , an evaluation
20 specimen (a rubber composition) was prepared i n t h e following
manner. With MIXTROW BB MIXER (manufactured by Kobe S t e e l ,
Ltd., BB-4 model, volume 2.95 L, r o t o r 4 WH) , t h e r e were kneaded
300 p a r t s by mass of an ethylene copolymer composition (a
composition of any of Examples 4 t o 6 and Comparative Examples
4 t o 6) ( e t h y l e n e copolymer: 100 p a r t s by mass, p l a s t i c i z e r :
200 p a r t s by mass), 5 p a r t s by mass of z i n c o x i d e : "META-2102"
( p r o d u c t name, manufactured by Inoue Calcium C o r p o r a t i o n ) as
a v u l c a n i z a t i o n a i d , 1 p a r t by m a s s of stearic a c i d a s a
5 p r o c e s s i n g a i d , 2 p a r t s by mass of "PEG #40001' ( p r o d u c t name,
p o l y e t h y l e n e g l y c o l , manufactured by Lion C o r p o r a t i o n ) as an
a c t i v a t i n g a g e n t , 415 p a r t s by mass of carbon b l a c k : "ASAHI
#60Gm ( p r o d u c t name, manufactured by ASAHI CARBON CO., LTD.)
as a r e i n f o r c i n g a g e n t , 30 p a r t s bymass o f c a l c i u m b i c a r b o n a t e :
10 "WHITON SB" ( p r o d u c t name, manufactured by SHIRAISHI CALCIUM
KAISHA, LTD.) a s a n i n o r g a n i c f i l l e r , and 150 p a r t s by mass
of "Diana Process O i l PW-380" ( p r o d u c t name, manufactured by
Idemitsu Kosan Co., L t d . ) a s a p l a s t i c i z e r . The kneading
c o n d i t i o n s were such t h a t t h e r o t o r r o t a t i o n a l speed w a s 50
15 rpm, t h e f l o a t i n g weight p r e s s u r e w a s 3 kg/cm2, t h e kneading
t i m e was 5 minutes, and t h e kneadate d i s c h a r g e t e m p e r a t u r e was
145°C.
[0302]
Next, t h e o b t a i n e d r u b b e r composition was wrapped around
20 6-inchopen rollsandtherollingprocessabilitywas e v a l u a t e d .
The rollingprocessabilitywas e v a l u a t e d b a s e d o n t h e f o l l o w i n g
two c r i t e r i a .
[0303]
0: The composition e x h i b i t e d good wrapping p r o p e r t i e s
with respect to the rolls, and roll processing was carried out
appropriately.
[0304]
x: The roll processing treatment was difficult due to
5 sagging or sticking of the compound.
[a3051
[Hardness test]
The hardness (type A durometer, HA) of rubber shaped
articles was measured with respect to an approximately 12 mm
10 thick stack which consisted of six sheets of 2 mm thick rubber
shaped articles having flat surfaces, the sheets being stacked
on top of one another via flat portions. Here, test pieces
having contaminations, bubbles or scratches were rejected.
The size of the measurement face of the test piece was such
15 that the measurement could be performed while the tip of the
probe was placed at a position at least 12 mm away from the
end of the test piece.
[0306]
[Tensile test I
Rubber shaped articles (crosslinked products) were
subjected to a tensile test at a measurement temperature of
23°C and a stress rate of 500 mm/min in accordance with JIS
K 6251 to determine the tensile strength at break (TB) and the
elongation at break (EB).
[03071
[Permanent compression s e t ]
A sample was c o l l e c t e d from a vulcanized shaped a r t i c l e
i n a c c o r d a n c e w i t h J I S K 6250-6.5, andthepermanent compression
5 s e t a f t e r t r e a t m e n t a t 7 O 0 C x 2 2 h o u r s wasmeasuredinaccordance
with JIS K 6262 ( 1 9 9 7 ) .
