KR20050051940A - Thermoplastic resin composition having superior impact resistance, weather resistnace and molding appearance - Google Patents

Abstract

The present invention relates to a method for producing a thermoplastic resin composition having excellent impact resistance and weather resistance and excellent appearance quality of a molded article. More particularly, the present invention relates to styrene monomer and acryl in ethylene propylene rubber and styrene butadiene styrene rubber in a reaction solvent. Graft copolymerization of the nitrile-based monomer by a continuous bulk polymerization method comprising the step of polymerizing at least once at a temperature of 90 ° C. or more and less than 130 ° C. and at least one polymerization at a temperature of 130 ° C. or more and 160 ° C. or less. It relates to a method for producing an AES resin comprising a. AES resin produced by the present invention is excellent in impact resistance, weather resistance and excellent appearance quality of the molded article.

Description

Thermoplastic resin composition with excellent impact resistance, weather resistance and appearance quality of molded products {THERMOPLASTIC RESIN COMPOSITION HAVING SUPERIOR IMPACT RESISTANCE, WEATHER RESISTNACE AND MOLDING APPEARANCE}

The present invention relates to a method for producing a thermoplastic resin composition having excellent impact resistance and weather resistance and excellent appearance quality of molded articles. More particularly, the present invention relates to ethylene propylene rubber (EPR, EPDM) and styrene butadiene styrene ( SBS) Graft copolymerization of a styrene monomer and an acrylonitrile monomer in a rubber relates to a method for producing a thermoplastic resin composition (AES resin) excellent in impact resistance and weather resistance and excellent appearance quality of the molded article.

Acrylonitrile butadiene styrene resin (hereinafter referred to as ABS resin) is a thermoplastic resin that is used in many fields because of its excellent strength, heat resistance, and molding processability. However, ABS resin has a drawback in that the hydrogen of the methyl group adjacent to the remaining double bond in the molecule due to the butadiene component becomes an initiation point of the oxidation reaction by the action of light or oxygen, and the main chain causes a reaction, resulting in poor weather resistance.

In particular, this causes not only whitening or cracking of the resin surface, but also causes various performance degradations of the ABS resin. In order to add weatherability and balance the physical properties while maintaining the excellent properties of the ABS resin, a method of adding an ultraviolet stabilizer, coating, plating, or the like is usually taken, which is not an essential improvement.

Therefore, various resins have been developed in which ABS butadiene components, which are causes of deterioration, are replaced with rubbers having unsaturated bonds. One of them is an AES resin manufactured using ethylene propylene rubber instead of butadiene.

AES resin is obtained by copolymerizing styrene, acrylonitrile and the like with substantially no unsaturated bond in the main chain, and using ethylene propylene rubber (EPR) and ethylene propylene nonconjugated diene three-dimensional copolymer (EPDM) as rubber components. Graft copolymers. Compared with ABS resin using conjugated diene rubber, the AES resin is known to have a remarkably good resistance to ultraviolet rays, oxygen and ozone. However, since ethylene propylene rubber has little reaction active portion compared to butadiene rubber, it is difficult to graft react styrene and acrylonitrile, and it is often a blend of rubbery polymer and vinyl polymer resin. . Therefore, in the case of injection molding the obtained AES resin, the surface is stained and the gloss is remarkably low, and defects such as impact resistance and lowering of tensile strength are present, and in severe cases, peeling phenomenon of peeling off the injection surface is also observed. In addition, due to the difference in the glass transition temperature of the butadiene-based rubber and ethylene propylene-based rubber, the use range is significantly limited despite the great advantage that the cold resistance, particularly at low temperatures, impact resistance is lower than that of the ABS resin. In order to improve the impact resistance at low temperatures, attempts have been made to polymer blend ABS resins, but it is difficult to improve the impact resistance at low temperatures while maintaining the weather resistance of the AES resin.

According to the definition of the term ASTM D 1418, EPDM refers to an amorphous rubber in which ethylene ("E") and propylene ("P") and the third component diene ("D") are irregularly bonded. Here, "M" means that the polymer main chain is composed of methylene ("M") having no unsaturated group, and is generally called ethylene propylene rubber (EPR) or EP rubber including EPM and EPDM. The structure is as follows.

