Note: Descriptions are shown in the official language in which they were submitted.
_. 20~9845
THERMOPLASTIC RESIN COMPOSITION
BACKGROUND OF THE INVENTION
a) Field of the Invention
This invention relates to a novel thermoplastic
resin composition which can be utilized as a material for
producing molded articles by injection molding, extrusion
molding or a like means.
b) Related Art
Generally, polyphenylene ethers are excellent in
heat resistance, hot water resistance, dimension
stability, and mechanical and electrical properties. On
the other hand, they have disadvantages; for example, they
show unsatisfactory moldability due to their high melt
viscosity, poor chemical resistance, and low impact
resistance.
Known methods for improving moldability by lowering
the melt viscosity of polyphenylene ethers while
maintaining their excellent properties include use of a
mixture of a polyphenylene ether and a polystyrene resin.
However, these known methods still fail to improve
chemical resistance.
On the other hand, propylene polymers are not only
excellent in various properties such as moldability,
toughness, water resistance, chemical resistance, etc. but
also they have low specific gravity and are cheap in cost;
they have been widely used as a material for preparing
- 1 -
.~ 2~~9~45
various molded articles, films, sheets, etc.
However, the propylene polymers have defects or
points which need to be improved in heat resistance,
rigidity, impact resistance, coatability, adhesiveness,
etc., which makes an obstacle in developing new practical
utility. In particular, improvement in the heat
resistance and impact resistance tereof is strongly
desired.
Naturally, it may be expected to blend a poly-
phenylene ether and a propylene polymer to prepare a resin
composition which could have the advantages of the both
polymers and which could have improved moldability and
impact resistance, and thus a wide possibility of new
application would be open.
Blending a polyphenylene with a propylene polymer,
however, actually gives rise to a resin composition in
which compatibility of the both polymers is poor so that
molded articles obtained from such a blend as by injection
molding suffers phase separation between the polyphenylene
ether and the propylene polymer, thereby providing arti-
cles having extremely poor appearance and poor mechanical
properties, which are unsatisfactory for practical
purposes. However, there has been a strong demand for a
composition of polyphenylene ether having high impact
resistance and good weatherability while maintaining its
inherent heat resistance.
A method for improving the compatibility between a
polyphenylene ether and a propylene polymer is known as
- 2 -
2Q098~~
described in Unexamined Japanese Pantent Publication
No. 20349/1989, in which method a polyphenylene ether is
blended with a propylene polymer modified with a styrene
based monomer by graft copolymerization.
On the other hand, it is known as a method for
improving impact strength that a rubbery substance is
blended with and disperesed in a polyphenylene ether.
The rubbery substance has to be disperesed uniformly
in the polyphenylene ether resin so as to obtain a
composition having high impact strength .
However, where the rubbery substance is blended to a
composition comprising a polyphenylene ether and a
modified propylene polymer grafted with a styrene-based
monomer, or blended to a composition comprising a
polyphenylene ether and a composition containing the
modified propylene polymer and a propylene polymer, large
portion of the rubbery substance is inclined to disperse
in the polyphenylene ether or in the modified propylene
polymer, and thus this method fails to provide a
composition having high impact resistance.
In view of the above points, the present inventors
have studied intensively and extensively in order to
develop effective technology which lends itself to the
improvement of a resin composition composed of
polyphenylene ether, propylene polymer and rubbery
substance.
As the result, they have found that a new resin
composition having improved its impact resistance greatly
- 3 -
' 2009845
is obtained by using as rubbery substance two or more
..-
rubbery substances, at least one substance being
compatible with a polyphenylene ether or a composition
containing the polyphenylene ether, and at least one
substance being not compatible with a polyphenylene ether
or a composition containing the polyphenylene ether. This
find led to the present invention.
SUMMARY OF THE INVENTION
Therefore, this invention provides a thermoplastic
resin composition having excellent heat resistance,
processability, chemical resistance and impact resistance,
comprising:
(a) a polyphenylene ether resin or a resin
composition containing a polyphenylene ether,
(b) (i) a modified propylene polymer obtainable by
grafting a propylene polymer with a styrene-based monomer
or a mixture of a styrene-based monomer and a monomer
copolymerizable with the styrene-based monomer or (ii) a
composition containing said modified propylene polymer and
a propylene polymer, and
(c) two or more rubbery substances, at least one
rubbery substance being compatible with the component (a),
and at least one rubbery substance being not compatible
with the component (a).
DETAILED DESCRIPTION OF THE INVENTION
The polyphenylene ether used in this invention as
- 4 -
,.
the component (a) is a polymer obtainable by oxidative
polymerization of at least one phenol compound represented
by the general formula (1)
OH
. . R 1 R 5
(1)
R 2 ~ .R 4
R 3
wherein R1, R2, R3, R4 and R5, each independently
represents a hydrogen atom, a halogen atom, a hydrocarbon
group or a substituted hydrocarbon group, or a
hydrocarbylox group or a subustituted hydrocarbyloxy
group, provided that at least one of R1, R2, R3, R4 and R5
is a hydrogen atom, with oxygen or an oxygen-containing
gas using an oxidative coupling catalyst.
Concrete examples of the groups represented by R1,
R2, R3, R4 and R5 include a hydrogen atoms, chlorine,
bromine, fluorine, iodine, a methyl group, an ethyl group,
an n- or iso-propyl group, a pri-, sec- or tert-butyl
group, a chloroethyl group, a hydroxyethyl group, a
phenylethyl group, a benzyl group, a hydroxymethyl group,
a carboxyethyl group, a methoxycarbonylethyl group, a
cyanoethyl group, a phenyl group, a chlorophenyl group, a
methylphenyl group, a dimethylphenyl group, an ethylphenyl
group, an allyl group, etc.
Concrete examples of the compounds represented by
the general formula (1) include phenol, o-, m- or p-
- 5 -
2 ~(~98~5
cresol, 2,6-, 2,5- ,2,4- or 3,5-dimethylphenol, 2-methyl-6-
phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2-
methyl-6-ethylphenol, 2,3,5-, 2,3,6- or 2,4,6-trimethyl-
phenol, 3-methyl-6-tert-butylphenol, thymol, 2-methyl-6-
allylphenol, etc.
In addition, there may be used those phenol
compounds outside the scope of the general formula (1),for
example, those obtainable by copolymerizing a polyhydroxy
aromatic compound such as bisphenol A, tetra-
bromobisphenol A, resorcinol, hydroquinone, novolak resin,
etc. with one of the compounds represented by the general
formula (1).
