An impact-resistant resin composition having excellent impact resistance, weather resistance, surface appearance and wear characteristics is disclosed. The resin composition comprises: PA0 (A) a compound rubber type graft copolymer wherein at least one vinyl monomers is graft-polymerized onto a compound rubber that has an average particle diameter of 0.08 to 0.6 .mu.m and possesses such a structure that 10 to 90 wt. % of a polyorganosiloxane rubber component and 10 to 90 wt. % of a polyalkyl (meth)acrylate rubber component are entangled in an inseparable fashion, and the total amount of the polyorganosiloxane rubber component and the polyalkyl (meth)arcylate rubber component is 100 wt. %; and PA0 (B) a vinyl polymer obtained by polymerizing 70 to 100 wt. % of at least one vinyl monomer selected from the group consisting of aromatic alkenyl compounds, vinyl cyanide compounds, and alkyl (meth)acrylates with 0 to 30 wt. % of other vinyl monomer copolymerizable with them.

The present invention relates to an impact-resistant resin composition that 
can provide molded articles excellent in impact resistance, weather 
resistance, surface appearance, wear characteristics, moldability and 
fluidity. 
The present invention is to provide a resin composition, which can provide 
molded articles remarkably improved in impact resistance, weather 
resistance, wear characteristics and surface appearance, and is excellent 
in moldability and fluidity, by blending a compound rubber type graft 
copolymer, which has been obtained by graft-polymerizing at least one 
vinyl monomer onto a compound rubber consisting of a polyorganosiloxane 
rubber component and a polyalkyl (meth)acrylate rubber component, with a 
vinyl polymer prepared from a major proportion of at least one vinyl 
monomer selected from the group consisting of aromatic alkenyl compounds, 
vinyl cyanide compounds, and (meth)acrylates. 
An impact-resistant resin is generally made up of a rubber component and a 
matrix component, and it is said to be advantageous to use, for the rubber 
component, a resin having as low glass transition temperature as possible 
to absorb impact energy. This is evident from the fact that ABS resins 
which use, as a rubber, a polybutadiene resin having a glass transition 
temperature (hereinafter abbreviated as Tg) of -80.degree. C. are more 
excellent in impact resistance than impact-resistant resins which use a 
polybutyl acrylate resin having a Tg of -55.degree. C., at the same rubber 
content. Therefore, it is conceivable that if polydimethylsiloxanes having 
a Tg of -123.degree. C. can be utilized as a rubber source for an 
impact-resistant resin, a resin more excellent in impact resistance than 
ABS resins can be obtained. However, polyorganosiloxanes are generally 
poor in reactiveness with vinyl monomers, and they have been difficult to 
form chemical bonds. Although several methods to form bonds between those 
components have been disclosed, those methods have not been satisfactory. 
For example, in U.S. Pat. No. 3,898,300, it is reported that when a vinyl 
monomer is polymerized in an emulsion of a polydimethylsiloxane polymer 
containing vinyl siloxane or allyl siloxane, a graft copolymer having an 
improved impact strength is prepared. 
U.S. Pat. No. 4,071,577 has disclosed a method wherein a mercapto 
group-containing siloxane is used instead of a vinyl group-containing 
siloxane to further improve impact strength. That is, it is indicated in 
'577 Patent that because mercapto groups are contained in a 
polydimethylsiloxane/mercaptopropylsiloxane copolymer, the impact strength 
changed greatly and that the presence of the graft copolymer through 
mercapto groups improve the impact properties. 
Further, Japanese Laid-Open Patent Application No. 252613/1985 has 
disclosed that a methacryloyloxy group-containing polyorganosiloxane type 
graft copolymer improves the impact resistance of resin compositions. 
However, in these methods, molded articles obtained have imperfect surface 
appearance, and insufficient surface hardness and impact resistance due to 
defects of the silicone rubber structure. 
Taking the above circumstances into consideration, the extensive researches 
have been conducted on chemical composition of graft copolymers that use a 
polyorganosiloxane rubber for improving impact resistance, surface 
appearance. As the results of the researches, it has been found that by 
blending a compound rubber type graft copolymer, which has been obtained 
by graft-polymerizing a vinyl monomer at a high ratio onto a compound 
rubber consisting of a polyorganosiloxane rubber component and a polyalkyl 
(meth)acrylate rubber component, with a vinyl polymer, a resin composition 
can be obtained which provides molded articles having a good compatibility 
of the graft copolymer and the vinyl polymer and excellent impact 
resistance, weather resistance, wear characteristics, surface appearance 
moldability and fluidity. 
Therefore, the present invention is to provide an impact-resistant resin 
composition, which is obtained by blending: (A) a compound rubber type 
graft copolymer wherein at least one vinyl monomer is graft-polymerized 
onto a compound rubber that has an average particle diameter of 0.08 to 
0.6 .mu.m and possesses such a structure that 10 to 90 wt. % of a 
polyorganosiloxane rubber component and 10 to 90 wt. % of a polyalkyl 
(meth)acrylate rubber component are entangled in an inseparable fashion, 
and the total amount of the polyorganosiloxane rubber component and the 
polyalkyl (meth)acrylate rubber component is 100 wt. %; and (B) a vinyl 
polymer obtained by polymerizing 70 to 100 wt. % of at least one vinyl 
monomer selected from the group consisting of aromatic alkenyl compounds, 
vinyl cyanide compounds, and alkyl (meth)acrylates with 0 to 30 wt. % of 
other vinyl monomer copolymerizable with them. 
