DESCRIPTION
OLEFIN RESIN AND METHOD FOR PRODUCING SAME
TECHNICAL FIELD
5 [0001]
10
The present invention relates to an olefin resin and a method
for producing the same.
BACKGROUND ART
[0002]
Olefin resins are molded by various molding methods and used
in a variety of applications. Properties required for the olefin
resins vary depending on the molding methods or applications.
[0003]
Of the olefin resins, ethylene/or:-olefin copolymers such as
15 ethylene/propylene copolymer, ethylene/butene copolymer, and
ethylene/octene copolymer are widely used in automobile parts ,such
as bumpers and instrument panels, .packaging materials (such as
low temperature heat sealable films arid easy peel films), sporting
goods (such as midsoles in sports shoes), and wire coverings,
20 because of their excellent properties, such as being lightweight,
having a low specific gravity, flexibility, low melting point,
and excellent compatibility with other olefin resins, and being
easily recyclable. At the same time, improvements have been
demanded, because of the problems that ethylene/a-olefin
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copolymers have a poor heat resistance due to being
non-crystalline or low-crystalline polymers, and that the
resulting molded articles may be sticky depending on the
proportion of ethylene structural units.
5 [0004]
In order to solve the above mentioned problems, studies have
been reported in which an effort is made to arrange a crystalline
segment and a non-crystalline or low-crystalline segment in blocks
during the polymerization stage in the production of an olefin
10 copolymer. Patent Document 1 discloses a technique to produce
an olefin block copolymer in which a crystalline ethylene
homopolymer segment and an ethylene copolymer segment are arranged
on a straight-chain using a specific living polymerization
catalyst. Further, Patent Document 2 discloses that an olefin
15 block copolymer having a multi-block structure can be obtained
by using two different types of transition metal complex catalysts.
varying in copolymerizability, and by adding a zinc compound to
allow a reversible chain transfer reaction to occur through the
zinc compound.
20 [0005]
The copolymers disclosed in these documents are proposed
for the purpose of improving the heat resistance by incorporating
a crystalline segment into the polymer. However, the copolymer
disclosed in Patent Document 2, in particular, is associated with
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other problems that the zinc compound used as a chain transfer
agent remains in the finally resulting polymer component, and that
the improvement in reducing the stickiness is limited because of
the formation of a copolymerization component which remained
5 unincorporated into the block structure. Further, in the
copolymers obtained by the methods disclosed in the above
mentioned Patent Document 1 and Patent Document 2, the number of
free terminals of the crystalline segment per one molecule is
limited to 2 or less, in principle, and accordingly, the size of
10 spherulites formed during the crystallization process cannot be
controlled, possibly leading to a deterioration of mechanical
performance and optical properties.
CITATION LIST
15 PATENT DOCUMENTS
[0006]
Patent Document 1 JP 2004-204058 A
Patent Document 2 JP 2007-529617 A
20 SUMMARY OF THE INVENTION
PROBLEMS TO BE SOLVED BY THE INVENTION
[0007]
In view of the above background art, an object of the present
invention is to provide an olefin resin, in which problems
5
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associated with the existing olefin copolymers such as low heat
resistance and stickiness are improved, and which has excellent
optical properties and low temperature properties, as well as an
improved balance between these physical properties.
MEANS FOR SOLVING THE PROBLEMS
[0008]
The present inventors have found Out, as a result of
intensive studies to solve the above mentioned problems, that an
10 olefin resin that satisfies specific requirements improves
problems associated with the existing olefin copolymers such as
low heat resistance and stickiness, and has excellent optical
properties and low temperature properties, as well as an improved
balance between these physical properties.
15 [0009]
In. other words, .the-- present invention relat_es to_ the
following [1] to [7].
[0010]
[1] An olefin resin satisfying the following requirements (I)
20 to (V) :
I 0011]
(I) a melting peak (Tm) as measured by differential scanning
calorimetry (DSC) is observed within the range of from 60°C to
130°C, and the heat of fusion ~H at the melting peak is within
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5
the range of from 5 to 150 J/g;
[0012]
(II} the percentage E {wt%) of a portion soluble in
a-dichlorobenzene at or lower as measured by
5 cross-fractionation chromatography (CFC}, and the heat of fusion
LlH as described in (I) above, satisfy the following relationships:
10
[0013]
·when· the LlH is 5 J/g or more and less than 15 J/g,
the value E is 45 wt% or less,
·when the LlH is 15 J/g or more and less than 30 J/g,
the value E is 40 wt% or less, and
when the LlH is 30 J/g or more, the value E is 30
wt% or less;
{III) the glass transition temperature (Tg) as measured by
15 differential scanning calorimetry (DSC) is within the range of
-80 to -30-°C;
[0014 J
(IV) the spin-spin relaxation time (T2} of a component
having the highest mobility, as obtained in a four-component
20 approximation by a Lorentzian function performed for a free
induction decay curve obtained by Carr Purcell Meiboorn Gill method
in a pulsed nuclear magnetic resonance measurement (pulsed NMR)
at 200°C, is within the range of from 150 to 500 ms, and the
abundance ratio of the component is within the range of from 15
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to 50%; and
[0015]
(V) the intrinsic viscosity [~] as measured in decalin at
135°C is within the range of from 0.1 to 12 dl/g.
5 [0016]
[2] The olefin resin according to [1], wherein the olefin resin
has a tensile elastic modulus in accordance with ASTM D638 within
the range of from 2 to 120 MPa.
[0017]
10 [3] An olefin polymer (Rl) composed of a main chain polymer and
a side chain polymer satisfying the following requirements:
[0018]
{i) a main chain is composed of repeating units derived from
ethylene, and repeating units derived from at least one a-olefin
15 selected from a-olefins having from 3 to 20 carbon atoms, wherein
the content of the repeating units derived from the a-olefin in
the main chain is within the range of from 5 to 40 mol%;
[0019]
(ii) the main chain has an intrinsic viscosity [fl] as
20 measured in decalin at 135°C within the range of from 0.5 to 5
dl/g;
[0020]
(iii) a side chain(s) is/are composed of repeating units
derived from ethylene, and optional repeating units derived from
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at least one a-olefin selected from a-olefins having from 3 to
20 carbon atoms, wherein the content of the repeating units derived
from ethylene in the side chain(s) is within the range of from
95 to 100 mol%;
5 [0021]
(iv) the side chain{s) has/have a weight average molecular
weight within the range of from 500 to 10,000; and
[0022]
{v} the side chain(s} is/are bound to the main chain at a
10 ratio of 0. 5 to 20 side chains per 1, 000 main chain carbon atoms.
