WO2012018166A1 - Weather-resistant thermoplastic resin composition with excellent low gloss characteristic, dimensional stability, and surface impact resistance - Google Patents

Abstract

The present invention relates to a weather-resistant thermoplastic resin composition with excellent low gloss characteristic, dimensional stability, and surface impact resistance. The composition comprises: a thermoplastic resin (A) containing (meth)acrylic acid alkyl ester polymer (a) and aromatic vinyl-vinyl cyanide copolymer (b); and acrylic-based graft resin (C) wherein the (meth)acrylic acid alkyl ester polymer (a) forms a dispersed phase in a network form, and the aromatic vinyl-vinyl cyanide copolymer (b) forms a continuous phase.

Description

Weather resistant thermoplastic resin composition with low light properties, dimensional stability and surface impact resistance

The present invention relates to weather resistant thermoplastic resin compositions. More specifically, the present invention relates to a weatherproof thermoplastic resin composition having excellent low light properties, dimensional stability, and surface impact by controlling the shape of the thermoplastic resin, and a method of manufacturing the same.

Generally, ABS (Acrylonitrile-Butadiene-Styrene) resin has excellent impact resistance and processability, and has excellent mechanical strength and heat deformation temperature, and because of its beautiful appearance, it can be used in automobiles, electrical / electronics, office equipment, home appliances, toys, It is widely used in various applications such as stationery. However, the butadiene-based rubber component used in the ABS resin contains a chemically labile double bond, and is easily aged by sunlight and ultraviolet rays. Therefore, ABS resin is used only for electric and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, window frames, leisure / household goods, sporting goods, automobile goods, etc., which are used outdoors. In order to improve the weather resistance of the ABS resin, a method of adding a weather stabilizer is used, but the effect is not great, and it is replaced by ASA (acrylate-styrene-acrylonitrile) resin using chemically stable acrylic rubber instead of butadiene rubber. Research is actively underway.

On the other hand, in recent years, due to environmental problems, there is a tendency to directly use thermoplastic resins without coating or painting, and the demand for low-light thermoplastic resins is increasing to satisfy the emotional quality level of consumers who prefer luxury appearance. have. In particular, the ASA resin requires a lot of low light characteristics due to the characteristics used outdoors. Conventional techniques for expressing low light characteristics have been used to emboss the surface of the molding or to apply a low gloss material. However, these methods have disadvantages of high processing cost and insufficient surface gloss. . Therefore, various attempts have been made to modify the ASA resin itself to express sufficiently low gloss.

In addition, since the ASA resin used outdoors is often co-extruded with a material having a low linear thermal expansion coefficient such as PVC, there have been attempts to eliminate the warpage of the molded product by lowering the linear thermal expansion coefficient of the ASA resin.

US Pat. No. 6,696,165 adds 0.1 to 20 parts by weight of a crystalline polymer represented by polyalkyl terephthalate, and US Pat. No. 6,395,828 adds 0.5 to 15 parts by weight of a compound produced by the reaction of an epoxy and an amine compound to ASA. A method of lowering the gloss of resin is disclosed.

U.S. Pat.Nos. 5,475,053, 4,652,614 and the like disclose a method of lowering the gloss of resin using a spherical graft copolymer as a matting agent, and U.S. Pat. 2008-0036790 et al. Discloses a method of lowering the gloss using various copolymers as additives.

In addition, US Pat. Nos. 4,668,737 and 5,237,004 disclose a method of lowering gloss using rubber particles having a large particle diameter of a core / shell structure of 0.05-20 μm or 2-15 μm.

However, in the case of using the additive as described above, not only the manufacturing cost increases but also a problem of peeling, a reduction in surface impact, and a part of gloss may occur. In addition, the use of large rubber particles has the advantage that the gloss is lowered, but the impact strength is sharply worsened.

Meanwhile, ASA resins are manufactured by conventional techniques as disclosed in U.S. Patent Nos. 3,426,101, 6,187,862, Japanese Patent Laid-Open No. 7-316243, Korean Patent No. 10-0440474, and Korean Patent Application No. 2006-0051425. Method for preparing an alkyl acrylate-based latex core, graft polymerization of styrene and acrylonitrile on the core outer layer to produce a graft polymer and melt kneading the prepared graft polymer and styrene-based thermoplastic resin is average. However, manufacturing the ASA resin with such a multi-step manufacturing method has a disadvantage in that the manufacturing cost increases, and color characteristics are deteriorated due to various emulsifiers and stabilizers used in the latex manufacturing process.

In U.S. Pat. Disclosed is a method for producing an ASA resin by a method of converting the same. However, this method is not suitable for commercial use and has the disadvantage of requiring additional recovery of the final product from the suspension.

Korean Laid-Open Patent Publication No. 2009-0073608 discloses a method of improving the dimensional stability of weather resistant resin by adding 5 to 40% by weight of glass fiber, but this method may be effective in improving the dimensional stability of injection molded articles. However, in the case of manufacturing an extruded molded article alone, or in the case of manufacturing a molded article by co-extrusion with other materials such as PVC, the extrudability is not good, the surface properties are bad.

As described above, many technical attempts have been made to improve low light properties, dimensional stability, and surface impact properties of the ASA resin having excellent weather resistance, but the conventional technology has not obtained sufficient effects.

The present invention has been made to solve the above problems, and an object of the present invention is to provide a weather resistant thermoplastic resin composition excellent in low light properties, dimensional stability and surface impact properties.

It is another object of the present invention to provide a method for producing a weather resistant thermoplastic resin composition having excellent low light properties, dimensional stability and surface impact properties.

In one embodiment, the present invention provides a thermoplastic resin (A) comprising a (meth) acrylic acid alkyl ester polymer (a) and an aromatic vinyl-vinyl cyanide copolymer (b); And an acrylic graft resin (B), wherein the (meth) acrylic acid alkyl ester polymer (a) forms a network-shaped dispersion phase, and the aromatic vinyl-vinyl cyanide copolymer (b) forms a continuous phase. The present invention relates to a weather resistant thermoplastic resin composition having excellent low light characteristics, dimensional stability and surface impact properties.

The thermoplastic resin (A) of the present invention comprises about 5 to about 35 wt% of the (meth) acrylic acid alkyl ester polymer (a) and about 65 to about 95 wt% of the aromatic vinyl-vinyl cyanide copolymer (b). It may include.

