JPH0680853A - Thermoplastic resin composition excellent in wetherability, chemical resistance and impact resistance - Google Patents

Abstract

PURPOSE:To obtain the subject composition having weatherability, chemical resistance and impact resistance, and containing high nitrile styrene-acrylonitrile resin and a component in which rubber particles are dispersed in a high nitrile styreneacrylonitrile resin matrix. CONSTITUTION:(A) A graft copolymer comprises, in 50-300 pts.wt. matrix consisting of 10-50(wt.)% aromatic vinyl monomer residue, 50-90% vinyl cyanide residue and 0-40% methyl methacrylate residue, of 70-99.92% ester residue of 1-12C primary alcohol and acrylic acid ester, 0-27% vinyl monomer residue copolymerizable with the same and 0.08-3% polyfunctional vinyl monomer residue, and in which 100 pts.wt. crosslinked elastic rubber particles having 0.05-0.45mum average size are dispersed and (B) a copolymer consisting of 10-50% aromatic vinyl monomer residue, 50-90% vinyl cyanide monomer residue and 0-40% methyl methacrylate residue are blended so as to contain 5-40% component A to obtain the objective thermoplastic resin composition.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION

BACKGROUND OF THE INVENTION 1. Field 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 shows excellent impact resistance, and
Since it is easy to mold, it is widely used as a material for electric appliances, automobiles and other parts, casings and the like. In this case, a conjugated diene-based polymer such as polybutadiene, polyisoprene, styrene-butadiene copolymer (SBR) is widely used as the rubber elastic body. This is because the conjugated diene-based polymer has a double bond in the molecule, so that cross-linking is easy, and a graft bond with the matrix (continuous phase) is easily formed. This is because the excellent rubber-modified resin of, so-called ABS resin, can be easily obtained. On the other hand, these rubber-modified resins are
Since the rubber elastic body in which the double bond remains in the molecule is used as described above, the weather resistance is poor. In particular, the physical properties are remarkably deteriorated when exposed to the direct sunlight, and there has been a restriction on the use of the casing of outdoor equipment.

[0003]

2. Description of the Related Art As means for solving such a problem,
Double bond in the rubber elastic body such as polybutyl acrylate and other alkyl acrylate copolymers, ethylene-propylene-non-conjugated diene terpolymer (EPDM) and other monoolefin rubber elastic bodies It has been known to use a saturated rubber elastic body having no or only a small amount. However, although these saturated rubber-modified resins show remarkable improvement in weather resistance, they have a problem in mechanical properties such as impact resistance. This is because, according to the consideration of the present inventor, in the acrylic acid ester polymer, the grafting reaction to the latex, which is a commonly used technique, does not proceed sufficiently, and in EPDM etc., it is obtained in the latex state. Is difficult,
This is because the commonly used technique is the solution polymerization method, but EPDM and the like have not been able to sufficiently control the particle size distribution due to reasons such as poor solubility in monomers.

On the other hand, ABS resin is superior in chemical resistance to high-impact polystyrene because it contains acrylonitrile as a matrix component, but its application is
With the expansion of applications, further improvement in chemical resistance has been demanded, and for this reason, so-called high nitrile resins having a further increased acrylonitrile content in the matrix have been developed. However, as the content of acrylonitrile increases, the ABS resin containing a diene rubber as a base becomes more yellowish, causing problems such as coloring. Further, with respect to this high nitrile resin, applications that require chemical resistance and weather resistance are beginning to appear.

[Outline of the Invention]

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

[0006]

The thermoplastic resin composition according to the present invention is characterized by containing the following components (A) and (B) in predetermined amounts.

