U.S. patent application number 09/775655 was filed with the patent office on 2001-08-02 for thermoplastic resin composition having excellent long-term heat-aging properties.
This patent application is currently assigned to Techno Polymer Co., Ltd.. Invention is credited to Hosaka, Yukio, Kurata, Takashi.
Application Number | 20010011116 09/775655 |
Document ID | / |
Family ID | 16423332 |
Filed Date | 2001-08-02 |
United States Patent
Application |
20010011116 |
Kind Code |
A1 |
Kurata, Takashi ; et
al. |
August 2, 2001 |
Thermoplastic resin composition having excellent long-term
heat-aging properties
Abstract
The present invention relates to a thermoplastic resin
composition with excellent long-term heat-aging properties,
comprising: (I) 10 to 45% by weight of a rubber-modified
thermoplastic resin obtained by graft polymerizing at least one
monomer selected from the group consisting of aromatic vinyl
compounds, vinyl cyanide compounds and other vinyl monomers
copolymerizable therewith in the presence of a rubber-like polymer;
(II) 5 to 30% by weight of a thermoplastic resin obtained by
copolymerizing the monomers comprising an aromatic vinyl compound,
a vinyl cyanide compound and optionally other vinyl monomer
copolymerizable therewith; and (III) 50 to 70% by weight of a
polycarbonate resin, the content of the vinyl cyanide compound in
the whole produced composition being 3 to 12% by weight.
Inventors: |
Kurata, Takashi; (Tokyo,
JP) ; Hosaka, Yukio; (Tokyo, JP) |
Correspondence
Address: |
Nixon & Vanderhye P.C.
8th Floor
1100 N. Glebe Rd.
Arlington
VA
22201
US
|
Assignee: |
Techno Polymer Co., Ltd.
|
Family ID: |
16423332 |
Appl. No.: |
09/775655 |
Filed: |
February 5, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
09775655 |
Feb 5, 2001 |
|
|
|
09351298 |
Jul 12, 1999 |
|
|
|
Current U.S.
Class: |
525/67 ; 525/68;
525/69 |
Current CPC
Class: |
C08L 2666/02 20130101;
C08L 69/00 20130101; C08L 69/00 20130101 |
Class at
Publication: |
525/67 ; 525/68;
525/69 |
International
Class: |
C08L 069/00; C08L
051/00; C08L 051/04 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 15, 1998 |
JP |
10-200378 |
Claims
What is claimed is:
1. A thermoplastic resin composition with excellent long-term
heat-aging properties, comprising: (I) 10 to 45% by weight of a
rubber-modified thermoplastic resin obtained by graft polymerizing
at least one monomer selected from the group consisting of aromatic
vinyl compounds, vinyl cyanide compounds and other vinyl monomers
copolymerizable therewith in the presence of a rubber-like polymer,
the graft ratio of the polymerizate being 10 to 100% and the
intrinsic viscosity .eta. of the methyl ethyl ketone solubles at
30.degree. C being 0.2 to 0.8 dl/g; (II) 5 to 30% by weight of a
thermoplastic resin obtained by copolymerizing the monomers
comprising an aromatic vinyl compound, a vinyl cyanide compound and
optionally other vinyl monomer copolymerizable therewith, the
weight ratio of aromatic vinyl compound/vinyl cyanide
compound/other vinyl monomer being 50-90/10-20/0-30, and the
intrinsic viscosity .eta. of the methyl ethyl ketone solubles at
30.degree. C. being 0.3 to 0.6 dl/g; and (III) 50 to 70% by weight
of a polycarbonate resin, the total amount of (I), (II) and (III)
being 100% by weight, and the content of the vinyl cyanide compound
in the whole produced composition being 3 to 12% by weight.
2. A thermoplastic resin composition according to claim 1, wherein
the weight ratio of aromatic vinyl compound/vinyl cyanide
compound/other vinyl monomer of (II) thermoplastic resin is
72-85/15-18/0-10.
3. A thermoplastic resin composition according to claim 1, wherein
the intrinsic viscosity .eta. of (II) thermoplastic resin is 0.35
to 0.4.
4. A thermoplastic resin composition according to claim 1, wherein
the rubber-like polymer is at least one substance selected from the
group consisting of ethylene-propylene rubber,
ethylene-propylene-nonconjugated diene rubber, acrylic rubber and
silicone rubber.
5. A thermoplastic resin composition according to claim 4, wherein
the rubber-like polymer is ethylene-propylene rubber,
ethylene-propylene-nonc- onjugated diene rubber or mixture
thereof.
6. A thermoplastic resin composition according to claim 1, which
further comprises (IV) 0 to 2% by weight of a heat-aging resistor,
based on 100% by weight of total amount of (I), (II), (III) and
(IV).
7. A thermoplastic resin composition according to claim 6, wherein
the amount of (I) rubber-modified thermoplastic resin is not less
than 10% and less than 45% by weight and the amount of (IV)
heat-aging resistor is more than 0% and not more than 2% by weight
based on 100% by weight of total amount of (I), (II), (III) and
(IV).
8. A thermoplastic resin composition according to claim 6, wherein
the heat-aging resistor (IV) is a three-type mixture comprising a
phenol type, a phosphorus type and a sulfur type.
Description
BACKGROUND OF THE INVENTION
[0001] The present invention relates to a thermoplastic resin
composition having excellent long-term heat-aging properties. More
particularly, it relates to a thermoplastic resin composition
having excellent impact resistance, heat resistance, chemical
resistance and weather resistance, and further remarkably improved
in long-term heat-aging properties.
[0002] Polycarbonate (PC) resins have excellent heat resistance and
mechanical properties, the molded products thereof are excessively
reduced in impact strength when they are flawed because of high
notch sensitivity. PC resins also have a disadvantage that it is
necessitated to set the molding temperature in a high range due to
too high heat resistance, so that they are inexpedient for molding
of large-sized articles.
[0003] On the other hand, ABS resins
(acrylonitrile-butadiene-styrene resins) are a material having a
good balance of properties such as moldability, impact strength and
dimensional stability, and widely used for a variety of commercial
products such as automobiles, domestic electrical appliances, OA
machines, etc., but they have a disadvantage that they are low in
heat resistance. Japanese Patent Publication (KOKOKU) No. 38-15225
proposes blending of a PC resin with an ABS resin having good
compatibility with the PC resin to thereby improve such properties
as notched impact strength, molding workability and heat
resistance. The PC resin/ABS resin polymer alloys (which may
hereinafter be referred to as "PC/ABS polyblends") are now one of
the typical resin compositions popularly used in the fields of OA
machines, vehicles and such.
[0004] Another drawback to the ABS resins is poor weather
resistance due to use of butadiene rubber. Japanese Patent
Publication (KOKOKU) No. 51-24540 proposes polyblending of a PC
resin and an AES resin using ethylene-propylene (EP) rubber to
improve stain resistance. Japanese Patent Publication (KOKOKU) No.