In addition, the (meth) acrylic acid alkyl ester polymer (a) may include a unit derived from a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, and a compound having two or more hydroxyl groups. In addition, the mixture may further include an aromatic vinyl compound and a vinyl cyanide compound. The specific content of each component constituting the mixture is about 60 to about 95 wt% of the (meth) acrylic acid alkyl ester compound, about 1 to about 20 wt% of the unsaturated carboxylic acid or anhydride thereof, and about 0 to about 20 of the aromatic vinylic compound. Weight%, and about 0 to about 10 weight% of a vinyl cyanide compound, wherein the compound having two or more hydroxy groups is preferably polymerized in a ratio of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof. Do.

In addition, the (meth) acrylic acid alkyl ester polymer (a) includes a (meth) acrylic acid alkyl ester unit and an unsaturated carboxylic acid or its anhydride unit as a main chain, and the carboxyl group of the unsaturated carboxylic acid or its anhydride unit is 2 The compound having two or more hydroxy groups is connected by an ester bond, so that the (meth) acrylic acid alkyl ester polymer (a) chains are connected to each other to form a network-shaped dispersed phase.

The aromatic vinyl cyanide copolymer (b) of the present invention may be prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound, and may be polymerized by further including an (meth) acrylic acid alkyl ester compound. At this time, each component of the polymer is contained in about 60 to about 95% by weight of the aromatic vinyl compound, about 5 to about 40% by weight of the vinyl cyanide compound, and about 0 to about 10% by weight of the (meth) acrylic acid alkyl ester compound. Can be. The weight average molecular weight of the aromatic vinyl cyanide copolymer (b) may be about 150,000 to about 300,000 g / mol.

The acrylic graft resin (B) of the present invention may be prepared by graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in a (meth) acrylic rubber, preferably a (meth) acrylic rubber From about 10 to about 60% by weight of the aromatic vinyl compound-vinyl cyanide compound copolymer is about 40 to about 90% by weight grafted copolymer. In addition, the average rubber particle diameter of the acrylic graft resin (B) is preferably about 0.05 to about 1 ㎛.

The weatherable thermoplastic resin of the present invention is a thermoplastic resin (A) comprising a (meth) acrylic acid alkyl ester polymer (a) forming a network-shaped dispersed phase and an aromatic vinyl-vinyl cyanide copolymer (b) forming a continuous phase. 70 to about 85 parts by weight and about 15 to about 30 parts by weight of the acrylic graft resin (B) may be prepared by melt mixing. The weatherable thermoplastic resin thus prepared is characterized in that the rubber particles of the acrylic graft resin (B) are dispersed in a resin component constituting a continuous phase and a network-shaped dispersed phase, resulting in an excellent surface impact improvement effect.

In another aspect, the present invention is to polymerize the first monomer mixture comprising a (meth) acrylic acid alkyl ester compound and a saturated carboxylic acid or its anhydride continuously to the first reactor of a plurality of reactors connected in series to polymerize step; Preparing a thermoplastic resin (A) by continuously adding the polymer, a second monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound, and a compound having two or more hydroxy groups to a second reactor to polymerize the polymer; Apart from the above step, polymerizing an aromatic vinyl compound and a vinyl cyanide compound to an acrylic rubber to prepare an acrylic graft resin (B); And melting and mixing the thermoplastic resin (A) and the acrylic graft resin (B). The present invention relates to a method of manufacturing a weather resistant thermoplastic resin composition having excellent low light characteristics, dimensional stability, and surface impact resistance.

The thermoplastic resin composition according to the present invention may adjust the shape of the ASA (acrylate-styrene-acrylonitrile) resin and disperse and apply rubber particles, thereby providing excellent physical properties such as weather resistance, heat resistance, peeling properties, yellowness, fluidity, and the like. In addition, it is characterized by having excellent low light properties, dimensional stability and surface impact at the same time.

Therefore, various exterior materials and components requiring weather resistance, low light characteristics and surface impact at the same time, in particular, electrical and electronic components, agricultural equipment materials, road signs, building materials, door panels, window frames, leisure / household goods, sports It can be usefully applied in the manufacture of articles, automobile articles and the like.

The weather resistance thermoplastic resin composition excellent in the low light characteristic, the dimensional stability, and the surface impact property of the present invention is a thermoplastic resin (A) comprising a (meth) acrylic acid alkyl ester polymer (a) and an aromatic vinyl-vinyl cyanide copolymer (b); And an acrylic graft resin (B), wherein the (meth) acrylic acid alkyl ester polymer (a) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (b) forms a continuous phase. It is characterized by.

Hereinafter, the configuration of the present invention in more detail.

(A) thermoplastic resin

The thermoplastic resin composition may include about 5 wt% to about 35 wt% of the (meth) acrylic acid alkyl ester polymer (a) and about 65 wt% to about 95 wt% of the aromatic vinyl-vinyl cyanide copolymer (b). Comprises about 5% to about 25% by weight of the (meth) acrylic acid alkyl ester polymer (a) and about 75% to about 95% by weight of the aromatic vinyl-vinyl cyanide copolymer (b). In the content range, it is possible to obtain a simultaneous improvement effect of low light properties and dimensional stability and surface impact.

The (meth) acrylic acid alkyl ester polymer (a) forming a network-shaped dispersed phase in the thermoplastic resin composition of the present invention is a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or anhydride thereof, and a compound having two or more hydroxyl groups. It characterized in that it comprises a unit derived from. Specifically, the (meth) acrylic acid alkyl ester compound and an unsaturated carboxylic acid or anhydride thereof are polymerized to include (meth) acrylic acid alkyl ester units and unsaturated carboxylic acid or anhydride units thereof as a main chain, and thus (meth) acrylic acid The chains of the alkyl ester polymer (a) are constituted. And the carboxyl group of the said unsaturated carboxylic acid or its anhydride unit is connected by the hydroxyl group and ester bond of the compound which has the said 2 or more hydroxyl group. Accordingly, the chains of the (meth) acrylic acid alkyl ester polymer (a) are connected to each other to form a dispersed phase.