[03081
[Example 311
[Production of rubber composition]
P r i o r t o c r o s s l i n k i n g of rubber composition, t h e r e were
kneaded, with t h e use of MIXTRON BB MIXER (manufactured by Kobe
S t e e l , Ltd., BB-4 model, volume 2.95 L, r o t o r 4 WH) , 300 p a r t s
by mass of a n e t h y l e n e copolymer composition ( t h e e t h y l e n e
copolymer composition of Example 11) (ethylene copolymer-1:
15 100 p a r t s by mass, p l a s t i c i z e r : 200 p a r t s by mass), 5 p a r t s
by mass of zinc oxide : "META-Z102" (product name, manufactured
by Inoue Calcium Corporation) as a v u l c a n i z a t i o n a i d , 1 p a r t
by mass of s t e a r i c acid as a processing a i d , 2 p a r t s by mass
of polyethylene glycol "PEG #40001' (product name, manufactured
20 by Lion Corporation) as an a c t i v a t i n g agent, 415 p a r t s by mass
of carbon black "ASAHI #60Gn (product name, manufactured by
ASAHI CARBON CO., LTD.) as a r e i n f o r c i n g agent, 30 p a r t s by
mass of calcium bicarbonate: "WHITON SB" (product name,
manufacturedbySHIRAISH1 CALCIUMKAISHA, LTD.) as a n i n o r g a n i c
f i l l e r , and 150 p a r t s by mass of "Diana Process O i l PW-380"
(product name, manufactured by Idemitsu Kosan Co., L t d . ) a s
a p l a s t i c i z e r . The kneading conditions were such t h a t t h e
r o t o r r o t a t i o n a l s p e e d w a s 50 rpm, t h e f l o a t i n g weight p r e s s u r e
5 was 3 kg/cmz, t h e kneading time was 5 minutes, and t h e kneadate
discharge temperature was 145'C.
[0309]
After t h e t e m p e r a t u r e o f t h e b l e n d w a s confirmedtobecome
40°C, t h e blend was supplied t o 8-inch r o l l s and was kneaded
10 together with 1.0 p a r t by mass of "Sanceler M" (product name,
manufactured by SANSHIN CHEMICAL INDUSTRY CO., LTD.) as a
v u l c a n i z a t i o n a c c e l e r a t o r , 1.0 p a r t by mass of "Sanceler TT"
(product name, manufactured by SANSHIN CHEMICAL INDUSTRY CO.,
LTD.) as a v u l c a n i z a t i o n a c c e l e r a t o r , 1 . 5 p a r t s by mass of
15 "Sanceler Bz" (product name, manufactured by SANSHIN CHEMICAL
INDUSTRY CO., LTD. ) as a v u l c a n i z a t i o n a c c e l e r a t o r , 1.5 p a r t s
by mass of "Sanceler 22" (product name, manufactured by SANSHIN
CHEMICAL INDUSTRY CO., LTD.) as a v u l c a n i z a t i o n a c c e l e r a t o r ,
1.5 p a r t s by mass of s u l f u r as a v u l c a n i z i n g a g e n t , and 5 p a r t s
20 by m a s s of "VESTA 18" (product name, manufactured by Inoue
Calcium Corporation) as a moisture absorber. The kneading
conditions f o r r o l l i n g were such t h a t the r o l l temperatures
were f r o n t r o l l / r e a r r o l l = 50°C/500C, t h e r o l l r o t a t i o n a l
speeds were f r o n t r o l l / r e a r r o l l = 18 rpm/l5 rpm, t h e r o l l gap
was 3 mm, and t h e kneading t i m e was 8 minutes.
[a3101
(Production of c r o s s l i n k e d products)
The above blend was v u l c a n i z e d w i t h a p r e s s forming
5 machine a t 170°C f o r 10 minutes t o give a c r o s s l i n k e d product
which was a 2 mm t h i c k rubber s h e e t . F u r t h e r , a rubber block
f o r t h e t e s t i n g of permanent compression set was prepared by
v u l c a n i z a t i o n a t 170°C f o r 15 minutes.
[a3111
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r compositionand t h e
c r o s s l i n k e d products a r e d e s c r i b e d i n Table 5.
