WO2019124857A2 - Thermoplastic resin composition and molded product manufactured therefrom - Google Patents

Abstract

A thermoplastic resin composition of the present invention is characterized by comprising: a base resin containing a rubber-modified vinyl-based graft copolymer, a large-diameter rubber polymer having an average particle size of about 3 to about 8μm, and an aromatic vinyl-based copolymer resin; and polyorganosilsesquioxane fine particles having an average particle size of about 0.1 to about 10μm. The thermoplastic resin composition is excellent in low gloss, weather resistance, and the like.

Description

Thermoplastic resin composition and molded article produced therefrom

The present invention relates to a thermoplastic resin composition and a molded article produced therefrom. More specifically, the present invention relates to a thermoplastic resin composition excellent in low light resistance, weather resistance and the like, and a molded article produced therefrom.

The thermoplastic resin composition has a lower specific gravity than glass and metal and is excellent in properties such as moldability and impact resistance and is useful for a housing for an electric / electronic product, an automobile interior / exterior material, and a building exterior material.

In addition, there is an increasing demand for unpainted materials capable of manifesting appearance and surface characteristics such as color and gloss without further processing, in order to reduce environmental friendliness and process cost. In particular, in the fields of interior / exterior materials such as automobiles, electric / electronic products, and building exterior materials, it is required to develop a low-gloss product to satisfy consumers demanding a luxurious appearance.

In order to lower the surface gloss of a molded product (inner / outer surface material, etc.) formed from a thermoplastic resin composition without a post-coating step, the rubber size in the thermoplastic resin composition may be made to be several micrometers or more, Or an inorganic quencher such as talc may be used. However, in the thermoplastic resin composition to which the conventional extinction agent is applied, when the extinction agent is used in an excessive amount, the extinction agent may protrude from the surface, thereby deteriorating the appearance characteristics.

In addition, a molded article produced from such a thermoplastic resin composition may cause deterioration of physical properties such as discoloration when used over a long period of time, and a method for improving weather resistance (discoloration resistance) has been studied. As a method for improving weatherability, there is a method of using an acrylic rubber-like polymer as a rubber-like polymer of a rubber-modified aromatic vinyl-based copolymer resin, or adding a weather-resistant stabilizer.

However, in the acrylic rubber-modified aromatic vinyl copolymer resin, as the content of the acrylic rubber-like polymer increases, there is a fear that the impact resistance and the like are lowered, and the price is increased, which is not economical. In addition, the weatherability stabilizer has disadvantages in that when it is used in an excessive amount, problems such as deterioration of appearance characteristics and mechanical properties may occur due to generation of gas and the like, and thus the increase is not easy.

Therefore, there is a need to develop a thermoplastic resin composition excellent in low light resistance, weather resistance, and the like without deteriorating appearance characteristics and the like.

The background art of the present invention is disclosed in Korean Patent No. 10-1452020.

An object of the present invention is to provide a thermoplastic resin composition excellent in low light resistance, weather resistance and the like.

Another object of the present invention is to provide a molded article formed from the thermoplastic resin composition.

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

1. One aspect of the present invention relates to a thermoplastic resin composition. Wherein the thermoplastic resin composition comprises a base resin comprising a rubber-modified vinyl-based graft copolymer, an adducted rubbery polymer having an average particle size of about 3 to about 8 탆, and an aromatic vinyl-based copolymer resin; And polyoxyalkoxysquioxane particulates having an average particle size of from about 0.1 to about 10 microns.

2. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises about 30 to about 70 wt% of the rubber-modified vinyl-based graft copolymer, about 1 to about 15 wt% of the glass- About 100 parts by weight of a base resin comprising about 25 to about 65% by weight; And about 0.1 to about 10 parts by weight of the polyoxyalkoxysquioxane particulate.

3. The rubber-modified vinyl-based graft copolymer according to any one of the above 1 or 2, wherein the rubber-like polymer having an average particle size of about 100 to about 600 nm, a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer, Polymerized.

4. The rubber-modified vinyl-based graft copolymer according to any one of 1 to 3, wherein the rubber-modified vinyl-based graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer (g-ABS) or an acrylate-styrene- acrylonitrile graft copolymer g-ASA).

5. In the above-mentioned Embodiments 1 to 4, the large-diameter gum polymer is a rubber polymer having a viscosity of about 150 cps or more in a 5 wt% styrene solution, an aromatic vinyl monomer and a monomer copolymerizable with the aromatic vinyl monomer, (A mixture of an aromatic vinyl copolymer resin having an average particle size of about 3 to about 8 占 퐉 and a continuous-phase rubbery polymer having a mean particle size of from about 3 to about 8 占 퐉) dispersed in the rubber-modified aromatic vinyl copolymer resin may be included in the thermoplastic resin composition .

6. In the above-mentioned embodiments 1 to 5, the aromatic vinyl-based copolymer resin may be an aromatic vinyl-based monomer and a polymer of a monomer copolymerizable with the aromatic vinyl-based monomer.

7. The process of any one of claims 1 to 6, wherein said polyorganosilsesquioxane particles are mixed with organotrialkoxysilane such that the organochlorosilane has a concentration of from about 100 to about 2,000 ppm, To obtain a transparent sol, and maintaining the pH of the mixed solution at about 8 to about 11.

8. In the above-mentioned Embodiments 1 to 7, the polyorganosilsesquioxane fine particles may have an average particle size of about 4 to about 7 탆.