In addition, the mixture for preparing the (meth) acrylic acid alkyl ester polymer (a) may further include an aromatic vinyl compound and a vinyl cyanide compound. In this case, the specific content of each component constituting the mixture is about 60 to about 95 wt% of the (meth) acrylic acid alkyl ester compound, about 1 to about 20 wt% of the unsaturated carboxylic acid or anhydride thereof, and about 0 to about about aromatic vinyl compound 20 wt%, and about 0 to about 10 wt% of a vinyl cyanide compound, wherein the compound having two or more hydroxy groups is polymerized at a ratio of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof. desirable. More preferably, about 75% to about 95% by weight of the (meth) acrylic acid alkyl ester compound, about 1% to about 10% by weight of an unsaturated carboxylic acid or anhydride thereof, about 1% to about 10% by weight of an aromatic vinyl compound, and a vinyl cyanide compound About 1 to about 8% by weight, the compound having two or more hydroxy groups may be polymerized in a ratio of about 0.1 to about 2.5 equivalents relative to the unsaturated carboxylic acid or anhydride thereof. Most preferably, about 80% to about 95% by weight of (meth) acrylic acid alkyl ester compound, about 1% to about 5% by weight of unsaturated carboxylic acid or anhydride thereof, about 2% to about 8% by weight of aromatic vinyl compound, and vinyl cyanide compound About 1 to about 5% by weight, the compound having two or more hydroxy groups may be polymerized in a ratio of about 0.5 to about 2.0 equivalents relative to the unsaturated carboxylic acid or anhydride thereof.

When the content of each component is included in the above composition range, the thermoplastic resin composition can sufficiently express weather resistance, low light properties, dimensional stability and surface impact properties. In particular, when the equivalence ratio of the compound having two or more hydroxy groups relative to the unsaturated carboxylic acid or anhydride thereof is about 0.1 to about 3, the connection between the polymer (a) chains is sufficient to form a network-shaped dispersed phase. In addition, the compound having two or more hydroxyl groups that do not participate in the reaction when the excessive input is present in the continuous phase to act as a plasticizer to prevent the heat resistance deteriorates sharply.

It is preferable that the (meth) acrylic-acid alkylester compound which comprises the said (meth) acrylic-acid alkylester type polymer (a) is a (meth) acrylic-acid alkylester compound which has a C1-C10 alkyl group. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethyl hexyl methacrylate Latex, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate and the like can be used, preferably butyl Acrylate, but is not necessarily limited thereto. These may be applied alone or in mixture of two or more.

As the aromatic vinyl compound, styrene, alphamethyl styrene, α-methyl styrene, p-methyl styrene, or the like may be used, and preferably, styrene, but is not limited thereto. These may be applied alone or in mixture of two or more.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like may be used, and preferably acrylonitrile, but is not limited thereto. These may be applied alone or in mixture of two or more.

The unsaturated carboxylic acid or anhydride thereof may include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, fumaric anhydride, and the like. May be used, preferably acrylic acid, but is not necessarily limited thereto. These may be applied alone or in mixture of two or more.

It is preferable that the compound which has the said 2 or more hydroxyl group has 2-10 hydroxyl groups, and it is more preferable that it has 2-5 hydroxyl groups. In addition, the compound having two or more hydroxy groups is preferably a saturated compound in which all carbon atoms in the molecule are bonded with only a single bond. Examples of the compound having two or more hydroxy groups include alkanediols having 2 to 10 carbon atoms, polyalkylene glycols, polyols, mixtures thereof, and the like. These may be applied alone or in mixture of two or more. Examples of the alkanediol having 2 to 10 carbon atoms include ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, and 1,8- Octanediol and the like, but is not necessarily limited thereto. Examples of the polyalkylene glycol may include polyethylene glycol, polypropylene glycol, and the like, and polyethylene glycol (PEG) may include PEG300, PEG600, PEG1500, etc., depending on molecular weight, without being limited thereto. Examples of the polyol include xylitol, glycerin, erythitol, sorbitol, and acrylic or ether polyols having a hydroxy value of about 50 to 500 and a molecular weight of about 500 to 5000, and the like. Do not.

The aromatic vinyl-vinyl cyanide copolymer (b) forming the continuous phase of the thermoplastic resin composition of the present invention may be prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound, and adding a (meth) acrylic acid alkyl ester compound. It can be included and polymerized. Each component constituting the aromatic vinyl-vinyl cyanide copolymer (b) includes about 60 to about 95 wt% of an aromatic vinyl compound, about 5 to about 40 wt% of a vinyl cyanide compound, and a (meth) acrylic acid alkyl ester compound. It can be included in the polymerization of about 0 to about 10% by weight, preferably about 60 to about 84% by weight of the aromatic vinyl compound, about 15 to 35% by weight of the vinyl cyanide compound, and (meth) acrylic acid alkyl ester compound About 1 to about 5 weight percent. When the content of each component is included in the composition range, there is an advantage that the basic physical properties of the weather resistance thermoplastic resin composition, such as impact resistance, yellowness, flow characteristics, etc. does not change rapidly and is stable.

Styrene, alphamethyl styrene, paramethyl styrene, etc. may be used as the aromatic vinyl compound constituting the aromatic vinyl-vinyl cyanide copolymer (b), but is preferably styrene, but is not necessarily limited thereto. These may be applied alone or in mixture of two or more.

Acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like may be used as the vinyl cyanide compound used in the aromatic vinyl-vinyl cyanide copolymer (b). It is not limited. These may be applied alone or in mixture of two or more.

The (meth) acrylic acid alkyl ester compound constituting the aromatic vinyl-vinyl cyanide copolymer (b) is preferably a (meth) acrylic acid alkyl ester compound having an alkyl group having 1 to 10 carbon atoms. For example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethyl hexyl methacrylate Latex, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate and the like can be used, preferably butyl Acrylate, but is not necessarily limited thereto. These may be applied alone or in mixture of two or more.

The weight average molecular weight of the aromatic vinyl cyanide copolymer (b) is about 150,000 to about 300,000 g / mol, preferably about 180,000 to about 250,000 g / mol. It is possible to secure the size of the appropriate dispersed phase in the weight average molecular weight range, there is no peeling, there is an advantage in excellent impact strength and low light properties.

