JP3142593B2 - Thermoplastic resin composition excellent in weather resistance, chemical resistance and impact resistance - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[Background of the Invention]

The present invention relates to a thermoplastic resin composition having excellent weather resistance, chemical resistance and impact resistance.

A rubber-modified resin having a composition in which rubber elastic particles are dispersed in a matrix composed of a styrene-acrylonitrile copolymer or the like exhibits excellent impact resistance,
Because it is easy to mold, it is widely used as a material for electrical appliances, automobiles and other parts, housings, and the like. 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 the conjugated diene-based polymer has double bonds in the molecule, so that it is easy to crosslink, and it has characteristics such as easy formation of a graft bond with a matrix (continuous phase). This is because an excellent rubber-modified resin, that is, a so-called ABS resin, can be easily obtained.
As described above, since the rubber elastic body in which the double bond remains in the molecule is used, the weather resistance is poor. In particular, physical properties are significantly degraded when exposed to direct sunlight, and there are restrictions on the use of housings and the like of outdoor equipment.

[0003]

2. Description of the Related Art As means for solving such a problem,
Double bond in molecule such as polybutyl acrylate or other alkyl acrylate copolymer, ethylene-propylene-non-conjugated diene terpolymer (EPDM) or other mono-olefin rubber elastic material for rubber elastic material It has been known to use a saturated rubber elastic body having no or only a small amount of rubber. However, although these saturated rubber-modified resins have remarkable improvements in weather resistance, they have problems in mechanical properties such as impact resistance. This is because, according to the consideration of the present inventor, the grafting reaction to the latex, which is a commonly used technique, does not sufficiently proceed in the case of an acrylate polymer. Is difficult,
The commonly used technique is a solution polymerization method. However, EPDM and the like cannot sufficiently control the particle size distribution due to poor solubility in monomers and the like.

[0004] On the other hand, ABS resin is superior in chemical resistance to acrylonitrile because it contains acrylonitrile in the matrix component, compared to high impact polystyrene.
With the expansion of applications, further improvement in chemical resistance has been required, and for that purpose, so-called high nitrile resins having an increased acrylonitrile content in the matrix have been developed. However, with an increase in the content of acrylonitrile, the yellow tint of an ABS resin based on a diene rubber has increased, and problems such as coloring have arisen. Further, with respect to this high nitrile resin, applications requiring weather resistance as well as chemical resistance have begun to appear.

[Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide a weather-resistant and chemical-resistant impact-resistant resin composition which does not have such problems. It is based on the finding that it is effective to have a resin component containing a vinyl cyanide monomer as a main component in a matrix.

[0006]

The thermoplastic resin composition according to the present invention comprises the following components (A) and (B), and the component (A) contains 5 to 40 rubber elastic particles in the composition. % By weight.

Component (A): 10 to 50% by weight of aromatic vinyl monomer residues, 50 to 90% by weight of vinyl cyanide monomer residues and 0 to 40% by weight of methyl methacrylate residues The total amount of the monomer residues is 100% by weight. The same applies to the following.) 50 to 300 parts by weight of a matrix composed of a monovalent alkyl alcohol having 1 to 12 carbon atoms and an ester of acrylic acid. 70 to 99.92% by weight of residues, 0 to 27% by weight of residues of a vinyl monomer copolymerizable with the acrylate, and 0.08 to 3% by weight of residues of a polyfunctional vinyl monomer. A graft copolymer (A) in which 100 parts by weight of crosslinked rubber elastic particles having an average particle size of 0.05 to 0.45 μm are dispersed, and

Component (B): a copolymer comprising 10 to 50% by weight of aromatic vinyl monomer residues, 50 to 90% by weight of vinyl cyanide monomer residues and 0 to 40% by weight of methyl methacrylate residues. Coalescing (B).

[Specific description of the invention]

The thermoplastic resin composition according to the present invention comprises a mixture of the graft copolymer (A) and the thermoplastic copolymer (B). Is blended such that the content of rubber elastic modulus in the graft copolymer (A) is 5 to 40% by weight in the composition.