Of the above-described phenol compounds, preferred
examples include homopolymers of 2,6-dimethylphenol or 2,6-
diphenylphenol, or copolymers of a large amount of 2,6-
dimethylphenol and a small amount of 3-methyl-6-tert-
butylphenol or 2,3,6-trimethylphenol.
The oxidative coupling catalyst which can be used in
the oxidative polymerization of the phenol compounds is
not limited particularly but any catalysts can be used
that can catalyze such polymerization reaction.
Representative examples thereof include catalysts
comprising a copper (I) salt and a tertiary amine such as
copper (I) chloride-triethylamine and copper (I) chloride-
pyridine; catalysts comprising a copper (II) salt, an
amine and an alkali metal hydroxide such as copper (II)
chloride-pyridine-potassium hydroxide; catalysts
comprising a manganese salt and a primary amine such as
- 6 -
manganese chloride-ethanolamine and manganese acetate-
ethylenediamine; catalysts comprising a manganese salt and
an alcoholate or phenolate such as manganese chloride-
sodium methylate and manganese chloride-sodium phenolate;
catalysts comprising a cobalt salt and a tertiary amine,
and the like.
It is known that the physical properties and the
like of polyphenylene ethers vary depending on the
reaction temperature of oxidative polymerization to obtain
the polymer, i.e., high temperature polymerization, which
is performed at temperatures higher than 40°C, and low
temperature polymerization, which is carried out at
temperatures not higher than 40°C, result in the production
of polyphenylene ethers with different physical
properties. In this invention, both the high and low
temperature polymerization reactions can be used.
The polyphenylene ethers which can be used in this
invention as the component (a) also includes, modified
products obtained by grafting the above-mentioned polymer
or copolymer with other polymer.
For example, the modified polymers include those
obtained by oxidative polymerization of the phenol
compound of the general formula (1)
OH
R 1 R 5
(1)
R 2 ~ R 4
R 3
wherein R1, R2, R3, R4 and R5 have the same meaning as
defined above, in the presence of an ethylene-propylene-
polyene terpolymer, those obtained by oxidative
polymerization of the phenol compound of the general
formula (1)
OH
R 1 R 5
(1)
v
R 2 R 4
R 3
wherein R1, R2, R3, R4 and R5 have the same meaning as
defined above, in the presence of a polystyrene, those
obtained by subjecting one or more styrene monomers and/or
other copolymerizable monomers to organic peroxide graft
polymerization in the presence of a polyphenylene ether as
described in, for example, Japanese Patent Publication
Nos. 4~862/19~2, 1219~/19~3, 5623/194, 38596/197 and
30991/19W , and those obtained by melt-kneading the
polyphenylene ether together with the polystyrene based
polymer and a radical generating agent (e.g., peroxide) as
described in, for example, Unexamined Japanese Patent
Publication No. 142~99/19W .
The resin composition containing the polyphenylene
ether as the component (a) used in this invention is a
resin composition comprising the polyphenylene ether above
descibed and one or more other high molecular weight
compounds.
_ g _
20fl98~45
Examples of the other high molecular weight
compounds include polyolefins such as polymethylpentene;
homopolymers and copolymers of various vinyl compounds
such as polyvinyl chloride, polymethyl methacrylate,
polyvinyl acetate, polyvinylpyridine, polyvinylcarbazole,
polyacrylamide, polyacrylonitrile, ethylene-vinyl acetate
copolymer, and alkenyl aromatic resins; polycarbonate,
polysulfone, polyethylene terephthalate, polybutylene
terephthalate, polyarylene esters (e. g., U polymer
produced by Unitika Co.), polyphenylene sulfide;
polyamides such as Nylon-6, Nylon-6,6, Nylon-12, etc.;
condensed high molecular weight compounds such as
polyacetals, etc. Futhermore, various thermosetting
resins can be used, examples of which include silicone
resins, fluorinated resins, polyimides, polyamideimides,
phenol resins, alkyd resins, unsaturated polyester resins,
epoxy resins, diallylphthalate resins, etc.
The proportion at which the polyphenylene ether and
the other high molecular weight compound are mixed each
other can be varied widely, for example, in the range of 1
to 99~ by weight of the polyphenylene ether and 99 to 1~
by weight of the other high molecular weight compound.
Within this range, optimal composition can be selected
depending on the object and desired application.
The component (b) used in this invention is (i) a
modified propylene polymer obtainable by grafting a
propylene polymer with a styrene-based monomer or a
mixture of a styrene-based monomer and a monomer
- g _
z~~~~~~
copolymerizable with the styrene-based monomer or (ii) a
composition containing said modified propylene polymer and
a propylene polymer.
By the term "modified propylene polymer" is meant a
copolymer comprising 100 parts by weight of propylene
polymer and 0.2 to 150 parts by weight, preferably 2 to 90
parts by weight, more preferably 3 to '10 parts by weight
of a styrene-based monomer or a mixture of a styrene-based
monomer and a monomer copolymerizable with the styrene-
based monomer which is obtained by graft copolymerization.
When the the amount of the monomer to be graft-
polymerized is smaller than 0.2 part by weight, the effect
of modification of resins is not observed. On the other
hand, the chemical resistance of the resin is deteriorated
when the amount of the monomer to be graft-polymerized is
larger than 150 parts by weight.
The propylene polymer (inclusive of the raw one to
be modified) used in the component (b) of this invention
is a propylene homopolymer or a propylene copolymer. By
the term "propylene copolymer" is meant a random or block
copolymer of propylene and an a-olefin having 2 to 18
carbon atoms.
Specific examples of the propylene copolymer include
ethylene-propylene copolymer, propylene-butene-1
copolymer, propylene-hexene-1 copolymer, propylene-4-
methylpentene-1 copolymer, and propylene-octene-1
copolymer.
The propylene polymer may be the propylene
- 10 -
__ __.. ~ _.___ _~ ..__..__._ _ __
2QU~8~4J''
homopolymer or the propylene copolymer alone, or it may be
a mixture of one or more of them. Futhermore, the
propylene polymer may be blended with an ethylene-a-olefin
copolymer, if desired or necessary.
As for the ethylene-a-olefin copolymer blended with
the propylene polymer, there can be preferably used ones
which have a density of 0.82 to 0.92 g/cm3.
In the present invention, highly crystalline
propylene polymer may be used as the propylene polymer in
the component (b), if desired.
