JP2955944B2 - Thermoplastic resin composition with improved fatigue properties - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having improved fatigue properties.

(Prior art) As a thermoplastic resin having excellent impact resistance, a rubber-modified thermoplastic resin represented by an ABS resin and a high impact polystyrene is widely used. In particular, ABS resins are widely used because of their excellent moldability, impact resistance, etc., and good appearance of molded products. However, ABS resin lacks heat resistance, so 90
There is a limit to use at relatively high temperatures, such as above ° C. Therefore, various methods for improving the heat resistance of the ABS resin have been proposed. For example, JP-B-35-18194, JP-B-5-18194
JP-A-7-60373 describes that a resin composition having excellent heat resistance can be obtained by blending a copolymer of α-methylstyrene and acrylonitrile with an ABS resin.

Japanese Patent Publication No. 38-15225 discloses a method of improving impact resistance by blending a polycarbonate resin with an ABS resin.
JP-B-55-27579, JP-B-58-12300, JP-B-58-46269, JP-A-57-40536, JP-A-58
-149938 and JP-A-57-12047.

(Problems to be Solved by the Invention) However, the resin composition obtained by blending the above ABS resin with a polymer composed of α-methylstyrene and acrylonitrile has improved heat resistance, but generally has a reduced impact strength. In fact, they cannot be used like ABS resin. On the other hand, the method of blending the polycarbonate resin with the ABS resin is almost satisfactory in terms of heat resistance and impact resistance, but has a problem that the strength when repeated stress is applied, that is, the fatigue strength is insufficient.

(Means for Solving the Problems) As a result of intensive studies to solve the above problems, the present inventors have found that polyolefin which is obtained by copolymerizing glycidyl methacrylate with a composition comprising polycarbonate and a specific graft polymer is mainly used. By blending a copolymer having a vinyl polymer as a side chain and a side chain, it has been found that heat resistance, impact resistance can be provided, and a composition having improved fatigue strength can be provided. Reached.

 That is, the present invention.

(A) polycarbonate resin: 15 to 90 parts by weight (B) at least one selected from the group consisting of polybutadiene rubber, crosslinked acrylic rubber, organosiloxane rubber and ethylene-propylene-non-conjugated diene rubber
In the presence of 15 to 85 parts by weight of the rubbery polymer (a), 15 to 40% by weight of vinyl cyanide monomer 25 to 85% by weight of aromatic vinyl monomer Other vinyl monomer 0 to 35 85 to 15 parts by weight of a vinyl monomer (b) composed of 100% by weight (the total amount of these components is 100% by weight)
(The total amount of (b) and (b) is 100 parts by weight). Graft polymer obtained by graft polymerization: 10 to 85 parts by weight (C) Aromatic vinyl monomer, vinyl cyanide monomer and methacrylate Polymer obtained by polymerizing at least one selected from the group consisting of monomers: 0 to 60 parts by weight (D) 5 to 30% by weight based on 100 parts by weight of the thermoplastic resin composition Less than 2 to 20 parts by weight of a copolymer having a main chain of a polyolefin copolymerized with glycidyl methacrylate having a side chain of a polymer composed of a vinyl cyanide monomer and an aromatic vinyl monomer. Is a thermoplastic resin composition.

 Each component of the present invention will be described.

(A) About polycarbonate resin.

The polycarbonate resin (A) in the present invention is obtained from dihydroxydiarylalkane and may be arbitrarily branched. These polycarbonate resins are produced by a known method, and are generally produced by reacting a dihydroxy or polyhydroxy compound with phosgene or a diester of carbonic acid.

Suitable dihydroxydiarylalkanes are those having an alkyl, chlorine or bromine atom ortho to the hydroxy group. Preferred specific examples of the dihydroxyarylalkane include 4,4-dihydroxy-2,2-diphenylpropane (= bisphenol A), tetramethylbisphenol A and bis- (4
-Hydroxyphenyl) -p-diisopropylbenzene and the like.

The branched polycarbonate is produced, for example, by substituting a part of the dihydroxy compound, for example, 0.2 to 2 mol% with polyhydroxy. Specific examples of the polyhydroxy compound include phlorogrisinol, 4,6-
Dimethyl-2,4,6-tri- (4-hydroxyphenyl)
-Heptene, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl-benzene) and the like.

The amount of the polycarbonate resin (A) used is
15 out of 100 parts of the total amount of (A), (B) and (C)
If the amount is less than 15 parts by weight, the impact resistance and heat resistance of a molded article obtained from the obtained resin composition are inferior, and if it exceeds 90 parts by weight, the moldability is inferior.

