WO2012091299A2

WO2012091299A2 - Low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance

Info

Publication number: WO2012091299A2
Application number: PCT/KR2011/008986
Authority: WO
Inventors: 홍재근; 진영섭; 이병도; 선호룡
Original assignee: 제일모직 주식회사
Priority date: 2010-12-29
Filing date: 2011-11-23
Publication date: 2012-07-05
Also published as: WO2012091299A9; WO2012091299A3

Abstract

The present invention relates to a low-gloss thermoplastic resin composition having excellent heat resistance and weather resistance. The low-gloss thermoplastic resin composition includes: a thermoplastic resin forming a first dispersed phase; and an acrylic-based resin forming a second dispersed phase. The first dispersed phase is in a network configuration.

Description

【Specification】

[Name of invention]

Low-light thermoplastic resin composition excellent in heat resistance and weather resistance [Technical field]

The present invention relates to a low light thermoplastic resin composition excellent in heat resistance and weather resistance. More specifically, the present invention relates to a low-light thermoplastic resin composition having excellent heat and weather resistance, as well as heat resistance, weather resistance and low light properties, and excellent balance of physical properties such as laminar strength and fluidity by introducing a heat-resistant aromatic vinyl copolymer into a resin having a specific morphology. will be.

Background Art

Generally, ABS (Acrylonitrile-Butadiene-Styrene) resin has excellent layer toughness and processability, and has excellent mechanical strength and heat deformation temperature.Because of its beautiful appearance, it can be used in automobiles, electrical and electronic equipment, office equipment, home appliances, toys, It is widely used in various applications such as stationery. Butadiene-based rubber components used in ABS resins contain chemically labile double bonds and are 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, windows, 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.

However, in the case of resin compound reinforced with a layered acrylic rubber, due to the inherent properties of the rubber used to improve the layer strength, the heat resistance loss of the final product is high, and it is difficult to apply to applications requiring high heat resistance. In this regard, researches to improve final heat resistance have been steadily researched in comparison with resins having excellent heat resistance.

In addition, recently, as interest in sensitizing resins deviating from the cold plastic feeling of such weatherable resins is steadily increasing, there is an increasing demand for resins that can be manufactured without low light smooth surfaces and coatings. In particular, as environmental regulations tighten, the application range of low-gloss resins that can be directly molded while being able to omit the coating process is gradually expanding. To manufacture such a low gloss weathering resin There are three main methods. The most widely used method is to apply matting additives-quenching agents, using inorganic layering agents or acrylic resins or crosslinked styrene resins. The second method is to remove the gloss in the post-processing process. Such a method includes a method of producing a low light effect through an injection or painting process using a corrosion mold. The third method is to adjust the size of the dispersed phase particles in the matrix to form a microscale rough surface. The surface thus formed scatters incident light to lower gloss.

The first method, the matting additive-quenching agent to implement the low light effect is convenient in many aspects, but the uniformity of the gloss is not constant depending on the dispersion state of the additive has a limitation in quality. In addition, the high specific gravity of the additives commonly used may result in a higher specific gravity of the final product. The second method of injection or painting through a corrosive mold also introduces an additional process, which increases manufacturing costs and may cause pollution, which is disadvantageous in terms of environment. For the conventional ASA product having a low light characteristics largely on the volume of the dispersed phase sikimeuro each other aggregation of small dispersed phase to a method for implementing a low-light characteristics ^■ being used as an alternative but to ungjip such a dispersed phase to the manufacturing method for implementing a low-light characteristic is to be distributed In addition to the need for an additional process of reaggregating the particles after the polymerization process, there is a fundamental technical problem such as re-dispersion of the agglomerated phase in the manufacturing process of the product.

US Patent Nos. 6,696 and 165 add about 0.1 to about 20 parts by weight of a crystalline polymer, which can be represented by polyalkyl terephthalate, and US Patent No. 6,395,828 discloses compounds 0.5 to 0.5 produced by reaction of epoxy and amine compounds. A method of lowering the glossiness of an ASA resin by adding 15 parts by weight is disclosed.

U.S. Patent Nos. 5,475,053, Crab 4,652,614 and the like disclose a method of lowering the gloss of resin by using a spherical graft copolymer as a matting agent, and U.S. Patents 4,169,869, Crab 4, 460, 742, 5,580,924, Korean Patent Publication No. 2008- 0036790 and the like discloses a method for lowering the gloss using various copolymers as an additive.

In addition, U.S. Patent Nos. 4,668,737 and 5,237,004 and the like have 0.05-20 / m or

A method of lowering gloss is disclosed using rubber particles having a large particle diameter of a core / shell structure of 2-15.

However, if the additive is used as in the above technique, not only the manufacturing cost increases but also the problem of peeling, deterioration of properties, and partly glossiness may occur. Can be. In addition, the use of large rubber particles has the advantage that the gloss is lowered, but there is a disadvantage that the laminar strength sharply worsens.

Accordingly, there is a need for development of a low-light thermoplastic resin having excellent heat resistance and weather resistance and without deteriorating physical properties such as laminar strength and fluidity.

[Detailed Description of the Invention]

[Technical problem]

An object of the present invention is to provide a low-light thermoplastic resin composition excellent in heat resistance and weather resistance while maintaining the lamella strength and mechanical properties.

Another object of the present invention is to provide a low light thermoplastic resin composition excellent in low light properties and fluidity.

Still another object of the present invention is to provide a low light thermoplastic resin composition which is particularly suitable for outdoor products, road signs, building finishes, automobile parts, etc. due to excellent balance of physical properties such as heat resistance, weather resistance, low light properties, and mechanical strength.

The above and other objects of the present invention can be achieved by the present invention described below.

Technical Solution

One aspect of the present invention relates to a low light thermoplastic resin composition excellent in heat resistance and weather resistance. The composition comprises (A) a thermoplastic resin forming a first dispersed phase; And (B) an acrylic resin forming a second dispersed phase, wherein the first dispersed phase has a network shape.

In a specific embodiment, the low light thermoplastic resin composition may further include (C) a heat resistant aromatic vinyl copolymer.

The thermoplastic resin (A) is a (al) (meth) acrylic acid alkyl ester polymer and

(a2) an aromatic vinyl-vinyl cyanide copolymer, wherein the (meth) acrylic acid alkyl ester polymer (al) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (a2) is a continuous phase Can be reached.

The acrylic resin (B) forming the system 2 dispersed phase may be an acrylic graft copolymer resin.

