JPH0468341B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a thermoplastic resin composition having excellent weather resistance and impact resistance. Rubber-modified resin, which has a composition in which rubber elastic particles are dispersed in a matrix made of styrene-acrylonitrile copolymer, etc., exhibits excellent impact resistance and is easy to mold, so it can be used in electrical appliances, automobiles, and other applications. Widely used as a material for parts, housings, etc. In this case, conjugated diene polymers such as polybutadiene, polyisoprene, and styrene-butadiene copolymer (SBR) are widely used as the rubber elastic body. This is because conjugated diene polymers have double bonds in their molecules.
Easy to crosslink and matrix (continuous phase)
This is because a rubber-modified resin with excellent impact resistance, so-called ABS resin, can be easily obtained because it has characteristics such as easy formation of graft bonds with
On the other hand, these rubber-modified resins use a rubber elastic body with double bonds remaining in the molecule as mentioned above, so their weather resistance, especially when exposed to direct sunlight, deteriorates significantly, and they cannot be used outdoors. It could not be used for the casings of the equipment used. As a means to solve this problem, rubber elastic materials such as polybutyl acrylate and other acrylic acid alkyl ester polymers, ethylene-propylene-nonconjugated diene terpolymer (EPDM), and other monoolefin rubber elastic materials have been proposed. It has been known to use a saturated rubber elastic material having no or only a small amount of double bonds in its molecules.
Although these saturated rubber-modified resins have shown remarkable effects in improving weather resistance, they have had problems with mechanical properties such as impact resistance. This is due to the fact that the grafting reaction does not proceed sufficiently with acrylic ester polymers, and that EPDM
This is due to the fact that particle size distribution could not be sufficiently controlled due to poor solubility in monomers, difficulty in obtaining rubber elastic bodies in latex state, etc. be. As a result of intensive research aimed at obtaining a weather-resistant and impact-resistant resin composition that does not have such problems, the present inventor has discovered that even when using a saturated rubber elastic material, the rubber elastic particles have a bimodal distribution. The present invention was achieved by discovering that it is effective to have aromatic vinyl monomer residues of 10 to 90% by weight, vinyl cyanide monomer residues of 10 to 40% by weight, and In 50 to 300 parts by weight of a matrix consisting of 0 to 80% by weight of methyl methacrylate residues, residues of an ester of acrylic acid and a monohydric alcohol having 2 to 12 carbon atoms are added.
70-98% by weight, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-
Consists of 1.92 to 27% by weight of vinyl toluene or alkyl methacrylate monomer residues and 0.08 to 3% by weight of polyfunctional vinyl monomer residues, and has an average particle size of
Graft copolymer (A) formed by dispersing 100 parts by weight of rubber elastic particles having a size of 0.05 to 0.45 μm, 10 to 90% by weight of aromatic vinyl monomer residues, and 10 to 10 to 90% by weight of vinyl cyanide monomer residues. 100 parts by weight of ethylene-propylene-nonconjugated diene rubber elastic particles having an average particle size of 0.5 to 5 μm are dispersed in 20 to 1500 parts by weight of a matrix consisting of 40% by weight and 0 to 80% by weight of methyl methacrylate residues. Graft copolymer (B) obtained by the following methods: 10 to 90% by weight of aromatic vinyl monomer residues, 10 to 40% by weight of vinyl cyanide monomer residues, and 0 to 80% by weight of methyl methacrylate residues A composition comprising a copolymer (C) consisting of
A weather-resistant and impact-resistant resin composition containing 40% by weight of a rubber elastic body, in which an amount corresponding to 30 to 97% by weight of the rubber elastic body is contained in the copolymer (A). achieved by. Examples of the aromatic vinyl monomer used in the present invention include styrene, α-methylstyrene, p-vinyltoluene, and other vinyltoluenes. Suitable vinyl cyanide monomers include acrylonitrile and methacrylonitrile. Copolymer (A) is preferably produced by emulsion polymerization in terms of productivity and physical properties of the obtained copolymer, but suspension polymerization or emulsion-suspension polymerization may also be used. The acrylic esters used in the production of the copolymer (A) include acrylic acid and carbon atoms of 2 to 12,