[0312]
[Example 321
A rubber composition and c r o s s l i n k e d products were
15 obtained i n t h e same manner a s i n Example 31, except t h a t t h e
e t h y l e n e copolymer composition used i n Example 31 was replaced
by t h e ethylene copolymer composition from Example 12.
[0313]
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r c o m p o s i t i o n a n d t h e
20 c r o s s l i n k e d products a r e described i n Table 5.
[03141
[Example 331
A rubber composition and c r o s s l i n k e d products were
obtained i n t h e same manner a s i n Example 31, except t h a t t h e
e t h y l e n e copolymer composition u s e d i n Example 31 w a s r e p l a c e d
by t h e e t h y l e n e copolymer composition from Example 13.
[0315]
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r composition and t h e
5 c r o s s l i n k e d p r o d u c t s are d e s c r i b e d i n Table 5.
[0316]
[Comparative Example 311
A r u b b e r composition and c r o s s l i n k e d p r o d u c t s were
o b t a i n e d i n t h e same manner as i n Example 31, e x c e p t t h a t t h e
10 e t h y l e n e copolymer composition u s e d i n Example 31was r e p l a c e d
by t h e e t h y l e n e copolymer composition f r o m c o m p a r a t i v e Example
11.
[0317]
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r composition and t h e
15 c r o s s l i n k e d p r o d u c t s a r e d e s c r i b e d i n Table 5.
[0318]
[Comparative Example 321
A r u b b e r composition and c r o s s l i n k e d p r o d u c t s were
o b t a i n e d i n t h e same manner as i n Example 31, e x c e p t t h a t t h e
20 e t h y l e n e copolymer composition u s e d i n Example 31was r e p l a c e d
by t h e e t h y l e n e copolymer composition fromcomparative Example
12.
[0319]
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r composition and t h e
crosslinked products a r e described i n Table 5.
[0320]
[Comparative Example 331
A rubber composition and c r o s s l i n k e d products were
5 obtained i n the same manner a s i n Example 31, except t h a t the
ethylene copolymer composition u s e d i n Example 31was replaced
by t h e ethylene copolymer composition fromcomparative Example
13.
[0321]
The p r o p e r t i e s o f t h e o b t a i n e d r u b b e r compositionand the
crosslinked products a r e described i n Table 5.
[Table 51
Table 5
15 [0323]
P r o p e r t i e s of films or s h e e t s formed from ethylene
copolymer compositions of examples and comparative examples
were measured i n accordance with t h e following methods.
[0324]
[Calendering p r o c e s s a b i l i t y ]
The ethylene copolymer composition weighing 150 g was
wrapped around two r o l l s (6-inch r o l l s manufactured by NIPPO
KOHKI K . K . ) and was c u t f o r 3 minutes a t a r o l l temperature
of 100°C, a guide width of 20 cm and a r o l l gap of 0.7 mm.
T h e r e a f t e r , the r o l l gap was s e t a t 0.5 mm, and the composition
10 was allowed t o stand f o r 5 minutes and removed from t h e r o l l s .
The workability on t h e r o l l s , t h e shape of the bank during
kneading, a n d t h e s u r f a c e t e x t u r e o f formedsheetwereevaluated
based on t h e following c r i t e r i a .
(1) Workability ( p r o c e s s a b i l i t y ) on r o l l s
0: Good (The c u t t i n g of the composition was f e a s i b l e ,
and t h e composition was removed from t h e r o l l s e a s i l y . )
A: R e l a t i v e l y d i f f i c u l t (The r e l e a s a b i l i t y f r o m t h e r o l l s
was low, and t h e s h e e t c o l l a p s e d . )
x: D i f f i c u l t (The c u t t i n g was d i f f i c u l t , and t h e
20 composition could not be removed i n t h e form of s h e e t . )
(2) Shape of bank
0: The bank had a r e g u l a r and uniform shape.
[0325]
A: The shape became i r r e g u l a r a t times.