Component (A): Aromatic vinyl monomer residue 10
.About.50% by weight, vinyl cyanide monomer residue 50 to 90% by weight and methyl methacrylate residue 0 to 40% by weight (the total amount of the monomer residues is 100% by weight). The same applies to the following.) Matrices 50 to 300
70 parts by weight of an ester of a monohydric alcohol having 1 to 12 carbon atoms and acrylic acid, and 0 parts of a residue of a vinyl monomer copolymerizable with the acrylic acid ester in 0 parts by weight.
~ 27 wt% and polyfunctional vinyl monomer residue 0.08 ~
3% by weight, with an average particle size of 0.05 to 0.45 μm
Graft copolymer (A) having 100 parts by weight of crosslinked rubber elastic particles dispersed therein, and component (B): 10 to 50% by weight of aromatic vinyl monomer residue, vinyl cyanide monomer Copolymer (B) consisting of residues 50 to 90% by weight and methyl methacrylate residues 0 to 40% by weight.

However, this thermoplastic resin composition has
It shall contain 40% by weight of the rubber elastic particles.

DETAILED DESCRIPTION OF THE INVENTION The thermoplastic resin composition according to the present invention contains specific components (A) and (B) in a predetermined amount.

That is, the thermoplastic resin composition according to the present invention contains the graft copolymer (A) and the thermoplastic copolymer (B), and the content of the rubber elastic body in the graft copolymer (A) is: It is contained in an amount of 5 to 40% by weight.

<Component (A)><Content 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 cross-linked acrylic rubber obtained by emulsion polymerization as described below,
It is produced by undergoing a graft polymerization process.
This 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) according to the present invention comprises firstly an alkyl acrylate monomer residue 70 to 9 having an alkyl group having 1 to 12 carbon atoms.
9.92% by weight, residues of vinyl monomer copolymerizable with the above alkyl acrylate 0 to 27% by weight, and polyfunctional vinyl monomer 0.08 to 3% by weight (% by weight is based on the total amount) ) Consists of. When the content of the alkyl acrylate residue is less than 70% by weight, the elastic modulus of the acrylic rubber increases, which is not preferable. The residue of the polyfunctional vinyl monomer facilitates intermolecular crosslinking of the acrylate copolymer, graft bonding with the matrix,
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,
It should preferably be selected in the range of 0.1 to 2% by weight. When the content of this 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 is low. (Gloss) becomes poor, and it becomes difficult to improve impact resistance. On the other hand, if it exceeds 3% by weight, the resulting swelling ratio and grafting ratio of the acrylic rubber of the graft copolymer (A) will be poor, and various properties of the rubber will be deteriorated, such being undesirable. The content of residues of the third component, the "optional" monomer, must be chosen in the range of 0 to 27% by weight. If the content of the copolymerizable vinyl monomer exceeds 27% by weight, the elastic modulus becomes large and various properties as the acrylic rubber are deteriorated, which is not preferable.

The acrylic rubber has an average rubber particle size 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 the component (A) is produced from the rubber latex, and Impact resistance and surface gloss of the resulting composition are deteriorated, which is not preferable. In particular, the graft copolymer (component (A)) obtained by graft-polymerizing a vinyl cyanide compound / aromatic vinyl compound having a specific monomer ratio, which will be described later, produces the highest physical property balance when the component (B) is blended. In order to achieve this, the average rubber particle diameter is preferably in the range of 0.1 to 0.35 μm. "Average particle size" is expressed as a weight average. The rubber particle size in the composition of the present invention can be considered to be substantially the same as the particle size of the latex obtained when the rubber elastic body is produced by emulsion polymerization.

Such a crosslinked acrylic rubber is produced by subjecting a monomer giving a predetermined monomer residue to an appropriate polymerization condition, preferably emulsion polymerization condition, temporarily or stepwise. You can

That is, first, the alkyl acrylate monomer which is a constituent of this acrylic rubber is an alkyl acrylate having an alkyl group having 1 to 12 carbon atoms, preferably 4 to 8 carbon atoms (that is, an alcohol giving an alkyl group is Monohydric alcohol), and specific examples thereof include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, butyl acrylate,
Examples thereof include alkyl acrylates such as amyl acrylate, hexyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate and dodecyl acrylate. These may be one kind or a mixture of two or more kinds. Preferred acrylates are n-butyl acrylate and / or 2-
It is ethylhexyl acrylate.

