KR20090119573A - Weatherable thermoplastic resin composition - Google Patents

Abstract

PURPOSE: A weather resistant thermoplastic resin composition is provided to improve heat resistance, low gloss characteristic and shock resistance, and to facilitate the molding of electrical and electronics products and automobiles. CONSTITUTION: A weather resistant thermoplastic resin composition comprises an acrylic grafted copolymer resin 30 - 60 weight% with an average rubber particle diameter of 0.5 - 1 μm; a diene grafted copolymer resin 5 - 30 weight% with an average rubber particle diameter of 1 - 20 μm; and an aromatic vinyl compound-vinyl cyanide copolymer resin 10 - 50 weight%.

Description

Weatherable Thermoplastic Resin Composition

Field of invention

The present invention relates to weather resistant thermoplastic resin compositions. More specifically, the present invention is formulated with a specific amount of acrylic graft copolymer resin, diene graft copolymer resin and aromatic vinyl compound-vinyl cyan compound copolymer resin to balance the physical properties such as impact strength, fluidity and heat resistance as well as weather resistance A weather resistant thermoplastic resin composition having excellent low light properties.

Background of the Invention

In general, ABS (acrylonitrile-butadiene-styrene) resin has excellent mechanical and thermal properties including physical properties such as styrene processability, stiffness and chemical resistance of acrylonitrile, and impact resistance of butadiene. It is widely used in various applications such as pipes, automobiles, electrical and electronic equipment, office equipment, general office supplies, home appliances, toys, stationery, and the like. However, such an ABS resin has a problem in that the unsaturated π bond is broken due to the unsaturated π bond in the butadiene rubber, resulting in aging of the resin such as color change or cracking of the resin. In addition, there is a limit to being used in a product that heat deformation is likely to occur at high temperatures and heat resistance properties are required.

In order to solve this disadvantage, ASA (acrylate-styrene-acrylonitrile) resin using acrylic rubber instead of butadiene rubber has been applied. ASA resins do not have unsaturated π bonds and are known as a good alternative to the problem of poor weather resistance due to butadiene rubber.

U.S. Patent No. 4,753,988 and U.S. Patent No. 4,801,646 disclose weather resistant resins, but have problems in that the particle size and distribution are not appropriate and the impact strength and heat resistance characteristics are not good.

On the other hand, as the interest in the emotional quality resins has recently increased, the demand for low-gloss resins has increased. In particular, the development of a product having a low gloss property is required to satisfy consumers who prefer a luxurious appearance in automobile interior materials, electronic product exterior materials, and the like.

U.S. Patent 4,460,742 discloses a low gloss resin composition in which a copolymer crosslinked by an allyl function is added. As such, most low-gloss resins use large-diameter rubber particles or matting agents to reduce gloss, or use corrosion molds for injection molding.

However, when a large diameter rubber particle or a matting agent is added to reduce glossiness, not only does not exhibit a sufficient low light effect, but there is a problem that the impact strength is sharply lowered when an excessive amount is added. In addition, in the case of using a corrosion mold, since the mold must be manufactured separately according to the degree of gloss, there is a problem in that the mold production cost is large, and the degree of gloss adjustment of the desired degree is not easy.

Korean Patent No. 717926 discloses a low light ASA composition in which a flame retardant is added to an acrylic graft copolymer prepared through emulsion polymerization and a matte ABS prepared through bulk polymerization. However, the composition is not suitable for use in interior and exterior materials such as electronic products or automobiles due to the lack of heat resistance and impact resistance.

The general weather resistant thermoplastic resin can prevent the aging of the resin due to ultraviolet rays, but the heat resistance is low, there is a limit in being used in products requiring heat resistance, such as automotive interiors, exterior materials due to heat deformation when exposed to high temperatures for a long time.

In order to improve the heat resistance, a method of introducing a monomer such as α-methylstyrene or maleimide having excellent heat resistance or adding an inorganic material to a part of the composition constituting the weather resistant thermoplastic resin is used, but there is a problem that the impact strength is lowered.

In another method, a heat-resistant copolymer resin containing a monomer such as α-methylstyrene or maleimide having excellent heat resistance may be mixed with a weather resistant thermoplastic resin or an acrylic rubber, but there is a disadvantage in that sufficient impact strength cannot be obtained.

