KR20080022747A - Thermoplastic resin composition having good weatherability and scratch resistant property - Google Patents

Abstract

A thermoplastic resin composition is provided to improve weather resistance and scratch resistance without the deterioration of fluidity, tensile strength, color and thermal stability. A thermoplastic resin composition comprises 100 parts by weight of a base resin which comprises 20-50 parts by weight of an acrylonitrile-butadiene-styrene-based graft copolymer and 10-80 parts by weight of an acrylate-styrene-acrylonitrile-based terpolymer; 0.2-1.0 parts by weight of a high viscosity silicone resin; and optionally 30 parts by weight or less of a styrene-acrylonitrile-based copolymer. Preferably the styrene-acrylonitrile-based copolymer comprises 30-90 parts by weight of a styrene-based monomer and 10-70 parts by weight of an acrylonitrile-based monomer.

Description

Thermoplastic resin composition excellent in weatherability and scratch resistance {THERMOPLASTIC RESIN COMPOSITION HAVING GOOD WEATHERABILITY AND SCRATCH RESISTANT PROPERTY}

The present invention relates to a thermoplastic resin composition, and more particularly, it is applied to an extrusion sheet and a building material which are left in the outdoor due to the drastic improvement of weather resistance and scratch resistance while maintaining physical properties such as fluidity, tensile strength, color, and thermal stability. It relates to a thermoplastic resin composition suitable for the following.

Acrylonitrile-butadiene-styrene (ABS) resin is a typical resin that combines functionality and versatility, and has excellent properties such as impact strength, tensile strength, elastic modulus, and flame retardancy. It is widely used for applications such as electronic components.

However, ABS resins are susceptible to discoloration as the double bonds of butadiene rubber used for impact reinforcement are decomposed by oxygen, ozone, light, etc. in the air when exposed to UV light for a certain period of time. There is a problem that the quality is degraded and the strength is also weakened a lot.

Due to these problems, in most cases, efforts have been made to reinforce the weather resistance of the ABS resin and improve the appearance quality through a plating or painting process.

As a method for reinforcing the weather resistance of ABS resin, Korean Patent No. 0316364 describes that a mixed resin of ABS resin and polycarbonate resin (PC) forms a support layer, and polymethyl methacrylate resin (PMMA) having excellent weather resistance is a surface layer. The multilayer sheet which can comprise the structure and which can reinforce the weather resistance of the whole sheet is opened. However, in order to manufacture such a multilayer sheet, a facility investment for a multilayer sheet is required, and there is a problem that an increase in manufacturing cost is inevitable because PC resin is contained in the support layer by 50 wt% or more.

In US Pat. No. 6,048,617, a curable resin, which is a mixture of acrylic resin, organic metallic compound, and silicone compound having a molecular weight of 2,000 to 30,000 in a PC resin and an ABS resin, is applied to a surface by heating or photo-irradiation. A method of applying and curing to improve weather resistance, scratch resistance and thermal stability of plastic products is disclosed. However, after the injection of the PC resin and ABS resin, an additional process such as the process of applying and curing the mixture is required, and there is a problem that defective products may occur during the coating process and it is difficult to recycle.

Therefore, there is a need for the development of a thermoplastic resin composition which is excellent in both weather resistance and scratch resistance and is recyclable without additional equipment investment and process step.

In order to solve the problems of the prior art as described above, the present invention is applied to the extrusion sheet and the building material which is left in the outdoors by significantly improving weather resistance and scratch resistance while maintaining physical properties such as fluidity, tensile strength, color and thermal stability. It is an object to provide a thermoplastic resin composition suitable for the following.

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

In order to achieve the above object, the present invention is a basic resin comprising 20 to 50 parts by weight of acrylonitrile-butadiene-styrene graft copolymer and 10 to 80 parts by weight of acrylate-styrene-acrylonitrile terpolymer And it provides a thermoplastic resin composition comprising 0.2 to 1.0 parts by weight of a high viscosity silicone resin based on 100 parts by weight of the base resin.

Hereinafter, the present invention will be described in detail.

The thermoplastic resin composition of the present invention is characterized by including a high viscosity silicone resin in a base resin comprising an acrylonitrile-butadiene-styrene graft copolymer and an acrylate-styrene-acrylonitrile terpolymer.