[0023]
[4] A method for producing the olefin resin according to [1]
or [2], the method comprising the step of copolymerizing ethylene
and at least one a-olefin selected from a-olefins having from 3
15 to 20 carbon atoms in the presence of an olefin polymerization
catalyst comprising each of the following components (A) to .(C):
[0024]
(A) a transition metal compound of a transition metal of
Group 4 in the periodic table, the compound comprising a ligand
20 having a cyclopentadienyl skeleton;
(B) at least one transition metal compound selected from
compounds represented by the following general formulae [BO] , [Bl] ,
and [82]; and
(C) at least one compound selected from an organometallic
SF-2910
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compound (C-1), an organoaluminum oxy compound (C-2}, and a
compound (C-3) which reacts with the transition metal compound
(A) or the transition metal compound (B) to form an ion pair;
[0025]
5 [Chern. 1]
· · • [ B 0 l
[0026]
(wherein in the general formula [BO],
M represents a transition metal atom of Group 4 or 5 in the
10 periodic table;
m represents an integer of from 1 to 4;
R1 represents an acyclic hydrocarbon group (Cn•H2n•tt 1 n' =
1 to 20) having from 1 to 20 carbon atoms or a hydrogen atom;
R2 to R6
, which may be the same or different from each other,
15 each represents a hydrogen atom, a halogen atom, a hydrocarbon
group, a heterocyclic compound residue, an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
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tin-containing group, and two or more of these are optionally bound
together to form a ring;
in cases where m is two or more, two of the groups represented
by R2 to R6 are optionally bound to each other; n is a number
5 satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
10 halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group, or a
tin-containing group; and
in cases where n is two or more1 Xs may be the same or
different from each other 1 and a plurality of groups represented
15 by X may be bonded to each other to form a ring)
[0027]
[Chern. 2]
• • • [B 1 ]
[0028]
SF-2910
10
(wherein in the general formula [B1] 1
M represents a transition metal of the Group 4 or 5 in the
periodic table; m represents an integer of from 1 to 4;
R1 represents an alicyclic hydrocarbon group of a 3- to 10-
5 membered ring, optionally including one or more substituents; R2
to R6 , which may be the same or different from each other, each
represents a hydrogen atom,. a halogen atom, a hydrocarbon group,
a heterocyclic compound residue, an -oxygen-containing grOUp, a
nitrogen-containing group, a boron-containing group, a
10 sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, and two or more of these are optionally bound
together to form a ring;
in cases where m is two or more, two of the groups represented
15 by R2 to R6 are optionally bound to each other; n is a number
sati-~fying the valence of M;
X represents a hydrogen atom,. a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
20 aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group, or a
tin-containing group; and
in cases where n is two or more, Xs may be the same or
!
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different from each other, and a plurality of groups represented
by X may be bonded to each other to form a ring)
[0029]
[Chern. 3]
M represents a transition metal of the Group 4 or 5 in the
periodic table; m represents an integer of from 1 to 4;
10 R1 represents a hi cyclic aliphatic hydrocarbon group having
from 4 to 20 carbon atoms, optionally containing one or more
substitu.ents, wherein the two.rings of the bicyclic aliphatic
hydrocarbon group share at least one or more carbon atoms;
R2 to R6, which may be the same or different from each other,
15 each represents a hydrogen atom, a halogen atom, a hydrocarbon
group, a heterocyclic compound residue, an oxygen-containing
group, a nitrogen~containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
20 tin-containing group, and two or more of these are optionally bound
5
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together to form a ring;
in cases where m is two or more, two of the groups represented
by R2 to R6 are optionally bound to each other; n is a number
satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
alUminuffi.:::~o~tai~ing group, a phosphorus-containing g·rciup, a
halogen-containing group, a heterocyclic compound residue, a
10 silicon-containing group, a germanium-containing group, or a
tin-containing group; and
15
in cases where n is two or more, Xs may be the same or
different from each other, and a plurality of groups represented
by X may be bonded to_ each other to form a ring) .
[ 5] The method for producing the olefin resin, according to [ 4],
wherein the transition metal compound {A) is a bridged metallocene
compound represented by the following general formula (I):
[0031]
[Chem. 4]
r- -- . - -·--·---- --- ---- ---·-----~--
SF-2910
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... (I)
[0032]
(wherein in the formula (I),
R1
, R2
, R3
, R4
, R5
1 R8
, R9 and R12 each independently represents
5 a hydrogen atom, a hydrocarbon group, a silicon-containing group,
or a hetero atom-containing group other than silicon-containing
groups, and two adjacent groups of the groups represented by R1
to R4 are optionally bound together to form a ring;
R6 and R11 are the same atom· or the same group selected from
10 hydrogen atom, hydrocarbon groupsr silicon-containing groups,
and hetero atom-containing .groups other than the
silicon-containing groups; R7 and R10 are the same atom or the same
group selected from hydrogen atom, hydrocarbon groups,
silicon-containing groups, and hetero atom-containing groups
15 other than the silicon-containing groups; R6 and R7 are optionally
bound together to form a ring; and R10 and R11 are optionally bound
together to form a ring; with the proviso that not all of R6, R7,
R10 and R11 are hydrogen atoms;
5
10
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R13 and R14 each independently represent an aryl group;
M represents a titanium atom, a zirconium atom or a hafnium
atom;
y 1 represents a carbon atom or a silicon atom;
Q represents a halogen atom, a hydrocarbon group, a
halogenated hydrocarbon group, a neutral conjugated or
non-conjugated diene having from 4 to 10 carbon atoms, an anionic
ligand or a neutral ligand capable of being coordinated with a
lone pair of electrons;
j represents an integer of from 1 to 4; and
in cases where j is an integer of two or more, a plurality
of Qs may be the same as or different from each other) .
[6] The method for producing the olefin resin, according to [4)
or [5), wherein the step of copolymerizing is carried out by a
15 solution polymerization method at a temperature within the range
20
of from 80 to 300°C.
[0033]
[7] A molded article obtainable from the olefin resin according
to [1] or [2].
EFFECT OF THE INVENTION
[0034]
The olefin resin according to the present invention has a
feature of having an excellent heat resistance and markedly
I
I
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reduced stickiness, as compared to the existing olefin copolymers
having an excellent flexibility and low temperature properties.
Further, the olefin resin according to the present invention has
a feature of achieving comparable or improved optical properties
5 as compared to the currently available products, which properties
have been sacrificed in the existing olefin copolymers for the
purpose of improving the above mentioned characteristics. Still
further, the olefin resin according to the present invention has
an excellent flexibility and low temperature properties.
10
BRIEF DESCRIPTION OF THE DRAWINGS
[0035]
FIG. 1 is an image of the olefin resin produced in Example
7 obtained by transmission electron microscope observation (at
15 a magnification of 4, ODD-fold).,
FIG. 2 is an image of the olefin resin produced in
Comparative Example 6 obtained by transmission electron
microscope observation (at a magnification of 4,0DO-fold).
FIG. 3 shows the 13C-NMR spectra of the olefin resin produced
2D in Example 7.
FIG. 4 shows the 13C-NMR spectra (enlarged views of the region
of from 33 to 44 ppm) of the olefin resin produced in Example 7.
FIG. 5 shows the 13C-NMR spectrum of the olefin resin produced
in Comparative Example 6.
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FIG. 6 shows the 13C-NMR spectrum (an enlarged view of the
region of from 33 to 44 ppm) of the olefin resin produced in
Comparative Example 6.
FIG. 7 shows enlarged views of the region around 38 ppm
5 (upper portion: Example 7, mid-portion: Example 10, and lower
portion: Comparative Example 9) of the 13C-NMR spectra of the
olefin resins produced in Example 7, Example 10, and Comparative
Example 9.
10 MODE FOR CARRYING OOT THE INVENTION
I 0036]
The olefin resin [R] according to the present invention and
the method for producing the olefin resin will now be described
in detail.
15 [0037]

The olefin resin (R] according to the present invention may
be composed of one type of olefin polymer alone, or two or more
types of olefin polymers, but has a feature of necessarily
20 satisfying all of the following requirements (I) to (V) :
[0038]
{I) a melting peak (Tm) as measured by differential scanning
calorimetry {DSC) is observed within the range of from 60cC to
130cC, and the heat of fusion (nH) calculated from the melting
SF-2910
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peak area is within the range of from 5 to 150 J/g.
