Thermoplastic resin composition and method for preparing the same

There is here provided a thermoplastic resin composition containing PA0 (I) 99 to 1% by weight of a polypropylene, PA0 (II) 1 to 99% by weight of at least one kind of resin selected from the group consisting of an aromatic polyester resin, a polycarbonate resin, a polyamide resin, a polyphenylene ether resin or a mixture of the polyphenylene ether resin and a styrene polymer and an ABS resin, and PA0 (III) 0.1 to 100 parts by weight, based on 100 parts by weight of the aforesaid resins (I)+(II), of a multi-phase structure thermoplastic resin which is composed of 5 to 95% by weight of a polyolefin and 95 to 5% by weight of a vinyl polymer or copolymer obtained from at least one kind of vinyl monomer, either of both the components being in the state of a dispersion phase having a particle diameter of 0.001 to 10 .mu.m. A method for preparing the above-mentioned thermoplastic resin composition is also provided here.

BACKGROUND OF THE INVENTION 
(1) Field of the Invention 
The present invention relates to a thermoplastic resin composition having 
excellent chemical resistance, moldability, impact resistance, heat 
resistance, coating properties, mechanical properties and appearance of 
molded articles made therefrom, and a method for preparing the same. This 
composition of the present case can be widely utilized as materials for 
electrical and electronic parts, machine parts, automobile parts and the 
like. 
(2) Description of the Prior Art 
The so-called engineering plastics such as aromatic polyester resins, 
polycarbonate resins, polyamide resins and polyphenylene ether resins have 
excellent mechanical properties, heat resistance, stiffness and impact 
resistance. Furthermore, ABS resins and polypropylenes are widely used for 
various molded articles because of having excellent chemical resistance, 
moldability and the like, and because of being inexpensive. 
In recent years, with regard to not only the engineering plastics but also 
the ABS resins and polypropylenes, new additional functions are demanded, 
and various attempts have been made to achieve the same. One of them is a 
composition comprising a combination of plastics, and this composition has 
features of the respective plastics and is known as a polymer alloy. 
For example, combinations of engineering plastics such as an aromatic 
polyester resin/a polyphenylene ether resin and a polycarbonate resin/an 
ABS resin have been known for a relatively long time, but examples of 
polymer alloys of polypropylenes and the engineering plastics are 
extremely limited. If a material can be provided with mechanical 
properties, heat resistance, stiffness, impact resistance and coating 
properties and the like, maintaining moldability and chemical resistance 
as well as inexpensiveness which are characteristics of the polypropylene, 
such a material will be industrially useful. 
However, the polypropylene and each of such plastics as mentioned above are 
difficult to mix, and therefore merely by melting and mixing these 
materials, the polymer alloy cannot be obtained. In Japanese Patent 
Unexamined Publication Nos. 61-62542 and 61-64741, examples are disclosed 
in which polyamide resins are blended with a polypropylene, and in 
Japanese Patent Unexamined Publication Nos. 61-60744 and 61-60746, 
examples are disclosed in which aromatic polyester resins are blended with 
a polypropylene. In these examples, acid anhydride-modified polypropylenes 
and epoxy group-containing ethylene copolymers are used to facilitate the 
mixing of these resins. In this case, the compatibility of the two resins 
with each other is higher than when they are simply mixed, but there are 
drawbacks such as the increase in melting viscosity. 
In addition, with regard to resins other than the polyamide resins and 
aromatic polyesters, examples of improved compatibility have not been 
present. 
SUMMARY OF THE INVENTION 
The inventors of the present application have intensively researched to 
solve the above-mentioned problems, and as a result, they have found that 
when a specific multi-phase structure thermoplastic resin is used, the 
compatibility of polypropylene with an aromatic polyester resin, a 
polycarbonate resin, a polyamide resin, a polyphenylene ether resin or the 
like can be improved, so that a thermoplastic resin composition can be 
obtained which retains excellent moldability and chemical resistance of 
the polypropylene and which additionally has good heat resistance, 
mechanical properties, stiffness, impact resistance and coating 
properties. 
That is, the first aspect of the present invention is directed to a 
thermoplastic resin composition containing 
(I) 99 to 1% by weight of polypropylene, 
(II) 1 to 99% by weight of at least one kind of resin selected from the 
group consisting of an aromatic polyester resin, a polycarbonate resin, a 
polyamide resin, a polyphenylene ether resin or a mixture of the 
polyphenylene ether resin and a styrene polymer and an ABS resin, and 
(III) 0.1 to 100 parts by weight, based on 100 parts by weight of the 
aforesaid resins (I)+(II), of a multi-phase structure thermoplastic resin 
which is composed of 5 to 95% by weight of a polyolefin and 95 to 5% by 
weight of a vinyl polymer or copolymer obtained from at least one kind of 
vinyl monomer, either or both the components being in the state of a 
dispersion phase having a particle diameter of 0.001 to 10 .mu.m. 
The second aspect of the present invention is directed to a method for 
preparing a thermoplastic resin composition which comprises the step of 
melting and mixing a polypropylene (I) and at least one kind of resin (II) 
selected from the group consisting of an aromatic polyester resin, a 
polycarbonate resin, a polyamide resin, a polyphenylene ether resin or a 
mixture of the polyphenylene ether resin and a styrene polymer and an ABS 
resin, with 
1 to 100% by weight of a graft polymerization precursor (A) which is 
obtained by first adding at least one kind of vinyl monomer, at least one 
kind of radical polymerizable or copolymerizable organic peroxide and a 
radical polymerization initiator to an aqueous suspension of a polyolefin, 
then heating the suspension under such conditions that the decomposition 
of the radical polymerization initiator does not occur substantially, in 
order to impregnate the polyolefin with the vinyl monomer, the radical 
polymerizable or copolymerizable organic peroxide and the radical 
polymerization initiator, and raising the temperature of this aqueous 
suspension, when the degree of the impregnation has reached 50% by weight 
of the original total weight of the vinyl monomer, peroxide and initiator, 
in order to copolymerize the vinyl monomer with the radical polymerizable 
or copolymerizable organic peroxide in the polyolefin, 
0 to 99% by weight of the polyolefin (B), and 
0 to 99% by weight of a vinyl polymer or copolymer (C) obtained by 
polymerizing at least one kind of vinyl monomer, 
or alternatively melting and mixing the components (A), (B) and (C) 
previously at a temperature in the range of 150.degree. to 350.degree. C. 
in order to form a multi-phase structure thermoplastic resin (III), and 
then melting and mixing the resin (III) with the resins (I) and (II).

DETAILED DESCRIPTION OF THE INVENTION 
The polypropylene (I) used in the present invention is a crystallizable 
polypropylene, and examples of the polypropylene include, in addition to 
the homopolymer of the propylene, block and random copolymers of the 
propylene and .alpha.-olefins such as ethylene and butene-1. 
The aromatic polyester used in the present invention is a polyester having 
an aromatic ring on a chain unit thereof, and it is a polymer or copolymer 
obtained by subjecting, to condensation reaction, an aromatic dicarboxylic 
acid (or its ester-forming derivative) and a diol (or its ester-forming 
derivative) as main components. 
Examples of the aromatic dicarboxylic acid mentioned above include 
terephthalic acid, isophthalic acid, phthalic acid, 
2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 
bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 
4,4'-diphenyldicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 
1,2-bis(phenoxy)ethane-4,4'-dicarboxylic acid, and ester-forming 
derivatives thereof. 
Examples of the above-mentioned diol component include aliphatic diols 
having 2 to 10 carbon atoms, i.e., ethylene glycol, propylene glycol, 
1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 
decamethylene glycol and cyclohexanediol; long-chain glycols each having a 
molecular weight of 400 to 6,000, i.e., polyethylene glycol, 
poly(1,3-propylene glycol) and polytetramethylene glycol; and mixtures 
thereof. 
Typical and preferable examples of the thermoplastic aromatic polyester 
resin used in the present invention include polyethylene terephthalate, 
polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene 
terephthalate, polyethylene-2,6-naphtalate and 
polyethylene-1,2-bis(phenoxy)ethane-4,4'-dicarboxylate. Of these examples, 
polyethylene terephthalate and polybutylene terethphalate are more 
preferable. 
The intrinsic viscosity of the thermoplastic aromatic polyester resin is 
preferably in the range of 0.4 to 4.0 dl/g at 25.+-.0.1.degree. C. at a 
concentration of 0.32 g in 100 milliliters of trifluoric acid 
(25)/methylene chloride (75). When the intrinsic viscosity is less than 
0.4 dl/g, the thermoplastic aromatic polyester resin cannot exert 
mechanical strength sufficiently. Inversely, when it is in excess of 4.0 
dl/g, the flowability of the resin deteriorates, which leads to the 
decline of the surface gloss on molded articles thereof. 
The polycarbonate resins used in the present invention include 
4,4-dioxyallylalkane polycarbonates typified by a polycarbonate of 
4,4-dihydroxydiphenyl-2,2-propane (generally called bisphenol A), but 
above all, 4,4-dihydroxydiphenyl-2,2-propane polycarbonate having a number 
average molecular weight of 15,000 to 80,000 is preferable. This 
polycarbonate may be prepared by an optional method. For example, 
4,4-dihydroxydiphenyl-2,2-propane polycarbonate may be prepared by blowing 
phosgene in 4,4-dihydroxydiphenyl-2,2-propane as a dioxine compound in the 
presence of an aqueous caustic alkali solution and a solvent, or 
alternatively by carrying out ester interchange between 
4,4-dihydroxydiphenyl-2,2-propane and diester carbonate in the presence of 
a catalyst. 
The polyphenylene ether resin used in the present invention is a polymer 
obtained by oxidizing and polymerizing a phenolic compound represented by 
the general formula 
##STR1## 
wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 is selected 
from the group consisting of a hydrogen atom, a halogen atom, a 
hydrocarbon group or a substituted hydrocarbon group, and at least one of 
them is a hydrogen atom, with oxygen or an oxygen-containing gas in the 
presence of a coupling catalyst. 