<Component (A)><Contents of Component (A)> The graft copolymer (A) constituting the resin composition according to the present invention comprises a matrix and crosslinked rubber elastic particles dispersed therein. However, typically, the graft copolymer is a crosslinked acrylic rubber obtained by emulsion polymerization as described below,
It is manufactured by passing through a graft polymerization step.
The graft copolymer (A) is a high nitrile resin based on an acrylonitrile / acrylic rubber / styrene copolymer (AAS resin).

The acrylic rubber for producing the graft copolymer (A) in the present invention is prepared by first preparing an alkyl acrylate monomer residue having an alkyl group of 1 to 12 carbon atoms of 70 to 9;
9.92% by weight, 0 to 27% by weight of residues of a vinyl monomer copolymerizable with the alkyl acrylate, and 0.08 to 3% by weight of a polyfunctional vinyl monomer (% by weight is based on the total amount). ). When the content of the alkyl acrylate residue is less than 70% by weight, the elastic modulus of the acrylic rubber is undesirably increased. Due to the residue of the polyfunctional vinyl monomer, intermolecular cross-linking of the acrylate copolymer, graft bonding with a matrix and the like are facilitated,
The impact resistance of the composition of the present invention is improved. However, the content of the residue of the polyfunctional vinyl monomer is 0.08 to 3% by weight,
Preferably, it should be selected in the range of 0.1 to 2% by weight. When the amount of the polyfunctional vinyl monomer residue is less than 0.08% by weight, the resulting acrylic rubber has a low degree of crosslinking and tends to be plastically modified, so that the appearance of the resulting thermoplastic resin composition (Gloss) is poor, and it is difficult to improve impact resistance. On the other hand, if it exceeds 3% by weight, the swelling rate and grafting rate of the acrylic rubber of the obtained graft copolymer (A) become poor, and various properties of the rubber are undesirably reduced. The content of the residues of the "optional" monomer, the third component, must be selected in the range of 0 to 27% by weight. If the content of the copolymerizable vinyl monomer exceeds 27% by weight, the modulus of elasticity increases and various properties as an acrylic rubber are undesirably reduced.

The acrylic rubber has an average rubber particle diameter of 0.05 to 0.45 μm, preferably 0.1 to 0.45 μm.
It is in the range of 0.35 μm. If the average particle size of the rubber elastic body is less than 0.05 μm, the impact resistance is not improved, and if it exceeds 0.45 μm, the latex becomes unstable when producing the component (A) from rubber latex, and The impact resistance, surface gloss and the like of the resulting composition are undesirably reduced. Particularly, a graft copolymer (component (A)) obtained by graft-polymerizing a vinyl cyanide compound / aromatic vinyl compound having a specific monomer ratio described later produces the highest balance of physical properties when the component (B) is blended. In order to do so, the average rubber particle diameter is preferably in the range of 0.1 to 0.35 μm. "Average particle size" is represented by weight average. The rubber particle diameter in the composition of the present invention can be considered to be substantially the same as the particle diameter of the latex obtained when this rubber elastic body is produced by emulsion polymerization.

[0014] Such a crosslinked acrylic rubber is produced by subjecting a monomer giving a predetermined monomer residue, either temporarily or stepwise, to appropriate polymerization conditions, preferably emulsion polymerization conditions. Can be.

That is, first, the alkyl acrylate monomer which is a component of the acrylic rubber is an alkyl acrylate having an alkyl group having 12 carbon atoms, preferably 4 to 8 carbon atoms (that is, the alcohol giving the alkyl group is a monohydric alcohol). Is). Specific examples thereof include alkyl acrylates such as methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, and dodecyl acrylate. be able to. These may be one kind or a mixture of two or more kinds. Preferred acrylates are n-butyl acrylate and / or 2-ethylhexyl acrylate.

If the carbon number is outside the above range, sufficient rubber elasticity cannot be obtained, which is not preferable.