9. The thermoplastic resin composition according to any one of 1 to 8, wherein the thermoplastic resin composition has a gloss of about 5 to about 25% for a 1.5 mm thick specimen measured at a 60 angle according to ASTM D523.

10. The thermoplastic resin composition according to any one of the above 1 to 9, wherein the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) is measured using a colorimeter for a 50 mm × 90 mm × 3 mm size injection sample The injection specimen was subjected to weather resistance test for 2,000 hours in accordance with ASTM D4459, and the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter, The calculated color change ([Delta] E) may be from about 0.5 to about 3.0:

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

11. The thermoplastic resin composition according to any one of the above 1 to 10, wherein the rubber-modified vinyl-based graft copolymer, the adducted rubbery polymer and the polyorganosilsesquioxane microparticles are dispersed in a continuous phase comprising an aromatic vinyl- Lt; / RTI >

12. Another aspect of the present invention relates to a molded article. Wherein the molded article is formed from the thermoplastic resin composition according to any one of 1 to 11 above.

INDUSTRIAL APPLICABILITY The present invention has the effect of providing a thermoplastic resin composition excellent in low light resistance, weather resistance and the like and a molded article formed therefrom.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition according to the present invention comprises (A) a base resin comprising (A1) a rubber-modified vinyl-based graft copolymer, (A2) an adherend rubbery polymer, and (A3) an aromatic vinyl copolymer resin; And (B) polyorganosilsesquioxane microparticles.

In the present specification, "a to b" representing numerical ranges are defined as "? A and? B".

(A) Base resin

The base resin of the present invention may comprise (A1) a rubber-modified vinyl-based graft copolymer, (A2) an adherend rubbery polymer, and (A3) an aromatic vinyl copolymer resin.

(A1) rubber-modified aromatic vinyl-based graft copolymer

The rubber-modified vinyl-based graft copolymer according to one embodiment of the present invention can improve the impact resistance, chemical resistance, and the like of the thermoplastic resin composition. The rubber-modified vinyl-based graft copolymer can be obtained by copolymerizing an aromatic vinyl monomer and a monomer containing a vinyl cyanide monomer The mixture may be graft polymerized. For example, the rubber-modified vinyl-based graft copolymer can be obtained by graft-polymerizing a monomer mixture containing an aromatic vinyl monomer and a vinyl cyan monomer to the rubber-like polymer, and if necessary, And a monomer capable of imparting heat resistance can be further graft-polymerized. The polymerization may be carried out by a known polymerization method such as emulsion polymerization or suspension polymerization. Further, the rubber-modified vinyl-based graft copolymer may form a core (rubbery polymer)-shell (copolymer of a monomer mixture).

In a specific example, the rubbery polymer may be a diene rubber (rubbery polymer) such as polybutadiene, poly (styrene-butadiene) or poly (acrylonitrile-butadiene), saturated rubber hydrogenated to the diene rubber, isoprene rubber , An acrylic rubber (rubbery polymer) such as polybutyl acrylate, and an ethylene-propylene-diene monomer terpolymer (EPDM), but the present invention is not limited thereto. These may be used alone or in combination of two or more. For example, a diene rubber, an acrylic rubber, or the like can be used. Specifically, polybutadiene, polybutyl acrylate and the like can be used.

In embodiments, the rubbery polymer (rubber particles) may have an average particle size (D50) as measured by a particle size analyzer of from about 100 to about 600 nm, such as from about 200 to about 400 nm. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In embodiments, the content of the rubbery polymer may be from about 20 to about 70 weight percent, such as from about 30 to about 65 weight percent, of the total 100 weight percent of the rubber modified vinyl based graft copolymer, and the monomer mixture Vinyl monomers and vinyl cyanide monomers) may be from about 30 to about 80% by weight, for example from about 35 to about 70% by weight, based on 100% by weight of the total rubber-modified vinyl-based graft copolymer. Within the above range, the thermoplastic resin composition may have excellent impact resistance and appearance characteristics.

In an embodiment, the aromatic vinyl-based monomer may be graft-copolymerized with the rubbery polymer, and may be selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, Monochlorostyrene, dichlorostyrene, dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more. The content of the aromatic vinyl monomer may be about 10 to about 90 wt%, for example about 40 to about 90 wt%, based on 100 wt% of the monomer mixture. Within the above range, the processability and impact resistance of the thermoplastic resin composition can be excellent.

In the specific examples, the vinyl cyanide monomer is copolymerizable with the aromatic vinyl system, and examples thereof include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, For example. These may be used alone or in combination of two or more. For example, acrylonitrile, methacrylonitrile and the like can be used. The content of the vinyl cyanide monomer may be about 10 to about 90% by weight, for example about 10 to about 60% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition may have excellent chemical resistance and mechanical properties.

In the specific examples, examples of the monomer for imparting the above processability and heat resistance include, but are not limited to, (meth) acrylic acid, maleic anhydride, N-substituted maleimide and the like. When the monomer for imparting processability and heat resistance is used, the content thereof may be about 15% by weight or less, for example, about 0.1 to about 10% by weight, based on 100% by weight of the monomer mixture. Within the above range, the thermoplastic resin composition can be imparted with processability and heat resistance without deteriorating other physical properties.

