KR0147781B1 - Thermoplastic resin composition - Google Patents

Abstract

The thermoplastic resin composition of the present invention is (A) 40 to 55% by weight of polyamide resin; (B) graft polymerization of (b ₁ ) 25 to 70 wt% rubbery polymer, (b ₂ ) 40 to 90 wt% aromatic vinyl monomer, and (b ₃ ) 10 to 60 wt% vinyl cyanide monomer 20 to 50% by weight of the graft copolymer; (C) (c ₁ ) 40 to 90% by weight of an aromatic vinyl monomer, (c ₂ ) 10 to 60% by weight of vinyl cyanide monomer, and (c ₃ ) polymerization to (c ₁ ) and (c ₂ ) above. 0 to 5% by weight of polymerized polymer, possibly 0 to 40% by weight of other vinyl monomers; (D) 1 to 25% by weight of ethylene-prepared by reacting 0 to 2% by weight of organic peroxide and 0.1 to 10% by weight of reactive monomer having unsaturated carboxylic acid or acid anhydride group with melt-kneading to ethylene-propylene rubber Propylene-based radish; And (E) (e ₁ ) 30 to 70% by weight of an aromatic vinyl monomer, (e ₂ ) 30 to 50% by weight of maleimide monomer, and (e ₃ ) 1 to 20% by weight of unsaturated dicarboxylic anhydride 3 to 10 weight percent maleimide-based copolymer obtained by copolymerizing a monomer and (e ₄ ) 0 to 50 weight percent of another copolymerizable monomer; Characterized in that consists of.

Description

[Name of invention]

Thermoplastic resin composition having excellent low temperature impact resistance

Detailed description of the invention

[Field of Invention]

The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition having excellent low temperature impact resistance as a composition comprising a styrene resin and a polyamide resin.

[Background of invention]

In general, polyamide resins are used in various parts of automobiles, electrical and electronic products because of their excellent chemical resistance and moldability. However, molded articles molded from polyamide resins have the drawback of low impact resistance, in particular notched impact strength. Therefore, recently, studies on resin compositions having remarkably improved impact strength by adding thermoplastic elastomers to polyamide have been actively conducted, and the resin compositions are disclosed in US Patent Nos. 4,299,977 and 4,321,336.

Styrene-based resins used for various uses have a drawback in that moldability and chemical resistance are somewhat lower than polyamide resins, and heat resistance is particularly poor. Accordingly, development of blends having improved physical properties by admixing polyamide resins and styrene resins has also been in progress. If the styrene-based resin and the polyamide resin are simply mixed, there is no compatibility between the two resins. Therefore, phase separation in the molded product may occur remarkably or peeling may occur.

U.S. Patent No. 4,321,336 discloses a high impact of polyamide and aliphatic polyolefins, olefinic copolymers, styrene copolymers, polymers of aliphatic dienes and acrylonitrile, and at least one polymer selected from the group consisting of polydimethyl siloxanes. Polyamide mixtures are disclosed. U. S. Patent No. 4,496, 690 discloses a polymer composition consisting of a copolymer of polyamide and styrene, acrylonitrile and ethylene-unsaturated carbonamide or a polymer grafted onto a rubber-based polymer. In addition, Japanese Patent Publication No. Hei 2-240158 discloses a thermoplastic resin composition having a high impact resistance composed of an ABS resin polyamide resin and a modified styrene copolymer, and Japanese Patent Publication No. Hei 2-311545 discloses a maleimide type. Addition of an olefin rubber such as modified EPR and EPEM copolymerized with a maleimide resin and an unsaturated carboxylic acid to a thermoplastic resin composition comprising a copolymer, a polyamide, a modified polyolefin polymer, and a thermoplastic resin such as an ABS resin Disclosed is a technique.