The vinyl monomers copolymerizable with the alkyl acrylate include aromatic vinyl monomers described below,
Vinyl cyanide monomer to be described later, acrylamide, methacrylic amide, vinyl or vinylidene chloride, alkyl (C ₁ -C about ₆₎ vinyl ethers, alkyl (C
₁ -C about ₆₎ methacrylate, vinyl esters such as vinyl acetate, and the monofunctional vinyl monomer of the halogen-substituted compounds, and the like. As these "optional" monomers, those having a function of improving and improving the properties of an acrylic rubber obtained by copolymerization as a reinforcing rubber, graft polymerization reactivity, and the like are preferable. Specific examples include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-vinyltoluene and other vinyltoluenes, alkyl methacrylate, 2-chloroethyl vinyl ether, monochlorovinyl acetate, and methoxyethyl acrylate. In addition, as is clear from exemplifying the acrylic compound, "vinyl monomer"
Has the same meaning as “ethylenically unsaturated monomer”. These may be one kind or a mixture of two or more kinds.

Another group of vinyl monomers that can be copolymerized with the alkyl acrylates described above are polyfunctional vinyl monomers.

In the present invention, the polyfunctional vinyl monomer is
In order to crosslink the acrylic rubber, 2
A vinyl monomer containing two or more vinyl groups. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene; methacrylates and acrylates of polyhydric alcohols such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate. , Diallyl malate,
Diallyl fumarate, triallyl isocyanurate, diallyl phthalate, allyl methacrylate, allyl acrylate and the like. These may be one kind or a mixture of two or more kinds.

The acrylic rubber in the present invention is preferably prepared by a known emulsion polymerization method using water as a medium, the types and amounts of an emulsifier and a polymerization catalyst and their addition methods, the addition method of each monomer, the polymerization temperature, It can be manufactured by appropriately selecting and combining various conditions such as a method for adjusting rubber particles. A suspension polymerization method or the like other than the emulsion polymerization method may be used, but the emulsion polymerization method is preferable because the particle size and the degree of crosslinking are easily controlled, and the graft polymerization is easy.

The emulsion polymerization process itself can be conventional,
Specifically, a predetermined amount of the above monomer mixture is dispersed in water using an emulsifier, and polymerization is started using an appropriate initiator.
As the emulsifier, those of ordinary anionic, cationic, nonionic and the like can be used. In addition, fatty acid salts such as tallow soap, sodium stearate, and sodium oleate are preferred because the salting out operation is easy. Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide and the like, and L-
A redox type in combination with a reducing agent such as ascorbic acid, Rongalit, sodium acid sulfite, ferrous chloride and the like, benzoyl peroxide, lauryl peroxide, azobisisobutyronitrile and the like can be used. Other polymerization conditions may be ordinary polymerization conditions.

A rubber elastic body in the graft copolymer (A),
That is, the average particle diameter of the acrylate polymer is suitably 0.05 to 0.45 μm, and 0.1 to 0.1 μm.
As described above, it is more preferable that the thickness be 35 μm.

Since the particle size of the crosslinked acrylic rubber particles of the latex thus obtained is the average particle size of the acrylic rubber latex used for the graft polymerization, the acrylate polymer obtained by the above emulsion polymerization is used. If the average particle size of the latex is smaller than the desired value,
It is preferable 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 and performing a so-called particle size enlarging operation for coagulating and expanding the latex particles.

<Production of Component (A)> The component (A) has a structure in which the above-mentioned acrylic rubber particles are dispersed in a matrix having a specific composition. It is produced by polymerizing or emulsifying the body in an acrylic rubber latex.

That is, first, if necessary, the particle size of the acrylic rubber latex is adjusted to a desired value, and then 10 to 50% by weight of an aromatic vinyl monomer and 50 to 90% by weight of a vinyl cyanide monomer. And a monomer mixture comprising 0 to 40% by weight of methyl methacrylate in an amount of 50 to 300 parts by weight per 100 parts by weight of the solid content of the acrylate copolymer latex.
Emulsion graft polymerization is carried out by adding an amount corresponding to parts by weight to the latex at one time, or in batches or continuously in divided portions. In this case, a polymerization initiator and other auxiliaries are added as necessary. Rubber elastic, that is,
Acrylic ester copolymer latex solids 100
The amount of the monomer mixture to be added is 50 to 30 parts by weight.
0 parts by weight, preferably 66 to 200 parts by weight, is suitable. If the amount of the monomer mixture is out of the above range, it may be difficult to adjust the content of the rubber elastic body in the composition according to the present invention, and the impact resistance may be undesirably reduced. Further, if the composition of the monomer mixture is out of the above range, chemical resistance and compatibility deteriorate, which is not preferable.