Typical examples of R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 in the 
above-mentioned general formula include hydrogen, chlorine, fluorine, 
iodine, bromine, methyl, ethyl, propyl, butyl, chloroethyl, hydroxyethyl, 
phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, 
cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl and 
ethylphenyl. 
Typical examples of the phenolic compounds having the above-mentioned 
general formula include phenol, o-, m- and p-cresols, 2,6-, 2,5-, 2,4- and 
3,5-dimethylphenols, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 
2,6-dimethylphenol, 2-methyl-6-ethylphenol, and 2,3,5-, 2,3,6- and 
2,4,6-trimethylphenols. These phenolic compounds may be used in 
combination of two or more thereof. 
Other examples of the phenolic compound used in the present invention 
include copolymers of the phenolic compounds having the above general 
formula with divalent phenols such as bisphenol A, tetrabromobisphenol A, 
resorcin and hydroquinone. 
Examples of the styrene polymer used in the present invention include 
homopolymers such as polystyrene, poly(.alpha.-methylstyrene) and 
poly(p-methylstyrene), polystyrenes modified with butadiene rubber, 
styrene-butadiene copolymer, styrene modified ethylene-propylene copolymer 
and ethylene-propylene-diene copolymer, styrene-maleic anhydride 
copolymer, styreneacrylonitrile copolymer, styrene-acrylonitrile-butadiene 
copolymer and styrene-methylmethacrylate copolymer. The styrene copolymer 
is used in an amount of 0 to 95% by weight with respect to the 
polyphenylene ether resin. 
Examples of a polyamide resin used in the present invention include 
aliphatic polyamide resins such as 6-nylon, 6,6-nylon, 6,10-nylon, 
6,12-nylon, 11-nylon, 12-nylon and 4,6-nylon; aromatic polyamide resins 
such as polyhexamethylenediamine terephthalamide, polyhexamethylenediamine 
isophthalamide and xylene group-containing polyamide; modified compounds 
of these polyamides; and mixtures thereof. The particularly preferable 
polyamides are 6-nylon and 6,6-nylon. 
The ABS resin used in the present invention is a graft copolymer (a) 
obtained by polymerizing, in the presence of a conjugated diene rubber, 
two or more compounds selected from the group consisting of vinyl cyanide 
compounds, aromatic vinyl compounds and alkyl ester compounds of 
unsaturated carboxylic acids. If desired, the ABS resin may contain a 
copolymer (b) obtained by polymerizing two or more compounds selected from 
the group consisting of vinyl cyanide compounds, aromatic vinyl compounds 
and alkyl ester compounds of unsaturated carboxylic acids. 
The composition ratio between the conjugated diene rubber and the 
above-mentioned compound in the graft copolymer (a) is not particularly 
limited, but the preferable composition ratio is 5 to 80% by weight of the 
conjugated diene rubber and 95 to 80% by weight of the above-mentioned 
compound. Furthermore, the composition ratio among the respective 
compounds mentioned above is preferably 0 to 30% by weight of the vinyl 
cyanide compound, 30 to 80% by weight of the aromatic vinyl compound and 0 
to 70% by weight of the alkyl ester compound of an unsaturated carboxylic 
acid. With regard to the particle diameter of the conjugated diene rubber, 
it is not particularly limited, but preferably it is in the range of 0.05 
to 1 .mu.m. 
In the case of the copolymer (b), the preferable composition ratio of the 
respective compounds is 0 to 30% by weight of the vinyl cyanide compound, 
50 to 90% by weight of the aromatic vinyl compound and 0 to 40% by weight 
of the alkyl ester of an unsaturated carboxylic acid. The intrinsic 
viscosity [30.degree. C., dimethylformamide (DMF)]of the copolymer (b) is 
not particularly limited either, but it is preferably in the range of 0.25 
to 1.0. 
Examples of the conjugated diene rubber include polybutadienes, 
butadiene-styrene copolymers and butadieneacrylonitrile copolymers. 
Moreover, examples of the vinyl cyanide compound include acrylonitrile and 
methacrylonitrile; examples of the aromatic vinyl compound include 
styrene, .alpha.-methylstyrene, vinyltoluene, dimethylstyrene and 
chlorostyrene; and exampIes of the alkyl ester compound of an unsaturated 
carboxylic acid include methyl acrylate, ethyl acrylate, butyl acrylate, 
methyl methacrylate and hydroxyethyl acrylate. 
The ABS resin may be prepared in accordance with, for example, an emulsion 
polymerization process, a suspension polymerization process, a solution 
polymerization process, a mass polymerization process or an 
emulsion-suspension polymerization process. 
The multi-phase structure thermoplastic resin (III) used in the present 
invention is a polyolefin or a vinyl polymer or copolymer matrix in which 
another vinyl polymer or copolymer or polyolefin is uniformly dispersed in 
a spherical form. 
The polyolefin mentioned above is at least one copolymer selected from the 
group consisting of a propylene polymer and/or an epoxy group-containing 
ethylene copolymer, an ethylene-unsaturated carboxylic acid or its alkyl 
ester copolymer, or its metallic salt, and an ethylene-vinyl ester 
copolymer. 
The propylene polymer may be different from the above-mentioned 
polypropylene (I), and examples of the propylene polymer include the 
homopolymer of propylene, block and random copolymers of propylene and, 
for example, .alpha.-olefins such as ethylene and butene-1, 
ethylene-propylene copolymer rubber, and ethyelene-propylene-diene 
copolymer rubber. 
In particular, when the aromatic polyester and polyamide are used, it is 
preferred that not only the propylene polymer but also the ethylene 
copolymer is employed as the additional polyolefin, because the 
compatibility of the polyolefins with the aromatic polyester and polyamide 
can be remarkably improved. Above all, the epoxy group-containing ethylene 
copolymer reacts with the aromatic polyester and polyamide, and therefore 
its effect is surprising. 
The polymer dispersed in the multi-phase structure thermoplastic resin has 
a particle diameter of 0.001 to 10 .mu.m, preferably 0.01 to 5 .mu.m. When 
the particle diameter of the dispersed polymer is less than 0.001 .mu.m or 
is more than 10 .mu.m, the compatibility of the polypropylene (I) with the 
resin (II), for example, the above-mentioned aromatic polyester is bad, 
with the result that impact resistance deteriorates. 
The vinyl polymer or copolymer in the multi-phase thermoplastic resin (III) 
used in the present invention has a number average polymerization degree 
of 5 to 10,000, preferably 10 to 5,000. 
When the number average polymerization degree is less than 5, impact 
resistance of the thermoplastic resin composition regarding the present 
invention can be improved, but heat resistance deteriorates. Inversely, 
when it is in excess of 10,000, melting viscosity is high, moldability 
deteriorates, and surface gloss falls off. 
The multi-phase thermoplastic resin (III) used in the present invention 
comprises 5 to 95% by weight, preferably 20 to 90% by weight, of the 
polyolefin. Therefore, the content of the vinyl polymer or copolymer is 95 
to 5% by weight, preferably 80 to 10% by weight. 
When the polyolefin is less than 5% by weight, its compatible effect with 
the polypropylene is not exerted sufficiently, and when it is more than 
95% by weight, heat resistance and dimensional stability of the 
thermoplastic resin regarding the present invention are impaired. 
The ethylene copolymer in the multi-phase structure thermoplastic resin 
used in the present invention is at least one ethylene copolymer selected 
from the group consisting of an epoxy group-containing copolymer, an 
ethylene-unsaturated carboxylic acid or its alkyl ester copolymer, or its 
metallic salt, and an ethylene-vinyl ester copolymer. This ethylene 
copolymer can be preferably prepared by a high-pressure radical 
polymerization. 
The epoxy group-containing ethylene copolymer mentioned above is a 
copolymer of ethylene and an unsaturated glycidyl group-containing 
monomer, a three-dimensional copolymer of an olefin, an unsaturated 
glycidyl group-containing monomer and another unsaturated monomer, or a 
multi-dimensional copolymer. The preferable epoxy group-containing 
ethylene copolymer is composed of 60 to 99.5% by weight of ethylene, 0.5 
to 40% by weight of a glycidyl group-containing monomer and 0 to 39.5% by 
weight of the other unsaturated monomer. 
Examples of the unsaturated glycidyl group-containing monomer include 
glycidyl acrylate, glycidyl methacrylate, itaconic acid monoglycidyl 
ester, butenetricarboxylic acid monoglycidyl ester, butenetricarboxylic 
acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, vinyl 
glycidyl ethers and glycidyl esters of maleic acid, crotonic acid and 
fumaric acid, allyl glycidyl ether, glycidyloxy ethylvinyl ether, glycidyl 
ethers such as styrene p-glycidyl ether, and p-glycidyl styrene. The 
particularly preferable ones are glycidyl methacrylate and allyl glycidyl 
ether. 
Other examples of the unsaturated monomers include olefins, vinyl esters, 
.alpha.,.beta.-ethylenic unsaturated carboxylic acids and their 
derivatives. Typical examples of such unsaturated monomers include olefins 
such as propylene, butene-1, hexene-1, decene-1, octene-1 and styrene, 
vinyl esters such as vinyl acetate, vinyl propionate and vinyl benzoate, 
acrylic acid, methacrylic acid, esters such as methyl, ethyl, propyl, 
butyl, 2-ethylhexyl, cyclohexyl, dodecyl and octadecyl acrylates and 
methacrylates, maleic acid, maleic anhydride, itaconic acid, fumaric acid, 
maleic monoesters and diesters, vinyl ethers such as vinyl chloride, vinyl 
methyl ether and vinyl ethyl ether, and acrylic amide compounds. 
Particularly, acrylic and methacrylic esters are preferable. 
Typical examples of the epoxy group-containing ethylene copolymer include 
ethylene-glycidyl methacrylate copolymer; ethylene-vinyl acetate-glycidyl 
methacrylate copolymer; ethylene-ethyl acrylate-glycidyl methacrylate 
copolymer; ethylene-carbon monoxide-glycidyl methacrylate copolymer; 
ethylene-glycidyl acrylate copolymer; and ethylene-vinyl acetate-glycidyl 
acrylate copolymer. Above all, ethyleneglycidyl methacrylate copolymer, 
ethylene-ethyl acrylateglycidyl methacrylate copolymer and ethylene-vinyl 
acetateglycidyl methacrylate copolymer are preferred. These epoxy 
group-containing olefin copolymers can be used in a mixture thereof. 