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

As the vinyl monomer copolymerizable with the alkyl acrylate, there are aromatic vinyl monomers described below,
Vinyl cyanide monomer, acrylic amide, methacrylic amide, vinyl chloride or vinylidene, alkyl (about C _{1 to} C ₆ ) vinyl ether, 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 "arbitrary" monomers, those having a function of improving and improving the properties of the acrylic rubber obtained by copolymerization as a reinforcing rubber and the graft polymerization reactivity are preferable. Specific examples thereof include acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, p-vinyltoluene and other vinyltoluenes, alkyl methacrylate, 2-chloroethyl vinyl ether, monochlorovinyl acetate and methoxyethyl acrylate. As is clear from the example of the acrylic compound, "vinyl monomer"
Is synonymous with “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 above alkyl acrylates are polyfunctional vinyl monomers.

The polyfunctional vinyl monomer in the present invention is
To crosslink the acrylic rubber, 2 in 1 molecule of monomer
A vinyl monomer containing one or more vinyl groups. Specific examples of the polyfunctional vinyl monomer include aromatic polyfunctional vinyl monomers such as divinylbenzene and divinyltoluene, and methacrylates and acrylates of polyhydric alcohols such as ethylene glycol dimethacrylate and trimethylolpropane triacrylate. , Diallylmaleto,
Examples thereof include diallyl fumarate, triallyl isocyanurate, diallyl phthalate, allyl methacrylate and allyl acrylate. These may be one kind or a mixture of two or more kinds.

The acrylic rubber according to the present invention is preferably prepared by a known emulsion polymerization method using water as a medium, the types and amounts of the emulsifier and the polymerization catalyst and the addition method thereof, the addition method of each monomer, the polymerization temperature, It can be produced by appropriately selecting and combining various conditions such as a method for adjusting rubber particles. A suspension polymerization method 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 controlled, and the graft polymerization is easy.

The emulsion polymerization process itself may be conventional,
Specifically, a predetermined amount of the above monomer mixture is dispersed in water by using an emulsifier, and polymerization is started by using an appropriate initiator.
As the emulsifier, those of ordinary anion type, cation type, nonion type and the like can be used, but of synthetic emulsifiers such as dodecylbenzene sulfonate, sulfosuccinate salt, polyoxyethylene alkyl ether sulfate, alkyl diphenyl ether disulfonate, etc. In addition, fatty acid salts such as tallow soap, sodium stearate, sodium oleate and the like are preferable because the salting out operation is easy. Examples of the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide, and L-
A redox system in combination with a reducing agent such as ascorbic acid, rongalite, acidic sodium 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.

Rubber elastic material in the graft copolymer (A),
That is, the average particle size of the acrylic acid ester-based polymer is preferably 0.05 to 0.45 μm, and 0.1 to 0.
As described above, the thickness of 35 μm is more preferable.

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 in the graft polymerization, the acrylate polymer obtained by the above emulsion polymerization. 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 to carry out a so-called particle size enlarging operation for coagulating and expanding the latex particles.

<Production of Component (A)> Component (A) has a structure in which the above-mentioned acrylic rubber particles are dispersed in a matrix having a specific composition, and such a structure is typically a monomer which gives the matrix. It is produced by polymerizing or emulsion polymerizing the body in 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 the aromatic vinyl monomer and 50 to 90% by weight of the vinyl cyanide monomer. And a monomer mixture consisting of 0 to 40% by weight of methyl methacrylate in an amount of 50 to 300 per 100 parts by weight of a solid content of an acrylic acid ester-based copolymer latex.
Emulsion graft polymerization is carried out by adding an amount corresponding to parts by weight to the above-mentioned latex at one time or in batches or continuously. In this case, if necessary, a polymerization initiator and other auxiliary agents are added. Rubber elastic body, that is,
Acrylic ester-based copolymer latex solid content 100
The amount of the monomer mixture added is 50 to 30 parts by weight.
0 parts by weight, preferably 66 to 200 parts by weight are 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 further the impact resistance is deteriorated, which is not preferable. Further, if the composition of the monomer mixture is out of the above range, chemical resistance and compatibility are deteriorated, which is not preferable.

