JPH0367110B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermoplastic composite resin composition that has excellent heat and impact resistance and exhibits high melt flowability during molding.More specifically, the present invention relates to a thermoplastic composite resin composition comprising (1) a vinyl aromatic monomer and an unsaturated dicarboxylic acid anhydride. A copolymer resin, (2) a graft copolymer resin consisting of a rubber-modified vinyl aromatic monomer and an unsaturated nitrile monomer or a methacrylic acid ester monomer, (3) a rubber-modified vinyl A graft copolymer resin consisting of an aromatic monomer and an unsaturated dicarboxylic anhydride monomer, and (4) a block copolymer consisting of a vinyl aromatic monomer and a fatty acid diene compound, which has high heat and impact resistance. The present invention relates to a highly fluid resin composition. Styrene-maleic anhydride copolymer resin (hereinafter referred to as SMA
(abbreviated as “resin”) is well known. This resin has high strength and hardness, good workability, and high heat deformation resistance, making it suitable for use under harsher thermal conditions than the known styrene acrylonitrile resin (hereinafter referred to as SAN resin). ing. however
The above-mentioned copolymer resins, typified by SMA resins, generally have low impact resistance, and their uses are naturally limited. The graft copolymer of (2) above, which is obtained by graft copolymerizing a vinyl aromatic monomer and an unsaturated nitrile compound or a methacrylic acid ester monomer in the presence of polybutadiene or styrene-butadiene (random or block) copolymer rubber. The above graft copolymer resin (3), which is obtained by graft copolymerizing a vinyl aromatic monomer and an unsaturated dicarboxylic acid anhydride in the presence of a resin, polybutadiene or styrene-butadiene copolymer rubber, is also known. ABS resin, MBS
Examples include resin or rubber-modified styrene-maleic anhydride copolymer resin (hereinafter abbreviated as SMA-B resin). Among these resins, ABS resin and MBS
Graft copolymer resins such as resins have extremely high impact resistance, and are useful resins that are widely used in applications that cannot be used with SAN resins, SMA resins, etc., such as housings of home appliances and parts of automobile interiors.
However, these graft copolymer resins have poor heat resistance and have problems in their application as home appliance parts having heat-generating parts or automobile interior parts exposed to direct sunlight. On the other hand, there are examples of graft copolymer resins mentioned in (3) above, such as SMA-B resin, having heat resistance close to 100℃.
Although the characteristics of SMA-B resin can be demonstrated for applications that require long-term use at high temperatures, which was a problem with conventional ABS resins, this resin also still has problems with low impact resistance and low melt flow. . Many attempts have been made to obtain a resin that compensates for the drawbacks of these resins and has overall excellent physical properties by combining the above-mentioned component resins, and the following examples are examples thereof. Special Publication No. 50775, No. 88953:
Composite of SMA resin and ABS resin JP-A-54-96555: ABS resin and SMA-B
Composite of resin These are both SMA resin, ABS resin or SMA
It is possible to obtain a composite composition that mutually compensates for the shortcomings of each resin, such as the -B resin. It is true that according to these examples, the heat resistance is 5 to 15 times higher than that of ordinary ABS resin, etc.