The second dispersed phase may be in the form of particles.

In an embodiment the low light thermoplastic resin composition comprises (A) about 20 to about 50 weight percent of a thermoplastic resin having a network-shaped dispersed phase; (B) about 5 to about 40 weight of acrylic resin and (C) about 10 to about 50 heat resistant aromatic vinyl copolymer And may comprise a weight of ¾.

The thermoplastic resin (A) may comprise about 5 to about 35 weight ¾ of the (meth) acrylic acid alkyl ester polymer (al) and about 65 to about 95 weight% of the aromatic vinyl-vinyl cyanide copolymer (a2). have.

The (meth) acrylic acid alkyl ester polymer (al) may include units 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 embodiments, the (meth) acrylic acid alkyl ester polymer (al) 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 vinyl compound about 0 to about 10 weight% of a vinyl cyanide compound; And about 0.1 to about 3 equivalents of a compound having two or more hydroxyl groups per 1 equivalent of the unsaturated carboxylic acid or its anhydride.

In embodiments, the compound having two or more hydroxy groups may be one or more selected from the group consisting of alkanediol, polyalkylene glycol, poly and combinations thereof having 2 to 10 carbon atoms.

In one embodiment, the (meth) acrylic acid alkyl ester polymer (al) comprises (meth) acrylic acid alkyl ester units, and unsaturated carboxylic acid or anhydride units thereof as a main chain, and the saturated carboxylic acid or anhydride thereof. The carboxyl group of the unit may be linked by an ester bond with the hydroxy group of the compound having two or more hydroxy groups to form a network-shaped dispersed phase.

In another embodiment, the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated compound having a hydroxy group, and a compound having two or more carboxyl groups. .

In another embodiment, the (meth) acrylic acid alkyl ester polymer (al) is

Units derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound, and a compound having two or more hydroxy groups. The aromatic vinyl-vinyl cyanide copolymer (a2) may contain about 60 to about 95 wt% of an aromatic vinyl compound unit, about 5 to about 40 wt% of a vinyl cyanide compound unit, and about 0 of (meth) acrylic acid alkyl ester compound unit. To about 10% by weight.

In embodiments, the weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (a2) may be about 150,000 to 300,000 g / n l.

The acrylic resin (B) is (bl) (meth) acrylic rubber about 10 to about 60 From about 40% to about 90% by weight (b2) of the aromatic vinyl compound-vinyl cyanide compound copolymer may be grafted.

The aromatic vinyl compound-vinyl cyanide compound copolymer (b2) may be a copolymer of about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound.

The (bl) (meth) acrylic rubber particles may have an average particle diameter of about 0.05 to about 1.

The (C) heat resistant aromatic vinyl copolymer may include an aromatic vinyl compound unit, a vinyl cyanide compound unit, and a crosslinkable monomer unit. In embodiments, the (C) heat-resistant aromatic vinyl copolymer is based on 100 parts by weight of the monofunctional vinyl compound containing about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound. About 0.01 to about 0.05 parts by weight of the crosslinkable monomer.

In another embodiment, the resin composition may further include (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a copolymer including a maleic anhydride compound, or a mixture thereof.

The (D) aromatic vinyl compound-vinyl cyanide compound copolymer may include more than about 0 and about 40 wt% or less of the total resin composition.

The copolymer including the maleic anhydride-based compound (E) may include more than about 0 and about 20% by weight or less of the total resin composition. In embodiments, the copolymer including the maleic anhydride-based compound (E) may include about 40 to about 60% by weight of maleic anhydride, N-substituted maleate or a mixture thereof.

The composition includes antimicrobial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, stabilizers, lubricants, antistatic agents, colorants, flame retardants, weather agents, colorants, UV absorbers, ultraviolet rays. It may contain one or more additives such as a barrier, flame retardant, layering agent, nucleating agent, adhesion aid, pressure-sensitive adhesive.

In embodiments, the composition has a glossiness of about 30 GU or less, measured using a 75 degree polisher, a Vicat softening point of about 100 to 150 ^° C., a ΔΕ of about 2.8 or less, as measured by UL 746C, and ASTM D256. The Izod notch layer strength measured by 1/8 "thick may be about 8 kgf. Cm / cm or more.

Other of the Invention _. The viewpoint relates to a molded article molded from the composition. The molded article has a morphology of a continuous phase and a dispersed phase, and the continuous phase includes an aromatic vinyl-vinyl cyanide copolymer and a heat resistant aromatic vinyl copolymer, wherein the dispersed phase is a network-shaped first dispersion phase and a particle-type type 2 dispersed phase. It consists of The first disperse phase is formed of a (meth) acrylic acid alkyl ester polymer, the second disperse phase is formed of an acrylic resin, and has an I / 8 notch layer strength of about 8 kgf-cm measured by ASTM D256. / cm or more, Vicat softening point can form a molded article of about 100 ~ 150t :.

Advantageous Effects

The thermoplastic resin composition according to the present invention has excellent heat resistance and weather resistance while maintaining impact strength and mechanical properties, excellent light properties and fluidity, and excellent physical property balance, making it particularly suitable for outdoor products, road signs, building finishes, automobile parts, etc. It has the effect of providing the thermoplastic resin composition.

[Brief Description of Drawings]

Fig.1 (a) (b) is a TEM photograph of the thermoplastic resin (A) which has a network-shaped dispersion phase used in the Example. ((a) magnification 7,000 times (b) magnification 12,000 times)

[Best form for implementation of the invention]

Hereinafter, specific embodiments of the present invention will be described in detail. However, this is presented as an example, by which the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Unless stated otherwise in the specification, "(meth) acrylate"

It means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" also means that both "acrylic acid" and "methacrylic acid" are possible. The low-light thermoplastic resin composition excellent in heat resistance and weather resistance of the present invention includes (A) a thermoplastic resin forming a monodisperse phase; And (B) an acrylic resin forming a second dispersed phase, wherein the first dispersed phase has a network shape.

In embodiments, (C) may include a heat-resistant aromatic vinyl copolymer.

In another embodiment, the resin composition may further include a copolymer including (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a maleic anhydride compound, or a mixture thereof.

Hereinafter, each component of this invention is demonstrated in detail below.