<Basic Resin>

The base resin includes (I) acrylonitrile-butadiene-styrene graft copolymer and (II) acrylate-styrene-acrylonitrile terpolymer.

The base resin further includes (III) styrene-acrylonitrile-based copolymer.

(I) Acrylonitrile-butadiene-styrene (ABS) type graft copolymer

The acrylonitrile-butadiene-styrene graft copolymer includes 100 parts by weight of conjugated diene-based polymer, 30 to 60 parts by weight of styrene monomer, and 10 to 30 parts by weight of acrylonitrile monomer.

The conjugated diene-based rubbery polymer is first prepared with a small-diameter rubbery polymer, and the small-diameter rubbery polymer is fused with an acid to prepare a large-diameter rubbery polymer.

The average particle diameter, gel content and the like of the conjugated diene rubber polymer have a great influence on impact strength, processability, etc. of the ABS copolymer. In general, the smaller the average particle diameter of the rubbery polymer, the lower the impact strength and workability, and the larger the average particle diameter, the higher the impact strength. However, the content of the rubbery polymer is increased, the larger the average particle diameter, the lower the graft rate, there is a problem that a lot of ungrafted rubbery polymer is present in the ABS copolymer, thereby deteriorating physical properties such as thermal stability. Therefore, it is important to prepare a conjugated diene-based rubbery polymer having an appropriate average particle diameter, and graft polymerization of the styrene-based monomer and acrylonitrile-based monomer to the conjugated diene-based rubbery polymer, but polymerizing it to have an appropriate graft ratio.

The acrylonitrile-butadiene-styrene graft copolymer is (i) a conjugated diene-based rubber prepared by first preparing a small-diameter rubbery polymer, and (ii) fusing a small-diameter rubbery polymer with an acid. It is prepared by graft polymerization of (iii) styrene monomer and acrylonitrile monomer to the polymer.

(Ⅰ) Preparation of small diameter conjugated diene rubber polymer

Small-diameter conjugated diene-based rubbery polymers are prepared by mixing and emulsion-polymerizing conjugated diene-based monomers, emulsifiers, polymerization initiators, electrolyte materials, molecular weight regulators and ion-exchanged water.

As the conjugated diene monomer, butadiene, isoprene or chloroisoprene may be used alone or in combination of two or more thereof, and it is preferable to use butadiene.

As the emulsifier, alkyl aryl sulfonates, alkali metal alkyl sulfates, sulfonated alkyl esters, fatty acid soaps, or rosin acid alkali salts, or the like can be used alone or in combination of two or more thereof, based on 100 parts by weight of the conjugated diene monomer. It is preferred to use 1 to 4 parts by weight.

The polymerization initiator is a water-soluble persulfate initiator such as sodium persulfate or potassium persulfate, cumene hydroperoxide, diisopropylbenzene hydroperoxide, azobis isobutyronitrile, tertiary butyl hydroperoxide, para-methane hydro Fat-soluble initiators, such as a peroxide or benzoyl peroxide, or an oxidation-reduction initiator, etc. can be used. The polymerization initiator is preferably used in 0.1 to 0.6 parts by weight based on 100 parts by weight of the conjugated diene monomer.

As the electrolyte material, KCl, NaCl, KHCO ₃ , NaHCO ₃ , K ₂ CO ₃ , Na ₂ CO ₃ , KHSO ₃ , NaHSO ₃ , K ₄ P ₂ O ₇ , K ₃ PO ₄ , Na ₃ PO ₄ , K ₂ HPO ₄ or Na ₂ HPO ₄ and the like can be used alone or in combination of two or more, it is preferable to use 0.1 to 1 parts by weight based on 100 parts by weight of the conjugated diene monomer.

As the molecular weight regulator, t-dodecyl mercaptan or n-octyl mercaptany may be used, and it is preferable to use 0.1 to 0.5 parts by weight based on 100 parts by weight of the conjugated diene monomer.

The ion-exchanged water is preferably used in 90 to 130 parts by weight based on 100 parts by weight of the conjugated diene monomer.

