Resin composition comprising unsaturated dicarboxylic acid anhydride polymer, polycarbonate resin and modified olefin polymer

A thermoplastic resin composition having excellent physical properties such as heat resistance and impact resistance and being improved in resistance to heat decomposition which comprises: PA0 (A) an unsaturated dicarboxylic acid anhydride polymer produced by polymerization of (a-1) at least one unsaturated dicarboxylic acid anhydride and (a-2) at least one of aromatic vinyl compounds, unsaturated nitrile compounds and unsaturated carboxylic acid esters in the presence or absence of (a-3) at least one rubbery material, PA0 (B) a polycarbonate resin, PA0 (C) a modified olefin polymer, and optionally PA0 (D) a rubber-reinforced resin produced by polymerizing (d-1) at least one of aromatic vinyl compounds, unsaturated nitrile compounds and unsaturated carboxylic acid esters in the presence of (d-2) a rubber polymer.

The present invention relates to a thermoplastic resin composition. More 
particularly, it relates to a thermoplastic resin composition comprising 
an unsaturated dicarboxylic acid anhydride polymer, a polycarbonate resin 
and a modified polyolefin and being excellent in physical properties such 
as resistance to heat decomposition, heat resistance, impact resistance 
and weld strength. 
As well known, copolymers of unsaturated dicarboxylic acid anhydrides such 
as maleic anhydride with aromatic vinyl compounds such as styrene are 
excellent in heat resistance but inferior in impact resistance. In order 
to overcome this defect, there have been made various proposals, which 
include, for instance, polymerization of maleic anhydride and styrene in 
the presence of a rubbery material (Japanese Patent Publication 
(unexamined) No. 42091/73), incorporation of a polycarbonate resin into a 
maleic anhydride/styrene copolymer (Japanese Patent Publication (examined) 
No. 27133/82), incorporation of a polycarbonate resin into a rubber 
modified maleic anhydride/styrene copolymer (Japanese Patent Publication 
(examined) Nos. 28339/78 and 27134/82 and U.S. Pat. No. 3,966,842), etc. 
However, polymers comprising units of maleic anhydride are apt to be 
decomposed due to heat during granulating or molding so that their impact 
resistance is deteriorated and also the impact resistsance improving 
effect by polycarbonate resins or rubbers introduced therein is lowered. 
Since the melt viscosity of polycarbonate resins is high, the compositions 
incorporated therewith require a high temperature, for their processing. 
Further, the allowable temperature range is small, and therefore the 
processing conditions for manufacture of high quality products are quite 
restricted. 
For suppression of the heat decomposition, the content of maleic anhydride 
may be decreased, but in such case, the heat resistance is lowered. In 
addition, the compatibility with polycarbonate resins is deteriorated, and 
even the impact resistance is reduced. When the rubber content is 
increased, the balance between heat resistance and processability becomes 
inferior. 
As a reult of the extensive study, it has now been found that a 
thermoplastic resin composition comprising an unsaturated dicarboxylic 
acid anhydride polymer, a polycarbonate resin and a modified olefin 
polymer as the essential components show excellent physical properties. It 
is particularly notable that such thermoplastic resin composition is 
highly resistant to heat decomposition while maintaining good heat 
resistance, high impact strength and excellent weld strength. 
The thermoplastic resin composition of the invention comprises: 
(A) an unsaturated dicarboxylic acid anhydride polymer produced by 
polymerization of (a-1) at least one unsaturated dicarboxylic acid 
anhydride and (a-2) at least one of aromatic vinyl compounds, unsaturated 
nitrile compounds and unsaturated carboxylic acid esters in the presence 
or absence of (a-3) at least one rubbery material, 
(B) a polycarbonate resin, 
(C) a modified olefin polymer, and optionally 
(D) a rubber-reinforced resin produced by polymerizing (d-1) at least one 
of aromatic vinyl compounds, unsaturated nitrile compounds and unsaturated 
carboxylic acid esters in the presence of (d-2) a rubbery polymer. 
The unsaturated dicarboxylic acid anhydride polymer (A) is a polymer 
obtainable by polymerization of (a-1) at least one unsaturated 
dicarboxylic acid anhydride and (a-2) at least one of aromaic vinyl 
compounds, unsaturated nitrile compounds and unsaturated carboxylic acid 
esters in the presence or absence of (a-3) a rubbery material. 
With respect to the weight proportion of the components (a-1), (a-2) and 
(a-3), any particular limitation is not present. For realization of high 
heat resistance and good processability, however, the content of the 
component (a-1) in the unsaturated dicarboxylic acid anhydride polymer (A) 
is preferred to be from 5 to 30% by weight. In case of the rubbery 
material as the component (a-3) being not used, the remainder is the 
component (a-2). In case of the rubbery material being used, the contents 
of the components (a-2) and (a-3) are preferred to be form 50 to 90% by 
weight and from 5 to 25% by weight, respectively. In usual, the 
unsaturated dicarboxylic dicarboxylic acid anhydride polymer (A) is 
preferred to have an intrinsic viscosity of about 0.3 to 1.5 (when 
determined on dimethylformamide solution at 30.degree. C.) in order to 
achieve high mechanical strength and good processability. 
Examples of the unsaturated dicarboxylic acid anhydride as the component 
(a-1) are maleic anhydride, itaconic anhydride, citraconic anhydride, 
aconitic anhydride, etc. These may be used solely or in combination. Among 
them, the use of maleic anhydride is favorable. 
As the aromatic vinyl compound which may be one of the component (a-2), 
there may be exemplified styrene, alpha-methylstyrene, p-methylstyrene, 
p-t-butylstyrene, dimethylstyrene, etc. Among them, the use of styrene 
and/or alpha-methylstyrene is preferred. Examples of the unsaturated 
nitrile compound are acrylonitrile, methacrylonitrile, maleonitrile, etc. 