Additional examples of the epoxy group-containing ethylene copolymer of the 
present invention include modified compounds prepared by the addition 
reaction of the above-mentioned unsaturated glycidyl group-containing 
monomers to conventional olefin homopolymers and copolymers. 
Examples of the above-mentioned ethylene polymer include low-density, 
medium-density and high-density polyethylenes, ethylene-propylene 
copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, 
ethylene-4-methylpentene-1 copolymer, copolymers with other 
.alpha.-olefins mainly comprising ethylene such as ethylene-octene-1 
copolymer, ethylene-vinyl acetate copolymer, ethyleneacrylic acid 
copolymer, ethylene-methacrylic acid copolymer copolymers of ethylene and 
methyl, ethyl, propyl, isopropyl and butyl acrylate and methacrylate, 
ethylene-maleic acid copolymer, ethylene-propylene copolymer rubber, 
ethylene-propylene-diene-copolymer rubber, ethylene-vinyl acetate-vinyl 
chloride copolymer, mixtures thereof, and mixtures of these compounds with 
other kinds of synthesized resins and rubbers. 
Examples of an unsaturated carboxylic acid as well as its alkyl ester and 
vinyl ester monomers for the ethylene-unsaturated carboxylic acid or its 
alkyl ester copolymer, or its metallic salt, and the ethylene-vinyl ester 
copolymer include unsaturated carboxylic acids such as acrylic acid, 
methacrylic acid, maleic acid, fumaric acid, maleic anhydride and itaconic 
anhydride; unsaturated alkyl carboxylate monomers such as methyl acrylate, 
methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, 
propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl 
acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl 
methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, 
stearyl methacrylate, monomethyl maleate, monoethyl maleate, diethyl 
maleate and monomethyl fumarate; and vinyl ester monomers such as vinyl 
propionate, vinyl acetate, vinyl caproate, vinyl caprylate, vinyl laurate, 
vinyl stearate and vinyl trifluoroacetate. Of these compounds, ethyl 
acrylate and vinyl acetate are particularly preferable. The 
above-mentioned monomers can be used in the form of a mixture thereof. 
Furthermore, in the ethylene polymer used in the present invention, an 
ion-crosslinked ethylene copolymer (ionomer) is also included, and the 
ion-crosslinked ethylene copolymer may be prepared by reacting a metallic 
compound having a valence of 1 to 3 in the groups I, II, III, IV-A and VI 
of the periodic table with a modified copolymer obtained by the addition 
polymerization of the above-mentioned unsaturated carboxylic acid such as 
acrylic acid, maleic acid or maleic anhydride to a low-density, 
medium-density or high-density polyethylene or ethylene-.alpha.-olefin 
copolymer, or with the above-mentioned modified copolymer obtained by 
random or addition polymerization. 
Preferable examples of the metallic compound include borates, acetates, 
oxides, hydroxides, methoxides, ethoxides, carbonates and bicarbonates. 
Examples of the metallic ion include Na.sup.+, K.sup.+, Ca.sup.++, 
Mg.sup.++, Zn.sup.++, Ba.sup.++, Fe.sup.++, Fe.sup.+++, Co.sup.++, 
Ni.sup.++ and Al.sup.+++. Of these ions, Na.sup.+, Mg.sup.++ and Zn.sup.++ 
are particularly preferable. These metallic compounds may be used in a 
combination of two or more thereof, if necessary. 
The ethylene copolymer may be prepared by a high-pressure radical 
polymerization, i.e., by simultaneously or stepwise contacting and 
polymerizing a monomer mixture of 60 to 99.5% by weight of the 
above-mentioned ethylene, 0.5 to 40% by weight of one or more unsaturated 
glycidyl group-containing monomer, and 0 to 39.5% by weight of at least 
one other unsaturated monomer, or a monomer mixture of 50 to 99.5% by 
weight of ethylene, 50 to 0.5% by weight of at least one monomer selected 
from the group consisting of an unsaturated carboxylic acid, its alkyl 
ester and/or a vinyl ester and 0 to 49.5% by weight of another unsaturated 
monomer in the presence of 0.0001 to 1% by weight of a radical 
polymerization initiator based on the total weight of all the monomers at 
a polymerization pressure of 500 to 4,000 kg/cm.sup.2, preferably 1,000 to 
3,500 kg/cm.sup.2, at a reaction temperature of 50 to 400.degree. C., 
preferably 100 to 350.degree. C., using a chain transfer agent and, if 
necessary, some auxiliaries in an autoclave or tubular reactor. 
Examples of the above-mentioned radical polymerization initiator include 
usual initiators such as peroxides, hydroperoxides, azo-compounds, amine 
oxide compounds and oxygen. 
Examples of the chain transfer agent include hydrogen, propylene, butene-1, 
saturated aliphatic hydrocarbons having 1 to 20 carbon atoms such as 
methane, ethane, propane, butane, isobutane, n-hexane, n-heptane and 
cycloparaffins; halogen-substituted hydrocarbons such as chloroform and 
carbon tetrachloride; saturated aliphatic alcohols such as methanol, 
ethanol, propanol and isopropanol; saturated aliphatic carbonyl compounds 
having 1 to 20 or more carbon atoms such as carbon dioxide, acetone and 
methyl ethyl ketone; and aromatic compounds such as toluene, 
diethylbenzene and xylene. 
Typical examples of the vinyl polymer and copolymer in the multi-phase 
structure thermoplastic resin (III) used in the present invention include 
polymers and copolymers prepared by polymerizing one or more of vinyl 
monomers such as vinyl aromatic monomers, for example, styrene, 
nucleus-substituted styrenes such as methylstyrene, dimethylstyrene, 
ethylstyrene, isopropylstyrene and chlorostyrene, and .alpha.-substituted 
styrene such as .alpha.-methylstyrene and .alpha.-ethylstyrene; acrylate 
and methacrylate monomers, for example, alkyl esters having 1 to 7 carbon 
atoms of acrylic acid or methacrylic acid such as methyl, ethyl, propyl, 
isopropyl and butyl acrylate and methacrylate; acrylonitrile and 
methacrylonitrile monomers; vinyl ester monomers such as vinyl acetate and 
vinyl propionate; acrylamide and methacrylamide monomers; and monoesters 
and diesters of maleic anhydride and maleic acid. Above all, the vinyl 
polymer and copolymer containing 50% by weight or more of a vinyl aromatic 
monomer are particularly preferable. 
As a grafting technique used to prepare the multi-phase structure 
thermoplastic resin regarding the present invention, there may be employed 
a well known process such as a chain transfer process and an ionizing 
radiation process, but the following process is most preferable, because 
grafting efficiency is high, secondary cohesion due to heat does not 
occur, and therefore performance can be exerted effectively. 
Now, a method for preparing the thermoplastic resin composition of the 
present invention will be described in detail. 
Water is suspended in 100 parts by weight of a polyolefin. Afterward, 5 to 
400 parts by weight of at least one vinyl monomer is added to the 
suspension, and in the mixture, a solution is added in which there are 
dissolved 0.1 to 10 parts by weight, based on 100 parts by weight of the 
vinyl monomer, of one or a mixture of radical polymerizable or 
copolymerizable organic peroxides represented by the undermentioned 
general formula (a) or (b) and 0.01 to 5 parts by weight, based on 100 
parts by weight of the total of the vinyl monomer and the radical 
polymerizable or copolymerizable organic peroxide, of a radical 
polymerization initiator in which the decomposition temperature to obtain 
a half-life period of 10 hours is from 40.degree. to 90.degree. C.. The 
mixture is then heated under conditions that the decomposition of the 
radical polymerization initiator does not occur substantially, in order to 
impregnate the polyolefin with the vinyl monomer, the radical 
polymerizable or copolymerizable organic peroxide and the radical 
polymerization initiator. When the impregnation ratio has reached 50% by 
weight or more of the original total weight of the monomer, peroxide and 
initiator, the temperature of this aqueous suspension is raised to 
copolymerize the vinyl monomer with the radical polymerizable or 
copolymerizable organic peroxide in the polyolefin, thereby obtaining a 
graft polymerization precursor (A). 
This graft polymerization precursor (A) also is the multi-phase structure 
thermoplastic resin. 
Therefore, in order to obtain the thermoplastic resin composition of the 
present invention, this graft polymerization precursor may be directly 
mixed under melting with at least one resin (II) selected from the group 
consisting of a polypropylene, an aromatic polyester resin, a 
polycarbonate resin, a polyamide resin, a polyphenylene ether resin alone 
or a mixture of the polyphenylene ether resin and a styrene polymer, and 
an ABS resin, but in the best case, the multi-phase thermoplastic resin 
(III) obtained by kneading the graft polymerization precursor is mixed 
with a polypropylene and the resin (II). 
The above-mentioned radical polymerizable or copolymerizable organic 
peroxides are compounds represented by the general formulae (a) and (b): 
##STR2## 
wherein R.sub.1 is a hydrogen atom or an alkyl group having 1 or 2 carbon 
atoms, each of R.sub.2 and R.sub.7 is a hydrogen atom or a methyl group, 
R.sub.6 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 
each of R.sub.3, R.sub.4, R.sub.8 and R.sub.9 is an alkyl group having 1 
to 4 carbon atoms, each of R.sub.5 and R.sub.10 is an alkyl group having 1 
to 12 carbon atoms, a phenyl group, an alkyl-substituted phenyl group or a 
cycloalkyl group having 3 to 12 carbon atoms, m is 1 or 2, and n is 0, 1 
or 2. 