The small-diameter conjugated diene-based rubbery polymer includes 100 parts by weight of the conjugated diene monomer, 1 to 4 parts by weight of an emulsifier, 0.1 to 0.6 parts by weight of a polymerization initiator, 0.1 to 1 parts by weight of an electrolyte material, 0.1 to 0.5 parts by weight of a molecular weight regulator, and ion exchanged water. It can be prepared by mixing 90 to 130 parts by weight and emulsion polymerization.

The same ingredients are added to the reactor in a batch for the first polymerization at 50 to 65 ℃ for 7 to 12 hours, and 0.05 to 1.2 parts by weight of the molecular weight modifier is added to polymerize at 55 to 70 ℃ for 5 to 15 hours. Can be.

It is preferable that the small diameter conjugated diene rubber polymer prepared above has an average particle diameter of 600-1500 mmPa. In the case of the average particle diameter, mechanical properties such as impact strength and tensile strength, thermal stability, and colorability are excellent.

(Ii) Preparation of large diameter conjugated diene rubber polymer

The large-diameter conjugated diene-based rubbery polymer is treated with an acid of the small-diameter conjugated diene-based rubbery polymer prepared in (iii) to fusion of small-diameter conjugated diene-based rubbery polymer particles, thereby preparing into enlarged large-diameter particles.

The acid is not particularly limited, and hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, hydroxyl acid, nitric acid, propionic acid, benzoic acid, formic acid, citric acid, lactic acid, or maleic acid may be used alone or in combination of two or more thereof. 2.5 to 4.5 parts by weight based on 100 parts by weight of the caliber conjugated diene rubber polymer.

The large-diameter conjugated diene-based rubbery polymer is slowly added and stirred at 2.5 to 4.5 parts by weight of an acid to 100 parts by weight of the small-diameter conjugated diene-based rubbery polymer prepared in (i) for 1 hour to fusion of the small-diameter conjugated diene-based rubbery polymer particles. After allowing it to occur, it can be prepared by enlarging the particles by staying for a predetermined period of time.

The prepared large-diameter conjugated diene-based rubbery polymer preferably has an average particle diameter of 2500 to 5000 mm 3. In the case of the average particle diameter, there is no problem that the graft ratio is lowered, and the mechanical properties such as impact strength and tensile strength are excellent, and fluidity and glossiness are improved.

(Iii) Preparation of Acrylonitrile-Butadiene-Styrene Graft Copolymer

The acrylonitrile-butadiene-styrene graft copolymer is an emulsifier, a molecular weight regulator, a polymerization initiator, and an ion in a reaction mixture comprising the large-diameter conjugated diene rubber polymer, the styrene monomer, and the acrylonitrile compound prepared in the above (ii). It is prepared by adding exchanged water and emulsion polymerization.

As the styrene monomer, styrene, α-methyl styrene, p-methyl styrene, ο-ethyl styrene, p-ethyl styrene or vinyltoluene may be used alone or in combination of two or more thereof, and it is preferable to use styrene. . The styrene monomer may be used in an amount of 30 to 60 parts by weight, preferably 38 to 57 parts by weight, based on 100 parts by weight of the large-diameter conjugated diene rubber polymer. When used in the above content, there is no phenomenon that the resin is yellowish, and there is an excellent compatibility with the styrene-acrylonitrile resin (SAN) which is a matrix.

As the acrylonitrile-based monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used alone or in combination of two or more thereof, and acrylonitrile is preferably used. The acrylonitrile monomer is preferably used in an amount of 10 to 30 parts by weight, preferably 13 to 29 parts by weight, based on 100 parts by weight of the large-diameter rubbery polymer. When used in the above content is excellent compatibility with the styrene-acrylonitrile resin (SAN) of the matrix, there is an effect that the color of the resin is not yellowish (yellowish).

The emulsifier may be the same as the one used in the preparation of the small-diameter conjugated diene rubber polymer of (iii), it is preferable to use 0.2 to 1 parts by weight based on 100 parts by weight of the large-diameter conjugated diene rubber polymer.

As the molecular weight modifier, the same ones used in the preparation of the small-diameter conjugated diene-based rubbery polymer of (iii) can be used, and it is preferable to use 0.2 to 0.6 parts by weight based on 100 parts by weight of the large-diameter conjugated diene-based rubbery polymer.