Therefore, in order to solve the above problems, the present inventors blended an acrylic graft copolymer, a diene graft copolymer resin having a matte property, and an aromatic vinyl compound-vinyl cyan compound copolymer resin having heat resistance at a specific ratio. By doing so, it is possible to develop a weather resistant thermoplastic resin composition having improved heat resistance, low light properties and impact resistance.

An object of the present invention is to provide a weather resistant thermoplastic resin composition.

Another object of the present invention is to provide a weather resistant thermoplastic resin composition with improved heat resistance, low light properties and impact resistance.

It is still another object of the present invention to provide a weather resistant thermoplastic resin composition which is excellent in fluidity and is easy for molding various products such as electric and electronic products and automobiles.

The above object of the present invention can be achieved by the present invention described below.

Summary of the Invention

The weather resistant thermoplastic resin composition of this invention contains (A) acrylic graft copolymer resin, (B) diene graft copolymer resin, and (C) aromatic vinyl compound-vinyl cyan compound copolymer resin.

In the specific example, the weatherable thermoplastic resin composition may include (A) 30 to 60 wt% of an acrylic graft copolymer resin having an average rubber particle diameter of 0.05 to 1 μm, and (B) a diene graft air having an average rubber particle size of 1 to 20 μm. 5 to 30% by weight of the copolymer resin, and 10 to 50% by weight of the (C) aromatic vinyl compound-vinyl cyan compound copolymer resin.

The acrylic graft copolymer (A) is a copolymer in which 40 to 90% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer is grafted to 10 to 60% by weight of a (meth) acrylate rubber.

The diene graft copolymer resin (B) is a copolymer obtained by grafting 80 to 93 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer to 7 to 20 wt% of a diene rubber.

The diene graft copolymer resin (B) has a 60 degree glossiness of 3 to 30% measured by a Gardner Gloss Meter on a 1/8 "thick specimen according to ASTM D523.

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) is a copolymer of 60 to 80% by weight of an aromatic vinyl compound containing α-methylstyrene and 20 to 40% by weight of a vinyl cyan compound.

In a specific example, the diene graft copolymer resin (B) and the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) are prepared by continuous bulk polymerization.

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) has a weight average molecular weight of 80,000 to 120,000, and a molecular weight distribution of 2.5 or less.

In an embodiment, the resin composition may include an additive selected from the group consisting of flame retardants, antibacterial agents, antistatic agents, antidropping agents, mold release agents, antioxidants, heat stabilizers, lubricants, UV stabilizers, impact modifiers, fillers, inorganic additives, stabilizers, pigments, and dyes. It may further comprise one or more.

The thermoplastic resin composition of the present invention has an weather resistance (ΔE) of 0.1 to 2 measured by Weather-O-Meter (AT5000 Ci5000) according to ASTM G155, and an Izod impact of a 1/8 "thick specimen measured by ASTM D256. Vicat softening point (5kgf, 50 ° C / hr) as measured by ISO R306, with strength of 15 to 80 kgfcm / cm, flowability (220 ° C, 10kg) measured by ASTM D1238, 2.5 to 10 g / 10 min. ) Is 103-150 ° C., and the 60-degree glossiness, measured by a Gardner Gloss Meter on a 1/8 ”thick specimen according to ASTM D523, has a value of 30-60%.

This invention includes the molded article which shape | molded the said resin composition. Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

(A) Acrylic Graft Copolymer

The acrylic graft copolymer (A) of the present invention is a graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in an acrylic rubber, and is well known by those skilled in the art. It is The polymerization method may be a conventional polymerization method such as bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, preferably prepared by the emulsion graft polymerization method.

The acrylic graft copolymer (A) is a grafted 40 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer to 10 to 60% by weight of the (meth) acrylate rubber. In one embodiment, the acrylic graft copolymer (A) is grafted with 45 to 85% by weight of the aromatic vinyl compound-vinylcyan compound copolymer to 15 to 55% by weight of the (meth) acrylate rubber.

As the acrylic rubber for preparing the acrylic graft copolymer, a polymer of alkyl (meth) acrylate having 2 to 8 carbon atoms may be used. Specifically, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate may be used, These can be used individually or in mixture of 2 or more types. Among these, butyl acrylate is preferable.