Typical examples of the radical polymerizable or copolymerizable organic 
peroxides represented by the general formula (a) include 
t-butylperoxyacryloyloxyethyl carbonate, t-amylperoxyacryloyloxyethyl 
carbonate, t-hexylperoxyacryloyloxyethyl carbonate, 
1,1,3,3-tetramethylbutylperoxyacryloyloxyethyl carbonate, 
cumylperoxyacryloyloxyethyl carbonate, p-isopropylperoxyacryloyloxyethyl 
carbonate, t-butyl peroxymethacryloyloxyethyl carbonate, 
t-amylperoxymethacryloyloxyethyl carbonate, 
1,1,3,3-tetramethylbutylperoxymethacryloyloxyethyl carbonate, 
cumylperoxymethacryloyloxyethyl carbonate, 
p-isopropylperoxymethacryloyloxyethyl carbonate, 
t-butylperoxyacryloyloxyethoxyethyl carbonate, 
t-amylperoxyacryloyloxyethoxyethyl carbonate, 
t-hexylperoxyacryloyloxyethoxyethyl carbonate, 
1,1,3,3-tetramethylbutylperoxyacryloyloxyethoxyethyl carbonate, 
cumylperoxyacryloyloxyethoxyethyl carbonate, 
p-isopropylperoxyacryloyloxyethoxyethyl carbonate, 
t-butylperoxymethacryloyloxyethoxyethyl carbonate, 
t-amylperoxymethacryloyloxyethoxyethyl carbonate, 
t-hexylperoxymethacryloyloxyethoxyethyl carbonate, 
1,1,3,3-tetramethylbutylperoxymethacryloyloxyethoxyethyl carbonate, 
cumylperoxymethacryloyloxyethoxyethyl carbonate, 
p-isopropylperoxymethacryloyloxyethoxyethyl carbonate, 
t-butylperoxyacryloyloxyisopropyl carbonate, 
t-amylperoxymacryloyloxyisopropyl carbonate, 
t-hexylperoxyacryloyloxyisopropyl 
1,1,3,3-tetramethylbutylperoxyacryloyloxyisopropyl carbonate, 
cumylperoxyacryloyloxyisopropyl carbonate, 
p-isopropylperoxyacryloyloxyisopropyl carbonate, 
t-butylperoxymethacryloyloxyisopropyl carbonate, 
t-amylperoxymethacryloyloxyisopropyl carbonate, 
t-hexylperoxymethacryloyloxyisopropyl carbonate, 
1,1,3,3-tetramethylbutylperoxymethacryloyloxyisopropyl carbonate, 
cumylperoxymethacryloyloxyisopropyl carbonate, 
p-isopropylperoxymethacryloyloxyisopropyl carbonate. 
Typical examples of the compounds represented by the general formula (b) 
include t-butylperoxyallyl carbonate, t-amylperoxyallyl carbonate, t 
hexylperoxyallyl carbonate, 1,1,3,3-tetramethylbutylperoxyallyl carbonate, 
p-menthaneperoxyallyl carbonate, cumylperoxyallyl carbonate, 
t-butylperoxymethallyl carbonate, t-amylperoxymethallyl carbonate, 
t-hexylperoxymethallyl carbonate, 1,1,3,3-tetramethylbutylperoxymethallyl 
carbonate, p-menthaneperoxymethallyl carbonate, cumylperoxymethallyl 
carbonate, t-butylperoxyallyloxyethyl carbonate, t-amylperoxyallyloxyethyl 
carbonate, t-butylperoxymethallyloxyethyl carbonate, 
t-amylperoxymethallyloxyethyl carbonate, t-hexylperoxymethallyloxyethyl 
carbonate, t-butylperoxyallyloxyisopropyl carbonate, 
t-amylperoxyallyloxyisopropyl carbonate, t-hexylperoxyallyloxyisopropyl 
carbonate, t-butylperoxymethallyloxyisopropyl carbonate, 
t-hexylperoxymethallyloxyisopropyl carbonate. 
Of these compounds, preferable ones are t-butylperoxyacryloyloxyethyl 
carbonate, t-butylperoxymethacryloyloxyethyl carbonate, t-butylperoxyallyl 
carbonate and t-butylperoxymethallyl carbonate. 
In the present invention, the amounts of the above-mentioned resins (I) and 
(II) depend upon the purpose of the composition of the present invention. 
That is, when it is desired that features of the polypropylene (I) are 
retained and poor stiffness, heat resistance and dimensional stability 
which are drawbacks of the polypropylene (I) are improved, there is 
required 50 to 99% by weight, preferably 60 to 95% by weight, of the 
polypropylene. 
When the polypropylene is less than 50% by weight, excellent moldability 
and chemical resistance which are features of the polypropylene are 
impaired, and when it is in excess of 99% by weight, the improvement 
effect of stiffness, heat resistance and dimensional stability which is 
one of the purposes of the present invention is not obtained. 
On the other hand, if it is intended that physical properties are improved 
by the polypropylene, maintaining features of the resin (II), the content 
of the resin (II) is suitably from 50 to 99% by weight. 
That is, if it is desired that low notched impact strength which is the 
drawback of the aromatic polyester resin is improved, maintaining other 
features thereof, it is necessary that the content of the aromatic 
polyester resin is from 50 to 99% by weight, preferably from 60 to 95% by 
weight. When the content of the aromatic polyester resin is less than 50% 
by weight, stiffness and dimensional stability which are features of the 
aromatic polyester resin are impaired. 
If it is desired that chemical resistance and moldability are improved, 
retaining other features of the polycarbonate, there is required 50 to 99% 
by weight, preferably 60 to 95% by weight, of the polycarbonate. 
When the amount of the polycarbonate is less than 50% by weight, excellent 
impact resistance and stiffness which are the features of the 
polycarbonate is impaired, and when it is in excess of 99% by weight, the 
improvement effect of chemical resistance and moldability which is one of 
the purposes of the present invention is not obtained. 
If it is desired that features of the polyphenylene ether are retained and 
the poor moldability and chemical resistance which are drawbacks of the 
polyphenylene ether are improved, there is required 50 to 99% by weight, 
preferably 60 to 95% by weight, of the polyphenylene ether. 
When the amount of the polyphenylene ether is less than 50% by weight, heat 
resistance and dimensional stability of the polyphenylene ether are 
impaired, and when it is in excess of 99% by weight, the improvement 
effect of moldability and chemical resistance which is one of the purposes 
of the present invention is not obtained. 
When it is desired that poor hygroscopicity and dimensional stability of 
the polyamide resin are improved, retaining other features thereof, 50 to 
99% by weight, preferably 60 to 95% by weight of the polyamide resin is 
necessary. 
When the polyamide resin is less than 50% by weight, the features of the 
polyamide resin are impaired, and when it is in excess of 99% by weight, 
the improvement effect of hygroscopicity and dimensional stability thereof 
which is one of the purposes of the present invention cannot be expected. 
If it is intended that chemical resistance of the ABS resin is improved, 
retaining other features thereof, 50 to 99% by weight, preferably 60 to 
95% by weight of the ABS resin is necessary. 
When the content of the ABS resin is less than 50% by weight, the features 
of the ABS resin are impaired, and when it is in excess of 99% by weight, 
the improvement effect of the chemical resistance cannot be expected. 
In the present invention, the multi-phase structure thermoplastic resin is 
used in an amount of 0.1 to 100 parts by weight, preferably 1 to 50 parts 
by weight, based on 100 parts by weight of the total weight of the resins 
(I)+ (II). When the amount of the multi-phase structure thermoplastic 
resin is less than 0.1 part by weight, no compatibility effect is present, 
impact strength deteriorates, and delamination occurs on molded articles, 
with the result that the appearance of the articles is degraded. When it 
is in excess of 100 parts by weight, stiffness and heat resistance of the 
composition of the present invention deteriorate. 
In the present invention, the inorganic filler (IV) can be used in an 
amount of 1 to 150 parts by weight based on 100 parts of the components 
(I)+(II)+(III). 
The inorganic filler may be used in granular, lamellar, scaly, needle, 
spherical, balloons and fibrous forms, and examples of these inorganic 
fillers include granular fillers such as calcium sulfate, calcium 
silicate, clay, diatomaceous earth, talc, alumina, siliceous sand, glass 
powder, iron oxide, metallic powder, graphite, silicon carbide, silicon 
nitride, silica, boron nitride, aluminum nitride and carbon black; 
lamellar and scaly fillers such as mica, glass plate, sericite, 
pyrophyllite, metallic foil, for example, aluminum flake, and graphite; 
balloon fillers such as Shirasu balloon, metallic balloon, glass balloon 
and pumice; and mineral fibers such as glass fiber, carbon fiber, graphite 
fiber, whisker, metallic fiber, silicon carbide fiber, asbestos and 
wollastonite. 
When the content of the filler is in excess of 150 parts by weight, the 
impact strength of molded articles deteriorates. Inversely, when it is 
less than 1 part by weight, a modification effect cannot be exerted. 
The surface of the inorganic filler is preferably treated by the use of 
stearic acid, oleic acid, palmitic acid or a metallic salt thereof, 
paraffin wax, polyethylene wax or a modified material thereof, an organic 
silane, an organic borane or an organic titanate. 
Furthermore, in the present invention, the thermoplastic resin composition 
can be brought into a flame resistant state by blending therewith a flame 
retardant (V) in an amount of 5 to 150 parts by weight based on 100 parts 
by weight of the thermoplastic resin composition (I)+(II) +(III). 
As the flame retardants, there can be used organic flame retardants of 
halogen series and phosphorus series, and inorganic flame retardants. 
The halogen series flame retardants include brominated and chlorinated 
paraffins such as tetrabromobisphenol (TBA), hexabromobenzene, 
decabromodiphenyl ether, tetrabromoethane (TBE), tetrabromobutane (TBB) 
and hexabromocyclodecane (HBCD), chlorine series flame retardants such as 
chlorinated paraffin, chlorinated polyphenyl, chlorinated polyethylene, 
chlorinated diphenyl, perchloropentacyclodecane and chlorinated 
naphthalene, usual halogen series flame retardants such as halogenated 
diphenyl sulfides, halogenated polystyrenes such as brominated 
polystyrene, brominated poly-.alpha.-methylstyrene and derivatives 
thereof, halogenated polycarbonates such as brominated polycarbonates, 
halogenated polyesters such as polyalkylene tetrabromoterephthalate and 
brominated terephthalic acid series polyesters, halogenated epoxy 
compounds such as halogenated bisphenol series epoxy resins, halogenated 
polyphenylene oxide compounds such as poly(dibromophenylene oxide), and 
high-molecular type halogen-containing polymers such as cyanuric acid 
ester compounds of halogenated bisphenols. 