(B) About the graft copolymer.

The graft copolymer (B) in the present invention is obtained by graft polymerization of a vinyl cyanide monomer and an aromatic vinyl monomer in the presence of a rubbery polymer. As the rubbery polymer, a polybutadiene rubber; a copolymer containing 50% by weight or more of butadiene units and containing inferior amounts of styrene units and acrylonitrile units, for example, styrene-butadiene copolymer and acrylonitrile-butadiene copolymer Polyacrylate rubber such as polybutyl acrylate; polyorganosiloxane rubber; ethylene-propylene-non-conjugated diene rubber; and polybutadiene / polybutyl acrylate 2 in which polybutyl acrylate is provided on the outer layer of polybutadiene.
A composite rubber such as a stepped rubbery polymer; a rubber having a structure in which a polysiloxane rubber and a polyacrylic acid rubber are entangled with each other; or a composite rubber composed of the above rubbery polymer components composed of other combinations; or Mixtures of two or more of these are raised. Those having a rubbery polymer content of 15 to 80% by weight in the graft copolymer (B) are preferably used.

Examples of the vinyl cyanide monomer used for the graft polymerization include acrylotrile, methacrylonitrile, ethacrylonitrile, fumaronitrile and the like, and these can be used alone or in combination. The ratio of the vinyl cyanide monomer in the graft monomer is 15 to 40% by weight.
It is. If the amount is less than 15% by weight, the resulting resin composition tends to have poor impact resistance and chemical resistance, which is not preferable. Also, 40
If the amount is more than about 10% by weight, the resulting resin composition is undesirably colored when molded and the impact resistance is reduced.

As the aromatic vinyl monomer used for the graft polymerization, styrene, α-methylstyrene, o-methylstyrene, 1,3-dimethylstyrene, p-methylstyrene, t
-Butylstyrene, halogenated styrene, p-ethylstyrene, and the like, which can be used alone or in combination. The proportion of the aromatic vinyl monomer to the graft monomer is 25 to 85% by weight, and if it is outside these ranges, at least one of impact resistance and moldability is inferior.

Other copolymerizable vinyl monomers that can be used at the time of graft polymerization include maleimide monomers such as methyl methacrylate, ethyl methacrylate and N-phenylmaleimide, but are not particularly limited thereto. It is not something to be done. The other vinyl monomer capable of being copolymerized is optionally used in a range of up to 35% by weight in the graft monomer.

The amount of the graft copolymer (B) used is (A),
The total amount of (B) and (C) is 10 to 85 parts by weight out of 100 parts by weight, and if less than 10 parts by weight, the impact resistance of a molded article from the obtained resin composition is inferior. If it exceeds, the heat resistance is inferior.

(C) About a polymer.

The polymer (C) in the present invention is a polymer obtained by polymerizing at least one selected from the group consisting of an aromatic vinyl monomer, a vinyl cyanide monomer and a methacrylate monomer. . The vinyl cyanide monomer and the aromatic vinyl monomer used here are the same as the monomers used in the graft polymer (B). The methacrylate monomer is not particularly limited, but preferably methyl methacrylate, ethyl methacrylate, propyl methacrylate and the like are used.

The polymer (C) may be obtained by polymerizing another copolymerizable monomer in addition to the above monomer up to 30% by weight. Examples of the copolymerizable monomer include an acrylate monomer, a maleimide monomer, and a pyridine monomer, but are not particularly limited thereto.

The polymer (C) is used as needed for the purpose of improving moldability, heat resistance and elastic modulus. The amount of the polymer (C) used is 0 to 60 parts by weight of the total of 100 parts by weight of the components (A), (B) and (C). It cannot be a resin composition, which is not preferred. The intrinsic viscosity of the polymer (C) is preferably 0.3 to 1.5 from the viewpoint of moldability and impact resistance.

(D) About the copolymer.

One of the features of the present invention is that the copolymer (D) is blended. By blending the copolymer (D), fatigue properties can be improved. This copolymer (D) is a copolymer having a main chain of a polyolefin copolymerized with glycidyl methacrylate and a side chain of a polymer composed of a vinyl cyanide monomer and an aromatic vinyl monomer, and The glycidyl methacrylate in the polyolefin copolymerized with glycidyl methacrylate is 5% by weight or more and less than 30% by weight.