[0039]
(II) the percentage E (wt%) of a portion soluble in
a-dichlorobenzene at or lower as measured by
5 cross-fractionation chromatography (CFC), and the heat of fusion
LlH as described in (I) above, satisfy the following relationships:
10
[0040]
· when 'the ~H is 5 J/g or ffiore and less than 15 J/g,
the value E is 45 wt% or less,
·when the LlH is 15 J/g or more and less than 30 J/g,
the value E is 40 wt% or less, and
when the LlH is 30 J/g or more, the value E is 30
wt% or less;
(III) the glass transition temperature (Tg) as measured by
15 differential scanning calorimetry (DSC} is within the range of
-80 to -30°C;
[0041]
(IV) the spin-spin relaxation time (T2) of a component
having the highest mobility, as obtained in a four-component
20 approximation by a Lorentzian function performed for a free
induction decay curve obtained by Carr Purcell Meiboom Gill method
in a pulsed nuclear magnetic resonance measurement (pulsed NMR)
at 200°C, is within the range of from 150 to 500 ms, and the
abundance ratio of the component is within the range of from 15
SF-2910
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to 50%; and
[0042]
(V) the intrinsic viscosity [~] as measured in decalin at
135°C is within the range of from 0.1 to 12 dl/g.
5 [0043]
The olefin resin [R] according to the present invention
preferably includes an olefin polymer [Rl] to be described later,
and the olefin polymer [Rl] is efficiency produced by a
polymerization method to be described later. When the olefin
10 resin [R] according to the present invention is composed of one
type of olefin polymer alone, the olefin polymer is preferably
the olefin polymer [Rl]. When the olefin resin [R] according to
the present invention is composed of two or more types of olefin
polymers, the olefin resin preferably includes the olefin polymer
15 [Rl], and an olefin polymer (s) [R2] other than the olefin polymer
[Rl] to be included in th~ resin may be, for example, a polymer
or copolymer of ethylene and one or more olefins selected from
a-olefins having from 3 to 20 carbon atoms, obtained by using a
metallocene catalyst, a post-metallocene catalyst or a Ziegler
20 catalyst; or a high-pressure method low density polyethylene
produced by high pressure radical polymerization method. Further,
the olefin polymer [R2] may be, for example, a polymer by-produced
during the polymerization process in the production of the olefin
polymer [Rl] , specifically, an ethylene polymer or an
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ethylene/a-olefin copolymer. When the olefin resin [R] is
composed of two or more types of olefin polymers, the composition
ratio of the olefin polymer [Rl] and the olefin polymer [R2], and
the type of the olefin polymer [R2] are not particularly limited,
5 as long as [Rl] and [R2] can be blended and a resultant blended
resin satisfies the above mentioned requirements (I) to (V) at
the same time. However, the composition ratio is usually selected
such that the ratio of the olefin polyme:r [Rl] in the olefin resin
[R) is from 40 to 99 wt%, preferably from 45 to 95 wt%, and still
10 more preferably, from 50 to 90 wt%. In a preferred embodiment
of the olefin resin [R] according to the present invention, the
olefin resin [R] is usually composed of the olefin polymer [R1]
alone, from the viewpoint of being able to eliminate treatment
steps, such as blending. On the other hand, when it is intended
15 to further and markedly improve 'the specific performance(s) of
the olefin polymer [Rl], or_ to add a new capability{ies) that the
olefin polymer [Rl] does not originally have, the olefin polymer
[Rl] is used as a blend with the olefin polymer [R2] as described
above.
20 [0044]
In a preferred and typical embodiment of the present
invention, the olefin resin [R] according to the present invention
includes the olefin polymer [Rl] produced by the polymerization
method to be described later, as a structural component. The
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olefin polymer [Rl] has a structure of a graft copolymer having
as the main chain a so-called ethylene/a-olefin copolymer unit
composed of repeating units derived from ethylene and repeating
units derived from one or more a-olefins selected from a-ole fins
5 having from 3 to 20 carbon atoms, and having as the side chains
a specific number of so-called ethylene polymer units composed
of repeating units derived substantially from ethylene.
[0045]
In the present invention, the term "graft copolymer" refers
10 to a so-called comb-shaped polymer in which one or more side chains
are bound to a main chain. A polymer having only one side chain
is a T-shaped polymer. Note, however, that the side chains can
include repeating units other than those derived from ethylene,
without departing from the gist of the invention.
15 [0046]
The olefin resin [R] according to the present invention
satisfies the requirements (I) to- (V) at the same time. These
requirements {I) to (V) will now be described specifically.
[ 004 7]
20 [Requirement (I): melting peak (Tm) and heat of fusion (~H)]
The olefin resin according to the present invention has a
melting peak (Tm) as measured by differential scanning calorimetry
(DSC) within the range of from 60 to 130°C, preferably from 80
to 125°C, and more preferably from 90 to 120°C.
SF-2910
21
[0048]
Further, the heat of fusion ,..,_Hat the above mentioned melting
peak, specifically, the heat of fusion (,..,_H) calculated from the
melting peak area, is within the range of from 5 to 150 J/g,
5 preferably from 10 to 120 J/g, more preferably from 15 to 100 J/g,
and still more preferably from 20 to 80 J/g.
[0049]
The melting peak (Trn) and the heat of fusion (ll.H) are
obtained using DSC by: melting a sample through a first
10 temperature-increasing step; then allowing the melted sample to
crystallize through a cooling step to 30°C; and then subjecting
the resultant to a second temperature-increasing step (at a
temperature rise rate of l0°C/min) and analyzing the endothermic
peak observed at this step.
15 [0050]
The melting peak (Tm) observed within the above mentioned
range is mainly derived from ethylene polymer moiety of the olefin
polymer [Rl] contained in the olefin- resin, and the fact that the
heat of fusion (~H) is observed within the above mentioned range
20 indicates that the olefin resin contains a significant amount of
the ethylene polymer moiety of the olefin polymer [Rl], in other
words, the side chain moiety of the olefin polymer [Rl]. In the
olefin resin according to the present invention, the ethylene
polymer moiety of the olefin polymer (Rl] serves to impart heat
SF-2910
22
resistance to, as well as to reduce the stickiness of, the entire
resin. When the heat of fusion (L1H) is within the above mentioned
range, in particular, it is possible to improve the heat resistance
and reduce the stickiness, while maintaining the properties such
5 as flexibility and low temperature properties. On the other hand,
when the heat of fusion (6H) is lower than the above mentioned
range, it indicates a low content of the ethylene polymer moiety,
and sufficient heat resistance and sufficient reduction in the
stickiness cannot be obtained. Further, when the heat of fusion
10 {LlH) exceeds the above mentioned range, there are cases where the
properties such as flexibility and low temperature properties may
be significantly impaired, even though sufficient heat resistance
and reduction in the stickiness can be achieved.
15
[0051]
In order for the olefin resin according to the present
invention to have the melting peak (Tm} and the heat of fusion
(~H) as specified above, it is necessary that the content of a
component composed of the ethylene polymer moiety of the olefin
polymer [Rl] be within the range of from about 2 to 60% by weight
20 in the olefin resin. To adjust the content within the above range,
it is preferred to adjust the amount to be added to the
polymerization vessel of an ethylene polymer having a terminal
double bond, as a raw material of the side chains, and to use an
olefin polymerization catalyst having an excellent capability to
SF-2910
23
introduce the ethylene polymer having a terminal double bond into
the main chain, in the polymerization reaction. Descriptions
regarding the specific amount of the ethylene polymer to be added
and regarding the olefin polymerization catalyst will be given
5 later.
[ 0 0 52]
[Requirement (II): a-dichlorobenzene-soluble portion]
In the olefin resin according to the present invention, the
percentage E of a portion soluble in a-dichlorobenzene at 20°C
10 or lower as measured by cross-fractionation chromatography (CFC}
satisfies, in connection with the heat of fusion (LlH) as described
in the above requirement (I), the following requirements:
[0053]
when the ~H is 5 J/g or more and less than 15 J/g, the
15 value E is 45 wt-% or less,
20
·when the LlH is.l5 J/g or more and less than 30 J/g,. the
value E is 40 wt% or less, .and
· when the .llH is 30 J/g or more, the value E is 30 wt% or
less.