Of these flame retardants, oligomers and polymers of the aromatic halides 
are particularly preferred. 
In addition, phosphorus series flame retardants include phosphates and 
halogenated phosphates such as tricresyl phosphate, 
tri(.beta.-chloroethyl) phosphate, tri(dibromopropyl) phosphate and 
2,3-dibromopropyl-2,3-chloropropyl phosphate, phosphonic acid compounds 
and phosphonic acid derivatives. 
Examples of other flame retardants include guanidine compounds such as 
guanidine nitride. 
The above-mentioned organic flame retardants may be used alone or as a 
mixture of two or more thereof. 
The organic flame retardant is used in an amount of 5 to 50 parts by 
weight, preferably 7 to 40 parts by weight based on 100 parts by weight of 
the thermoplastic resin composition (I)+(II)+(III). When the content of 
the flame retardant is less than 5 parts by weight, the flame-resistive 
effect is poor, and when it is more than 50 parts by weight, the flame 
resistive effect is not improved any more and cost rises. 
These organic flame retardants, particularly halogen series flame 
retardants can exert a synergistic effect, when used together with a flame 
resistive auxiliary. 
Examples of the flame-resistive auxiliary include antimony halides such as 
antimony trioxide, antimony pentaoxide, antimony trichloride and antimony 
pentaoxide, and antimony compounds such as antimony trisulfide, antimony 
pentasulfide, sodium antimonate, antimony tartrate and metallic antimony. 
In addition, examples of the inorganic flame retardants used in the present 
invention include aluminum hydroxide, magnesium hydroxide, zirconium 
hydroxide, basic magnesium carbonate, dolonite, hydrotalcite, calcium 
hydroxide, barium hydroxide, hydrate of stannous hydroxide, hydrates of 
inorganic metallic compounds of borax and the like, zinc borate, zinc 
metaborate, barium metaborate, zinc carbonate, magnesum-calcium carbonate, 
calcium carbonate, barium carbonate, magnesium oxide, molybdenum oxide, 
zirconium oxide, stannous oxide and red phosphorus. These inorganic flame 
retardants may be used alone or as a mixture of two or more thereof. Of 
these flame retardants, hydrates of metallic compounds of aluminum 
hydroxide, magnesium hydroxide, zirconium hydroxide, basic magnesium 
carbonate, dolonite, hydrotalcite are particularly preferable. Above all, 
aluminum hydroxide and magnesium hydroxide are effective as the flame 
retardants and are economically advantageous. 
The particle diameter of the inorganic flame retardant depends upon its 
kind, but in the cases of aluminum hydroxide and magnesium hydroxide, the 
average particle diameter is 20 .mu.m or less, preferably 10 .mu.m or 
less. 
The inorganic flame retardant is used in an amount of 30 to 150 parts by 
weight, preferably 40 to 120 parts by weight based on 100 parts by weight 
of the thermoplastic resin composition (I)+(II)+(III). When the content of 
the inorganic flame retardant is less than 30 parts by weight, the 
flame-resistive effect is poor in its single use, and thus it is necessary 
to add the organic flame retardant thereto. Inversely, when it is more 
than 150 parts by weight, impact strength and mechanical strength 
deteriorate. 
In the present invention, the above-mentioned inorganic filler and flame 
retardant may be employed simultaneously, whereby the content of the flame 
retardant can be decreased, and other characteristics can be acquired 
additionally. 
In the preparation of the thermoplastic composition of the present 
invention, melting and mixing are carried out at a temperature of 150 to 
350.degree. C., preferably 180.degree. to 320.degree. C.. When the above 
temperature is less than 150.degree. C., the melting is insufficient, 
melting viscosity is high, the mixing is poor, and the resin tends to peel 
off in a layer state. Inversely when it is in excess of 350.degree. C., 
decomposition and gelation of the resin take place inconveniently. 
In melting and mixing, there may be used a usual kneader such as a Banbury 
mixer, a pressure kneader, a kneading extruder, a biaxial extruder and 
mixing rolls. 
In the present invention, the following materials can be additionally used, 
in so far as they do not deviate from the gist of the present invention. 
Examples of such materials include resins such as polyolefin resins, 
polyvinyl chloride resin, polyvinylidene chloride resin, polyphenylene 
sulfide resin, polysulfone resin; rubbers such as a natural rubber and a 
synthetic rubber; and additives such as an antioxidant, an ultraviolet 
inhibitor, a lubricant, a dispersant, a foaming agent, a crosslinking 
agent and a colorant. 
Now, the present invention will be described in detail in reference to 
examples. 
PREATION EXAMPLE 1 
(Preparation of Multi-phase Structure Thermoplastic Resin IIIa) 
In a 5-liter stainless steel autoclave was placed 2,500 g of pure water, 
and 2.5 g of polyvinyl alcohol was further dissolved therein as a 
suspending agent. In the solution was placed 700 g of a polypropylene 
(trade name Nisseki Polypro J130G; made by Nippon Petrochemicals Co., 
Ltd.), followed by stirring to suspend the polypropylene therein. 
Separately, in 300 g of styrene as a vinyl monomer were dissolved 1.5 g of 
benzoylperoxide as a radical polymerization initiator (trade name Nyper B; 
made by Nippon Oils & Fats Co., Ltd.) and 6 g of 
t-butylperoxymethacryloyloxyethyl carbonate as a radical polymerizable or 
copolymerizable organic peroxide, and the resulting solution was then 
placed in the above-mentioned autoclave, followed by stirring. 
Afterward, the autoclave was heated up to a temperature of 60.degree. to 
65.degree. C., and stirring was then continued for 2 hours, so that the 
polypropylene was impregnated with the vinyl monomer containing the 
radical polymerization initiator and the radical polymerizable or 
copolymerizable organic peroxide. After it had been confirmed that the 
total amount of the impregnated vinyl monomer, radical polymerizable or 
copolymerizable organic peroxide and radical polymerization initiator was 
50% by weight or more of the original total weight thereof, the 
temperature of the mixture was raised up to a level of 80.degree. to 
85.degree. C., and this temperature was then maintained for 7 hours to 
complete polymerization, followed by water washing and drying, thereby 
obtaining a graft polymerization precursor IIIa'. 
Next, this graft polymerization precursor was extruded at 240.degree. C. by 
a plastomill monoaxial extruder (Toyo Seiki Seisaku-sho Ltd.) to perform 
graft reaction, whereby a multi-phase structure thermoplastic resin IIIa 
was obtained. 
This multi-phase structure thermoplastic resin (PP-g PSt) was then observed 
by a scanning type electron microscope (trade name JEOL JSM T300; made by 
JEOL, Ltd.), and it was found that it was a multi-phase structure 
thermoplastic resin in which spherical resin particles each having a 
diameter of 0.3 to 0.4 .mu.m were uniformly dispersed, as shown in FIG. 1. 
In this case, the graft efficiency of the styrene polymer was 77.1% by 
weight. 
PREATION EXAMPLE 2 
(Preparation of Multi-phase Structure Thermoplastic Resin IIIb) 
The same procedure as in Preparation Example 1 was repeated with the 
exception that 300 g of styrene as the monomer was replaced with 210 g of 
styrene and 90 g of acrylonitrile as monomers was used, thereby preparing 
a graft polymerization precursor IIIb'. According to the iodine metory 
process, the active oxygen amount of this precursor was 0.13% by weight. 
Furthermore, when this precursor was extracted with xylene by the use of a 
Soxhlet extractor, no xyleneinsoluble substance was present. 
This precursor was then kneaded at 180.degree. C. at 50 rpm for 10 minutes 
by the use of a plastomill monoaxial extruder as in Preparation Example 1 
in order to perform graft reaction. The copolymer which had not been 
grafted was then extracted from the resulting reaction product with ethyl 
acetate by the Soxhlet extractor, and a graft efficiency was measured. The 
graft efficiency of a styrene-acrylonitrile copolymer was 51% by weight. 
Moreover, extraction was then made with xylene, it was found that the 
amount of insoluble substances was 12.6% by weight. 
PREATION EXAMPLE 3 
(Preparation of Multi phase Structure Thermoplastic Resin IIIc) 
The procedure of Preparation Example 1 was repeated with the exception that 
the polypropylene (trade name Nisseki Polypro J130G; made by Nippon 
Petrochemicals Co., Ltd.) was replaced with an ethylene-glycidyl 
methacrylate copolymer (content of glycidyl methacrylate=15% by weight) 
(trade name Rexpearl J-3700; Nippon Petrochemicals Co., Ltd.) as an epoxy 
group-containing ethylene copolymer, in order to obtain a graft 
polymerization precursor IIIc'. Styrene polymer was then extracted from 
this graft polymerization precursor with ethyl acetate, and according to 
GPC, the number average polymerization of the styrene polymer was 900. 
Next, this graft polymerization precursor was extruded at 200.degree. C. as 
in Preparation Example 1, to perform graft reaction, whereby a multi-phase 
structure thermoplastic resin IIIc was obtained. 
This multi-phase structure thermoplastic resin (EGMA-g-PSt) was then 
observed, and it was found that it had a multi-phase structure in which 
spherical resin particles each having a diameter of 0.3 to 0.4 .mu.m were 
uniformly dispersed, as shown in FIG. 2. In this case, the graft 
efficiency of the styrene polymer was 49.0% by weight. 