The polymerization initiators include peroxide and sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrrolate, including cumene hydroperoxide, diisopropylbenzene hydroperoxide or persulfate. Or an redox-based initiator consisting of a mixture of reducing agents comprising sodium sulfite. The polymerization initiator is preferably used in 100 parts by weight of the large diameter conjugated diene rubber polymer.

The ion-exchanged water is preferably used at 80 to 150 parts by weight based on 100 parts by weight of the conjugated diene monomer.

The acrylonitrile-butadiene-styrene graft copolymer includes 100 parts by weight of the large-diameter conjugated diene rubber polymer prepared in (ii), 30 to 60 parts by weight of styrene monomer and 10 to 30 parts by weight of acrylonitrile monomer. 0.2 to 1 parts by weight of an emulsifier, 0.2 to 0.6 parts by weight of a molecular weight regulator, 0.1 to 0.5 parts by weight of a polymerization initiator, and 80 to 150 parts by weight of ion-exchanged water may be added to the reaction mixture.

The above components may be prepared by dividing or multiplying the components in multiple stages or by emulsion polymerization at 45 to 80 ° C. for 3 to 5 hours to produce latex having a polymerization conversion of 95% or more. In the case of the divided input or continuous input, the graft ratio of the latex to be manufactured is improved, and the solidified solids produced are minimized to improve the polymerization stability of the latex. After the emulsion polymerization is finished, an additive such as an antioxidant and an ultraviolet stabilizer may be further added, aggregated into an aqueous sulfuric acid solution at a temperature of 80 ° C. or higher, and then dehydrated and dried to prepare a powder.

The solidified solid content of the acrylonitrile-butadiene-styrene graft copolymer prepared above was measured by the following Equation 1, through which the polymerization stability of the latex was evaluated.

Solid coagulation content (%) = (weight of product coagulum in the reactor (g) / total weight of rubbery polymer and monomer (g)) × 100

The acrylonitrile-butadiene-styrene graft copolymer preferably has a solid coagulation content of less than 0.7%. The solid coagulant is excellent in the polymerization stability of the latex in the content, there is no effect of obtaining a large amount of coagulant produced acrylonitrile-butadiene-styrene graft copolymer suitable for the present invention.

In addition, the graft ratio of the acrylonitrile-butadiene-styrene graft copolymer is measured by Equation 2 after treatment in the following manner. 2 g of acrylonitrile-butadiene-styrene (ABS) -based graft copolymer powder prepared above was added to 300 ml of acetone and stirred for 24 hours. After the stirred solution is separated using an ultracentrifuge, the separated acetone solution is dropped in methanol to obtain an grafted portion, which is dried and weighed.

Graft Rate (%) = (weight of grafted monomer (g) / gross weight of rubbery polymer (g)) × 100

The acrylonitrile-butadiene-styrene graft copolymer preferably has a graft ratio of 26 to 60%. In the graft ratio, the thermal stability does not decrease, and the mechanical properties are excellent.

The acrylonitrile-butadiene-styrene graft copolymer (I) is 100 parts by weight of a basic resin (acrylonitrile-butadiene-styrene graft copolymer + acrylate-styrene-acrylonitrile terpolymer) It is preferably included in 20 to 50 parts by weight. When included in the content, the impact strength is excellent, the flowability of the resin is excellent, the workability is good, and the weather resistance and scratch resistance is improved.

(II) acrylate-styrene-acrylonitrile (ASA) terpolymer

The acrylate-styrene-acrylonitrile terpolymer comprises 40 to 60 parts by weight of the acrylate monomer, 10 to 40 parts by weight of the styrene monomer and 3 to 30 parts by weight of the acrylonitrile monomer.

The acrylate-styrene-acrylonitrile terpolymer is prepared by mixing the monomer component and the reaction medium, adding an antioxidant, a molecular weight regulator and an organic peroxide polymerization initiator and bulk polymerization.

As the acrylate monomer, methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate may be used alone or in combination of two or more thereof. Preference is given to using methacrylates. The acrylate monomer is preferably used in 40 to 60 parts by weight of 100 parts by weight of the total monomer components. When used in the above content, the refractive index is lowered, haze (haze) is reduced, the viscosity of the reactants do not increase rapidly, there is an effect that the polymerization proceeds constantly.