1-57699 proposes addition of a specific plasticizer to the PC
resin/AES resin polymer alloys (which may hereinafter be referred
to as "PC/AES polyblends") to improve weld strength. Further,
Japanese Patent Publication KOKOKU) No. 3-40064 proposes
optimization of the rubber content, graft ratio and molecular
weight of the PC/AES polyblends to improve weld appearance and
coating properties. Japanese Patent Publication (KOKOKU) No.
1-17501 proposes polyblending of the three types of resin, i.e. PC
resin, ABS resin and AES resin, to improve low-temperature impact
strength, weld strength and color development. Japanese Patent
Publication (KOKOKU) No. 4-29696 proposes addition of
.alpha.-alkylstyrene as the graft resin component of the PC/AES
polyblends to improve thermal decomposability in the course of
granulation and molding work. Japanese Patent Publication (KOKOKU)
No. 4-56063 proposes optimization of melt viscosity of the AES
resin in the PC/AES polyblends to improve weld strength. Japanese
Patent Publication (KOKOKU) No. 5-79699 proposes optimization of
the rubber content of the PC/AES polyblends to improve
low-temperature impact strength.
[0005] As viewed above, since the PC/ABS and PC/AES polyblends have
excellent properties, various use for them are found. But when
these resins once molded into a product are exposed to high
temperatures for a long time in a practical use environment, their
properties are deteriorated drastically. This is attributable to
such causes as deterioration of the PC resin, deterioration of the
grafted or ungrafted resin and deterioration of the rubber, but no
proposal of the attempt for solving these problems has ever been
made in the past.
[0006] As a result of the present inventors' earnest studies to
solve the above problems, it has been found that a thermoplastic
resin composition comprising a specific rubber-modified
thermoplastic resin, a specific thermoplastic resin, a
polycarbonate resin and a heat-aging resistor, with the content of
vinyl cyanide compound in the whole composition being defined, has
excellent long-term heat-aging properties.
[0007] The present invention has been attained on the basis of the
above finding.
SUMMARY OF THE INVENTION
[0008] The object of the present invention is to provide a
thermoplastic resin composition having excellent long-term
heat-aging properties as well as high impact strength and heat
resistance by adding a specific thermoplastic resin to a polymer
alloy of a polycarbonate resin and a rubber-modified thermoplastic
resin.
[0009] To attain the above aim, in the first aspect of the present
invention, there is provided a thermoplastic resin composition with
excellent long-term heat-aging properties, comprising:
[0010] (I) 10 to 45% by weight of a rubber-modified thermoplastic
resin obtained by graft polymerizing at least one monomer selected
from the group consisting of aromatic vinyl compounds, vinyl
cyanide compounds and other vinyl monomers copolymerizable
therewith in the presence of a rubber-like polymer,
[0011] the graft ratio of the polymerizate being 10 to 100% and the
intrinsic viscosity .eta. of the methyl ethyl ketone solubles at
30.degree. C. being 0.2 to 0.8 dl/g;
[0012] (II) 5 to 30% by weight of a thermoplastic resin obtained by
copolymerizing the monomers comprising an aromatic vinyl compound,
a vinyl cyanide compound and optionally other vinyl monomer
copolymerizable therewith,
[0013] the weight ratio of aromatic vinyl compound/vinyl cyanide
compound/other vinyl monomer being 50-90/10-20/0-30, and the
intrinsic viscosity .eta. of the methyl ethyl ketone solubles at
30.degree. C. being 0.3 to 0.6 dl/g; and
[0014] (III) 50 to 70% by weight of a polycarbonate resin,
[0015] the total amount of (I), (II) and (III) being 100% by
weight, and
[0016] the content of the vinyl cyanide compound in the whole
produced composition being 3 to 12% by weight.
[0017] In the second aspect of the present invention, there is
provided a tthermoplastic resin composition with excellent
long-term heat-aging properties, comprising:
[0018] (I) 10 to 45% by weight of a rubber-modified thermoplastic
resin obtained by graft polymerizing at least one monomer selected
from the group consisting of aromatic vinyl compounds, vinyl
cyanide compounds and other vinyl monomers copolymerizable
therewith in the presence of a rubber-like polymer,
[0019] the graft ratio of the polymerizate being 10 to 100% and the
intrinsic viscosity I of the methyl ethyl ketone solubles at
30.degree. C. being 0.2 to 0.8 dl/g;
[0020] (II) 5 to 30% by weight of a thermoplastic resin obtained by
copolymerizing the monomers comprising an aromatic vinyl compound,
a vinyl cyanide compound and optionally other vinyl monomer
copolymerizable therewith,
[0021] the weight ratio of aromatic vinyl compound/vinyl cyanide
compound/other vinyl monomer being 50-90/10-20/0-30, and the
intrinsic viscosity .eta. of the methyl ethyl ketone solubles at 30
.degree. C. being 0.3 to 0.6 dl/g;
[0022] (III) 50 to 70% by weight of a polycarbonate resin; and
[0023] (IV) 0 to 2% by weight of a heat-aging resistor,
[0024] the total amount of (I), (II), (III) and (IV) being 100% by
weight, and
[0025] the content of the vinyl cyanide compound in the whole
produced composition being 3 to 12% by weight.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The rubber-modified thermoplastic resin (I) used in the
present invention can be obtained by graft polymerizing at least
one monomer selected from the group consisting of aromatic vinyl
compounds, vinyl cyanide compounds and other vinyl monomers
copolymerizable therewith in the presence of a rubber-like polymer.
The graft ratio of the polymerizate is 10 to 100%, and the
intrinsic viscosity [.eta.] of the methyl ethyl ketone solubles at
30.degree. C. is 0.2 to 0.8 dl/g.
[0027] The rubber-like polymers usable for the preparation of the
rubber-modified thermoplastic resin (I) include, for example,
polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile
copolymer, ethylene-propylene-(nonconjugated diene) copolymer,
ethylene-butene-1-(nonconjugated diene) copolymer, ethylene/hexene
copolymer, ethylene/octene copolymer, isobutylene-isoprene
copolymer, acrylic rubber, styrene-butadiene-styrene block
copolymer, styrene-isoprene-styrene block copolymer, hydrogenated
diene-based (block, random or homo) polymers such as SEBS,
polyurethane rubber, and silicone rubber. In case of using silicone
rubber, if a graft crosslinking agent (such as the one containing a
vinyl group, .gamma.-methacryloxypropylmethyldimethoxysilane or the
like) is contained in the silicone rubber in an amount of about
0.01 to 10% by weight, there can be obtained a thermoplastic resin
composition of the present invention with excellent impact
resistance.
[0028] The rubber-like polymer used in the present invention is
preferably selected from ethylene-propylene rubber,
ethylene-propylene-nonconjugated diene rubber, acrylic rubber and
silicone rubber, more preferably selected from ethylene-propylene
rubber and ethylene-propylene-nonconjuga- ted diene rubber.