Among them, the use of acrylonitrile is favored. Examples of the 
unsaturated carboxylic acid ester are alkyl acrylates (e.g. methyl 
acrylate, ethyl acrylate, butyl acrylate), alkyl methacrylates (e.g. 
methyl methacrylate, ethyl methacrylate, butyl methacrylate), hydroxyalkyl 
acrylates (e.g. hydroxethyl acrylate, hydroxypropyl acrylate), 
hydroxyalkyl methacrlates (e.g. hydroxethyl methacrylate, hydroxypropyl 
methacrylate), etc. Preferred are methyl methacrylate, ethyl methacrylate, 
etc. From these monomers, one or more may be chosen as the component 
(a-2), and the use of the aromatic vinyl compound alone or in combination 
with the other monomer(s), particularly the saturated nitrile compound, is 
favorable. 
As the rubbery material which is the component (a-3), there are exemplified 
polybutadiene, styrene/butadiene copolymer, acrylonitrile/butadiene 
copolymer, ethylene/propylene copoymer, ethylene/propylene/non-conjugated 
diene (e.g. dicyclopentadiene, ethylidenenorbornene, 1,4-cyclohexadiene, 
1,4-cycloheptadiene, 1,5-cyclooctadiene) copolymer, butyl methacrylate 
polymer, ethylene/vinyl acetate copolymer, chlorinated polyethylene, etc. 
These may be used solely or in combination. 
For preparation of the unsaturated dicarboxylic acid anhydride polymer (A), 
there may be adopted any conventional polymerization procedure such as 
emulsion polymerization, suspension polymerization, bulk polymerization, 
solution polymerization, emulsion-suspension polymerization and 
bulk-suspension polymerization, among which bulk polymerization, solution 
polymerization and bulk-suspension polymerization are preferred. 
One of the typical procedures for preparation of the unsaturated 
dicarboxylic acid anhydride polymer (A) comprises introducing, for 
instance, sytrene and maleic anhydride in the presence or absence of 
finely cut polybutadiene rubber into a reactor, adding a polymerization 
initiator and a chain transfer agent thereto respectively in amounts of 
0.001 to 5 parts by weight and of 0.01 to 1.0 part by weight to 100 parts 
of the monomers and subjecting the resultant mixture to bulk 
polymerization at a temperature of 50.degree. to 250.degree. C. The 
reaction mixture is poured in a great amount of methanol to deposit the 
produced polymer, which is then collected. 
Another typical procedure comprises introducing, for instance, styrene and 
maleic anhydride in the presence or absence of finely cut polybutadiene 
rubber into a reactor, adding a polymerization initiator and a chain 
transfer agent thereto respectively in amounts of 0.001 to 5 parts by 
weight and of 0.01 to 1.0 part by weight to 100 parts of the monomers and 
subjecting the resultant mixture to bulk polymerization at a temperature 
of 50.degree. to 250.degree. C. until the coversion reaches to 5-60%. To 
the reaction mixture, a suspending agent is added, and a polymerization 
initiator is added thereto in an amount of 0.01 to 1 part by weight to 100 
parts by weight of the monomers. The resulting mixture is subjected to 
suspension polymerization at a temperature of 50.degree. to 150.degree. C. 
From the reacton mixture, the produced polymer is recovered by 
dehydration. 
As the polymerization initiator, there may be used any one chosen from azo 
compounds (e.g. 2,2'-azobisisobutyronitrile), organic peroxides (e.g. 
t-butyl peroxypivalate lauroyl peroxide, 3,5,5-trimethylhexanoyl peroxide, 
benzoyl peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxylaurate, 
t-butyl peroxybenzoate, dicumyl peroxide, di-t-butyl peroxide), etc. 
Examples of the chain transfer agent are alkylmercaptan, thioglycolic 
esters, terpinolene, isotetralin, etc. As the suspending agent, there may 
be exemplified inorganic compounds hardly soluble in water (e.g. magnesium 
hydroxide, calcium phosphate, hydroxy apatite), water-soluble high 
molecular compounds (e.g. partially saponified polyvinyl alcohol, sodium 
polyacrylate, polyalkylene oxide, methyl cellulose, ethyl cellulose, 
hydroxypropyl methyl cellulose), etc. 
As the polycarbonate resin (B), there are exemplified aromatic 
polycarbonates, aliphatic polycarbonates, aliphatic-aromatic 
polycarbonates, etc., among which aromatic polycarbonates are particularly 
favorable. In usual, polymers and copolymers of bisphenols such as 
2,2-bis(4-hydroxphenyl)alkanes, bis(4-hydroxyphenyl)ethers, 
bis(4-hydroxyphenyl)sulfones, bis(4-hydroxyphenyl)sulfides and 
bis(4-hydroxyphenyl)sulfoxides, etc. and/or halogenated bisphenols may be 
employed. Typical examples of the polycarbonate resin and their production 
are described in various textbooks and literatures including Encyclopedia 
of Polymer Science and Technology, Vol. 10, pages 710 to 764 (1969). While 
any particular limitation is present on the molecular weight of the 
polycarbonate resin (B), it is usually of not less than about 10,000, 
preferably from about 20,000 to 40,000. 
The modified olefin polymer (C) may be the one chosen from (C-I) an 
olefin/alkyl unsaturated carboxylate copolymer, (C-II) an unsaturated 
carboxylic acid-modified olefin polymer and (C-III) an epoxy 
group-containing olefin polymer. 
The olefin/alkyl unsaturated carboxylate copolymer (C-I) may be the one 
obtainable by polymerization of at least one olefin and at least one alkyl 
unsaturated carboxylate with or without at least one other polymerizable 
monomer. The weight percentages of the olefin units, the alkyl unsaturated 
carboxylate units and the other polymerizable monomer units are preferred 
respectively to be from about 30 to 95%, from about 5 to 70% and from 
about 0 to 20%. 
Examples of the olefin are ethylene, propylene, butene-1, 
4-methylpentene-1, etc. Among them, ethylene and propylene are preferred. 
Examples of the alkyl unsaturated carboxylate are alkyl acrylates (e.g. 
methyl acrylate, ethyl acrylate, butyl acrylate), alkyl methacrylates 
(e.g. methyl methacrylate, elthyl methacrylate, butyl methacrylate), 
hydroxyalkyl acrylates (e.g. hydroxyethyl acrylate, hydroxypropyl 
acrylate), hydroxyalkyl methacrylates (e.g. hydroxyethyl methacrylate, 
hydroxypropyl methacrylate), etc. As the other polymerizable monomer, 
there are exemplified ethylenically unsaturated monomers such as vinyl 
saturated carboxylates wherein the saturated carboxylate moiety has 2 to 6 
carbon atoms, vinyl halides, vinyl ethers, N-vinyl-lactams and 
carbonamides. 