The compound rubber type graft copolymer (A) used in the present invention 
refers to a copolymer wherein at least one vinyl monomer is 
graft-polymerized onto a compound rubber that has an average particle 
diameter of 0.08 to 0.6 .mu.m and possesses such a structure that 10 to 90 
wt. % of a polyorganosiloxane rubber component and 10 to 90 wt. % of a 
polyalkyl (meth)acrylate rubber component are entangled in an inseparable 
fashion, with the total amount of the polyorganosiloxane rubber component 
and the polyalkyl (meth)acrylate rubber component being 100 wt. %. 
It is impossible to obtain the excellent properties of the resin 
composition of the present invention even if either the polyorganosiloxane 
rubber component or the polyalkyl (meth)acrylate rubber component, or a 
simple mixture of the two rubber components is used as the rubber source 
instead of the above-mentioned compound rubber. When the 
polyorganosiloxane rubber component and the polyalkyl (meth)acrylate 
rubber component are entangled to form a unitary composite, it is for the 
first time possible to obtain a resin composition that can provide molded 
articles having excellent impact resistance, weather resistance, friction 
characteristics, and surface appearance. 
If the polyorganosiloxane rubber component constituting the compound rubber 
exceeds 90 wt. %, the surface appearance of a molded articles of the 
obtained resin composition becomes deteriorated, while if the polyalkyl 
(meth)acrylate rubber component exceeds 90 wt. %, the impact resistance of 
a molded article of the obtained resin composition becomes deteriorated. 
Therefore, each of the two rubber components constituting the compound 
rubber is required to be in the range of from 10 to 90 wt. % (provided 
that the total amount of the two rubber components is 100 wt. %), 
preferably in the range of 20 to 80 wt. %. The average particle diameter 
of said compound rubber is required to be in the range of from 0.08 to 0.6 
.mu.m. If the average particle diameter is less than 0.08 .mu.m, the 
impact resistance of a molded article of the obtained resin composition 
becomes deteriorated, while if the average particle diameter exceeds 0.6 
.mu.m, the impact resistance of a molded article from the obtained resin 
composition becomes deteriorated, and also the surface appearance of the 
molded article becomes deteriorated. Emulsion polymerization is most 
suitable to obtain the compound rubber having such an average particle 
diameter. It is preferred that firstly a latex of the polyorganosiloxane 
rubber is prepared, and then the rubber particles of the 
polyorganosiloxane rubber latex are impregnated with an alkyl 
(meth)acrylate and the alkyl (meth)acrylate is subjected to 
polymerization. 
The polyorganosiloxane rubber constituting the above compound rubber may be 
prepared by emulsion polymerization using an organosiloxane and a 
crosslinking agent (I) as described hereinafter. At that time, a grafting 
agent (II) may be used additionally. 
Examples of the organosiloxane include various types of cyclic siloxanes of 
at least three-membered ring, preferably from 3- to 6-membered 
cyclosiloxanes. For example, hexamethylcyclotrisiloxane, 
octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, 
dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, 
tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane 
can be mentioned, which may be used alone or in combination as a mixture 
of two or more different types. The organosiloxane is used in an amount of 
50 wt. % or over, preferably 70 wt. % or over, of the polyorganosiloxane 
rubber component. 
As the crosslinking agent (I), can be used a trifunctional or 
tetrafunctional silane type crosslinking agent, such as 
trimethoxymethylysilane, triethoxyphenylsilane, tetramethoxysilane, 
tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. 
Particularly, tetrafunctional crosslinking agents are preferable, and of 
these, tetraethoxysilane is especially preferable. The crosslinking agent 
is used in an amount of 0.1 to 30 wt. % of the polyorganosiloxane rubber 
component. 
As the grafting agent (II), can be used, for example, a compound capable of 
forming a unit represented by the formula: 
##STR1## 
wherein R.sup.1 is a methyl group, an ethyl group, a propyl group, or a 
phenyl group, R.sup.2 is a hydrogen atom, or a methyl group, n is 0, 1, or 
2, and p is a number of 1 to 6. A (meth)acryloyloxysiloxane capable of 
forming the unit of the formula (II-1) has a high graft efficiency and 
thus is capable of forming effective graft chains, and it is advantageous 
from the viewpoint of providing impact resistance. A 
methacryloyloxysiloxane is particularly preferable as the compound capable 
of forming the unit of the formula (II-1). Specific examples of the 
methacryloyloxysiloxane include 
.beta.-methacryloyloxyethyldimethoxymethylsilane, 
.gamma.-methacryloyloxypropylmethoxydimethylsilane, 
.gamma.-methacryloyloxypropyldimethoxymethylsilane, 
.gamma.-methacryloyloxypropyltrimethoxysilane, 
.gamma.-methacryloyloxypropylethoxydiethylsilane, 
.gamma.-methacryloyloxypropyldiethoxymethylsilane, and 
.delta.-methacryloyoxybutyldiethoxymethylsilane. The grafting agent is 
used in an amount of 0 to 10 wt. % of the polyorganosiloxane rubber 
component. 
The latex of this polyorganosiloxane rubber component may be produced by a 
process disclosed, for example, in U.S. Pat. Nos. 2,891,290, and 
3,294,725. In the present invention, such a latex is preferably produced, 
for example, in such a manner that a solution mixture of the 
organosiloxane, the crosslinking agent (I), and, if desired, the grafting 
agent (II) are subjected to shear-mixing with water by means of e.g. a 
homogenizer in the presence of a sulfonic acid type emulsifier such as an 
alkylbenzenesulfonic acid and an alkylsulfonic acid. An 
alkylbenzenesulfonic acid is preferable since it serves not only as an 
emulsifier for the organosiloxane but also as a polymerization initiator. 
Further it is preferable to combine a metal salt of an 
alkylbenzenesulfonic acid, or a metal salt of an alkylsulfonic acid, since 
such combined use is effective for maintaining the polymer under a 
stabilized condition during the graft polymerization. 