The thermoplastic resin (A) according to the present invention can be produced by continuous bulk polymerization. In general, the dispersion phase described above is not easy to be prepared by the method of emulsion polymerization or suspension polymerization, which is a method of preparing a rubber phase, and separately prepared aromatic vinyl-vinyl cyanide copolymers constituting the continuous phase. This is because it is difficult to efficiently manufacture a weather resistant thermoplastic resin composition having excellent low light characteristics because the final product must be manufactured by a method such as melt extrusion.

(B) Acrylic Graft Resin

The acrylic graft resin (B) of the present invention may be prepared by graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in a (meth) acrylic rubber, preferably a (meth) acrylic rubber About 40 to about 90 weight percent of an aromatic vinyl compound-vinyl cyanide compound copolymer is grafted to 10 to about 60 weight percent of the copolymer. Within this content range it is possible to ensure the appropriate impact strength and fluidity. The polymerization method of the acrylic graft resin may be used a conventional method known in the art, for example, emulsion polymerization, suspension polymerization and the like is possible, preferably emulsified graft polymerization method is used.

As the acrylic rubber for preparing the acrylic graft copolymer (B), 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, Preferably butyl acrylate. These can be used individually or in mixture of 2 or more types.

The average particle diameter of the acrylic rubber particles may range from about 0.05 to about 1 μm, preferably from about 0.07 to about 0.7 μm, more preferably from about 0.1 to about 0.5 μm. Appropriate impact strength can be secured in the average particle size range.

The aromatic vinyl compound-vinyl cyanide compound copolymer grafted to the acrylic rubber may be a copolymer of about 60 to about 80 wt% of the aromatic vinyl compound and about 20 to about 40 wt% of the vinyl cyanide compound. Within this content range it is possible to ensure the appropriate impact strength and fluidity.

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

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

The thermoplastic resin composition of the present invention has very low light properties compared to conventional weather resistant thermoplastic resin compositions. Preferably, the thermoplastic resin composition has a glossiness of about 30 or less, preferably about 21 or less, measured using a 75 degree gloss machine.

The thermoplastic resin composition of the present invention has very excellent dimensional stability as compared to the conventional weather resistant thermoplastic resin composition. Preferably, the thermoplastic resin composition has a CLTE (Coefficient of Linear Thermal Expansion) measured at a temperature range of 20 ° C. to 130 ° C. according to ASTM D 696, about 100 μm / m ° C. or less.

The thermoplastic resin composition according to the present invention has excellent low light properties, dimensional stability and surface impact, while maintaining excellent fluidity, heat resistance, peeling properties, yellowness, and the like, which are basic physical properties of weatherable thermoplastic resins. Therefore, the thermoplastic resin may be widely used in electrical and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, window frames, leisure / biochemical products, sporting goods, automobile products, etc. which require both weather resistance, low light characteristics, and surface impact properties. have.

As a method of molding the thermoplastic resin composition according to the present invention to manufacture such products, (co) extrusion, injection or casting may be widely applied, but is not necessarily limited thereto. The molding method can be easily carried out by those skilled in the art.

On the other hand, the thermoplastic resin composition according to the present invention can be prepared according to the method for producing a thermoplastic resin composition according to the present invention to be described later.

The weatherproof thermoplastic resin composition having excellent low light properties, dimensional stability, and surface impact properties of the present invention comprises a plurality of reactors connected in series with a first monomer mixture comprising a (meth) acrylic acid alkyl ester compound and a saturated carboxylic acid or anhydride thereof. Continuously adding to the first reactor in the polymerization; Preparing a thermoplastic resin (A) by continuously adding the polymer, a second monomer mixture including an aromatic vinyl compound and a vinyl cyanide compound, and a compound having two or more hydroxy groups to a second reactor to polymerize the polymer; Apart from the above step, polymerizing an aromatic vinyl compound and a vinyl cyanide compound to an acrylic rubber to prepare an acrylic graft resin (B); And melting and mixing the thermoplastic resin (A) and the acrylic graft resin (B).

Thermoplastic resin (A) manufacturing step

First, the thermoplastic resin (A) is prepared, specifically, a (meth) acrylic acid alkyl ester compound and an unsaturated carboxylic acid or anhydride thereof are mixed to prepare a first monomer mixture. The first monomer mixture is continuously added to a first reactor of a plurality of reactors connected in series to polymerize the first monomer mixture to prepare a polymer. The first monomer mixture may optionally further include an aromatic vinyl compound and a vinyl cyanide compound. Preferably the first monomer mixture is about 60 to about 95 weight percent of the (meth) acrylic acid alkyl ester compound, about 1 to about 20 weight percent of the unsaturated carboxylic acid or anhydride thereof, and about 0 to about 20 weight percent of the aromatic vinylic compound. And about 0 wt% to about 10 wt% of the vinyl cyanide compound. When the content of each component in the first monomer mixture is included in the composition range, the final thermoplastic resin composition may sufficiently exhibit weatherability, low light properties, and dimensional stability.

The (meth) acrylic acid alkyl ester compound and the unsaturated carboxylic acid or anhydride thereof contained in the first monomer mixture make up the main chain of the (meth) acrylic acid alkyl ester polymer (a) through a polymerization reaction in the first reactor. do. In addition, when the first monomer mixture further includes an aromatic vinyl compound and a vinyl cyanide compound, the chains of the polymer (a) further include an aromatic vinyl compound unit and a vinyl cyanide compound unit.

When the polymer is prepared from the first monomer mixture in the first reactor, the polymer is continuously introduced into the second reactor, and at the same time, the second monomer mixture containing the aromatic vinyl compound and the vinyl cyanide compound and two or more hydroxy groups are added. The compound having is continuously introduced into the second reactor. And the polymer, the second monomer mixture and the compound having two or more hydroxy groups are polymerized in a second reactor. The second monomer mixture may optionally further comprise a (meth) acrylic acid alkyl ester compound. Preferably, the second monomer mixture comprises about 60 to about 95 weight percent of an aromatic vinyl compound, about 5 to about 40 weight% of a vinyl cyanide compound, and about 0 to about 10 weight% of a (meth) acrylic acid alkyl ester compound. can do. When the content of each component in the second monomer mixture is included in the composition range, the surface impact properties, yellowness, flow characteristics, etc., which are basic physical properties of the thermoplastic resin composition, do not change rapidly and have a stable advantage.