By the term "highly crystalline propylene polymer"
is meant a propylene homopolymer or block copolymer which
has an isotactic pentad fraction of 0.9'10 or higher,
defined as an isotactic pentad fraction in the boiling
heptane-insoluble portion of the propylene homopolymer or
of a propylene homopolymer portion of the propylene block
copolymer that is the first segment polymerized in the
first step of propylene homopolymer or block copolymer
formation, or a propylene polymer which has an isotactic
pentad fraction defined as above of 0.9T0 or higher and a
content of a heptane-soluble portion of 5.0°6 by weight or
less and a content of a 20°C xylene-soluble portion of 2.096
by weight or less.
The above-described type of highly crystalline
propylene polymers can be prepared by methods described
in, for example, Unexamined Japanese Patent Publication
Nos. 28405/1985, 228504/1985, 208606/1986 and 28'191T/1986.
For applications to those fields where high rigidity
- 11 -
~r~~~~'~~
is required for, it is preferred to blend the propylene
polymer with a nuclei generating agent. It is known that
addition of, for example, aluminum or sodium salts of
aromatic carboxylic acids (Unexamined Japanese Patent
Publication No. 80829/1983) and aromatic carboxylic acids,
metal salts of aromatic phosphoric acids or sorbitol
derivatives (Japanese Patent Publication No. 12460/1980
and Unexamined Japanese Patent Publication
No. 129036/1983) or the like gives rise to nuclei of
crystal grains thus serving a nuclei generating agent
(hereinafter, referred to as a nucleating agent).
It is also known that a polymer of vinylcycloalkane
having 6 or more carbon atoms is effective as a nucleating
agent (Unexamined Japanese Patent Publication
No. 1'138/198'1) .
That is, a composition which comprises the propylene
polymer blended with the polymer of vinylcycloalkane
polymer having 6 or more carbon atoms and which contains
from 0.05 to 10,000 ppm by weight of vinylcycloalkane
units in the composition has a higher crystallinity.
Furthermore, a propylene polymer having a high
rigidity can be obtained by blending the propylene polymer
having a high crystallinity with the vinylcycloalkane
polymer.
As the propylene polymer, there can be used
propylene homopolymer or propylene copolymer alone, or in
the form of a mixture of two or more of them.
The styrene-based monomer in the component (b) which
- 12 -
2QQ~98~5
can be used in the modification of the propylene polymers
is represented by the general formula (2)
R 6 R 7
(2)
CH 2=C R 8
I
R11
R10 R 9
wherein R6, R~, R8, R9 and R1~, each represents a hydrogen
atom, a halogen atom, an unsubstituted or substituted
hydrocarbyl group, or an unsubstituted or substituted
hydrocarbyloxy group, and R11 represents a hydrogen atom,
or a lower alkyl group having 1 to 4 carbon atoms.
Specific examples of R6, R~, R8, R9 and R1~ in the
general formula (4) include a hydrogen atom, a halogen
atom such as chlorine, bromine and iodine, a hydrocarbyl
group such as a methyl group, an ethyl group, a propyl
group, a vinyl group, an allyl group, a benzyl group and a
methylbenzyl group, a substituted hydrocarbyl group such
as a chloromethyl group and a bromomethyl group, a
hydrocarbyloxy group such as a methoxy group, an ethoxy
group and a phenoxy group, and a substituted
hydrocarbyloxy group such as a monochloromethoxy group.
Specific e~tamples of R11 include a hydrogen atom and
a lower alkyl group such as a methyl group and an ethyl
group.
Specific examples of the styrene monomer include
styrene, 2,4-dichlorostyrene, p-methoxystyrene, p-methyl-
- 13 -
~~o~~~
styrene, p-phenylstyrene, p-divinylbenzene, p-chloro-
methoxystyrene, a-methylstyrene, o-methyl-a-methylstyrene,
m-methyl-a-methylstyrene, p-methyl-a-methylstyrene and p-
methoxy-a-methylstyrene. They may be used alone or in
admixture. Of these, styrene is preferred.
As for the modified propylene polymer of the
component (b) in this invention, there can be used a
modified propylene polymer obtained by graft
copolymerizing the styrene based monomer with one or more
other monomers copolymerizable therewith.
Thermoplastic resins having high mechanical
properties can be obtained by appropriately selecting
monomers with the styrene based monomer, and incorporating
them by graft copolymerizing with the propylene polymer.
Specific examples of the monomer copolymerizable
with the styrene-based monomer include acrylonitrile,
methacrylonitrile, fumaric acid, malefic acid, vinyl
ketone, malefic anhydride, acrylic acid, methacrylic acid,
vinylidene chloride, maleate ester, methyl methacrylate,
ethyl methacrylate, propyl methacrylate, butyl
methacrylate, methyl acrylate, ethyl acrylate, propyl
acrylate, butyl acrylate, vinyl chloride, vinyl acetate,
divinyl benzene, ethylene oxide, isobutene, alkyl vinyl
ether, anethole, indene, coumarone, benzofuran, 1,2-
dihydronaphthalene, acenaphthylene, isoprene, chloroprene,
trioxane, 1,3-dioxolane, propylene oxide, /3-propiolactone,
vinyl biphenyl, 1,1-Biphenyl-ethylene, 1-vinylnaphthalene,
2-vinylnaphthalene, 2-vinyl-pyridine, 4-vinylpyridine, 2,3-
- 14 -
~~o~s~~
dimethylbutadiene, ethylene, propylene,
allyltrimethylsilane, 3-butenyl-trimethylsilane, vinyl
carbazole, N,N-diphenylacrylamide, and fumarnitrile.
Derivatives of these monomers can also be used. They may
be used alone or in combination with one another.
Preferable among them are malefic anhydride, methyl
methacrylate, acrylonitrile, etc.
The amount of the styrene-based monomer in the
mixture of the styrene-based monomer and the monomer
copolymerizable with the styrene-based monomer may vary in
the range of 1 to 100 wt~, depending on the intended use
of the resin composition.
In this invention, there is no particular limitation
on the methods of preparing the modified propylene polymer
by grafting a propylene polymer with a styrene-based
monomer, or a mixture of a styrene-based monomer and a
monomer copolymerizable with the styrene-based monomer,
and ordinary known methods such as suspension
polymerization methods, emulsion polymerization methods,
solution polymerization methods and bulk polymerization
methods (inclusive of methods using not only polymeization
vessels but extruders) can be used for the purpose.