Next, the polyalkyl (meth)acrylate rubber component constituting the 
compound rubber may preferably be prepared by using an alkyl 
(meth)acrylate, a crosslinking agent (III) and a graftlinking agent (IV) 
as described hereinafter. 
Examples of the alkyl (meth)acrylate include alkyl acrylates such as methyl 
acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 
2-ethylhexyl acrylate, and alkyl methacrylates such as hexyl methacrylate, 
2-ethylhexyl methacrylate, and n-lauryl methacrylate, with n-butyl 
acrylate preferably used. 
Examples of the crosslinking agent (IV) include ethylene glycol 
dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol 
dimethacrylate, and 1,4-butylene glycol dimethacrylate. 
Examples of the grafting agent (IV) include allyl methacrylate, triallyl 
cyanurate and triallyl isocyanurate. Allyl methacrylate can be used also 
as a crosslinking agent. 
These crosslinking agents and grafting agents may be used alone or in 
combination as a mixture of two or more different types. The total amount 
of such crosslinking agent and graftlinking agent is 0.1 to 20 wt. % of 
the polyalkyl (meth)acrylate rubber component. 
The polymerization for preparing the polyalkyl (meth)acrylate rubber 
component is conducted by adding a monomer mixture of the alkyl 
(meth)acrylate, the crosslinking agent and the graftlinking agent into the 
latex of the polyorganosiloxane rubber component neutralized by the 
addition of an aqueous solution of an alkali such as sodium hydroxide, 
potassium hydroxide, or sodium carbonate to have the polyorganosiloxane 
rubber particles impregnated with the monomer mixture, followed by 
addition of a usual radical polymerization initiator and heating them to 
polymerize. As the polymerization progresses, a cross-linked network of a 
polyalkyl (meth)acrylate rubber entangled with the cross-linked network of 
the polyorganosiloxane rubber will be formed to obtain a latex of a 
compound rubber wherein the polyorganosiloxane rubber component and the 
polyalkyl (meth)acrylate rubber component are entangled in an inseparable 
manner. In carrying out the present invention, as the compound rubber, it 
is preferable to use a compound rubber wherein the main skeleton of the 
polyorganosiloxane rubber component has repeating units of 
dimethylsiloxane, and the main skeleton of the polyalkyl (meth)acrylate 
rubber component has repeating units of n-butyl acrylate. 
The compound rubber thus prepared by emulsion polymerization is 
graft-copolymerizable with a vinyl monomer. Further, the 
polyorganosiloxane rubber component and the polyalkyl (meth)acrylate 
rubber component are firmly entangled, so that they cannot be separated by 
extraction with a usual organic solvent such as acetone or toluene. The 
gel content of the compound rubber measured by extraction with toluene at 
90.degree. C. for 12 hours is at least 80 wt. %. 
The vinyl monomer to be graft-polymerized onto this compound rubber may be 
various vinyl monomers including an aromatic alkenyl compound such as 
styrene, .alpha.-methylstyrene, or vinyltoluene; a methacrylate such as 
methyl methacrylate or 2-ethylhexyl methacrylate; an acrylate such as 
methyl acrylate, ethyl acrylate, or butyl acrylate; and a vinyl cyanide 
compound such as acrylonitrile, methacrylonitrile, or N-phenylmaleimide. 
These vinyl monomers may be used alone or in combination as a mixture of 
two or more different types. 
The proportions of the compound rubber and the vinyl monomer in the 
compound rubber type graft copolymer (A) are preferably such that the 
compound rubber is 30 to 95 wt. %, preferably 40 to 90 wt. %, and the 
vinyl monomer is 5 to 70 wt. %, preferably 10 to 60 wt. %, based on the 
weight of the graft copolymer (A). If the vinyl monomer is less than 5 wt. 
%, the dispersion of the graft copolymer (A) in the resin composition is 
not enough, while if it exceeds 70 wt. %, the effect for the improvement 
of the impact strength lowers. 
The vinyl monomer is added to a latex of the compound rubber and then 
polymerized in a single step or in multi-steps by a radical polymerization 
technique to obtain a latex of the compound rubber type graft copolymer 
(A). The latex thus obtained is poured into hot water in which a metal 
salt such as calcium chloride or magnesium sulfate is dissolved, followed 
by salting out and coagulation to separate and recover the compound rubber 
type graft copolymer (A). 
The vinyl polymer (B) used in the present invention is a homopolymer or a 
copolymer of 70 to 100 wt. % of at least one vinyl monomer selected from 
the group consisting of aromatic alkenyl compounds, vinyl cyanide 
compounds, and (meth)acrylates with 0 to 30 wt. % of other vinyl monomer 
copolymerizable with them. Examples of the aromatic alkenyl compound 
include styrene, .alpha.-methylstyrene, and vinyltoluene, examples of the 
vinyl cyanide compound include acrylonitrile, and methacrylonitrile, 
examples of the acrylate include methyl acrylate, ethyl acrylate, and 
butyl acrylate, and examples of the methacrylate include methyl 
methacrylate, and 2-ethylhexyl methacrylate, which may be used alone or in 
combination as a mixture of two or more types. The copolymerizable other 
vinyl monomer is used if desired, and the amount of the other vinyl 
monomer to be used is up to 30 wt. % of the vinyl polymer (B). Examples of 
the copolymerizable other vinyl monomer include ethylene, and vinyl 
acetate. In carrying out the present invention, the vinyl polymers (B) may 
be used alone or in combination as a mixture of two or more types. There 
is no limitation on the process of the production of the vinyl polymer 
(B), and the vinyl polymer (B) can be obtained, for example, by an 
emulsion polymerization process, a suspension polymerization process, or a 
mass polymerization process. 