As the styrene-based monomer, styrene, α-methyl styrene, p-methyl styrene, or styrene in which one or more hydrogens of benzene nuclei are optionally substituted with an alkyl group having 1 to 5 carbon atoms or halogen may be used alone or in combination of two or more thereof. It is preferable to use styrene. The styrene monomer is preferably used in 10 to 40 parts by weight of 100 parts by weight of the total monomer components. When used in the above content, the viscosity of the reactants is not high, and thus the processability and fluidity of the final copolymer are excellent, and the refractive index is low, thereby improving transparency.

As the acrylonitrile-based monomer, acrylonitrile, methacrylonitrile, ethacrylonitrile, or the like may be used alone or in combination of two or more thereof. Acrylonitrile is preferably used. The monomer is preferably used in 3 to 30 parts by weight of 100 parts by weight of the total monomer components. When used in the above content does not occur heat discoloration, there is an effect of excellent chemical resistance.

The reaction medium acts as a reaction lubricant rather than a reaction solvent, and may use an aromatic hydrocarbon compound optionally substituted with an alkyl group having 1 to 3 carbon atoms or a halogen, and may be used alone or in combination of two or more kinds of ethylbenzene, toluene or xylene. It is preferable to use. The reaction solvent is preferably used in 20 to 30 parts by weight based on 100 parts by weight of the total monomer components. When used in the above content, it is possible to prepare the final copolymer having a high molecular weight by appropriately adjusting the viscosity of the reactants, there is an effect of improving the productivity.

The antioxidant may be used alone or hindered phenolic antioxidants in a high temperature volatile tank, or may be used by mixing the hindered phenolic antioxidants and phosphite antioxidants.

Examples of the hindered phenolic antioxidant include tetrakis methylene 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate methane, 1,3,5-tris- (4-t-butyl -3-hydroxy-2,6-dimethyl benzyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione or 1,3,5-tris -(3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione may be used alone or in combination of two or more thereof. The phosphite-based antioxidant may be tris (2,4-t-butyl phenyl) phosphite or tris- (nonylphenyl) phosphite.

When a mixture of the hindered phenolic antioxidant and the phosphite antioxidant is used, 9: 1 to 1: 5, preferably 5: 1 to 1: 3, more preferably 2: 1 to 1: It is used by mixing in the weight ratio of 2. When used by mixing in the weight ratio there is an effect that is not vulnerable to thermal history during the bulk polymerization or in the volatilization and processing step.

The antioxidant is preferably used in 0.01 to 1 parts by weight based on 100 parts by weight of the total monomer components. When used in the above content, the effect of suppressing yellowing due to thermal history in the high temperature volatilization step is excellent, there is an effect of increasing the conversion rate and decrease the refractive index.

The molecular weight regulator is to control the molecular weight of the acrylate-styrene-acrylonitrile terpolymer in order to prevent a sharp rise in viscosity during bulk polymerization, t-dodecyl mercaptan or n-octyl mer Captans may be used alone or in combination of two or more, and it is preferable to use from 0.01 to 1 part by weight based on 100 parts by weight of the total monomer components. In the case of using the content, it is easy to operate in the process by adjusting the viscosity, the impact strength is excellent by controlling the molecular weight.

As the organic peroxide polymerization initiator, 1,1-bis (t-butyl peroxy) -3,3,5-trimethyl cyclohexane, 1,1-bis (t-butyl peroxy) cyclohexane or 1,1-bis (t-butyl peroxy) 2-methyl cyclohexane may be used alone or in combination of two or more thereof, and it is preferable to use 0.01 to 0.1 parts by weight based on 100 parts by weight of the total monomer components. When used in the above content it is possible to control the reaction pressure and the heat of reaction by controlling the polymerization reaction rate to reduce the viscosity of the reactants, there is an effect to improve the yield.

The acrylate-styrene-acrylonitrile terpolymer is mixed with 100 parts by weight of the monomer component and 20 to 30 parts by weight of the reaction medium, 0.01 to 1 part by weight of antioxidant, 0.01 to 1 part by weight of molecular weight regulator and organic peroxide polymerization initiator. 0.01 to 0.1 parts by weight can be prepared by mass polymerization.