Examples of the nonconjugated dienes usable here include alkenyl
norbornenes, cyclic dienes, aliphatic dienes and the like, of which
5-ethylidene-2-norbornene and dicyclopentadiene are preferred.
These nonconjugated dienes may be used singly or as a mixture of
two or more of them.
[0029] The said rubber-like polymers may also be used either singly
or as a mixture or composite.
[0030] By use of two or more types of graft polymer
(rubber-modified thermoplastic resins) differing in rubber particle
size, a thermoplastic resin composition with even higher impact
resistance and a better balance of properties is obtained. It is
preferred to use, for instance, two types of rubber-like polymer,
one having a particle size of 800 to 3,000 angstroms and the other
5.000 to 10,000 angstroms. In this case, it is possible to
synthesize the graft polymers (rubber-modified thermoplastic
resins) in the presence of two rubber-like polymers differing in
particle size, or to blend two rubber-modified thermoplastic resins
differing in rubber particle size.
[0031] The molecular weight of the rubber-like polymers used in the
present invention is preferably not less than 60,000, more
preferably not less than 70,000, in terms of polystyrene-reduced
weight-average molecular weight. When the molecular weight of the
rubber-like polymers is less than 60,000, the preferred impact
resistance may not be obtained. The rubber-like polymers may have a
three-dimensional crosslinked structure.
[0032] The percentage of the rubber-like polymers in the
rubber-modified thermoplastic resin (I) is preferably 10 to 80% by
weight, more preferably 20 to 70% by weight (feed percentage). When
the said percentage is less than 10% by weight, the preferred
impact resistance may not be obtained, while when the said
percentage exceeds 80% by weight, there may arise the problems in
moldability of the composition and visual appearance of its
moldings.
[0033] The aromatic vinyl compounds usable as a monomer in the
rubber-modified thermoplastic resin (I) include, for example,
styrene, .alpha.-methylstyrene, methylstyrene, vinylxylene,
monochlorostyrene, dichlorostyrene, monobromostyrene,
dibromostyrene, fluorostyrene, p-t-butylstyrene, ethylstyrene and
vinylnaphthalene. These compounds may be used singly or as a
mixture of two or more of them. The preferred aromatic vinyl
compound for use in the present invention is styrene or an aromatic
vinyl compound containing styrene in an amount of not less than 50%
by weight.
[0034] The percentage of the aromatic vinyl compound(s) in the
monomers is preferably 60 to 90% by weight, more preferably 65 to
85% by weight.
[0035] The vinyl cyanide compounds usable as another monomer
include acrylonitrile, methacrylonitrile and the like, of which
acrylonitrile is preferred.
[0036] The percentage of the vinyl cyanide compound in the monomers
is preferably 10 to 40% by weight, more preferably 15 to 35% by
weight.
[0037] Other copolymerizable vinyl monomers usable for graft
polymerization in the present invention include (meth)acrylic ester
monomers, for example, acrylic esters such as methyl acrylate,
ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate,
hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl
acrylate and phenyl acrylate, and methacrylic esters such as methyl
methacrylate, ethyl methacrylate, propyl methacrylate, butyl
methacrylate, amyl methacrylate, hexyl methacrylate, octyl
methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate,
dodecyl methacrylate, octadecyl methacrylate, phenyl methacrylate
and benzyl methacrylate; unsaturated acid anhydrides such as maleic
anhydride and itaconic anhydride; unsaturated acids such as acrylic
acid and methacrylic acid; and maleimide monomers, for example,
imide compounds of .alpha., .beta.-unsaturated dicarboxylic acids
such as N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide and
N-cyclohexylmaleimide. Of these vinyl monomers, methyl
methacrylate, N-phenylmaleimide and N-cyclohexylmaleimide are
preferred. These other vinyl monomers can be used either singly or
as a mixture of two or more of them.
[0038] The percentage of the said other vinyl monomer(s) in the
monomer mixture is preferably not more than 50% by weight, more
preferably not more than 30% by weight.
[0039] The rubber-modified thermoplastic resin (I) used in the
present invention can be produced by the known polymerization
methods such as emulsion polymerization, solution polymerization
and suspension polymerization. In case where the resin (I) is
produced by emulsion polymerization, it is usually purified by
coagulating it with a coagulant, washing the produced powder with
water and drying the product. As the coagulant, usually an
inorganic salt such as calcium chloride, magnesium sulfate,
magnesium chloride, sodium chloride or the like is used. It is to
be noted that when the produced rubber-modified thermoplastic resin
(I) is blended in a polycarbonate resin (III), there may arise the
problem of causing a reduction of molecular weight of the
polycarbonate resin (III) due to the residual salt or emulsifier in
the component (I). It is therefore preferable to use an acid such
as sulfuric acid as the coagulant.
[0040] As the radical initiator for the graft polymerization, it is
possible to use the commonly used ones, such as, for example,
cumene hydropeoxide, diisopropylbenzene hydroperoxide, potassium
persulfate, azobisisobutylonitrile, benzoyl peroxide, lauroyl
peroxide, t-butyl peroxylaurate, and t-butyl
peroxymonocarbonate.
[0041] The amount of the radical initiator used is usually 0.05 to
5% by weight, preferably 0.1 to 1% by weight, based on the
monomers.
[0042] The objective effect of the present invention can be
obtained by properly selecting an organic peroxide or a solvent for
allowing progress of uniform graft reaction in graft
polymerization, synthesizing a rubber-like polymer by emulsion
polymerization, carrying out graft polymerization by emulsion
polymerization, initiating the polymerization by uniformly
dissolving the rubber-like polymer, and designing appropriate
polymerization means such as conducting solution or bulk
polymerization by dissolving the melted and kneaded monomeric
mixture in a solution or conducting emulsion or suspension
polymerization of the re-emulsified product.
[0043] The graft ratio of the thus obtained rubber-modified
thermoplastic resin (I) is 10 to 100%, preferably 30 to 80%. When
the graft ratio is below 10%, the interfacial adhesion strength
between resin and rubber lowers, making it unable to obtain high
impact strength. On the other hand, when the graft ratio exceeds
100%, the interfacial layer is enlarged in thickness and also a
grafted resin layer is created in the inside of the rubber to cause
a decrease of rubber elasticity, resulting in an unsatisfactory
impact strength of the composition.
[0044] The said graft ratio can be easily adjusted by changing the
type and amount of the rubber-like polymer, polymerization
initiator, chain transfer agent, emulsifier, etc., and the
polymerization conditions such as polymerization time and
polymerization temperature.
[0045] The "graft ratio (%)" referred to herein is the value given
from the following equation:
Graft ratio (%)=[(y-x)/x].times.100
[0046] wherein x is rubber moiety in the component (I) and y is
methyl ethyl ketone insolubles in the component (I).