The average particle diameter of the acrylic rubber particles may be in the range of 0.05 to 1 μm, preferably in the range of 0.07 to 0.7 μm, more preferably in the range of 0.1 to 0.5 μm. If the average particle size of the particles is less than 0.05 ㎛, the impact strength is not small enough to play a role as a rubber, if more than 1 ㎛ also brings about the impact strength of the final weather resistant thermoplastic resin.

The aromatic vinyl compound-vinyl cyan compound copolymer grafted to the acrylic rubber is a copolymer of 60 to 80% by weight of aromatic vinyl compound and 20 to 40% by weight of vinyl cyan compound.

As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, etc. may be used, and these may be used alone or in combination of two or more thereof.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, and these may be used alone or in combination of two or more thereof.

In another embodiment of the present invention, in addition to the aromatic vinyl compound and the vinyl cyan compound, other copolymerizable monomers may be selectively applied when necessary to prepare the aromatic vinyl compound-vinyl cyan compound copolymer. Applicable monomers may be added with acrylic acid, methacrylic acid, alkyl (meth) acrylates, maleic anhydride, N-substituted maleimides and the like.

The acrylic graft copolymer (A) is preferably included in 30 to 60% by weight, more preferably 35 to 55% by weight relative to 100% by weight of the weather resistant thermoplastic resin that is the final product. When less than 30% by weight, the rubber content of the weather-resistant thermoplastic resin, which is the final product, may be lowered, and thus impact resistance may be lowered.When the amount is more than 60% by weight, the vinyl cyanide compound-diene-based rubber-aromatic vinyl compound copolymer resin having matt characteristics A relatively low amount of aromatic vinyl compound-vinylcyan compound copolymer resin having a heat resistance and a low light property and heat resistance may be difficult to implement.

(B) diene graft copolymer resin

The diene graft copolymer resin (B) of the present invention is obtained by grafting an aromatic vinyl compound-vinyl cyan compound copolymer to a diene rubber.

The diene graft copolymer resin (B) is added to provide matting properties and impact strength, and 60 degrees glossiness measured by a Gardner Gloss Meter is measured on a 1/8 "thick specimen according to ASTM D523. It has a value of 3 to 30%.

In a specific example, the diene graft copolymer resin (B) is a copolymer obtained by grafting 80 to 93 wt% of an aromatic vinyl compound-vinyl cyan compound copolymer to 7 to 20 wt% of a diene rubber.

The rubber used in the diene graft copolymer resin (B) is a diene rubber, and polybutadiene, butadiene-styrene copolymer or a mixture thereof may be used. In embodiments, the diene rubber has a viscosity of 5 wt% styrene solution of 150 to 300 cps. In the present invention, the average rubber particle size dispersed in the diene graft copolymer resin (B) is preferably about 1 to 20 µm, more preferably 5 to 20 µm, and most preferably 6 to 20 µm. If the rubber particle diameter is less than 1 μm, the low light properties of the weatherable thermoplastic resin, which is the final product, cannot be effectively exhibited. If the rubber particle diameter is more than 20 μm, the low light property of the weather resistant thermoplastic resin, which is the final product, is better, but the impact strength is sharply lowered. Can be imported.

The aromatic vinyl compound-vinyl cyan compound copolymer grafted to the diene rubber is a copolymer of 60 to 90% by weight of aromatic vinyl compound and 10 to 40% by weight of vinyl cyan compound. Preferably, the aromatic vinyl compound-vinyl cyan compound copolymer is a copolymer of 70 to 85% by weight of aromatic vinyl compound and 15 to 30% by weight of vinyl cyan compound.

As the aromatic vinyl compound, styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, vinyl toluene, etc. may be used, and these may be used alone or in combination of two or more thereof.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, and these may be used alone or in combination of two or more thereof.

In addition to the aromatic vinyl compound and the vinyl cyan compound, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be optionally added as necessary to impart processability and heat resistance.

The diene graft copolymer resin (B) having the above matt characteristics may be prepared by emulsion polymerization, suspension polymerization, solution polymerization, continuous bulk polymerization, and the like. It is preferably prepared by continuous bulk polymerization.