103261
x: The shape w a s i r r e g u l a r c o n s t a n t l y and t h e normal bank
was n o t formed.
(3) S u r f a c e t e x t u r e of shaped articles
5 0: E x c e l l e n t .
[0327]
A: R e l a t i v e l y i n f e r i o r .
[0328]
x: I n f e r i o r ( o r t h e composition could not be removed i n
10 t h e form of s h e e t ) .
[0329]
[Example 4 1 1
With an MS p r e s s u r e kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by mass
15 o f t h e e t h y l e n e copolymer-1 fromExample1was k n e a d e d t o g e t h e r
with 200 p a r t s by m a s s of p r o c e s s o i l : "PW-380" (product name,
manufactured by Idemitsu Kosan Co., L t d . ) as a p l a s t i c i z e r .
[03301
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
20 r o t a t i o n a l speed w a s 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cmz, t h e kneading t i m e w a s 20 minutes, and t h e kneadate
d i s c h a r g e t e m p e r a t u r e w a s 150°C. The c a l e n d e r i n g
p r o c e s s a b i l i t y of t h e o b t a i n e d e t h y l e n e copolymer composition
is d e s c r i b e d i n Table 6.
[0331]
[Example 421
The procedures i n Example 4 1 were repeated, except t h a t
t h e ethylene copolymer-l used i n Example 4 1 was replaced by
5 t h e ethylene copolymer-2 from Example 2. The calendering
p r o c e s s a b i l i t y of t h e o b t a i n e d e t h y l e n e copolymer composition
is described i n Table 6.
[0332]
[Example 431
The procedures i n Example 4 1 were repeated, except t h a t
t h e ethylene copolymer-1 used i n Example 4 1 was replaced by
t h e ethylene copolymer-3 from Example 3. The calendering
p r o c e s s a b i l i t y o f t h e o b t a i n e d e t h y l e n e copolymer composition
is described i n Table 6.
15 [0333]
[Example 441
The procedures i n Example 4 1 were repeated, except t h a t
t h e ethylene copolymer-1 used i n Example 4 1 was replaced by
t h e ethylene copolymer-4 from Example 4 . The calendering
20 p r o c e s s a b i l i t y o f t h e o b t a i n e d e t h y l e n e copolymer composition
is described i n Table 6.
[0334]
[Comparative Example 411
The procedures i n Example 4 1 were r e p e a t e d , except t h a t
the ethylene copolymer-1 used in Example 41 was replaced by
the ethylene copolymer-5 from Comparative Example 1. The
calendering processability ofthe obtained ethylene copolymer
composition is described in Table 6.
5 [03351
[Comparative Example 421
The procedures in Example 41 were repeated, except that
the ethylene copolymer-l used in Example 41 was replaced by
the ethylene copolymer-6 from Comparative Example 2. The
10 calendering processability ofthe obtained ethylene copolymer
composition is described in Table 6.
103361
[Comparative Example 431
With an MS pressure kneader (manufactured by MORIYAMA
15 COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 175 parts by mass
of EP98 (terpolymer: 100 parts by mass + extender oil: 75 parts
bymass) describedinComparativeExample3was kneadedtogether
with 125 parts by mass of process oil: PW-380 (product name,
manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer.
20 [0337]
The kneading conditions were such that the rotor
rotational speed was 50 rpm, the floating weight pressure was
3 kg/cm2, the kneading time was 20 minutes, and the kneadate
discharge temperature was 142'C. The calendering
p r o c e s s a b i l i t y o f t h e o b t a i n e d e t h y l e n e copolymer composition
is described i n Table 6.
[0338]
[Comparative Example 441
5 The procedures i n Example 4 1 were r e p e a t e d , except t h a t
t h e ethylene copolymer-1 used i n Example 4 1 was replaced by
t h e ethylene copolymer-7 from Comparative Example 4 . The
calendering p r o c e s s a b i l i t y of t h e obtained ethylene copolymer
composition is described i n Table 6.
10 [0339]
[Table 61
Table 6
P r o p e r t i e s of films ( s h e e t s ) obtained i n examples and
EX.