For example, the grafting of a propylene polymer
with a styrene monomer and an acrylonitrile may be
accomplished as follows. First, a copolymer is prepared
from the styrene monomer and the acrylonitrile by anionic
polymeization. Secondly, the copolymer is melt-mixed with
a propylene polymer and a peroxide to give a modified
- 15 -
200~84~
propylene polymer.
Alternatively, a propylene polymer may be
copolymerized with a styrene monomer and glycidyl
methacrylate by radical polymerization.
The peroxide used to prepare the modified propylene
polymer is not specifically limited; it may be selected
from the following organic peroxides.
2,2'-azobisisobutyronitrile,
2,2'-azobis(2,4,4-trimethylvaleronitrile),
methyl ethyl ketone peroxide,
cyclohexanone peroxide,
3,3,5-trimethylcyclohexanone peroxide,
2,2-bis(t-butylperoxy)butane,
t-butyl hydroperoxide,
cumene hydroperoxide,
diisopropylbenzene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxide,
di-t-butyl peroxide,
1,3-bis(t-butylperoxyisopropyl)benzene,
2,5-dimethyl-2,5-di(t-butylperoxy)hexane,
2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,
lauroyl peroxide,
3,3,5-trimethylhexanoyl peroxide,
benzoyl peroxide,
t-butyl peracetate,
t-butylperoxy isobutyrate,
t-butyloxy pivalate,
t-butyloxy-2-ethylhexanoate,
- 16 -
~~a~845
t-butylperoxy-3,5,5-trimethylhexanoate,
t-butyl peroxylaurate,
t-butyl peroxybenzoate,
di-t-butyl peroxyisophthalate,
2,5-dimethyl-2,5-di(benzoylperoxy)hexane,
t-butyl peroxymaleic acid,
t-butyl peroxyisopropyl carbonate, and
polystyrene peroxide.
Component (b) in the resin composition of the
present invention is (i) a propylene polymer modified with
the above-mentioned styrene monomer or a mixture of the
styrene monomer and a monomer copolymerizable with the
styrene monomer, or (ii) a composition containing said
modified propylene polymer and a propylene polymer.
If necessary, the component (b) in the thermoplastic
resin composition of the present invention may be
incorporated with a variety of additives such as
antioxidant, heat stabilizer, light stabilizer, antistatic
agent, inorganic and organic colorant, corrosion
inhibitor, crosslinking agent, blowing agent, slip agent,
plasticizer, fluorescent agent, surface smoothing agent,
and surface brightener.
In the thermoplastic resin composition of the
present invention, two or more rubbery substances, at
least one being compatible with the component (a) and at
least one being not compatible with the component (a) are
used as component (c).
More particularly, at least two rubbery substances
- 1Z -
~Q~ss~s
are used as component (c), that is, at least one rubbery
substance (hereinafter, referred to as c-1) is compatible
with the component (a) and have at least one alkenyl
aromatic chain in the same molecule, and at least one
rubbery substance (hereinafter, referred to as c-2) is not
compatible with the component (a) and does not have
alkenyl aromatic chain in the same molecule.
The "rubbery substance" used herein refers to any
natural and synthetic polymeric material which is elastic
at room temperature.
Of the rubbery substance used in this invention as
the component (c), specific examples of the rubbery
substance (c-1) which are compatible with the
polyphenylene ether as component (a) include butadiene-
styrene copolymers inclusive of random copolymers such as
SBR rubber, block copolymers such as SBS rubber, and graft
copolymers, etc.) or their hydrogenated products (e. g.
SEBS), styrene-isoprene copolymers (SI) or their
hydrogenated products (SEP), styrene-butylene copolymers,
styrene-ethylene-propylene copolymers, ethylene-propylene-
styrene copolymers, etc.
Furthermore, styrene-modified products of natural or
synthetic polymer materials which are elastic at room
temperature, are used as the rubbery substance (c-1). Of
these, a butadiene-styrene copolymer, a styrene-modified
ethylene-propylene copolymer, etc. can be used preferably.
These rubbery substances (c-1) which are compatible
with a polyphenylene ether can be used alone, on in the
- 18 -
_ _~.~. ..r._~.~..._ ~ __
2i3098~S
form of a mixture of two or more of them.
On the other hand, specific examples of the rubbery
substance (c-2) which are not compatible with a
polyphenylene ether as component (a) include natural
ruber, butadiene polymer, isoprene polymer,
chlorobutadiene polymer, butadiene-acrylonitrile
copolymer, isobutylene polymer, isobutylene-butadiene
copolymer, isobutylene-isoprene copolymer, ethylene-
propylene copolymer, ethylene-butene copolymer,
perfluororubber, fluororubber, chloroprene rubber, butyl
rubber, silicone rubber, ethylene-propylene-nonconjugated
diene copolymer, thiokol rubber, polysulfide rubber,
polyurethane rubber, polyether rubber (such as
polypropylene oxide), epichlorohydrin rubber, polyester
elastomer, polyamide elastomer, and epoxy group-containing
copolymer.
The "epoxy group-containing polymer" used herein
refers to a copolymer composed of an unsaturated epoxy
compound and an ethylenically unsaturated compound.
The epoxy group-containing polymer is not
specifically limited in its composition; but it should
preferably contain an unsaturated epoxy compound in an
amount of 0.1-50 wt~, more preferably 1-30 wt~.
The unsaturated epoxy compound is a compound which
has in the molecule an epoxy group and an unsaturated
group copolymerizable with an ethylenically unsaturated
compound.
Examples of the unsaturated epoxy compound are
- 19 -
~0~95~~
unsaturated glycidyl esters and unsaturated glycidyl
ethers represented by the general formulas (3) and (4)
below, respectively.
R-C-0-CH 2-CH-CH
II \/ (3)
0 O
wherein R represents a C2-1$ hydrocarbyl group having an
ethylenically unsaturated bond.
R-X-CH Z-CH-CH Z (4)
\/
O
wherein R represents a C2-1$ hydrocarbyl group having an
ethylenically unsaturated bond, and X is a
O-
group represented by -CH2-0- or .
Amoung the above examples of rubbery substances
(c-2) not compatible with the component (a), it is
preferable to use a rubbery substance which is compatible
with a modified propylene polymer of the component (c).