In the copolymer (D), the olefin used for the main chain copolymer is ethylene, propylene, or butene-1, preferably 50 mol% or more of ethylene. In the copolymer (D), the vinyl cyanide monomer and the aromatic vinyl monomer used for the side chain polymer are the monomers used in the graft copolymer (B). The same is used. The polymer serving as a side chain may optionally be polymerized with other copolymers up to 30% by weight in addition to the above monomers. Examples of the copolymerizable monomer include a methacrylate monomer, an acrylate monomer, and a maleimide monomer, but are not particularly limited thereto. Further, the weight ratio of the vinyl cyanide monomer to the aromatic vinyl monomer in the polymer serving as the side chain is preferably in the range of 10:90 to 60 from the viewpoint of impact resistance and moldability.

Further, the content of glycidyl methacrylate in the polyolefin copolymerized with glycidyl methacrylate is 5% by weight or more and 30% by weight or less. If it is less than 5% by weight, the effect of improving the impact resistance is small, and if it exceeds 30% by weight, the impact resistance is improved but the moldability is poor, so that it is not preferable.

The content of the main chain of the polyolefin copolymerized with glycidyl methacrylate in the copolymer (D) is not particularly limited, but is preferably 10 to 90% by weight, and more preferably 40 to 90% by weight.
80% by weight is used.

The blending amount of the copolymer (D) is 2 to 20 parts by weight based on 100 parts by weight of the total of the components (A), (B) and (C). Less effective
If it exceeds 20 parts by weight, the composition of the present invention is not obtained, for example, the rigidity at high temperatures is inferior.

The method for producing the copolymer (D) is not limited, but the method described in JP-A-63-312312 is mentioned as an example.

The thermoplastic composition of the present invention may contain a reinforcing material and a flame retardant.

As the reinforcing material to be blended in the present invention, glass fibers, inorganic fibers such as carbon fibers and wollastonite, talc,
It is at least one selected from inorganic fillers such as mica powder, glass foil, and potassium titanate. The amount of the reinforcing material
The amount is 0 to 60 parts by weight, preferably 0 to 50 parts by weight, based on 100 parts by weight of the total amount of the components (A), (B) and (C).
When the amount of the reinforcing material exceeds 60 parts by weight, the composition obtained does not have the desired impact resistance because the resulting composition has poor impact resistance.

As the flame retardant compounded in the present invention, usually, ABS
Inorganic flame retardants such as halogen compounds and antimony compounds used for flame retardation of polyesters and thermoplastic polyesters are used. As halogen compounds, halogenated diphenyl ethers such as degabrom diphenyl ether and octabromo diphenyl ether and halogenated polycarbonates are used. And a halogen compound represented by the following formula.

(Wherein n is an average degree of polymerization of 1.5 to 100, x is hydrogen, chlorine or bromine, i, j, k and l are each an integer of 1 to 4, and R and R ′ are hydrogen, methyl group, Epoxypropyl group, phenyl group, Is shown. Examples of the inorganic flame retardant include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, and aluminum hydroxide.
It is not particularly limited to these. The compounding amount of the halogen compound is the total amount of the components (A), (B) and (C).
0 to 35 parts by weight, preferably 0 to 30 parts by weight based on 100 parts by weight, that of the antimony compound is 0 to 25 parts by weight,
Preferably it is in the range of 0 to 20 parts by weight.

Further, various additives such as a modifier, a release agent, a stabilizer against light or heat, and a dye or pigment may be appropriately added to the thermoplastic resin composition of the present invention, if necessary.

As a method for adjusting the thermoplastic resin composition of the present invention, a device such as a Henschel mixer or a tumbler which is usually used for blending resins can be used. Also in the shaping, a device used for a normal shaping such as a single screw extruder, a twin screw extruder, an injection molding machine and the like can be used.

Examples Hereinafter, the present invention will be described in more detail with reference to Examples. In the following Examples and Comparative Examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

In addition, the evaluation method of each physical property in each Example and Comparative Example was based on the following method.

(1) Izod impact strength Measured according to ASTM D-256. (Unit: kg · cm / cm) (1
(/ 4 inch thickness, using a notched specimen) (2) Vicat softening temperature Measured according to ISO-306. (Unit: ° C) (3) Fatigue strength ASTM D-671 No. 1 specimen was molded at 250 ° C using a Toshiba IS-50EP injection molding machine. Using a constant stress fatigue tester (manufactured by Toyo Seiki Co., Ltd.), the number of times for the obtained specimen to reach a fracture at a stress of 150 kg / cm ² was determined.