4 1
processability
(1)Rollruorkability
(2) Bank shape
(3) Surface texture
15 comparative examples were measured i n accordance with t h e
following methods.
Calendering I
EX.
4 2
0 I 0 I 0 I 0 I A
[Amount of extender o i l ]
Afilm ( s h e e t ) was c u t t o a specimenrihichwas a c o l l e c t i o n
EX.
43
x I x
20 of approximately 1 mm x 1 mm x 1 mm cubes, and 1 g (WO) of t h e
A
0 1 ° 1 0 1 0 1 A
specimen was weighedandplacedin a g l a s s f i l t e r (G3). Methyl
Ex.
44
e t h y l ketone 200 m l was placed i n t o a f l a s k and was heated with
A A
Comp.
Ex. 41
0
0 I 0 I 0 I 0 I x
Comp.
Ex. 42
x
Comp.
Ex. 43
x
Comp.
Ex. 44
x
a heater. When the liquid boiled, the glass filter containing
the specimen was placed therein and extraction was performed
for 2 hours. After the extraction, the specimen was dried at
105'C for 1 hour, and the weight (Wl) of the specimen was
5 measured. The amount of extender oil was determined by the
following equation.
[0342]
Amount of extender oil (phr) = (WO - W1) /W1 x 100
[Hardness test I
The hardness (type A durometer, HA) of the sheet was
measured with respect to an approximately 12 mm thick stack
which consisted of twelve sheets of 1 mm thick rubber shaped
articles having flat surfaces, the sheets being stacked on top
of one another via flat portions. Here, test pieces having
15 contaminations, bubbles or scratches were rejected. The size
of the measurement face of the test piece was such that the
measurement could be performed while the tip of the probe was
placed at a position at least 12 mm away from the end of the
test piece.
20 [03431
[Tensile test]
A tensile test was carried out at a measurement
temperatureof 23"Candastress rateof 500mm/mininaccordance
with JIS K 6251 to determine the tensile strength at break (TB)
and t h e e l o n g a t i o n a t b r e a k (EB) of t h e s h e e t .
LO3441
[Example 511
With an MS p r e s s u r e kneader ( m a n u f a c t u r e d b y MORIYAMA
5 COMPANY LTD., DS3-1OMWB-E, volume 3.0 L ) , 100 p a r t s by m a s s
o f t h e e t h y l e n e copolymer-1 fromExample l w a s k n e a d e d t o g e t h e r
with 120 p a r t s by mass of p r o c e s s o i l : "PW-380" ( p r o d u c t name,
manufactured by I d e m i t s u Kosan Co., L t d . ) as a p l a s t i c i z e r .
[0345]
The kneading c o n d i t i o n s were such t h a t t h e r o t o r
r o t a t i o n a l speed w a s 50 rpm, t h e f l o a t i n g weight p r e s s u r e was
3 kg/cm2, t h e kneading t i m e was 20 minutes, and t h e kneadate
d i s c h a r g e t e m p e r a t u r e was 156°C.
[0346]
Next, 120 g of t h e copolymer composition w a s wrapped
a r o u n d t w o r o l l s (6-inchrollsmanufacturedbyNIPPOKOHKI K . K . )
and w a s c u t f o r 3 minutes at a r o l l t e m p e r a t u r e of 150°c, a
guide width of 30 cm and a r o l l gap of 1 mrn. T h e r e a f t e r , t h e
composition was allowed t o s t a n d f o r 5 minutes and w a s removed
20 from t h e r o l l s . Thus, a s h e e t with a t h i c k n e s s of 1 rnm was
o b t a i n e d .
[0347]
The p r o p e r t i e s of t h e o b t a i n e d s h e e t are d e s c r i b e d i n
Table 7.
[0348]
[Example 521
A sheet was obtained in the same manner as in Example 51,
except that the amount of the plasticizer used in Example 51
5 was changed to 200 parts by mass.
[0349]
The properties of the obtained sheet are described in
Table 7.