Examples of the modified propylene polymer include
an ethylene-a-olefin copolymer rubber such as an ethylene-
propylene copolymer and an ethylene-a-olefin-nonconjugated
diene copolymer rubber such as a ethylene-propylene-
nonconjugated copolymer.
As for the ethylene-a-olefin copolymer rubber it is
preferable to use copolymer rubbers of ethylene and
another a-olefin such as propylene, butane-1, pentane-1,
hexane-1, 4-methylpentene-1 and octane-1, or ternary
- 20 -
2Q~09~45
copolymer rubbers such as ehtylene-propylene-butene-1
copolymer. Of these, ethylene-propylene copolymer rubber
is preferred.
The ethylene content of the ethylene-a-olefin
copolymer rubber is 15 to 85~ by weight, preferably 40 to
80i by weight. The highly crystalline copolymer having an
ethylene content of more than 85~ by weight is difficult
to process under ordinary rubber molding conditions while
that having an ethylene content of less than 15°b by weight
tends to suffer increase in glass transition point (Tg,),
resulting in the deterioration of rubbery properties,
which is not desirable. It is preferred that the ethylene-
a-olefin copolymer rubber has a glass transition point of
not higher than -10°C.
The Mooney viscosity (ML1+4, 121°C) of the copolymer
rubber is preferably 5 to 120.
These rubbery substances (c-2) which are not
compatible with a polyhenyiene ether can be used alone, on
in the form of a mixure of two or more of them.
The rubbery substance used in this invention as the
component (c) may be produced by any process (e. g.,
emulsion polymerization and solution polymerization) using
any catalyst (e. g., peroxide, trialkyl aluminum, lithium
halide, and nickel-based catalyst).
Moreover, the rubbery substance may have a varied
degree of crosslinking, a varied ratio of microstructure
(e. g., cis-structure, trans-structure, and vinyl group),
and a varied average rubber particle diameter.
- 21 -
~~0~8~~
In addition, the above-mentioned copolymer as the
rubbery substance may be in the form of random copolymer,
block copolymer, or graft copolymer. These copolymers may
also be used in a modified form. Examples of the modifier
include malefic anhydride, glycidyl methacrylate and
carboxylic acid-containing compounds. They may be used
alone or in combination with one another.
In the component (c) of this invention, the ratio of
the rubbery substance (c-1) compatible with the component
(a) to the rubbery substance (c-2) not compatible with the
component (a) may be 1-99 wt°b to 99-1 wt°6, preferably 5-95
wt% to 95-5 wt%.
With the rubbery sunbstance (c-1) less than 1 wt~ or
more than 99 wt~, the improvement of impact strength is
poor.
The rubbery substance as the component (c) can be
used in an amount of 1 to 50 parts by weight per 100 parts
by weight of the sum of the components (a) and (b).
When the rubbery substance is contained in an amount
of less than 1 part by weight, the improvement of impact
resistance by the addition of the rubbery substance is
poor. On the other hand, with the rubbery substance in an
amount of exceeding 50 parts by weight, the excellent
properties which polyphenylene etrher has inherently are
weakened, which in not desirable.
In practicing this invention, the thermoplastic
resin composition may be kneaded together with a
reinforcing agent such as glass fiber or carbon fiber, an
- 22 -
2Q~9$~4~5
inorganic or organic filler such as carbon black, silica
or Ti02, a plasticizer, a stabilizer, a flame retardant, a
dye, a pigment, etc.
More particularly, the reinforcing agent is to
increase mechanical and thermal properties such as bending
strength, flexural modulus, tensile strength, modulus in
tension, and heat distortion temperature when it is
admixed. Examples thereof include alumina fiber, carbon
fiber, glass fiber, high modulus polyamide fiber, high
modulus polyester fiber, silicon carbide fiber, titanate
whisker, etc.
As for the amount of the reinforcing agent, it is
sufficient that the reinforcing agent is contained in
amounts effective for reinforcing the thermoplastic resin
composition and usually it is preferred to use about 5 to
100 parts by weight of the reinforcing agent per 100 parts
by weight of the resin composition of this invention.
Particularly preferred reinforcing filler is glass,
and it is preferred to use glass fiber filament composed
of borosilicate glass containing a relatively small amount
of sodium, which is made of gypsum and aluminium
borosilicate. This glass is known as "~" glass. However,
in the case where electric properties are not so
important, other glass such as one known as "C" glass,
which contains sodium in small amounts, is also useful.
The glass fiber filament can be produced by conventional
methods, for example, steam or air blowing, flame blowing,
and mechanical drawing. Filaments suitable for
- 23 -
~oo~s~s
reinforcing plastics can be produced by mechanical
drawing. The diameter of the filament ranges from about 2
to 20 ,um, which is not so strict in this invention.
In this invention, the length and form of the glass
fiber filament are not limited particularly. The
filaments may be stranded into multifilament fibers, which
may then be stranded into threads, ropes or rovings. The
filaments may also be woven to obtain mats. However, it
is convenient to use glass filaments cut in the form of
strands about 0.3 to about 3 cm, preferably about 0.6 cm
or less, in length.
To be in detail on the flame retardant, those flame
retardants useful in this invention include a group of
compounds well known to one skilled in the art.
Generally, more important compounds in the known
compounds are compounds containing elements capable of
imparting flame retardance such as bromine, chlorine,
antimony, phosphor and nitrogen. For example, there can
be used halogenated organic compounds, antimony oxide, a
mixture of antimony oxide and a halogenated organic
compound, a mixture of antimony oxide and a phosphor
compound, a phosphor element, a phosphor compound, a
mixture of a phosphor compound or a compound containing a
phosphor-nitrogen bond and a halogen-containing compound,
and mixtures of two or more of these.
The amount of the flame retardant is not limited
particularly and it is sufficient to use it in amounts
effetive for imparting flame retardancy. It is
- 24 -
20~98~~
disadvantageous to use too much of it since the physical
properties of the resulting composition is deteriorated,
i.e., the softening point of the resin composition, for
example, decreases. An appropriate amount of the flame
retardant is 0.5 to 50 parts by weight, preferably 1 to 25
parts by weight, and more preferably 3 to 15 parts by
weight, per 100 parts by weight of the polyphenylene ether
(a) or a resin composition containing the polyphenylene
ether (a).