℃ has been improved, and attempts have been made to improve the practical physical properties of these composite compositions and make them more useful by adding impact modifiers to minimize the drop in impact resistance. However, it has been found that these known techniques have the drawback of being inferior in melt fluidity, which is another important factor in the practical performance of resin compositions. The melt flow performance of the resin affects the appearance of the molded product and the performance of the molded product itself, such as internal distortion, and is an important index directly related to the productivity of the so-called molding cycle when molding the resin into a final product. be. The present inventors have discovered that SMA resin, ABS resin (or
In the process of studying how to improve the physical properties of a ternary resin composite system of SMA-B resin (MBS resin) and SMA-B resin, we found that SMA resin and ABS resin or MBS resin
A block copolymer consisting of a vinyl aromatic monomer and an aliphatic diene compound as a melt flowability improver is added to the ternary resin composite system with SMA-B resin, and its melt flow index is 200°C. ,
Addition of a compound in the range of 1.0 to 20.0 g/10 minutes under measurement conditions of 5 kg load significantly improves the melt flowability of the composite resin composition and improves the impact resistance, which is a characteristic behavior. We have arrived at the present invention. That is, the present invention provides: (1) 65% of the vinyl aromatic monomer based on the weight of the copolymer resin;
~95% by weight, unsaturated dicarboxylic anhydride 5-35
A copolymer resin A obtained by copolymerizing 0 to 30 wt% of a vinyl monomer copolymerizable with these and (2) polybutadiene or styrene-butadiene copolymer based on the weight of the graft copolymer resin. Polymerized rubber 15-70
A graft copolymer resin B obtained by graft copolymerizing 30 to 85% by weight of a mixture of a vinyl aromatic monomer and an unsaturated nitrile monomer or a methacrylic acid ester monomer in the presence of % by weight; 3) Polybutadiene or styrene-butadiene copolymer rubber 5 to 50% by weight of graft copolymer resin
% by weight of a mixture of a vinyl aromatic monomer, an unsaturated dicarboxylic acid anhydride, and optionally a vinyl monomer copolymerizable with these. Copolymer resin C and (4) vinyl aromatic monomer 55 to 55% based on copolymer weight
It is made by block copolymerizing 95% by weight and 5 to 45% by weight of an aliphatic diene compound, and its melt flow index is in the range of 1.0 to 20.0 g/10 minutes at 200°C and a load of 5 kg. It consists of block copolymer D, and the proportions of these components A, B, C, and D are
C is 5 to 40 parts by weight for a total of 100 parts by weight of A30 to 70 parts by weight and B70 to 30 parts by weight, and A, B and C
This relates to a highly fluid heat-resistant and impact-resistant resin composition in which D is 5 to 20 parts by weight based on a total of 100 parts by weight. A specific example of the copolymer resin A that forms the main component of the composition of the present invention is a styrene-maleic anhydride copolymer resin. A wide variety of polymerization methods such as batch or continuous bulk or solution polymerization methods can be employed for the polymerization of this resin. A mixture of saturated dicarboxylic acid anhydride monomers is subjected to conventional radical copolymerization under heating or using a radical initiator in an inert gas atmosphere. Combinations of electron-accepting monomers and electron-donating monomers, such as styrene and maleic anhydride, have strong alternating copolymerizability under normal polymerization conditions, and the resulting alternating copolymerized resins can be molded. Since it is difficult to process and is impractical, it is necessary to obtain a copolymer resin A having a desired uniform composition by paying attention to the initial monomer composition ratio and the additional monomer addition during polymerization. In this case, the content of unsaturated dicarboxylic acid anhydride in the copolymer needs to be 5% by weight or more in order to maintain the heat resistance of the final composite composition at a high level, while also facilitating moldability. Due to necessity, it is necessary to set the upper limit to 35% by weight or less. Furthermore, in order to maintain the heat resistance of the resin composition of the present invention at a high level, copolymer resin A must be present in the final composition at or above the lower limit of the range specified above. In order to avoid the decrease, it is desirable that it be below the above upper limit. It is possible to copolymerize a third monomer into this copolymer if necessary, and specifically acrylonitrile or methyl methacrylate is used. However, from the viewpoint of maintaining the present copolymer resin A and the final composition, melt flow, and impact resistance, the amount of copolymerization is preferably 30% by weight or less. Next, preferred specific examples of graft copolymer resin B are:
These are ABS resin and MBS resin. There are already many commercially available products for these resins, and it is up to you which one to use, but it should be selected in order to maintain a high level of impact resistance in the final composition. There are restrictions on the composition of ingredients. That is, resin B
The rubber content inside should be as high as possible, specifically 15% by weight or more. While the rubber content is 70
If it exceeds % by weight, a crosslinking reaction occurs during molding, making it impractical. More preferred is 30 to 60% by weight. The composition ratio of the matrix-forming resin is preferably one in which vinyl aromatic monomers such as styrene account for the majority. If the content of the resin component B exceeds the upper limit of the range specified above, the heat resistance will decrease, and if it falls below the lower limit, the impact resistance will decrease, which is not preferable. Next, a specific example of the graft copolymer resin component C is a rubber graft styrene maleic anhydride copolymer resin. This resin C can also be produced by polymerizing in the same way as ABS resins and MBS resins, but for example, polybutadiene or styrene-butadiene copolymers are combined with vinyl aromatic monomers such as styrene and unsaturated resins such as maleic anhydride. A predetermined amount of the compound may be dissolved in a mixture of dicarboxylic acid anhydride monomers, and graft copolymerization may be carried out by radical polymerization using substantially the same method as that described for the polymerization of copolymer resin A. For the polymerization of this resin C, thermal polymerization at 100 to 140°C or initiator polymerization using a radical initiator at 80 to 120°C is suitable, and it is desirable to employ non-aqueous bulk polymerization or solution polymerization. Although it is possible to increase the rubber content in the resin slightly by using a solvent during the initial dissolution process, the rubber content is practically limited due to problems such as thickening of the system and difficulty in controlling polymerization.