CH ₃ CH ₃

         ┃ ┃

CH ₂ = CH ₂ + CH = CH ₂ → [-(CH ₂ -CH ₂ ) m (CH-CH ₂ )-]

(a) copolymer (EPM)

(b) terpolymer (EPDM)

EP rubber has very good ozone resistance, weather resistance, heat resistance, oxidation resistance, etc. because there is no double bond in the polymer main chain, and because it is a hydrocarbon structure, it has excellent low temperature characteristics, electrical properties, and resistance to polar substances. However, in the graft copolymerization reaction, the conditions for the graft reaction are difficult because there are no double bonds in the main chain.

On the other hand, the manufacturing method of the AES resin, which is a thermoplastic resin, is an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, a method using a suspension polymerization and a bulk polymerization together, a method of using an emulsion polymerization and a bulk polymerization together, and the like. Can be mentioned. Among these methods, the production site mainly uses emulsion polymerization and bulk polymerization. The AES resin prepared by the emulsion polymerization method has an average size of 0.2 to 1.5 mm of rubber particles present in the dispersed phase in a continuous styrene-acrylonitrile copolymer (SAN copolymer), and has good mechanical properties and gloss. However, due to the nature of the emulsion polymerization process, emulsifiers and flocculants, which must be used, are not completely removed in the flocculation and dehydration process but remain in the final product to cause deterioration of physical properties, and it is difficult to treat contaminated water used as a polymerization medium. In addition, since the process of flocculation and dehydration after polymerization is required separately, it is less economical than the bulk polymerization which is a continuous process.

The bulk polymerization is made by dissolving a certain amount of ethylene propylene rubber in a solution in which a predetermined proportion of styrene monomer and acrylonitrile monomer are dissolved in a reaction medium, and then mixed with an appropriate amount of a reaction initiator, a molecular weight regulator and other additives, followed by heating. By polymerization. As the polymerization proceeds, SAN is formed as a copolymer of styrene-based monomers and acrylonitrile-based monomers as the polymerization proceeds, and at this time, the styrene-based monomer and acrylonitrile-based monomers are dissolved and reacted with ethylene propylene-based rubber. To produce a copolymer. The resulting SAN copolymer forms two phases without mixing with the rubber dissolved in the reaction medium from the beginning of the reaction to make the entire polymerization solution non-uniform. In the heterogeneous phase, the rubber phase dissolved in the polymerization solution forms a continuous phase at the beginning of the polymerization reaction with low conversion rate, but the upper blood of the copolymer of styrene or styrene derivatives and acrylonitrile or acrylonitrile derivatives increased as the reaction proceeds. If is greater than the upper blood of the rubber in the polymerization solution, the former copolymer forms a continuous phase. This phenomenon is called 'phase inversion' and the point at which the volume of the copolymer phase and the rubber phase become equal is called the phase inversion point. After the phase inversion occurs, the rubber phase becomes a dispersed phase to form rubber particles in the finally prepared resin. Thus prepared AES resin is excellent in moldability, weather resistance, impact resistance has been applied to various fields such as home appliances, office equipment parts, automobile parts and outdoor facilities.

U.S. Patent No. 4,437,171 introduces a method for producing AES resin by reaction extrusion of styrene acrylonitrile resin and ethylene propylene diene rubber in the presence of a radical initiator. Thus prepared resin has a disadvantage in that the mechanical properties are lowered due to the lack of compatibility between the rubber and the matrix resin than the AES resin produced by the polymerization process.

US Patent No. 4814388 discloses a process for preparing an AES resin by copolymerizing styrene and acrylonitrile by solution polymerization in ethylene propylene rubber having a specific polydispersity index (PDI) and toluene, which is a reaction medium to ethylene propylene diene rubber. US Patent No. 3984496 discloses a method for preparing AES resin by solution polymerization using various reaction media. Since the resin composition thus prepared has excellent mechanical properties but an excessive amount of solvent is used, since chain transfer to the solvent is inevitable, the molecular weight of the polymer is lower than that of other polymerization methods and the polymerization rate is also slow. In addition, the process of recovering the solvent is complicated and the production cost is higher than that of the bulk polymerization method.

In the preparation of AES resin, U.S. Patent No. 5,067,78 has prepared a resin having improved mechanical properties, colorability, appearance appearance, and transparency by adding methyl methacrylate and hydrogenated butadiene to the polymerization solution. In -302339, an AES resin having excellent weather resistance, chemical resistance, and molding appearance was prepared using three types of rubbers, ethylene butene copolymer or ethylene octene copolymer rubber, ethylene propylene rubber or ethylene propylene diene rubber, and hydrogenated butadiene. Still, the balance between mechanical properties, weather resistance and molding appearance is not satisfactory.