In one embodiment, the continuous bulk polymerization method comprises preparing a reaction solution by mixing a polymerization initiator and a molecular weight regulator in a mixed solution of an aromatic vinyl compound, a vinyl cyanide compound, a diene rubber, and a solvent, and preparing the reaction solution as a first solution. It was introduced into the reactor to polymerize up to 30-40% conversion, the polymerized polymer in the first reactor was introduced into the second reactor to polymerize up to 70-80% conversion, and devolatilized the polymerized in the second reactor. Are prepared in steps. The mixed solution includes 40 to 60% by weight of an aromatic vinyl compound, 10 to 25% by weight of a vinyl cyanide compound, 7 to 20% by weight of a diene rubber, and 5 to 30% by weight of a solvent. The polymerization initiator may have a half life of 10 minutes or less at the polymerization temperature. The solvent may be ethylbenzene, xylene, toluene or mixtures thereof. The method for producing the diene graft copolymer resin (B) is disclosed in Korean Patent Application No. 2007-141056, and the present invention includes it as a whole.

In the present invention, the small diameter rubber particles of the acrylic graft copolymer (A) and the large diameter rubber particles of the diene graft copolymer resin (B) may be formed in a bimodal form to exhibit excellent impact strength at an appropriate content.

In the present invention, the diene graft copolymer resin (B) is preferably included in an amount of 5 to 30% by weight, more preferably 7 to 27% by weight, most preferably based on 100% by weight of the weather resistant thermoplastic resin as a final product. Is 10 to 25% by weight. If less than 5% by weight can not fully exhibit the low light effect, when more than 30% by weight may cause a problem of deterioration of weather resistance due to excessive unsaturated π bond.

(C) Aromatic vinyl compound-vinyl cyan compound copolymer resin

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) is added to impart heat resistance.

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) of the present invention may be prepared by copolymerizing a monomer comprising 60 to 80 wt% of an aromatic vinyl compound and 20 to 40 wt% of a vinyl cyan compound.

In one embodiment, the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) comprises 60 to 80 wt% of an aromatic vinyl compound including α-methylstyrene and 100 wt% of a monomer including 20 to 40 wt% of a vinyl cyan compound. It is a copolymer of 0.01-0.1 weight part of polyfunctional vinyl compounds with respect to a part.

An aromatic vinyl compound may be used alone or in combination with an aromatic vinyl monomer such as styrene, α-ethyl styrene, p-methyl styrene, 2,4-dimethyl styrene, or vinyl toluene. Can be used.

As the vinyl cyan compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used, and these may be used alone or in combination of two or more thereof.

As the polyfunctional vinyl compound, divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, diallyl phthalate, diallyl maleate, triallyl isocyanurate, and the like may be used. It can be applied by mixing.

In addition to the aromatic vinyl compound and the vinyl cyan compound, monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide may be optionally added as necessary to impart processability and heat resistance.

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) of the present invention can be produced by emulsion polymerization, suspension polymerization, solution polymerization, continuous bulk polymerization and the like. Preferred of these is continuous bulk polymerization. In one embodiment of the present invention, the continuous bulk polymerization is sequentially carried out by continuously inputting a mixed raw material containing an aromatic vinyl compound, a vinyl cyan compound, and a polyfunctional vinyl compound including α-methylstyrene into a plurality of reactors connected in series. It is prepared by polymerization, wherein it is characterized in that by controlling the conversion rate of each reactor to 10 ~ 25%. Three to five reactors are suitable. Method for producing the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) is disclosed in Korean Patent Application No. 2007-115737, the present invention includes it as a whole.

The aromatic vinyl compound-vinyl cyan compound copolymer resin (C) of the present invention has a weight average molecular weight of 80,000 to 120,000, preferably a molecular weight distribution of 2.5 or less, more preferably a weight average molecular weight of 90,000 to 115,000, molecular weight distribution Is 1.8 to 2.4. When the weight average molecular weight is less than 80,000, the impact resistance of the weather resistant thermoplastic resin, which is the final product, may be lowered. When the weight average molecular weight is more than 120,000, the impact resistance of the weather resistant thermoplastic resin, which is the final product, may be improved, but the fluidity may be lowered, resulting in poor workability.