Preparation of the olefin-alkyl unsaturated carboxylate polymer (C-I) may 
be accomplished by a per se conventional polymerization procedure. 
For instance, an olefin and an alkyl unsaturated carboxylate with or 
without any other polymerizable monomer are charged into a reactor, an 
organic peroxide is added thereto, and polymerization is effected at a 
temperature of 40.degree. to 300.degree. C. under a pressure of 50 to 
4,000 atm. 
The unsaturated carboxylic acid-modified olefin polymer (C-II) is a polymer 
comprising units of at least one of unsaturated carboxylic acids and their 
anhydrides and units of at least one of olefins with or without units of 
at least one of other polymerizable monomers. The weight percentages of 
the units of unsaturated carboxylic acids and/or their anhydrides, the 
units of olefins and and the units of other polymerizable monoers are 
respectively preferred to be from about 0.01 to 40%, from about 10 to 
99.99% and from about 0 to 50%. 
Examples of the unsaturated carboxylic acids and their anhydrides are 
monocarboxylic acids (e.g. acrylic acid, methacrylic acid), dicarboxylic 
acids (e.g. maleic acid, fumaric acid, itaconic acid), dicarboxylic acid 
anhydrides (e.g. maleic anhydride, itaconic anhydride), etc. Among them, 
the use of dicarboxylic acid anhydrides is favorable. Examples of the 
olefins are ethylene, propylene, butene-1, 4-methylpentene-1-etc., among 
which ethylene and propylene are preferred. As the other polymerizable 
monomer, there are exemplified ethylenically unsaturated monomers such as 
vinyl saturated carboxylates wherein the saturated carboxylate moiety has 
2 to 6 carbon atoms, alkyl acrylates or methacrylates wherein the alkyl 
moiety has 1 to 8 carbon atoms, alkyl maleates wherein the alkyl moiety 
has 1 to 8 carbon atoms, vinyl halides, vinyl ethers, N-vinyl-lactams and 
carbonamides. 
Preparation of the unsaturated carboxylic acid-modified olefin polymer 
(C-II) may be accomplished, for instance, by reacting a polymer comprising 
units of at least one olefin and optionally units of at least one other 
polymerizable monomer with an unsaturated carboxylic acid or its anhydride 
while heating. 
Like the olefin-alkyl unsaturated carboxylate polymer (C-I), the 
unsaturated carboxylic acid-modified olefin polymer (C-II) can be 
efficiently produced by polymerization under elevated pressure. 
Alternatively, it may be produced by melt-kneading polyolefin with an 
unsaturated carboxylic acid anhydride in the presence of a polymerization 
initiator. 
The epoxy group-containing olefin polymer (C-III) is a copolymer of at 
least one of unsaturated epoxy compounds and at least one of olefins with 
or without at least one of other polymerizable monomers. While no special 
limitation is present on the composition of these monomers, the content of 
the unsaturated epoxy compound units is preferred to be from about 0.05 to 
95% by weight, particularly from about 0.1 to 50% by weight. 
As the unsaturated epoxy compound, there may be used the one having an 
unsaturated group, copolymerizable with an olefin and any other 
polymerizable monomer, and an epoxy group in the molecule. For instance, 
unsaturated glycidyl esters, unsaturated glycidyl ethers, epoxyalkenes, 
p-glycidylstyrenes, etc. are usable. Those of the following formulas are 
also usable: 
##STR1## 
wherein R is a C.sub.2 -C.sub.18 hydrocarbon group having an ethylenic 
unsaturation, R' is a hydrogen atom or a methyl group and X is 
##STR2## 
More specifically, the following compounds are exemplified: glycidyl 
acrylate, glycidyl methacrylate, glycidyl itaconate, butenecarboxylates, 
allyl glycidyl ether, 2-methylallyl glycidyl ether, styrene-p-glycidyl 
ether, 3,4-epoxybutene, 3,4-epoxy-3-methyl-1-butene, 3,4-epoxy-1-pentane, 
3,4-epoxy-3-methylpentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide, 
p-glycidylstyrene, etc. Among them, preferred are glycidyl acrylate and 
glycidyl methacrylate. Examples of the olefin are ethylene, propylene, 
butene-1, 4-methylpentene-1, etc. As the other polymerizable monomer, 
there are exemplified ethylenically unsaturated compounds such as vinyl 
esters having a C.sub.2 -C.sub.6 saturated carboxylic acid moiety, acrylic 
and methacrylic esters having a C.sub.1 -C.sub.8 saturated alcohol moiety, 
maleic esters having a C.sub.1 -C.sub.8 saturated alcohol moiety, vinyl 
halides, vinyl ethers, N-vinyllactams, carbonamides, etc. These 
ethylenically unsaturated compounds may be copolymerized with the 
unsaturated epoxy compound and the olefin in an amount of not more than 
about 50% by weight, especially from about 0.1 to 45% by weight based on 
the total weight of the monomers to be copolymerized. 
The epoxy group-containing olefin polymer (c-3) may be prepared by various 
procedures, of which one typical example comprises contacting the 
unsaturated epoxy compound(s) and the olefin(s) with or without the other 
polymerizable monomer(s) onto a radical generating agent (e.g. benzoyl 
peroxide) at a temperature of about 40.degree. to 300.degree. C. under a 
pressure of about 50 to 4000 atm. Another typical example comprises 
irradiating gamma-rays to a mixture of polyolefin with the unsaturated 
epoxy compound(s), for instance, at a critical temperature of 9.9.degree. 
C. under a critical pressure of 50.7 atm. 
Among the components (c-1), (c-2) and (c-3), one or more may be chosen and 
used. Preferred is the use of the component (c-3), i.e. the epoxy 
group-containing olefin polymer, or its combination with the components 
(c-1) and/or (c-2). 