In order to solve the above problems, the present invention is a ethylene propylene rubber (EPR, EPDM) and styrene acrylic by adding a small amount of styrene butadiene styrene (SBS) rubber to the polymerization solution in the production of AES resin by a continuous bulk polymerization method It is an object to produce a thermoplastic resin having excellent impact resistance and weather resistance and excellent appearance quality of molded articles by increasing the graft reaction between ronitrile copolymers.

In order to achieve the above object, the present invention comprises the step of graft copolymerization of styrene monomer and acrylonitrile monomer in ethylene propylene rubber and styrene butadiene styrene rubber in the reaction solvent by a continuous bulk polymerization method, AES It provides a method for producing a resin.

The continuous bulk polymerization method preferably comprises one or more polymerization at a temperature of 90 ° C. or more and less than 130 ° C .; And polymerizing at least once at a temperature of 130 ° C. or higher and 160 ° C. or lower.

In addition, the present invention is obtained by graft copolymerization of a styrene monomer and an acrylonitrile monomer in ethylene propylene rubber and styrene butadiene styrene rubber in a reaction solvent by a continuous bulk polymerization method, a graft ratio of 45% or more AES resin to provide.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

In order to provide an AES resin having excellent impact strength and weather resistance and excellent molding appearance quality, the method for preparing AES resin according to the present invention is characterized in that a styrene-butadiene styrene rubber is added to ethylene propylene rubber to perform a multi-step polymerization process. It is done.

According to the present invention, a polymerization solution prepared by dissolving ethylene propylene rubber (EPR, EPDM) and styrene butadiene styrene (SBS) rubber in a mixed solution in which a styrene monomer and an acrylonitrile monomer are dissolved in a reaction solvent by a continuous bulk polymerization method. , An initiator and a molecular weight modifier are added to the reactor continuously, and polymerized at least once at a temperature of 90 ° C. or more and less than 130 ° C., and polymerization is performed one or more times at a temperature of 130 ° C. or more and 160 ° C. or less to prepare an AES resin. Thereafter, when the polymerization conversion rate is 65 to 95%, unreacted monomer and the reaction medium are removed at a temperature of 200 to 260 ° C. in a volatilization tank to prepare pellets of AES resin.

In the present invention, the polymerization process is preferably by continuous bulk polymerization, which is polymerized one or more times at a temperature of 90 ° C. or more and less than 130 ° C. Polymerization at least once at a temperature of (hereinafter referred to as 'two-step polymerization' for convenience). By the one-stage polymerization, phase inversion occurs smoothly so that the upper blood of the copolymer of styrene and acrylonitrile is larger than the upper blood of the rubber in the polymerization solution. In addition, by the two-stage polymerization, the polymerization conversion rate after the phase inversion time is increased. If the polymerization temperature is less than 90 ℃ in the one-step polymerization, the phase inversion is not performed smoothly, the rubber particles in the final resin may be uneven. If the polymerization temperature is 130 ℃ or more, the polymer is transferred to each reactor by excessive polymerization Problems that are difficult to occur occur. In the two-stage polymerization, as a process for conversion of the final resin, when the polymerization temperature is less than 130 ° C. or more than 160 ° C., a problem of poor transport of the resin may occur or the rubber content of the final resin may be high, thereby making it difficult to balance physical properties. In the present invention, it is preferable to perform the two-stage polymerization two or more times, and it is preferable to gradually increase the temperature in the two-stage polymerization. For example, the two stage polymerization may include polymerization at 130 ° C., polymerization at 140 ° C., and polymerization at 145 ° C.

The reaction solvent is used to lower the viscosity of the polymerization solution, and may be selected from one or more selected from the group consisting of toluene, ethylbenzene, and xylene, and toluene is preferable. In addition, the content of the reaction solvent is preferably 10 to 45% by weight, it is difficult to control the high viscosity at less than 10% by weight, if more than 45% by weight effectively control the form of the rubber particles produced during the polymerization process can not do.

The styrene monomers are styrene, α-methylstryene, p-bromostryene, p-methylstryene, p-chlorostryene , o-bromostryene and mixtures thereof, and the content thereof is preferably 40 to 60% by weight.