PREATION EXAMPLE 4 
(Preparation of Multi-phase Structure Thermoplastic Resin IIId) 
The same procedure as in Preparation Example 1 was repeated with the 
exception that the ethylene-glycidal methacrylate copolymer as the epoxy 
group-containing ethylene copolymer was replaced with an ethylene-ethyl 
acrylate copolymer (content of ethyl acrylate=20% by weight) (trade name 
Rexlon EEA A-4200; made by Nippon Petrochemicals Co., Ltd.), in order to 
obtain a multi-phase structure thermoplastic resin IIId. In this case, the 
number average polymerization of a styrene polymer was 900, and an average 
grain diameter was from 0.3 to 0.4 .mu.m 
REFERENCE EXAMPLE 1 
(Preparation of Blend) 
In a 5-liter reaction tank equipped with a cooling pipe and a thermometer 
was placed 3 kg of water in which 6 g of a partially saponified polyvinyl 
alcohol was dissolved, and it was then stirred and heated up to 80.degree. 
C.. Styrene in which 5 g of benzoyl peroxide was dissolved was added 
thereto, and polymerizaion was performed for 7 hours. After the 
polymerization, the resulting polymer was filtered, washed and dried to 
obtain 950 g of polystyrene. The latter was then mixed with a 
polypropylene homopolymer (trade name Nisseki Polypro J130G; made by 
Nippon Petrochemicals Co., Ltd.) under melting. The mixing ratio of 
polypropylene:polystyrene was 70 parts by weight:30 parts by weight. This 
melting/mixing process was carried out at 230.degree. C. at a screw 
revolution speed of 100 rpm by the use of an extruder having a screw 
diameter of 20 mm and L/D=24 (trade name Labo Plastomill; made by Toyo 
Seiki Seisaku-sho Ltd.). The resulting composition was observed through an 
electron microscope, and the results are shown in FIG. 3. In this Figure, 
particles of the polystyrene are not observed, and fine fibrous peeled 
layers are seen, which indicates that mixing is not made sufficiently. 
EXAMPLES 1 TO 8 
A polypropylene homopolymer (trade name Nisseki Polypro J130G; made by 
Nippon Petrochemicals Co., Ltd.) of MFR 4.0, polybutylene terephthalate 
(which is represented with PBT in tables given hereinafter) having an 
intrinsic viscosity of 3.5 dl/g as an aromatic polyester, and multi-phase 
structure thermoplastic resin IIIa, IIIc and IIId were mixed in ratios 
shown in Table 1. 
The melting/mixing process was carried out by feeding the respective 
materials into a one-directional twin-screw extruder (made by Plastic 
Engineering Institute) and then mixing them under melting in a cylinder 
thereof. The mixed resin was then formed into granules, and the latter 
were then dried at 150.degree. C. for 3 hours, followed by injection 
molding in order to prepare specimens. 
Sizes of the specimens and standard tests were as follows: 
______________________________________ 
Specimens for notched izod impact strength 
13 .times. 65 .times. 6 mm 
(JIS K7110) 
Specimens for heat distortion temperature 
13 .times. 130 .times. 6 mm 
(JIS K7207) 
Specimens for flexural strength 
10 .times. 130 .times. 4 mm 
(JIS K7203) 
______________________________________ 
State of Delamination: 
The state of delamination was ranked as follows by visually observing the 
state of the broken surface of each molded article. 
O: Delamination was not present at all. 
.DELTA.: Delamination was slightly present. 
X: Delamination was perceptibly present. 
TABLE 1 
______________________________________ 
Example 1 2 3 4 5 6 7 8 
______________________________________ 
Poly- 90 80 70 70 40 30 30 10 
propylene 
(wt %) 
PBT (wt %) 
10 20 30 30 60 70 70 90 
Multi-Phase 
10 10 10 10 10 5 5 5 
Structure 
Themoplastic 
Resin IIIa* 
Multi-Phase 
5 5 8 -- 15 -- 15 20 
Structure 
Themoplastic 
Resin IIIc* 
Multi-Phase 
-- -- -- 10 -- 20 -- -- 
Structure 
Themoplastic 
Resin IIId* 
Notched Izod 
8 10 14 12 18 20 23 21 
Impact 
Strength 
(kg .multidot. cm/cm) 
Heat 68 70 69 70 67 70 70 69 
Distortion 
Temperature 
(.degree.C.) 
(18.6 kg/cm.sup.2) 
Flexural 420 450 490 470 620 650 630 680 
Strength 
(kg/cm.sup.2) 
State of O O O O O O O O 
Delamination 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PBT. 
EXAMPLES 9 TO 15 
The same procedure as in the above-mentioned examples was repeated with the 
exception that the multi-phase structure thermoplastic resin (IIIa) and 
(IIIc) were replaced with graft polymerization precursors (IIIa'), (IIIc') 
and (IIId') obtained in Preparation Examples 1, 3 and 4, and the results 
are set forth in Table 2. 
TABLE 2 
______________________________________ 
Example 9 10 11 12 13 14 15 
______________________________________ 
Polypropylene 
90 80 40 40 30 20 20 
(wt %) 
PBT (wt %) 
10 20 60 60 70 80 80 
Graft Poly- 
10 10 10 10 5 5 5 
merization 
Precursor 
(IIIa')* 
Graft Poly- 
5 5 15 -- 15 15 -- 
merization 
Precursor 
(IIIc')* 
Graft Poly- 
-- -- -- 15 -- -- 15 
merization 
Precursor 
(IIId')* 
Notched Izod 
8 12 20 17 21 22 20 
Impact 
Strength 
(kg .multidot. cm/cm) 
Heat 68 64 59 58 52 50 52 
Distortion 
Temperature 
(.degree.C.) 
(18.6 kg/cm.sup.2) 
Flexural 400 430 600 560 630 660 610 
Strength 
(kg/cm.sup.2) 
State of O O O O O O O 
Delamination 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PBT. 
EXAMPLE 16 TO 24 
In these examples, a glass fiber as an inorganic filler was blended in 
which an average fiber length was 5.0 mm and a fiber diameter was 10 
.mu.m. The results are set forth in Table 3. 
TABLE 3 
__________________________________________________________________________ 
Example 16 17 18 19 20 21 22 23 24 
__________________________________________________________________________ 
Polypropylene 
80 70 70 70 30 30 20 20 20 
(wt %) 
PBT (wt %) 
20 30 30 30 70 70 80 80 80 
Multi-Phase 
10 10 -- -- 10 -- 10 -- -- 
Structure 
Themoplastic 
Resin IIIa* 
Multi-Phase 
10 10 -- -- 10 -- 15 -- -- 
Structure 
Themoplastic 
Resin IIIc* 
Graft Poly- 
-- -- 10 10 -- 10 -- 10 10 
merization 
Precursor 
(IIIa')* 
Graft Poly- 
-- -- 10 -- -- 10 -- -- -- 
merization 
Precursor 
(IIIc')* 
Graft Poly- 
-- -- -- 10 -- -- -- -- 15 
merization 
Precursor 
(IIId')* 
Glass Fiber** 
30 30 30 30 30 30 30 30 30 
Notched Izod 
13 16 15 13 16 15 17 17 15 
Impact 
Strength 
(kg .multidot. cm/cm) 
Heat 130 
138 
140 135 
140 
145 
159 162 
160 
Distortion 
Temperature 
(.degree.C.) 
(18.6 kg/cm.sup.2) 
__________________________________________________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PBT. 
**Parts by weight based on 100 parts by weight of polypropylene + PBT + 
multiphase structure thermoplastic resin (graft polymerization precursor) 
 
EXAMPLES 25 to 30 
The same procedure as in Examples 16 and 22 was repeated with the exception 
that flame retardants and auxiliaries were used, in order to prepare 
combustion specimens (1/4".times.1/2".times.5") having compositions shown 
in Table 4, and vertical flame tests were then carried out in accordance 
with UL-94 standard 
TABLE 4 
______________________________________ 
Example 25 26 27 28 29 30 
______________________________________ 
Polypropylene 
80 80 80 80 20 20 
(wt %) 
PBT (wt %) 
20 20 20 20 80 80 
Multi-Phase 
10 10 10 10 10 10 
Structure 
Themoplastic 
Resin IIIa*.sup.1 
Multi-Phase 
10 10 10 10 15 15 
Structure 
Themoplastic 
Resin IIIc*.sup.1 
Glass Fiber*.sup.2 
30 30 30 30 30 30 
Brominated 
5 7 25 -- 10 -- 
Polystyrene*.sup.3 
Magnesium -- -- -- 50 -- 100 
Hydroxide*.sup.4 
Antimony 2 2 10 -- 4 -- 
Trioxide 
UL-94 Flame 
V-0 V-0 V-0 V-2 V-0 V-2 
Properties 
______________________________________ 
*.sup.1 Parts by weight based on 100 parts by weight of polypropylene + 
PBT. 
*.sup.2 Parts by weight based on 100 parts by weight of polypropylene + 
PBT + multiphase structure thermoplastic resin. 
##STR3## 
*.sup.4 Average grain diameter was 5 .mu.m. 
COMATIVE EXAMPLES 1 TO 5 
The procedure of the above-mentioned examples was repeated with the 
exception that the blends obtained in Reference Example 2, the 
ethylene-glycidyl methacrylate copolymer used in Preparation Example 3 and 
a modified polypropylene (amount of added maleic acid=0.15% by weight). 
The results are set forth in Table 5. 
TABLE 5 
______________________________________ 
Comp. Example 
1 2 3 4 5 
______________________________________ 
Polypropylene 
40 40 40 40 40 
(wt %) 
PBT (wt %) 60 60 60 60 60 
Blend 10 -- -- -- -- 
Ethylene-Glycidyl 
-- 5 10 -- 10 
Methacrylate 
Copolymer 
Modified Poly- 
-- -- -- 25 25 
propylene 
Notched Izod 
2 5 7 6 8 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
49 58 56 54 53 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Flexural Strength 
500 620 500 510 480 
State of X X X X O 
Delamination 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PBT. 
EXAMPLES 31 TO 36 
The procedure of Example 1 was repeated with the exception that the 
polybutylene terephthalate and multiphase structure thermoplastic resin 
(IIIa) used therein were replaced with a polycarbonate resin having a 
number average molecular weight of 62,000 and the multi-phase structure 
thermoplastic resin (IIIb) obtained in Preparation Example 2, and 
melting/mixing was made in ratios shown in Table 6. 