In a preferred and typical embodiment of the present
invention, the olefin resin according to the present invention
includes the olefin polymer [Rl] . The olefin polymer [Rl] has
a structure of a graft copolymer having an ethylene/a-olefin
copolymer, which is a non-crystalline or low-crystalline
SF-2910
24
component, as the main chain, and an ethylene polymer, which is
a crystalline component, as the side chain(s).
[0054]
Usually, an ethylene/~-olefin copolymer is mostly soluble
5 in a-dichlorobenzene at 20°C or lower, since it is a
non-crystalline or low-crystalline component. Further, an
ethylene polymer_ is insoluble in a-dichlorobenzene at 20°C or
' ' .
lower, sinCe it is a 'crystalline Component. In contrast, in the
olefin polymer [Rl], since the ethylene polymer moiety of the side
10 chains is insoluble in a-dichlorobenzene at 20°C or lower, the
ethylene/a-olefin copolymer moiety of the main chain which is
chemically bound with the side chains is also hardly soluble in
a-dichlorobenzene.
[0055]
15 When the olefin resin according to the present invention
includ$s the olefin polymer [Rl], an ethylene polymer and an
ethylene/a-olefin copolymer(s) are produced as byproducts,
during the production process of the olefin polymer [Rl] .
[0056]
20 Accordingly, when the olefin resin according to the present
invention includes the olefin polymer [Rl], the value E of the
olefin resin according to the present invention corresponds to
the content of the component obtained by subtracting the amount
of the crystalline component consisting of the ethylene polymer
SF-2910
25
and the amount of the olefin polymer [Rl] from the total amount
of the olefin resin according to the present invention. That is
to say, the value E corresponds to the content of the
non-crystalline or low-crystalline component consisting of the
5 ethylene/ex-olefin copolymer, contained in the olefin resin
according to the present invention.
[0057]
In other words, since the olefin resin according to the
present invention includes a significant amount of the olefin
10 polymer [Rl] as described above, in a preferred and typical
embodiment, the percentage of the portion soluble in
a-dichlorobenzene at 20°C or lower is lower than the percentage
of the non-crystalline or low-crystalline component (the
ethylene/a-olefin copolymer and a component composed of the
15 ethylene/a-olefin copolymer moi'ety corresponding to the main
chain of the olefin polymer [Rl]) actually contained.
[0058]
As described above, the heat o{ fusion .6..H of the crystalline
component (the ethylene polymer and a component composed of the
20 ethylene polymer moiety corresponding to the side chains of the
olefin polymer [Rl]) can be used as an index for the content of
the crystalline component. Further, since the content of the
non-crystalline or low-crystalline component (the
ethylene/a-olefin copolymer and the component composed of the
SF-2910
26
ethylene/a-olefin copolymer moiety corresponding to the main
chain of the olefin polymer [Rl]) is the amount obtained by
subtracting the content of the crystalline component {the ethylene
polymer and the component composed of the ethylene polymer moiety
5 corresponding to the side chains of the olefin polymer [Rl]) from
the total amount of-the olefin resin, the above mentioned ~H can
also be used as an index for the content of the non-crystalline
or low-crystalline comporient (the ethylene/~-olefin copolymer
and the component composed of the ethylene/a-olefin copolymer
10 moiety corresponding to the main chain of the olefin polymer [Rl]).
In other words, a higher value of the LlH indicates a lower
percentage of the ethylene/a-olefin copolymer and the component
composed of the ethylene/a-olefin copolymer moiety corresponding
to the main chain of the olefin polymer [Rl], whereas a lower value
15 of the liH indicates a higher percentage of the ethylene/a-olefin
copolym~r and- the component composed of the ethylene/o:--olefin
copolymer moiety corresponding to_the main chain of the olefin
20
polymer [Rl].
[0059]
As described above, since the olefin resin according to the
present invention includes a significant amount of the olefin
polymer [Rl] in a preferred and typical embodiment, the value of
the ~H and the value E satisfy the following relationship.
[0060]
5
SF-2910
27
When the ~H is 5 J/g or more and less than 15 J/g, the
value E is 45 wt% or less, preferably 40 wt% or less, and more
preferably within the range of from 10 to 35 wt%.
[0061]
Although it varies depending on the molecular weight of the
ethylene polymer or the ethylene polymer moiety corresponding to
the side chains of the olefin polymer [Rl] and the content of the
olefin polymer [Rl], when the ~His 5 J/g or more and less than
15 J/g 1 the content of the crystalline component composed of the
10 ethylene polymer and the ethylene polymer moiety corresponding
to the side chains of the olefin polymer [Rl] can be estimated
to be about 3 to 10 wt%. Therefore, the content of the
non-crystalline or low-crystalline component composed of the
ethylene/a-olefin copolymer and the ethylene/a-olefin copolymer
15 moiety corresponding to the main chain of the olefin polymer [Rl]
is about 90 to 97 wt%. When the l:!H is within the above menti,oned
range, the value E of the olefin resin according to the present
invention is set to be 45 wt% or less, which is significantly lower
as compared to the content of the non-crystalline or
20 low-crystalline component estimated from the l:!H.
[ 0 0 62)
When the ~H is 15 J/g or more and less than 30 J/g, the
value E is 40 wt% or less, preferably 35 wt% or less, and more
preferably within the range-of from 5 to 30 wt%.
SF-2910
28
[0063]
Although it varies depending on the molecular weight of the
ethylene polymer or the ethylene polymer moiety corresponding to
the side chains of the olefin polymer [Rl] and the content of the
5 olefin polymer [Rl] , when the ~H is 15 J/g or more and less than
30 J/g, the content of the crystalline component composed of the
ethylene polymer and the ethylene polymer moiety corresponding
to the side chains of the olefin polymer [Rl] can be estimated
to be about 10 to 25 wt%. Therefore, the content of the
10 non-crystalline or low-crystalline component composed of the
ethylene/a-olefin copolymer and the ethylene/~-olefin copolymer
moiety corresponding to the main chain of the olefin polymer [Rl]
is about 7 5 to 90 wt%. When the LlH is within the above mentioned
range, the value E of the olefin resin according to the present
15 invention is set to be 40 wt% or less, which is significantly lower
as compared to the content of the non-crystalline or
low-crystalline component estimated from the LlH.
[0064]
· When the LlH is 30 J/g or more, the value E is 30 wt% or
20 less, and preferably 25 wt% or less.
[0065]
Although it varies depending on the molecular weight of the
ethylene polymer or the ethylene polymer moiety corresponding to
the side chains of the olefin polymer [Rl] and the content of the
SF-2910
29
olefin polymer [Rl], when the ~His 30 J/g or more and 150 J/g
or less, the content of the crystalline component composed of the
ethylene polymer and the ethylene polymer moiety corresponding
to the side chains of the olefin polymer [Rl] is estimated to be
5 about 25 to 60 wt%. Therefore, the content of the non-crystalline
or low-crystalline component composed of the ethylene/a-olefin
copolymer and the ethylene/a-olefin copolymer moiety
corresponding to the main chain of the olefin polymer [Rl] is about
40 to 75 wt%. When the ~His within the above mentioned range,
10 the value E of the olefin resin according to the present invention
is set to be 30 wt% or less, which is significantly lower as
compared to the content of the non-crystalline or low-crystalline
component estimated from the ~H.
15
[0066]
On the other hand, in a blended product obtained by simply
blending the component consisting of the ethylene polymer and the
component consisting of the ethylene/a-olefin copolymer, which
product contains substantially no- olefin polymer [Rl], the
percentage of the component consisting of the ethylene/a-olefin
20 copolymer, which is non-crystalline or low-crystalline, takes a
value close to the value E, and the relationship between the ~H
and the value E does not satisfy the above mentioned range
requirements.