~50% by weight is advantageous. The proportion of unsaturated dicarboxylic acid anhydride in the matrix resin is preferably within a range not exceeding that in the above-mentioned copolymer resin A. On the other hand, if it is too small, the heat resistance will be low, so it is preferably 5 to 20% by weight. Addition of the third monomer as a matrix-forming resin component to resin C is particularly effective when component resin A is a ternary copolymer resin containing the third monomer. It is more desirable that the chemical structure of the monomer is matched to that of the third monomer of resin A. Even in that case, in order to maintain mutual compatibility between the resins, it is better not to exceed 30% by weight of the matrix resin component of Resin C. When the ratio of resin C to the total amount of resins A and B is less than 5% by weight, the effect of improving physical properties is poor, and when it exceeds 40% by weight, the impact resistance is significantly reduced. Next, the necessary requirements and effects of block copolymer D, which is an important component of the present invention, will be explained in detail.
This block copolymer D contains 55 to 95 parts by weight of a vinyl aromatic monomer such as styrene and 5 parts by weight of an aliphatic diene compound.
It is a copolymer with a monoblock copolymer structure consisting of ~45 parts by weight, and its melt flow rate (hereinafter abbreviated as MFR) is measured using a melt indexer at 200°C and a load of 5 kg.
It is necessary to satisfy the condition of 1.0 to 20.0 g/10 minutes.
Examples of such resins include styrene-butadiene block copolymers, styrene-isoprene block copolymers, and the like. The copolymerization mode of this copolymer is block-like, the vinyl aromatic monomer composition such as styrene accounts for the majority, and the melt flow rate is 1.0 to 20.0 g/min under measurement conditions of 200°C and 5 kg load. It is important that the heating time be within the range of 10 minutes in order to obtain a resin composition that has heat resistance, impact resistance, and high fluidity, which is the object of the present invention. The inventors' speculations regarding the mechanism by which the effect of block copolymer D is expressed will be described below, but the present invention is not limited thereto. In other words, ABS resins and MBS resins, which often use rubbery polymers containing many unsaturated bond components such as polybutadiene as modified components, and composite resin compositions containing these resins as constituent components, The melt flow is lower than that of a graft copolymer resin (for example, AES resin) whose modified component is a rubbery polymer containing little or no unsaturated bond component. The reason for this is thought to be that the unsaturated bonds are thermally crosslinked by radicals generated during heating, which increases the apparent molecular weight of the rubbery polymer and increases the entanglement between polymer chains. Therefore, attempts to improve the melt flow of composite compositions composed of ABS resins and the like containing unsaturated bond components include, for example, the addition of radical scavengers (thermal stabilizers) to prevent thermal crosslinking or the addition of polymers. It is widely practiced to add plasticizers to reduce the mutual intermolecular forces. However, even if these thermal stabilizers and low-molecular plasticizers can be used as fluidity improvers in composite compositions to improve the melt fluidity, these additives inherently have a strong property of melting and fluidizing at low temperatures; The heat deformation temperature of objects decreases. Furthermore, there are almost no examples of its use as a plasticizer for polymers such as vinyl polymers for the purpose of maintaining a high level of heat resistance. There are no examples of using an aromatic monomer copolymer as a melt flowability improver for a composite composition. In the present invention, simply adding polystyrene, which has a high melt flow rate, will reduce the impact resistance of the composite system. Resin A and ABS
It is intended to be localized at the interface of resin B, such as a resin, to serve as a polymer plasticizer that not only reinforces the viewing surface but also alleviates the intermolecular interaction between these polymers. FIG. 1 shows an example that proves that styrene-butadiene block copolymer D is localized at the phase interface of styrene-maleic anhydride copolymer resin A and ABS resin B. This figure shows a reproduction of a transmission electron micrograph of a composite composition of Resin A, Resin B, Resin C, and Copolymer D obtained in Example 1, which will be described later. In this figure, 1.5 cm corresponds to 1 μm. This figure shows one of the nearly circular dispersed phases.
The size of ~several μm is the added SMA-B.
Resin C also has a small particle dispersed phase of 0.1 to 0.5 μm.