Examples of the rubber-modified vinyl-based graft copolymer include acrylonitrile-butadiene-styrene graft copolymer (g-ABS), acrylate-styrene-acrylonitrile graft copolymer (g-ASA) For example.

In the specific example, the rubber-modified vinyl-based graft copolymer is prepared by mixing 100% by weight of the base resin (rubber-modified vinyl-based graft copolymer (A1), large-diameter rubbery polymer (A2) and aromatic vinyl- To about 70% by weight, such as from about 35% to about 65% by weight. Within the above range, the thermoplastic resin composition may have excellent light fastness, appearance, impact resistance, fluidity (moldability), and the like.

(A2) Admixed rubbery polymer

The bulky rubbery polymer according to one embodiment of the present invention has an average particle size (D50, volume average) as measured by a particle size analyzer of about 3 to about 8 탆, for example, about 4 to about 7 탆. The thermoplastic resin composition It is possible to improve the light-emitting property of the light-emitting layer. When the average particle size of the above-mentioned highly-gelled rubbery polymer is less than about 3 탆, the light resistance of the thermoplastic resin composition may deteriorate. When the average particle size exceeds about 8 탆, the impact resistance and the like of the thermoplastic resin composition may decrease have.

In an embodiment, the bulky rubbery polymer is a rubber-modified aromatic polymer prepared by continuous solution polymerization of a rubbery polymer having a viscosity of about 150 cps or more in a 5 wt% styrene solution, an aromatic vinyl monomer, and a monomer copolymerizable with the aromatic vinyl monomer In the form of a vinyl copolymer resin (a part or whole of a dispersed phase of an aromatic vinyl copolymer resin (A3) having an average particle size of about 3 to about 8 탆 and an overbrown rubber polymer (A2) and a continuous phase aromatic vinyl copolymer resin (A3) .

Specifically, in the rubber-modified aromatic vinyl-based copolymer resin, a polymerization initiator and a molecular weight regulator are mixed in a mixed solution in which the rubbery polymer, the aromatic vinyl-based monomer and the monomer copolymerizable with the aromatic vinyl-based monomer and the solvent are mixed, ; Introducing the reaction solution into a first reactor to polymerize at a conversion of about 30 to about 40%; And polymerizing the polymerized polymer in the first reactor into a second reactor to obtain a polymer having a conversion of about 70 to about 80%.

In an embodiment, the mixed solution comprises about 3 to about 15 weight percent of the rubbery polymer, about 50 to about 85 weight percent of the aromatic vinyl-based monomer, and about 5 to about 30 weight percent of a monomer copolymerizable with the aromatic vinyl- . ≪ / RTI >

In a specific example, the rubbery polymer contained in the mixed solution may be a diene rubber (rubbery polymer) such as polybutadiene, poly (styrene-butadiene) or poly (acrylonitrile-butadiene) But are not limited to, acrylate rubber (rubber polymer) such as saturated rubber, isoprene rubber and polybutyl acrylate, and ethylene-propylene-diene monomer terpolymer (EPDM). These may be used alone or in combination of two or more. For example, a diene rubber can be used, and specifically, a polybutadiene rubber can be used. In addition, the rubbery polymer may have a viscosity in a 5 wt% styrene solution of about 150 cps or more, such as about 150 to about 300 cps, specifically about 160 to about 200 cps. In the styrene solution viscosity range, a large amount of the gum polymer can be prepared.

In an embodiment, the aromatic vinyl-based monomer contained in the mixed solution is at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, , Dibromostyrene, vinylnaphthalene, and the like. These may be used alone or in combination of two or more.

In an embodiment, examples of the monomer copolymerizable with the aromatic vinyl monomer contained in the mixed solution include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile , And fumaronitrile. These monomers may be used singly or in combination of two or more.

In an embodiment, the content of the aromatic vinyl-based monomer is about 20 to about 90% by weight, for example about 30 to about 80% by weight, of the aromatic vinyl-based monomer and 100% And the content of the monomer copolymerizable with the aromatic vinyl monomer is from about 10 to about 80% by weight, for example, from about 20 to about 80% by weight, based on 100% by weight of the total of the aromatic vinyl monomer and the monomer copolymerizable with the aromatic vinyl monomer About 70% by weight.

In an embodiment, an aromatic organic solvent may be used as the solvent. For example, ethylbenzene, xylene, toluene, etc. may be used, and these may be used alone or in combination.

In the specific examples, the polymerization initiator preferably has a half life of not more than 10 minutes at the polymerization temperature of the reactor, and examples thereof include 1,1-bis (t-butylperoxy) -2-methylcyclohexane, Bis (4-di-t-butylperoxycyclohexane) propane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxycyclohexane, -Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxy laurate, 2,5-dimethyl-2,5-bis (m-toluoylperoxy) Butyl peroxybenzoate, t-butyl peroxybenzoate, 2,5-dimethyl-2,5-bis (benzoyl peroxy) hexane, t-butyl peroxyacetate, A radical initiator such as 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butylperoxy) valerate, . The amount of the polymerization initiator to be used may be about 0.007 to about 0.07 part by weight, for example, about 0.01 to about 0.05 part by weight based on about 100 parts by weight of the mixed solution. Within the above range, deterioration of the appearance characteristics due to the residual polymerization initiator and the like can be reduced.