In the present invention, the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) is preferably included in an amount of 10 to 50% by weight based on 100% by weight of the weather resistant thermoplastic resin that is the final product. If less than 10% by weight can not fully exhibit the heat-resistant effect, when more than 50% by weight may result in a decrease in physical properties.

The thermoplastic resin composition of the present invention is optionally flame retardant, antibacterial, antistatic, anti-dropping agent, mold release agent, antioxidant, heat stabilizer, lubricant, UV stabilizer, impact modifier, filler, inorganic additive, stabilizer, pigment and dye Additives, such as these, can be used. The additives may be used alone or in mixture of two or more thereof. The additive is used in the range of 20 parts by weight or less based on 100 parts by weight of the thermoplastic resin composition.

In one embodiment, the thermoplastic resin composition of the present invention has a weather resistance (ΔE) of 0.1 to 2 as measured by Weather-O-Meter (AT5000 Ci5000) according to ASTM G155, and is 1/8 "thick as measured by ASTM D256. The Izod impact strength of the specimen was 15 to 80 kgf · cm / cm, the fluidity (220 ° C., 10 kg) measured by ASTM D1238 was 2.5 to 10 g / 10 min, and the Vicat softening point (5 kgf, measured by ISO R306). 50 ° C./hr) is 103 to 150 ° C., and the 60 degree glossiness measured by a Gardner Gloss Meter on a 1/8 ”thick specimen is ASTM 30-60%.

The thermoplastic resin composition of this invention can be manufactured by a well-known method. For example, the above components may be mixed in a known mixing method using an extruder, a kneader, a mixer, or the like, and then extruded to be prepared in pellet form or in various moldings.

The thermoplastic resin composition of the present invention has excellent balance of physical properties such as impact strength, fluidity, and heat resistance as well as weather resistance, and has low light properties, so that the thermoplastic resin composition can be suitably applied to interior and exterior materials such as various electric and electronic products, automobile parts, and building materials. have.

The invention can be better understood by the following examples, which are intended for purposes of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

The specifications of the components used in the following Examples and Comparative Examples are as follows.

(A) Acrylic graft copolymer resin: ASA copolymer resin having 50% by weight of butyl acrylate rubber, 35% by weight of styrene, and 15% by weight of acrylonitrile was used.

(B) diene graft copolymer resin: ABS copolymer resin having 15% by weight of polybutadiene rubber having a rubber particle diameter of 7 µm, 65% by weight of styrene, and 20% by weight of acrylonitrile was used.

(C) Aromatic vinyl compound-vinyl cyan compound copolymer resin: 0.15 parts by weight of divinylbenzene, 1,1-Bis (t) based on 100 parts by weight of a monomer mixture composed of 70 parts by weight of α-methylstyrene and 30 parts by weight of acrylonitrile. -Butylperoxy) cyclohexane mixed with 0.15 parts by weight of raw materials were continuously added to a continuous polymerization reactor equipped with two 2-liter stainless steel reactors in which the reaction temperature and agitation were controlled in series. The reaction was discharged continuously after maintaining the average residence time in the reactor to 2 hours. At this time, the conversion rate in each reactor was 30% so that the conversion rate of the final reactant was 60%. The reactant discharged from the reactor was continuously added to a devolatilizer maintained at 240 ° C. and 20 Torr to remove unreacted monomers, and a heat resistant copolymer was obtained in pellet form using a pelletizer. Using the THF as a mobile phase through the room temperature gel permeation chromatography (Water PC GPC, LF-804 column) for the prepared copolymer to obtain the elution curve of the sample and relative number average molecular weight, weight average molecular weight based on the standard polystyrene polymer And a molecular weight distribution was calculated, and a copolymer resin having a weight average molecular weight of 100,000 and a molecular weight distribution of 2.5 was used.