The dyed phase of the rubber particles containing the "salami structure" of ABS resin B is shown. On the other hand, the continuous phase other than the above is the SMA resin A phase. What is characteristic about this phase structure is that a so-called "onion structure", which indicates the presence of the styrene-butadiene block copolymer D, shown in a striped pattern, can be seen here and there surrounding the dispersed rubber particles. It is. The fact that each component resin in the composite composition exhibits such a special morphology and the melt flow index (MFR) of the styrene-butadiene block copolymer described below
It is considered that when the following factors are satisfied, the above-mentioned effect as a melt fluidity improver is manifested. Regarding the melt flow index (MFR) that should be maintained by the vinyl aromatic monomer-aliphatic diene compound copolymer D as a melt flowability improver, if it is too high, it may be difficult to improve the melt flowability of the composite system. Even if it is possible, other physical properties, especially heat resistance, will deteriorate, which is undesirable. On the other hand, if it is too low, the melt fluidity of the composite system cannot be improved. As a result of various studies aimed at maintaining a balance between melt fluidity and other physical properties, especially heat and shock resistance, the required MFR range of Copolymer D was 1.0 to 20.0 g under measurement conditions of 200°C and 5 kg load. /
10 minutes is valid. The higher the vinyl aromatic monomer content in copolymer D is, the better it is as a melt fluidity improver. However, if it is too high, the impact resistance of the final composite composition will decrease, so it is necessary to copolymerize some aliphatic diene compounds, and a range of 55 to 95 parts by weight, in which the vinyl aromatic monomer accounts for the majority, is desirable. . The proportion of this copolymer D is at least 5% by weight based on the total of resins A, B, and C in order to improve fluidity, and at most 20% by weight or less in order to minimize the decrease in heat resistance of the composition. It is desirable to do so. Examples of the vinyl aromatic monomer-aliphatic diene compound block copolymer include Asaflex 810 (D ₁ ) and Asaflex 800 (D ₂ ) manufactured by Asahi Kasei Co., Ltd., and the former has a bonded styrene content of approx. 70% by weight, the latter approximately 80% by weight. Moreover, the melt index of both was 5.0 g/10 min under the conditions of 200° C. and 5 kg load. As the vinyl aromatic monomer used in the present invention, styrene, α-methylstyrene, α-chlorostyrene, nuclear-substituted styrene, etc. are arbitrarily selected, but styrene and/or α-methylstyrene are more preferable. It is. Maleic anhydride is the most preferred and common unsaturated dicarboxylic anhydride, but a portion thereof can also be replaced with aconitic anhydride, citraconic anhydride, or the like. Typical unsaturated nitrile compounds include acrylonitrile, methacrylonitrile, and the like, with acrylonitonyl being more preferred. The methacrylate monomer can be selected from a wide range of methyl methacrylate, ethyl methacrylate, methyl acrylate, etc., but methyl methacrylate is more convenient. The vinyl monomer copolymerizable with the above monomer can be arbitrarily selected from various substituted olefins, but it is suitable for the purpose to select it from the monomer group listed above. Next, the following method can be adopted as a method for preparing the final composition. That is, component resins A, B, and C
and Copolymer D are weighed as desired. The weighed ratio of each component at this time can be changed appropriately within the range specified in the present invention depending on the performance required of the final composition, but for example, for a formulation that places more emphasis on heat resistance, component resin A may be used. In order to increase the amount and ensure a high level of impact resistance, the amount of component resin B may be increased. The weighed component mixtures are thoroughly mixed using a mixer, etc., and then kneaded using a roll, Banbury mixer, kneading press, etc., preferably at a temperature of 240° C. or less and a residence time of about several minutes. Further, during mixing, a solution blending method using a common solvent for each component resin is also possible, but in a multicomponent system such as the present resin composite system, a mechanical kneading method is more preferable. The kneaded resin composition is pulverized or pelletized using a pelletizer and then transferred to a molding process. This process is performed by press molding, injection molding, extrusion molding, etc. In addition, prior to kneading and molding, other properties such as increasing rigidity, coloring, and various fillers to prevent thermal deterioration during molding are added to the resin composite system.
There is no problem in mixing pigments and additives.