(A) A thermoplastic resin having a network-shaped first dispersed phase

The thermoplastic resin (A) of the present invention is an (al) (meth) acrylic acid alkyl ester polymer And (a2) aromatic vinyl-vinyl cyanide copolymers. The (meth) acrylic acid alkyl ester polymer 1) forms a network-shaped first dispersed phase, and the aromatic vinyl-vinyl cyanide copolymer 2) forms a continuous phase.

In one embodiment, the (meth) acrylic acid alkyl ester polymer (al) may include units 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. .

The (meth) acrylic acid alkyl ester polymer (al) includes (meth) acrylic acid alkyl ester units and unsaturated carboxylic acid or anhydride units thereof as a main chain, and the carboxyl groups of the unsaturated carboxylic acid or anhydride units thereof are two The hydroxyl group of the compound which has the above hydroxyl group is connected by ester bond, and can form the Crab 1 dispersed phase of network shape.

In another embodiment, the (meth) acrylic acid alkyl ester polymer (al) is a (meth) acrylic acid alkyl ester compound, an unsaturated carboxylic acid or an anhydride thereof, an aromatic vinyl compound, a vinyl cyanide compound, and a compound having two or more hydroxyl groups. It may include units derived from. For example, the (meth) acrylic acid alkyl ester polymer (al) may comprise 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; Aromatic vinylic compound about 0 to about 20 weight ¾>; From about 0 to about 10 weight ¾ of vinyl cyanide compound; And about 0.1 to about 3 equivalents of a compound having two or more hydroxyl groups per 1 equivalent of the unsaturated carboxylic acid or its anhydride. Within this range, the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent. In this case, an unsaturated carboxyl compound or anhydride thereof is included in the chains of the thermoplastic resin (A) as part of the repeating unit, and the compound having two or more hydroxy groups serves to connect the chains.

More preferably, about 75 to about 95 weight percent (meth) acrylic acid alkyl ester compound, about 1 to about 10 weight% of unsaturated carboxylic acid or its anhydride, about 1 to about 10 weight% of aromatic vinyl-based compound, vinyl cyanide Compound About 1 to about 8 by weight, the compound having two or more hydroxyl groups may be polymerized in a ratio of about 0.1 to 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, vinyl cyanide compound About 1 to about 5% by weight, wherein the compound having two or more hydroxy groups is about about unsaturated carboxylic acid or anhydride thereof It may be polymerized in a ratio of 0.5 to about 2.0 equivalents.

It is preferable that the (meth) acrylic acid alkyl ester compound is 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, nuclear chamber methacrylate, heptyl methacrylate, octyl methacrylate, 2-ethyl nuclear chamber methacrylate Acrylate, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, nucleus acrylate, heptyl acrylate, octyl acrylate, 2-ethyl nucleus acrylate and the like can be used, preferably butyl Acrylate, but is not necessarily limited thereto. These may be applied alone or in combination of two or more.

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

The compound having two or more hydroxy groups preferably has 2 to 10 hydroxy groups, more preferably 2 to 5 hydroxy 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, polyalkylene glycols, polyols and mixtures thereof having 2 to 10 carbon atoms. These may be applied alone or in combination of two or more. Examples of the alkanediol having 2 to 10 carbon atoms include ethylene glycol, propylene glycol, 1,4-butanedi, 1,5-pentanediol, 1,6-nucleic acid diol, 1,7-heptanediol, 1, 8 -Octanediol, and the like, but not necessarily limited thereto. Examples of the polyalkylene glycol may include polyethylene glycol, polypropylene glycol, and the like, and polyethylene glycol (PEG) may vary depending on molecular weight. PEG300, PEG600, PEG1500, and the like, but are not necessarily limited thereto. Examples of the polyol include xyl, glycerin, erythriitol, sorbitol, and acrylic or ether polys having a hydroxy value of about 50-500 and a molecular weight of about 500-5000 g / mol. It includes, but is not necessarily limited thereto.

In another embodiment the (meth) acrylic acid alkyl ester polymer (al) is

Units derived from a (meth) acrylic acid alkyl ester compound, an unsaturated compound having a hydroxy group, and a compound having two or more carboxyl groups may be included. For example, about 60% to about 95% by weight of (meth) acrylic acid alkyl ester compound, about 1% to about 20% by weight of unsaturated compound having hydroxy group, about 0% to about 20% by weight of aromatic vinyl compound, about 0% to vinyl cyanide compound To about 10% by weight, and about 1 to about 3 equivalents, preferably about 0.5 to about 2 equivalents, of the compound having two or more carboxyl to 1 equivalent of the unsaturated compound having a hydroxy group. Within this range, the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent. In this case, an unsaturated compound having a hydroxy group is included in the chains of the thermoplastic resin (A) as part of the repeating unit, and the compound having two or more carboxyl groups serves to link the chains.

As the unsaturated compound having a hydroxy group, an alkyl (meth) acrylate containing a hydroxy group may be used. For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, etc. are mentioned.

In another embodiment, the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound, and a compound having two or more hydroxyl groups. Can be. For example, about 60 to about 95 weight percent of (meth) acrylic acid alkyl ester compound, about 1 to about 20 weight% of (meth) acrylic acid glycidyl ester compound, about 0 to about 20 weight% of aromatic vinyl-based compound, vinyl cyanide From about 0.1 to about 3 equivalents, preferably from about 0.5 to about 2 equivalents, of the compound having from about 0 to about 10 weight ¾, and the compound having at least two hydroxyl groups relative to one equivalent of the (meth) acrylic acid alkyl ester compound It may include. Within this range, the (meth) acrylic acid alkyl ester polymer (al) can be divided into chains to form a dispersed phase, and the heat resistance is excellent.

In another embodiment, the (meth) acrylic acid alkyl ester polymer (al) may include units derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound, and a compound having two or more carboxyl groups. Can be. The (meth) acrylic acid alkyl ester compound and the (meth) acrylic acid glycidyl ester compound are polymerized to contain (meth) acrylic acid alkyl ester units and (meth) acrylic acid glycidyl ester units as main chains, and (meth) acrylic acid It constitutes the chains of the alkyl ester polymer. The epoxy group of the (meth) acrylic acid glycidyl ester unit is connected by an hydroxy group and an ester bond of a compound having two or more carboxyl groups or a compound having two or more hydroxy groups. Accordingly, the chains of the (meth) acrylic acid alkyl ester polymer (al) are connected to each other to form a dispersed phase. For example, about 60 to about 95 weight percent of (meth) acrylic acid alkyl ester compound, about 1 to about 20 weight% of (meth) acrylic acid glycidyl ester compound, about 0 to about 20 weight% of aromatic vinyl-based compound, vinyl cyanide From about 0 to about 10 percent by weight of the compound, and about 0.1 to about 3 equivalents, preferably about 0.5 to about 2 equivalents, of the compound having two or more carboxyl groups relative to one equivalent of the (meth) acrylic acid alkyl ester compound can do. Within this range, the (meth) acrylic acid alkyl ester polymer (al) can be divided into chain-linked all-layers to form a dispersed phase, and the heat resistance is excellent.