Preferably, esters with 4 to 8 monohydric alcohols are suitable. Specifically, butyl acrylate, 2-ethylhexyl acrylate, etc. are preferred. If the number of carbon atoms is outside the above range, sufficient rubber elasticity cannot be obtained, which is not preferable. These esters may be used alone or in combination of two or more. The monomers of acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-vinyltoluene, or alkyl methacrylate constituting the rubber elastic body in the copolymer (A) can be used together with the acrylic ester constituting the rubber elastic body. polymerize,
Two or more of these monomers may be used in combination to improve the reinforcing rubber properties and graft polymerization reactivity of the resulting acrylic rubber. Examples of polyfunctional vinyl monomers include divinylbenzene, ethylene glycol dimethacrylate,
Diallyl maleate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, trimethylolpropane triacrylate,
Examples include allyl methacrylate. (In addition,
The allyl group refers to a _CH2 = _CHCH2- group. ) Use of these polyfunctional vinyl monomers facilitates intermolecular crosslinking of the acrylic acid ester copolymer, graft bonding with a matrix, etc., thereby improving the impact resistance of the composition according to the present invention. The acrylic ester copolymer used for the copolymer (A) may be produced by suspension polymerization, etc., but emulsion polymerization is preferable because it is easier to control the particle size and graft polymerization. preferable. In that case, a predetermined amount of the above monomer mixture is emulsified and dispersed in water using an emulsifier, and polymerization is carried out using a suitable initiator. As the emulsifier, conventional anionic, cationic, and nonionic emulsifiers can be used, but fatty acid salts such as beef tallow soap, sodium stearate, and sodium oleate are preferred because they facilitate salting out operations. Examples of polymerization initiators include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, etc., or redoxes in combination of these with reducing agents such as L-ascorbic acid, Rongarit, acidic sodium sulfite, and ferrous chloride. In addition, benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile, etc. can be used. Other polymerization conditions may be normal polymerization conditions. The average particle diameter of the rubber elastic body in the graft copolymer (A), that is, the above acrylic ester polymer is 0.05.
~0.45 μm is suitable, and 0.1 to 0.35 μm is more preferred. Note that the "average particle size" is expressed as a weight average. The particle size of such rubber elastic particles depends on the average particle size of the rubber elastic body latex used for graft polymerization, so the average particle size of the acrylic acid ester polymer latex obtained by the above emulsion polymerization is determined to be a desired value. If the particle size is smaller than , it is recommended to adjust the particle size of the latex particles by adding an acidic substance such as phosphoric acid, sulfuric acid, or acetic anhydride to the latex to coagulate and enlarge the latex particles. preferable. If the average particle size of the rubber elastic body is less than 0.05 μm, the impact resistance will not be improved, and if it exceeds 0.45 μm, the latex will become unstable, and the impact resistance, surface gloss, etc. of the resulting composition will decrease. Therefore, it is not desirable. If necessary, after adjusting the particle size of the latex to a desired value, add 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. A monomer mixture consisting of to carry out emulsion graft polymerization. In this case, a polymerization initiator and other auxiliary agents are added as necessary. The appropriate amount of the monomer mixture to be added to 100 parts by weight of the solid content of the rubber elastic body, that is, the acrylic ester copolymer latex, is 50 to 300 parts by weight. If the amount of the monomer mixture is outside the above range, it will be difficult to adjust the rubber elastic material content in the composition according to the present invention, and impact resistance will further deteriorate, which is not preferable. Furthermore, if the composition of the monomer mixture is outside the above range, chemical resistance and compatibility will decrease, which is not preferable. When emulsion graft polymerization is completed, MgSO ₄ , Al ₂
An aqueous solution of an electrolyte such as (SO ₄ ) ₃ , NaCl, HCl, CaCl ₂ is added for salting out, and the obtained crumb is dehydrated and dried. The ethylene-propylene-nonconjugated diene rubber elastic body used in the production of copolymer (B) is usually
It is called EPDM and has an ethylene-propylene (weight ratio) of 80/20 to 30/70, preferably 70/30 to 40/60, and a non-conjugated diene content of 0.1 to 10 mol%. These are common. Note that as the non-conjugated diene, dicyclopentadiene, alkylidene norbornene, 1,4-hexadiene, etc. are used. 100 parts by weight of such EPDM is mixed with 20-1500 parts by weight of a monomer mixture consisting of 10-90% by weight of aromatic vinyl monomer, 10-40% by weight of vinyl cyanide monomer, and 0-80% by weight of methyl methacrylate. , preferably 20