The vinyl polymer (B) is blended for the purpose of improving moldability, 
etc., and the amount of the vinyl polymer (B) to be blended is preferably 
in the range of 5 to 85 wt. % based on the weight of all the resin 
composition. 
The resin composition of the present invention may further contain, if 
necessary, a stabilizer, a plastisizer, a lubricant, a flame retardant, a 
pigment, a filler, etc.

EXAMPLES 
Now, the present invention will be described in further detail with 
reference to Examples. However, it should be understood that the present 
invention is by no means restricted by such specific Examples. In these 
Examples, "parts" means "parts by weight". 
The physical properties in Examples and Comparative Examples were measured 
as follows: 
Izod impact strength: Izod impact strength was measured according to ASTM D 
256 using a notched test piece of 1/4 thickness. 
Vicat softening temperature: Vicat softening temperature was measured 
according to ISO R 306. 
Gloss: Gloss was measured according to ASTM D 523-62T (60.degree. specular 
glossiness). 
Dynstat strength retention ratio: Dynstat strength retention ratio was 
measured according to DIN 53435. 
Assuming the Dynstat strength of the test piece before the exposure to a 
sunshine weatherometer to be 100% the ratio of the Dynstat strength of the 
test piece after the exposure to the sunshine weatherometer to the Dynstat 
strength of the test piece before the exposure was assigned to be the 
retention ratio. 
REFERENCE EXAMPLE 1 
Production of a compound rubber type graft copolymer (S-1) 
Two parts of tetraethoxysilane, 0.5 parts of 
.gamma.-methacryloyloxypropyldimethoxymethylsilane, and 97.5 parts of 
octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a siloxane 
mixture. Then, 100 parts of the siloxane mixture were added to 200 parts 
of distilled water having 1 part of sodium dodecylbenzene sulfonate and 1 
part of dodecylbenzene sulfonic acid dissolved therein. The mixture was 
preliminarily stirred at 10,000 rpm by a homomixer and then emulsified and 
dispersed by a homogenizer under a pressure of 300 kg/cm.sup.2 to obtain 
an organosiloxane latex. This mixture was transferred to a separable flask 
equipped with a condenser and a stirrer, and it was heated at 80.degree. 
C. for 5 hours under stirring, and then left at 20.degree. C. for 48 
hours. Then, this latex was neutralized to pH 7.5 with an aqueous sodium 
hydroxide solution to stop the polymerization to obtain a 
polyorganosiloxane rubber latex 1. The ratio of polymerization of the 
organosiloxane was 88.5%, and the average particle diameter of the 
polyorganosiloxane rubber was 0.16 .mu.m. 
Then, 119 parts of the polyorganosiloxane rubber latex 1 were introduced 
into a separable flask equipped with a stirrer, and 57.5 parts of 
distilled water were added thereto. After flushing with nitrogen, the 
mixture was heated to 50.degree. C., and a mixed solution comprising 33.95 
parts of n-butyl acrylate, 1.05 parts of allyl methacrylate, and 0.26 
parts of tert-butyl hydroperoxide was charged, and the mixture was stirred 
for 30 min to impregnate the mixed solution into the polyorganosiloxane 
rubber particles. Then, a mixed solution comprising 0.002 parts of ferrous 
sulfate, 0.006 parts of disodium ethylenediaminetetraacetate, 0.26 parts 
of Rongalit and 5 parts of distilled water was charged thereto to initiate 
radical polymerization, and the internal temperature was maintained at 
70.degree. C. for 2 hours to complete the polymerization reaction to 
obtain a compound rubber latex. A part of this latex was sampled, and the 
average particle diameter was measured to find to be 0.19 .mu.m. This 
latex was dried to obtain a solid product, which was extracted with 
toluene at 90.degree. C. for 12 hours, whereby the gel content was 
measured to find to be 97.3 wt. %. To this compound rubber latex, a mixed 
solution comprising 0.12 parts of tert-butyl hydroperoxide, 22.5 parts of 
styrene, and 7.5 parts of acrylonitrile was added dropwise at 70.degree. 
C. over a period of 15 min, and the mixture was maintained at 70.degree. 
C. for 4 hours to complete the graft polymerization of the styrene and 
acrylonitrile to the compound rubber. The ratio of polymerization of the 
styrene was 98.4%, and the ratio of polymerization of the acrylonitrile 
was 97.2%. The graft copolymer latex thus obtained was added dropwise to 
200 parts of hot water containing 1.5 wt. % of calcium chloride and 
coagulated, and the coagulated product was separated, washed and dried at 
75.degree. C. for 16 hours to obtain 98.1 parts of a compound rubber type 
graft copolymer (hereinafter referred to as S-1) as a dry powder. 
REFERENCE EXAMPLE 2 
Production of a compound rubber type graft copolymer (S-2) 
Two parts of tetraethoxysilane, and 98 parts of 
octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a mixed 
siloxane. Then, 100 parts of the mixed siloxane were added to 200 parts of 
distilled water having 1 part of sodium dodecylbenzene sulfonate and 1 
part of dodecylbenzene sulfonic acid dissolved therein. The mixture was 
preliminarily dispersed by a homomixer and then emulsified and dispersed 
by a homogenizer in the same way as for the production of graft copolymer 
S-1. The dispersed product was then heated to 80.degree. C. for 5 hours, 
cooled, allowed to stand for 48 hours at 20.degree. C., and finally 
neutralized to a pH of 7.5 with an aqueous sodium hydroxide solution to 
stop the polymerization thereby obtaining a polyorganosiloxane rubber 
latex 2. The ratio of polymerization of the organosiloxane was 88.9%, and 
the average particle diameter of the polyorganosiloxane was 0.16 .mu.m. 