[0067]
SF-2910
30
While an ethylene/a-olefin copolymer usually has excellent
low temperature properties and flexibility, a phenomenon in which
the copolymer migrates to the surface of a molded article to be
exuded therefrom, which is called bleed-out, could occur, causing
5 problems such as "blocking" when formed into pellets, or surface
stickiness when formed into a molded article. However, when the
ethylene polymer moiety, \olhich is crystalline, is chemically bound
to the ethylene/a-olefin copolymer, which is non-crystalline or
low-crystalline, the polymer chain of the copolymer is unable to
10 migrate freely at a temperature equal to or less than the melting
point of the crystalline ethylene polymer moiety, and thus, there
is no chance that the copolymer exudes from the surface of the
molded article.
15
[0068]
In the olefin resin according to the present invention,
sincl$ the relationship between the l:IH and the value E satisfies
the above mentioned range requirements, as previously described,
it includes a significant amount of the component in which the
crystalline ethylene polymer moiety is chemically bound to the
20 ethylene/a-olefin copolymer component.
[0069]
Accordingly, although the olefin resin according to the
present invention includes the non-crystalline or
low-crystalline component composed of the ethylene/a-olefin
···---·---
SF-2910
31
copolymer and the ethylene/a-olefin copolymer moiety
corresponding to the main chain of the olefin polymer [Rl] in an
amount sufficient to exhibit properties such as flexibility and
low temperature properties, the stickiness and the blocking of
5 the resin can also be prevented.
[0070]
[Requirement (III): glass transition temperature (Tg)]
The-olefin resin according to the present invention has a
glass transition temperature as measured by differential scanning
10 calorimetry (DSC) within the range of from -80°C to -30°C,
preferably, from -80°C to -40°C, and more preferably from -80°C
to -50°C.
[0071]
The olefin resin according to the present invention includes
15 the non-crystalline or low-crystalline component composed of the
ethyle.ne/a,...olefin copolymer and the. ethylene/a-olefin copol.yme_:z:.
moiety, and the glass transition· temperature (Tg} is derived from
the non-crystalline or low-crystalline component. When the
olefin resin has a glass transition temperature {Tg) within the
20 range of from -80°C to -30°C, for example, from -80°C to -40°C,
properties as an elastomer such as flexibility and low temperature
properties are exhibited. The glass transition temperature {Tg)
within the above mentioned range is achieved by controlling the
type and the composition of the a-olefin as a comonomer.
SF-2910
32
[0072]
[Requirement (IV) : pulsed NMR]
In the olefin resin according to the present invention, the
spin-spin relaxation time (T2) of a component having the highest
5 mobility, as obtained in a four-component approximation by a
Lorentzian function performed for a free induction decay curve
obtained by Carr Purcell M~iboom Gill (CPMG) method in a pulsed
nuclear magnetic resonance rneasuremen:t- {pulsed NMR) at 200°C, is
within the range of from 150 to 500 ms, and the abundance ratio
10 of the component is within the range of from 15 to 50%.
[0073]
The pulsed NMR is an analysis commonly used as a method for
evaluating the mobility of polymer molecular chains and the state
of interaction between different components, and the evaluation
15 is carried out by measuring the· 1H transverse relaxation times
of all the components constituting .a resin. The lower- the
mobility of a polymer chain, the shorter the relaxation time, and
thus the faster the attenuation of signal intensity; and
accordingly, a relative signal intensity with respect to 100% of
20 the initial signal intensity is decreased in a shorter time.
Further, the higher the mobility of the polymer chain, the longer
the relaxation time, and thus the slower the attenuation of signal
intensity; and accordingly, the relative signal intensity with
respect to 100% of the initial signal intensity is decreased slowly
SF-2910
33
over a longer period of time.
[0074]
When the four-component approximation by the Lorentzian
function is performed for the free induction decay curve (FID)
5 of 1H nuclei obtained in the pulsed NMR measurement carried out
by CPMG method, at a measurement temperature of 200°C, with an
observed pulse width of 2. 0 J1 sec and a repetition time of 4 sec,
a component with the longes·t T2 can be considered to be derived
from a component having the highest polymer mobility. In
10 particular, when the T2 is from 150 to 500 ms, it can be said that
the T2 is derived from the mobility of the free terminal of the
polymer chain.
[0075]
Since the olefin resin according to the present invention
15 includes a significant amount ·of a so-called graft polymer
composed of the non-:-crystalline or low-crystalline
ethylene/a-olefin copolymer moiety as the main chain, and the
crystalline ethylene polymer moiety as the side chains which are
chemically bound to the main chain, the olefin resin has more
20 terminal structures as compared to straight-chain polymers.
[0076]
Therefore, in the olefin resin according to the present
invention, the abundance ratio of the component having the highest
mobility is within the range of from 15 to 50%, and preferably,
SF-2910
34
within the range of from 15 to 40%.
[0077]
Thus, it is considered that the higher ratio of the free
terminals of the crystalline polymer chains derived from the
5 ethylene polymer moiety accelerates the crystallization rate of
the ethylene polymer moiety during the cooling process in molding,
thereby resulting in a refinement of the spherulites of the
ethylene polymer formed during the crystallization. This allows
the olefin resin according to the present invention to achieve
10 a high light transmittance and to have excellent optical
properties.
[0078]
[Requirement (V): intrinsic viscosity [Il]]
The olefin resin according to the present invention
15 preferably has an intrinsic viscosity [!]] as measured in decalin
at 135°C within the range of from 0.1 to 12 dl/g, more preferably
from 0.2 to 10 dl/g, and still more preferably from 0.5 to 5 dl/g.
By adjusting the intrinsic viscosity [~] to be within the above
mentioned range, a balance between practical physical properties
20 and moldability can be obtained.
[0079]
[Other physical properties]
Elastic modulus
The olefin resin according to the present invention
SF-2910
35
preferably has a tensile elastic modulus in accordance with ASTM
0638 within the range of from 2 to 120 MPa, more preferably from
3 to 100 MPa, and still more preferably from 5 to 90 MPa. By
adjusting the tensile elastic modulus to be within the above
5 mentioned range, a sufficient flexibility and practical strength
can be obtained.
[0080]
When the proportion of the ethylene/a-olefin copolymer and
the component composecl of the ethylene/a-olefin copolymer moiety
10 corresponding to the main chain of the olefin polymer [Rl] is
increased, the elastic modulus is decreased; and when the
proportion of the ethylene/a-olefin copolymer and the component
composed of the ethylene/a-olefin copolymer moiety corresponding
to the main chain of the olefin polymer [Rl] is decreased, and
15 the proportion of the ethylene polymer and the component composed
of the ethylene polymer moiety corresponding to the side ch-ains
of the olefin polymer [Rl] is increased instead, the elastic
modulus is increased.
20
[0081]
The olefin resin according to the present invention has a
high flexibility, because it includes a large amount of the
ethylene/a-olefin copolymer and the component composed of the
ethylene/a-olefin copolymer moiety corresponding to the main
chain of the olefin polymer [Rl]. In other words, the olefin resin
SF-2910
36
according to the present invention has an elastic modulus within
the above mentioned range, and thus, properties such as
flexibility and low temperature properties are exhibited.
[0082]
5 Transmission electron microscope observation
In the olefin resin according to the present invention, a
phase representing the crystalline component observed by a
transmission electron microscope is preferably a discontinuous
phase of micrometer order. In order to confirm if the olefin resin
10 has the above mentioned phase structure or not, the observation
is carried out, for example, as follows.