As the (meth) acrylic acid glycidyl ester compound, glycidyl acrylate, glycidyl methacrylate, and the like may be used, but are not necessarily limited thereto. These may be applied alone or in combination of two kinds. Among these, glycidyl methacrylate is preferable.

The compound having two or more carboxyl groups preferably has 2 to 10 carboxyl groups, and more preferably 2 to 5 carboxyl groups. In addition, the compound having two or more carboxyl groups is preferably a saturated compound in which all carbon atoms in the molecule are bonded by a single bond only. Examples of the compound having two or more carboxyl groups include alkanedioic acid having 2 to 10 carbon atoms, polyacid, a mixture thereof, and the like.

Examples of the alkanedioic acid having 2 to 10 carbon atoms include butanedioic acid (succinic acid), pentanedioic acid (glutaric acid), nucleic acid diioic acid (adipic acid), heptanedioic acid (pimelic acid), and octanodioic acid. (Suberic acid), nonanodioic acid (azelaic acid), decandioic acid (watermelon), and the like, but are not necessarily limited thereto.

The poly acid has an acid value of about 30-300 and a weight average molecular weight of about 1,000-5,000 g / mol. Specific examples of the polyacid include poly (meth) acrylic acid, styrene- (meth) acrylic acid polymer, styrene-maleic acid polymer, and the like, but are not necessarily limited thereto. Specifically, Rohm as the polyacid Morez-101, Morez-100 from Haas; Joncry 1—678, Joncry 1-690 by BASF, Soluryl-20, Sol ury 1-70, etc. of Hanwha Chemical Co., Ltd. may be used. The aromatic vinyl-vinyl cyanide copolymer 2) 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 further comprising a (meth) acrylic acid alkyl ester compound. It can be included and polymerized. Each component constituting the aromatic vinyl-vinyl cyanide co-polymer (a2) is about 60 to about 95 wt% of an aromatic vinyl compound, about 5 to about 40 wt% of a vinyl cyanide compound, and about 0 to about (meth) acrylic acid alkyl ester compound. To about 10 weight ¾> to polymerize, preferably about 60 to about 84 weight ¾ of aromatic vinyl compound, about 15 to about 35 weight ¾ of vinyl cyanide compound, and about (meth) acrylic acid alkyl ester compound 1 to about 5 weight percent. Within this range, the layer resistance, yellowness, flow characteristics and the like are excellent.

The aromatic vinyl cyanide copolymer. As the aromatic vinyl compound forming (b), styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, preferably styrene, but is not necessarily limited thereto. These may be applied alone or in combination 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 combination 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, nuclear chamber methacrylate, heptyl methacrylate, octyl methacrylate 2-ethyl nuclear chamber methacrylate , Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, nucleus acrylate, heptyl acrylate, octyl acrylate, 2-ethyl nucleus acrylate can be used, preferably butyl acrylate However, it is not necessarily limited thereto. These may be applied alone or in combination of two or more.

The weight average molecular weight of the aromatic vinyl-vinyl cyanide copolymer (b) is about 150,000 to about 300,000 g / mol, preferably about 180,000 to about 250,000 g / ti) l. The size of the dispersed phase can be properly maintained in the above range Impact strength and low light characteristics can be obtained and peeling can be prevented.

The thermoplastic resin (A) having a network-shaped first dispersed phase according to the present invention can be produced by continuous bulk polymerization. In general, the dispersion phase described above is not easy to be produced by the method of preparing the rubber phase, such as the emulsion polymer polymerization method or the suspension polymerization method, and the aromatic vinyl-vinyl cyanide copolymers constituting the continuous phase are separately prepared. This is because it is difficult to efficiently manufacture a weather-resistant thermoplastic resin composition excellent in low light properties since the final product must be manufactured by a method such as melt extrusion. For example, about 60% to about 95% by weight of (meth) acrylic acid alkyl ester, about 1% to about 20% by weight of unsaturated carboxylic acid or anhydride thereof, about 0% to about 20% by weight of aromatic vinyl compound and about 0% to about 0% of vinyl cyanide compound About 10% by weight of the mixture is mixed to prepare the first monomer mixture. The C 1 monomer mixture is continuously added to a first reactor in a plurality of reactors connected in series, and the system 1 monomer mixture is polymerized to obtain a polymerization conversion of 85 to 95% to prepare a polymer. When the polymer is prepared from the first monomer mixture in the first reactor, the polymer is continuously added to the second reaction vessel, and at the same time, about 60 to about 95 weight of the aromatic vinyl compound and about 5 to about 40 weight of the vinyl cyanide compound %, And about 2 to about 10% by weight of a (meth) acrylic acid alkyl ester and a compound having two or more hydroxy groups and a compound having two or more hydroxy groups are continuously added to the crab 2 reactor. In this case, the compound having two or more hydroxy groups is added at a ratio of about 0.1 to about 3 equivalents relative to the unsaturated carboxylic acid or anhydride thereof added to the first reaction group. And the polymer, the crab dimer monomer mixture and the compound having two or more hydroxy groups are polymerized in a 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 is about 0 to about 0.5 based on 100 parts by weight of the second monomer mixture. It is preferred to be added in parts by weight.

The plurality of reactions may be made up of two to five reactions, and the polymerization reaction may proceed continuously through each reaction. In the final reaction stage at the end of the polymerization, the final polymerization conversion to the thermoplastic resin is adjusted to about 50 to about 70%, preferably about 50 to about 65%.

In another embodiment, after preparing a final polymer composed of a network-like dispersed phase and a continuous phase through a continuous polymerization process in a plurality of reactors as described above, from the final polymerized product from the final polymer using a devolatilization tank of high temperature and vacuum The step of separating may be further roughened. The prepared thermoplastic resin may be formed into pellets using a pelletizer or the like. The manufacturing method of the thermoplastic resin (A) having the dispersed phase of the network shape is described in detail in Korean Patent Publication No. 2010-47672, and the present invention is incorporated by reference.