Examples 1 to 5 and Comparative Examples 1 to 5 The components used in Examples and Comparative Examples are as follows.

(A) Polycarbonate resin Mitsubishi Chemical Corporation: Novalex 7025A was used.

(B) Graft copolymer Graft polymer (B) was produced as follows.

Production of graft copolymer (B-1).

50 parts of polybutadiene latex having a solid content of 35% and average particles of 0.08 μm (as solid content), 85 parts of n-butyl acrylate units and 15 parts of methacrylic acid units 1 part of a copolymer latex having an average particle diameter of 0.08 μm (As solid content)
Was added with stirring, and stirring was continued for 30 minutes to obtain an average particle size of 0.
A 28 μm enlarged rubber latex was obtained.

The obtained enlarged rubber latex is added to the reaction vessel, and 50 parts of distilled water, 2 parts of wood rosin emulsifier, Demol N
(Product name, manufactured by Kao Corporation, naphthalenesulfonic acid formalin condensate) 0.2 part, sodium hydroxide 0.02 part, dextrose 0.35 part, ethyl acrylate 10 parts and cumene hydroperoxide 0.1 part are added with stirring and heated. At an internal temperature of 60 ° C., 0.05 parts of ferrous sulfate, 0.2 parts of sodium pyrophosphate and 0.03 part of sodium dithionite were added, and the mixture was maintained at an internal temperature of 60 ° C. for 1 hour. After holding for 1 hour, a mixture of 12 parts of acrylonitrile, 14 parts of styrene, 14 parts of α-methylstyrene, 0.2 part of cumene hydroperoxide and 0.5 part of tert-dodecyl mercaptan was continuously dropped for 90 minutes, and then held for 1 hour. Cool. After the obtained graft copolymer latex was coagulated with dilute sulfuric acid, it was washed, filtered and dried to obtain a graft copolymer (B-1).

Production of graft copolymer (B-2).

2.0 parts of tetraethoxysilane, 0.5 part of γ-methacryloylpropyldimethoxymethylsilane and 97.5 minutes of octamethyltetracyclosiloxane were mixed to obtain 100 parts of mixed siloxane. Dodecylbenzenesulfonic acid and sodium dodecylbenzenesulfonate were added to 1.0
100 parts of the mixed siloxane was added to 200 parts of distilled water in which the parts were dissolved, and after preliminary stirring at 10,000 rpm with a homomixer,
The mixture was emulsified and dispersed with a homogenizer at a pressure of 300 kg / cm ² to obtain an organosiloxane latex. This mixed solution was transferred to a separable flask equipped with a condenser and a stirring blade, and heated at 80 ° C. for 5 hours while stirring and mixing.
The mixture was allowed to stand at 20 ° C., and after 48 hours, the pH of the latex was neutralized to 6.9 with an aqueous solution of sodium hydroxide to complete the polymerization and obtain a polyorganosiloxane rubber latex. The polymerization rate of the obtained polyorganosiloxane rubber was 89.7%, and the average particle size of the polyorganosiloxane rubber was 0.16 μm.

100 parts of this polyorganosiloxane rubber latex (solid content: 30%) was collected and placed in a separable flask equipped with a stirrer, and 120 parts of distilled water was added thereto, followed by purging with nitrogen.
° C, 37.5 parts of n-butyl acrylate, 2.5 parts of allyl methacrylate and tert-butyl hydroperoxide
0.3 parts of the mixture was charged and stirred for 30 minutes, and the mixture was permeated into the polyorganosiloxane rubber particles. Then
A mixture of 0.0003 parts of ferrous sulfate, 0.001 part of disodium ethylenediaminetetraacetic acid, 0.17 part of Rongalit and 3 parts of distilled water was charged to start radical polymerization, and then the internal temperature was increased to 70%.
C. for 2 hours to complete the polymerization to obtain a composite rubber latex. A part of this latex was collected and the average particle diameter of the composite rubber was measured to be 0.19 μm. The latex was dried to obtain a mixture. The mixture was extracted with toluene at 90 ° C. for 12 hours, and the gel content was measured to be 90.3%. A mixture of 0.3 part of tert-butyl hydroperoxide, 9 parts of acrylonitrile and 21 parts of styrene was added dropwise to the composite rubber latex at 70 ° C. for 45 minutes.
C. for 4 hours to complete the graft polymerization to the composite rubber.