When the emulsion graft polymerization is completed, MgSO 4
₄ , Al ₂ (SO ₄ ) ₃ , NaCl, HCl, CaCl
An aqueous solution of an electrolyte such as ₂ is added and salted out, and the resulting slurry is dehydrated and dried.

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

The 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 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) is 10 to 50% by weight of the aromatic vinyl monomer residue, preferably 20 to 45.
% By weight, 50 to 90% by weight of vinyl cyanide monomer residue,
The copolymer is preferably composed of 55 to 80% by weight, and a methyl methacrylate residue of 0 to 40% by weight, preferably 0 to 30% by weight. 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 the component (B) can be found in the examples given above for the monomer for the component (A) and are those selected for the component (A). The same or different one may be used.

The copolymer of the component (B) is known as a so-called AS resin or MAS resin (which is a high nitrile), and is a known substance per se, and bulk polymerization is carried out 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), but the content of the rubber elastic body, that is, the acrylic ester 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 entire 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 is lowered, and the molding processability is also lowered, which is not preferable.

The blending of component (A) and component (B) can be done by any method that provides a uniform composition of both components. This method is generally accompanied by melting of both components, and specifically, for example, one or a mixture of two or more of these components in the form of powder, beads or pellets is mixed with a single-screw extruder, The resin composition can be prepared by using an extruder such as a shaft extruder or a kneading machine such as a Banbury mixer, a pressure kneader, or a two-roll mill. Wet compounding can be performed in place of such dry compounding (the former is preferred). That is, it is also possible to adopt a method in which one or more of these copolymers that have been polymerized are mixed in an undried state, for example, as an emulsion, precipitated, washed, dried, and kneaded. it can.

Since the resin composition according to the present invention falls within the category of a thermoplastic resin composition, according to a conventional method, a lubricant, a release agent, a type and an amount which do not impair the properties of the resin are used. Various resin additives such as a colorant, an ultraviolet absorber, a light resistance stabilizer, a heat resistance stabilizer, a filler, a fibrous reinforcing material, a flame retardant, and a mildew proofing agent can be appropriately combined and added.

The resin composition according to the present invention is produced by the injection molding method,
By various molding methods such as extrusion molding method and blow hollow molding method, it has excellent chemical resistance (methanol resistance, gasoline resistance, resistance to methanol, etc.) as molded products such as automobile parts, electric parts, industrial parts, packaging containers, etc. Gasohol property, grease resistance, etc.)
Can be used in applications where

[0038]

EXAMPLES The following examples and comparative examples are for specifically explaining the present invention. Reference Example 1 "Production of acrylic acid ester-based copolymer (acrylic rubber latex)"

Reference Example 1-1 A 3 L glass flask was charged with 1520 g of deionized water (hereinafter simply referred to as water), 20 g of higher fatty acid soap (sodium salt of fatty acid having 18 carbon as a main component), and 10 g of sodium bicarbonate. 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)
Then, 40 g of a monomer mixture consisting of 62.5 g of acrylonitrile (AN) and 5 g of methacrylic acid allyl ester (AMA) was charged. Fever occurs in about a few minutes,
The initiation of polymerization was confirmed. 15 minutes after the first charging of the monomers, 0.75 g / 20 ml of an aqueous potassium persulfate solution was further added, and at the same time, continuous addition of the remaining monomer mixture was started.
The addition was completed at the time of 30 minutes, but an aqueous solution of 6 g of fatty acid soap (dissolved in 20 ml) was added at the time of 1 hour and 30 minutes on the way. After the completion of the addition of the monomer, the polymerization was allowed to proceed for another hour at the same temperature. The obtained acrylic rubber latex had a conversion rate of 98% and an average particle size of 0.08 μm.