It is dissolved in ~580 parts by weight and graft polymerized by bulk-suspension or bulk polymerization method while stirring. In this case, since EPDM is poorly soluble in vinyl cyanide monomer, if the amount of the monomer mixture is small, add a non-polymerizable organic solvent such as heptane, hexane, octane, etc. to the monomer mixture, or add an aromatic It is preferable to dissolve the group vinyl monomer alone or in a mixture of an aromatic vinyl monomer and methyl methacrylate and add the vinyl cyanide monomer during polymerization. As the polymerization initiator, those that easily cause graft polymerization are preferred, such as benzoyl peroxide, lauryl peroxide, and di-ter.-butyl peroxide [(CH ₃ ) ₃ C-O-O-C(CH ₃ ) ₃ ]. . If the ratio of the monomer mixture forming the matrix is outside the above range, it is undesirable because it is difficult to adjust the rubber elastic material content in the composition according to the present invention and the impact resistance decreases. Furthermore, chemical resistance etc. are reduced. When producing the copolymer (B), EPDM is dissolved in a predetermined amount of an aromatic vinyl monomer or a mixture of it and methyl methacrylate, and then emulsified and dispersed in water. The emulsion-dispersed latex may be subjected to emulsion graft polymerization. In this case, the obtained EPDM latex and the acrylic ester copolymer latex obtained in the polymerization process of copolymer (A) are mixed, and then the required amount of the monomer mixture is added to carry out graft polymerization. By doing so, polymerization and blending of copolymers (A) and (B) can be performed in one step. The average particle size of the rubber elastic particles in the copolymer (B) is 0.5 to 5 μm, preferably
A suitable thickness is 0.6 to 2 μm. By setting the particle size of the rubber elastic body particles in the copolymers (A) and (B) within the above range, the impact resistance of the composition according to the present invention can be improved. Copolymer (C) is produced by bulk polymerization or suspension polymerization of a mixture consisting of 10 to 90% by weight of aromatic vinyl monomer, 10 to 40% by weight of vinyl cyanide monomer, and 0 to 80% by weight of methyl methacrylate. It can be obtained by polymerization using a bulk-suspension polymerization method or the like. In this case, the use of a crosslinking agent is not preferable because it reduces compatibility. If the composition of each monomer is outside the above range, the compatibility with other copolymers will decrease, which is not preferable. In the composition according to the present invention, the content of the rubber elastic body, that is, the total amount of the acrylic ester copolymer in the copolymer (A) and the EPDM in the copolymer (B) is
It is necessary to account for 5 to 40% by weight of the total composition. If it is less than 5% by weight, the impact resistance will not be sufficient, and if it exceeds 40% by weight, the amount of rubber elastic body will be excessive and the rigidity will decrease, which is not preferable. Furthermore, it is necessary that 30 to 97% by weight of the rubber elastic body contained in the composition according to the present invention be the rubber elastic body contained in the copolymer (A), that is, the acrylic ester copolymer. . If it is outside the above range, the ratio of large and small rubber elastomer particles, that is, the particle size distribution, will be inappropriate, and the balance between impact resistance and the appearance of the resulting molded product, especially gloss (gloss), will be inappropriate. This is not preferable because it becomes defective. The copolymers (A), (B) and (C) are blended using a conventional extruder or the like. The composition according to the present invention has extremely excellent weather resistance, and also has excellent impact resistance because, unlike conventional weather-resistant rubber-modified resins, the particle size distribution of the rubber elastic body has a bimodal distribution. Next, the present invention will be specifically explained based on Examples and Comparative Examples. Production Example 1 [Production of acrylic ester copolymer (acrylic rubber/latex)] Production Example 1-1 3 In a glass flask, 1520 g of deionized water (hereinafter simply referred to as water), higher fatty acid soap (carbon number
20g of sodium salt of fatty acids whose main component is 18),
10 g of sodium bicarbonate was charged, and the temperature was raised to 75°C under a nitrogen stream. After adding 0.75 g/20 ml of potassium persulfate aqueous solution, 5 minutes later, 937.5 g of acrylic acid butyl ester (BA) and 62.5 g of acrylonitrile (AN) were added.