The polymerized polymer in the first reactor is reacted with a compound having two or more hydroxyl groups in the second reactor to form a network-shaped dispersed phase. Specifically, the carboxyl groups present in the unsaturated carboxylic acid or anhydride units included in the chains of the polymerized polymer in the first reactor are connected by ester bonds with the hydroxy groups present in the compound having two or more hydroxy groups to form a network. It forms a dispersed phase and expresses excellent low light characteristics. In addition, a second monomer mixture comprising an aromatic vinyl compound, a vinyl cyanide compound, and optionally a (meth) acrylic acid alkyl ester compound is polymerized in a second reactor to form a continuous phase.

Each component introduced into the first reactor and the second reactor is the same as described in the (meth) acrylic acid alkyl ester polymer (a) and the aromatic vinyl-vinyl cyanide copolymer (b), and thus will be omitted to avoid duplication.

In the production method of the present invention, the polymerization conversion rate from the first reactor to the polymer is preferably about 85 to about 95%, more preferably about 90 to about 95%. When the polymerization conversion rate in the first reactor is in the above range, almost no unreacted material remains, so that the dispersion phase is easily formed in a subsequent reaction, and the polymerization time is appropriate, thereby saving manufacturing costs.

The first monomer mixture is polymerized by being introduced into the first reactor together with the initiator, and optionally, a solvent and a molecular weight modifier may be further used. In addition, the second monomer mixture is also introduced into the second reactor with the initiator and polymerized, and optionally, a solvent and a molecular weight regulator may be further used.

In the first reactor, the solvent is preferably added in an amount of about 5 to about 200 parts by weight, the initiator is added in an amount of about 0.1 to about 0.4 parts by weight, and the molecular weight regulator is about 100 parts by weight of the first monomer mixture. It is preferably added in an amount of 0 to about 0.2 parts by weight. In the second reactor, the solvent is preferably added in an amount of about 0 to about 20 parts by weight, the initiator is added in an amount of about 0.01 to about 0.05 parts by weight, and the molecular weight regulator, based on 100 parts by weight of the second monomer mixture. Is preferably added in an amount of about 0 to about 0.5 parts by weight.

Ethylbenzene, xylene, toluene, methyl ethyl ketone and the like may be used as the solvent, but are not necessarily limited thereto. These may be applied alone or in mixture of two or more. The solvent may be used for effective heat transfer and stirring of the reactants in the polymerization process.

Examples of the initiator include azobisisobutyronitrile, benzoyl peroxide, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2 -Bis (4,4-di-t-butylperoxy cyclohexane) propane, t-hexyl peroxy isopropyl monocarbonate, t-butyl peroxymaleic acid, t-butyl peroxy-3,5,5-trimethyl Hexanoate, t-butyl peroxylaurate, 2,5-dimethyl-2,5-bis (m-toluoyl peroxy) hexane, t-butyl peroxy isopropyl monocarbonate, t-butyl peroxy 2- Ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, 2,2-bis (t-butyl peroxy) Butane, t-butyl peroxybenzoate, n-butyl-4,4-bis (t-butyl peroxy) valerate and mixtures thereof may be selected and used, but are not necessarily limited thereto.

As the molecular weight modifier, t-dodecyl mercaptan, n-dodecyl mercaptan and mixtures thereof may be used, but are not necessarily limited thereto. The molecular weight modifier serves to control the molecular weight of the dispersed phase.

In addition, in the above production method of the invention, the reaction temperature of the first reactor is preferably about 60 ~ 120 ℃, more preferably about 70 ~ 100 ℃. The residence time in the first reactor is preferably about 6 to 10 hours, more preferably about 7 to 9 hours. In addition, the reaction temperature of the second reactor is preferably about 90 ~ 130 ℃, more preferably about 100 ~ 120 ℃. The residence time in the second reactor is preferably about 1 to 4 hours, more preferably about 1 to 3 hours.

In the present invention, about 5 to about 15% by weight of the reactant introduced into the second reactor is polymerized in the first reactor, and the sum of the second monomer mixture and the compound having two or more hydroxy groups is about 85 to about 95 weight It is desirable to adjust the flow rate to be in%. When the composition of the reactant introduced into the second reactor is adjusted as described above, about 5 to about 35 wt% of the (meth) acrylic acid alkyl ester polymer (a) and the aromatic vinyl-vinyl cyanide copolymer (b) about 65 to about 95 A thermoplastic resin (A) comprising weight percent can be prepared.

In addition, the compound having two or more hydroxyl groups to be added to the second reactor is preferably added in an amount of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or an anhydride thereof added to the first reactor, it is preferably about 0.1 to about 2.5 equivalents It is more preferable to add in an amount of about 0.5 to about 2.0 equivalents, and more preferably. When the compound having two or more hydroxy groups is introduced in the equivalent ratio range relative to the unsaturated carboxylic acid or its anhydride, the connection between the (meth) acrylic acid alkyl ester polymer (a) chains is sufficient to form a dispersed phase, Compounds having two or more carboxyl groups or compounds having two or more hydroxy groups which do not participate in the reaction when excessively present are present in the continuous phase to act like a plasticizer, thereby preventing the heat resistance from deteriorating rapidly.

In the present invention, the plurality of reactors are composed of about 2 to 5 reactors, the polymerization is preferably carried out continuously through each reactor.

And the final polymerization conversion rate in the final reactor where the thermoplastic resin (A) polymerization is finished is preferably about 50 to about 70%, more preferably about 50 to about 65%. When the final polymerization conversion rate is in the above range, the amount of the thermoplastic resin composition produced per unit time is appropriately commercially useful, there is an advantage that it is easy to control and transfer the heat of reaction by maintaining the appropriate viscosity.

In addition, after preparing the final polymer consisting of a dispersed phase and a continuous phase through a continuous polymerization process in a plurality of reactors as described above, using a devolatilization tank of high temperature and vacuum state to separate the unreacted material from the final polymer further It may include.

Acrylic graft resin (B) manufacturing step

This step is separate from the thermoplastic resin (A) manufacturing step, the acrylic graft resin (B) is prepared by polymerizing an aromatic vinyl compound and a vinyl cyanide compound on the acrylic rubber. Preferably, about 10 to about 60 parts by weight of the acrylic synthetic rubber may be prepared by a conventional emulsion graft polymerization method by mixing about 90 to about 40 parts by weight of an aromatic vinyl compound and a vinyl cyanide compound mixture.