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 then kept at 50 ° C. 320 g of 2.5% phosphoric acid aqueous solution was added under weak agitation in about 1 minute, then left for 2 minutes, then 23.4 g of 25% caustic solution and 14 g of DBS 25% aqueous solution.
And were 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 Nanosizer) was obtained.

Reference Example 1-2 900 g of BA, 100 g of styrene (St) and 5 of AMA
A crosslinked acrylic rubber latex having an average particle size of 0.24 μm was obtained by the same method 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
(Rubber content 450 g) was placed in a 2 L flask and heated to 80 ° C. under a nitrogen stream. BA45g, AN5g and TMP
The mixture of T1.25g was continuously charged in about 15 minutes,
Before that, 0.5 g / 15 ml of an aqueous potassium persulfate solution was added. During this time, the system pH was maintained at 7.5. A crosslinked acrylic rubber latex having a conversion rate 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
(Rubber content 500g) equipped with a stirrer, reflux condenser, etc. 3
The mixture was placed in an L flask and heated up to 80 ° C. 1.86 g / 50 ml of potassium persulfate aqueous solution was added, and at the same time St
Continuous addition of a mixed monomer of 371 g and AN557 g was started, and 15 minutes later, 5.57 g / 1 aqueous potassium persulfate solution was added.
A continuous addition of 47 ml was also started. Start adding monomer 30
Minutes, 1 hour, 10 minutes, and 2 hours later, 16.3 g of 25% caustic potash aqueous solution and higher fatty acid soap aqueous solution 4.
29 g / 35 ml and 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 potassium persulfate solution 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 was added to a large amount of calcium chloride aqueous solution and filtered,
After drying, a powdery graft copolymer was obtained. The conversion rate of the polymerization was 98.5%.

Reference Example 2-2 The acrylic rubber latex obtained in Reference Example 1-4 (rubber content 5
Graft polymerization was carried out in the same manner as in Reference Example 2-1 except that 100 g) was used. Polymerization conversion rate is 96.5%
Met.

Reference Example 3 "Production of Component (B)" A 30 L pressure resistant polymerization tank equipped with a heating and cooling device, a curved turbine type stirring device, a thermometer, and a raw material auxiliary agent adding device was charged with the following raw material auxiliary agents. 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

While stirring, the temperature in the polymerization tank was raised to 106 ° C., 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 starting the polymerization, styrene 2
While continuously adding 9.5 parts at a constant rate for 4 hours and 30 minutes, the temperature of the polymerization system was simultaneously increased over 4 hours and 30 minutes,
The temperature was raised to 128 ° C.

4 hours and 30 minutes after the initiation of the polymerization, the continuous addition of styrene to the polymerization system was terminated, and then the temperature of the polymerization system was raised to 145 ° C. over 45 minutes. After 5 hours and 15 minutes from the start of the polymerization, stripping was further performed for 1 hour while maintaining the temperature of the polymerization system at 145 ° C.
The suspension system after the stripping was cooled, filtered, washed with water, and dried to obtain a bead-shaped copolymer.

Example 1 485.7 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 as an antioxidant in di-t-butylpara. Cresol (DT
BPC) 3 g and magnesium stearate (Mg-St) 5 g as a lubricant were kneaded in a Banbury mixer, pelletized, and then 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, Isolated, 23 ° C): ASTM D-
256-54T Tensile Strength (23 ° C): ASTM D-
638-61T Weatherability Test: Sunshine Weather O Meter W
Tensile elongation retention ratio (% /%) to the initial value by E (Toyo Rika) (after 200hrs test / after 400hrs test) Critical strain value: Bending foam of a test piece compression-molded into a strip of 35mm x 230mm x 2mm ( Set to a bending strain jig (maximum strain value 1.0%) similar to the 1/4 elliptical jig. Methanol was applied at a temperature of 23 ° C., and 17 hours later, the presence or absence of crazes or cracks was visually determined. The results are shown in Table 1.