g, and 5 g of methacrylic acid allyl ester (AMA).
I prepared g. Heat generation occurred in about a few minutes, and the initiation of polymerization was confirmed. 15 minutes after the initial monomer charge, 0.75 g/20 ml of potassium persulfate aqueous solution was added, and at the same time, continuous addition of the remaining monomer mixture was started for 2 hours.
The addition was finished at the 30 minute mark, but in the middle the addition was completed for 1 hour and 30 minutes.
At the minute point, an aqueous solution of 6 g of fatty acid soap (dissolved in 20 ml) was added. After the monomer addition was completed, polymerization was continued for another hour at the same temperature. The conversion rate was 98% and the average particle size was 0.08 μm. Pour half of this latex into 3 flasks,
After mixing with 685 ml of water and 5 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate (DBS), the mixture was kept at 50°C.
Add 320 g of 2.5% phosphoric acid aqueous solution over about 1 minute with weak stirring, then add 25% caustic potassium aqueous solution after standing for 2 minutes.
23.4 g and 14 g of a 25% DBS aqueous solution were added and stirred thoroughly. Acrylic rubber latex with an average particle size of 0.23 μm (measured with a nanosizer) was obtained. Production example 1-2 BA900g, styrene (Sh) 100g and AMA5g
Production Example 1- except that a monomer mixture consisting of
Rubber latex with an average particle size of 0.24 μm was obtained in the same manner as in Example 1. Production Example 1-3 A rubber latex with an average particle size of 0.25 μm was obtained in the same manner as Production Example 1-1, except that a monomer mixture consisting of 900 g of BA, 100 g of methacrylic acid methyl ester (MMA), and 5 g of AMA was used. Production Example 1-4 A monomer mixture consisting of 95 g of BA, 5 g of AN, and 1 g of trimethylolpropane triacrylate (TMPT), 0.5 g of lauroyl peroxide, and Hytenol N-07 (Daiichi Kogyo Seiyaku) as an emulsifier.
(manufactured by Co., Ltd.) was dissolved. Separately, a flask 1 containing 300 g of water was prepared, and the monomer mixture solution was gradually added to the flask while stirring using a tabletop homomixer to emulsify and obtain a homogeneous emulsion. The flask was set in a state where polymerization could occur, and the temperature was raised to 60°C under a nitrogen stream to initiate polymerization. 2 hours later, BA95g, AN5
The addition of a monomer mixture consisting of 1 g of TMPT and 1 g of TMPT was started and ended at 4 hours, but the temperature was kept at the same temperature for 1 hour. A crosslinked rubber latex with a conversion rate of 96% and an average particle size of 0.24 μm was obtained. Production Example 1-5 2116g of rubber latex obtained in Production Example 1-1
(450 g of rubber) was placed in two flasks and heated to 80°C under a nitrogen stream. BA45g and AN5g and
A mixture of 1.25 g of TMPT was continuously charged in about 15 minutes, but before that, 0.5 g of potassium persulfate aqueous solution/15
ml was added. During this time, the pH of the system was maintained at approximately 7.5.