The acrylonitrile monomer may be selected from the group consisting of acrylonitrile, methacrylonitrile, ethacrylonitrile, and mixtures thereof, the content of which is 10 to 25% by weight. Is preferably.

The ethylene propylene rubber may be selected from the group consisting of ethylene-propylene rubber (ethylene-propylene rubber, EPR) and ethylene-propylene diene rubber (EPDM), the content of which is 5 to 12 weight It is preferable that it is%. Ethylene propylene-based rubber is a rubber without a double bond in the main chain, so when the content thereof is less than 5% by weight, the impact resistance is lowered, and when it exceeds 12% by weight, SAN (styrene-acrylonitrile copolymer) resin and rubber Since compatibility between the problem is reduced, the molding appearance is reduced due to the reduced graft reaction.

The composition ratio of ethylene (C2) / propylene (C3) directly affects the low temperature characteristics. This is because the glass transition temperature changes according to the composition ratio because the glass transition temperature (Tg) of ethylene and propylene is different. In view of the low temperature characteristics, the ethylene content is preferably 45 to 80% by weight and the propylene content is 20 to 55% by weight . The composition ratio of the ethylene propylene is a factor involved in the impact properties and low temperature properties of the rubber, the impact resistance is increased when the ethylene content is increased, but the low temperature characteristics are lowered, the low temperature characteristics are increased, but the impact resistance is lowered when the propylene content is increased Therefore, an appropriate content ratio should be maintained between them.

As diene monomer added to impart crosslinking properties to EPDM, ethylene norbornene (ENB), dicyclopentadiene (DCPD), hexadiene (HD) and the like having the following structure can be used, and the content thereof is preferably 13 weight% or less. The content of the diene monomer is generally used in the production of EPDM. If the content is increased by more than 13% by weight, the cost of the EPDM rubber is high, which is not preferable. Ethylene norbornene (5-ethylene-2-norbonene) is the most widely used because of its relatively high crosslinking rate, and dicyclopentadiene (DCPD) has a low crosslinking rate, a bad smell, low cost, and hexa Dienes (1,4-hexadiene) have a crosslinking rate intermediate between ENB and DCPD.

The pattern viscosity is a representative index indicating the molecular weight of rubber. As the pattern viscosity increases, tensile strength, tear strength, crosslink density, and the like increase. As for the pattern viscosity of the ethylene propylene rubber used for this invention, 20-90 are preferable. If the range of the pattern viscosity is too high or low outside the above range, there is a problem of non-uniformity in the production of rubber particles.

In addition, the weight average molecular weight of the ethylene propylene rubber is preferably 150,000 to 400,000, more preferably 200,000 to 350,000.

In the present invention, styrene butadiene styrene rubber is added during polymerization together with ethylene propylene rubber to improve impact strength, weather resistance and molding appearance. The styrene butadiene styrene rubber contains a double bond in the main chain and thus has a reactive active point, thereby increasing the graft rate, and also acting as a compatibilizer between ethylene propylene-based rubber and styrene acrylonitrile matrix resin, thereby making it compatible with rubber and matrix resin. To increase sex. That is, the grafting of SAN, which is a copolymer of styrene monomer and acrylonitrile monomer, is well performed. Styrene butadiene styrene rubber is a diblock copolymer having a styrene content of 20 to 50% by weight, the structure may be linear or radial, and the weight average molecular weight is preferably 80,000 to 400,000, more preferably 150,000 to 300,000. In addition, the content is preferably 0.5 to 5% by weight. If the content of styrene butadiene styrene rubber is less than 0.5% by weight, the increase in graft ratio is insufficient, and thus the molding appearance is not satisfactory.

In the present invention, the organic peroxide initiator is used to initiate the polymerization reaction and to control the graft reaction and the conversion rate, the content of which is preferably 0.01 to 0.1 parts by weight based on 100 parts by weight of the total raw material. As the organic peroxide initiator, 1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane {1,1-bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane}, 1,1-bis (t-butylperoxy) cyclohexane {1,1-bis (t-butylperoxy) cyclohexane}, 1,1-bis (t-butylperoxy) -2-methyl cyclohexane {1,1 -bis (t-butylperoxy) -2-methyl cyclohexane}, 2,2-bis (4,4-di-t-butylperoxy cyclohexyl) propane {2,2-bis (4,4-di-t- butylperoxy cyclohexyl) propane}.