The rubber-reinforced resin (D) is a resin obtained by polymerization of 
(d-1) at least one of aromatic vinyl compounds, unsaturated nitrile 
compounds and unsaturated carboxylic acid esters in the presence of (d-2) 
a rubbery polymer. 
Examples of the aromatic vinyl compounds, the unsaturated nitrile compounds 
and the unsaturated carboxylic acid esters may be those as explained on 
the component (a-1). Also, examples of the rubbery polymer may be those as 
exemplified on the component (a-3). One or more chosen from the materials 
under the category of the component (d-1) may be polymerized in the 
presence of one or more chosen from the materials under the categroy of 
the component (d-2). Taking enhancement of the impact strength and the 
processability into consideration, the use of aromatic vinyl compounds 
with unsaturated nitrile compounds and/or unsaturated carboxylic acid 
esters as the component (d-1) is favorable. In this case, the other 
monomer may be used additionally. 
No particular limitation is present on the proportion of the components 
(d-1) and (d-2). In general, the weight proportion of the components (d-1) 
and (d-2) is preferred to be from about 95:5 to 20:80 for higher impact 
resistance and better processability. 
Production of the rubber-reinforced resin (D) may be accomplished by any 
conventional polymerization procedure such as emulsion polymerization, 
suspension polymerization, bulk polymerization, solution polymerization, 
emulsion-suspension polymerization or bulk-suspension polymerization. 
In the thermoplastic resin composition of the invention, the weight 
proportion of the unsaturated dicarboxylic acid anhydride polymer (A), the 
polycarbonate resin (B), the modified olefin polymer (C) and optionally 
the rubber-reinforced resin (D) may be appropriately decided depending 
upon the desired physical characteristics. In general, the weight 
proportion of the unsaturated dicarboxylic acid anhydride polymer (A) and 
the polycarbonate resin (B) may be usually from about 10:90 to 90:10. When 
the rubber-reinforced resin (D) is employed, the weight proportion of the 
unsaturated dicarboxylic acid anhydride polymer (A), the polycarbonate 
resin (B) and the rubber-reinforced resin (D) may be about 
5-60:30-90:5-50. In the case wherein the unsaturated dicarboxylic acid 
anhydride polymer (A) comprises the rubbery material, the weight 
proportion of (A), (B) and (D) is preferred to be 5-50:30-90:5-50. In the 
case wherein the unsaturated dicarboxylic acid anhydride polymer (A) does 
not comprise the rubbery material, the weight proportion of (A), (B) and 
(D) is favorable to be about 10-60:30:-80:10-50. The modified olefin 
polymer (C) may be used normally in an amount of about 0.1 to 100 parts by 
weight to 100 parts by weight of the combined amount of the unsaturated 
dicarboxlyic acid anhydride polymer (A), the polycarbonate resin (B) and, 
when used, the rubber reinforced resin (D). 
For preparation of the thermoplastic resin composition of the invention, 
the unsaturated dicarboxylic acid anhydride polymer (A), the polycarbonate 
resin (B), the modified olefin polymer (C) and optionally the rubber 
reinforced resin (D) may be mixed together by the use of any conventional 
mixing apparatus such as a Banbury mixer, a single screw extruder or a 
twin screw extruder. If desired, any conventional additive(s) such as 
dyestuffs, pigments, antioxidants, plasticizers, antistatic agents, 
ultraviolet ray absorbers, flame retardant agents, lubricants, metallic 
fibers, glass fibers and inorganic fillers may be incorporated into the 
thermoplastic resin composition.

Practical and presently preferred embodiments of the invention are 
illustratively shown in the following Examples wherein % and part(s) are 
by weight unless otherwise indicated. 
REFERENCE EXAMPLE 1 
Preparation of the unsaturated dicarboxylic acid anhydride polymer (A): 
According to a per se conventional bulk or bulk-suspension polymerization 
procedure, monomers as shown in Table 1 were polymerized to make the 
unsaturated dicarboxylic acid anhydride polymer (A). 
TABLE 1 
______________________________________ 
Unsaturated dicarboxylic acid 
anhydride polymer (A) (Parts(s)) 
Components A-1 A-2 
______________________________________ 
Maleic anhydride 
13 13 
Styrene 87 62 
Acrylonitrile -- 25 
Product (Intrinsic 
0.58 0.63 
viscosity) 
Polymerization B B-S 
procedure* 
______________________________________ 
Note: * 
B The polymerization was carried out by bulk polymerization. 
BS The polymerization was carried out by bulksuspension polymerization. 
REFERENCE EXAMPLE 2 
Preparation of the modified olefin polymer (C): 
(C-1) Ethylene and glycidyl methacrylate as well as a catalyst were charged 
into an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-1), i.e. ethylene/glycidyl methacrylate (90:10 by 
weight) copolymer. 
(C-2) Ethylene, glycidyl methacrylate and vinyl acetate as well as a 
catalyst were charged into an autoclave type apparatus for production of 
polyethylene, and bulk polymerization was carried out at a temperature of 
150.degree. to 300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to 
make a modified olefin polymer (C-2), i.e., ethylene/glycidyl 
methacrylate/vinyl acetate (85:10:5 by weight) copolymer. 
(C-3) Powdery polyethylene (100 parts) and maleic anhydride (1 part) were 
mixed together and melt kneaded by the aid of two rolls for about 3 
minutes to make a modified olefin polymer (C-3), i.e. maleic 
anhydride-modified polyethylene containing maleic anhydride in an amount 
of 1% by weight. 
(C-4) Ethylene and methyl methacrylate as well as a catalyst were charged 
into an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-4), i.e. ethylene/methyl methacrylate (90:10 by weight) 
copolymer. 
EXAMPLES 1 TO 9 AND COMATIVE EXAMPLES 1 TO 4 
THe unsaturated dicarboxylic acid anhydride polymer (A-1 or A-2) as 
obtained in Reference Example 1, the polycarbonate resin (an aromatic 
polycarbonate resin comprising bisphenol A; molecular weight, 25,000) and 
the modified olefin polymer (C-1, C-2, C-3 or C-4) as obtained in 
Reference Example 2 were mixed well and melt kneaded by the aid of a 
single screw extruder (resin temperature, 260.degree. C.) to make a 
thermoplastic resin composition. 