After the one-step polymerization for 2 to 4 hours at the reaction temperature of 120 to 140 ℃ while adding the above components to the reactor, and performing the two-step polymerization continuously for 2 to 4 hours at a reaction temperature of 130 to 150 ℃ It can manufacture. When the polymerization proceeds and the polymerization conversion rate is about 60% or more, the unreacted monomer and the reaction medium may be removed in a volatilizer at a temperature of 200 to 240 ° C. to prepare pellets.

When the components are introduced into the reactor, the monomer components may be mixed first and then other components may be added, and the monomer components and other components may be simultaneously added to the reactor.

The reaction temperature during the one-step polymerization is 120 to 140 ℃, the reaction time is preferably 2 to 4 hours. Under the polymerization conditions, the initiator reacts efficiently, the polymerization conversion rate is improved, the molecular weight is increased, and the viscosity of the reactants is controlled, thereby making it easy to operate in the process.

In the two-step polymerization, the reaction temperature is 130 to 150 ° C., and the reaction time is preferably 2 to 4 hours. Under the polymerization conditions, the polymerization conversion rate is high, the yield is increased, the molecular weight is increased, the refractive index is low, and the impact strength is excellent.

The acrylate-styrene-acrylonitrile terpolymer is 10 to 80 parts by weight of a basic resin (acrylonitrile-butadiene-styrene graft copolymer + acrylate-styrene-acrylonitrile terpolymer) It is preferably included in parts by weight. When included in the content has an excellent impact strength and weather resistance.

(III) Styrene-Acrylonitrile (SAN) Copolymer

Styrene-acrylonitrile-based copolymer is a resin that is additionally included in the base resin consisting of acrylonitrile-butadiene-styrene graft copolymer and acrylate-styrene-acrylonitrile terpolymer, and is a conventional continuous bulk polymerization Resin prepared by the method is used.

The styrene-acrylonitrile copolymer comprises 30 to 90 parts by weight of styrene monomer and 10 to 70 parts by weight of acrylonitrile monomer.

The styrene-acrylonitrile-based copolymer is 100 wt% of basic resin (acrylonitrile-butadiene-styrene graft copolymer + acrylate-styrene-acrylonitrile terpolymer + styrene-acrylonitrile copolymer) It is preferably included in 30 parts by weight or less. When included in the content has an excellent weather resistance and scratch resistance.

<High viscosity silicone resin>

As the high viscosity silicone resin, polydimethylsiloxane or a silicone resin in the form of a master batch thereof may be used.

Silicone resins that are commonly used have a viscosity of 10,000 centistokes (cst). In the present invention, a silicone resin having a viscosity of 10,000 to 200,000 centistokes (cst) is used as the high viscosity silicone resin, and a silicone resin having a viscosity of 100,000 to 200,000 centistokes (cst) at 25 ° C is preferably used. In the case of the said viscosity, there exists an effect excellent in scratch resistance.

The high viscosity silicone resin is preferably included in 0.2 to 1.0 parts by weight based on 100 parts by weight of the base resin. When it is included in the content, it is easy to knead with the base resin and does not migrate to the surface after processing, and has excellent scratch resistance.

The thermoplastic resin composition including the base resin and the high viscosity silicone resin may further include a lubricant, an antioxidant, an antistatic agent, a mold releasing agent, or an ultraviolet stabilizer which is commonly used according to a use.

The lubricant may be used singly or in combination of two or more kinds of ethylene bis stearamide, polyethylene oxide wax or magnesium stearate, and 0.1 to 5 parts by weight, preferably 0.5 to 2, based on 100 parts by weight of the thermoplastic resin composition. It can be used in parts by weight.

As the antioxidant, IR1076 (manufactured by Ciba Geige), which is a phenol-based antioxidant, and the like may be used, and it is preferable to use 0.5 to 2 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

As the UV stabilizer, TINUVIN 327 (manufactured by Ciba Specialty), which is an ultraviolet absorber, may be used, and may be used in an amount of 0.05 to 3 parts by weight, preferably 0.2 to 1 part by weight, based on 100 parts by weight of the thermoplastic resin.