Then, 117 parts of the polyorganosiloxane rubber latex 2 were introduced 
into a separable flask equipped with condenser and a stirrer, and 57.5 
parts of distilled water were added thereto. After flushing with nitrogen, 
the mixture was heated to 50.degree. C., and a mixed solution comprising 
33.95 parts of n-butyl acrylate, 1.05 parts of allyl methacrylate, and 
0.26 parts of tert-butyl hydroperoxide was charged and the mixture was 
stirred for 30 min. Polymerization of the n-butyl acrylate and allyl 
methacrylate was carried out in the same way and under the same conditions 
as for the production of graft copolymer S-1 to obtain a compound rubber 
latex. The average particle diameter of the compound rubber was 0.20 
.mu.m, and the gel content of the rubber measured by the toluene 
extraction method in the same way as in Reference Example 1 was 92.4 wt. 
%. A mixture of 22.5 parts of styrene, 7.5 parts of acrylonitrile, and 
0.12 parts of tert-butyl hydroperoxide was added to the compound rubber 
latex thus obtained, and the graft polymerization of the styrene and 
acrylonitrile was carried out under the same conditions as for graft 
copolymer S-1. The graft copolymer latex thus obtained was coagulated, and 
the coagulated product was separated, washed and dried in the same way as 
in Reference Example 1 to obtain 97.6 parts of a dry powder of a compound 
rubber type graft copolymer (hereinafter referred to as S-2). 
REFERENCE EXAMPLE 3 
Production of compound rubber type graft copolymers (S-3to S-6) 
The polyorganosiloxane rubber latex 1 prepared in the production of the 
compound rubber type graft copolymer S-1 was used to produce compound 
rubber type graft copolymers under the same conditions as in Reference 
Example 1 except that such amounts of distilled water, n-butyl acrylate 
and allyl methacrylate as shown in Table 1 below were used to form butyl 
acrylate rubber component. 
TABLE 1 
______________________________________ 
Compound rubber latex 
Component 3 4 5 6 
______________________________________ 
Polyorganosiloxane 
17.0 67.8 169.5 220.4 
rubber latex 1 
(parts) 
Distilled water 
150 150 0 0 
(parts) 
Butyl acrylate 
63.1 48.5 19.7 4.9 
(parts) 
Allyl methacrylate 
2 1.5 0.3 0.1 
(parts) 
Tert-Butyl 0.26 0.26 0.08 0.02 
hydroperoxide 
(parts) 
Average particle 
0.30 0.23 0.16 0.14 
diameter of compound 
rubber (.mu.m) 
Gel content of 
96.3 94.5 90.4 93.2 
compound rubber 
(wt. %) 
______________________________________ 
A mixture of 22.5 parts of styrene, 7.5 parts of acrylonitrile, and 0.12 
parts of the tert-butyl hydroperoxide was added to each of the compound 
rubber latices, then the graft polymerization of the styrene and 
acrylonitrile onto the compound rubber was carried out under the same 
conditions as in Reference Example 1 mentioned above, and after the 
completion of the polymerization reaction each of the latices thus 
obtained was coagulated, and the coagulated product was separated, and 
dried in the same way as in Reference Example 1 to obtain dry powders of 
compound rubber type graft copolymers (hereinafter referred to as S-3 to 
S-6 respectively). 
REFERENCE EXAMPLE 4 
Production of compound rubber type graft copolymers (S-7 and S-8) 
Using the polyorganosiloxane rubber latex 1 prepared when the compound 
rubber type graft copolymer S-1 was produced, two types of compound rubber 
type graft copolymers were prepared that were different in the amount of 
the acrylonitrile and styrene monomers. 
That is, 119 parts of the polyorganosiloxane rubber latex 1 were introduced 
together with 200 parts of distilled water into a separable flask equipped 
with a stirrer. After flushing with nitrogen, the mixture was heated to 
50.degree. C., a mixed solution comprising 33.95 parts of n-butyl 
acrylate, 1.05 parts of allyl methacrylate, and 0.26 parts of tert-butyl 
hydroperoxide was charged, the mixture was stirred for 30 min, and then, a 
mixed solution comprising 0.002 parts of ferrous sulfate, 0.006 parts of 
disodium ethylenediaminetetraacetate, 0.26 parts of Rongalit and 5 parts 
of distilled water was charged thereto to initiate polymerization thereby 
preparing a compound rubber latex. The average particle diameter of the 
compound rubber was 0.19 .mu.m, and the gel content of the rubber measured 
by the toluene extraction method in the same way as in Reference Example 1 
was 97.3 wt. %. To this compound rubber latex, a mixed solution comprising 
37.5 parts of styrene, 12.5 parts of acrylonitrile, and 0.2 parts of 
tert-butyl hydroperoxide was added dropwise at 70.degree. C. over a period 
of 15 min, and the mixture was maintained at 70.degree. C. for 4 hours to 
complete the graft polymerization of the styrene and acrylonitrile. 
Thereafter, the coagulation, separation, and drying were carried out in 
the same manner as in Reference Example 1 to prepare a dry powder of a 
compound rubber type graft copolymer (hereinafter referred to as S-7). 
Graft polymerization was carried out in the same manner as for S-7, except 
that a mixed solution comprising 7.5 parts of styrene, 2.5 parts of 
acrylonitrile, and 0.04 parts of tert-butyl hydroperoxide was added to the 
compound rubber latex. Thereafter, the coagulation, separation and drying 
were carried out in the same manner as in Reference Example 1 to prepare a 
dry powder of a compound rubber type graft copolymer (hereinafter referred 
to as S-8). 