[0047] The intrinsic viscosity [.eta.] (measured in methyl ethyl
ketone at 30.degree. C.) of the methyl ethyl ketone solubles in the
rubber-modified thermoplastic resin (I) of the present invention is
0.2 to 0.8 dl/g, preferably 0.3 to 0.7 dl/g. With the intrinsic
viscosity [.eta.] falling within the above-defined range, it is
possible to obtain a thermoplastic resin composition of the present
invention with excellent impact resistance and molding workability
(fluidity). The said intrinsic viscosity [.eta.] can be easily
controlled by changing the type and amount of the polymerization
initiator, chain transfer agent, emulsifier, solvent, etc., and the
polymerization conditions such as polymerization time and
polymerization temperature.
[0048] Examples of the rubber-modified thermoplastic resins (I)
usable in the present invention include ABS resins, AES resins, ASA
resins (polymers obtained by grafting AS resins to acrylic rubber),
and ASS resins (polymers obtained by grafting AS resins to silicone
rubber). Of these resins, AES resins, ASA resins and ASS resins are
preferred, and AES resins being especially preferred.
[0049] The percentage of the rubber-modified thermoplastic resin
(I) in the thermoplastic resin composition of the present invention
is 10 to 45% by weight, preferably not less than 10% and less than
45% by weight, more preferably 20 to 40% by weight based on 100% by
weight of total amount of (I), (II), (III) and (IV). When the said
percentage is less than 10% by weight, the composition tends to
have unsatisfactory impact strength, while when the said percentage
exceeds 45% by weight, fluidity of the composition and visual
appearance of its moldings may be deteriorated.
[0050] The thermoplastic resin (II) used in the present invention
is obtained by copolymerizing the monomers comprising an aromatic
vinyl compound, a vinyl cyanide compound and, if necessary, other
vinyl monomer copolymerizable therewith. The weight ratio of
aromatic vinyl compound/vinyl cyanide compound/other
copolymerizable vinyl monomer is 50-90/10-20/0-30, and the
intrinsic viscosity [I] of the methyl ethyl ketone solubles at
30.degree. C. is 0.3 to 0.6 dl/g.
[0051] The aromatic vinyl compound, vinyl cyanide compound and
other vinyl monomer used in the thermoplastic resin (II) are the
same as those used for the preparation of the rubber-modified
thermoplastic resin (I) mentioned above.
[0052] The thermoplastic resin (II) used in the present invention
can be produced by known polymerization methods such as emulsion
polymerization, solution polymerization and suspension
polymerization. In case where the resin (II) is produced by
emulsion polymerization, it is usually purified by coagulating the
polymerization product with a coagulant, washing the obtained
powder with water and drying it. As the coagulant, usually an
inorganic salt such as calcium chloride, magnesium sulfate,
magnesium chloride or sodium chloride is used. It is to be noted
that when the obtained thermoplastic resin (II) is blended in a
polycarbonate resin (III), there may take place a reduction of
molecular weight of the polycarbonate resin (III) due to the
residual salt or emulsifier in the component (II). It is therefore
preferable to use an acid such as sulfuric acid as the
coagulant.
[0053] In the thermoplastic resin (II) used in the present
invention, the ratio by weight of aromatic vinyl compound/vinyl
cyanide compound/other vinyl monomer is 50-90/10-20/0-30,
preferably 72 to 85/15 to 18/0 to 10. When the ratio of the
aromatic vinyl compound is less than 50% by weight, compatibility
of the resin (II) with the polycarbonate resin (III) may lower,
resulting in unsatisfactory impact strength and heat stability of
the composition. When the ratio of the aromatic vinyl compound
exceeds 90% by weight, also compatibility of the resin (II) with
the polycarbonate resin (III) may lower, causing deterioration of
impact strength and chemical resistance of the composition. When
the ratio of the vinyl cyanide compound is less than 10% by weight,
compatibility with the polycarbonate resin (III) may lower
excessively, giving rise to such problems as reduction of impact
strength and exfoliation of the surface layer, and when the ratio
of the vinyl cyanide compound exceeds 20% by weight, the heat-aging
properties of the composition may be deteriorated. It is a feature
of the present invention that a vinyl cyanide compound is used in a
defined range of ratio, i.e. 10 to 20% by weight, for markedly
improving the heat-aging properties of the composition. When other
vinyl monomer is used in excess of 30% by weight, compatibility
with the polycarbonate resin (III) may deteriorate to reduce impact
strength of the composition. It is preferred that the ratio by
weight of aromatic vinyl compound/vinyl cyanide compound/other
vinyl monomer in the thermoplastic resin (II) is different from the
ratio by weight of aromatic vinyl compound/vinyl cyanide
compound/other vinyl monomer in the thermoplastic resin (I)
[0054] The intrinsic viscosity [.eta.] at 30.degree. C. of the
methyl ethyl ketone solubles in the thermoplastic resin (II)
according to the present invention is 0.3 to 0.6 dl/g, preferably
0.35 to 0.45 dl/g. When the viscosity is less than 0.3 dl/g, the
produced composition may be poor in impact strength, and when the
viscosity exceeds 0.6 dl/g, the composition may be greatly reduced
in fluidity.
[0055] The percentage of the thermoplastic resin (II) in the
thermoplastic resin composition of the present invention is 5 to
30% by weight, preferably 10 to 20% by weight based on 100% by
weight of total amount of (I), (II), (III) and (IV). When the
percentage of the resin (II) is less than 5% by weight, the
heat-aging properties may be deteriorated excessively, and when it
exceeds 30% by weight, impact strength of the composition may be
greatly reduced.
[0056] The polycarbonate resins (III) usable for the preparation of
the thermoplastic resin composition of the present invention
include those obtained from the reactions between various
dihydroxyarryl compounds and phosgene (phosgene method) and those
obtained from the ester exchange reactions between dihydroxyarryl
compounds and diphenyl carbonate (ester exchange method). The
preferred polycarbonate resins for use in the present invention are
the aromatic polycarbonate resins, a typical example of which is
2,2'-bis(4-hydroxyphenyl)propane, that is, a polycarbonate resin
obtained from the reaction between bisphenol A and phosgene.