The thermoplastic resin (A) having the network-shaped dispersed phase comprises about 5 to about 35 weight% of (meth) acrylic acid alkyl ester polymer (al) and about 65 to about 95 weight% of aromatic vinyl-vinyl cyanide copolymer (a2) And preferably 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). Within this range, it is possible to obtain a good balance of low light properties and layer strength.

The thermoplastic resin (A) having the network-shaped dispersed phase also comprises from about 20 to about 50 weight percent of the total composition. It is possible to implement the target low light characteristics in the above range, it is possible to prevent the degradation of the layer resistance. Preferably from about 25 to about 45 weight percent. (B) acrylic resin

The acrylic resin (B) forms a crab 2 dispersed phase. The acrylic resin (B) can be produced by graft polymerization of a monomer mixture containing an aromatic vinyl compound and a vinyl cyanide compound in a (meth) acrylic rubber. Preferably, the acrylic resin (B) is a copolymer in which about 40 to about 90 weight% of the aromatic vinyl compound-vinyl cyanide compound copolymer is grafted to about 10 to about 60 weight% of the (meth) acrylic rubber. The polymerization method of the acrylic graft copolymer resin may be used a conventional method known in the art, for example, emulsion polymerization, suspension polymerization, etc. are possible, preferably using an emulsion graft polymerization method.

As the acrylic rubber for producing 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-ethylnuclear acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate may be used, These may be used alone or in combination of two or more. Among these, butyl acrylate is preferable.

The average particle diameter of the acrylic rubber particles may be in the range of about 0.05 to about 1, preferably in the range of about 0.07 to about 0.7 /, more preferably in the range of about 0.1 to about 0.5; It is possible to implement the stratification strength in the above range.

Aromatic vinyl compound-vinyl cyanide compound grafted to the said acrylic rubber The copolymer may be a copolymer of about 60 to about 80 weight percent aromatic vinyl compound and about 20 to about 40 increments ¾ of the vinyl cyanide compound.

As the aromatic vinyl compound, styrene, α-methylstyrene, Ρ-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.

Acrylonitrile, methacrylonitrile, ethacrylonitrile and the like may be used as the vinyl cyanide compound. These may be used alone or in combination of two or more thereof.

The acrylic graft copolymer (β) comprises about 5 to about 40 weight percent of the total composition. Within this range, the balance between layer resistance, low light characteristics and fluidity can be obtained. Preferably from about 15 to about 30 weight percent.

(C) Heat-resistant aromatic vinyl copolymer

The heat resistant aromatic vinyl copolymer (C) may include an aromatic vinyl compound unit, a vinyl cyanide compound unit, and a crosslinkable monomer unit. In embodiments, the (C) heat-resistant aromatic vinyl copolymer is based on 100 parts by weight of the monofunctional vinyl compound containing about 60 to about 80 weight% of the aromatic vinyl compound and about 20 to about 40 weight% of the vinyl cyanide compound. About 0.01 to about 0.2 parts by weight of the crosslinkable monomer. Preferably about 0.01 to about 0.05 parts by weight of the crosslinkable monomer based on 100 parts by weight of the monofunctional vinyl compound comprising about 65 to about 75 weight percent of the aromatic vinyl compound and about 25 to about 35 weight% of the vinyl cyanide compound. do.

As the aromatic vinyl compound, styrene, alphamethylstyrene, or a mixture thereof may be used.

As the vinyl cyanide compound, acrylonitrile, methacrylonitrile or a mixture thereof may be used.

The crosslinkable monomer is a monomer containing two or more unsaturated groups, for example, divinylbenzene, ethylene glycol dimethacrylate, allyl methacrylate, allyl acrylate, triallyl cyanurate, triallyl isocyanurate, Diallyl phthalate, diallyl maleate, divinyl adipate, divinylbenzene ethylene glycol dimethacrylate, divinylbenzene ethylene glycol diacrylate, diethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene Glycol Dimethacrylate, Triethylene Glycol Diacrylate, Trimethylol Propane Trimethacrylate, Trimethylol Propane Triacrylate Tetramethylol Methane Tetramethacrylate, tetramethylolmethane tetraacrylate, dipropylene glycol dimethacrylate and dipropylene glycol diacrylate, 3—butanediol diacrylate, 1,3-butanedi dimethacrylate, 1,4- Butanedi diacrylate, 1,4-butanedi dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate and the like can be used, but is not necessarily limited thereto. These may be used alone or in combination of two or more.

In the present invention, the crosslinkable monomer is included in an amount of about 0. to about 0.2 parts by weight based on 100 parts by weight of the monofunctional vinyl compound. By using the crosslinkable monomer in the above range, the molecular weight can be easily controlled and there is an advantage of improving the layer physical properties of the final product.

In addition, the (C) heat-resistant aromatic vinyl copolymer may optionally further add monomers such as acrylic acid, methacrylic acid, maleic anhydride, and N-substituted maleimide as necessary to impart processability and heat resistance.

The (C) heat-resistant aromatic vinyl copolymer can be produced by a method such as a bulk polymerization method, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, or the like, which are conventional polymerization methods. Preferred of these is continuous bulk polymerization.

In one embodiment of the present invention it is prepared by sequentially polymerizing the mixed raw materials containing an aromatic vinyl compound, a vinyl cyan compound and a polyfunctional vinyl compound containing α- methylstyrene in a plurality of reactors connected in series with each other in sequence At this time, it is characterized by adjusting the conversion rate for each semi-ungunggi to about 10-25%. Three to five reactors are suitable. The method for producing the heat resistant aromatic vinyl copolymer (C) is disclosed in Korean Patent Application No. 2007-115737, and the present invention includes it as a whole.

The weight average molecular weight of the heat-resistant aromatic vinyl copolymer (C) that can be used in the present invention may be used in the range of about 80,000 to about 120,000 g / mol, it can be given heat resistance with excellent layer resistance and fluidity in the above range Can be.