[0083]
First, using a hydraulic hot press molding machine
controlled at 170°C, the olefin resin is preheated for 5 minutes
15 followed by molding for one minute under a pressure of 10 MPa.
20
Then the resultant is cooled at 20°C for 3 minutes under a pressure
of 10 MPa to give a sheet having a predetermined thickness, to
be used as a test specimen.
[0084]
The above mentioned pressed sheet is formed into a small
piece of 0.5 mrn square, and dyed with ruthenium acid (Ru04}. The
resulting piece is then cut into an ultra-thin slice having a film
thickness of about 100 nm, using an ultramicrotome with a diamond
knife. Thereafter, carbon is deposited on the ultra-thin slice,
------- ---"" ----
SF-2910
37
and the resultant is observed by a transmission electron
microscope {acceleration voltage: lOOkV).
[0085]
In the above mentioned observation method, the component
5 composed of the ethylene polymer and the ethylene polymer moiety
corresponding to the side chains of the olefin polymer [Rl] is
observed with a higher contrast, because an inter-crystal
non-crystalline moiety in a lamellar structure formed by the
component is selectively dyed with osmic acid.
10 [0086]
In the olefin resin according to the present invention, the
thus observed phase representing the crystalline component
composed of the ethylene polymer and the ethylene polymer moiety
corresponding to the side chains of the olefin polymer [Rl] is
15 a discontinuous phase of micrometer order, and such a finely
dispersed crystalline component allows for improving the .heat
resistance of the entire sample.
[0087]
Since, in a preferred and typical embodiment, the olefin
20 resin includes a considerable amount of the olefin polymer (R1]
in which the non-crystalline or low-crystalline main chain and
the crystalline side chains are covalently bound, as described
above, the non-crystalline or low-crystalline component composed
of the ethylene/a-olefin copolymer and the ethylene/a-olefin
SF-2910
38
copolymer moiety, and the crystalline component composed of the
ethylene polymer and the ethylene polymer moiety corresponding
to the main chain of the olefin polymer [Rl], are highly compatible,
which is thought to be the reason for the formation of the above
5 described microphase-separated structure.
[0088]

In a preferred and typical embodirn9r1t of the Present
invention, the olefin resin [R] according to the present invention
10 includes the olefin polymer [Rl] . The olefin polymer [Rl]
included in the olefin resin [R] according to the present invention
refers to a graft copolymer having a main chain and a side chain {s) ,
as described above. In the present invention, the olefin polymer
[Rl] is preferably composed of the main chain and the side chains
15 satisfying the following requirements {i) to (v) .
[0089]
(i) The main chain is composed of a copolymer of ethylene
and at least one a-olefins selected from ~-olefins having from
3 to 20 carbon atoms, and the content of repeating units derived
20 from ethylene is within the range of from 60 to 97 mol%, and the
content of repeating units derived from the o-olefin is within
the range of from 3 to 40 mol%.
[0090]
(ii) The main chain moiety has an intrinsic viscosity [~]
SF-2910
of from 0.5 to 5.0 dl/g.
[0091]
39
(iii) The side chains are composed of the repeating units
derived from ethylene.
5 [0092]
(iv) The weight average molecular weight of the side chains
is within the range of from 500 to 10,000.
[0093]
(v) The side chains are bound to the main chain at a ratio
10 of 0.5 to 20 side chains per 1,000 main chain carbon atoms.
[0094]
These requirements (i) to (v) will now be specifically
described.
[0095]
15 [Requirement (i)]
The. main chain of th~ ol!3fin polymer [Rl] is compose,d of
the ethylene/a-olefin copolymer, and, as the ethylene/a-olefin
copolymer unit, serves as a moiety· responsible for exhibiting
properties such as flexibility and low temperature properties.
20 Accordingly, the main chain of the olefin Polymer [Rl] is composed
of repeating units derived from ethylene and repeating units
derived from at least one ex-olefin selected from a-olefins having
from 3 to 20 carbon atoms.
[ 0096]
SF-2910
40
The a-olefin having from 3 to 20 carbon atoms to be
copolymerized with ethylene is preferably an a-olefin having from
3 to 10 carbon atoms, and more preferably, an a-olefin having from
3 to 8 carbon atoms. Specific examples of the a-olefin include:
5 linear olefins such as propylene, 1-butene, 1-pentene, 1-hexene,
1-octene, and 1-decene; and branched olefins such as
4-methyl-1-pentene, 3-methyl-1-pentene, and 3-methyl-1-butene.
Preferred are propylene, 1-butene, 1-hexene, and
4-methyl-1-pentene.
10 [0097]
The molar ratio of the repeating units derived from ethylene
with respect to the total repeating units in the main chain of
the olefin polymer [Rl], is within the range of from 60 to 97 mol%,
preferably from 60 to 95 mol%, and more preferably from 65 to 90
15 mol%. Further, the molar ratio 'of the repeating units derived
from the a-olefin with respect to the _tota_l-repeating units in
the main chain is within the range of from 3 to 40 mol%, preferably
from 5 to 40 mol%, and more preferably from 10 to 35 mol%. As
used herein, when an olefin (for example, ethylene or an 0'-olefin)
20 constituting a certain (co) polymer is defined as X, an expression
"structural units derived from X" means "structural units
corresponding to X", in other words, structural units each having
a pair of dangling bonds formed by opening of a rr-bond constituting
the double bond of X.
I
!
SF-2910
41
[0098]
When the molar ratios of the ethylene-derived repeating
units and the a-olefin-derived repeating units in the main chain
are within the above mentioned ranges, the moiety constituting
5 the main chain of the olefin polymer [Rl] will have a high
flexibility and excellent low temperature properties, and thus
the olefin resin according to the present invention will also have
the same properties. On the other hand, when the molar ratios
of the ethylene-derived repeating units and the a-olefin-derived
10 repeating units are lower than the above mentioned ranges, the
resulting resin will have a poor flexibility and/or low
temperature properties. Further, when the molar ratios of the
ethylene-derived repeating units and the a-olefin-derived
repeating units are higher than the above mentioned ranges, they
15 have a disadvantageous effect , in the copolymerization of a
macromonomer forming the side chains to be described later,
resulting in a failure to introduce a desired amount of side
chains.
[0099]
20 The molar ratios of the above described ethylene-derived
repeating units and the ~-olefin-derived repeating units in the
main chain can be adjusted by controlling the concentrations of
ethylene and the a-olefin to be present in the polymerization
reaction system in the production of the main chain.
SF-2910
42
[0100]
The molar ratio (mol%) of the a-olefin-derived units in the
main chain, namely, the composition ratio of the a-olefin in the
main chain, can be calculated and defined by the following method.
5 [0101]
(1) The a-olefin composition in a component consisting of
an ethylene/a-olefin copolymer ( s) by-produced in the production
process of the olefin resin [R] is defined as the unit derived
from the a-olefin in the main chain. Since the by-produced
10 ethylene/a-olefin copolymer corresponds to the portion soluble
in a-dichlorobenzene at 20°C or lower, when the olefin resin [R]
is placed therein, the a-olefin composition in the soluble portion
can be calculated by a known method using a carbon nuclear magnetic
resonance analysis ( 13C-NMR) .
15 [0102]
(2) A polymer consisting of the main chain moiety is
separately synthesized under reasonable conditions, in view of
the conditions for producing the olefin resin [R], and the a-olefin
composition of the resulting ethylene/a-olefin copolymer is
20 analyzed, and indirectly defined as the a-olefin composition of
the main chain of the olefin polymer [Rl]. The reasonable
conditions refers to conditions under which a polymer equivalent
to the main chain moiety of the olefin polymer [Rl] in principle
is formed, such as the concentrations of ethylene and the a-olefin
SF-2910
43
and the molecular abundance ratio of ethylene to hydrogen in the
polymerization system. Particularly, in cases where a production
method of the olefin resin [R] is used in which an ethylene polymer
moiety (macromonomer) corresponding to the side chains is
5 synthesized in advance, followed by copolymerizing the
macromonomer, ethylene and the a-olefin, a separate
polymerization is carried out under the same conditions except
that no macromonomer is added, and the a-olefin composition of
the resulting ethylene/a-olefin copolymer is analyzed, and
10 indirectly defined as the a-olefin composition of the main chain
of the olefin polymer [Rl].