In the specific examples, alkylmercaptan such as t-dodecylmercaptan, n-dodecylmercaptan and the like may be used as the molecular weight modifier. The amount of the molecular weight regulator to be used may be about 0.02 to about 1 part by weight, for example, about 0.03 to about 0.5 part by weight, relative to about 100 parts by weight of the mixed solution.

In the concrete examples, the continuous solution polymerization is preferably carried out by circulating the refrigerant through a jacket, a coil, or the like, because a heat generation due to the polymerization reaction may occur in the reactor.

In an embodiment, the polymerization initiator and the reaction solution to which the molecular weight regulator is added may be added to the first reactor to polymerize at a conversion rate of about 30 to about 40%, for example, about 32 to about 38%. Stable polymerization can be carried out without excessive load on the agitator within the above range.

In embodiments, the reaction temperature in the first reactor may be from about 60 to about 150 캜, such as from about 70 to about 130 캜. The reaction temperature may be varied depending on the reactor, the stirring speed, the kind of the polymerization initiator, and the like.

In embodiments, the stirring rate in the first reactor may be from about 60 to about 150 rpm, such as from about 80 to about 120 rpm, specifically from about 90 to about 130 rpm. The stirring speed may be changed according to the size of the reactor, the kind of the polymerization initiator, the reaction temperature, and the like.

In an embodiment, the polymerized polymer in the first reactor is introduced into a second reactor and polymerization can be carried out until the conversion is from about 70 to about 80%. In the above range, a bulky rubbery polymer can be prepared.

In embodiments, the reaction temperature in the second reactor may be from about 80 to about 170 캜, such as from about 120 to about 160 캜. The reaction temperature may be varied depending on the reactor, the stirring speed, the kind of the polymerization initiator, and the like.

In embodiments, the stirring rate in the second reactor may be from about 50 to about 100 rpm, such as from about 60 to about 95 rpm, specifically from about 65 to about 90 rpm. The stirring speed may be changed according to the size of the reactor, the kind of the polymerization initiator, the reaction temperature, and the like.

In an embodiment, the continuous solution polymerization may further include devolatilizing the polymerized polymer in the second reactor to remove unreacted monomers and residual solvent. The devolatilization process may be performed using a defolouring process. In one embodiment, the devolatilizing process may be performed using a single devolatilization, and in another embodiment, the devolatilizing process may remove remaining unreacted material in the first vertically coupled devolatilizer and the second devolatilization. When the devolatilization process is performed, the residual monomer content may be about 1,500 ppm or less, for example, about 1,000 ppm or less, specifically about 700 ppm or less.

In an embodiment, a fall-stranding DEVO type is suitable for the deflection (demagnetizing device). The Paul-Stranding type devolatilizer is designed so that the angle of the cone is designed to minimize residence time and can be effectively transferred to the lower gear pump.

In a specific example, when the first devolatilizer and the second devolatilization are used in combination, they can be vertically connected to the upper and lower sides to minimize the connection line between the DEVOs. In addition, it is preferable that a control valve or a regulator is installed in the first dehydration (DV-1) so that the pressure can be adjusted.

In embodiments, the first devolatilizer can be operated at a pressure of from about 100 to about 600 torr, such as from about 200 to about 500 torr, at a temperature of from about 160 to about 240 캜, such as from about 180 to about 220 캜, Min or less. In this range, impurities such as residual monomers can be reduced and productivity can be improved. Also, the second devolatilizer can be operated at a pressure of about 1 to about 50 torr, at a temperature of about 210 to about 250 DEG C for a residence time of about 10 minutes or less, for example, about 5 minutes or less. The color of the rubber-modified aromatic vinyl-based copolymer resin produced in the above range may be excellent.

In an embodiment, the aromatic vinyl-based copolymer resin of the rubber-modified aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of about 10,000 to about 300,000 g / mol, From about 15,000 to about 150,000 g / mol. Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

Here, the aromatic vinyl-based copolymer of the rubber-modified aromatic vinyl-based copolymer resin may be the same composition as the aromatic vinyl-based copolymer resin (A3), and the (first) aromatic vinyl The content of the aromatic vinyl copolymer resin (A3) in the thermoplastic resin composition can be adjusted by adding a separate (second) aromatic vinyl copolymer resin in addition to the copolymer based copolymer.

In an embodiment, the bulking gum polymer may comprise from about 1 to about 15 weight percent, for example from about 2 to about 10 weight percent, of 100 weight percent of the base resin (A1), (A2) and (A3) have. Within the above range, the thermoplastic resin composition may have excellent light fastness, appearance, impact resistance, fluidity (moldability), and the like.

(A3) The aromatic vinyl-based copolymer resin

The aromatic vinyl-based copolymer resin according to one embodiment of the present invention may be an aromatic vinyl-based copolymer resin used in a conventional rubber-modified vinyl-based copolymer resin. For example, the aromatic vinyl-based copolymer resin may be a polymer of a monomer mixture comprising a monomer copolymerizable with the aromatic vinyl-based monomer such as an aromatic vinyl-based monomer and a vinyl cyanide-based monomer. Here, the aromatic vinyl-based copolymer resin (A3) is a copolymer of the rubber-modified aromatic vinyl-based copolymer resin (the dispersed phase of the aromatic vinyl-based copolymer resin having an average particle size of about 3 to about 8 [ (A3) of the thermoplastic resin composition in addition to the aromatic vinyl-based copolymer resin of the aromatic vinyl-based copolymer resin of the thermoplastic resin composition.