The thermoplastic resin composition disclosed in the above-mentioned patent or patent application maintains a certain level of impact strength at room temperature but exhibits a markedly lowered impact strength at low temperature of -20 ° C or lower. Typically preferred 1/8 inch notch impact strengths range from about 70 to 80 kgcm / cm at room temperature. However, the 1/8 inch notch impact strength at low temperatures, ie, −20 ° C., of the thermoplastic resin compositions disclosed above is usually in the range of about 10 to 40 kg · cm / cm. Accordingly, the present invention is to provide a thermoplastic resin composition having high impact resistance at low temperature, which improves the 1/9 inch notch impact strength at low temperature, that is, at −20 ° C. to about 60 to 80 kg · cm / cm. Korean Patent Application No. 94-21,721 discloses a thermoplastic resin composition having excellent impact resistance at low temperatures consisting of a polyamide resin, a g-ABS resin, a SAN copolymer, a modified styrene resin and a maleimide copolymer. In contrast, the inventors of the present invention are polyamide resins, graft-acrylonitrile / butadiene / styrene (g-ABS) resins, styrene / acrylonitrile (SAN) copolymers, modified ethylene-propylene rubbers, and maleimide-based resins. It has been found that the resin composition composed of the copolymer has good impact resistance at room temperature as well as at low temperature.

[Summary of invention]

The thermoplastic resin composition of the present invention

(A) 40 to 55% by weight of polyimide resin;

(B) graft polymerization of (b ₁ ) 25 to 70 wt% rubbery polymer, (b ₂ ) 40 to 90 wt% aromatic vinyl monomer, and (b ₃ ) 10 to 60 wt% vinyl cyanide monomer 20 to 50% by weight of the graft copolymer;

(C) (C ₁ ) 40 to 90% by weight of an aromatic vinyl monomer, (c ₂ ) 10 to 60% by weight of vinyl cyanide monomer, and (c ₃ ) the polymerization of (c ₁ ) and (c ₂ ) 0 to 5% by weight of polymerized polymer, possibly 0 to 40% by weight of other vinyl monomers;

(D) 1 to 25% by weight of ethylene-prepared by reacting 0 to 2% by weight of organic peroxide and 0.1 to 10% by weight of reactive monomer having an unsaturated carboxylic acid or its anhydride group with melt kneading to ethylene-propylene rubber. Propylene rubbers; And

(E) (e ₁ ) 30 to 70% by weight of an aromatic vinyl monomer, (e ₂ ) 30 to 50% by weight of maleimide monomer, (e ₃ ) 1 to 20% by weight of unsaturated dicarboxylic acid or its 3 to 10% by weight of maleimide-based copolymer obtained by copolymerizing a reactive monomer having an anhydride group and (e ₄ ) 0 to 35% by weight of another copolymerizable monomer;

Characterized in that consists of.

Detailed description of the invention

(A) polyamide resin, (B) graft copolymer (g-ABS resin), (C) copolymer (SAN copolymer), and (D) modified ethylene-propylene system which are each component of the thermoplastic resin composition of this invention The rubber and the (E) maleimide copolymer are described in detail below.

(A) polyamide resin

Polyamide resins that can be used in the present invention include polycaprolactam (nylon 6), poly11-aminoundecanoic acid (nylon 11), polylauryl lactam (nylon 12), polyhexamethyleneadipamide (nylon 6,6 ), Polyhexaethylene azelamide (nylon 6,9), polyhexamethylene sebacamide (nylon 6,10), and polyhexamethylene dodecanodiamide (nylon 6,12) and nylon resins and copolymers thereof nylon copolymer resins such as nylon 6 / nylon 6,10, nylon 6 / nylon 6,6, and nylon 6 / nylon 12. In the present invention, at least one resin may be used among the nylon resin and the nylon copolymer resin.

In view of the physical properties and heat resistance of the resin composition, polyamide resins having a melting point of 200 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1 wt% of polyamide resin to m-cresol) are preferably 2.0 or higher.