[0103]
[Requirement (ii)]
The intrinsic viscosity [lll as measured in a decalin solvent
15 at 135°C, as an index for the molecular weight of the main chain
of the olefin polymer [Rl], is preferably ~n the range of -from
0.1 to 12 dl/g, more preferably from 0.2 to 10 dl/g, and still
more preferably from 0.5 to 5 dl/g.
20
[0104]
Since the intrinsic viscosity of the main chain primarily
controls the intrinsic viscosity [11] of the olefin polymer [Rl],
when the intrinsic viscosity [11] of the main chain is within the
above mentioned range, the balance between the practical physical
properties and workability will be improved.
SF-2910
44
[0105]
The intrinsic viscosity [11] of the main chain of the olefin
polymer [Rl] can be adjusted by controlling the concentration of
ethylene in the polymerization system in the production process
5 to be described later. The concentration of ethylene can be
controlledT for example, by adjusting the partial pressure of
ethylene or adjusting the polymerization temperature. The
adjustment of the intrinsic viscosity [nl of the main chain can
also be achieved by supplying hydrogen into the polymerization
10 system.
[0106]
The intrinsic viscosity [11] of the main chain can be obtained
by producing an ethylene/a-olefin copolymer according to the
method described above in the section of "Requirement (i) ", for
15 calculating and defining the, molar ratio (mol%) of the
a-olefin-derived units, and then measuring the intr~nsic
viscosity [~] of the resulting polymer by a usual method.
20
[0107]
[Requirement (iii)]
The side chain of the olefin polymer [Rl] is an ethylene
polymer moiety composed of repeating units derived substantially
from ethylene, and is a crystalline ethylene polymer chain.
[0108]
The ethylene polymer composed of repeating units derived
SF-2910
45
substantially from ethylene refers to an ethylene polymer
consisting of repeating units derived from ethylene (namely, an
ethylene homopolymer), and a copolymer including repeating units
derived from ethylene and a small amount of repeating units derived
5 from a comonomer(s) other than ethylene. The ethylene polymer
composed of repeating units derived substantially from ethylene
represents a polymer in which the! molar ratiO of the repeating
units derived from ethylene with respect to the total repeating
units contained in the ethylene polymer is preferably from 95.0
10 to 100 mol%, more preferably from 98.0 to 100 mol%, and still more
preferably from 99.5 to 100 mol%. In other words, the "ethylene
polymer moiety composed of repeating units derived substantially
from ethylene" which constitutes the side chains of the olefin
polymer [Rl] may include one or more types of repeating units
15 derived from an a-olefin(s) other than ethylene, to the extent
that the r:ole and the character,istics thereof are .not impaired~
Examples of the a-olefin other than ethylene include a-ol~fi-ns
having from 3 to 20 carbon atoms.
20
[0109]
In the olefin resin [R] according to the present invention,
the side chains of the olefin polymer [Rl] are responsible for
reducing the stickiness and providing a heat resistance by forming
physical crosslinking points.
[0110]
SF-2910
46
The fact that the side chains of the olefin polymer [Rl]
are crystalline ethylene polymer chains can be confirmed when the
melting peak (Tm) of the olefin resin according to the present
invention as measured by differential scanning calorimetry (DSC)
5 is observed within the range of from 60°C to 130°C1 in other words,
when the olefin resin has a melting peak {Tm) within the range
[0111]
[Requirement (iv)]
10 The side chains of the olefin polymer [Rl] has a weight
average molecular weight within the range of from 500 to 10,000,
and the weight average molecular weight is preferably within the
range of from 500 to 5,000, and more preferably within the range
of from 500 to 3,000.
15 [0112]
When the weight average mole_cular weight of the side ·cha-ins
of the olefin polymer [Rl] is within the above mentioned range,
it is possible to reduce the stickiness, and to effectively provide
a heat resistance due to the formation of the physical crosslinking
20 points.
[0113]
The olefin polymer [Rl] can be obtained by copolymerizing
a macromonomer, which is the ethylene polymer chain, with ethylene
and an a-olefin(s). In other words, the weight average molecular
SF-2910
47
weight of the macromonomer corresponds to the weight average
molecular weight of side chains of the olefin polymer [Rl] .
[0114]
When the weight average molecular weight of the side chains
5 is lower than the above mentioned range, the melting point of the
crystalline component composed of the ethylene polymer moiety in
the olefin polymer [Rl] is decreased, thereby reducing the heat
resistance. At the same time, the physical crosslinking points
formed by the crystalline component are weakened, possibly
10 resulting in a polymer having poor mechanical properties.
[0115]
On the other hand, when the weight average molecular weight
of the side chains is higher than the above mentioned range, the
relative amount of the non-crystalline or low-crystalline
15 component composed of the ethylene/a-olefin copolymer moiety
corresponding t_~ the main chain is reduced, possibly resulting
in a failure to secure the flexibility of the polymer as a whole.
[0116]
The weight average molecular weight of the side chains can
20 be obtained by performing the GPC analysis of: the ethylene polymer
moiety (macromonomer) corresponding to the side chains, which is
separated as an eluted component on the low molecular weight-side
in GPC by the method described in the section of "Requirement
(iii) u above; or a previously synthesized ethylene polymer moiety
SF-2910
48
(macromonomer) corresponding to the side chains.
[0117]
The weight average molecular weight of the side chains can
be adjusted, for example, by changing the type of a transition
5 metal compound used as a catalyst for producing a vinyl-terminated
macromonomer to be described later, or by adjusting the
polymerization conditions.
10
[0118]
(Requirement {v}]
The side chains of the olefin polymer [Rl] are bound to the
main chain at a ratio of from 0.5 to 20, preferably from 0.5 to
15, and more preferably from 0. 5 to 10 side chains per 1, 000 main
chain carbon atoms, namely, per 1,000 carbon atoms contained in
the main chain. Stated more strictly, the side chains of the
15 olefin polymer [Rl] are present at an average frequency of from
0. 3 to 20 per 1, 000 carbon atoms in the main chain polymer molecular
chain, namely, per 1, 000 carbon atoms contained in the main chain.
The side chains are preferably preSent at an average frequency
of from 0.5 to 15, and more preferably, at an average frequency
20 of from 0.5 to 10 per 1,000 main chain carbon atoms.

CLAIMS
1. An olefin resin satisfying the following requirements (I)
to (V) :
5 (I) a melting peak (Tm) as measured by differential scanning
calorimetry (DSC) is observed within the range of from 60°C to
130°C, and the heat of fusion ~H at the melting peak is within
the range of from 5 to 150 J/g;
(II) the percentage E (wt%) of a portion soluble in
10 a-dichlorobenzene at or lower as measured by
15
cross-fractionation chromatography (CFC), and the heat of fusion
LlH as described in (I) above, satisfy the following relationships:
· when the LlH is 5 J/g or more and less than 15 J/g,
the value E is 45 wt% or less,
·when the ~H is 15 J/g or more and less than 30 J/g,
the value E is 40 wt% or less, and
when the 8H is 30 J/g or more, the value E is 30
wt% or less;
(III) the glass transition temperature (Tg) as measured by
20 differential scanning calorimetry (DSC) is within the range of
-80 to -30"C;
(IV) the spin-spin relaxation time (T2) of a component
having the highest mobility, as obtained in a four-component
approximation by a Lorentzian function performed for a free
induction decay curve obtained by Carr Purcell Meiboom Gill method
in a pulsed nuclear magnetic resonance measurement (pulsed NMR)
at 200°C, is within the range of from 150 to 500 ms, and the
abundance ratio of the component is within the range of from 15
5 to 50%; and
(V) the intrinsic viscosity [n] as measured in decalin at
135°C is within the range of from 0.1 to 12 dl/g.