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 DTBPC / Mg-St 3 g / 5 g A test piece was obtained by blending and molding in the same manner as in 1. The results are shown in Table 1.

Example 3 Graft copolymer (A) obtained by using the acrylic rubber latex of Reference example 1-2 in the same manner as in Reference example 2-1 485.7 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. The results are shown in Table 1.
Shown in.

Example 4 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. The results are shown in Table 1.
Shown in.

Example 5 Graft copolymer (A) obtained in Reference Example 2-2 485.7 g Copolymer (B) obtained in Reference Example 3 514.3 g DTBPC / Mg-St 3 g / 5 g It was molded and evaluated in the same manner as in 1. The results are shown in Table 1.
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 the same method as in Reference Example 1-1 except that AMA was omitted from the monomer mixture. Copolymer 486.7 g Copolymer (B) obtained in Reference Example 3 514.3 g DTBPC / Mg-St 3 g / 5 g was molded and evaluated by the same method as in Example 1. The results are shown in Table 1. Compared with Example 1, the obtained molded product was inferior in gloss (gloss) and flow marks were recognized.

Comparative Example 2 SBR (styrene-butadiene copolymer) latex was used in place of the acrylic ester rubber latex as a rubber component to carry out polymerization, and blending and molding were carried out in the same manner as in Example 1, A test piece was obtained. The results are shown in Table 1.

Comparative Example 3 Using the rubber latex of Reference Example 1-2, the amount of St and acrylonitrile in Reference Example 2-1 was 650 g and 278.6 g, respectively, and the graft copolymer (A) 485. 7 g AS resin (St 70% by weight, AN 30% by weight) 514.3 g DTBPC / Mg-St 3 g / 5 g was molded and evaluated by the same method as in Example 1. The results are shown in Table 1.

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 ℃ (kg ・ cm / 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 ℃ (kg ・ cm / 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 co Polymer

[0061]

EFFECT OF THE INVENTION The composition according to the present invention has extremely excellent weather resistance. Further, unlike the conventional weather resistant rubber-modified resin, since the matrix contains a large amount of vinyl cyanide monomer component, chemical resistance, Particularly, it has excellent resistance to methanol and gasohol, and also has excellent impact resistance. Further, it has less yellowish tint than the case of using a diene rubber, and is particularly excellent in tintability of a light color.

Claims (1)

[Claims] 1. A thermoplastic resin composition excellent in weather resistance, chemical resistance and impact resistance, which comprises the following components (A) and (B) in predetermined amounts. Component (A): 10 to 50% by weight of an aromatic vinyl monomer residue, 50 to 90% by weight of a vinyl cyanide monomer residue, and 0 to 40% by weight of a methyl methacrylate residue (a single amount is used). The total amount of body residues is 100% by weight. The same shall apply hereinafter), in 50 to 300 parts by weight of the matrix consisting of
70 to 99.92% by weight of a residue of an ester of a C1-12 monohydric alcohol and acrylic acid, and 0 to 27% by weight of a residue of a vinyl monomer copolymerizable with the acrylic ester.
And a graft copolymer having 100 parts by weight of a crosslinked rubber elastic body particle composed of 0.08 to 3% by weight of a polyfunctional vinyl monomer residue and having an average particle diameter of 0.05 to 0.45 μm. Combined (A) and component (B): from 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 Copolymer (B). However, this thermoplastic resin composition is 5-40
It is assumed to contain the rubber elastic body particles by weight.