A rubber latex with a conversion rate of 96% and an average particle size of 0.25 μm was obtained. Production Example 2 (Production of Copolymer (A)) Production Example 2-1 2358 g (500 g of rubber) of the acrylic rubber latex obtained in Production Example 1-1 was placed in 3 flasks equipped with a stirrer, reflux condenser, etc. The temperature was raised to 80°C. 1.86g/50ml of potassium persulfate aqueous solution was added, and at the same time, continuous addition of mixed monomers of St650g and AN278.6g was started, and after 15 minutes, potassium persulfate aqueous solution 5.57g/50ml was added.
Continuous addition of g/147ml was also started. 30 minutes after the start of monomer addition, 1 hour 10 minutes, and 2 hours later, respectively.
25% caustic potassium aqueous solution 16.3g, higher fatty acid soap aqueous solution 4.29g/35ml and the same soap aqueous solution 4.29g/35
ml and 5.57 g of terpinolene were added. Continuous addition of the monomer and potassium persulfate aqueous solution was completed in 3 hours and 45 minutes, and then the mixture was left at the same temperature for 30 minutes to complete polymerization. The graft polymer thus obtained is
The latex was poured into a large amount of calcium chloride aqueous solution and then filter-dried. The conversion rate of polymerization was 98.5%. Production Example 2-2 Production Example 2-1 except that the acrylic rubber latex (500 g of rubber) obtained in Production Example 1-5 was used.
Graft polymerization was carried out in the same manner as described above. The polymerization conversion rate was 96.5%. Production Example 3 (Production of Copolymer (B)) Production Example 3-1 St552g, EPDM [Mooney viscosity ML ₁ + ₄
(100℃) 45, iodine value 25, ethylidenenorbornene as the third component] 140g and n-heptane 100g
After preparing and purging with nitrogen, heat at 50℃ for 2 hours.
It was completely dissolved by stirring at 100 rpm. Next, under the same stirring, 258 g of AN was charged at a rate of 40 g/10 minutes, and then 0.5 g of di-ter.-butyl peroxide was added.
0.13 g of ter.-butyl peracetate and 0.5 g of terpinolene were charged, and bulk polymerization was carried out at 97° C. for 7 hours and 20 minutes. Approximately 30 minutes before the end of bulk polymerization, 1.5 g of di-ter.-butyl peroxide and 1.5 g of terpinolene were dissolved in 50 g of St and charged. The average particle size of the EPDM rubber at the end of polymerization was 1.6 μm. The syrup obtained in the above bulk polymerization process was mixed with water.
3 containing an aqueous solution containing 2.5 g of suspending agent (acrylic acid-acrylic acid ester copolymer) in 1100 g
After charging the autoclave (equipped with a stirrer with 3 swept blades) and purging with nitrogen, this aqueous suspension system was subjected to suspension polymerization at 130°C and 500 rpm for 2 hours, and then the temperature was raised to 150°C. Then, stripping was performed for 1 hour. The obtained resin composition was washed with water and then dried at 100°C to obtain 920 g of graft copolymer resin. Production Example 3-2 In Production Example 3-1, 140g of EPDM and St.
380g, n-heptane 100g, AN 215g,
A graft copolymer resin was obtained in the same manner except that MMA was changed to 215 g and the entire amounts of AN and MMA were changed to post-feeding. The average particle size of the rubber was 1.8 μm. Production example 3-3 In 2 flasks equipped with a stirrer
St520g, EPDM130g, oil-soluble emulsifier (Hitenol N-08, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) 9.75g and water
32.5 ml of the solution was charged and stirred at 55°C for 3 hours under a nitrogen atmosphere to uniformly dissolve the solution. Next, 163 ml of water was added over several minutes with stirring, and then 585 ml of water was added all at once to invert the phase. The average particle size of the rubber component of the emulsion obtained was 0.82 μm (as measured by Coulter counter). Separately, AN77.1g, TMPT0.75g, sodium dodecylbenzenesulfonate 1.17g and water 91.4g
St-AN- by preparing an emulsion from g and mixing it with 500.9 g of the above emulsion.