In addition, the present invention uses a molecular weight regulator to adjust the viscosity of the resin, the size of the particles and the distribution of particles, the content is preferably used in 0.01 to 0.1 parts by weight based on 100 parts by weight of the total raw material. As said molecular weight regulator, thiol type compounds, such as t-dodecyl mercaptan and n-octyl mercaptan, can be used.

In addition, the present invention provides an AES resin prepared by the above production method. The AES resin of the present invention is characterized by having a graft ratio of 45% or more and having excellent impact resistance, weather resistance and molding appearance.

Hereinafter, the present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to the examples.

EXAMPLE

Example 1

After dissolving 7.2% by weight of ethylene propylene diene (EPDM) rubber in a mixed solution of 41.6% by weight of styrene and 10.4% by weight of acrylonitrile in 40% by weight of toluene as a reaction solvent, 0.8% of styrene butadiene styrene (SBS) rubber was used. 1% of bis (t-butylperoxy) -3,3,5-trimethyl cyclohexane (1,1-Bis (t-butylperoxy) -3,3,5-trimethyl cyclo is added as an initiator. hexane) was added 0.05% by weight based on the total amount to prepare a polymerization solution. The prepared polymerization solution was introduced into a 26L reactor at a rate of 12 L / hr, polymerized at a temperature of 125 ° C. in the first reactor, polymerized at a temperature of 130 ° C. in the second reactor, and 140, respectively in the third reactor and the fourth reactor. When the polymerization was carried out at a temperature of 145 DEG C, and the polymerization conversion was 90%, the unreacted monomer and the reaction medium were removed at a temperature of 230 DEG C in a volatilization tank to prepare an AES resin in pellet form.

The physical properties of the AES resin thus prepared were measured, and the results are shown in Table 1.

Example 2

AES resin was prepared in the same manner as in Example 1, except that 6.4% EPDM rubber and 1.6% SBS rubber were added when preparing the polymerization solution, and the physical properties of the AES resin thus prepared were measured. Is shown in Table 1.

Example 3

AES resin was prepared in the same manner as in Example 1, except that 5.6% EPDM rubber and 2.4% SBS rubber were added when preparing the polymerization solution, and the physical properties of the AES resin thus prepared were measured. Is shown in Table 1.

 Comparative Example 1

AES resin was prepared in the same manner as in Example 1, except that 8.0% of EPDM rubber was added without adding SBS rubber when preparing the polymerization solution, and the physical properties of the AES resin thus prepared were measured and the result was measured. Table 1 shows.

Comparative Example 2

AES resin was prepared in the same manner as in Example 1, except that 8.0% of SBS rubber was added without adding EPDM rubber when preparing the polymerization solution, and the physical properties of the AES resin thus prepared were measured, and the result was measured. Table 1 shows.

Example 4

AES resin was prepared in the same manner as in Example 1, except that ethylene propylene rubber was used instead of EPDM rubber in preparing the polymerization solution. The physical properties of the AES resin thus prepared were measured, and the results are shown in Table 1. It was.

Physical properties of the AES resins prepared in Examples and Comparative Examples were measured by the following method.

◎ Average particle size of rubber particles: 0.5 g of AES resin was dissolved in 100 mL of methylethylkenone, and the average particle diameter of the rubber particles was measured using a Coulter counter (Beckman Coulter LS230).

Izod Impact: Measured by ASTM D256 method.

◎ Tensile strength and elongation: It was measured by ASTM D638 method.

◎ Gloss: An injection test piece having a thickness of 3 mm was prepared and measured according to ASTM 1003.

Graft rate: A certain amount of AES resin (X) is introduced into acetone and vibrated with a vibrator for 24 hours to dissolve the free resin. The solution is centrifuged at 14,000 rpm for 1 hour using a centrifuge to obtain insolubles. The insoluble content thus obtained is dried at 140 ° C. for 2 hours using a vacuum dryer to obtain an insoluble content (Y). The graft ratio was calculated by the following equation.

Graft Rate (%) = {Y-XR} / XR * 100

(R: rubber fraction in AES resin constant amount (X))

◎ Weatherability: The retention rate was calculated by exposing to a Sunshine Weatherometer (Wather-6, WEL-6XL-DC, Suga Tester Co., Ltd.) using carbon arc as a light source for 1,000 hours.