(B) graft copolymer (g-ABS resin)

The graft copolymer used in the present invention is usually a graft acrylonitrile / butadiene / styrene (ABS) resin, and the copolymer is a copolymer obtained by grafting an aromatic vinyl monomer and a vinyl cyanide monomer to a rubbery polymer. . In the present invention, it is preferable that 20 to 95% by weight of the aromatic vinyl monomer and the vinyl cyanide monomer are grafted. In the present invention, one or more rubbers selected from the group consisting of diene rubbers, ethylene rubbers, and ternary copolymer rubbers of ethylene / propylene / diene monomers may be used. Aromatic vinyl monomers include styrene, para-t-butylstyrene, alpha-methylstyrene, beta-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene, and Divinylbenzine, and vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile. As an aromatic vinylic monomer, acrylonitrile is preferable. In the present invention, the content of the rubbery polymer is preferably 25 to 70 parts by weight and more preferably 35 to 60 parts by weight based on 100 parts by weight of the total of (B) and (C). If the amount of the rubbery polymer is 35 parts by weight or less, the hardness, tensile strength, flexural strength and heat resistance are improved, but the impact resistance is sharply reduced, and when the amount is 60 parts by weight or more, the impact resistance is excellent, but the production is difficult and the physical properties of the resin composition are inferior. .

The method for preparing the g-ABS resin is already well known to those skilled in the art. Representative methods for producing g-ABS resins include emulsion graft polymerization as a polymerization initiator by introducing an aromatic vinyl monomer and a vinyl cyanide monomer in the presence of a rubbery polymer.

(C) copolymer (SAN copolymer)

The copolymer used in the present invention is a styrene / acrylonitrile (SAN) copolymer, which is a copolymer obtained by polymerizing an aromatic vinyl monomer, a vinyl cyanide monomer, and another vinyl monomer polymerizable with the monomers. .

Aromatic vinyl monomers include styrene, para-t-butylstyrene, alpha-methylstyrene, beta-methylstyrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene, and Divinylbenzine, and vinyl cyanide monomers include acrylonitrile, methacrylonitrile, and ethacrylonitrile. As the aromatic vinyl monomer, styrene and alpha-methyl styrene are preferable, and as the vinyl cyanide monomer, acrylonitrile is preferable.

Other vinyl monomers polymerizable with the aromatic vinyl monomer and vinyl cyanide monomer include (meth) acrylic acid ester monomers of methyl, ethyl, propyl, and n-butyl; Maleimides such as maleimide, N-methyl maleimide, and N-phenyl maleimide; And acrylimides.

Methods of preparing the SAN copolymers are already well known to those of ordinary skill in the art. That is, a method of producing a SAN copolymer is a method by emulsion polymerization, suspension polymerization, bulk polymerization, and continuous polymerization.

The thermoplastic resin composition of the present invention may not contain a SAN copolymer, and is usually used in the range of 30% by weight or less with respect to the resin composition.

(D) Modified Ethylene-Propylene Rubber

The modified ethylene-propylene rubber used in the present invention is a modified ethylene-propylene rubber obtained by reacting an unsaturated carboxylic acid or an anhydride with ethylene-propylene rubber. The modified ethylene-propylene rubber is a copolymer obtained by grafting ethylene-propylene rubber with an unsaturated carboxylic compound having a carboxylic acid group or an acid anhydride group using an organic peroxide.

The ethylene-propylene rubber may be an ethylene-propylene rubber (hereinafter referred to as EPR) or an ethylene-propylene-diene rubber (hereinafter referred to as EPDM). Among the diene components of EPDM, 1,4-hexadiene, dicyclopentadiene, 5-vinylnorbornene, 2,5-ethylidene norbornene, and the like may be used, and the composition is 2 to 100 parts by weight of EPDM. It is preferable to use 8 parts by weight.

The unsaturated carboxylic compounds having a carboxylic acid group or an acid anhydride group used in the present invention include maleic anhydride, maleic acid, fumaric acid, acrylic acid, and methacrylic acid esters, of which maleic anhydride is preferable. In addition, as the organic peroxide used in the present invention, diisopropylene hydroperoxide, di-t-butyl peroxide, p-ethane hydroperoxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl 2 , 5-di (t-butylperoxy) hexane, di-t-butyldiperoxyphthalate, persuccinate peroxide, t-butylperoxybenzoate, t-butylperoxymaleic acid, t-butylperoxyisopropylcarbo Nate, methyl ethyl ketone peroxide, and cyclohexanone peroxide, one or more mixtures of which can be used and dicumylperoxide is preferred in consideration of double reactivity and processability.