2. The olefin resin according to claim 1, wherein the olefin
10 resin has a tensile elastic modulus in accordance with ASTM D638
15
20
within the range of from 2 to 120 MPa.
3. An olefin polymer {Rl) composed of a main chain polymer and
a side chain polymer satisfying the following requirements:
(i) a main chain is composed of repeating units derived from
ethylene, and repeating units derived from at least one ex-olefin
selected from o::-olefins having from 3 to 20 carbon atoms, wherein
the content of the repeating units derived from the a-olefin in
the main chain is within the range of from 5 to 40 mol%;
(ii) the main chain has an intrinsic viscosity [n] as
measured in decalin at 135°C within the range of from 0.5 to 5
dl/g;
(iii) a side chain(s) is/are composed of repeating units
derived from ethylene, and optional repeating units derived from
5
SF-2910
226
at least one a-olefin selected from a-olefins having from 3 to
20 carbon atoms, wherein the content of the repeating units derived
from ethylene in the side chain(s) is within the range of from
95 to 100 mol%;
(iv) the side chain(s) has/have a weight average molecular
weight within the range of from 500 to 10,000; and
(v) the side chain(s) is/are bound to the main chain at a
ratio of D. 5 to 20 side chains per 1,000 main chain carbon atoms.
10 4. A method for producing the olefin resin according to claim
15
1 or 2, the method comprising the step of copolymerizing ethylene
and at least one a-olefin selected from a-olefins having from 3
to 20 carbon atoms in the presence of an olefin polymerization
catalyst comprising each of the following components (A} to (C):
(A) a transition metal compound of a transition metal of
Group 4 in the periodic table, __ the compound comprising a li_gand
having a cyclopentadienyl skeleton;
(B) at least one transition m'etal compound selected from
compounds represented by the following general formulae [BO], [Bl] 1
20 and [B2] ; and
(C) at least one compound selected from an organometallic
compound (C-1), an organoaluminum oxy compound (C-2), and a
compound (C-3) which reacts with the transition metal compound
(A) or the transition metal compound (B) to form an ion pair;
SF-2910
[Chern. 1]
(wherein in the general formula [BO],
M repr·e.sents a transition metal atom of Group 4 or 5 in the
5 periodic table,
m represents an integer of from 1 to 4;
R1 represents an acyclic hydrocarbon group (Cn'H2n'+lt n' =
1 to 20) having from 1 to 20 carbon atoms or a hydrogen atom;
R2 to R6
, which may be the same or different from each other,
10 each represents a hydrogen atom, a halogen atom, a hydrocarbon
group, a heterocyclic compound ,residue, an oxygen-containing
group, a nitrogen-containing group, a boron-contai_ning gro~p, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
15 tin-containing group, and two or more of these are optionally bound
together to form a ring;
in cases where m is two or more, two of the groups represented
by R2 to R6 are optionally bound to each otheri
n is a number satisfying the valence of M;
20 X represents a hydrogen atom, a halogen atom, a hydrocarbon
SF-2910
228
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
5 silicon-containing group, a germanium-containing group, or a
tin-containing group; and
in cases where n is two or more, Xs may be the same or
different from each other, and a plurality of groups represented
by X are may be bonded to each other to form a ring)
10 [Chern. 2]
• • [B 1]
{wherein in the general formula [Bl],
M represents a transition metal of the Group 4 or 5 in the
periodic table;
15 m represents an integer of from 1 to 4;
R1 represents an alicyclic hydrocarbon group of a 3- to 10-
membered ring, optionally including one or more substituents;
R2 to R6
, which may be the same or different from each other,
each represents a hydrogen atom, a halogen atom, a hydrocarbon
20 group, a heterocyclic compound residue, an oxygen-containing
SF-2910
229
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, and two or more of these are optionally bound
5 together to form a ring;
in cases where m is two or more, two of the groups represented
by R2 to R6 are optionally bound to each other;
n is a number satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
10 group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group, or a
15 tin-containing group; and
20
in cases where n is two or more, Xs may be the same or
different from each other, and a plurality of groups represented
by X may be bonded to each other t6 form a ring)
[Chem. 3]
{wherein in the general formula [B2],
M represents a transition metal of the Group 4 or 5 in the
periodic table;
rn represents an integer of from 1 to 4;
R1 represent-s a bicyclic aliphatic hydrocarbon group having
from 4 to 20 carbon atoms, optionally containing one or more
substi tuents, wherein ,the two rings of the bicyclic aliphatic
hydrocarbon group share at least one or more carbon atoms;
R2 to R6, which may be the same or different from each other,
10 each represents a hydrogen atom, a halogen atom, a hydrocarbon
group, a heterocyclic compound residue, an oxygen-containing
group, a nitrogen-containing group, a boron-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
15 tin-containing group, and two or more of these are optionally bound
together to form a ring;
20
in cases where m is two or more_, two of the groups represented
by R2 to R6 are optionally bound to each other;
n is a number satisfying the valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
SF-2910
231
silicon-containing group, a germanium-containing group, or a
tin-containing group; and
in cases where n is two or more, Xs may be the same or
different from each other, and a plurality of groups represented
5 by X may be bonded to each other to form a ring) .
5. The method for producing the olefin resin, according to
claim 4, wherein the transition metal compound (A) is a bridged
metallocene compound represented by the following general formula
10 I I) :
[Chern. 4]
. . • ( !)
(wherein in the formula (I),
R1 ,R2, R,3 R,4 R,5 R,8 R9 and R12 each independently represents
15 a hydrogen atom, a hydrocarbon group, a silicon-containing group,
or a hetero atom-containing group other than silicon-containing
groups, and two adjacent groups of the groups represented by R1
to R4 are optionally bound together to form a ring;
'. ,_ -
SF-2910
232
R6 and R11 are the same atom or the same group selected from
hydrogen atom, hydrocarbon groups, silicon-containing groups,
and hetero atom-containing groups other than the
silicon-containing groups; R7 and R10 are the same atom or the same
5 group selected from hydrogen atom, hydrocarbon groups,
silicon-containing groups, and hetero atom-containing groups
other than the silicon-containing groups; R6 and R7 are optionally
bound toge.ther to form a ring; and R10 and R11 are optionally bOund
:-: together to form a ring; with the proviso that not all of R6, R7
10 R10 and R11 are hydrogen atoms;
R13 and R14 each independently represent an aryl group;
M represents a titanium atom, a zirconium atom or a hafnium
atom;
Y1 represents a carbon atom or a silicon atom;
15 Q represents a halogen atom, a hydrocarbon group, a
halogenated hydroca-rbon group, a neutral conjugated, or
non-conjugated diene having from 4- .to 10 carbon atoms, an anionic
ligand or a neutral ligand capable of being coordinated with a
lone pair of electrons;
20 j represents an integer of from 1 to 4; and
in cases where j is an integer of two or more, a plurality
of Qs may be the same as or different from each other}.
6. The method for producing the olefin resin 1 according to
cLlim 4 or 5, wherein the step of copolymerizing is carried o1,\'lt:
by a solution polymerization method at a temperature within the
range of from 80 to 300°C.
7 . A molded article obtainable from the olefin resin according
to claim 1 or 2.