REFERENCE EXAMPLE 5 
Production of a graft copolymer (S-9) 
119 parts of the polyorganosiloxane rubber latex 1 were introduced together 
with 57.5 parts of distilled water into a separable flask equipped with a 
stirrer. After flushing with nitrogen, the mixture was heated to 
50.degree. C., and a mixed solution comprising 33.95 parts of n-butyl 
acrylate, and 0.26 parts of tert-butyl hydroperoxide was added thereto, 
followed by stirring for 30 min. Thereafter, the same polymerization 
initiator in the same amount as used in Reference Example 1 was charged to 
effect the emulsion polymerization to prepare a rubber latex. This case 
was different from Reference Example 1 in that allyl methacrylate was not 
added. The average particle diameter of the polymer of this rubber latex 
and the gel content of the rubber measured by the toluene extraction 
method were 0.22 .mu.m, and 63 wt. %, respectively. To this compound 
rubber latex, a mixed solution comprising 22.5 parts of styrene, 7.5 parts 
of acrylonitrile, and 0.12 parts of tert-butyl hydroperoxide was added 
dropwise at 70.degree. C. over a period of 15 min, and the mixture was 
maintained at 70.degree. C. for 4 hours to complete the graft 
polymerization. After the completion of the polymerization reaction, the 
coagulation, separation, and drying were carried out in the same manner as 
in Reference Example 1 to prepare a dry powder of a compound rubber type 
graft copolymer (hereinafter referred to as S-9). 
REFERENCE EXAMPLE 6 
Production of a graft copolymer (S-10) 
119 parts of the polyorganosiloxane rubber latex 1 were introduced together 
with 57.5 parts of distilled water into a separable flask equipped with a 
stirrer. After flushing with nitrogen, a mixed solution comprising 35 
parts of n-butyl acrylate, 22.5 parts of styrene, 7.5 parts of 
acrylonitrile, and 0.26 parts of tert-butyl hydroperoxide was added 
dropwise thereto at 70.degree. C. over 30 min in the presence of the same 
amount of the same polymerization initiator as used in Reference Example 
1. Thereafter, the temperature was maintained at 70.degree. C. for 4 hours 
to complete the polymerization reaction, and then, the coagulation, 
separation, and drying were carried out in the same manner as in Reference 
Example 1 to prepare a dry powder of a graft copolymer (hereinafter 
referred to as S-10). 
REFERENCE EXAMPLE 7 
Production of a compound rubber type graft copolymer (S-11) 
Two parts of tetraethoxysilane, 0.5 parts of 
.gamma.-methacrylolyloxypropyldimethoxymethylsilane and 97.5 parts of 
octamethylcyclotetrasiloxane were mixed to obtain 100 parts of a mixed 
siloxane. Then, 100 parts of the mixed siloxane were added to 200 parts of 
distilled water having 4 parts of dodecylbenzene sulfonic acid and 2 parts 
of sodium dodecylbenzene sulfonate dissolved therein. The mixture was 
preliminarily dispersed by a homomixer and then emulsified and dispersed 
by a homogenizer in the same way as for the production of graft copolymer 
S-1. The dispersed product was then heated to 80.degree. C. for 5 hours, 
cooled, allowed to stand for 48 hours at 20.degree. C., and finally 
neutralized to a pH of 7.0 with an aqueous sodium hydroxide solution to 
stop the polymerization thereby obtaining a polyorganosiloxane rubber 
latex 3. The ratio of polymerization of the organosiloxane was 89.6%, and 
the average particle diameter of the polyorganosiloxane was 0.05 .mu.m. 
117 parts of the polyorganosiloxane rubber latex 3 were weighed, and 57.5 
parts of distilled water were added thereto. Then a mixed solution 
comprising 33.95 parts of n-butyl acrylate, 1.05 parts of allyl 
methacrylate, and 0.26 parts of tert-butyl hydroperoxide was charged, and 
the polymerization was carried out under the same conditions as for the 
production of graft copolymer S-1 to obtain a compound rubber. The average 
particle diameter of the compound rubber was 0.07 .mu.m, and the gel 
content of the rubber measured by the toluene extraction method in the 
same way as in Reference Example 1 was 95.8 wt. %. A mixture of 22.5 parts 
of styrene, 7.5 parts of acrylonitrile, and 0.12 parts of tert-butyl 
hydroperoxide was added to the compound rubber latex thus obtained, and 
the graft polymerization was carried out under the same conditions and in 
the same way as for graft copolymer S-1. The graft copolymer latex thus 
obtained was coagulated, and the coagulated product was separated and 
dried in the same way as in Reference Example 1 to obtain a dry powder of 
a compound rubber type graft copolymer (hereinafter referred to as S-11). 
REFERENCE EXAMPLE 8 
Production of compound rubber type graft copolymers (S-12 and S-13) 
211.5 parts of a compound rubber latex prepared in Reference Example 1 were 
introduced into a separable flask equipped with a condenser and a stirrer. 
After flushing with nitrogen, the temperature was elevated to 60.degree. 
C., then a mixed solution comprising 0.24 parts of tert-butyl 
hydroperoxide, and 30 parts of styrene were added dropwise over 1 hour, 
and then the reaction temperature was maintained at 60.degree. C. for 2 
hours to complete the polymerization reaction. After the completion of the 
polymerization reaction, the graft copolymer latex was coagulated, and the 
coagulated product was separated and dried in the same way as in Reference 
Example 1 to obtain a dry powder of a compound rubber type graft copolymer 
(hereinafter referred to as S-12). 