The method for preparing the modified ethylene-propylene copolymer is not particularly limited, but after mixing EPR or EPDM with an organic peroxide and a reactive monomer, graft reaction in a melt kneading state using a short-barrier mixer or a vented extruder It is preferable. This is because the melt viscosity of the modified ethylene-propylene copolymer is high, which serves to prevent poor workability.

The alpha, beta unsaturated carboxylic acid compound having a carboxylic acid group or an acid anhydride group is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight based on 100 parts by weight of the resulting modified ethylene-propylene rubber. When the amount of the unsaturated carboxylic acid added is less than 0.2 part by weight, the modified ethylene-propylene rubber does not exhibit the effect of improving the impact strength of the final thermoplastic resin composition, and when the amount is 5 parts by weight or more, unreacted carboxyl Due to the presence of a large amount of the compound, the production process of the modified ethylene-propylene rubber becomes difficult and the impact strength is significantly reduced. In addition, when the organic peroxide is used in an amount of 2 parts by weight or more, the rubber property decreases due to the crosslinking reaction, thereby reducing the impact strength.

(E) Maleimide Copolymer

Maleimide-based copolymers include 30 to 70 weight percent aromatic vinyl monomers, 30 to 50 weight percent maleimide monomers, 1 to 20 weight percent unsaturated dicarboxylic acid anhydride monomers, and 0 to 35 weight percent other copolymers. It is a copolymer which copolymerized the possible monomer. More preferred maleimide copolymers are 50 to 60% by weight of aromatic vinyl monomers, 40 to 50% by weight of maleimide monomers, 1 to 10% by weight of unsaturated dicarboxylic acid anhydride monomers, and other copolymerizable compounds. Monomers in the range of 0 to 30% by weight. When the aromatic vinyl monomer is more than 70% by weight or the maleimide monomer is less than 30% by weight, the heat resistance of the molded product of the thermoplastic resin composition is lowered. In addition, when the maleimide monomer exceeds 50% by weight, the processability of the thermoplastic resin composition becomes poor. If the unsaturated dicarboxylic acid anhydride monomer is less than 1% by weight, the compatibility with the polyamide is not effective, and the average particle diameter of the maleimide-based copolymer particles is increased, resulting in a decrease in physical properties. When the unsaturated dicarboxylic acid anhydride monomer exceeds 20% by weight, the average particle diameter of the maleimide-based copolymer particles becomes small, resulting in poor workability and lowering of the molded article's thermal stability.

Examples of the aromatic vinyl monomer used in the preparation of the maleimide copolymer include styrene, alpha-methylstyrene, vinyltoluene, and t-butylstyrene. Examples of maleimide monomers include maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-hexyl maleimide, N-dichlorohexyl maleimide, N-phenyl maleimide, and N- Trimaleimide. Examples of unsaturated dicarboxylic anhydride monomers include maleic anhydride, methylmaleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride, and phenylmaleic anhydride. Examples of other copolymerizable monomers include acrylonitrile, methyl methacrylate, ethyl (meth) acrylate, butyl methacrylate, hexyl methacrylate, dichlorohexyl methacrylate, decyl (meth) acrylate, and octadecyl methacryl. Latex, hydroxyethyl (meth) acrylate, and glycidylmethacrylate, which may be used in one or two or more mixtures.

The maleimide copolymer is prepared by reacting an aromatic vinyl monomer, a maleimide monomer, an unsaturated dicarboxylic acid anhydride monomer, and other copolymerizable monomers with ammonia or primary amine. The production reaction is one of the imidization reaction methods, and a maleimide polymer having an imide group can be produced using this method. Many imidation reaction methods are already known, and are also disclosed by Japanese Patent Application No. 61-26936 and No. 62-845.