After the completion of the emulsion graft polymerization, MgSO 4
₄ , Al ₂ (SO ₄ ) ₃ , NaCl, HCl, CaCl
An aqueous solution of an electrolyte such as ₂ is added for salting out, and the obtained slurry is dehydrated and dried.

Here, specific examples of the aromatic vinyl monomer include unsubstituted and core- and / or side-chain-substituted styrene,
Examples thereof include α-alkylstyrene such as styrene and α-methylstyrene, nuclear-substituted alkylstyrene such as p-methylstyrene and vinylxylene, halo-substituted styrene such as monochlorostyrene and dichlorostyrene, and vinylnaphthalene. Of these, styrene is preferably used. These may be one kind or a mixture of two or more kinds.

On the other hand, specific examples of the vinyl cyanide monomer include acrylonitrile, methacrylonitrile and the like, among which acrylonitrile is preferably used. These may be one kind or a mixture of two or more kinds.

This monomer mixture may contain methyl methacrylate. When the matrix of the component (A) contains methyl methacrylate, the amount of the aromatic vinyl monomer can be reduced, so that the effect of improving the transparency can be obtained.

The molecular weight of the matrix portion of the component (A) is such that the weight average molecular weight in terms of polystyrene by GPC (gel permeation chromatography) is 50,
It is preferably about 000 to 500,000.

<Component (B)> The component (B) comprises 10 to 50% by weight, preferably 20 to 45% by weight, of an aromatic vinyl monomer residue.
% By weight, 50 to 90% by weight of a vinyl cyanide monomer residue,
It is preferably a copolymer comprising 55 to 80% by weight and 0 to 40% by weight, preferably 0 to 30% by weight of methyl methacrylate residues. If the composition of each monomer is out of the above range, the compatibility with the copolymer (A) decreases, which is not preferable.

Specific examples of these monomers for component (B) can be found in the illustrations given above as monomers for component (A), and those selected for component (A) The same or different ones may be used.

The copolymer of component (B) is what is known as so-called AS resin or MAS resin (but it is hynitrile), which is known per se and is prepared by bulk polymerization according to a conventional method. , Suspension polymerization, bulk-suspension polymerization or emulsion polymerization, and suitable ones can be found on the market.

<Composition of the Present Invention> The composition according to the present invention comprises the component (A) and the component (B). The content of the rubber elastic body, that is, the acrylate in the copolymer (A) It is necessary that the content of the system copolymer accounts for 5 to 40% by weight, preferably 10 to 30% by weight of the whole composition. If it is less than 5% by weight, the impact resistance is not sufficient, and if it exceeds 40% by weight, the amount of the rubber elastic body becomes excessive and the rigidity decreases, and the molding processability also decreases, which is not preferable.

The components (A) and (B) can be blended by any method that provides a homogeneous composition of both components. This method generally involves melting of both components. Specifically, for example, one or more mixtures of these components in the form of powder, beads, or pellets are mixed with a single screw extruder, The resin composition can be prepared by an extruder such as a shaft extruder, or a kneader such as a Banbury mixer, a pressure kneader, or a two-roller. Instead of such dry blending, wet blending can be performed (the former is preferred). That is, a method in which one or more of these copolymers after polymerization are mixed in an undried state, for example, an emulsion, precipitated, washed, dried, and kneaded may be employed. it can.

Since the resin composition according to the present invention falls within the category of thermoplastic resin composition, according to a commonly used method, the kind and amount of lubricant, release agent, Various resin additives such as a coloring agent, an ultraviolet absorber, a light resistance stabilizer, a heat resistance stabilizer, a filler, a fibrous reinforcing material, a flame retardant, and a fungicide can be added in an appropriate combination.