Examples 1-4

To the ingredients as described above in Table 1, 0.2 parts by weight of antioxidant (Di-Stearyl-Pentaerythritol-Diphosphite), heat stabilizer (Octadecyl 3- (3,5-Di, T, Butyl-4- 0.3 parts by weight of hydrixy phenyl) propionate), 0.02 parts by weight of dimethyl polysiloxane, 0.6 parts by weight of magnesium stearate (EBS), UV stabilizer (Bis (2,2,6,6-Tetramethyl-4-piperidyl) sebacate ) 1.0 part by weight was added to the mixture, followed by melting and kneading to prepare a pellet. At this time, L / D = 32, 25mm diameter twin screw extruder was used and the cylinder temperature was set to 220 ℃. The prepared pellets were injected into the pellets at 220 ° C. under the condition of preparing physical properties specimens. The physical properties were measured according to the following method, and the results are shown in Table 1 below.

Property measurement method

(1) Izod impact strength (kgfcm / cm, 1/8 "Notched): measured by ASTM D256.

(2) Weather Resistance (ΔE): Measured by ASTM G155. Specimens 1/8 "thick were measured with ATALS Ci5000 Weather-O-Meter.

(3) Flowability (220 degreeC, 10 kg): It measured by ASTM D1238.

(4) Vicat softening point (5kgf, 50 ℃ / hr): measured by ISO R306 to evaluate the heat resistance.

(5) Glossiness (60): measured by ASTM D523.

TABLE 1

As shown in Table 1, the weather-resistant thermoplastic resin was prepared so that the composition of the acrylic graft copolymer (A), the diene graft copolymer (B), and the aromatic vinyl-vinyl cyan copolymer (C) is within the scope of the present invention. When manufacturing, it can be seen that the impact strength of 15 or more, weather resistance (ΔE) of 2 or less, heat resistance of 103 ° C or more, glossiness of 60 or less have excellent characteristics.

In addition, by adding the amount of the diene graft copolymer (B) having an unsaturated π bond to an appropriate content or less, it was possible to minimize the problem of lowering the weather resistance.

Comparative Examples 1-7

In Comparative Example 1, the diene graft copolymer (B) component of the present invention was not used. In Comparative Example 2, an acrylic graft copolymer (A) and a heat-resistant aromatic vinyl-vinyl cyan copolymer (C) were used. It did not apply. Comparative Examples 3 and 5 are applied outside the ratio of the present invention. In Comparative Example 4, the heat-resistant aromatic vinyl-vinyl cyan copolymer (C) of the present invention was not applied. Comparative Examples 6 and 7 apply diene-based graft copolymers that deviate from the rubber particle size of the diene graft copolymer (B) of the present invention instead of the diene graft copolymer (B) of the present invention. Except for changing the content of each component as described in Table 2 was carried out in the same manner as in the above Example.

TABLE 2

As shown in Table 2, Comparative Example 1 in which the diene graft copolymer resin (B) is not included does not have unsaturated π bond and has excellent weather resistance, while showing high gloss in gloss. Not suitable for Comparative Example 2 composed of 100 parts by weight of a diene graft copolymer resin (B) having a matte property is excellent in terms of glossiness, but contains a large amount of unsaturated π bonds, and thus has poor weather resistance and good heat resistance characteristics. It is not suitable for the present invention. Comparative Example 3 in which the diene graft copolymer resin (B) content having a matte property is more than 30% by weight also contains a large amount of unsaturated π bonds, which is poor in weatherability. In Comparative Example 4, which does not include the aromatic vinyl-vinyl cyan copolymer (C) having heat resistance properties, weather resistance and low light properties were satisfied, and high impact strength was shown due to excessive rubber content, but the heat resistance properties were not good. In Comparative Example 5 in which the content of the acrylic graft copolymer (A) was less than 30 wt%, the low light and heat resistance were excellent, but the rubber content was low, so that the impact strength was lowered. In Comparative Example 6 in which a diene graft copolymer having a rubber particle diameter smaller than that of the diene graft copolymer (B) was applied, weather resistance and impact strength were satisfactory. Not good. In Comparative Example 7 in which a diene graft copolymer having a rubber particle diameter larger than that of the diene graft copolymer (B) was applied, satisfies weather resistance and low light characteristics, but impact strength was reduced due to too large rubber particle diameter. It became.