The heat resistant aromatic vinyl copolymer (C) comprises from about 10 to about 50 weight percent of the total composition. Within this range, it is possible to obtain a balance of layer resistance, fluidity and heat resistance. Preferably from about ₁₅ to about 30 weight ¾. (D) Aromatic vinyl compound-vinyl cyanide compound copolymer

The aromatic vinyl compound-vinyl cyanide compound copolymer (D) is mixed with about 10 to about 60 parts by weight of the vinyl cyanide compound to about 40 to about 90 parts by weight of the aromatic vinyl compound, and is a bulk polymerization method and a solution polymerization. It can be manufactured by a method such as a method, an emulsion polymerization method or a suspension polymerization method. As the aromatic vinyl compound used in the (D) aromatic vinyl copolymer resin, styrene, alphamethyl styrene, paramethyl styrene, or the like may be used, but is not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, styrene is preferable.

Acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used as the vinyl cyanide compound used in the aromatic vinyl copolymer resin (D), but is not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, acrylonitrile is preferable.

The weight average molecular weight of the aromatic vinyl compound-vinyl cyanide compound copolymer (D) may be used in the range of about 80,000 to about 300,000 g / mol, it can give a good balance of physical properties of fluidity and layer resistance in the above range.

The aromatic vinyl compound-vinyl cyanide compound copolymer (D) may comprise within about 40% by weight of the total composition. In embodiments, greater than about 0 and up to about 40 weight percent, preferably about 10 to about 35 weight percent. It is possible to obtain a good balance of physical properties of fluidity and layer resistance within the above range.

(E) Copolymer containing maleic anhydride type compound

The copolymer (E) comprising the maleic anhydride compound is mixed with maleic anhydride, N-substituted maleate or a mixture thereof and an aromatic vinyl compound to form a bulk polymerization method, a solution polymerization method, and an emulsion polymerization. It can be produced by the method of suspension, suspension polymerization method.

In an embodiment, about 40 to about 60 weight percent of maleic anhydride, N-substituted maleate, or a combination thereof, and about 40 to about 60 weight percent of an aromatic vinylic compound. It is possible to impart excellent heat resistance and flow property balance in the above range.

As the aromatic vinyl compound used in the copolymer (E) including the maleic anhydride compound, styrene, alphamethyl styrene, paramethyl styrene, etc. may be used, but are not necessarily limited thereto. These may be applied alone or in combination of two or more. Among these, styrene is preferable.

Copolymer (E) comprising the maleic anhydride-based compound may include within 20 weight ¾ »of the total composition. In embodiments, greater than about 0 and up to about 20 weight%, preferably 3 to 15 weight%. It is possible to obtain a good balance of physical properties of fluidity, layer resistance and heat resistance in the above range. The resin composition of the present invention may further add a conventional additive in addition to the above components. have. For example, antibacterial agents, heat stabilizers, antioxidants, mold release agents, light stabilizers, inorganic additives, surfactants, coupling agents, plasticizers, compatibilizers, stabilizers, lubricants, antistatic agents, colorants, flame retardants, weather agents, colorants, UV absorbers, Additives, such as a sunscreen, a flame retardant, a layer agent, a nucleating agent adhesion | attachment adjuvant, an adhesive, can be added, These can be added individually or in mixture of 2 or more types.

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 G.U. Or less, and preferably about 21 G.U. or less.

In addition, the resin composition has a Vicat softening point of about 100 to 150 ^° C., ΔΕ measured by UL 746C is about 2.8 or less, preferably about 0.1 to about 2.5.

The resin composition has an Izod notched lamella strength of at least about 8 kgf cm / cm, preferably about 10 to about 50 kgf cm / cm, as measured by ASTM D256.

As described above, the thermoplastic resin composition according to the present invention has excellent balance of physical properties such as impact strength, mechanical strength and fluidity while maintaining excellent weather resistance, heat resistance and low light properties. Therefore, the thermoplastic resin can be widely used in electrical and electronic parts, agricultural equipment, road signs, building finishing materials, door panels, windows, leisure / life supplies, sporting goods, automotive supplies and the like.

As a method of molding the thermoplastic resin composition according to the present invention to manufacture such products, 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.

Another aspect of the present invention is a molded article molded from the resin composition. The molded article is a continuous phase comprising 2) an aromatic vinyl-vinyl cyanide copolymer and (C) a heat-resistant aromatic vinyl copolymer, wherein the (al) (meth) acrylic acid alkyl ester polymer forms a network-shaped first dispersed phase. The acrylic resin (B) may form a dispersed phase in the form of particles.

In addition, (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a copolymer containing a maleic anhydride-based compound or a mixture thereof may further be included in a continuous phase. 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. The scope of the 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. [Form for implementation of invention]

The specification of each component used in the following Example and the comparative example is as follows.

(A) A thermoplastic resin having a network-shaped dispersed phase

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) to 100 parts by weight of toluene 100 parts by weight, benzoyl peroxide (BP0) 0.2 part by weight and 0.05 part by weight of t-dodecyl mercaptan (TDM) were mixed to prepare a first reactant. The prepared first reaction product was introduced at a rate of 1 kg / hr into a first reactor (R-1) of a continuous polymerization reaction reactor in which three reaction reactors, in which a jacket was installed and easy to control reaction temperature, were connected in series, at a temperature of 80 ^° C. Polymerization was prepared by allowing the polymerization to proceed for a residence time of 8 hours. At this time, the polymerization conversion rate was 90%, and the polymer prepared 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 1,1-bis (100 parts by weight of a second monomer mixture consisting of 72 parts by weight of styrene (SM), 25 parts by weight of acrylonitrile (AN), and 3 parts by weight of butyl acrylate (BA)). 0.02 parts by weight of t-butylperoxy) cyclonucleic acid (PHX-C), 0.1 parts by weight of t-dodecyl mercaptan (TDM) and 1.47 parts by weight of polyethylene glycol (PEG600) having a molecular weight of 600 (1.0 equivalent ratio) 2 reactions were prepared. The prepared crab 2 reactant was introduced into the second reaction vessel (R-2) of the continuous polymerization reaction reactor at a rate of 8.5 kg / hr, and the polymerization was performed at a temperature of 110 ^° C. for 2 hours. 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 a residence time of 2 hours at 130 ^° C temperature. The polymerization conversion rate at this time was 55%.

The polymerization resultant discharged from the third reaction vessel (R-3) was continuously added to a devolatilization tank maintained at 240 ^° C and 20 Torr to remove unbanung monomer and solvent, and pellet form using pelletizer. A thermoplastic resin (A) was produced. The prepared thermoplastic resin (A) confirmed the network dispersed phase through a TEM photograph, and is shown in FIG. 1 ((a) magnification of 7,000 times (b) magnification of 12,000 times). (B) acrylic resin

ASA resin (trade name: CHAS) manufactured by Cheil Industries Co., Ltd. was used.