The resin composition according to the present invention can be obtained by an injection molding method,
Various molding methods such as extrusion molding and blow molding can be used to produce molded articles such as automobile parts, electric parts, industrial parts, packaging containers, etc., with especially excellent chemical resistance (methanol resistance, gasoline resistance, Gasohol properties, grease resistance, etc.)
Can be used for applications requiring

[0038]

The following examples and comparative examples are provided to specifically explain the present invention. Reference Example 1 "Production of acrylate copolymer (acrylic rubber latex)"

Reference Example 1-1 1520 g of deionized water (hereinafter simply referred to as water), 20 g of a higher fatty acid soap (sodium salt of a fatty acid having 18 carbon atoms as a main component) and 10 g of sodium bicarbonate were charged into a 3 L glass flask. The temperature was raised to 75 ° C. under a nitrogen stream. After adding an aqueous solution of potassium persulfate (0.75 g / 20 ml), the mixture was divided into 5 minutes, and 937.5 g of butyl acrylate (BA) was added.
And 40 g of a monomer mixture consisting of acrylonitrile (AN) and 62.5 g of acrylonitrile (AN), and 5 g of allyl methacrylate (AMA). Fever occurs in about a few minutes,
The initiation of polymerization was confirmed. Fifteen minutes after the initial monomer charge, 0.75 g / 20 ml of an aqueous potassium persulfate solution was further added, and continuous addition of the remaining monomer mixture was started at the same time.
At 30 minutes, the addition was completed. At 1 hour 30 minutes, an aqueous solution of 6 g of fatty acid soap (dissolved in 20 ml) was added. After the addition of the monomer was completed, the polymerization was further continued at the same temperature for 1 hour. The obtained acrylic rubber latex had a conversion of 98% and an average particle size of 0.08 μm.

A half of this latex was placed in a 3 L flask, mixed with 685 ml of water and 5 g of a 10% aqueous solution of sodium dodecylbenzenesulfonate (DBS), and kept at 50 ° C. 320 g of a 2.5% aqueous phosphoric acid solution was added in about 1 minute under mild stirring, and then allowed to stand for 2 minutes.
Was added, and the mixture was sufficiently stirred. Average particle size 0.23μ
An acrylic rubber latex having an enlarged particle size of m (measured by a Nanosizer) was obtained.

Reference Example 1-2 900 g of BA, 100 g of styrene (St) and AMA5
g of a crosslinked acrylic rubber latex having an average particle size of 0.24 μm was obtained in the same manner as in Production Example 1-1 except that the monomer mixture consisting of g was used.

Reference Example 1-3 A crosslinked acrylic resin having an average particle size of 0.25 μm was prepared in the same manner as in 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. A rubber latex was obtained.

Reference Example 1-4 2116 g of the acrylic rubber latex obtained in Reference Example 1-1
(450 g of rubber) was placed in a 2 L flask and heated to 80 ° C. under a nitrogen stream. BA 45g, AN 5g and TMP
T1.25g of the mixture was continuously charged in about 15 minutes.
Prior to that, 0.5 g / 15 ml of an aqueous potassium persulfate solution was added. During this time, the pH of the system was kept at 7.5. A crosslinked acrylic rubber latex having a conversion of 96% and an average particle size of 0.25 μm was obtained.

Reference Example 2 "Production of Component (A)" Reference Example 2-1 2358 g of the acrylic rubber latex obtained in Reference Example 1-1
(500 g of rubber) was equipped with a stirrer, a reflux condenser, etc.
The mixture was placed in an L flask and heated to 80 ° C. and heated. 1.86 g / 50 ml of an aqueous solution of potassium persulfate was added, and St.
Continuous addition of a mixed monomer of 371 g and AN557 g was started, and after 15 minutes, 5.57 g / 1 of an aqueous potassium persulfate solution was added.
A continuous addition of 47 ml was also started. Start of monomer addition 30
After 1 minute, 1 hour, 10 minutes, and 2 hours, 16.3 g of 25% aqueous solution of sodium hydroxide was used, and aqueous solution of higher fatty acid soap was added.
29 g / 35 ml, 4.29 g / 35 ml of the same aqueous soap solution and 5.57 g of "terpinolene" were added. The continuous addition of the monomer and the aqueous solution of potassium persulfate was completed in 3 hours and 45 minutes, and then left at the same temperature for 30 minutes to complete the polymerization. The latex of the graft copolymer thus obtained is put into a large amount of an aqueous solution of calcium chloride, filtered,
After drying, a powdery graft copolymer was obtained. The conversion of the polymerization was 98.5%.