In a specific example, the separate aromatic vinyl-based copolymer resin may be obtained by mixing an aromatic vinyl-based monomer and a monomer copolymerizable with an aromatic vinyl-based monomer, and then polymerizing the monomer. The polymerization may be carried out by emulsion polymerization, Polymerization, and the like.

In an embodiment, the aromatic vinyl monomer is at least one monomer selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, pt-butylstyrene, ethylstyrene, vinylxylene, monochlorostyrene, dibromostyrene , Vinyl naphthalene and the like can be used. These may be used alone or in combination of two or more. The content of the aromatic vinyl-based monomer may be about 20 to about 90% by weight, for example about 30 to about 80% by weight, based on 100% by weight of the entire aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

Examples of the monomer copolymerizable with the aromatic vinyl-based monomer include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenyl acrylonitrile,? -Chloroacrylonitrile, and fumaronitrile. Vinyl cyanide monomers, and the like. These monomers may be used singly or in combination of two or more. The content of the monomer copolymerizable with the aromatic vinyl-based monomer may be about 10 to about 80% by weight, for example about 20 to about 70% by weight, based on 100% by weight of the total aromatic vinyl-based copolymer resin. The impact resistance and fluidity of the thermoplastic resin composition can be excellent in the above range.

In embodiments, the aromatic vinyl-based copolymer resin has a weight average molecular weight (Mw), as measured by gel permeation chromatography (GPC), of from about 10,000 to about 300,000 g / mol, such as from about 15,000 to about 150,000 g / . Within the above range, the thermoplastic resin composition may have excellent mechanical strength and moldability.

In an embodiment, the aromatic vinyl-based copolymer resin comprises about 25 to about 65 weight percent, for example about 30 to about 60 weight percent, of 100 weight percent of the base resin ((A1), (A2) and (A3) . Within the above range, the thermoplastic resin composition may have excellent light fastness, appearance, impact resistance, fluidity (moldability), and the like.

The base resin according to one embodiment of the present invention may be a structure in which a rubber-modified vinyl-based graft copolymer (A1) and a larger-diameter rubbery polymer (A2) dispersed in a dispersed phase are dispersed in an aromatic vinyl copolymer resin (A3) have. For example, the base resin may be prepared by preparing a rubber-modified aromatic vinyl-based copolymer resin in which a substituted rubber polymer (A2, dispersed phase) is dispersed in an aromatic vinyl copolymer resin (A3, continuous phase) Modified vinyl-based graft copolymer (A1). In order to adjust the component content of the base resin, a separate aromatic vinyl-based copolymer resin (A3) can be added.

(B) polyorganosilsesquioxane fine particles

The polyorganosiloxanesquioxane microparticles of the present invention can improve the low light resistance, weather resistance, etc. of the thermoplastic resin composition and have an average particle size (D50) measured by a particle size analyzer of about 0.1 to about 10 m, for example, about 4 to about 7 [mu] m. When the average particle size of the polyisocyanurate silsesquioxane particles is less than about 0.1 탆, the light resistance of the thermoplastic resin composition may deteriorate. When the average particle size of the polyisocyanurate silsesquioxane particles is more than about 10 탆, the impact resistance, May be deteriorated.

In an embodiment, the polyorganosilsesquioxane microparticles are prepared by mixing organotrialkoxysilane with organotin octyloxysilane such that the organochlorosilane has a concentration of from about 100 to about 2,000 ppm, mixing water to the mixture to obtain a transparent sol, and And maintaining the pH of the mixed solution at about 8 to about 11.

In an embodiment, the organotrialkoxysilane may be represented by the following formula (1).

[Chemical Formula 1]

R ¹ Si (OR ² ) ₃

R ¹ is an alkyl group having 1 to 6 carbon atoms, a vinyl group, or an aryl group having 6 to 10 carbon atoms, and R ² is an alkyl group having 1 to 5 carbon atoms. For example, R ¹ may be a methyl group, an ethyl group, or a phenyl group, and R ² may be a methyl group, an ethyl group, a propyl group, or a butyl group. Specifically, it is industrially preferable that R ¹ and R ² are methyl groups.

In an embodiment, the organotrialkoxysilane can be used in an amount of from about 5 to about 50 weight percent, for example, from about 10 to about 30 weight percent, based on the total reaction solution. Within the above range, the reaction yield and average particle size can be easily controlled.

In an embodiment, the organochlorosilane may be an alkoxy group which is fully or partially substituted by a chlorine group and may be represented by the following formula (2).

(2)

R ¹ Si (OR ² ) _{3 - x} Cl _x

Wherein R ¹ is an alkyl group having 1 to 6 carbon atoms, a vinyl group, or an aryl group having 6 to 10 carbon atoms, R ² is an alkyl group having 1 to 5 carbon atoms, and x ranges from 1 to 3.

For example, the organochlorosilane can be an organotrichlorosilane in which all of the alkoxy groups are replaced by chlorine groups.

In an embodiment, the organochlorosilane can be mixed with the organotrialkoxysilane in an amount of about 100 to about 2,000 ppm. Within this range, polyisocyanurate particles having a desired particle size can be easily obtained, and the impurity treatment can be facilitated.

In an embodiment, the mixing can be carried out using a high efficiency mixer. High-efficiency mixers include high-speed emulsification / dispersion equipment such as a homomixer, homogenier, microfluidizer, Agitation equipment in the form of a combination of disturbance plates can be used.