The thermoplastic resin composition thus obtained was subjected to 
determination of the physical characteristics by the following procedures: 
Resistance to heat decomposition: 
(1) Falling ball impact strength after retention 
The thermoplastic resin composition was retained in the cylinder of an 
injection molding machine (resin temperature, 270.degree. C.) for 15 
minutes and then subjected to injection molding with a molding cycle of 10 
seconds in injection time and 20 seconds in cooling time to make a plate 
of 60 mm long, 60 mm wide and 3 mm high. Thereafter, retention was further 
continued for 15 minutes, and then a plate was prepared in the same manner 
as above. Likewise, there were prepared 10 plates, which were subjected to 
test for falling ball impact strength using a steel ball of 1 kg at 
23.degree. C. 
(2) Weight loss 
The thermoplastic resin composition was retained at a resin temperature of 
280.degree. C. for 15 minutes, and the weight loss was measured by the use 
of DSC-II manufactured by Perkin-Elmer. 
(3) Silver 
By the use of an injection molding machine (resin temperature, 270.degree. 
C.), 10 plates (each being 90 mm long, 150 mm wide and 3 mm high) were 
continuously manufactured with the thermoplastic resin under the molding 
cycle of 10 seconds in injection time and 230 seconds in cooling time. 
Observation was made on the presence or absence of silver streak. 
Weld strength: 
The thermoplastic resin composition in a melt state was injected through 
two gates (each being 2.5.times.2.0 mm) with a distance of 40 mm to make a 
test piece of 60 mm long, 60 mm wide and 3 mm high. The test piece was 
placed on cylinder of 50 mm in inner diameter, 56 mm in outer diameter and 
60 mm in height. An anvil having a point of impact (1/4 inch R) was placed 
thereon. A steel ball was fallen down onto the anvil to measure the 
maximum energy value at which the test piece was not broken. 
Notched Izod impact strength: 
According to ASTM D-256, the strength was measured on the test piece of 1/4 
inch in thickness. 
Heat deformation temperature: 
According to ASTM D-648, the temperature was measure on the test piece of 
1/4 inch in thickness. 
Processability: 
Using a Koka flow tester (nozzle diameter, 1 mm; length, 10 mm), the flow 
amount was measured at a temperature of 230.degree. C. under a pressure of 
60 kg/cm.sup.2. 
The physical characteristics of the thermoplastic resin composition thus 
determined are shown in Table 2. 
TABLE 2 
__________________________________________________________________________ 
(part(s) by weight) 
Example Comparative 
Composition 1 2 3 4 5 6 7 8 9 1 2 3 4 
__________________________________________________________________________ 
Unsaturated di- 
carboxylic acid an- 
hydride polymer (A) 
A-1 80 -- 50 50 50 -- -- -- 30 80 80 50 -- 
A-2 -- 60 -- -- -- 40 40 40 -- -- -- -- 40 
Polycarbonate resin (B) 
20 40 50 50 50 60 60 60 70 20 20 50 60 
Modified olefin polymer 
(C) 
C-1 5 -- 1 -- 10 3 -- 20 -- -- -- -- -- 
C-2 -- 0.5 
-- -- -- -- -- -- 3 -- -- -- -- 
C-3 -- -- -- 1 -- -- -- -- -- -- -- -- -- 
C-4 -- -- -- -- -- -- 3 -- -- -- -- -- -- 
Polyethylene 
-- -- -- -- -- -- -- -- -- -- 5 -- -- 
Resistance to heat 
decomposition 
Falling ball impact 
70 90 100 
80 150 
140 
120 
170 
150 
&lt;10 &lt;10 &lt;10 &lt;10 
strength (kg .multidot. cm) 
Weight loss (%) 
2.9 
2.2 
1.6 
1.5 
0.8 
0.8 
0.7 
0.6 
0.8 
10.5 
7.7 8.9 5.7 
Silver No No No No No No No No No Yes Yes Yes Yes 
Weld strength 
23.degree. C. (kg .multidot. cm) 
40 45 70 50 100 
100 
85 150 
130 
&lt;10 &lt;10 &lt;10 &lt;10 
-30.degree. C. (kg .multidot. cm) 
20 20 35 20 45 45 30 70 55 &lt;10 &lt;10 &lt;10 &lt;10 
Notched Izod impact 
3.5 
7.5 
11.0 
10.5 
15.5 
13.3 
12.5 
18.9 
25.1 
1.0 1.0 2.4 7.2 
strength (23.degree. C.) 
(kg .multidot. cm/cm) 
Heat deformation 
110 
113 
114 
114 
111 
118 
117 
113 
122 
111 107 115 120 
temperature 
(.degree.C.) 
Processability 
1.1 
0.93 
0.88 
0.88 
0.55 
0.50 
0.51 
0.30 
0.25 
1.3 1.5 0.97 
0.78 
(230.degree. C. 60 kg/cm.sup.2) 
(ml/min) 
__________________________________________________________________________ 
When the thermoplastic composition comprises the polycarbonate resin (B) 
alone, the following physical characteristics were given: weld strength at 
23.degree. C. and at -30.degree. C., more than 500 kg.cm; notched Izod 
impact strength at 23.degree. C., 14.1 kg.cm/cm; heat deformation 
temperature, 135.degree. C.; processability at 230.degree. C. under 60 
kg/cm.sup.2, 0.01 ml/min. 
From the above results, it is understood that the polycarbonate resin is 
excellent in heat resistance and weld strength. However, it is remarkably 
inferior in processability. With increase of the amount of the unsaturated 
dicarboxylic acid anhydride polymer incorporated into the polycarbonate 
resin, the processability is improved but the notched Izod impact strength 
and the heat deformation temperature are lowered. Particularly, the weld 
strength is markedly decreased with incorporation of the unsaturated 
dicarboxylic acid andhyride polymer irrespective of its amount. 
The composition of the invention is markedly enhanced in weld strength, 
notched Izod impact strength and resistance to heat decomposition in 
comparison with the polycarbonate resin incorporated with the unsaturated 
dicarboxylic acid anhydride polymer. Further, the impact strength, the 
heat resistance and the processability are well balanced. 