The present invention has the effect of providing a weather-resistant thermoplastic resin composition, which is excellent in fluidity, low light properties and impact resistance, and is excellent in fluidity, which is easy to mold various products such as electric and electronic products and automobiles.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (14)

(A) 30 to 60% by weight of the acrylic graft copolymer resin having an average rubber particle diameter of 0.05 to 1 µm; (B) 5 to 30% by weight of a diene graft copolymer resin having an average rubber particle diameter of 1 to 20 µm; And (C) 10 to 50% by weight of an aromatic vinyl compound-vinyl cyan compound copolymer resin; Weather resistant thermoplastic resin composition comprising a. The acrylic graft copolymer (A) is characterized in that 40 to 90% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer is grafted to 10 to 60% by weight of the (meth) acrylate rubber. Weather resistant thermoplastic resin composition. According to claim 2, wherein the (meth) acrylate rubber is a polymer of alkyl (meth) acrylate having 2 to 8 carbon atoms, the aromatic vinyl compound-vinyl cyan compound copolymer is 60 to 80% by weight of an aromatic vinyl compound and Weatherproof thermoplastic resin composition, characterized in that the copolymer of 20 to 40% by weight of the vinyl cyan compound. According to claim 1, wherein the diene graft copolymer resin (B) weather resistance, characterized in that 80 to 93% by weight of the aromatic vinyl compound-vinyl cyan compound copolymer is grafted to 7 to 20% by weight of the diene rubber. Thermoplastic resin composition. According to claim 4, wherein the diene rubber is 5 wt% styrene solution viscosity of 150 to 300 cps, the aromatic vinyl compound-vinyl cyan compound copolymer is 60 to 90% by weight aromatic vinyl compound and 10 to 40 vinyl cyan compound Weatherproof thermoplastic resin composition, characterized in that the copolymer by weight. The diene graft copolymer resin (B) according to claim 1, wherein the diene graft copolymer resin (B) has a 60 degree glossiness of 3 to 30% measured by a Gardner Gloss Meter on a 1/8 "thick specimen according to ASTM D523. Weather resistant thermoplastic resin composition, characterized in that. According to claim 1, wherein the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) is a copolymer of 60 to 80% by weight aromatic vinyl compound containing α-methylstyrene and 20 to 40% by weight of vinyl cyan compound Weather resistant thermoplastic resin composition. The monomer of claim 1, wherein the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) comprises 60 to 80% by weight of an aromatic vinyl compound including α-methylstyrene and 20 to 40% by weight of a vinyl cyan compound. It is a copolymer of 0.01-0.1 weight part of polyfunctional vinyl compounds with respect to a weight part, The weatherproof thermoplastic resin composition characterized by the above-mentioned. The method of claim 8, wherein the polyfunctional vinyl compound is composed of divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, diallyl phthalate, diallyl maleate, triallyl isocyanurate and mixtures thereof. Weather resistant thermoplastic resin composition, characterized in that selected from the group. The weatherproof thermoplastic resin composition according to claim 1, wherein the diene graft copolymer resin (B) and the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) are produced by continuous bulk polymerization. The weatherproof thermoplastic resin composition according to claim 1, wherein the aromatic vinyl compound-vinyl cyan compound copolymer resin (C) has a weight average molecular weight of 80,000 to 120,000 and a molecular weight distribution of 2.5 or less. According to claim 1, wherein the resin composition is flame retardant, antibacterial, antistatic agent, anti-drip agent, release agent, antioxidant, heat stabilizer, lubricant, UV stabilizer, impact modifier, filler, inorganic additives, stabilizers, pigments and dyes from the group Weather resistant thermoplastic resin composition comprising at least one selected additive. According to claim 1, wherein the resin composition has a weather resistance (ΔE) of 0.1 to 2 as measured by Weather-O-Meter (AT5000 Ci5000) by ASTM G155, 1/8 "thick specimen measured by ASTM D256 Vicat softening point (5kgf, 50) measured by ISO R306 with Izod impact strength of 15-80 kgfcm / cm, fluidity (220 ° C, 10kg) measured by ASTM D1238, 2.5-10 g / 10 min. ℃ / hr) is 103 to 150 ℃, weather resistant thermoplastic resin characterized in that the 60 degree glossiness measured by the Gardner Gloss Meter (1/8 "thick specimen according to ASTM D523) is 30 to 60% Composition. The molded article which shape | molded the resin composition of any one of Claims 1-13.