An emulsion consisting of EPDM was obtained. 1110.6 g (255 g of rubber) of the acrylic rubber latex obtained in Production Example 1-5 was charged into 3 flasks, and the temperature was raised to 80°C. Subsequently, at the same time as adding 1 g/25 ml of potassium persulfate aqueous solution, the St-AN-
Continuous charging of 671.3 g of EPDM emulsion and 3.34 g/84 ml of potassium persulfate aqueous solution was started. 1 hour 20
The charging of the emulsion was completed in minutes, and then continuous charging of 300 g of the monomer mixture (St 210 g, AN 90 g) was started at a uniform rate over a period of 2 hours. During the polymerization, 30 minutes after its initiation, 1 hour 15 minutes and 2
7.5 g of 25% caustic potash aqueous solution at each hour,
2.57 g/20 ml of higher fatty acid soap aqueous solution, 2.57 g/20 ml of the same soap, and 3.34 g of terpinolene were added.
After the monomer was charged, the temperature was kept at the same temperature for 30 minutes to complete the polymerization. The conversion rate was 98%. The copolymer latex was poured into a large amount of water containing calcium chloride, washed with water, and dried to obtain 829.5 g of a graft copolymer. Production Example 3-4 1208.6g (277.5g of rubber) of the acrylic rubber latex obtained in Production Example 1-5, St-AN-
335.6g EPDM emulsion, 428.5g monomer
833.7g at a conversion rate of 97% using the same method as Production Example 3-3 except that
A graft copolymer was obtained. Example 1 Graft polymer (A) obtained in Production Example 2-1 485.7g Graft polymer (B) obtained in Production Example 3-1 214.3g Copolymer (C) (AS resin St 70% by weight, AN 30% by weight ) was mixed with 3 g of di-ter.-butyl para-cresol (DTBPC) as an antioxidant and 5 g of magnesium stearate (Mg-St) as a lubricant in a Banbury mixer, pelletized, and then molded in a 7-OZ injection molding machine. Cylinder temperature 220℃, mold temperature 40℃
It was molded with. The test pieces were evaluated for impact strength, tensile strength, and weather resistance using the following methods. Impact strength (notched, izod, 23℃)
ASTM D-256-54T Tensile Strength (23℃) ASTM D-638-61T Weather Resistance Test Sunshine Weatherometer
By WE-SON-HC (Toyo Rika),
Tensile elongation retention rate (%/%) with respect to initial value (after 200 hrs test/after 400 hrs test) The results are shown in Table 1. Further, the flow rate of the resin composition was measured according to ASTM D1238, and the results are shown in Table 1.