(C) Heat-resistant aromatic vinyl copolymer

TJ-5380 containing 0.05 parts by weight of divinylbenzene was used in 100 parts by weight of the monomer mixture including 70% by weight of _α -methylstyrene and 30% by weight of acrylonitrile manufactured by Cheil Industries Co., Ltd.

(D) Aromatic vinyl compound-vinyl cyanide compound copolymer

SAN resin (trade name: AP-30) containing 71.5% by weight of styrene and 28.5% by weight of acrylonitrile, manufactured by Cheil Industries, Ltd., and having a weight average molecular weight of 130,000 g / mol was used.

(E) Copolymer containing maleic anhydride type compound

DENKA IP, a copolymer of styrene-N-phenylmaleimide from DENKA, was used. Examples 1-7, Comparative Examples 1-2

0.5 parts by weight of octadil-3 (4—hydroxy-3,5-di-tert-butylphenyl) propionate as a hindered phenolic antioxidant after each component was added in an amount as shown in Table 1 below. A part was added and extruded by a twin screw extruder having a L / B of 29 and a diameter of 45 mm to prepare pellets. After drying the prepared pellets at 80 ^° C for 3 hours, using a 6 oz injection molding machine, by injection molding under the conditions of the molding temperature 180 ~ 280 ^° C, mold temperature 40-80 ^° C to prepare a physical specimen. The prepared physical property specimens were measured for physical properties by the following method and the results are shown in Table 1 below.

TABLE 1

1. Flow index (MI): measured at 220 ^° C / 10 kg conditions by ASTM D-1238. (Unit: g / 10 min)

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

3. Vicat softening point: measured at 5kg, 5C C / HR conditions by ISO R 306. (Unit: ^° C)

4. Glossiness (GLOSS): 75 degree glossiness was measured using a BYK-Gardner Gloss Meter. (Unit: G.UJ

5. Weather resistance: ΔΕ values were measured by UL 746C. As shown in Table 1 to Table 3, the thermoplastic resin composition of the present invention prepared in Examples 1 to 7 was confirmed that the excellent low light properties, heat resistance and weather stability while maintaining the laminar strength and other physical properties . On the other hand, (A) Comparative Example 1, which does not use the thermoplastic resin having the first dispersed phase of the network shape, can not realize the target low light characteristics, and it can be seen that the flow characteristics and weather resistance is significantly reduced. In addition, (B) in the case of Comparative Example 2 that does not use the acrylic resin can be confirmed that can not implement the target excellent layer strength. Simple modifications and variations of the present invention can be easily made 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. [Range of request]

1. (A) a thermoplastic resin forming a first dispersed phase; And

(B) an acrylic resin which forms a crab bidisperse phase;

Wherein the first dispersed phase has a network shape, wherein the low-light thermoplastic resin composition is excellent in heat resistance and weather resistance.

2. The low light thermoplastic resin composition according to claim 1, wherein the low light thermoplastic resin composition further comprises (C) a heat resistant aromatic vinyl copolymer.

3. The method according to claim 1, wherein the thermoplastic resin (A) comprises (al) (meth) acrylic acid alkyl ester polymer and 2) aromatic vinyl-vinyl cyanide copolymer, and the (meth) acrylic acid alkyl ester polymer (al) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (a2) forms a continuous phase, wherein the low-light thermoplastic resin composition having excellent heat resistance and weather resistance.

4. The low light thermoplastic resin composition having excellent heat resistance and weather resistance according to item 1, wherein the acrylic resin (B) forming the second dispersed phase is an acrylic graft copolymer.

5. The low light thermoplastic resin composition of claim 1, wherein the second dispersed phase is in the form of particles.

6. The low light thermoplastic resin composition of claim 2, wherein the low light thermoplastic resin composition comprises (A) about 20 to about 50 weight percent of a thermoplastic resin having a network-shaped dispersed phase; (B) about 5 to about 40 weight percent of an acrylic resin; And (C) about 10 to about 50% by weight of a heat resistant aromatic vinyl copolymer. 7. The thermoplastic resin of claim 3, wherein the thermoplastic resin (A) is about 5 to about 35 weight% of the (meth) acrylic acid alkyl ester polymer (al) and the aromatic vinyl-vinyl cyanide copolymer 2) about 65 to about A low-light thermoplastic resin composition having excellent heat resistance and weather resistance, comprising 95% by weight.

Claims

[Range of request]

1. (A) Thermoplastic resin which forms a 1st dispersed phase; And

(B) an acrylic resin forming a second dispersed phase;

It includes, The system 1 dispersed phase is a low light thermoplastic resin composition excellent in heat resistance and weather resistance, characterized in that the network shape.

3. The thermoplastic resin (A) according to claim 1, wherein the thermoplastic resin (A) comprises (al) (meth) acrylic acid alkyl ester polymer and (a2) aromatic vinyl-vinyl cyanide copolymer, and the (meth) acrylic acid alkyl ester system The low light thermoplastic resin composition having excellent heat resistance and weather resistance, wherein the polymer (al) forms a dispersed phase in a network shape, and the aromatic vinyl-vinyl cyanide copolymer (a2) forms a continuous phase.

4. The low light thermoplastic resin composition according to claim 1, wherein the acrylic resin (B) forming the second dispersed phase is an acrylic graft copolymer.

6. The low light thermoplastic resin composition of claim 2, wherein the low light thermoplastic resin composition comprises (A) 20 to about 50 weight percent of a thermoplastic resin having a network-shaped dispersed phase; (B) about 5 to about 40 weight ¾ acrylic resin; And (C) about 10 to about 50% by weight of a heat resistant aromatic vinyl copolymer.

7. The thermoplastic resin of claim 3, wherein the thermoplastic resin (A) is about 5 to about 35 weight percent of the (meth) acrylic acid alkyl ester polymer (al) and about 65 to about the aromatic vinyl-vinyl cyanide copolymer (a2). Low light thermoplastic resin composition having excellent heat resistance and weather resistance.

8. The method according to claim 3, wherein the (meth) acrylic acid alkyl ester polymer (al) 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 low light thermoplastic resin composition having excellent heat resistance and weather resistance, comprising: a.