Useful halogen-containing compounds include those
represented by the general formula (5)
(Y )d (X1) a (X1)d
I I I (5)
A r R A r' n
a 12 b c
wherein n is an integer of 1 to 10, R12 represents a
member selected from the class consisting of an alkylene
group, an alkylidene group or an alicyclic group (e.g., a
methylene group, an ethylene group, a propylene group, an
isopropylene group, an isopropylidene group, a butylene
group, an isobutylene group, an amylene group, a
cyclohexylene group, a cyclopentylidene group, etc.), an
ether group, a carbonyl group, an amine group, a sulfur-
containing group (e. g, sulfide group, sulfoxide group,
sulfone group, etc.), a carbonate group, and a phosphor-
containing group.
R12 may be a group which is composed of two or more
alkylene or alkylidene groups bonded to each other with a
group such as an aromatic group, an amino group, an ether
- 25 -
200~~~~
group, an ester group, a carbonyl group, a sulfide group,
a sulfoxide group, a sulfone group, or a phosphor-
containing group. Ar and Ar' each are a monocyclic or
polycyclic carbocyclic aromatic residue such as a
phenylene group, a biphenylene group, a terphenylene
group, or naphthylene.
Ar and Ar' may be the same or different.
Y represents a substituent group selected from the
class consisting of an organic group, an inorganic group
or an organometallic group. The substituent groups
represented by Y may be (1) e.g., halogen atoms such as
chlorine, bromine, iodine or fluorine, (2) an ether group
represented by the general formula -OE wherein E is a
monovalent hydrocarbyl group which is the same as those
represented by X1 below, (3) -OH group, (4) a monovalent
hydrocarbyl group, or (5) other substituent groups such as
a nitro group, or a cyano group. When a is 2 or more, Y's
may be the same or different.
X1 is a monovalent hydrocarbyl group such as an
alkyl group, e.g., a methyl group, an ethyl group, a
propyl group, an isopropyl group, a butyl group, a decyl
group, etc., an aryl group, e.g., a phenyl group, a
naphthyl group, a biphenyl group, a xylyl group, a tolyl
group, etc., an aralkyl group, e.g., a benzyl group, an
ethylphenyl group, etc., an alicyclic group, e.g., a
cyclopentyl group, a cyclohexyl group, etc., or a
monovalent hydrocarbyl group containing an inert
substituent group therein. When two or more Xls are used
- 26 -
200~8~~
they may be the same or different.
d is an integer of from 1 to maximum number of
hydrogen atoms on the aromatic ring Ar or Ar' which
hydrogen atoms can be substituted.
a is 0 or an integer of 1 to a maximum number of
hydrogen atoms on R12 which hydrogen atoms can be
substituted.
a, b and c are integers inclusive of 0. When b is
not 0, neither a nor c is 0. Alternatively, only one of a
and c may be 0. When b is 0, the aromatic groups are
bonded to each other directly through a carbon-carbon
bond.
The hydroxy group or the substituent groups
represented by Y one the aromatic residue Ar and Ar' may
be present at any desired positions) out of ortho-, meta-
and para-positions on the aromatic ring.
Specific examples of the compound represented by the
general formula (5) include the following compounds:
2,2-bis(3,5-dichlorophenyl)propane,
Bis(2-chlorophenyl)methane,
1,2-bis(2,6-dichlorophenyl)ethane,
1,1-bis(4-iodophenyl)ethane,
1,1-bis(2-chloro-4-iodophenyl)ethane,
1,1-bis(2-chloro-4-methylphenyl)ethane,
1,1-bis(3,5-dichlorophenyl)ethane,
2,2-bis(3-phenyl-4-bromophenyl)ethane,
2,3-bis(4,6-dichloronaphthyl)propane,
2,2-bis(2,6-dichlorophenyl)pentane,
- 2T -
2Q(~98~5
2,2-bis(3,5-dichlorophenyl)hexane,
Bis(4-chlorophenyl)phenylmethane,
Bis(3,5-dichlorophenyl)cyclohexylmethane,
Bis(3-nitro-4-bromophenyl)methane,
Bis(4-hydroxy-2,6-dichloro-3-methoxyphenyl)methane,
2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane,
2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, and
2,2-bis(3-bromo-4-hydroxyphenyl)propane.
In addition, there can be used those bis-aromatic
compounds which contain a sulfide group, a sulfoxy group,
etc. in place of the two aliphatic groups contained in the
above-described specific examples, for example,
tetrabromobenzene, hexachlorobenzene, hexabromobenzene,
2,2'-dichlorobiphenyl, 2,4'-dibromobiphenyl, 2,4'-
dichlorobiphenyl, hexabromobiphenyl, octabromobiphenyl,
decabromobiphenyl, halogenated diphenyl ether containing 2
to 10 halogen atoms, oligomers composed of 2,2-bis(3,5-
dibromo-4-hydroxyphenyl)propane and phosgene and having a
degree of polymerization of 1 to 20, etc.
The halogen compound which is preferable as a flame
retardant in this invention includes aromatic halogenated
compounds such as chlorinated benzene, brominated benzene,
chlorinated biphenyl, chlorinated terphenyl, brominated
biphenyl, and brominated terphenyl, compounds containing
two phenyl nuclei separated by an intervening divalent
alkylene group and also containing at least two chlorine
or bromine atoms per one phenyl nucleus, and mixtures of
two or more of the above-described compounds.
- 28 -
2Qa~845
Particularly preferred are hexabromobenzene, chlorinated
biphenyl or terphenyl, and mixtures thereof with antimony
oxide.
Reparesentative phosphoric compounds which are
suitably used as a flame retadant in this invention
include compounds represented by the general formula (6)
and nitrogen-containing similar compounds.
O
II
Q-O-P-O-Q
I (6)
O
I
Q
wherein Q's, which may be the same or different, each
represent a hydrocarbyl group such as an alkyl group, a
cycloalkyl group, an aryl group, an alkyl-substituted aryl
group and an aryl-substituted alkyl group; a halogen atom;
a hydrogen atom; or a combination of these. Suitable
examples of the phosphoric acid esters include phenyl
bisdodecyl phosphate, phenyl bisneopentyl phosphate,
phenyl ethylene hydrogen phosphate, phenyl bis(3,5,5'-
trimethylhexyl) phosphate, ethyl diphenyl phosphate, 2-
ethylhexyl di(p-tolyl) phosphate, diphenyl hydrogen
phosphate, bis(2-ethylhexyl) p-tolyl phosphate, tritolyl
phosphate, bis(2-ethylhexyl) phenyl phosphate,
tri(nonylphenyl) phosphate, phenyl methyl hydrogen
phosphate, di(dodecyl) p-tolyl phosphate, triphenyl
phosphate, halogenated triphenyl phosphate,dibutyl phenyl
phosphate, 2-chloroethyl diphenyl phosphate, p-tolyl
- 29 -
_ ___.___ ._ _
2f~~~~4~
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl
diphenyl phosphate, and diphenyl hydrogen phosphate. The
most preferred phosphoric acid ester is triphenyl
phosphate. It is also preferred to use triphenyl
phosphate together with hexabromobenzene, or triphenyl
phosphate together with antimony oxide.