The measurement conditions were 220°C and 10 kg, and the unit of measurement was g/10 minutes. Example 2 Graft polymer (A) obtained in Production Example 2-1 485.7g Production Example 3-2 graft copolymer (B) 214.3g Copolymer (C) (same as Example 1) 300.0g DTBPC/ A test piece was obtained by blending and molding 3g/5g of Mg-St in the same manner as in Example 1. The results are shown in Table 1. Example 3 Graft polymer (A) obtained in Production Example 2-1 using the rubber latex of Production Example 1-2 485.7g Production Example 3-1 graft polymer (B) 214.3g Copolymer (C) ) (same as Example 1) 300.0g DTBPC/Mg-St 3g/5g was molded and evaluated in the same manner as Example 1. The results are shown in Table 1. Example 4 Graft polymer (A) obtained in Production Example 2-1 using the rubber latex of Production Example 1-3 485.7g Production Example 3-1 graft copolymer (B) 214.3g Copolymer ( C) (Same as Example 1) 300.0g DTBPC/Mg-St 3g/5g was blend-molded in the same manner as Example 1 to obtain a test piece. The results are shown in Table 1. Example 5 Graft polymer (A) obtained in Production Example 2-1 using the rubber latex of Production Example 1-5 485.7g Production Example 3-1 graft copolymer (B) 214.3g Copolymer ( C) (same as Example 1) 300.0g DTBPC/Mg-St 3g/5g was used as a test piece in the same manner as Example 1 and evaluated. The results are shown in Table 1. Example 6 Graft copolymer of Production Example 3-3 414.0g Copolymer (C) (same as Example 1) 586.0g DTBPC/Mg-St 3g/5g were prepared as test pieces by the same method as Example 1. ,evaluated. The results are shown in Table 1. Comparative Example 1 Graft polymer (A) of Production Example 2-1 571.4g Copolymer (C) (same as Example 1) 428.6g DTBPC/Mg-St 3g/5g were blended in the same manner as Example 1. , molded and evaluated. The results are shown in Table 1. Comparative Example 2 1000 g of the graft polymer (B) of Production Example 3-1 and 3 g/5 g of DTBPC/Mg-St were blended and evaluated in the same manner as in Example 1. The results are shown in Table 1. Comparative Example 3 A copolymer obtained by graft polymerization in the same manner as in Production Example 2-1 using a latex obtained by polymerizing only butyl acrylate in the same manner as in Production Example 1-1. 486.7g Production Copolymer (B) of Example 3-1 214.3g DTBPC/Mg-St 3g/5g Molded and evaluated in the same manner as in Example 1. The results are shown in Table 1. Compared to Example 1, the obtained molded product had poor gloss (gloss) and flow marks were observed. 【table】

Claims (1)

[Scope of Claims] 1. Matrix 50 consisting of 10 to 90% by weight of aromatic vinyl monomer residues, 10 to 40% by weight of vinyl cyanide monomer residues, and 0 to 80% by weight of methyl methacrylate residues. ~300 parts by weight, 70 to 98% by weight of residues of esters of monohydric alcohols having 2 to 12 carbon atoms and acrylic acid, acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p
- Consisting of 1.92 to 27% by weight of vinyl toluene or alkyl methacrylate monomer residues and 0.08 to 3% by weight of polyfunctional vinyl monomer residues, with an average particle size of
Graft copolymer (A) formed by dispersing 100 parts by weight of rubber elastic particles having a diameter of 0.05 to 0.45 μm, 10 to 90% by weight of aromatic vinyl monomer residues, and 10 to 90% by weight of vinyl cyanide monomer residues. 100 parts by weight of ethylene-propylene-nonconjugated diene rubber elastic particles having an average particle size of 0.5-5 μm are dispersed in 20-1500 parts by weight of a matrix consisting of 40% by weight and 0-80% by weight of methyl methacrylate residues. Graft copolymer (B) obtained by the following methods: 10 to 90% by weight of aromatic vinyl monomer residues, 10 to 40% by weight of vinyl cyanide monomer residues, and 0 to 80% by weight of methyl methacrylate residues A composition comprising a copolymer (C) consisting of 5
Contains ~40% by weight of a rubber elastic body, and an amount corresponding to 30 to 97% by weight of the rubber elastic body is a copolymer (A).
A weather-resistant and impact-resistant resin composition characterized by being a rubber elastic body contained in. 2 Copolymer (B) has 10 to 90 aromatic vinyl monomer residues
wt%, vinyl cyanide monomer residue 10-40 wt%
and 20 to 580 parts by weight of a matrix consisting of 0 to 80% by weight of methyl methacrylate residues with an average particle size of 0.5%.
2. The composition according to claim 1, which is a graft copolymer prepared by dispersing 100 parts by weight of ethylene-propylene-nonconjugated diene rubber elastic particles having a diameter of ~5 μm.