The present invention will be explained below using Examples and Comparative Examples, but the present invention is not limited by these Examples. The physical properties of the molded test pieces in the examples were evaluated according to the following test method. Heat Distortion Temperature ASTM D-256 Impact Resistance Test ASTM D-648 Melt Flow Index JIS K-6760 First, the preparation methods of component resins used in Examples and Comparative Examples will be shown as reference examples. Reference Example 1 [Polymerization of styrene-maleic anhydride copolymer resin (SMA resin)] Styrene and anhydrous were placed in a stainless steel reaction vessel No. 5 equipped with a stirring device, a reflux condenser, an automatic temperature control function, a heat medium circulation device, etc. 2.98Kg of maleic acid each
Add 0.02Kg and stir well. After performing _N2 substitution, the temperature inside the reaction tank was raised to 120°C. Internal temperature is 110℃
Polymerization was started when the temperature reached 100 mL, and the polymerization was continued for 3 hours thereafter. In this polymerization system, when only the above-mentioned initial charge is used, the composition ratio of the copolymer produced gradually shifts toward the styrene side, so it is necessary to additionally add maleic anhydride to the system in order to keep the composition ratio of the copolymer constant. There is. After the specified additional addition and polymerization time are completed, the polymerization system is cooled and added as a heat stabilizer in the reactor.
Irganox 1010 (manufactured by Ciba Geigy) was added to the total solid content.
The mixture was added in an amount of 0.2% by weight, mixed well, and then transferred to a vacuum dryer and devolatilized under vacuum for 5 hours at a temperature of 150° C. and a degree of vacuum of 2 Torr. The recovery rate in this case was 56.3%. This copolymer resin is designated as _A1 . In addition, 2.99 kg of styrene and 0.01 kg of maleic anhydride were put into the same reactor as above, and after dissolving, the temperature was raised to 120°C, and another copolymer resin A ₂ was obtained while additionally adding maleic anhydride. Ta. The recovery rate was 45%. The analytical values of A ₁ and A ₂ are shown in Table 1. Reference Example 2 [Polymerization of rubber grafted styrene-maleic anhydride copolymer resin (SMA-B resin)] Using the same reactor as in the polymerization of Reference Example 1, 0.6 kg of polybutadiene was mixed with 2.99 kg of styrene and maleic anhydride.
It was dissolved in a mixture of 0.01Kg and 0.5Kg of xylene as a solvent. After replacing with _N2 , the internal temperature of the reactor was raised to 120°C. Polymerization was started when the internal temperature reached 110°C, and as in Reference Example 1, the polymerization was interrupted while sequentially adding maleic anhydride. The polymerization temperature is
The temperature was maintained at 120°C. When the polymerization time reached 5 hours, the contents were rapidly cooled, and at the same time, a heat stabilizer was added to the polymerization solution.
Irganox1010, 0.2% by weight of total solids calculated
Add, mix, and transfer to a vacuum dryer at a temperature of 180℃.
Vacuum devolatilization was carried out for 5 hours at a vacuum degree of 1 Torr. The lumpy resin after devolatilization was pulverized into powder. Rubber graft copolymers C ₁ and C ₂ of the same type were obtained by changing the additional addition of maleic anhydride using the above method. The analysis results of these resins are shown in Table-1. Example 1 60 parts by weight of copolymer resin A ₁ of Reference Example 1, rubber grafted styrene-acrylonitrile copolymer resin manufactured by Japan Gosei Rubber Co., Ltd. (ABS resin: rubber content 42% by weight, acrylonitrile content in matrix resin phase) About 24% by weight (hereinafter referred to as B ₁ ) was added to 40 parts by weight, and the rubber grafted styrene-maleic anhydride copolymer resin C ₁ of Reference Example 2 was added to 20 parts by weight as a styrene-butadiene block copolymer manufactured by Asahi Kasei Corporation. Asaflex 810 (MI 5.0 at temperature 200℃ and load 5kg)
g/10 minutes, combined styrene content (approximately 70% by weight) was added, 0.2% by weight of Sumilizer WXR manufactured by Sumitomo Chemical Co., Ltd. was added as a heat stabilizer, and the mixture was thoroughly mixed. It was pelletized using a 40mmφ extruder. Cylinder temperature is 230℃, screw rotation speed is 40rpm
It is. The pellets were molded into test pieces using an injection molding machine manufactured by Nissei Jushi Kogyo Co., Ltd., and their physical properties were evaluated using the method described above. The results are shown in the table. The molded pieces of the final composition had a glossy surface and an excellent appearance, as well as high heat and impact resistance and very good melt flowability. Comparative Example 1 The same procedure as in Example 1 was repeated except that the block copolymer Asaflex 810 was not used as the fluidity improver, and the physical properties of the obtained molded test pieces were evaluated. The results are shown in the table. Example 2 Kneading, molding, and physical property evaluation were carried out in exactly the same manner as in Example 1, except that _{60 parts by weight of copolymer resin A 2 of} Reference Example 1 was used instead of copolymer resin A 1. The physical property evaluation results are shown in Table 1. In this case as well, the final composition had a good appearance, excellent physical properties, and high melt flow. Comparison Row 2 Evaluation was carried out in exactly the same manner as in Example 2 except that the copolymer Asaflex 810 as the fluidity improver was not used. As shown in the table, the appearance of the resin,
There were no particular problems with other physical properties, except for the melt flow behavior. Example 3 In Example 1, Asahi Kasei Corporation's Asaflex 800 (MI 5.01 g/10 min, bound styrene content approximately 80
Evaluation was made in exactly the same manner except that 10 parts by weight (% by weight) was used. The physical properties are shown in Table 1. In particular, the impact resistance was slightly lower than that of Example 1, but the melt fluidity was rather high. Comparative Examples 3 and 4 In Example 1, polystyrene Styron 679 (MFR=27) from Mitsui Toatsu Co., Ltd. and SB from Asahi Kasei were used instead of Asaflex 810 as the fluidity improver.