Reference Example 2-2 The acrylic rubber latex (rubber content 5
The graft polymerization was carried out in the same manner as in Reference Example 2-1 except for using 00g). The polymerization conversion rate is 96.5%.
Met.

Reference Example 3 "Production of Component (B)" The following raw material auxiliaries were charged into a 30 L pressure-resistant polymerization tank equipped with a heating / cooling device, a curved turbine type stirring device, a thermometer, and a raw material auxiliaries adding device. The inside of the polymerization system was replaced with nitrogen gas. Acrylonitrile 67 parts Styrene 3.5 parts Terpinolene 0.6 parts Di-t-butyl-p-cresol Acrylic acid / ethyl acrylate 2 ethylhexyl copolymer 0.03 parts Sodium sulfate 0.4 parts Deionized water 7.0 parts

The temperature in the polymerization vessel was increased to 106 ° C. while stirring, and 1-t-butyl-azo-1 dissolved in a small amount of styrene was used.
-0.15 parts of cyanocyclohexane was added, and the polymerization reaction was started at the same temperature.

Immediately after the start of the polymerization, styrene 2
9.5 parts were continuously added at a constant rate for 4 hours and 30 minutes, and at the same time, the temperature of the polymerization system was increased over 4 hours and 30 minutes.
The temperature was raised to 128 ° C.

After 4 hours and 30 minutes from the start of the polymerization, the continuous addition of styrene to the polymerization system was terminated, and the temperature of the polymerization system was raised to 145 ° C. over 45 minutes. Five hours and fifteen minutes after the start of the polymerization, stripping was further performed for one hour while maintaining the temperature of the polymerization system at 145 ° C.
The suspension after completion of the stripping was cooled, separated by filtration, washed with water and dried to obtain a beaded copolymer.

Example 1 485.7 g of graft copolymer (A) obtained in Reference Example 2-1 514.3 g of copolymer (B) obtained in Reference Example 3 was used as an antioxidant as di-t-butylparaffin. Cresol (DT
The mixture was kneaded with a Banbury mixer together with 3 g of BPC) and 5 g of magnesium stearate (Mg-St) as a lubricant, pelletized, and molded into a test piece at a cylinder temperature of 220 ° C and a mold temperature of 40 ° C by a 7-OZ injection molding machine.

The test pieces were evaluated for impact strength, tensile strength and weather resistance by the following methods. Impact strength (notched, isot, 23 ° C): ASTM D-
256-54T Tensile strength (23 ° C): ASTM D-
638-61T Weathering Test: Sunshine Weather O Meter W
E (Toyo Rika) retention of tensile elongation to initial value (% /%) (after 200hrs test / after 400hrs test) Critical strain value: Bending form of a test piece compression-molded into a rectangular shape of 35mm × 230mm × 2mm Set to a bending strain jig similar to a 1/4 elliptical jig (maximum strain value 1.0%). Methanol was applied at a temperature of 23 ° C., and 17 hours later, the presence or absence of craze or crack was visually determined. Table 1 shows the results.

Example 2 485.7 g of the graft copolymer (A) obtained in Reference Example 2-1 514.3 g of the copolymer (B) obtained in Reference Example 3 was used to prepare 3 g / 5 g of DTBPC / Mg-St. A test piece was obtained by blending and molding in the same manner as in Example 1. Table 1 shows the results.

Example 3 485.7 g of the graft copolymer (A) obtained by using the acrylic rubber latex of Reference Example 1-2 in the same manner as in Reference Example 2-1 The copolymer obtained in Reference Example 3 (B) 514.3 g DTBPC / Mg-St 3 g / 5 g was molded and evaluated in the same manner as in Example 1. Table 1 shows the results
Shown in

Example 4 A graft copolymer (A) obtained by using the acrylic rubber latex of Reference Example 1-3 in the same manner as in Reference Example 2-1 485.7 g Copolymer obtained in Reference Example 3 (B) 514.3 g DTBPC / Mg-St 3 g / 5 g was molded and evaluated in the same manner as in Example 1. Table 1 shows the results
Shown in