[0057] Examples of the dihydroxarryl compounds usable as a starting
material of the said polycarbonate resins include
bis(4-hydroxyphenyl)met- hane, 1,1'-bis(4-hydroxyphenyl)ethane,
2,2'-bis(4-hydroxyphenyl)propane, 2,2'-bis(4-hydroxyphenyl) butane,
2,2'-bis(4-hydroxyphenyl)octane, 2,2'-bis(4-hydroxyphenyl)
phenylmethane, 2,2'-bis(4-hydroxy-3-methylpheny- l) propane,
2,2'-bis(4-hydroxy-3-t-butylphenyl) propane,
2,2'-bis(4-hydroxy-3-bromophenyl)propane,
2,2'-bis(4-hydroxy-3,5-dichloro- phenyl)propane,
1,1'-bis(4-hydroxyphenyl) cyclopentane, 1,1'-bis(4-hydroxyphenyl)
cylcohexane, 4,4 ,-dihydroxydiphenyl ether, 4,4
,-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl
sulfide, 4,4'-dihydroxy-3,3 ,-dimethylphenyl sulfide,
4,4'-dihydroxy-3, 3'-dimethylphenyl sulfoxide, 4,4
,-dihydroxyphenyl sulfoxide, 4,4'-dihydroxyphenylsulfone, 4,4
,-dihydroxy-3,3'-dimethylphenylsulfone,
1,1'-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
1,1'-bis(4-hydroxyphenyl)-3,3-dimethylcyclohexane,
1,1'-bis(4-hydorxyphenyl)-3,3,5-trimethylcyclopentane,
hydroquinone, and resorcin. These compounds may be use singly or in
combination. 2,2'-bis(4-hydroxyphenyl) propane, i.e. bisphenol A,
is especially preferred.
[0058] The viscosity-average molecular weight of the polycarbonate
resin (III) is preferably 15,000 to 40,000, more preferably 17,000
to 30,000, especially preferably 18,000 to 28,000. A higher
molecular weight provides a better notched impact resistance but
gives a lower fluidity. It is possible to use two or more types of
polycarbonate differing in molecular weight.
[0059] The percentage of the polycarbonate resin in the
thermoplastic resin composition (III) of the present invention is
50 to 70% by weight, more preferably 55 to 65% by weight based on
100% by weight of total amount of (I), (II), (III) and (IV). When
the polycarbonate resin percentage is less than 50% by weight, the
composition may be unsatisfactory in heat resistance, and when the
percentage exceeds 70% by weight, fluidity of the composition may
lower excessively.
[0060] As the heat-aging resistor (IV) in the thermoplastic resin
composition of the present invention, there can be used, for
instance, phenol type (phenol derivatives), phosphorus type
(heat-aging resistors containing phosphorus), sulfur type
(heat-aging resistors containing sulfur), lactone type and the
like. A phenol/phosphorus/sulfur three-type mixture is preferred.
By using this three-type mixture as the heat-aging resistor (IV),
the effect of enabling retention of tensile elongation can be
attained when the composition is exposed to a high temperature for
a long time.
[0061] Of these heat-aging resistors (IV), the phenol type includes
2,6-di-t-butylphenol derivatives, 2-methyl-6-t-butylphenol
derivatives, octadecyl-3(3,5-di-t-butyl-4-hydroxyphenyl)
propionate, 4,4 1-butylidene-bis(6-t-butyl-m-cresol),
pentaerythrityl-tetrakis[3-(3,5-di-- t-butyl-4-hydroxyphenyl)
propionate], 2[1-(2-hydroxy-3,5-di-t-pentylphenyl- )-ethyl
]-4,6-di-t-pentylphenyl acrylate, and 2-t-butyl-6(3-t-butyl-2-hydr-
oxy-5-methylbenzyl)-4-methylphenyl acrylate.
[0062] The phosphorus type includes tris(2,4-di-t-butylphenyl)
phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl
phosphite), distearylpentaerythritol diphosphite, sodium
dihydrogenphosphate, and disodium monohydrogenphosphate.
[0063] The sulfur type includes dodecyl 3,3'-thiobispropionate,
octadecyl 3,3'-thiobispropionate,
pentaerythritol-tetrakis-(3-laurylpropionate), and dilauryl-3,3
,-thiodipropionate.
[0064] The lactone type includes
5,7-di-t-butyl-3-(3,4-dimethylphenyl)-3 H-benzofuran-2-one.
[0065] The percentage of the heat-aging resistor (IV) in the
thermoplastic resin composition of the present invention is 0 to 2%
by weight, preferably not less than 0 but not greater than 2% by
weight, more preferably not less than 0 but not greater than 1% by
weight based on 100% by weight of total amount of (I), (II), (III)
and (IV). In the thermoplastic resin composition of the present
invention, the resins (components (I) and (II)) other than the
polycarbonate resin (III) are improved in their heat-aging
properties by the addition of a heat-aging resistor, but the
polycarbonate resin may be adversely affected by the addition of a
heat-aging resistor as it might act as a catalyst which promotes
hydrolysis. In view of these antagonistic effects, it is expedient
to add the heat-aging resistor in an amount not exceeding 2% by
weight for providing a maximal heat-aging resistance.
[0066] The percentage of the vinyl cyanide compound in the
thermoplastic resin composition of the present invention is 3 to
12% by weight, preferably 5 to 10% by weight. When the percentage
of the vinyl cyanide compound exceeds 12% by weight, the
composition may be deteriorated in heat-aging properties, and when
the percentage is less than 3% by weight, compatibility with the
polycarbonate resin may lower to deteriorate impact strength of the
composition.
[0067] The thermoplastic resin composition according to the present
invention may contain if necessary one or more types of filler such
as glass fiber, carbon fiber, glass beads, wollastonite, rock
filler, calcium carbonate, talc, mica, glass flakes, mild fiber,
barium sulfate, graphite, molybdenum disulfide, magnesium oxide,
zinc oxide whiskers, potassium titanate whiskers, etc. Blending of
such fillers affords rigidity and high-temperature deformation
resistance to the composition. Also, addition of talc, calcium
carbonate or the like provides a matte effect to the composition.
The preferred size of the glass fibers and carbon fibers for use in
the present invention is 6 to 60 .mu.m in diameter and 30 .mu.m or
more in length.
[0068] It is also possible to blend the known additives such as
weathering agent, lubricant, colorant, antistatic agent, silicone
oil, etc., in the thermoplastic resin composition of the present
invention. As the weathering agent, phosphorus type, benzotriazole
type, triazine type, benzophenone type and the like are preferred.
As the lubricant, ethylenebisstearylamide, hardened castor oil and
the like are preferably used. Carbon black, red oxide and the like
can be used as the colorant. Polyethers and sulfonates having alkyl
groups can be cited as examples of the antistatic agent.
[0069] The thermoplastic resin composition of the present invention
can be obtained by kneading the component materials by using
various types of extruder, Banbury mixer, kneader, rolls or the
like. Use of a double-screw extruder is preferred. Regarding the
way of kneading of the component materials, they may be either
kneaded all together or may be kneaded according to a multi-stage
addition system.
[0070] The thermoplastic resin composition of the present invention
may be molded into various products by the known molding methods
such as injection molding, sheet extrusion, vacuum forming, contour
extrusion, expansion molding, etc.
[0071] The thus obtained molded products can be used for various
applications by making use of their excellent properties; for
example, they can be used as disc tray material, housing material,
etc., for OA machines, domestic electrical appliances, vehicles,
etc.