Chemical resistance was then evaluated by immersing each specimen into 
methanol at 75.degree. C. for 30 days, then drying it at room temperature, 
measuring the deterioration ratio of tensile strength, and observing the 
appearance of the specimen. 
O: The specimen was not changed. 
X: Cracks and dissolution took place on the surface of the specimen. 
TABLE 6 
______________________________________ 
Example 31 32 33 34 35 36 
______________________________________ 
Polypropylene (wt %) 
25 25 50 50 80 80 
Polycarbonate (wt %) 
75 75 50 50 20 20 
Multi-phase 10 20 10 20 10 20 
Structure 
Thermoplastic 
Resin (IIIb)* 
Notched Izod 72 80 62 65 45 51 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
127 125 120 117 120 120 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Chemical Resistance 
Appearance O O O O O O 
Detrioration 10 8 5 5 3 2 
Ratio of Tensile 
Strength (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + 
polycarbonate. 
EXAMPLES 37 TO 40 
The procedure of the above-mentioned examples was repeated with the 
exception that the multi-phase structure thermoplastic resin (IIIb) used 
therein was replaced with a graft polymerization precursor (IIIb'). The 
results are set forth in Table 7. Functional effects in these cases are 
similar to those in cases of the grafted multi-phase structure 
thermoplastic resins. 
TABLE 7 
______________________________________ 
Example 37 38 39 40 
______________________________________ 
Polypropylene (wt %) 
25 25 50 80 
Polycarbonate (wt %) 
75 75 50 20 
Graft Polymerization 
10 20 20 20 
Precursor (IIIb')* 
Notched Izod 70 83 63 55 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 130 127 115 123 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Chemical Resistance 
Appearance O O O O 
Detrioration 11 10 6 3 
Ratio of Tensile 
Strength (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + 
polycarbonate. 
EXAMPLES 41 TO 44 
In the above-mentioned examples, a glass fiber having an average fiber 
length of 3. 0 mm and a diameter of 10 .mu.m was additionally blended. The 
results are set forth in Table 8. 
TABLE 8 
______________________________________ 
Example 41 42 43 44 
______________________________________ 
Polypropylene (wt %) 
25 25 50 80 
Polycarbonate (wt %) 
75 75 50 20 
Multi-phase 15 25 20 20 
Structure 
Thermoplastic 
Resin (IIIb)* 
Glass Fiber** 30 30 30 30 
Notched Izod 95 88 80 59 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 145 140 137 125 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + 
polycarbonate. 
**Parts by weight based on 100 parts by weight of polypropylene + PBT + 
multiphase structure thermoplastic resin (graft polymerization precursor) 
 
EXAMPLES 45 TO 52 
The procedure of Example 1 was repeated with the exception that the 
polybutylene terephthalate was replaced with 6,6-nylon (trade name Amilan 
CM3001-N; made by Toray Industries, Inc.), and melting/mixing was made in 
ratios shown in Table 9. Afterward, physical properties were then 
measured. 
Hygroscopicity was evaluated by immersing each specimen into water at 
23.degree. C. for 24 hours, then allowing it to stand at 23.degree. C. at 
a relative humidity of 65%, and making a calculation on the basis of a 
weight increment ratio. 
Furthermore, coating adhesive properties were evaluated by coating each 
specimen with an acrylic coating material, applying a cellophane adhesive 
tape on the surface of the coating material, tearing away it therefrom, 
and observing a state on the surface. 
O: The coating film was not delaminated at all. 
.DELTA.: The coating film was partially delaminated. 
X: The coating film was substantially all delaminated. 
TABLE 9 
______________________________________ 
Example 45 46 47 48 49 50 51 52 
______________________________________ 
Poly- 80 80 60 60 50 30 30 20 
propylene 
(wt %) 
6,6-Nylon 
20 20 40 40 50 70 70 80 
(wt %) 
Multi-phase 
10 5 10 10 10 5 5 5 
Structure 
Thermo- 
plastic 
Resin (IIIa)* 
Multi-phase 
10 15 10 -- 10 15 -- 20 
Structure 
Thermo- 
plastic 
Resin (IIIc)* 
Multi-phase 
-- -- -- 10 -- -- 15 -- 
Structure 
Thermo- 
plastic 
Resin (IIId)* 
Notched Izod 
18 16 19 17 20 20 22 25 
Impact 
Strength 
(kg .multidot. cm/cm) 
Heat 70 70 75 77 80 83 81 90 
Distortion 
Temperature 
(.degree.C.) 
(18.6 kg/cm.sup.2) 
Coating O O O O O O O O 
Adhesive 
Properties 
Hygro- 2.5 2.5 4.0 3.8 4.5 6.2 6.6 6.5 
scopicity (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + nylon. 
EXAMPLES 53 TO 60 
In the above-mentioned examples, a glass fiber having an average fiber 
length of 7.0 mm and a diameter of 10 .mu.m was additionally blended. The 
results are set forth in Table 10. 
TABLE 10 
______________________________________ 
Example 53 54 55 56 57 58 59 60 
______________________________________ 
Poly- 80 60 60 50 50 30 30 20 
propylene 
(wt %) 
6,6-Nylon 
20 40 40 50 50 70 70 80 
(wt %) 
Multi-phase 
10 10 10 10 10 5 5 5 
Structure 
Thermo- 
plastic 
Resin (IIIa)* 
Multi-phase 
10 10 -- 10 -- 15 -- 20 
Structure 
Thermo- 
plastic 
Resin (IIIc)* 
Multi-phase 
-- -- 10 -- 10 -- 15 1 
Structure 
Thermo- 
plastic 
Resin (IIId)* 
Glass Fiber 
35 35 35 35 35 35 35 35 
Notched Izod 
50 47 42 44 42 40 42 40 
Impact 
Strength 
(kg .multidot. cm/cm) 
Heat 128 135 143 140 138 157 155 165 
Distortion 
Temperature 
(.degree.C.) 
(18.6 kg/cm.sup.2) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + nylon. 
**Parts by weight based on 100 parts by weight of polypropylene + nylon + 
multiphase structure thermoplastic resin. 
EXAMPLES 61 TO 67 
In Examples 53 and 54, the same flame retardants and auxiliaries as in 
Example 25 were additionally blended, and a flame test was then carried 
out. The procedure of the test was the same as in Example 25. The results 
are set forth in Table 11. 
TABLE 11 
______________________________________ 
Example 61 62 63 64 65 66 67 
______________________________________ 
Polypropylene 
80 80 80 80 80 20 20 
(wt %) 
6,6-Nylon (wt %) 
20 20 20 20 20 80 80 
Multi-phase 10 10 10 10 10 5 5 
Structure 
Thermoplastic 
Resin (IIIa)* 
Multi-phase 10 10 -- 10 10 -- 20 
Structure 
Thermoplastic 
Resin (IIIc)* 
Multi-phase -- -- 10 -- -- 20 -- 
Structure 
Thermoplastic 
Resin (IIId)* 
Glass Fiber 35 35 35 35 35 35 35 
Brominated 5 10 10 25 -- 20 -- 
Polystyrene** 
Magnesium -- -- -- -- 100 -- 100 
Hydroxide** 
Antimony 2 5 5 10 -- 10 -- 
Trioxide** 
UL-94 Flame V-0 V-0 V-0 V-0 V-2 V-0 V-2 
Properties 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + nylon. 
**Parts by weight based on 100 parts by weight of polypropylene + nylon + 
multiphase structure thermoplastic resin. 
COMATIVE EXAMPLES 6 TO 11 
The procedure of Examples 43 was repeated with the exception that the 
multi-phase structure thermoplastic resin was replaced with a blend and a 
modified polypropylene, as in Comparative Examples 1 to 5. The results are 
set forth in Table 12. 
TABLE 12 
______________________________________ 
Comp. Example 6 7 8 9 10 11 
______________________________________ 
Polypropylene (wt %) 
80 80 80 50 40 30 
6,6-Nylon (wt %) 
20 20 20 50 60 70 
Blend -- 10 -- -- -- -- 
Modified Poly- -- -- 25 20 20 20 
propylene 
Notched Izod 5 6 12 14 15 20 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
60 62 67 77 77 79 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Coating Adhesive 
X X .DELTA. 
O O O 
Properties 
Hygroscopicity (%) 
3.0 3.1 2.7 4.8 5.3 6.6 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + nylon. 
EXAMPLES 68 TO 75 
The procedure of Example 1 was repeated with the exception that the 
polybutylene terephthalate was replaced with 
pol-2,6-dimethyl-1,4-phenylene ether (which is represented with PPE in 
tables), a modified PPE (trade name Nolyl 534J; made by Engineering 
Plastics Co., Ltd.) and the multi-phase structure thermoplastic resin 
(IIIa) obtained in Preparation Example 1. The results are set forth in 
Table 13. 
Chemical resistance was evaluated by immersing each specimen into gasoline 
for 1.5 hours, and then observing its appearance. 
O: The specimen was not changed at all. 
.DELTA.: The specimen was partially dissolved on its surface. 
X: The specimen was remarkably dissolved on its surface. 
TABLE 13 
__________________________________________________________________________ 
Example 68 69 70 71 72 73 74 75 
__________________________________________________________________________ 
Polypropylene (wt %) 
30 30 50 50 80 80 30 80 
PPE (wt %) 70 70 50 50 20 20 -- -- 
Modified PPE (wt %) 
-- -- -- -- -- -- 70 20 
Multi-phase 10 20 10 20 10 20 20 20 
Structure 
Thermoplastic 
Resin (IIIa)* 
Notched Izod 
22 32 25 30 15 20 28 18 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
127 
125 
120 
117 
120 
120 
129 
122 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Chemical Resistance 
O O O O O O O O 
__________________________________________________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PPE. 
EXAMPLES 76 TO 82 
The procedure of the above-mentioned examples was repeated with the 
exception that the multi-phase structure thermoplastic resin used therein 
was replaced with a graft polymerization precursor, and physical 
properties were then measured. The results are set forth in Table 14. 