Primary amines that can be used in the imidization reaction include methylamine, ethylamine, propylamine, butylamine, hexaamine, decylamine, aniline, naphthaleneamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, and Dibromophenylamine. This imidation reaction can be performed in a molten state, a molten state, or a suspended state using an autoclave. This reaction can also be carried out in a molten state in an extruder. Solvents used in the imidation reaction in the molten state include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and dichlorohexanone; Ethers such as tetrahydrofuran and 1,4-dioxane; Aromatic hydrocarbons such as toluene and xylene; Dimethyl bromide; And N-methyl-2-pyrrolidone.

The range of 50-350 degreeC is preferable, and, as for the temperature of the imidation reaction, the range of 100-300 degreeC is more preferable. The imidization reaction may be a catalyst, wherein the catalysts used are tertiary amines such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, and N, N-dimethylamine.

The thermoplastic resin composition of the present invention having excellent low temperature impact resistance includes (A) 30 to 70% by weight of polyamide resin, (B) 20 to 60% by weight of g-ABS resin, and (C) 0 to 20% by weight of SAN air. It comprises a copolymer, (D) 1-30 weight% modified ethylene-propylene rubber, and (E) 1-30 weight% maleimide type copolymer. The resin components are uniformly mixed and the mixture is extruded into pellets through an extruder to prepare a resin composition. The manufacturing method of this resin composition can be easily performed by those skilled in the art.

The additive necessary according to the use can be used for the thermoplastic resin composition of this invention. For example, glass fiber, carbon fiber, talc, silica, mica, and / or alumina may be added to the thermoplastic resin composition to improve the mechanical strength or heat distortion temperature of the molded article. Depending on their respective uses, ultraviolet absorbers, antioxidants, flame retardants, lubricants, dyes and / or pigments may be added.

The present invention will be further illustrated by the following examples, which are merely illustrative of the present invention and are not intended to limit or limit the scope of the present invention.

EXAMPLE

The resin component used in the embodiment of the present invention is as follows.

(A) polyamide resin

In the practice of the present invention, two kinds of polaramide resins (A1 and A2) were used. A1 is nylon 6 (trade name; KN-170) of KOLON Co., Ltd. of Korea, and A2 is nylon 6,6 (trade name; 40-IB) of Monsanto Co., USA. to be.

(B) graft copolymer (g-ABS resin)

A graft copolymer (g-ABS resin) was also prepared and used in two kinds (B1 and B2) as follows.

B1; 450 g of polybutadiene latex (based on solids), 390 g of styrene, and 160 g of acrylonitrile are placed in a reactor, and 2 g of dodecyl mercaptan, 5 g of potassium persulfate, and 5 g of sodium oleate are added to the mixture to emulsify. Polymerize. As a result, graft copolymer B1 is obtained.

B2; 450 g of polybutadiene latex (based on solids), 510 g of alphamethylstyrene, 90 g of styrene, and 250 g of acrylonitrile were placed in a reactor, in which 2 g of t-dodecyl mercaptan, 5 g of potassium persulfate, and 5 g of sodium oleate is added to emulsify. As a result, graft copolymer B2 is obtained.

(C) SAN copolymer

In the embodiment of the present invention, the following two types of SAN copolymers (C1 and C2) were used.

C1; 710 g of styrene and 270 g of acrylonitrile are placed in a reactor, and 5 g of t-dodecyl mercaptan is adsorbed to this mixture for suspension polymerization. As a result, SAN copolymer C1 is obtained.

C2; 710 g of styrene and 230 g of acrylonitrile are placed in a reactor and 5 g of t-dodecyl mercaptan is added to the mixture for emulsion polymerization. As a result, SAN copolymer C2 is obtained.