[0350]
10 [Example 531
A sheet was obtained in the same manner as in Example 52,
except that the ethylene copolymer-l used in Example 52 was
replaced by the ethylene copolymer-2 from Example 2.
[0351]
The properties of the obtained sheet are described in
Table 7.
[03521
[Example 541
A sheet was obtained in the same manner as in Example 52,
20 except that the ethylene copolymer-1 used in Example 52 was
replaced by the ethylene copolymer-3 from Example 3.
[03531
The properties of the obtained sheet are described in
Table 7.
[Example 551
The sheet obtained in Example 52 was irradiated with
electron beams at a dose of 60 kGy to produce a crosslinked
5 sheet.
The properties of the obtained sheet are described in
Table 7.
10 [Comparative Example 511
An attempt was made to prepare a sheet in the same manner
as in Example 52, except that the ethylene copolymer-1 used
in Example 52 was replaced by the ethylene copolymer-5 from
Comparative Example 1. However, the copolymer composition
15 exhibited heavy stickiness to make calendering difficult, and
the sheet production was infeasible.
[Table 71
Table 7
[Example 611
With an MS pressure kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 100 parts by mass
ofthe ethylene copolymer-4 fromExample 4 was kneadedtogether
with 250 parts by mass of process oil: PW-100 (product name,
5 manufactured by Idemitsu Kosan Co., Ltd.) as a plasticizer.
103591
The kneading conditions were such that the rotor
rotational speed was 50 rpm, the floating weight pressure was
3 kg/cm2, the kneading time was 20 minutes, and the kneadate
10 discharge temperature was 150°C. The obtained ethylene
copolymer composition was formed into a film with the
aforementioned six calender rolls. The results are described
in Table 8.
103601
15 [Comparative Example 611
With an MS pressure kneader (manufactured by MORIYAMA
COMPANY LTD., DS3-1OMWB-E, volume 3.0 L), 100 parts by mass
of the ethylene copolymer-7 from Comparative Example 4 was
kneaded together with 120 parts by mass of process oil: PW-100
20 (product name, manufactured by Idemitsu Kosan Co., Ltd.) as
a plasticizer.
[0361]
The kneading conditions were such that the rotor
rotational speed was 50 rpm, the floating weight pressure was
3 kg/cm2, the kneading time was 20 minutes, and the kneadate
discharge temperature was 150°C. The obtained ethylene
copolymer composition was formed into a film with the
aforementioned six calender rolls. The results are described
5 in Table 8.
[0362]
[Surface smoothness]
Calendering was performed with 200 I$ L x 700 mm complex
sixcalender rolls (manufacturedbyNipponRollMFG. Co., Ltd.).
10 The roll arrangement is illustrate din Fig. 1. The size of each
roll was 200 mrn in diameter and 700 mm in width, and the unit
was composed of complex six rolls. The temperatures of the
rolls were No. 1/No. 2/No. 3/No. 4/No. 5/No. 6 =
70/70/65/70/65/7O0C. The gap between the fifth roll and the
15 sixth roll was 0.45 mm. The surface condition of the obtained
film was evaluated.
[0363]
[Table 81
Table 8
The specimen in Comparative Example 61 had large die
Specimens
120 parts by mass)
600 pm
x: Poor
6
250 parts by mass)
Ex. 61
Ethylen..e .. . co-p--o ly..m .. .e.. -r.-. . .4. - .-
(Extended by PW-100:
Film thickness
(Surf ace smoothness)
Surface condition
Number of hollows
Comp. Ex. 61
.E. .t. hy-l. e. ne. - copo.l. y mer-7. . . .
(Extended by PW-100:
400 pm
0: Excellent
0
s w e l l i n g a n d a consequent l a r g e r f i l m t h i c k n e s s t h a n i n E x a m p l e
61.
Number of hollows: The number of hollows having a depth
equal t o o r l a r g e r than the film t h i c k n e s s x 0.1 i n an area
5 within 2 cm i n the TD:
[Example 711
The ethylene copolymer-4 obtainedinExample 4 was formed
i n t o a film with the aforementioned s i x calender r o l l s . Here,
t h e gap between the f i f t h r o l l and t h e s i x t h r o l l tias 0.31 mm.