TABLE 14 
______________________________________ 
Example 76 77 78 79 80 81 82 
______________________________________ 
Polypropylene 
30 30 50 20 20 30 20 
(wt %) 
PPE (wt %) 70 70 50 80 80 70 -- 
Modified PPE 
-- -- -- -- -- -- 80 
(wt %) 
Graft Polymeriza- 
10 20 20 10 20 20 20 
tion Precursor 
(IIIa') 
Notched Izod 
20 33 45 55 61 26 58 
Impact Strength 
(kg.multidot.cm/cm) 
Heat Distortion 
130 127 115 113 110 130 114 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Chemical Resistance 
O O O O O O O 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PPE. 
EXAMPLES 83 TO 89 
In the above-mentioned examples, a glass fiber having an average fiber 
length of 5.0 mm and a diameter of 10 .mu.m was additionally blended. The 
results are set forth in Table 15. 
TABLE 15 
______________________________________ 
Example 83 84 85 86 87 88 89 
______________________________________ 
Polypropylene 
25 25 25 50 80 25 80 
(wt %) 
PPE (wt %) 75 75 75 50 20 -- -- 
Modified PPE 
-- -- -- -- -- 75 20 
(wt %) 
Multi-phase 15 25 -- 20 20 20 20 
Structure 
Thermoplastic 
Resin (IIIa)* 
Graft Polymeriza- 
-- -- 25 -- -- -- -- 
tion Precursor 
(IIIa') 
Glass Fiber 30 30 30 30 30 30 30 
Notched Izod 
42 50 52 45 35 39 28 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
147 140 135 137 125 135 129 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PPE. 
**Parts by weight based on 100 parts by weight of polypropylene + PPE + 
multiphase structure thermoplastic resin (graft polymerization precursor) 
 
COMATIVE EXAMPLES 12 TO 18 
The procedure of the above-mentioned examples was repeated with the 
exception that the blend obtained in Reference Example 1 was replaced with 
ethylene-glycidyl methacrylate copolymer and a modified polypropylene 
(which was obtained by the addition reaction of 0.1% by weight of maleic 
anhydride to a polypropylene). The results are set forth in Table 16. 
TABLE 16 
______________________________________ 
Comp. Example 
12 13 14 15 16 17 18 
______________________________________ 
Polypropylene 
30 30 50 50 75 30 30 
(wt %) 
PPE (wt %) 70 70 50 50 25 70 70 
Blend -- -- -- -- -- 15 -- 
Ethylene-Glycidyl 
10 15 -- -- -- -- -- 
Methacrylate 
Copolymer 
Modified Poly- 
-- -- -- -- -- -- 15 
propylene 
Notched Izod 
9 5 11 7 4 2 4 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
117 110 95 98 91 88 91 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Chemical Resistance 
.DELTA. 
X .DELTA.-X 
X .DELTA.-X 
X .DELTA.-X 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + PPE. 
EXAMPLES 90 TO 97 
A polypropylene homopolymer (trade name Nisseki Polypro J130G; made by 
Nippon Petrochemicals Co., Ltd.) of MFR 4.0, an ABS resin in Table 17 and 
the multi-phase structure thermoplastic resin (IIIb) obtained in 
Preparation Example 2 were mixed under melting in a ratio shown in Table 
18. The procedure of the melting/mixing process and the measurement manner 
of mechanical properties were the same as in Example 1. 
Coating adhesive properties were evaluated by coating each specimen with an 
acrylic coating material, applying a cellophane adhesive tape on the 
surface of the coating material, tearing away it therefrom, and observing 
a state on the surface. The coating adhesive properties were ranked as 
follows: 
O: The coating film was not delaminated at all. 
.DELTA.: The coating film was partially delaminated. 
X: The coating film was substantially all delaminated. 
Furthermore, chemical resistance was evaluated by immersing each specimen 
into acetone for 1 hour, then drying it at room temperature, measuring the 
deterioration ratio of tensile strength, and observing the appearance of 
the specimen. 
O: The specimen was not changed at all. 
.DELTA.: The specimen was partially dissolved on its surface. 
X: The specimen was remarkably dissolved on its surface. 
TABLE 17 
______________________________________ 
Sample 
Composition ABS Resin [1] 
ABS Resin [2] 
______________________________________ 
Acrylonitrile (wt %) 
20 25 
Styrene (wt %) 
55 15 
.alpha.-Methylstyrene (wt) 
0 40 
Polybutadiene (wt %) 
25 20 
Intrinsic Viscosity 
0.60 0.65 
______________________________________ 
TABLE 18 
______________________________________ 
Example 90 91 92 93 94 95 96 97 
______________________________________ 
Polypropylene (wt %) 
25 25 25 50 50 50 80 80 
ABS Resin [1] (wt %) 
75 75 -- 50 50 -- 20 -- 
ABS Resin [2] (wt %) 
-- -- 75 -- -- 50 -- 20 
Multi-phase 20 10 20 20 10 20 20 20 
Structure 
Thermoplastic 
Resin (IIIb)* 
Notched Izod 35 27 26 23 20 20 20 17 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
75 78 75 73 73 75 81 80 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Coating Adhesive 
O O O O O O O O 
Properties 
Chemical Resistance 
Appearance O O O O O O O O 
Deterioration 7 8 7 5 5 5 3 2 
Ratio of Tensile 
Strength (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin. 
EXAMPLES 98 to 104 
The procedure of the above-mentioned examples was repeated with the 
exception that the grafted multi-phase structure thermoplastic resin was 
replaced with the graft polymerization precursor obtained in Preparation 
Example 2, and that a glass fiber having an average fiber length of 5.0 mm 
and a diameter of 10 .mu.m was additionally blended. The results are set 
forth in Table 19. 
TABLE 19 
______________________________________ 
Example 98 99 100 101 102 103 104 
______________________________________ 
Polypropylene 
25 50 50 80 80 80 25 
(wt %) 
ABS Resin [1] 
75 50 -- 20 -- -- 75 
(wt %) 
ABS Resin [2] 
-- -- 50 -- 20 20 -- 
(wt %) 
Multi-phase -- -- -- 20 20 -- 20 
Structure 
Thermoplastic 
Resin (IIIb)* 
Graft Polymeriza- 
20 20 20 -- -- 20 -- 
tion Precursor 
(IIIb') 
Glass Fiber -- -- -- 20 20 20 20 
Notched Izod 
24 22 19 17 15 17 18 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
74 74 73 110 108 110 100 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Coating Adhesive 
O O O O O O O 
Properties 
Chemical Resistance 
Appearance O O O O O O O 
Deterioration 
9 6 5 3 3 2 2 
Ratio of Tensile 
Strength (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin. 
**Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin + multiphase structure thermoplastic resin (graft polymerization 
precursor). 
EXAMPLES 105 TO 112 
In Examples 101, 102 and 104, the same flame retardants and auxiliaries as 
used in Example 25 were additionally used, and a flame test was then 
carried out. The procedure of the test was the same as in Example 25. The 
results are set forth in Table 20. 
TABLE 20 
__________________________________________________________________________ 
Example 105 
106 
107 
108 
109 
110 
111 
112 
__________________________________________________________________________ 
Polypropylene (wt %) 
80 80 80 80 80 25 25 25 
ABS Resin [1] (wt %) 
20 20 20 -- -- 75 75 75 
ABS Resin [2] (wt %) 
-- -- -- 20 20 -- -- -- 
Multi-phase 20 20 20 20 20 20 20 20 
Structure 
Thermoplastic 
Resin (IIIb)* 
Glass Fiber 30 30 30 30 30 30 30 30 
Brominated -- 10 25 10 25 -- -- 10 
Polystyrene* 
Magnesium 100 
-- -- -- -- 50 100 
-- 
Hydroxide** 
Antimony -- 7 10 7 10 -- -- 10 
Trioxide** 
UL-94 Flame V-2 
V-0 
V-0 
V-0 
V-0 
V-2 
V-1 
V-0 
Properties 
__________________________________________________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin. 
**Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin + multiphase structure thermoplastic resin. 
COMATIVE EXAMPLES 19 TO 25 
The procedure of Examples 90 to 92 was repeated with the exception that the 
multi-phase structure thermoplastic resin used therein was replaced with 
the blend obtained in Reference Example 1 and ethylene-vinyl acetate 
copolymer (content of vinyl acetate=30% by weight). The results are set 
forth in Table 21. 
TABLE 21 
______________________________________ 
Comp. Example 
19 20 21 22 23 24 25 
______________________________________ 
Polypropylene 
-- -- 25 25 25 25 25 
(wt %) 
ABS Resin [1] 
100 -- 75 -- -- 75 75 
(wt %) 
ABS Resin [2] 
-- 100 -- 75 -- -- 75 
(wt %) 
Blend* -- -- -- -- -- 20 20 
Ethylene-Vinyl 
-- -- 15 15 -- -- -- 
Acetate Copolymer* 
Notched Izod 
18 19 10 11 5 5 6 
Impact Strength 
(kg .multidot. cm/cm) 
Heat Distortion 
81 82 73 75 77 78 77 
Temperature (.degree.C.) 
(18.6 kg/cm.sup.2) 
Coating Adhesive 
O O .DELTA. 
.DELTA. 
.DELTA. 
X X 
Properties 
Chemical Resistance 
Appearance X X .DELTA. 
.DELTA. 
X X X 
Deterioration 
75 69 43 50 77 85 80 
Ratio of Tensile 
Strength (%) 
______________________________________ 
*Parts by weight based on 100 parts by weight of polypropylene + ABS 
resin. 
The thermoplastic resin composition of the present invention effectively 
has different features than the raw material resins, and it is excellent 
in moldability, chemical resistance, impact resistance, heat resistance, 
coating properties, mechanical properties and appearance of molded 
articles made therefrom. Degrees of impact strength, heat resistance and 
mechanical properties can be regulated by suitably selecting the ratio of 
resins and a multi-phase structure thermoplastic resin which are mixed 
with one another, and therefore the present invention can meet a variety 
of demands. 
As is apparent from the foregoing, the thermoplastic resin composition of 
the present invention can be widely utilized as materials for, e.g., 
automobile parts, electrical and electronic machine parts, and other 
industrial parts.