Similarly, 211.5 parts of a compound rubber latex prepared in Reference 
Example 1 were introduced into the flask. After flushing with nitrogen, 
the temperature was elevated to 60.degree. C., then a mixed solution 
comprising 0.24 parts of tert-butyl hydroperoxide, and 30 parts of methyl 
methacrylate were added dropwise over 1 hour, and then the reaction 
temperature was maintained at 60.degree. C. for 2 hours to complete the 
polymerization reaction. After the completion of the polymerization 
reaction, the graft copolymer latex was coagulated, and the coagulated 
product was separated and dried in the same way as in Reference Example 1 
to obtain a dry powder of a compound rubber type graft copolymer 
(hereinafter referred to as S-13). 
EXAMPLES 1 to 4 and COMATIVE EXAMPLES 1 to 5 
25 wt. % of each of graft copolymers S-1 to S-6, S-9, S-10, and S-11 
prepared in Reference Examples 1 to 3, and 5 to 7 and 75 wt. % of an 
acrylonitrile/styrene copolymer in which the acrylonitrile content was 27 
wt. % and the reduced viscosity (.eta.sp/C) of the copolymer measured in 
chloroform at 25.degree. C. was 0.59 dl/g were blended to prepare 9 types 
of resin compositions (Examples 1 to 4 and Comparative Examples 1 to 5). 
Each of these 9 resin compositions was supplied to an extruder, then melted 
and kneaded at a cylinder temperature of 230.degree. C., and shaped into 
pellets. After the pellets of each of the resin compositions were dried, 
they are supplied to an injection molder (Promat 165/75 manufactured by 
Sumitomo Heavy Industries, Ltd.), and were injection molded at a cylinder 
temperature of 230.degree. C., and a mold temperature of 60.degree. C. to 
obtain test pieces of the resin compositions. These test pieces were used 
to assess physical properties, and the results are shown in Table 2. 
TABLE 2 
______________________________________ 
Izod impact strength 
Graft copolymer 
(1/4" notch; 23.degree. C.) 
Gloss 
used (kg .multidot. cm/cm) 
(%) 
______________________________________ 
Example 1 S-1 19.4 95.0 
Example 2 S-2 18.1 94.3 
Example 3 S-4 14.6 93.2 
Example 4 S-5 20.2 90.2 
Comparative 
S-3 5.5 84.6 
Example 1 
Comparative 
S-6 15.2 81.2 
Example 2 
Comparative 
S-9 6.5 63.2 
Example 3 
Comparative 
S-10 3.8 54.5 
Example 4 
Comparative 
S-11 5.2 91.6 
Example 5 
______________________________________ 
It will be apparent first from the results of the experiments of Examples 1 
to 4 , and Comparative Examples 1 and 2 that unless a content of the 
polyorganosiloxane rubber component in the compound rubber is in a range 
from 10 to 90 wt. %, a resin composition of excellent properties could not 
be obtained. 
Then, it is understood that when the powder of the graft copolymer S-9 that 
did not contain a crosslinking agent in the polybutyl acrylate rubber 
component was used as the graft copolymer (Comparative Example 3), the 
impact resistance and the surface gloss of the molded article were poor. 
This is because the gel content of the rubber component is low and a 
compound rubber was not formed. 
Further, as shown by Comparative Example 4 that used the powder of the 
graft copolymer S-10, when a polymer wherein n-butyl acrylate, styrene, 
and acrylonitrile were simply graft-polymerized onto a polyorganosiloxane 
rubber was used, improvement in impact resistance and surface gloss of a 
molded article could not been attained This will be due to the fact that a 
compound rubber was not formed in the graft copolymer S-10 and a 
compatibility of a grafted resinous component of the graft copolymer with 
an acrylonitrile/styrene copolymer was not good. 
Further, it was found that when the compound rubber type graft copolymer 
S-11 having a small polyorganosiloxane rubber particle diameter had been 
used (Comparative Example 5), the impact resistance of the molded article 
had been low. 
EXAMPLES 5 and 6 
25 wt. % of each of the compound rubber type graft copolymers S-7 and S-8 
prepared in Reference Example 4 and 75 wt. % of the acrylonitrile/styrene 
copolymer used in Example 1 were blended. 
From these two resin compositions, test pieces were prepared by using the 
extruder and the injection molder used in Example 1 under the same 
conditions as in Example 1, and the physical properties were measured. The 
results are shown in Table 3. 
From the results shown in Table 3, it can be understood that even if the 
amount of grafting monomers onto the compound rubber was changed a little, 
the impact resistance and the glossiness of the molded articles were 
fairly excellent. 
TABLE 3 
______________________________________ 
Graft Izod impact strength 
copolymer 
(1/4" notch; 23.degree. C.) 
Gloss 
used (kg .multidot. cm/cm) 
(%) 
______________________________________ 
Example 5 S-7 16.2 95.8 
Example 6 S-8 20.5 93.4 
______________________________________ 
COMATIVE EXAMPLE 6 
Using a graft copolymer prepared by graft polymerization of styrene and 
acrylonitrile onto a polybutyl acrylate rubber, improvement of impact 
resistant was attempted. 
That is, a mixed solution comprising 58.8 parts of n-butyl acrylate, 1.8 
parts of allyl methacrylate, and 0.1 parts of tert-butyl hydroperoxide was 
emulsified in the flask into 120 parts of distilled water having 2 parts 
of sodium dodecylbenzenesulfonate dissolved therein. After flushing with 
nitrogen, the temperature was elevated to 60.degree. C., and the same 
polymerization initiator as in Reference Example 1 was added thereto to 
initiate the polymerization. After the completion of the polymerization of 
butyl acrylate and allyl methacrylate, a mixed solution comprising 30 
parts of styrene, 10 parts of acrylonitrile, and 0.1 parts of tert-butyl 
hydroperoxide was added dropwise to effect graft polymerization. After the 
completion of the polymerization, the coagulation, washing and drying were 
effected under the same conditions as in Reference Example 1 to obtain a 
graft copolymer. 