In a specific example, the transparent sol may be prepared and then treated with a basic aqueous solution (an aqueous solution of an alkali metal, alkaline earth metal, hydrogen carbonate, ammonia, or the like) at a pH of about 8 to about 11, Lt; RTI ID = 0.0 > 10 < / RTI > to obtain polystyrene nosilsesquioxane microparticles. In the above pH range, fine particles can be formed without the problem of dissolution of fine particles.

In the specific example, after the above process, the final fine particles can be obtained through filtration, washing with water, drying and the like. When drying, a spray dryer, a spin flash dryer or the like can be used to prevent particle-to-particle aggregation and to obtain fine particles in a simple state without a separate crushing step.

In embodiments, the polyorganosilsesquioxane microparticles may be included in an amount of from about 0.1 to about 10 parts by weight, for example, from about 1 to about 8 parts by weight, based on about 100 parts by weight of the base resin. Within the above range, the thermoplastic resin composition may be excellent in weather resistance, light fastness, and the like.

The thermoplastic resin composition according to one embodiment of the present invention may further include an additive contained in a conventional thermoplastic resin composition. Examples of the additives include, but are not limited to, quenching agents, stabilizers, flame retardants, fillers, antioxidants, antioxidants, lubricants, release agents, nucleating agents, antistatic agents, pigments, dyes and mixtures thereof. When the additive is used, the content thereof may be about 0.001 to about 40 parts by weight, for example, about 0.1 to about 10 parts by weight, relative to about 100 parts by weight of the base resin.

The thermoplastic resin composition according to one embodiment of the present invention is prepared by mixing the above components and melt-extruding at a temperature of about 200 to about 280 캜, for example, about 220 to about 250 캜, using a conventional twin-screw extruder. .

In an embodiment, the thermoplastic resin composition comprises a rubber-modified vinyl-based graft copolymer (A1) as a dispersed phase in an aromatic vinyl-based copolymer resin (A3) as a continuous phase, a gum- (B) may be dispersed.

In embodiments, the thermoplastic resin composition may have a gloss of less than or equal to about 25%, such as from about 5% to about 25%, of a 1.5 mm thick specimen measured at a 60 angle according to ASTM D523.

In an embodiment, the thermoplastic resin composition may be prepared by measuring the initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) using a colorimeter on a 50 mm × 90 mm × 3 mm sized injection specimen, The color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter according to ASTM D4459 for 2,000 hours and then the color change ΔE ) Can be from about 0.5 to about 3.0, such as from about 1.0 to about 2.5:

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

The molded article according to the present invention is formed from the thermoplastic resin composition. The thermoplastic resin composition may be produced in the form of pellets, and the produced pellets may be manufactured into various molded products through various molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. Since the molded article is excellent in low light resistance, weather resistance, weather resistance, impact resistance and fluidity (molding processability), it is useful for interior / exterior materials for electric / electronic products, automobile interior / exterior materials, and building exterior materials requiring low light property and weather resistance Do.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Hereinafter, specifications of each component used in Examples and Comparative Examples are as follows.

(A) Base resin

(A1) rubber-modified aromatic vinyl-based graft copolymer

G-ASA in which 55 wt% of styrene and acrylonitrile (weight ratio: 75/25) were graft copolymerized was used in 45 wt% of butyl acrylate rubber (average particle size: 310 nm).

(A2) Admixed rubbery polymer

(A2-1) A mixed solution of 53.4 parts by weight of a styrene monomer, 17.8 parts by weight of an acrylonitrile monomer, and 20 parts by weight of ethylbenzene as a reaction solvent was added to a butadiene rubber (BR-1) having a solution viscosity of 170 cps in a styrene solution of 5% 1: ASADENE 55AE) was dissolved in 8.8 parts by weight, 0.015 part by weight of 1,1-bis (t-butylperoxy) cyclohexane as a polymerization initiator and 0.07 part by weight of t-dodecyl mercaptan as a molecular weight regulator were added, Prepared. The prepared mixed solution was fed into the reactor at a rate of 25 kg / hr. The first reactor had a stirring speed of 130 rpm and a conversion rate of 35%. The second reactor was controlled to have a stirring speed of 70 rpm and a conversion of 75%. After the polymerization, the remaining unreacted material was removed by defoaming, and a pellet-shaped rubber-modified aromatic vinyl copolymer resin (ABS resin, (Content phase (dispersed phase: continuous phase): 12% by weight: 88% by weight) of an aromatic vinyl polymer resin (A2-1, dispersed phase) and an aromatic vinyl copolymer resin (SAN resin, A3-1, continuous phase) . Here, the average particle size of the large-diameter rubbery polymer (A2-1) was 5.16 占 퐉, and the weight average molecular weight of the SAN resin (A3-1) was 130,000 g / mol.

(A2-2) A rubber-modified aromatic vinyl copolymer resin (ABS resin, an adduct of a large-diameter rubber polymer (A2)) was prepared in the same manner as in the above-mentioned production process (A2-1) except that the stirring speed of the first reactor was changed to 100 rpm. (Content phase (dispersed phase: continuous phase): 12% by weight: 88% by weight) of an aromatic vinyl copolymer resin (A2-2, dispersed phase) and an aromatic vinyl copolymer resin (SAN resin, A3-2, continuous phase). The average particle size of the prepared large-diameter rubbery polymer (A2-2) was 8.58 탆, and the weight average molecular weight of SAN resin (A3-2) was 130,000 g / mol.