Similar evaluations were conducted as Comparative Examples 3 and 4 using block rubber Solprene 1205 (MFR<1, bound styrene content 25% by weight). The results are shown in Table 1, and the physical properties in these cases were inferior to those in Example 1. This is believed to indicate that the physical properties of the final composite composition strongly depend on the molecular structure of the flow improver, particularly its styrene content and melt flow index. Examples 4 and 5 In Example 1, rubber-grafted styrene-acrylonitrile copolymer resin (ABS resin) _B1 from Rohm and Haas was replaced with rubber-grafted styrene-acrylonitrile copolymer resin (ABS resin) B1.
Example 4 was prepared by using 40 parts by weight of methyl methacrylate copolymer resin (designated _B2 ), and rubber grafted styrene-maleic anhydride copolymer resin _C1.
The same evaluation as in Example 1 was conducted using 20 parts by weight of the same resin C ₂ of Reference Example 2 as Example 5 instead. The results are shown in Table 1, and the physical properties of this composite composition were excellent, and the melt fluidity was also high. Comparative Examples 5 and 6 The evaluation results in Examples 4 and 5 without using the fluidity improver Asaflex 810 are shown in Comparative Examples 5 and 6, respectively.
It is shown in the table as follows.

【table】

[Table] ◎: Excellent, glossy, with no sink marks, flow marks, etc. ○: Good, no sink marks, flow marks, etc. △: Some sink marks may be seen ○: Poor, with sink marks and surface unevenness

[Brief explanation of drawings]

FIG. 1 is a reproduction of a transmission electron micrograph of the composite resin composition of Example 1.

Claims (1)

[Claims] 1. 65 vinyl aromatic monomers based on the weight of the copolymer resin.
~95% by weight, 5~35% by weight of unsaturated dicarboxylic anhydride, and 0~95% of vinyl monomer copolymerizable with these
Copolymer resin A obtained by copolymerizing 30% by weight of vinyl aromatic monomer and unsaturated nitrile in the presence of 15 to 70% by weight of polybutadiene or styrene-butadiene copolymer rubber based on the weight of the graft copolymer resin. A graft copolymer resin B obtained by graft copolymerizing 30 to 85% by weight of a mixture of monomers or methacrylate monomers, and 5 to 50% by weight of polybutadiene or styrene-butadiene copolymer rubber based on the weight of the graft copolymer resin. % by weight of a mixture of a vinyl aromatic monomer, an unsaturated dicarboxylic acid anhydride, and optionally a vinyl monomer copolymerizable with these. Copolymer resin C and vinyl aromatic monomer 55 to 55% based on copolymer weight
It is made by block copolymerizing 95% by weight and 5 to 45% by weight of an aliphatic diene compound, and its melt flow index is in the range of 1.0 to 20.0 g/10 minutes at 200°C and a load of 5 kg. The proportion of these A, B, C and D components is A30~70.
C is 5 to 40 parts by weight for a total of 100 parts by weight of parts by weight and B70 to 30 parts by weight, and the total of A, B and C
A highly fluid heat-resistant and impact-resistant resin composition in which D is 5 to 20 parts by weight per 100 parts by weight.