10 The film obtained by calendering was i r r a d i a t e d with e l e c t r o n
beams a t a dose of 60 kGy t o produce a crosslinked s h e e t .
[0365]
The p r o p e r t i e s of t h e obtained film were measured by t h e
aforementionedmethods. The r e s u l t s a r e d e s c r i b e d i n Table 9 .
15 [0366]
[Comparative Example 711
The ethylene copolymer-7 o b t a i n e d i n Comparative Example
4 was formed i n t o a film with the aforementioned s i x calender
r o l l s . Here, t h e gap between the f i f t h r o l l and t h e s i x t h r o l l
20 was 0.31 mrn. The f i l m obtained by calendering was i r r a d i a t e d
w i t h e l e c t r o n beams a t a dose o f 60 kGyto produce a crosslinked
s h e e t .
[0367]
The p r o p e r t i e s of t h e obtained film were measured by the
aforementioned methods. The results are described in Table 9.
103681
[Table 91
Tahle 9
Ex. 71 Comp. Ex. 71
Ethylene
Ethylene copolymer-4
(Extended by PVI-100: 250 p a r t s by
copolymer-7
Specimens
weight)
(Extended by PW-100:
elongation
5 [03691
MD: Film machine direction, TD: Transverse direction
perpendicular to the film machine direction
INDUSTRIAL APPLICABILITY
103701
10 The films of the invention are excellent in calendering
properties and have flexibility and high stretchability. Due
to these characteristics, the inventive films are promising
alternatives to films such as vinyl chloride or silicon rubber
films, and can be used in various applications such as various
15 leathers, sheets, films and stacked films.
REFERENCE SIGNS LIST
[0371]
CLAIMS
[Claim 1]
An ethylene copolymer ( X ) comprising s t r u c t u r a l . u n i t s
derived from a component [ A ] , a component [B] and a component
5 [C] which are ethylene [ A ] , an a - o l e f i n of 3 t o 20 carbon atoms
[B] and a polyene and/or a c y c l i c o l e f i n LC],
(1) t h e content of s t r u c t u r a l u n i t s derived from t h e
ethylene [A] being i n t h e range of 50 t o 90 mol% i n 100 mol%
of a11 t h e s t r u c t u r a l u n i t s i n t h e copolymer ( X ) ;
(2) t h e content of s t r u c t u r a l u n i t s derived from t h e
polyene and/or t h e c y c l i c o l e f i n [C] being i n t h e range of 1 . 0
t o 5.0 mol% i n 100 mol% of a l l t h e s t r u c t u r a l u n i t s i n t h e
copolymer (X) ;
(3) t h e i n t r i n s i c v i s c o s i t y [q] o f t h e e t h y l e n e copolymer
15 ( X ) a s measured a t 135°C i n a d e c a l i n s o l u t i o n being i n t h e
range of 7.8 t o 13.0 d l / g .
[Claim 2]
The ethylene copolymer according t o claim 1, wherein t h e
component [C] is a t l e a s t one or more components s e l e c t e d from
20 polyenes.
[Claim 3]
Theethylenecopolymer ( X ) a c c o r d i n g t o c l a i m 1 o r 2 , which
s a t i s f i e s t h e following (i)a nd (ii):
(i)t h e value B obtained from a 1 3 ~ s-pec~tru~m ~bas ed
on t h e following equation is 0.9 t o 1.0:
value B = [ P o E ] / (.~[P EI .[Pol)
( i n t h e equation, [PE] is themolar f r a c t i o n o f t h e content
of t h e u n i t s derived from e t h y l e n e (a) i n t h e random copolymer,
5 [Po] is t h e molar f r a c t i o n of t h e content of the u n i t s derived
from t h e a - o l e f i n (b) i n t h e random copolymer, and [Po,] is the
p r o p o r t i o n o f t h e number of a - o l e f i n , e t h y l e n e c h a i n s r e l a t i v e
t o t h e number of a l l t h e dyad chains i n t h e random copolymer) ;
and
10 (ii) t h e l o s s tangent value, t a n 6, a s determined by
dynamic v i s c o e l a s t i c i t y measurement a t -lO°C and 1 Hz is not
more than 0.1.