(D) Modified Ethylene-Propylene Rubber

D1 ~ D6: After mixing EPR (Kumho Ipi Rubber Co.) or EPDM (Kumho Ipi Rubber Co.) Was used to prepare aggregates D1-D6 into pellets. At this time, the cylinder temperature was set to 150 ~ 190 ℃, screw rotation speed was set to 300rpm. The content of grafted maleic anhydride in the results shown in Table 1 was calculated by measuring the area of the characteristic band (1785 cm ^-1 ) of maleic anhydride by infrared spectroscopy after reprecipitation of the prepared pellets with toluene / methanol solution. In the results of Table 1, the content of GEL was measured and calculated by the weight of residual GEL by 쏙 sillet distillation (8 hours distillation).

D7: EXXELOR VA-1803 (product made in Germany Exxon Chemical Co., Ltd.)

(E) Maleimide Copolymer

In the examples of the present invention, two kinds of maleimide resins (E1 and E2) were used. E1 is POLYIMILEX PSX-371, a product of Nippon Catalyst Co., Ltd., and E2 is MS-NA, a product of Nippon Electrochemical Co., Ltd.

Example 1-10

In Examples 1-10, as shown in Table 2, by changing the type and content of each component (A), (B), (C), (D) and (E) of the thermoplastic resin composition of the present invention It is manufactured. In Example 1-10, the resin of each component is mixed with a Henschel mixer to uniformly disperse the resin. Was extruded at a temperature of 230 to 270 ° C. in a 40 mm extruder to prepare pellets. The pellets were dried at 80 ° C. for 6 hours, and injected at a molding temperature of 240 to 280 ° C. and a mold temperature of 60 to 80 ° C. in a 6 ounce injection machine to prepare specimens. Specimens prepared according to Examples 1-10 were measured for impact strength in accordance with Izod impact strength ASTM D256 (1/4 inch and 1/8 inch notch). The measurement results are shown in Table 3.

Comparative Example 1-7

Comparative Example 1-7 is an example in which the resin composition was prepared by excluding at least one component from components (A), (B), (C), (D), and (E) of the thermoplastic resin composition of the present invention. . The composition content of the resin composition of Comparative Example 1-7 is as shown in Table 4. The method of preparing a specimen from the resin composition prepared in Comparative Example 1-7 was the same as that of Example 1-10, and 0.2 parts by weight of an antioxidant and a heat stabilizer were added. Specimens prepared according to Comparative Examples 1-7 were measured for impact strength in accordance with Izod impact strength ASTM D256 (1/4 inch and 1/9 inch notch). The measurement results are shown in Table 5.

The results in Table 5 show that the impact strength at low temperatures drops rapidly if no denatured EPR is added or if any one of the polymers (A), (B), (C), (D) or (E) is added. Can be.

Claims (16)