[0072] The thermoplastic resin composition according to the present
invention can be used without suffering remarkable changes of
properties even in long-time use under high temperatures, and is
capable of prolonging the life of its products and contributing to
the safety thereof. The composition also has excellent fluidity and
is therefore preferred for large-sized moldings.
EXAMPLES
[0073] The present invention is described in further detail by
showing its Examples and Comparative examples, but it is to be
understood that these examples are merely intended to be
illustrative and not to be construed as limiting the scope of the
invention.
[0074] In the following Examples and Comparative Examples, all
"parts" and "%" are by weight unless otherwise noted. Various
evaluations in these Examples and Comparative Examples were made in
the manner described below.
[0075] (1) Average particle size
[0076] It was confirmed by electron microscopical observation that
the particle size of the latex previously synthesized in an
emulsified state was equal to the size of the dispersed particles
in the resin, so that the size of the dispersed particles in the
latex was measured by the light scattering method using a laser
particle size analyzing system LPA-3100 (mfd. by Otsuka Electronics
Co., Ltd.) according to the cumulant method (70 times
integration).
[0077] (2) Graft ratio
[0078] Already described above.
[0079] (3) Intrinsic viscosity [.eta.]
[0080] The sample was dissolved in methyl ethyl ketone as the
solvent, and the viscosity of the solution was measured by an
Ubbellohde viscometer at 30.degree. C.
[0081] (4) Izod impact strength
[0082] Measured according to ASTM D256 using the notched test
specimens, 2.5.times.1/2.times.1/4 inches.
[0083] (5) Fluidity (melt flow rate)
[0084] Measured according to ASTM D1238 at 240.degree. C. under a
load of 10 kg. Unit: g/10 min.
[0085] (6) Long-term heat-aging properties
[0086] In the tensile elongation at break test according to ASTM
D638, the initial elongation at break and the elongation at break
after left in a 110.degree. C. high-temperature environment for
2,400 hours were measured to determine retention of elongation at
break.
[0087] The component materials used in the Examples and Comparative
Examples are as follows.
[0088] (7) Preparation of component (I)
[0089] Preparation of ABS resin (I-1)
[0090] To a glass-made 7-liter flask equipped with a stirrer, 100
parts of ion exchange water, 1.5 parts of disproportionated sodium
rosinate, 0.1 part of t-dodecylmercaptan, 40 parts (calcd. as
solids) of polybutadiene (#0700 produced by JSR Corp.), 15 parts of
styrene and 5 parts of acrylonitrile were supplied and heated with
stirring. At a point when the temperature reached 45.degree. C., an
aqu eous activator solution comprising 0.1 part of sodium
ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2
part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of
ion exchange water, and 0.1 part of diisopropylbenzene
hydroperoxide were added, allowing the reaction to continue for one
hour. Thereafter, the increment polymerization materials comprising
50 parts of ion exchange water, 1 part of disproportionated sodium
rosinate, 0.1 part of t-dodecylmercaptan, 0.2 part of diisopropyl
hydroperoxide, 30 parts of styrene and 10 parts of acrylonitrile
were added continuously over a period of 3 hours to continue the
polymerization. After completion of the addition, the reaction
mixture was further stirred for one hour, then 0.2 part of
2,2-methylene-bis-(4-ethylene-6-t-butylphenol) was added, and the
reaction product was taken out of the flask. The reaction product
(latex) was coagulated with 2 parts of sulfuric acid, washed well
with water and dried at 75.degree. C. for 24 hours to obtain a
white powder. Polymerization conversion: 97.2%; graft ratio: 75%;
intrinsic viscosity: 0.44 dl/g.
[0091] Preparation of ABS resins (I-1-a) to (I-1-d)
[0092] The ABS resins specified in Table 1 were prepared in the
same way as the preparation of the ABS resin (I-1) described
above.
1 TABLE 1 ABS resins I-1-a I-1-b I-1-b I-1-b Graft ratio (%) 15 95
50 50 Intrinsic viscosity [.eta.] (dl/g) 0.5 0.5 0.2 0.8
[0093] Preparation of AES resin (I-2)
[0094] To a stainless 10-liter autoclave equipped with a ribbon
type stirrer, 20 parts of EPDM [EP-82 produced by JSR Corp.], 55
parts of styrene, 25 parts of acrylonitrile and 100 parts of
toluene were supplied, stirred and heated, and the produced
rubber-like polymer was completely dissolved to obtain a
homogeneous solution. Then 0.1 part of t-dodecylmercaptan, 0.5 part
of benzoyl peroxide and 0.1 part of dicumyl peroxide were added and
stirred at 200 rpm while controlling the temperature to stay
constant at 95.degree. C. to carry out polymerization. The
temperature was raised to 120.degree. C. using one hour after
passage of 6 hours from start of the reaction, and the reaction was
further continued for 2 hours and then terminated. The
polymerization conversion was 97%. After cooling the reaction
mixture to 100 .degree. C., 0.2 part of
2,2-methylene-bis-4-methyl-6-butylphenol was added and then the
reaction mixture was taken out from the autoclave and subjected to
steam distillation to remove the unreacted materials and the
solvent. The reaction product was finely ground and supplied to a
40 mm.o slashed. vented extruder (220.degree. C., 700 mmHg),
whereby the volatiles were substantially evaporated away and the
polymer was pelletized. Graft ratio: 70%; intrinsic viscosity: 0.42
dl/g.
[0095] Preparation of ASA resin (I-3)
[0096] To a 7-liter glass-made flask equipped with a stirrer, 100
parts of ion exchange water, 1.5 parts of sodium oleate, 0.1 part
of t-dodecylmercaptan, 40 parts (calcd. as solids) of acrylic
rubber (20LAR produced by Techno-Polymer Co., Ltd.), 15 parts of
styrene and 5 parts of acrylonitrile were supplied and heated with
stirring. At a point when the temperature reached 45.degree. C., an
aqueous activator solution comprising 0.1 part of sodium
ethylenediaminetetraacetate, 0.003 part of ferrous sulfate, 0.2
part of formaldehyde sodium sulfoxylate dihydrate and 15 parts of
ion exchange water, and 0.1 part of diisopropylbenzene
hydroperoxide were added and the reaction was continued for one
hour. Then the increment polymerization materials comprising 50
parts of ion exchange water, 1 part of sodium oleate, 0.1 part of
t-dodecylmercaptan, 0.2 part of diisopropylbenzene hydroperoxide,
30 parts of styrene and 10 parts of acrylonitrile were added
continuously over a period of 3 hours to carry out the
polymerization. After completion of the addition, the reaction
mixture was further stirred for one hour, then 0.2 part of
2,2-methylene-bis-(4-ethylene-6-t-butylphenol) was added, and the
reaction product was taken out from the flask. The reaction product
latex was coagulated with 2 parts of sulfuric acid, washed well
with water and then dried at 75.degree. C. for 24 hours to obtain a
white powder. Polymerization conversion: 96.5%; graft ratio: 55%;
intrinsic viscosity: 0.41 dl/g.