30 parts of this graft polymer and 70 parts of the acrylonitrile/styrene 
copolymer used in Example 1 were mixed, the mixture was melted and shaped 
to prepare test pieces in the same way as in Example 1. The properties of 
the test piece were measured to find out that the Izod impact strength was 
3.6 kg.cm/cm that was a poor level. From the results of this Comparative 
Example and Comparative Examples 1 and 2 as well as other Examples, it can 
be understood that when a polyorganosiloxane and a polybutyl acrylate were 
compounded, the impact strength and the surface gloss had become 
excellent. 
EXAMPLE 7 
The test pieces prepared in Example 1 and test pieces prepared using a 
commercially available ABS resin (Diapet.RTM. 3001 manufactured by 
Mitsubishi Rayon Co., Ltd.) in the same way as in Example 1 were exposed 
by using a sunshine weatherometer, and the retention ratio of the Dynstat 
strength and the retention ratio of the gloss were measured. The results 
were shown in Table 4. 
TABLE 4 
______________________________________ 
Exposure Resin composition of 
time by Example 1 ABS resin 
sunshine Dynstat Gloss Dynstat 
Gloss 
weathero- strength retention strength 
retention 
meter retention 
ratio retention 
ratio 
(hr) ratio (%) 
(%) ratio (%) 
(%) 
______________________________________ 
0 100 100 100 100 
200 91 86 20 48 
400 86 73 16 13 
600 82 65 14 8 
1000 75 58 14 3 
______________________________________ 
From the results shown in Table 4, it can be understood that the resin 
composition of the present invention were excellent in weather resistance 
and surface gloss retention property. 
EXAMPLE 8 
25 parts of the compound rubber type graft copolymer S-12 prepared in 
Reference Example 8 and 75 parts of a polystyrene having a melt index 
value of 8 gr/10 min at 200.degree. C. under a load of 5 kg were mixed, 
melted, and shaped to prepare test pieces in the same way as in Example 1, 
and when the properties were assessed, the Izod impact strength was 14.3 
kg.cm/cm, which was an excellent level. 
EXAMPLE 9 
30 parts of the compound rubber type graft copolymer S-13 prepared in 
Reference Example 8 and 70 parts of a polymethyl methacrylate having a 
melt index value of 7.8 gr/10 min at 230.degree. C. under a load of 10 kg 
were mixed, melted, and shaped to prepare test pieces in the same way as 
in Example 1, and when the Izod impact strength was measured, it was 8.5 
kg.cm/cm, which was an excellent level. 
EXAMPLE 10 
The test pieces prepared in Example 1 and the test pieces prepared by using 
a commercially available ABS resin (Diapet.RTM. 1001 manufactured by 
Mitsubishi Rayon Co., Ltd.) in the same way as in Example 1 were compared 
by a friction/wear test. The measurement was carried out by using a Toyo 
Baldwin EFM-III-E friction/wear testing machine, with the test piece whose 
rotation side and fixed side being the same resin finished with a sand 
paper No. 1500. The results of the measurement are shown in Table 5. 
TABLE 5 
______________________________________ 
Specific 
Co- worn amount .times. 
Conditions 
efficient 
10.sup.-7 of 
of mg/kg .multidot. mm 
measurement 
dynamic Rotation Fixed Sliding 
Material friction side side speed Load 
______________________________________ 
Test piece 
0.18 2.4 2.1 30 mm/sec 
2.4 kg 
of Example 1 
Test piece 
0.40 4.5 11 30 mm/sec 
2.4 kg 
of Diapet .RTM. 
1001 
Test piece 
0.19 3.6 3.1 30 mm/sec 
5.0 kg 
of Example 1 
Test piece 
0.42 58 34 30 mm/sec 
5.0 kg 
of Diapet .RTM. 
1001 
______________________________________ 
From the results shown in Table 5, it can be understood that the test piece 
prepared from the resin composition of the present invention had more 
excellent friction/wear property than that of the test piece of the 
commercially available ABS resin, and was low in coefficient of dynamic 
friction and specific worn amount. 
EXAMPLES 11 and 12 
30 wt. % of the compound rubber type graft copolymer S-1 obtained in 
Reference Example 1, and 70 wt. % of an 
acrylonitrile/.alpha.-methylstyrene copolymer prepared using monomer 
mixture comprising acrylonitrile/.alpha.-methylstyrene=30/70 (wt. %) by 
emulsion polymerization were blended, and 30 wt. % of the compound rubber 
type graft copolymer S-2 obtained in Reference Example 2, and 70 wt. % of 
an acrylonitrile/.alpha.-methylstyrene copolymer prepared using a monomer 
mixture comprising acrylonitrile/.alpha.-methylstyrene=30/70 (wt. %) by 
emulsion polymerization were blended in order to prepare two resin 
compositions. The two types of the resin compositions were melted and 
shaped into two types of pellets. From these two types of pellets, test 
pieces were prepared in the same way as in Example 1. Using the test 
pieces, the physical properties were measured. The results are shown in 
Table 6. 
TABLE 6 
______________________________________ 
Vicat 
Graft Izod impact strength 
softening 
copolymer 
(1/4" notch; 23.degree. C.) 
temperature 
used (kg .multidot. cm/cm) 
(.degree.C.) 
______________________________________ 
Example 11 
S-1 17.3 116 
Example 12 
S-2 16.5 115 
______________________________________ 
As apparent from the results shown in Table 6, it was found when a vinyl 
polymer containing .alpha.-methyl styrene was blended with the graft 
copolymer of the present invention, a resin composition having high heat 
resistance and impact resistant is obtained. In the case of the test piece 
of the resin composition, the Vicat softening temperature was 100.degree. 
C.