Example 5 The graft copolymer (A) obtained in Reference Example 2-2 485.7 g The copolymer (B) obtained in Reference Example 3 514.3 g DTBPC / Mg-St 3 g / 5 g was prepared in Example. Molding and evaluation were performed in the same manner as in Example 1. Table 1 shows the results
Shown in

Comparative Example 1 Graft polymerization was carried out in the same manner as in Reference Example 2-1 using a latex obtained by polymerization in the same manner as in Reference Example 1-1 except that AMA was omitted from the monomer mixture. 486.7 g of the copolymer 514.3 g of the copolymer (B) obtained in Reference Example 3 3 g / 5 g of DTBPC / Mg-St were molded and evaluated in the same manner as in Example 1. Table 1 shows the results. As compared with Example 1, the obtained molded article was inferior in gloss (glossy), and flow marks were observed.

Comparative Example 2 Polymerization was carried out using SBR (styrene-butadiene copolymer) latex instead of acrylate rubber latex as a rubber component, and blending and molding were carried out in the same manner as in Example 1. A test piece was obtained. Table 1 shows the results.

Comparative Example 3 Using the rubber latex of Reference Example 1-2, the graft copolymer (A) 485. obtained in Reference Example 2-1 with the amounts of St and acrylonitrile of 650 g and 278.6 g, respectively. 74.3 g AS resin (70 wt% St, 30 wt% AN) 514.3 g DTBPC / Mg-St 3 g / 5 g was molded and evaluated by the same method as in Example 1. Table 1 shows the results.

Table 1 Example 1 2 3 4 5 Matrix component (AN%) 61 60 59 62 60 Rubber component BA-AN BA-AN BA-St BA-MMA BA-AN IZOD, 23 ° C (kgcm / cm) 25 21 18 20 24 Tensile strength (kg / cm2) 550 560 545 568 555 Weather resistance (% /%) 100/50 100/50 100/50 100/50 100/50 YI 48 52 44 39 38 Critical strain (%, MeOH)>1.0>1.0>1.0>1.0> 1.0

Table 1 (continued) Comparative Example 1 2 3 Matrix component (AN%) 60 59 26 Rubber component BA-AN SBR BA-AN IZOD, 23 ° C (kgcm / cm) 9 35 6 Tensile strength (kg / cm2) 539 545 450 Weather resistance (% /%) 100/50 50/10 100/50 YI 42 82 24 Critical strain (%, MeOH) 1.0 0.5 0.7 (Note) BA: butyl acrylate, AN: acrylonitrile, St: styrene SBR: styrene-butadiene Polymer

[0061]

The composition according to the present invention has extremely excellent weather resistance, and further, unlike the conventional weather-resistant rubber-modified resin, contains a large amount of a vinyl cyanide monomer component in the matrix. In particular, it is excellent in methanol resistance and gasohol resistance, and also excellent in impact resistance. Furthermore, the yellowness is less than when a diene-based rubber is used, and the coloring property of a light color is particularly excellent.

Claims (1)

(57) [Claims] 1. A composition comprising the following components (A) and (B):
The rubber elastomer particles described below are used in an amount of 5 to 40 times in the composition.
A thermoplastic resin composition excellent in weather resistance, chemical resistance and impact resistance, characterized by being blended in a content of% by mass . Component (A): 10 to 50% by weight of aromatic vinyl monomer residue, 50 to 90% by weight of vinyl cyanide monomer residue and 0 to 40% by weight of methyl methacrylate residue (however, monomer residue The total amount is 100% by weight. The same applies to the following.) In a matrix of 50 to 300 parts by weight, a residue 70 of an ester of a monovalent alkyl alcohol having 1 to 12 carbon atoms and acrylic acid is added. -99.92% by weight, from 0 to 27% by weight of residues of a vinyl monomer copolymerizable with the acrylic acid ester, and from 0.08 to 3% by weight of residues of a polyfunctional vinyl monomer. Graft copolymer (A) in which 100 parts by weight of crosslinked rubber elastic particles having a diameter of 0.05 to 0.45 μm are dispersed, and component (B): aromatic vinyl monomer residues 10 to 50 % By weight, 50 to 90% by weight of vinyl cyanide monomer residue % Copolymer and 0 to 40% by weight of methyl methacrylate residues (B).