The polymerization rate of the obtained graft copolymer was 98.6%. The obtained graft copolymer latex is coagulated and separated by dropping it into hot water of 5% calcium chloride,
After washing, it was dried at 75 ° C. for 16 hours to obtain a composite rubber-based graft copolymer (B-2).

Production of graft copolymer (B-3).

20 parts (as solid content) of polybutadiene latex having a solid content of 35% and an average particle size of 0.08 μm were mixed with n-acrylic acid.
Add 0.4 parts (as solid content) of a copolymer latex of 85% butyl units and 15% methacrylic acid units with a mean particle size of 0.08 μm in total while stirring, and continue stirring for 30 minutes to enlarge diene with an average particle size of 0.28 μm. 20 parts (solid part) of the obtained enlarged diene-based rubber latex from which a rubber latex was obtained were transferred to a reaction vessel, and 1 part of disproportionated potassium rosinate and 150 parts of ion-exchanged water were added, followed by nitrogen replacement. The temperature was raised to 70 ° C (internal temperature). A solution prepared by dissolving 0.12 parts of potassium persulfate in 10 parts of ion-exchanged water was added thereto, and the following nitrogen-substituted monomer mixture was continuously optimized for 2 hours.

80 parts n-butyl acrylate 80 parts allyl methacrylate 0.32 parts ethylene glycol dimethacrylate
When the reaction was continued for 1 hour, the polymerization rate reached 98.8%, and a multi-layer acrylic rubber containing a diene-based enlarged rubber was obtained. The multi-layer acrylic rubber swelling degree (ratio of swelling weight and absolute dry weight after immersion in methyl ethyl ketone for 24 hours at 30 ° C.) was 6.4, gel content was 93.0%, and particle diameter was 0.28 μm.

A multi-layer acrylic rubber latex 50 (solid content) was taken in a reaction vessel, and 140 parts of ion-exchanged water was added for dilution, followed by heating to 70 ° C. Separately, 50 parts of a graft polymer mixture composed of acrylonitrile / styrene = 29/71 (weight ratio) was adjusted, and 0.35 part of benzoyl peroxide was dissolved and then replaced with nitrogen. This monomer mixture was added into the above reaction system at a rate of 15 parts / hour using a metering pump. After the completion of the injection of all the monomers, the temperature in the system was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The conversion was 99%.

Dilute sulfuric acid was added to a part of the latex, and the solidified and dried powder was extracted under reflux of methyl ethyl ketone, and the ηsp / C of the extracted portion was measured at 25 ° C. using dimethylformamide as a solvent, and it was 0.67.

The latex produced as described above was mixed with 0.15% of aluminum chloride (AlCl ₃ .6H ₂ O) three times the total latex.
The mixture was poured into an aqueous solution (90 ° C.) with stirring to coagulate.
After the addition of all the latex was completed, the temperature in the coagulation bath was raised to 93 ° C., and left as it was for 5 minutes. After cooling, it was drained and washed by a centrifugal dehydrator and dried to obtain a dry powder of the graft copolymer (B-3).

Structure of Graft Copolymer (B-4) Ethylene-propylene-non-conjugated diene rubber latex (average particle size: 0.5 μm, gel content: 45%, ethylidene norbornene used as a diene component) is 60 parts as solids and alkenyl succinic acid 2 parts of dipotassium salt, 0.5 part of sodium pyrophosphate, 0.005 part of ferrous sulfate, 0.6 part of dextrose,
200 parts of ion exchange were charged into a reactor and heated to 70 ° C. A separately prepared mixed solution of 6 parts of acrylonitrile, 14 parts of styrene, 0.075 part of triallyl cyanurate and 0.1 part of cumene hydroperoxide was added dropwise with stirring over 60 minutes, and then 6 parts of acrylonitrile, 14 parts of styrene and te
A mixed solution of 0.06 parts of rt-dodecyl mercaptan and 0.0075 parts of cumene hydroperoxide was added dropwise over 60 minutes. After completion of the dropwise addition, the temperature was maintained at 70 ° C., and stirring was further continued for 60 minutes to complete graft polymerization. The obtained graft copolymer was coagulated with dilute sulfuric acid, dehydrated and dried to collect a white powder. 1 g of a powder obtained by coagulating the latex of the above graft copolymer with isopropyl alcohol and drying with acetone
Dissolve and decompose in 200 ml and reflux at 70 ° C for 4 hours. The acetone dispersion was separated into a soluble component and an insoluble component by a centrifuge, and the insoluble component was dried to calculate the graft ratio.38
%Met. In addition, a free acrylonitrile-styrene copolymer (AS resin) was recovered by evaporation from the acetone-soluble matter. 0.1 g of this AS resin was dissolved in 50 ml of dimethylformamide, and the reduced viscosity (η _SP / C) at 25 ° C. was measured.
It was 0.41.