The acrylic synthetic rubber for preparing the acrylic graft resin (B) is preferably synthesized from alkyl acrylate having 2 to 8 carbon atoms. The average particle diameter of the acrylic synthetic rubber particles may be in the range of about 0.05 to about 1 μm, preferably about 0.1 to about 0.5 μm. When the average particle diameter of the particles is in the above range it can implement a suitable impact strength.

The aromatic vinyl compound and the vinyl cyanide compound mixture are used in an amount of about 80 to about 60 parts by weight of the aromatic vinyl compound, and about 20 to about 40 parts by weight of the vinyl cyanide compound, and the aromatic vinyl compound-vinyl cyanide compound grafted on the acrylic synthetic rubber Preferably, the coalescence is from about 40 to about 70 parts by weight relative to the total acrylic rubber. The alkyl acrylate, the aromatic vinyl compound, the vinyl cyanide compound, and the like are the same as those described for the acrylic graft resin (B), and are omitted to avoid duplication.

Melt mixing step of thermoplastic resin (A) and acrylic graft resin (B)

In this step, the thermoplastic resin (A) and the acrylic graft resin (B) are melt mixed to prepare a final weather resistant thermoplastic resin. At this time, it is preferable to add 70 to 85 parts by weight of the thermoplastic resin (A) and about 15 to about 30 parts by weight of the acrylic graft resin (B) to melt-mix. It is possible to secure the appropriate impact resistance, low light properties, heat resistance and dimensional stability of the weather-resistant thermoplastic resin in the above content range.

The shape of the weather resistant thermoplastic resin produced by the production method of the present invention is a (meth) acrylic acid alkyl ester-based polymer (a) in the aromatic vinyl-vinyl cyanide-based copolymer (b) in which the continuous phase, but the chain is They are connected to each other and have a network shape. The dispersed phases are connected to each other by ester bonds. In addition, the rubber particles of the acrylic graft resin (B) are thermoplastic resins comprising a (meth) acrylic acid alkyl ester polymer (a) forming a network-shaped dispersed phase and an aromatic vinyl-vinyl cyanide copolymer (b) forming a continuous phase. It forms a dispersed phase within.

The weatherable thermoplastic resin composition of the present invention may include general additives such as antioxidants, heat stabilizers, lubricants, UV stabilizers, impact modifiers, fillers, inorganic additives, stabilizers, pigments, dyes, and the like, and the general additives added may include the weatherable thermoplastics. It can be used within the range of about 0 to about 20 parts by weight based on 100 parts by weight of the resin.

The weatherable thermoplastic resin produced by the above method is excellent in physical properties such as weather resistance, heat resistance, peeling properties, yellowness, flowability, and at the same time, has excellent low light properties, dimensional stability and surface impact properties.

Hereinafter, the configuration and operation of the present invention through the preferred embodiment of the present invention will be described in more detail. However, the following examples are provided to help the understanding of the present invention, and the scope of the present invention is not limited to the following examples. Details that are not described herein will be omitted since those skilled in the art can sufficiently infer technically.

Production Examples 1-4, Comparative Production Examples 1-3. Manufacture of thermoplastic resin (A)

To prepare a thermoplastic resin (A) in the composition of Table 1 and Table 2, the specific manufacturing method is as follows.

Preparation Example 1

100 parts by weight of toluene in 100 parts by weight of the first monomer mixture consisting of 90 parts by weight of butyl acrylate (BA), 5 parts by weight of styrene (SM), 2 parts by weight of acrylonitrile (AN) and 3 parts by weight of acrylic acid (AA). Part 1, 0.2 parts by weight of benzoyl peroxide (BPO) and 0.05 parts by weight of t-dodecyl mercaptan (TDM) were mixed to prepare a first reactant. The prepared first reactant was introduced at a rate of 1 kg / hr into the first reactor (R-1) of a continuous polymerization reactor in which three reactors, in which a jacket is installed and easy to control reaction temperature, were connected in series. The polymerization was prepared by allowing the polymerization to proceed. At this time, the polymerization conversion rate was 90%, and the polymer produced in the first reactor (R-1) was continuously added to the second reactor (R-2) of the continuous polymerization reactor.

And 10 parts by weight of toluene, 100 parts by weight of the second monomer mixture consisting of 72 parts by weight of styrene (SM), 25 parts by weight of acrylonitrile (AN), 3 parts by weight of butyl acrylate (BA), 1,1-bis (t- A second reactant by mixing 0.02 part by weight of butylperoxy) cyclohexane (PHX-C), 0.1 part by weight of t-dodecyl mercaptan (TDM), and 1.47 part by weight (1.0 equivalent ratio) of polyethylene glycol (PEG600) having a molecular weight of 600 Was prepared. The prepared second reactant was introduced into the second reactor (R-2) of the continuous polymerization reactor at a rate of 8.5 kg / hr, and polymerization was performed at 110 ° C. for 2 hours at a residence time to prepare a polymer. At this time, the polymerization conversion rate was 25%.

The polymer produced in the second reactor (R-2) was continuously added to the third reactor (R-3) of the continuous polymerization reactor to proceed for 2 hours residence time at 130 ℃ temperature. The polymerization conversion rate at this time was 55%.

The polymerization product discharged from the third reactor (R-3) was continuously added to a devolatilization tank maintained at 240 ° C. and 20 Torr to remove unreacted monomers and solvents, and pelletized using a pelletizer. Resin (A) was prepared.

Preparation Example 2

Polyethylene glycol (PEG600) thermoplastic resin (A) in the same manner as in Preparation Example 1, except that 0.33 parts by weight (1.5 equivalents) of 1,4-butanediol (1,4-BDO) was used instead of 1.47 parts by weight (1.0 equivalent). ) Was prepared.

Preparation Example 3

A thermoplastic resin (A) was prepared in the same manner as in Preparation Example 1, except that 1.84 parts by weight (0.5 equivalents) of polyethylene glycol (PEG1500) having a molecular weight of 1500 was used instead of 1.47 parts by weight (1.0 equivalents) of polyethylene glycol (PEG600).