(A2-3) A rubber-modified aromatic (meth) acrylate copolymer (A2) was obtained in the same manner as in the above (A2-1) except that a butadiene rubber (BR-2: ASAPRENE 700A) having a solution viscosity of 45 cps in a 5 wt% A mixture (content (dispersed phase: continuous phase) of 12 parts by weight of a vinyl-based copolymer resin (ABS resin, large-diameter rubber polymer (A2-3, dispersed phase) and aromatic vinyl copolymer resin (SAN resin, A3-3, continuous phase) Weight%: 88% by weight)) was prepared. The average particle size of the prepared extruded rubbery polymer was 1.37 占 퐉, and the weight average molecular weight of SAN resin (A3-3) was 130,000 g / mol.

Here, the average particle size of the rubber-modified aromatic vinyl-based graft copolymer (A1) and the larger-diameter rubbery polymer (A2) refers to the volume average particle size measured using a particle size analyzer (Malvern's Mastersizer S Ver.2.14).

(A3) The aromatic vinyl-based copolymer resin

As the aromatic vinyl-based copolymer resin added in addition to the SAN resins (A3-1, A3-2, and A3-3), 75 wt% of styrene and 25 wt% of acrylonitrile were added to the SAN resin Weight average molecular weight: 130,000 g / mol) was used.

(B) polyorganosilsesquioxane fine particles

(B1) Methyltrimethoxysilane was mixed with methyltrichlorosilane to a concentration of 500 ppm, and then 280 g of the mixed solution was mixed with 1,720 g of ion-exchanged water. The mixture was then mixed at a high speed using a homomixer at 10,000 rpm for 1 minute, adjusted to pH 9.6 with 0.08 phr of ammonia water, and maintained for 4 hours. Thereafter, white polioganosilsesquioxane fine particles prepared by filtering and washing with water and drying with a spray dryer were used (average particle size: 5.5 μm). Here, the average particle size (volume average, D50) was measured using a particle size analyzer (Beckman Coulter Laser Diffraction Particle Size Analyzer LS I3 320 instrument).

(B2) The polyorganosilsesquioxane fine particles prepared in the same manner as in (B1) (average particle size: 15 μm) were used, except that the ammonia water was changed to 0.02 phr and the pH was changed.

(B3) The polyorganosilsesquioxane fine particles prepared in the same manner as in (B1) (average particle size: 0.05 탆) were used, except that the ammonia water was changed to 5 phr and the pH was changed.

(C) Extinguishing agent

PS / SAN copolymer the (manufacturer:: Chemtura社, product name BLENDEX BMAT ^®) was used.

Example  1 to 3 and Comparative Example  1 to 5

The above components were added in the amounts shown in Table 1, and then extruded at 230 캜 to prepare pellets. (A2-1, A2-2 and A2-3, dispersed phase) are added to the aromatic vinyl-based copolymer resin (A3-1, A3-2 and A3-3, continuous phase) Modified aromatic vinyl copolymer resin was prepared by adding a rubber-modified vinyl-based graft copolymer (A1, dispersed phase) and an aromatic vinyl copolymer resin (A3, continuous phase) .

The extruded product was extruded using a twin-screw extruder having an L / D of 36 and a diameter of 45 mm. The pellets were dried at 80 DEG C for 2 hours or more, and then extruded in a 6 Oz extruder (molding temperature 230 DEG C, mold temperature 60 DEG C) To prepare a specimen. The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 1 below.

How to measure property

(1) Surface gloss (unit:%): The gloss was measured at 60 ° by BYK-Gardner Gloss Meter by BYK, according to the evaluation method described in ASTM D523.

(L ₀ ^* , a ₀ ^* , and A ₀ ^* ) were measured using a colorimeter (KONICA MINOLTA, CM-3700A) for a 50 mm × 90 mm × 3 mm size injection mold. b ₀ ^*) measurement, and on the basis of the injection specimen in ASTM D4459, the color (L ₁ and then tested with the weather resistance test, and color difference meter for 2000 hours ^{_{*, a 1 *, b 1}} *) was measured, and then , And the color change (? E) was calculated according to the following formula (1).

[Formula 1]

Color change (ΔE) =

In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.

(3) IZOD Impact Strength (Unit: kgf · cm / cm): A notch was formed on a 1/4 "thick Izod sample according to the evaluation method described in ASTM D256.

(4) Melt Index (MI, unit: g / 10 min): Measured at 220 캜 and 10 kgf according to the evaluation method defined in ASTM D1238.

		Example			Comparative Example
		One	2	3	One	2	3	4	5
(A) (% by weight)	(A1)	50	50	50	50	50	50	50	50
	(A2-1)	4.8	4.8	4.8	4.8	4.8	4.8	-	-
	(A2-2)	-	-	-	-	-	-	4.8	-
	(A2-3)	-	-	-	-	-	-	-	4.8
	(A3-1)	35.2	35.2	35.2	35.2	35.2	35.2	-	-
	(A3-2)	-	-	-	-	-	-	35.2	-
	(A3-3)	-	-	-	-	-	-	-	35.2
	(A3)	10	10	10	10	10	10	10	10
(B) (parts by weight)	(B1)	2	6	8	-	-	-	6	6
	(B2)	-	-	-	6	-	-	-	-
	(B3)	-	-	-	-	6	-	-	-
(C) (parts by weight)		-	-	-	-	-	6	-	-
Glossiness (%)		25	10	5	10	40	30	8	15
Color change (ΔE)		2.5	1.2	1.0	2.5	3.0	4.0	1.5	1.2
Notch Izod impact strength		40	30	20	15	10	10	30	10
Melt Index		10	5.0	3.0	1.5	10	3.0	1.5	6.0

Parts by weight based on 100 parts by weight of the base resin (A)

From the above results, it can be seen that the thermoplastic resin composition of the present invention is excellent in low light resistance, weather resistance, impact resistance, flowability (processability) and the like.