◎ Molding appearance (flow mark): An injection test piece having a thickness of 3 mm was manufactured and the degree of occurrence of the flow mark was visually observed.

◎ Peeling: Whether or not the resin was peeled was observed using a tensile test piece according to the ASTM D638 method.

division Example Comparative example One 2 3 4 One 2 EPR or EPDM rubber content in the polymerization solution (wt%) 7.2 6.4 5.6 7.2 8 0 SBS rubber content in the polymerization solution (wt%) 0.8 1.6 2.4 0.8 0 8 Average Rubber Particle Size (㎛) 1.74 1.87 1.71 1.73 1.77 2.32 Tensile Strength (kgcm ² ) 420 414 409 436 432 371 Elongation (%) 17.4 18.2 20.9 15.5 9.8 21.4 Impact Strength (kgcm / cm) (1/4 ", 23 ℃) 22,3 23.6 25.7 23.7 14.4 15.7 (1/4 ", -30 ℃) 7.8 8.2 8.4 7.3 4.2 8.8 Graft Rate (%) _ 51 62 69 45 32 67 Weather resistance Impact strength retention rate (%) 82 85 87 84 88 49 Polish (%) 88 87 89 88 87 74 Molding appearance (Flomark ⁾ △ O O △ X O Peeling ^note) △ O O △ X O

Note) O: Does not occur, △: Slightly occurs, X: Occurs

As described above, the AES resin production method of the present invention has the effect of producing an AES resin excellent in impact strength, weather resistance and molding appearance.

While the invention has been described in detail above with reference to the described embodiments, it will be apparent to those skilled in the art that various modifications and variations are possible within the scope and spirit of the invention, and such modifications and variations fall within the scope of the appended claims. It is also natural.

Claims (12)

Graft copolymerization of styrene-based monomers and acrylonitrile-based monomers in ethylene propylene rubber and styrene butadiene styrene rubber in a reaction solvent by continuous bulk polymerization. 10. 45 wt% of a reaction solvent, 40-60 wt% of a styrene monomer, 10-30 wt% of an acrylonitrile monomer, 5-12 wt% of an ethylene propylene rubber, and 0.5 To 5% by weight of styrene butadiene styrene rubber. The method of claim 1, wherein the continuous bulk polymerization is performed at least once at a temperature of 90 ° C. or more and less than 130 ° C .; And polymerizing at least once at a temperature of 130 ° C. or higher and 160 ° C. or lower. The method of claim 1, wherein the reaction solvent is at least one selected from the group consisting of toluene, ethylbenzene, and xylene. The method of claim 1, wherein the ethylene propylene rubber is selected from the group consisting of ethylene-propylene rubber (ethylene-propylene rubber, EP) and ethylene-propylene-diene rubber (EPDM), the ethylene content This is 45 to 80% by weight, the propylene content is 20 to 55% by weight, the weight average molecular weight is 150,000 to 400,000. The method of claim 5, wherein the ethylene-propylene-diene rubber comprises up to 13 wt% diene monomer, wherein the diene monomer is selected from the group consisting of ethylene norbornene, dicyclopentadiene and hexadiene. The method of claim 1, wherein the styrene monomer is selected from the group consisting of styrene, α-methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene, o-bromostyrene, and mixtures thereof. Way. The method according to claim 1, wherein the acrylonitrile monomer is selected from the group consisting of acrylonitrile, methacrylonitrile and ethacrylonitrile. The method of claim 1, wherein the styrene butadiene styrene rubber is a diblock copolymer having a styrene content of 20 to 50 wt%, has a linear or radial structure, and has a weight average molecular weight of 80,000 to 400,000. The method according to claim 1, wherein 0.01 to 0.1 parts by weight of initiator is used based on 100 parts by weight of the total raw material, and the initiator is 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -2-methyl cyclohexane, and 2,2-bis (4,4-di-t-butyl And peroxy cyclohexyl) propane. The compound according to claim 1, wherein 0.01 to 1 part by weight of a molecular weight regulator is used based on 100 parts by weight of the total raw material, and the molecular weight regulator is selected from the group consisting of t-dodecyl mercaptan and n-octyl mercaptan. How to be. AES resin obtained by graft copolymerization of a styrene monomer and an acrylonitrile monomer to ethylene propylene rubber and styrene butadiene styrene rubber in a reaction solvent, and having a graft ratio of 45% or more.