REFERENCE EXAMPLE 3 
Preparation of the unsaturated dicarboxylic acid anhydride polymer (A): 
According to a per se conventional bulk or bulk-suspension polymerization 
procedure, monomers as shown in Table 3 were polymerized to make the 
unsaturated dicarboxylic acid anhydride polymer (A). 
TABLE 3 
______________________________________ 
Unsaturated dicarboxylic acid 
anhydride polymer (A) (Parts(s)) 
Components A-3 A-4 
______________________________________ 
Maleic anhydride 
15 15 
Styrene 70 60 
Acrylonitrile -- 15 
Polybutadiene rubber 
15 10 
Polymerization B-S B 
procedure* 
______________________________________ 
Note: * 
B The polymerization was carried out by bulk polymerization. 
BS The polymerization was carried out by bulksuspension polymerization. 
REFERENCE EXAMPLE 4 
Preparation of the modified olefin polymer (C): 
(C-5) Ethylene and glycidyl methacrylate as well as a catalyst were charged 
into an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-1), i.e. ethylene/glycidyl methacrylate (90:10 by 
weight) copolymer. 
(C-6) Ethylene, glycidyl methacrylate and vinyl acetate as well as a 
catalyst were charged into an autoclave type apparatus for production of 
polyethylene, and bulk polymerization was carried out at a temperature of 
150.degree. to 300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to 
make a modified olefin polymer (C-6), i.e. ethylene/glycidyl 
methacrylate/vinyl acetate (85:10:5 by weight) copolymer. 
(C-7) Powdery polyethylene (100 parts) and maleic anhydride (1 part) were 
mixed together and melt kneaded by the aid of two rolls for about 3 
minutes to make a modified olefin polymer (C-7), i.e. maleic 
anhydride-modified polyethylene containing maleic anhydride in an amount 
of 1% by weight. 
(C-8) Ethylene and ethyl acrylate as well as a catalyst were charged into 
an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-8), i.e. ethylene/ethyl acrylate (90:10 by weight) 
copolymer. 
EXAMPLES 10 TO 18 AND COMATIVE EXAMPLES 5 TO 7 
The unsaturated dicarboxylic acid anhydride polymer (A-3 or A-4) as 
obtained in Reference Example 3, the polycarbonate resin (an aromatic 
polycarbonate resin comprising bisphenol A; molecular weight, 25,000) and 
the modified olefin polymer (C-5, C-6, C-7 or C-8) as obtained in 
Reference Example 4 were mixed well and melt kneaded by the aid of a 
single screw extruder (resin temperature, 260.degree. C.) to make a 
thermoplastic resin composition. 
The thermoplastic resin composition thus obtained was subjected to 
determination of the physical characteristics in the same manner as above. 
The physical characteristics of the thermoplastic resin composition thus 
determined are shown in Table 4. 
TABLE 4 
__________________________________________________________________________ 
(part(s) by weight) 
Example Comparative 
Composition 10 11 12 13 14 15 16 17 18 5 6 7 
__________________________________________________________________________ 
Unsaturated di- 
carboxylic acid an- 
hydride polymer (A) 
A-3 70 50 50 50 -- -- 30 30 15 70 50 15 
A-4 -- -- -- -- 50 30 -- -- -- -- -- -- 
Polycarbonate resin (B) 
30 50 50 50 50 70 70 70 85 30 50 85 
Modified olefin polymer 
(C) 
C-5 3 5 -- -- -- -- -- -- 1 -- -- -- 
C-6 -- -- 10 -- -- 0.5 
-- 20 -- -- -- -- 
C-7 -- -- -- 5 -- -- 1 -- -- -- -- -- 
C-8 -- -- -- -- 10 -- -- -- -- -- -- -- 
Resistance to heat 
decomposition 
Falling ball impact 
150 
175 
225 
200 
150 
250 
300 
350 
325 
&lt;10 &lt;10 20 
strength (kg .multidot. cm) 
Weight loss (%) 
2.1 
1.2 
0.4 
1.0 
1.1 
1.7 
1.0 
0.5 
0.9 
10.4 
7.7 2.5 
Silver No No No No No No No No No Yes Yes Yes 
Weld strength (23.degree. C.) 
70 115 
115 
110 
115 
200 
215 
315 
235 
&lt;10 &lt;10 &lt;10 
(kg .multidot. cm) 
Notched Izod impact 
25 43 48 43 48 55 50 43 27 8 35 25 
strength (23.degree. C.) 
(kg .multidot. cm/cm) 
Heat deformation 
110 
113 
111 
113 
111 
120 
120 
115 
125 
111 115 127 
temperature 
(.degree.C.) 
Processability 
0.81 
0.33 
0.30 
0.33 
0.35 
0.24 
0.23 
0.16 
0.10 
0.85 
0.37 
0.11 
(230.degree. C. 60 kg/cm.sup.2) 
(ml/min) 
__________________________________________________________________________ 
From the above results, it is understood that in comparison with the 
polycarbonate resin incorporated with the unsaturated dicarboxylic acid 
anhydride polymer, the thermoplastic resin composition of the invention is 
excellent in resistance to heat decomposition. The composition of the 
invention is also excellent in notched Izod impact strength and strength 
at weld part. 
REFERENCE EXAMPLE 5 
Preparation of the unsaturated dicarboxylic acid anhydride polymer (A): 
According to a per se conventional bulk or bulk-suspension polymerization 
procedure, monomers as shown in Table 5 were polymerized to make the 
unsaturated dicarboxylic acid anhydride polymer (A). 
TABLE 5 
______________________________________ 
Unsaturated dicarboxylic acid 
anhydride polymer (A) (Parts(s)) 
Components A-5 A-6 
______________________________________ 
Maleic anhydride 
15 13 
Styrene 85 62 
Acrylonitrile -- 25 
Product (Intrinsic 
0.63 0.65 
viscosity) 
Polymerization B B-S 
procedure* 
______________________________________ 
Note: * 
B The polymerization was carried out by bulk polymerization. 
BS The polymerization was carried out by bulksuspension polymerization. 