[Claim 4]
The ethylene copolymer according t o any one of claims 1
15 t o 3, wherein t h e ethylene copolymer ( X ) has an i n t r i n s i c
v i s c o s i t y [q] i n the range of 8.0 t o 13.0 d l / g a s measured a t
135°C i n a d e c a l i n s o l u t i o n .
[Claim 5]
Theethylene copolymer according t o any one of claims 1
20 t o 4, wherein t h e component [C] is 5-ethylidene-2-norbornene
(ENB) .
[Claim 6]
The ethylene copolymer according t o any one of claims 1
t o 5, wherein t h e component [B] is propylene o r 1-butene.
[Claim 7]
An ethylene copolymer composition comprising 100 p a r t s
by mass of t h e ethylene copolymer (X) described i n any one of
claims 1 t o 6, and 100 t o 1000 p a r t s by mass of a p l a s t i c i z e r
5 (Y).
[Claim 8]
The ethylene copolymer composition according t o claim 7,
wherein t h e ethylene copolymer composition has a l o s s tangent
( t a n 6) a t 190°C and 0.01 r a d / s e c of 0.1 t o 1 . 0 .
10 [Claim 9]
A c r o s s l i n k e d product obtained by c r o s s l i n k i n g t h e
e t h y l e n e copolymer described i n any one of claims 1 t o 6, o r
the e t h y l e n e copolymer composition described i n any one of
claims 7 and 8.
15 [Claim 10]
A rubber shaped a r t i c l e comprising the c r o s s l i n k e d
product described i n claim 9.
[Claim 11]
A f i l m o r s h e e t comprising the ethylene copolymer (X) of
20 any one of claims 1 t o 6 including the s t r u c t u r a l u n i t s derived
from t h e component [ A ] , t h e component [B] and t h e component
[CI .
[Claim 12]
. . The f i l m o r s h e e t according t o claim 11, wherein t h e
component [C] is 5-ethylidene-2-norbornene (ENB) .
[Claim 13]
The f i l m o r sheet according t o c l a i m l l o r 12, comprising
100 t o 1000 p a r t s by mass of a p l a s t i c i z e r ( Y ) with r e s p e c t
5 t o 100 p a r t s by mass of t h e ethylene copolymer ( X ) .
[Claim 14]
The f i l m or sheet according t o claim 13, wherein t h e
p l a s t i c i z e r ( Y ) is a petroleum p l a s t i c i z e r .
[Claim 15]
10 The f i l m o r sheet according t o any one of claims 11 t o
1 4 , which has a durometer type A hardness measured by a method
s p e c i f i e d i n JIS K 6253 of 10 t o 80.
[Claim 16]
The f i l m or sheet according t o any one of claims 11 t o
15 15, wherein a t l e a s t p a r t of t h e ethylene copolymer (X) has
been c r o s s l i n k e d by e l e c t r o n beam c r o s s l i n k i n g .
[Claim 17]
The f i l m or sheet according t o claim 16, which has been
c r o s s l i n k e d with an e l e c t r o n beam a t a dose of 10 t o 200 kGy.
20 [Claim 18]
A method f o r forming films o r s h e e t s using the e t h y l e n e
copolymer ( X ) described i n any one o f claims 1 t o 6, o r t h e
ethylene copolymer composition described i n any one of claims
7 and 8.
[Claim 19] -.
Themethod f o r f o r m i n g f i l m s or s h e e t s according t o claim
18, wherein the films or s h e e t s a r e formed with a calendering
machine. . .
5 [Claim 20]
The f i l m or sheet according t o any one of claims 11 t o
17, which is a calendered a r t i c l e obtained by c a l e n d e r i n g .