Other flame retardant which can be used in this
invention includes compounds containing a phosphor-
nitrogen bond such as phosphorus nitride chloride,
phosphoric ester amide, phosphoric acid amide, phosphinic
acid amide, tris(aziridinyl) phosphine oxide or
tetrakis(hydroxymethyl) phosphonium chloride, etc.
There is no particular limitation on the methods of
preparing the resin composition of this invention, and
ordinary known methods can be used for the purpose. For
example, it is effective to mix the components in the form
of solutions and then evaporate the solvent or precipitate
the resin in a non-solvent. On an industrial scale,
however, practical method for the production uses kneading
the components in a melted state. For melt-kneading,
there can be used a kneading apparatus such as a single-
screw extruder or a twin-screw extruder generally used, or
various types of kneaders. A twin-screw extruder of high
shear type is particularly preferred.
Upon kneading, it is preferred to homogeneously mix
the respective resin components in the form of powder or
pellet in a tumbler, a Henschel mixer or a like apparatus.
However, mixing may be omitted, if desired, and they are
- 30 -
2f~C3~8~45
metered and fed separately to the kneading apparatus.
The kneaded resin composition can be molded by
injection molding, extrusion molding, press molding, blow
molding or various other molding methods. This invention,
however, includes methods in which the resin components
are dry blended upon injection molding or extrusion
molding and directly kneaded during melt-processing
operation to obtain molded articles.
In this invention, there is no particular limitation
on the order of kneading. For example, the components)
(a), (b) and (c) may be kneaded in a lump, or components
(a) and (b) may be kneaded previously followed by kneading
the rubbery substance (c). Other kneading orders may also
be used.
EFFECT OF THE INVENTION
As described hereinabove, the thermoplastic resin
compositions of this invention exhibit excellent effects
in that they have not only good moldability but also they
can give rise to molded articles whose physical properties
are well balanced.
Novel resin compositions provided by this invention
can be processed with ease by conventional molding methods
employed for ordinary polyphenylene ether based
thermoplastic resins, for example, injection molding,
extrusion molding, press molding and blow molding, and
provide products not only having well balanced physical
properties such as impact strength, heat resistance and
hardness but also having excellent homogeneity and
- 31 -
2Q0~8~45
smoothness in appearance.
In particular, it can be used as interior or
exterior fitting materials for automobile parts such as
bumper, instrument panel, fender, trim, door panel, wheel
cap, side protector, side seal garnish, trunk lid, hood,
quater panel, air intake, lower apron, spoiler, front
grille, radiator grill, mirror housing, air cleaner, core
material of seat, glove box, console box, cooling fan,
sirocco fan, brake oil tank, lamp housing, and roof.
It can also be used in machine parts which must be
heat resistant. In addition, it can be used for bicycle
parts such as covering material, muffler cover, leg
shield, etc. Furthermore, the resin composition of this
invention can be used for electric and electronic
partswhich need to have high strength and heat resistance
suchas housing, chassis, connector, printed substrate,
pulley, etc.
EXAMPLES
Hereinafter, this invention will be explained in
greater detail with reference to examples which should not
be construed as limiting this invention. Tests for the
heat deflection temperature under load or the heat
distortion temperature (H. D. T.) and the Izod impact
strength (thickness: 3.2 mm) was performed according to
JIS KZ20Z and JIS KZ110, respectively.
The reduced viscosity ('~sp/C) of the polyphenylene
ether was determined in a solution of chloroform of 0.5
g/dl at 25°C.
- 32 -
20098 45
For kneading the compositions, LABO PLASTOMILL
produced by TOYO SEIKI CO., LTD (Kneading temperature:
2T0'C) was used. The composition was press-molded to
prepare test pieces, which were then determined for their
physical properties.
Examples 1 to 5 and Comparative Examples 1 to 3
Component (a), (b) and (c) used in these examples
are undermentioned. These components were blended at
proportions shown in Table 1 to obtain the resin
compositions.
Component (a): Polyphenylene ether
Polyphenylene ether having a reduced viscosity of
~7sp/C = 0.58 produced by NIPPON POLYETHER CO., LTD was
used.
Component (b): Modified propylene polymer
In a 10-liter autoclave were charged pellets (1 kg)
of SIMITOMO NOBLEN*D501 (trade name for a product by
SUMITOMO CHEMICAL CO., LTD; MI = 0.4) together with 4
liters of water, 190 g of styrene monomer, 4 g of a
dispersing agent (METHOLOSE 90SH-100# trade name) and a
peroxide (PERBUTYL PV* trade name), and the mixture was
allowed to react at 120 for about 1 hour while blowing
nitorogen gas in. After cooling, the raction mixture was
extracted with methyl ethyl ketone to remove polystyrene
and thus the grafted propylene polymer was recovered.
The styrene-grafted product thus obtained is called
"MG-1" for brevity.
Component (c): Rubbery substance which is compatible with
* trade-mark
- 33 -
20098 45
the component (a).
This includes the following three species.
(i) SUMITOMO*SBR 150? (trade name for styrene-butadiene
random copolymer rubber (SBR) produced by SUMITOMO
CHEMICAL CO., LTD).
(ii) CARIFLEX*TR1116 (trade name for styrene-butadiene-
styrene block copolymer rubber (SBS) produced by SHELL
CHEMICAL CO., LTD).
(iii) KRATON*G1650 (trade name for styrene-ethylene-
butylene-styrene block copolymer rubber (SEBS) produced by
SHELL CHEMICAL CO., LTD).
Component (c): Rubbery substance which is not compatible
with the component (a).
This includes the following three species.
(i) SUMITOMO ESPREN*E201 (trade name for ethylene-
propylene rubber (EPR) produced by SUMITOMO CHEMICAL CO.,
LTD).
(ii) SUMITOMO ESPRE1~ E400 (trade name for ethylene-
propylene-diene rubber (EPDM) produced SUMITOMO CHEMICAL
CO., LTD).