[0097] Preparation of ASS resin (I-4)
[0098] 1.5 part of p-vinylphenylmethyldimethoxysilane and 98.5
parts of octamethylcyclotetrasiloxane were mixed and poured into
300 parts of distilled water in which 2.0 parts of
dodecylbenzenesulfornic acid had been dissolved, and the mixture
was stirred for 3 minutes by a homomixer to effect emulsification
and dispersion. The mixed solution was transferred into a separable
flask equipped with a condenser, a nitrogen inlet and a stirrer,
heated at 90.degree. C. for 6 hours with stirring, and then cooled
at 5.degree. C. for 24 hours to complete the condensation reaction.
The condensation rate of the obtained modified polyorganosiloxane
was 92.8%. The latex of this modified polyorganosiloxane was
neutralized to pH 7 with a sodium carbonate solution. The average
particle size of the obtained modified polyorganosiloxane latex was
2,800 angstroms.
[0099] To a 7-liter glass-made flask equipped with a stirrer, 100
parts of ion exchange water, 1.5 part of sodium
dodecylbenzenesulfonate, 0.1 part of t-dodecylmercaptan, 40 parts
(calcd. as solids) of the said modified polyorganosiloxane, 15
parts of styrene and 5 parts of acrylonitrile were supplied and
heated with stirring. At a point when the temperature reached
45.degree. C., an aqueous activator solution comprising 0.1 part of
sodium ethylenediaminetetraacetate, 0.003 part of ferrous sulfate,
0.2 part of formaldehyde sodium sulfoxylate and 15 parts of ion
exchange water, and 0.1 part of diisopropylbenzene hydroperoxide
were added and the reaction was continued for one hour. Then the
increment polymerization materials comprising 50 parts of ion
exchange water, 1 part of sodium dodecylbenzenesulfonate, 0.1 part
of t-dodecylmercaptan, 0.2 part of diisopropyl hydroperoxide, 30
parts of styrene and 10 parts of acrylonitrile were added
continuously over a period of 3 hours to carry out the
polymerization. After the end of the addition, the mixture was
further stirred for one hour, then 0.2 part of
2,2-methylene-bis-(4-ethylene-6-t-butylphenyl) was added, and the
reaction product was taken out from the flask. The produced latex
was coagulated with 2 parts of calcium chloride, washed well with
water and then dried at 75.degree. C. for 24 hours to obtain a
white powder. Polymerization conversion: 97.2%; graft ratio: 90%;
intrinsic viscosity: 0.47 dl/g.
[0100] Preparation of component (II) (II-1 to II-5)
[0101] To a 7-liter glass-made flask equipped with a stirrer, 300
parts of ion exchange water, 1.5 part of sodium oleate, 0.1 part of
t-dodecylmercaptan and a monomer shown in Table 2 were supplied and
heated with stirring. At a point when the temperature reached
45.degree. C., 0.8 part of potassium persulfate and 0.2 part of
acidic sodium sulfite were added and the reaction was continued for
3 hours. The reaction mixture was further stirred for one hour,
then 0.2 part of 2,2-methylene-bis-(4-ethylene-6-t-butylphenyl) was
added and the reaction product (latex) was taken out from the
flask. The produced latex was coagulated with 2 parts of sulfuric
acid, washed well with water and then dried at 75.degree. C. for 24
hours to obtain a white powder.
2TABLE 2 Thermoplastic resin II-1 II-2 II-3 II-4 II-5 Monomer
composition (parts) Styrene 88 83 80 73 50 Acrylonitrile 12 17 20
17 20 Methylmethacrylate -- -- -- 10 30 Polymerization conversion
(%) 97.2 97.8 97.7 97.5 97.8 Intrinsic viscosity [.eta.] (dl/g)
0.30 0.37 0.45 0.35 0.33
[0102] Preparation of component (III)
[0103] The following polycarbonate resins produced by Mitsubishi
Engineering-Plastics Corporation were used:
[0104] III-1: IUPIRON H2000
[0105] III-2: NOVAREX 7022PJ
[0106] Preparation of component (IV)
[0107] The following materials were used.
[0108] Phenol type
1:2[1-(2-hydroxy-3,5-di-t-pentylphenyl)-ethyl]-4,
6-di-t-pentylphenyl acrylate
[0109] Phenol type 2:4,4'-butylidene-bis(6-t-butyl-m-cresol)
[0110] Phosphorus type 1:tris(2,4-di-t-butylphenyl) phosphite
[0111] Phosphorus type 2: sodium dihydrogenphosphate
[0112] Sulfur type
1:pentaerythritol-tetrakis-(3-laurylthiopropionate)
[0113] Sulfur type 2:didodecyl 3,3'-thiobispropionate
[0114] Preparation of comparative materials for component (II) (C-1
to C-4)
[0115] To a 7-liter glass-made flask equipped with a stirrer, 300
parts of ion exchange water, 1.5 part of sodium oleate, 0.1 part of
t-dodecylmercaptan and a monomer shown in Table 3 were supplied and
heated with stirring. At a point when the temperature reached
45.degree. C., 0.8 part of potassium persulfate and 0.2 part of
acidic sodium sulfite were added and the reaction was continued for
3 hours. The reaction mixture was further stirred for one hour,
then 0.2 part of 2,2-methylene-bis-(4-ethylene-6-t-butyphenyl) was
added and the reaction product (latex) was taken out from the
flask. The produced latex was coagulated with 2 parts of sulfuric
acid, washed well with water and then dried at 75.degree. C. for 24
hours to obtain a white powder.
3TABLE 3 Comparative thermoplastic resin C-1 C2 C-3 C-4 Monomer
composition (parts) Styrene 75 95 83 83 Acrylonitrile 25 5 17 17
Polymerization conversion (%) 97.5 97.3 97.4 97.8 Intrinsic
viscosity [.eta.] (dl/g) 0.30 0.37 0.25 0.65
EXAMPLES 1 TO 22 AND COMPARATIVE EXAMPLES 1 TO 13
(Preparation of thermoplastic resin compositions)
[0116] The components (I) and (II) and the comparative polymers
were melted and kneaded by an extruder at the percentages shown in
Tables 4 to 8 and at 250.degree. C., and injection molded to make
the evaluation samples. Tables 4 to 6 show the results of the
Examples of the present invention, and Tables 7 and 8 show the
results of the Comparative Examples.
[0117] As is seen from the results shown in Tables 4 to 8, the
thermoplastic resin compositions according to the present invention
showed magnificent heat-aging properties and also had excellent
impact strength and fluidity. It is seen that by using a
thermoplastic resin (II) containing acrylonitrile in a specified
amount range, as explained in Examples 1 to 22, it is possible to
remarkably improve heat-aging properties without impairing the
other properties.