REFERENCE EXAMPLE 6 
Preparation of the modified olefin polymer (C): 
(C-9) Ethylene and glycidyl methacrylate as well as a catalyst were charged 
into an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-9), i.e. ethylene/glycidyl methacrylate (90:10 by 
weight) copolymer. 
(C-10) Ethylene, glycidyl methacrylate and vinyl acetate as well as a 
catalyst were charged into an autoclave type apparatus for production of 
polyethylene, and bulk polymerization was carried out at a temperature of 
150.degree. to 300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to 
make a modified olefin polymer (C-10), i.e. ethylene/glycidyl 
methacrylate/vinyl acetate (85:10:5 by weight) copolymer. 
(C-11) Powdery polyethylene (100 parts) and maleic anhydride (1 part) were 
mixed together and melt kneaded by the aid of two rolls for about 3 
minutes to make a modified olefin polymer (C-11), i.e. maleic 
anhydride-modified polyethylene containing maleic anhydride in an amount 
of 1% by weight. 
(C-12) Ethylene and ethyl acrylate as well as a catalyst were charged into 
an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-12), i.e. ethylene/ethyl acrylate (90:10 by weight) 
copolymer. 
REFERENCE EXAMPLE 7 
Preparation of the rubber-reinforced resin (D): 
(D-1) Styrene and acrylonitrile were graft polymerized on styrene-butadiene 
rubber latex (styrene content, 10% by weight; solid content, 50% by 
weight; particle size, 0.41 micron) according to a conventional emulsion 
graft polymerization procedure to give a rubber-reinforced resin (D) 
having a rubber content of 50% by weight and an acrylonitrile content of 
15% by weight. 
(D-2) Styrene and methyl methacrylate were graft polymerized on 
polybutadiene rubber latex (solid content, 50% by weight; particle size, 
0.35 micron) according to a conventional emulsion graft polymerization 
procedure to give a rubber-reinforced resin (D) having a rubber content of 
50% by weight and a methyl methacrylate content of 30% by weight. 
EXAMPLES 19 TO 28 AND COMATIVE EXAMPLES 8 TO 11 
The unsaturated dicarboxylic acid anhydride polymer (A-5 or A-6) as 
obtained in Reference Example 5, the polycarbonate resin (an aromatic 
polycarbonate resin comprising bisphenol A; molecular weight, 25,000) and 
the modified olefin polymer (C-9, C-10, C-11 or C-12) as obtained in 
Reference Example 6 and the rubber-reinforced resin (D-1 or D-2) as 
obtained in Reference Example 7 were mixed well and melt kneaded by the 
aid of a single screw extruder (resin temperature, 260.degree. C.) to make 
a thermoplastic resin composition. 
The thermoplastic resin composition thus obtained was subjected to 
determination of the physical characteristics in the same manner as above. 
The physical characteristics of the thermoplastic resin composition thus 
determined are shown in Table 6. 
TABLE 6 
__________________________________________________________________________ 
(part(s) by weight) 
Example Comparative 
Composition 19 20 21 22 23 24 25 26 27 28 8 9 10 11 
__________________________________________________________________________ 
Unsaturated di- 
carboxylic acid an- 
hydride polymer (A) 
A-5 30 30 30 40 -- 20 -- 20 15 10 50 30 30 20 
A-6 -- -- -- -- 40 -- 20 -- -- 15 -- -- -- -- 
Polycarbonate resin (B) 
50 50 50 50 50 70 70 70 70 70 50 50 70 70 
Modified olefin polymer 
(C) 
C-9 1 -- -- 15 -- -- -- -- 5 -- -- -- -- -- 
C-10 -- 5 -- -- 10 -- 20 -- -- 5 -- -- -- -- 
C-11 -- -- 5 -- -- 10 -- -- -- -- -- -- -- -- 
C-12 -- -- -- -- -- -- -- 5 -- -- -- -- -- -- 
Rubber-reinforced 
resin (D) 
D-1 20 20 20 10 -- -- 10 -- 15 -- -- 20 -- 10 
D-2 -- -- -- -- 10 10 -- 10 -- 5 -- -- -- -- 
Resistance to heat 
decomposition 
Falling ball impact 
150 
200 
225 
250 
175 
300 
275 
275 
325 
250 
&lt;10 20 &lt;10 15 
strength (kg .multidot. cm) 
Weight loss (%) 
1.2 
0.9 
0.7 
0.6 
1.0 
1.1 
0.7 
1.0 
0.4 
0.8 
8.9 7.5 6.4 6.1 
Silver No No No No No No No No No No Yes Yes Yes Yes 
Weld strength (23.degree. C.) 
100 
140 
130 
180 
155 
120 
118 
120 
120 
120 
&lt;10 &lt;10 &lt;10 &lt;10 
(kg .multidot. cm) 
Notched Izod impact 
36.8 
35.2 
33.1 
28.3 
28.5 
48.3 
43.5 
45.1 
55.2 
50.7 
2.4 37.0 
7.8 5.3 
strength (23.degree. C.) 
(kg .multidot. cm/cm) 
Heat deformation 
116 
113 
113 
112 
114 
120 
118 
120 
120 
122 
115 116 125 121 
temperature 
(.degree.C.) 
Processability 
0.38 
0.38 
9.38 
0.31 
0.33 
0.19 
0.18 
0.20 
0.25 
0.28 
0.97 
0.40 
0.38 
0.25 
(230.degree. C. 60 kg/cm.sup.2) 
(ml/min) 
__________________________________________________________________________ 
From the above results, it is understood that in comparison with the 
polycarbonate resin incorporated with the unsaturated dicarboxylic acid 
anhydride polymer and the polycarbonate resin incorporated with the 
unsaturated dicarboxylic acid anhydride polymer and the rubber-reinforced 
resin, the thermoplastic resin composition of the invention is excellent 
in resistance to heat decomposition. The composition of the invention is 
also excellent in notched Izod impact strength and strength at weld part. 
Further, it is well balanced in the relationship of processability, impact 
strength and heat resistance. 