Preparation Example 4

100 parts by weight of toluene, 100 parts by weight of the first monomer mixture consisting of 88 parts by weight of butyl acrylate (BA), 5 parts by weight of styrene (SM), 2 parts by weight of acrylonitrile (AN) and 5 parts by weight of methacrylic acid (MAA), 0.15 parts by weight of benzoyl peroxide (BPO) and 0.05 parts by weight of t-dodecyl mercaptan (TDM) were mixed to prepare a first reactant, which was fed to the first reactor (R-1) of the continuous polymerization reactor at a rate of 1 kg / hr. The polymerization was carried out at 85 ° C. for 8 hours, and the polymerization was carried out in the same manner as in Preparation Example 1 except that the polymerization conversion rate in the first reactor (R-1) was 94%. ) Was prepared.

Comparative Production Example 1

A thermoplastic resin (A) was prepared in the same manner as in Preparation Example 1, except that polyethylene glycol (PEG600) was not used at all.

Comparative Production Example 2

A thermoplastic resin (A) was prepared in the same manner as in Preparation Example 1, except that acrylic acid (AA) was not used at all.

Comparative Production Example 3

Polyethylene glycol (PEG600) A thermoplastic resin (A) was prepared in the same manner as in Preparation Example 1, except that 5.15 parts by weight (3.5 equivalent ratio) was used instead of 1.47 parts by weight (1.0 equivalent ratio).

Table 1

TABLE 2

Examples 1-7, Comparative Examples 1-6. Manufacture of thermoplastic resin (A) and acrylic graft resin (B) mixed resin

Thermoplastic resin (A) prepared by the method of the above production example and comparative production example, two kinds of acrylic graft resin (B) commercially produced by Cheil Industries Co., Ltd. (brand name: CHAS, CHAT) and aromatic vinyl-vinyl cyanide Using one copolymer (trade name: HR-5330) by melting and mixing in the compositions of various Examples 1 to 7 and Comparative Examples 1 to 6 as shown in Table 3 to produce a final thermoplastic resin.

Equal amounts of antioxidants (Di-Stearyl-Pentaerythritol-Diphosphite), heat stabilizers (Octadecyl 3- (3,5-Di, T, Butyl-4-hydrixy phenyl) propionate), lubricants (Magnesium Stearate, EBS), UV stabilizers (Bis (2,2,6,6-Tetramethyl-4-piperidyl) sebacate) and the like were then melted, kneaded and extruded to prepare pellets. At this time, the extrusion was used L / D = 32, 25mm diameter twin screw extruder, the cylinder temperature was set to 220 ℃.

CHAS of Cheil Industries is an acrylic graft resin in which 57 parts by weight of a styrene-acrylonitrile copolymer is grafted to 43 parts by weight of butyl acrylate rubber, and CHAT is styrene-acrylic to 50 parts by weight of butyl acrylate rubber. It is an acryl-type graft resin in which 50 parts by weight of a ronitrile copolymer is grafted.

Cheil Industries HR-5330 is a styrene-acrylonitrile copolymer composed of 72 parts by weight of styrene and 28 parts by weight of acrylonitrile.

Experimental Example Property evaluation

The fluidity was measured by the resin pellets prepared in Examples 1 to 7 and Comparative Examples 1 to 6, and injection molding was carried out to prepare a specimen for measuring physical properties, and physical properties such as Izod impact strength, yellowness, and Vicat softening point were measured. In addition, the thermoplastic resin was manufactured into an extruded sheet having a thickness of 1 mm using a T-die at 190 ° C to evaluate physical properties such as gloss, peeling property, surface impact strength, weather resistance, and CLTE, and the results are shown in Table 3. It was.

The evaluation method for each measurement item is as follows.

* Property measurement method

(1) Flow index: measured under the conditions of 220 ℃ / 10kg by ASTM D-1238. (Unit: g / 10 min)

(2) Izod impact strength: measured in 1/8 "Notched condition by ASTM D256. (Unit: kgf · cm / cm)

(3) Yellowness: Measured according to JIS K7105.

(4) Peeling characteristics: The surface state of the extruded sheet was visually observed and measured by giving a score between 1 and 5 points depending on the degree of peeling. Five points were given when no peeling was observed, and one point was given when peeling was observed over the entire compressed sheet. (5: Best, 4: Upper, 3: Middle, 2: Lower, 1: Lower)

(5) Vicat softening point: 5 kg, 50 ℃ / HR conditions were measured by ISO R 306. (Unit: ℃)

(6) Glossiness: 75 degree glossiness was measured using a BYK-Gardner Gloss Meter. (Unit: G.U.)

(7) Surface impact strength was measured by ASTM D4226. (Unit: J)

(8) Weather resistance: ΔE values were measured by UL 746C.

(9) Dimensional stability (CLTE): measured in the temperature range of 20 ℃ ~ 130 ℃ by ASTM D696. (Unit: μm / m ℃)

TABLE 3

As shown in Table 1 to Table 3, the thermoplastic resin composition of the present invention prepared in Examples 1 to 7 generally maintains excellent physical properties such as flow index, Izod impact strength, Vicat softening point and weather resistance of the thermoplastic resin composition While, it was found that the peeling properties and the yellowness is excellent, and it was confirmed that the 75-degree glossiness had excellent low light characteristics of 30 or less. In addition, it was confirmed that the thermoplastic resin compositions of Examples 1 to 7 had excellent surface impact strength and dimensional stability.

On the other hand, a thermoplastic resin (A) composed of a (meth) acrylic acid alkyl ester polymer (a) and an aromatic vinyl-vinyl cyanide copolymer (b) is not used, and only a general aromatic vinyl-vinyl cyanide copolymer is used. The thermoplastic resin composition of Comparative Example 1, which prepared the final thermoplastic resin, was found to have good Izod impact strength, Vicat softening point, weather resistance, etc., but very high glossiness and poor surface impact strength and dimensional stability.

On the other hand, Comparative Example 2 in which the acrylic graft resin (B) is added in excess of the range of the present invention, it can be confirmed that the glossiness increases and the dimensional stability is very low compared to Examples 1 to 7, on the contrary, acrylic graft Comparative Example 3 in which the resin (B) was added below the range of the present invention was confirmed that the Izod impact strength and the surface impact strength were lowered as compared with Examples 1 to 7.