(A) 40 to 55 parts by weight of a polyamide resin; (B) 25 to 70 weight of rubbery polymer 20 to 50 parts by weight of a vinyl graft copolymer obtained by graft polymerization of 40 to 90 parts by weight of an aromatic vinyl monomer and 75 to 30 parts by weight of a monomer mixture of 60 to 10 parts by weight of a vinyl cyanide monomer; (C) 0 to 5 parts by weight of a vinyl copolymer obtained by copolymerizing 40 to 90 parts by weight of an aromatic vinyl monomer, 60 to 10 parts by weight of a vinyl cyanide monomer, and 0 to 40 parts by weight of other vinyl monomers copolymerizable with these. D) 1 to 25 parts by weight kneading by kneading 0.4 to 6 parts by weight of a reactive monomer having an unsaturated carboxylic acid or an anhydride group with 0 to 2 parts by weight of an organic peroxide added to 100 parts by weight of ethylene-propylene rubber. Negatively modified ethylene-propylene rubber; And (E) 30-70 mol% of aromatic vinyl monomers, 30-50 mol% of maleimide monomers, 1-20 mol% of unsaturated carboxylic acids or reactive monomers having anhydride groups and 0-35 mol% of other copolymerizable monomers. 3 to 10 parts by weight of the maleimide copolymer prepared by copolymerizing; Thermoplastic resin composition having excellent low-temperature impact resistance, characterized in that consisting of. The rubbery polymer (b ₁ ) of the graft copolymer (B) is at least one selected from the group consisting of a diene rubber, an ethylene rubber, and a terpolymer copolymer rubber of ethylene / propylene / diene monomers. A thermoplastic resin composition having excellent low temperature impact resistance, characterized in that. The method of claim 1, wherein the aromatic vinyl monomer (b ₂ ) of the graft copolymer (B) is styrene, para-t-butyl styrene, alpha-methyl styrene, beta-methyl styrene, vinyl xylene, monochloro styrene, At least one selected from the group consisting of dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene, and divinyl benzine thermoplastic resin composition having excellent low-temperature impact resistance. The vinyl cyanide monomer (b ₃ ) of the graft copolymer (B) is at least one selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile. Thermoplastic resin composition having excellent low temperature impact resistance. The thermoplastic resin composition of claim 1, wherein the copolymer (C) is a SAN copolymer copolymerized with styrene and acrylonitrile. The polymerizable other vinyl monomer (c ₃ ) of the copolymer (C) is at least one selected from the group consisting of methacrylic acid ester monomers, maleimides, and acrylimides. Thermoplastic resin composition having excellent low temperature impact resistance. The thermoplastic resin composition according to claim 1, wherein the content of the rubbery polymer (b ₁ ) is 25 to 70 parts by weight based on 100 parts by weight of the total of (B) and (C). The thermoplastic resin composition according to claim 7, wherein the content of the rubbery polymer (b ₁ ) is 35 to 60 parts by weight based on 100 parts by weight of the total of (B) and (C). The thermoplastic resin composition according to claim 1, wherein the modified ethylene-propylene crab rubber (D) has an amount of 6% by weight or less of carboxylic acid or anhydride and includes an organic peroxide. The thermoplastic resin composition of claim 8, wherein the carboxylic acid or anhydride is at least one selected from the group consisting of maleic anhydride, fumaric acid, acyl acid, and methacrylic acid esters. The method according to claim 8, wherein the organic peroxide is diisopropylene hydroperoxide, di-t-butyl peroxide, P-ethane hydroperoxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5-dimethyl 2, 5-di (t-butylperoxy) hexane, di-t-butyldiperoxyphthalate, persuccinate peroxide, t-butylperoxybenzoate, t-butylperoxymaleic acid, t-butylperoxyisopropyl carbonate , Methyl ethyl ketone peroxide, and cyclohexanone peroxide is at least one selected from the group consisting of thermoplastic resin composition having excellent low-temperature impact resistance. The aromatic vinyl monomer (e ₁ ) of the maleimide copolymer (E) is at least one selected from the group consisting of styrene, alpha-methylstyrene, vinyl toluene, and t-butylstyrene. A thermoplastic resin composition having excellent low temperature impact resistance. The maleimide monomer (e ₂ ) of the maleimide copolymer (E) is maleimide, N-methyl maleimide, N-ethyl maleimide, N-butyl maleimide, N-hexyl maleimide. , N-dichlorohexyl maleimide, N-phenyl maleimide, N-tri maleimide is at least one selected from the group consisting of thermoplastic resin composition having excellent low-temperature impact resistance. The unsaturated dicarboxylic acid anhydride monomer (e ₃ ) of the maleimide copolymer (E) according to claim 1, wherein the maleic anhydride, methyl maleic anhydride, 1,2-dimethyl maleic anhydride, ethyl maleic anhydride, and phenyl anhydride Thermoplastic resin composition having excellent low temperature impact resistance, characterized in that at least one selected from the group consisting of maleic acid. The method of claim 1, wherein the other copolymerizable monomer (e ₄ ) of the maleimide copolymer (E) is acrylonitrile, methyl methacrylate, ethyl (meth) acrylate, butyl methacrylate, hexyl methacrylate. , At least one selected from the group consisting of dichlorohexyl methacrylate, decyl (meth) acrylate, octadecyl methacrylate, hydroxyethyl (meth) acrylate, and glycidyl methacrylate. Thermoplastic resin composition having impact resistance. The thermoplastic resin composition according to claim 1, wherein the content of the component (A) is always greater than that of the component (B), and the component (A) forms a continuous phase.