[0118] In contrast, the resin compositions of Comparative Examples
1 to 7, where the thermoplastic resin (II) of the present invention
was not used, are very poor in heat-aging properties. Particularly
in Comparative Example 5 where the acrylonitrile content in the
thermoplastic resin (II) was very small and in Comparative Example
6 where the intrinsic viscosity of the resin (II) was very low, the
produced resin compositions are low in Izod impact strength, too.
It is to be also noted that in Comparative Example 7 where the
intrinsic viscosity of the thermoplastic resin (II) was excessively
high, the obtained resin composition was low in fluidity.
[0119] Also, in the Comparative Examples where although the
thermoplastic resin (II) of the present invention was used the
contents of the resin (II) and the polycarbonate resin (III) were
outside the defined range of the present invention, the produced
resin compositions were poor in heat-aging properties, the product
of Comparative Example 8 being also poor in fluidity and the
products of Comparative Examples 9 and 10 being low in Izod impact
strength, too.
[0120] Further, in Comparative Examples 11 to 13 where it was
attempted to improve heat-aging properties only by the addition of
a heat-aging resistor, there was obtained almost no improving
effect, even if the aging resistor was added in large quantities,
which indicates that the attempts to improve heat-aging properties
by such means are inexpedient.
4TABLE 4 Example Example Example Example Example Example Example
Example Composition (parts) 1 2 3 4 5 6 7 8 Component (I): I-1 30
-- -- -- -- -- -- -- I-2 -- 30 -- -- 30 30 30 30 I-3 -- -- 30 -- --
-- -- -- I-4 -- -- -- 30 -- -- -- -- Component (II): II-1 -- -- --
-- 10 -- -- -- II-2 10 10 10 10 -- -- -- 10 II-3 -- -- -- -- -- 10
-- -- II-4 -- -- -- -- -- -- 10 -- Component (III): III-1 -- -- --
-- -- -- -- 60 III-2 60 60 60 60 60 60 60 -- Component (IV) -- --
-- -- -- -- -- -- Acrylonitrile content 6.2 9.2 6.2 6.2 8.7 9.5 9.2
9.2 in the composition (%) Properties Izod impact strength 60 55 45
48 52 55 48 47 (kgf.cm/cm) Fluidity (g/10 min) 45 42 37 40 43 42 39
55 Long-term heat-aging 60 86 82 84 65 58 58 85 characteristics
(%)
[0121]
5TABLE 5 Example Example Example Example Example Example Example
Composition (parts) 9 10 11 12 13 14 15 Component (I): I-1 -- -- --
-- -- 15 30 I-2 25 20 30 30 30 15 -- Component (II): II-1 -- -- --
-- -- -- -- II-2 5 30 10 10 10 10 10 Component (III): III-1 -- --
-- -- 30 -- -- III-2 70 50 60 60 30 60 60 Component (IV): Phenol
type 1 -- -- 0.1 -- -- -- 0.5 Phenol type 2 -- -- -- 0.1 -- -- --
Phosphorus type 1 -- -- 0.1 -- -- -- 0.5 Phosphorus type 2 -- -- --
0.1 -- -- -- Sulfur type 1 -- -- 0.1 -- -- -- 0.5 Sulfur type 2 --
-- -- 0.1 -- -- -- Acrylonitrile content 7.1 10.1 9.2 9.2 9.2 7.7
6.2 in the composition (%) Properties Izod impact strength 65 40 51
50 51 58 45 (kgf.cm/cm) Fluidity (g/10 min) 32 58 45 44 47 43 52
Long-term heat-aging 60 80 92 90 85 72 82 characteristics (%)
[0122]
6TABLE 6 Example Example Example Example Example Example Example
Composition (parts) 16 17 18 19 20 21 22 Component (I): I-1 -- --
-- -- 10 45 30 I-1-a 30 -- -- -- -- -- -- I-1-b -- 30 -- -- -- --
-- I-1-c 30 -- -- -- I-4-d -- -- -- 30 -- -- -- Component (II):
II-2 10 10 10 10 20 5 -- II-5 -- -- -- -- -- -- 10 Component (III):
III-1 -- -- -- -- -- -- -- III-2 60 60 60 60 70 50 60 Component
(IV) -- -- -- -- -- -- -- Acrylonitrile content 6.2 6.2 6.2 6.2 4.9
7.6 6.5 in the composition (%) Properties Izod impact strength 37
38 37 60 30 48 36 (kgf.cm/cm) Fluidity (g/10 min) 46 44 52 36 38 42
43 Long-term heat-aging 61 59 60 62 80 58 60 characteristics
(%)
[0123]
7TABLE 7 Comp. Comp. Comp. Comp. Comp. Comp. Comp. Composition
(parts) Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Example 7 Component (I): I-1 30 -- -- -- -- -- -- I-2 -- 30 -- --
30 30 30 I-3 -- -- 30 -- -- -- -- I-4 -- -- -- 30 -- -- --
Component (II): (Comparative component) C-1 10 10 10 10 -- -- --
C-2 -- -- -- -- 10 -- -- C-3 -- -- -- -- -- 10 -- C-4 -- -- -- --
-- -- 10 Component (III): III-1 -- -- -- -- -- -- -- III-2 60 60 60
60 60 60 60 Component (IV) -- -- -- -- -- -- -- Acrylonitrile
content 7.0 10.0 7.0 7.0 8.0 9.2 9.2 in the composition (%)
Properties Izod impact strength 51 45 37 41 15 21 40 (kgf.cm/cm)
Fluidity (g/10 min) 40 37 38 39 38 70 25 Long-term heat-aging 7 23
21 20 30 45 45 characteristics (%)
[0124]
8TABLE 8 Comp. Comp. Comp. Comp. Comp. Comp. Composition (parts)
Example 8 Example 9 Example 10 Example 11 Example 12 Example 13
Component (I): I-1 -- -- -- -- -- 30 I-2 37 10 40 30 30 --
Component (II): II-1 -- -- -- -- -- -- II-2 3 40 30 -- -- --
Comparative Component C-1 -- -- -- 10 10 10 Component (III): III-1
60 -- -- -- -- -- III-2 -- 50 30 60 60 60 Component (IV): Phenol
type 1 -- -- -- 0.1 1 1 Phenol type 2 -- -- -- -- -- -- Phosphorus
type 1 -- -- -- 0.1 1 1 Phosphorus type 2 -- -- -- -- -- -- Sulfur
type 1 -- -- -- 0.1 1 1 Sulfur type 2 -- -- -- -- -- --
Acrylonitrile content 9.8 9.3 15.1 10.0 10.0 7.0 in the composition
(%) Properties Izod impact strength 38 15 20 43 40 48 (kgf.cm/cm)
Fluidity (g/10 min) 26 65 72 38 45 46 Long-term heat-aging 23 45 28
24 24 8 characteristics (%)
* * * * *