On the other hand, in the case of Comparative Example 1 using the polyorganosilsesquioxane fine particles (B2) having an average particle size exceeding 10 mu m (15 mu m), it was found that the impact resistance and the fluidity were lowered and the average particle size was 0.1 In Comparative Example 2 using polyisocyanuric sesquioxane fine particles (B3) having a particle size of less than 탆 (0.05 탆), low light resistance, weather resistance, impact resistance and the like were found to be lowered. (PS / SAN copolymer (C)) in Comparative Example 3, it was found that the low light resistance, weather resistance, impact resistance, fluidity and the like were lowered. In addition, in Comparative Example 4 using an extruded rubbery polymer (A2-2) having an average particle size of 8.58 占 퐉, it was found that the flowability and the like were lowered, and the average particle size of the extruded rubbery polymer A2-3 ) In Comparative Example 5, the impact resistance and the like are lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (12)

1. A base resin comprising a rubber-modified vinyl-based graft copolymer, an average particle size of about 3 to about 8 占 퐉, and an aromatic vinyl copolymer resin; And

   Wherein the polyorganosiloxane particles have an average particle size of about 0.1 to about 10 microns.
2. The thermoplastic resin composition of claim 1, wherein the thermoplastic resin composition comprises about 30 to about 70 wt% of the rubber-modified vinyl-based graft copolymer, about 1 to about 15 wt% About 65% by weight of a base resin; And about 0.1 to about 10 parts by weight of the polyoxyalkoxysilicate microparticles.
3. The rubber-modified vinyl-based graft copolymer according to claim 1, wherein the rubber-modified vinyl-based graft copolymer is obtained by graft-polymerizing a monomer mixture comprising an aromatic vinyl monomer and a vinyl cyan monomer in a rubber polymer having an average particle size of about 100 to about 600 nm Wherein the thermoplastic resin composition is a thermoplastic resin composition.
4. The rubber-modified vinyl-based graft copolymer according to claim 1, wherein the rubber-modified vinyl-based graft copolymer is an acrylonitrile-butadiene-styrene graft copolymer (g-ABS) or an acrylate-styrene- acrylonitrile graft copolymer (g- And the thermoplastic resin composition is a thermoplastic resin composition.
5. The rubber composition according to claim 1, wherein the bulky rubbery polymer is a rubber prepared by continuous solution polymerization of a rubbery polymer having a viscosity of about 150 cps or more in a 5 wt% styrene solution, an aromatic vinyl monomer, and a monomer copolymerizable with the aromatic vinyl monomer A thermoplastic resin composition characterized by being contained in a thermoplastic resin composition in the form of a modified aromatic vinyl copolymer resin.
6. The thermoplastic resin composition according to claim 1, wherein the aromatic vinyl-based copolymer resin is a polymer of an aromatic vinyl-based monomer and a monomer copolymerizable with the aromatic vinyl-based monomer.
7. The process of claim 1 wherein said polyorganosilsesquioxane microparticles are mixed with organotrialkoxysilane such that the organochlorosilane has a concentration of from about 100 to about 2,000 ppm and water is mixed with said mixture to obtain a clear sol , And maintaining the pH of the mixed solution at about 8 to about 11. The thermoplastic resin composition of claim 1,
8. The thermoplastic resin composition according to claim 1, wherein the polyoxyalkoxysiloxane particles have an average particle size of about 4 to about 7 탆.
9. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has a gloss of from about 5 to about 25% for a 1.5 mm thick specimen measured at an angle of 60 degrees according to ASTM D523.
10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition has an initial color (L ₀ ^* , a ₀ ^* , b ₀ ^* ) measured using a colorimeter on a 50 mm × 90 mm × 3 mm size injection mold, The specimens were subjected to weather resistance test for 2,000 hours in accordance with ASTM D4459, the color (L ₁ ^* , a ₁ ^* , b ₁ ^* ) after the test was measured using a colorimeter, (? E) of from about 0.5 to about 3:

    [Formula 1]

    Color change (ΔE) =

    

    In the formula 1, ΔL ^* is a difference (L ₁ ^* -L ₀ ^*) in the L ^* values before and after the test, Δa ^* is the difference between _{^{(a 1 * - a 0 *}} ) of the a ^* values before and after the test and, Δb ^* Is the difference (b ₁ ^* - b ₀ ^* ) between the values of b ^* before and after the test.
11. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises a rubber-modified vinyl-based graft copolymer, an adduct of a rubber-like polymer and a polyorganosilsesquioxane microparticle in a dispersed phase in a continuous phase comprising an aromatic vinyl- Thermoplastic resin composition.
12. A molded article formed from the thermoplastic resin composition according to any one of claims 1 to 11.