REFERENCE EXAMPLE 8 
Preparation of the unsaturated dicarboxylic acid anhydride polymer (A): 
According to a per se conventional bulk or bulk-suspension polymerization 
procedure, monomers as shown in Table 7 were polymerized to make the 
unsaturated dicarboxylic acid anhydride polymer (A). 
TABLE 7 
______________________________________ 
Unsaturated dicarboxylic acid 
anhydride polymer (A) (Parts(s)) 
Components A-7 A-8 
______________________________________ 
Maleic anhydride 
15 15 
Styrene 70 60 
Acrylonitrile -- 15 
Polybutadiene rubber 
15 10 
Polymerization B-S B 
procedure* 
______________________________________ 
Note: * 
B The polymerization was carried out by bulk polymerization. 
BS The polymerization was carried out by bulksuspension polymerization. 
REFERENCE EXAMPLE 9 
Preparation of the modified olefin polymer (C): 
(C-13) Ethylene and glycidyl methacrylate as well as a catalyst were 
charged into an autoclave type apparatus for production of polyethylene, 
and bulk polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-13), i.e. ethylene/glycidyl methacrylate (90:10 by 
weight) copolymer. 
(C-14) Ethylene, glycidyl methacrylate and vinyl acetate as well as a 
catalyst were charged into an autoclave type apparatus for production of 
polyethylene, and bulk polymerization was carried out at a temperature of 
150.degree. to 300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to 
make a modified olefin polymer (C-14), i.e. ethylene/glycidyl 
methacrylate/vinyl acetate (85:10:5 by weight) copolymer. 
(C-15) Powdery polyethylene (100 parts) and maleic anhydride (1 part) were 
mixed together and melt kneaded by the aid of two rolls for about 3 
minutes to make a modified olefin polymer (C-15), i.e. maleic 
anhydride-modified polyethylene containing maleic anhydride in an amount 
of 1% by weight. 
(C-16) Ethylene and ethyl acrylate as well as a catalyst were charged into 
an autoclave type apparatus for production of polyethylene, and bulk 
polymerization was carried out at a temperature of 150.degree. to 
300.degree. C. under a pressure of 2,000 kg/cm.sup.2 to make a modified 
olefin polymer (C-16), i.e. ethylene/ethyl acrylate (90:10 by weight) 
copolymer. 
REFERENCE EXAMPLE 10 
Preparation of the rubber-reinforced resin (D): 
(D-3) Styrene and acrylonitrile were graft polymerized on styrene-butadiene 
rubber latex (styrene content, 10% by weight, solid content, 50% by 
weight; particle size, 0.41 micron) according to a conventional emulsion 
graft polymerization procedure to give a rubber-reinforced resin (D) 
having a rubber content of 50% by weight and an acrylonitrile content of 
15% by weight. 
(D-4) Styrene and methyl methacrylate were graft polymerized on 
polybutadiene rubber latex (solid content, 50% by weight; particle size, 
0.35 micron) according to a conventional emulsion graft polymerization 
procedure to give a rubber-reinforced resin (D) having a rubber content of 
50% by weight and a methyl methacrylate content of 30% by weight. 
EXAMPLES 29 TO 36 AND COMATIVE EXAMPLE 12 
The unsaturated dicarboxylic acid anhydride polymer (A-7 or A-8) as 
obtained in Reference Example 8, the polycarbonate resin (an aromatic 
polycarbonate resin comprising bisphenol A; molecular weight, 25,000), the 
modified olefin polymer (C-13, C-14, C-15 or C-16) as obtained in 
Reference Example 9 and the rubber-reinforced resin (D-3 or D-4) were 
mixed well and melt kneaded by the aid of a single screw extruder (resin 
temperature, 260.degree. C.) to make a thermoplastic resin composition. 
The thermoplastic resin composition thus obtained was subjected to 
determination of the physical characteristics in the same manner as above. 
The physical characteristics of the thermoplastic resin composition thus 
determined are shown in Table 8. 
TABLE 8 
__________________________________________________________________________ 
(part(s) by weight) 
Example Comparative 
Composition 29 30 31 32 33 34 35 36 12 
__________________________________________________________________________ 
Unsaturated di- 
carboxylic acid an- 
hydride polymer (A) 
A-7 40 -- 40 -- 10 -- 20 70 50 
A-8 -- 40 -- 40 -- 10 -- -- -- 
Polycarbonate resin (B) 
50 50 50 50 70 70 70 20 50 
Modified olefin polymer 
(C) 
C-13 5 -- -- -- 5 -- -- -- -- 
C-14 -- 10 -- -- -- -- 1 -- -- 
C-15 -- -- 15 -- -- -- -- 15 -- 
C-16 -- -- -- 5 -- 5 -- -- -- 
Rubber-reinforced 
resin (D) 
D-3 10 -- 10 5 20 -- -- 10 -- 
D-4 -- 10 -- 5 -- 20 10 -- -- 
Resistance to heat 
decomposition 
Falling ball impact 
225 
275 
300 
175 
350 
325 
310 
90 &lt;10 
strength (kg .multidot. cm) 
Weight loss (%) 
1.0 
1.3 
0.7 
0.9 
0.6 
0.4 
0.8 
1.7 
8.4 
Silver No No No No No No No No Yes 
Weld strength (23.degree. C.) 
130 
140 
160 
120 
255 
250 
220 
90 &lt;10 
(kg .multidot. cm) 
Notched Izod impact 
55 51 48 41 53 58 51 16 35 
strength (23.degree. C.) 
(kg .multidot. cm/cm) 
Heat deformation 
112 
110 
108 
113 
118 
117 
118 
106 
115 
temperature 
(.degree.C.) 
Processability 
0.22 
0.20 
0.21 
0.27 
0.30 
0.25 
0.36 
0.95 
0.37 
(230.degree. C. 60 kg/cm.sup.2) 
(ml/min) 
__________________________________________________________________________ 
From the above results, it is understood that in comparison with the 
polycarbonate resin incorporated with the unsaturated dicarboxylic acid 
anhydride polymer, the thermoplastic resin composition of the invention is 
excellent in resistance to heat decomposition. The composition of the 
invention is also excellent in notched Izod impact strength and strength 
at weld part. Further, it is excellent in heat resistance.