9. The (meth) acrylic acid alkyl ester polymer (al) according to claim 8, wherein the (meth) acrylic acid alkyl ester polymer (al) comprises about 60 to about 95 weight unsaturated carboxylic acid or about 1 to about 20 weight percent of an anhydride thereof; Aromatic vinylic compound about 0 to about 20 weight ¾; About 0 to about 10 weight percent of a vinyl cyanide compound; And about 0.1 to about 3 equivalents of a compound having two or more hydroxy groups per 1 equivalent of the unsaturated carboxylic acid or its anhydride.

10. The compound according to claim 8, 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. Low-light thermoplastic resin composition excellent in heat resistance and weather resistance.

11. The method according to claim 3, wherein the (meth) acrylic acid alkyl ester polymer (al) comprises a (meth) acrylic acid alkyl ester unit and an unsaturated carboxylic acid or an anhydride unit thereof as a main chain, and the unsaturated carboxylic acid or The carboxyl group of this anhydride unit is connected by the hydroxy group and ester bond of the compound which has two or more hydroxyl groups, and forms a dispersed phase of network shape, The low light thermoplastic resin composition excellent in heat resistance and weatherability characterized by the above-mentioned.

12. The method of paragraph 3, wherein the (meth) acrylic acid alkyl ester polymer (al) comprises a unit derived from a (meth) acrylic acid alkyl ester compound, an unsaturated compound having a hydroxy group and a compound having two or more carboxylations A low-light thermoplastic resin composition excellent in heat resistance and weatherability, characterized in that.

13. The unit according to claim 3, wherein the (meth) acrylic acid alkyl ester polymer (al) is a unit derived from a (meth) acrylic acid alkyl ester compound, a (meth) acrylic acid glycidyl ester compound and a compound having two or more hydroxy groups Low-light thermoplastic resin composition excellent in heat resistance and weather resistance, comprising a.

14. The method according to item 3, wherein the aromatic vinyl-vinyl cyanide copolymer (a2) comprises about 60 to about 95 weight percent of vinyl cyanide compound units, about 5 to about 40 weight percent, and (meth) acrylic acid A low light thermoplastic resin composition having excellent heat resistance and weather resistance, comprising about 0 to about 10 weight percent of an alkyl ester compound unit.

15. The low light thermoplastic resin composition of claim 3, wherein the aromatic vinyl-vinyl cyanide copolymer (a2) has a weight average molecular weight of about 150,000 to 300,000 g / n) l.

16. The method according to claim 1, wherein the acrylic resin (B) is about 10 to about 60 weight% of (bl) (meth) acrylic rubber and (b2) about 40 to about 90 weight% of an aromatic vinyl compound-vinyl cyanide compound copolymer A low light thermoplastic resin composition having excellent heat resistance and weather resistance, characterized by being grafted.

17. The copolymer of claim 16, wherein the aromatic vinyl compound-vinyl cyanide compound copolymer (b2) is a copolymer of aromatic vinyl compound about 60 to about 80 weight ¾ and vinyl cyanide compound about 20 to about 40 weight% Low-light thermoplastic resin composition excellent in heat resistance and weather resistance.

18. The low-light thermoplastic resin composition of claim 16, wherein the (bl) (meth) acrylic rubber has a particle average particle diameter in the range of about 0.05 to about 1. ，

19. The low-light thermoplastic having excellent heat resistance and weather resistance according to item 2, wherein the (C) heat-resistant aromatic vinyl copolymer comprises an aromatic vinyl compound unit, a vinyl cyanide compound unit, and a crosslinkable monomer unit. Resin composition.

20. The monofunctional vinyl compound according to item 19, wherein the heat resistant aromatic vinyl copolymer (C) comprises about 60 to about 80 weight% of an aromatic vinyl compound and about 20 to about 40 weight% of a vinyl cyanide compound. Heat resistance and weather resistance, characterized in that it comprises from about 0.01 to about 0.05 parts by weight of the crosslinkable monomer with respect to parts by weight Excellent low light thermoplastic resin composition.

21. The resin composition according to item 1, wherein the resin composition further comprises a copolymer comprising (D) an aromatic vinyl compound-vinyl cyanide compound copolymer, (E) a maleic anhydride compound or a mixture thereof. Low-light thermoplastic resin composition excellent in heat resistance and weather resistance.

22. The low light thermoplastic resin composition of claim 21, wherein the (D) aromatic vinyl compound-vinyl cyanide compound copolymer comprises more than about 0 and about 40 wt% or less of the total resin composition. .

23. The low light thermoplastic resin having excellent heat resistance and weather resistance according to 21 above, wherein the copolymer including the maleic anhydride compound (E) is more than about 0 and less than about 20 weight ¾> in the total resin composition. Composition.

24. The copolymer according to item 21, wherein the copolymer comprising maleic anhydride-based compound (E) comprises maleic anhydride, N-substituted maleate or a mixture thereof in an amount of about 40 to about 60% by weight. Low-light thermoplastic resin composition excellent in heat resistance and weather resistance.

25. The method of claim 1, wherein the composition is an antimicrobial agent, heat stabilizer, antioxidant, mold release agent, light stabilizer, inorganic additive, surfactant, coupling system, plasticizer, stabilizer, stabilizer, lubricant, antistatic agent, colorant, flame retardant, internal A low light thermoplastic resin composition having excellent heat resistance and weather resistance, comprising at least one additive selected from the group consisting of a post-treatment agent, a colorant, a ultraviolet absorber, a sunscreen agent, a flame retardant agent, a filler, a nucleation agent, an adhesion aid, and an adhesive.

26. The composition of item 1, wherein the composition has a glossiness of about 30 GU or less measured using a 75 degree polisher, a Vicat softening point of about 10C L50 ^° C, and a ΔΕ measured by UL 746C of about 2.8 or less. , A low light thermoplastic resin composition having excellent heat resistance and weather resistance, characterized in that the notched layer strength of 1/8 "thickness measured by ASTM D256 is about 8 kgf-cm / cm or more.

27. Has morphology of continuous and disperse phases, The continuous phase includes an aromatic vinyl-vinyl cyanide copolymer and a heat resistant aromatic vinyl copolymer,

The dispersed phase is composed of a network-shaped crab 1 dispersed phase and a particle-shaped second dispersed phase, the first dispersed phase is formed of a (meth) acrylic acid alkyl ester polymer, and the second dispersed phase is formed of an acrylic resin,

1/8 "thick Izod notched laminar strength measured by ASTM D256 with a Vicat softening point of about 100-150 ^° C and greater than about 8 kgf-cm / cm.