(iii) Epoxy group-containing copolymer.
The epoxy group-containing copolymer was produced by
the following method. That is, according to the method
described in Unexamined Japanese Patent Publication Nos.
23490/19?2 and 11888/19?3, a terpolymer of ethylene-vinyl
acetate-glycidyl methacrylate of 85 . 5 . 10 (% by weight)
having a melt flow rate of 8 g/10 minutes (190°C, load:
2.16 kg) was produced by high pressure radical
* trade-mark
- 34 -
_ z __._..
.. 20(~~84~
polymerization method. Hereafter, the epoxy group-
containing copolymer is called "E~GMA" for brevity.
The respective components were blended at proportions
shown in Table 1 and knead to obtain the resin
compositions.
The resulting compositions were press-molded to form
test pieces, which were then measured for their physical
properties, and the results obtained are shown in Table 1.
It is noted from Table 1 that the resin composition
of Examples 1 to 5 in which the polyphenylene ether
(Component (a)) and the modified propylene polymer were
blended with the rubbery substance compatible with the
component (a) and the rubbery substance not compatible
with the component (a) have much improved impact
resistance as compared with the resin composition of
Comparative Examples 1 in which only the rubbery substance
not compatible with the component (a) was blended, the
resin composition of Comparative Examples 2 in which only
the rubbery substance compatible with the component (a)
was blended, or the resin composition of Comparative
Example 3 in which the rubbery substance was not blended.
Examples 6 to 8 and Comparative Examples 4
Components (a), (b) and (c) used in these examples
are undermentioned. These components were blended at
propotions shown in Table 2 to obtain the resin
compositions.
Component (a): Polyphenylene ether
Polyphenylene ether having a reduced viscosity of
- 35 -
___~__~~ _._____.~_..__.__.. _ ~_ ..
~7sp/C = 0.43 produced by NIPPON POLYETHER CO., LTD was
used.
Component (b): Propylene polymer
SUMITOMO NOBLEN AD5'11 (trade name for propylene-
ethylene block copolymer having MI - 0.6, produced by
SUMITOMO CHEMICAL CO., LTD) was used.
Component (b): Modified propylene polymer
This includes the following two species.
(i) Pellets (1 kg) of the above-described SUMITOMO
NOBLEN AD5~1 were charged in a 10 1 autoclave together
with 4 1 of water, 40 g of styrene monomer, 52 g of methyl
methacrylate, 2.8 g of a dispersing agent (METHOLOSE 90SH-
100; trade name) and a peroxide (PERBUTYL PV; trade name),
and the resulting mixture was allowed to react at 120°C for
one hour while blowing nitorogen gas in. After cooling,
the reaction mixture was extracted with methyl ethyl
ketone to remove polystyrene and thus modified propylene
polymer composition grafted with styrene and methyl
methacrylate was recovered. Hereinafter, the polymer
composition thus obtained is called "MG-2" for brevity.
(ii) A styrene and acrylonitrile-grafted polymer was
prepared in the same manner as for MG-2, except that the
graft monomers were replaced by 28 g of styrene and 11 g
of acrylonitrile. Hereinafter, this polymer composition
is referred to as "MG-3" for brevity.
Component (c): Rubbery substance which is compatible with
the component (a)
This includes the following three species.
- 36 -
20098 45
'' (i) SUMITOMO*SBR 150T (trade name for styrene-butadiene
random copolymer rubber (SBR) produce by SUMITOMO CHEMICAL
CO., LTD).
(ii) KRATON*GiT0lX (trade name for styrene-ethylene-
propylene copolymer rubber (SEP) produced by SHELL
CHEMICAL CO., LTD).
(iii) Styrene-modified ethylene-propylene rubber.
The styrene modified ethylene-propylene rubber was
produced by the following method.
In a stainless steel autoclave equipped with a
stirrer were charged 1 kg of SUMITOMO ESPREN*E201 (trade
name for ethylene-propylene copolymer rubber (EPR)
produced by SUMITOMO CHEMICAL CO., LTD; ML1+4, 121°C = 2'1)
in the form of chips, 3.5 kg of pure water, 40 g calcium
tertiary phosphate and 40 g of PLURONIC F-68 (trade name
for a product by ASAHI DENKA CO., LTD) and stirred with
sufficient flow of nitrogen gas.
Thereafter, 43 parts by weight of styrene monomer
and Z.5 g of SUNPEROX*TO (trade name for a product by
SANKEN KAKOU CO., LTD) as a free radical initiator were
added to the resulting reaction mixture. After elevating
the temperature to 110°C in 80 minutes, the reaction is
continued for 1 hour. After cooling, styrene-grafted
copolymer rubber was taken out by filtration and the
filtrate was washed sufficiently with pure water followed
by drying under vacuum. Hereinafter, this modified
ethylene-propylene rubber is called "RG-1" for brevity.
Component (c): Rubbery substance which is not compatible
* trade-mark
- 3'I -
with the component (a)
This include the following four species.
(i) DIENE R35A (trade name for polybutadiene (BR)
produced by ASAHI CHEMICAL CO., LTD).
(ii) SUMITOMO ESPREN*E-201 (trade name for ethylene-
propylene rubber (EPR) produce by SUMITOMO CHEMICAL CO.,
LTD; ML1+4, 121°C = 33) .
(iii) SUMITOMO EXCELEN*CN1001 (trade name for ethylene-a-
olefin copolymer resin produced by SUMITOMO CHEMICAL CO.,
LTD; density = 0.90 g/cm3)
(iv) SUMITOMO ESPREN*E512P (trade name for ethylene-
propylene-diene rubber (EPDM) produced by SUMITOMO
CHEMICAL CO., LTD; ML1+4, 121°C = 68).
The respective components were blended at
proportions shown in Table 2 and kneaded to obtain the
resin compositions.
The resulting compositions were press-molded to form
test pieces, which were then measured for their physical
properties, and the results obtained are shown in Table 2.
It is noted from Table 2 that the resin compositions
of examples 6 to 8 in which the mixture of the
polyphenylene ether (component (a)), the modified
propylene polymer and if desired, the propylene polymer
(component (b)) were blended with the rubbery substance
compatible with the component (a) and the rubbery
substance not compatible with the component (a) exhibit
much improved impact resistance than that of the resin
composition of Comparative Example 4 in which the modified
* trade-mark
- 38 -
propylene polymer was absent.
-39-
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