In addition, in Comparative Example 4 using the thermoplastic resin (A) prepared without adding a compound having two or more hydroxyl groups, the dispersed phase of the network shape is not formed, the glossiness is increased, and the Izod impact strength and the surface impact strength are reduced, It turned out that the peeling characteristic is not good. In addition, in the case of Comparative Example 5 using the thermoplastic resin (A) prepared without the addition of unsaturated carboxylic acid or anhydride thereof, the network-like dispersed phase was not formed, so that the glossiness was increased and the Izod impact strength and the surface impact strength were reduced. And it was confirmed that the peeling characteristics are not good.

In addition, in Comparative Example 6 using the thermoplastic resin (A) prepared by adding a compound having two or more hydroxy groups in excess than those of Preparation Examples 1 to 4, the compound having an excess of non-reactive two or more hydroxy groups in the continuous phase In the same action as the plasticizer in the Vicat softening point was dropped sharply and other physical properties were also confirmed to decrease.

Through the above examples and comparative examples, it is confirmed that the thermoplastic resin composition according to the present invention has excellent physical properties such as weather resistance, heat resistance, peeling properties, yellowness, flowability, and at the same time, has excellent low light properties, dimensional stability, and surface impact properties. Could.

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

The thermoplastic resin composition according to the present invention not only has excellent physical properties such as weather resistance, heat resistance, peeling properties, yellowness, fluidity, etc., but also shows excellent low light properties, dimensional stability, and surface impact properties. It can be usefully applied in the manufacture of building materials, household goods and automobile products.

Claims (17)

Thermoplastic resin (A) comprising a (meth) acrylic acid alkyl ester polymer (a) and an aromatic vinyl-vinyl cyanide copolymer (b); And acrylic graft resin (B); wherein the (meth) acrylic acid alkyl ester polymer (a) in the thermoplastic resin (A) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (b) ) Is a weatherproof thermoplastic resin composition, characterized in that a continuous phase. The method of claim 1, wherein the thermoplastic resin (A) comprises about 5 to about 35 weight percent of the (meth) acrylic acid alkyl ester polymer (a) and about 65 to about 95 of the aromatic vinyl-vinyl cyanide copolymer (b). A weather resistant thermoplastic resin composition, characterized in that it comprises a weight percent. The polymer according to claim 1, wherein the (meth) acrylic acid alkyl ester polymer (a) comprises a unit derived from a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, and a compound having two or more hydroxyl groups. A weather resistant thermoplastic resin composition, characterized in that. The method according to claim 3, wherein the (meth) acrylic acid alkyl ester polymer (a) comprises about 60 to about 95 weight percent of the (meth) acrylic acid alkyl ester compound; About 1 to about 20 weight percent of an unsaturated carboxylic acid or anhydride thereof; About 0 to about 20 weight percent of an aromatic vinylic compound; And about 0 to about 10 weight percent of a vinyl cyanide compound; A weather resistant thermoplastic resin composition comprising a unit. The method of claim 3, wherein the (meth) acrylic acid alkyl ester polymer (a) comprises polymerizing a compound having two or more hydroxyl groups in an amount of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof. A weather resistant thermoplastic resin composition characterized by the above-mentioned. The method of claim 3, wherein the (meth) acrylic acid alkyl ester compound is methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, Octyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethyl hexyl acrylate and mixtures thereof Weatherproof thermoplastic resin composition, characterized in that at least one selected from. The method of claim 3, wherein the unsaturated carboxylic acid or its anhydride is acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, anhydrous. A weatherproof thermoplastic resin composition, characterized in that at least one selected from the group consisting of fumaric anhydride and mixtures thereof. The weatherproof thermoplastic according to claim 3, wherein the compound having two or more hydroxy groups is at least one selected from the group consisting of alkanediols, polyalkylene glycols, polyols and mixtures thereof having 2 to 10 carbon atoms. Resin composition. The said (meth) acrylic-acid alkylester type polymer (a) contains a (meth) acrylic-acid alkylester unit and unsaturated carboxylic acid or its anhydride unit as a principal chain, The said unsaturated carboxylic acid or its anhydride The carboxyl group of a unit is connected by the hydroxyl group and ester bond of the compound which has two or more hydroxyl groups, and forms a dispersed phase of network shape, The weatherproof thermoplastic resin composition characterized by the above-mentioned. The method of claim 1, wherein the aromatic vinyl-vinyl cyanide copolymer (b) comprises about 60 to about 95 wt% of an aromatic vinyl compound, about 5 to about 40 wt% of a vinyl cyanide compound, and (meth) acrylic acid alkyl ester A weather resistant thermoplastic resin composition, characterized in that it is prepared by polymerizing a mixture comprising about 0 to about 10% by weight of a compound. The weatherproof thermoplastic resin composition according to claim 1, wherein the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (b) is about 150,000 to about 300,000 g / mol. The acrylic graft resin (B) is about 40 to about 90% by weight of the aromatic vinyl compound-vinyl cyanide compound copolymer in about 10 to about 60% by weight of the (meth) acrylic rubber. A weather resistant thermoplastic resin composition. The copolymer of claim 12, wherein the aromatic vinyl compound-vinyl cyanide compound copolymer grafted to the (meth) acrylic rubber is a copolymer of about 60 to about 80 wt% of the aromatic vinyl compound and about 20 to about 40 wt% of the vinyl cyanide compound. A weather resistant thermoplastic resin composition, characterized in that. 13. The weatherproof thermoplastic resin composition according to claim 12, wherein the average particle diameter of the (meth) acrylic rubber particles is in the range of about 0.05 to about 1 mu m. The weatherable thermoplastic resin composition according to any one of claims 1 to 14, wherein the thermoplastic resin composition has a glossiness of about 30 or less measured using a 75 degree glossiness device. The weatherable thermoplastic according to any one of claims 1 to 14, wherein the thermoplastic resin composition has a CLTE measured in a temperature range of 20 ° C to 130 ° C by an ASTM D 696 method of about 100 µm / m ° C or less. Resin composition. The weathering thermoplastic resin composition of claim 1, comprising about 70 to about 85 weight percent of the thermoplastic resin (A) and about 15 to about 30 weight percent of the acrylic graft resin (B).