(C) Polymer The polymer (C) was produced as follows.

 Production of polymers (C-1) and (C-2).

Polymers (C-1) and (C-
2) was obtained by a suspension polymerization method.

The reduced viscosity η _SP at 25 ° C. of these polymers is also shown in Table 1. Note that η _{SP in} Table 1 is a 0.2% dimethylformamide solution for the polymer (C-1),
-2) is a value measured with a 1% chloroform solution.

(D) Copolymer Copolymers (D-1 to D-3) were produced as follows.

For a total of 100 parts of the epoxy group-containing ethylene copolymer, acrylonitrile, and styrene having the composition shown in Table 2, 250 parts of pure, 0.15 parts of benzoyl eroxide "Niper B" (trade name, manufactured by NOF Corporation) and formula; 0.6 part of the compound represented by
At 8 ° C. for 8 hours, polymerized, washed with water and dried. The obtained polymer was further subjected to 220/30 mm φ twin screw extruder with L / D = 25.
Extrusion at ℃ completed the grafting reaction.

As the flame retardant, a compound represented by the following formula and antimony trioxide were used.

The obtained polymer was blended in the proportions shown in Table 3 and mixed for 5 minutes with a Henschel mixer, and then pelletized with a twin screw extruder having a screw diameter of 30 mm. Using these pellets, various physical properties were evaluated by the methods described above. The results are shown in Table 3. Table 3 shows that the molded article obtained from the resin composition of the present invention has improved fatigue strength. That is, in the first embodiment,
40 parts of the component (A) polycarbonate, 20 parts of the component (B) graft copolymer (B-1), and the component (C) polymer (C
-1) A thermoplastic resin composition comprising 40 parts and a copolymer (D-1) of component (D) 5 parts. Comparative Example 1 is an example in which the component (D) was not blended in Example 1. When the thermoplastic resin composition of Example 1 is compared with the thermoplastic resin composition of Comparative Example 1, Example 1 has a slightly lower Vicat softening temperature than Comparative Example 1, but has a slightly higher Izod impact strength. It can be seen that the fatigue strength has been improved. Also, Example 2 and Comparative Example 2, Example 3 and Comparative Example 3,
Even when Example 4 and Comparative Example 4 are compared with each other, and Example 5 and Comparative Example 5 are compared with each other, there is the same tendency. As described above, the thermoplastic resin composition of the present invention reduces impact resistance by further blending the component (D) with the thermoplastic resin composition comprising the components (A), (B) and (C). In addition, the fatigue strength can be improved.

(Effect of the Invention) The composition of the present invention is excellent in heat resistance and impact resistance, and also excellent in strength when repeated stress is applied, that is, fatigue strength. It is extremely useful as a molding material for molded articles.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 51:04 25:04 51:06)

Claims (1)

(57) [Claims] (A) a polycarbonate resin: 15 to 90 parts by weight (B) at least one selected from the group consisting of a polybutadiene rubber, a crosslinked acrylic rubber, an organosiloxane rubber and an ethylene-propylene-non-conjugated diene rubber. 1
In the presence of 15 to 85 parts by weight of the rubbery polymer (a), 15 to 40% by weight of vinyl cyanide monomer 25 to 85% by weight of aromatic vinyl monomer Other vinyl monomer 0 to 35 85 to 15 parts by weight of a vinyl monomer (b) composed of 100% by weight (the total amount of these components is 100% by weight)
(The total amount of (b) and (b) is 100 parts by weight). Graft polymer obtained by graft polymerization: 10 to 85 parts by weight (C) Aromatic vinyl monomer, vinyl cyanide monomer and methacrylate Polymer obtained by polymerizing at least one selected from the group consisting of monomers: 0 to 60 parts by weight (D) 5 to 30% by weight based on 100 parts by weight of the thermoplastic resin composition Less than 2 to 20 parts by weight of a copolymer having a main chain of a polyolefin copolymerized with glycidyl methacrylate having a side chain of a polymer composed of a vinyl cyanide monomer and an aromatic vinyl monomer. Thermoplastic resin composition.