Hereinafter, preferred examples are provided to aid the understanding of the present invention, but the following examples are merely for exemplifying the present invention, and it will be apparent to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present invention. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Manufacture of Basic Resin

(I) Preparation of ABS Graft Copolymer

(Iii) Preparation of Small Diameter Rubbery Polymers

100 parts by weight of 1,3-butadiene, 1.2 parts by weight of potassium rosin salt and 1.5 parts by weight of potassium oleate salt, 0.1 parts by weight of sodium carbonate (Na ₂ CO ₃ ) and potassium hydrogen carbonate (KHCO) in a nitrogen-substituted polymerization reactor (autoclave) ₃ ) 0.5 parts by weight, 0.3 parts by weight of t-dodecyl mercaptan and 100 parts by weight of ion-exchanged water were collectively administered, the reaction temperature was raised to 55 ° C, and 0.3 parts by weight of potassium persulfate was collectively administered to initiate the reaction. After reacting for 10 hours, 0.05 parts by weight of t-dodecyl mercaptan was further administered, and reacted at 65 ° C. for 8 hours to terminate the reaction to prepare a small-diameter rubbery polymer. The prepared small-diameter rubbery polymer had an average particle diameter of 1000 GP, a gel content of 90%, and an swelling index of 18.

(Ii) Preparation of Large Diameter Rubbery Polymers

100 parts by weight of the prepared small-diameter rubbery polymer was added to the reactor, the stirring speed was adjusted to 10 rpm, and the reaction temperature was adjusted to 30 ° C., and then 3.0 parts by weight of 7% acetic acid aqueous solution was gradually added for 1 hour, followed by stirring. Large diameter butadiene rubber polymers were prepared by fusing a small diameter rubber polymer by stopping and standing for 30 minutes. The prepared large diameter rubbery polymer had an average particle diameter of 3100 mm 3 and a gel content of 90%.

(Iii) ABS based graft copolymer preparation

65 parts by weight of ion-exchanged water, 0.35 parts by weight of potassium rosin salt, 0.1 parts by weight of sodium ethylenediaminetetraacetate, 0.005 parts by weight of ferrous sulfate, formaldehyde in 100 parts by weight of the large diameter rubber polymer prepared above in a nitrogen-substituted polymerization reactor. 0.23 parts by weight of sodium sulfoxylate was dosed in a reactor and the temperature was raised to 70 ° C. Further, a mixture of 40 parts by weight of ion exchange water, 0.5 parts by weight of potassium rosin salt, 32.0 parts by weight of styrene, 13.7 parts by weight of acrylonitrile, 0.3 parts by weight of t-dodecyl mercaptan, and 0.3 parts by weight of diisopropylene hydroperoxide was added. After continuous addition for 2 hours, 10 parts by weight of ion-exchanged water, 0.1 parts by weight of potassium rosin salt, 16.0 parts by weight of styrene, 5.0 parts by weight of acrylonitrile, 0.1 parts by weight of t-dodecyl mercaptan and diiso 0.1 parts by weight of a mixture of propylene hydroperoxide was continuously added for 1 hour, and then heated to 80 ° C., and further aged for 1 hour to terminate the reaction to prepare an ABS-based graft copolymer latex. At this time, the polymerization conversion rate was 97.5%, the solid coagulation content was 0.2%, and the graft rate was 37%.

The prepared ABS graft copolymer latex was coagulated with an aqueous sulfuric acid solution, washed, and dried to prepare a powder.

(II) Preparation of ASA terpolymer

20 parts by weight of toluene, 1,1-bis (t-butylperoxy) -3,3,5 in 100 parts by weight of a monomer mixture of 25 parts by weight of styrene, 40 parts by weight of methyl methacrylate and 15 parts by weight of acrylonitrile 0.02 parts by weight of trimethyl cyclohexane, 0.08 parts by weight of t-dodecyl mercaptan, and 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3, A polymerization reaction mixture containing 0.1 parts by weight of 5-triazine-2,4,6- (1H, 3H, 5H) -trione was added to a 26 L reactor at a rate of 14 L / hr, and the reactor was heated at 140 ° C in the first reactor. One-step polymerization at temperature, two-step polymerization at 150 ° C. in a second reactor, when the polymerization conversion rate is about 60% or more, unreacted monomer and reaction medium are removed at a temperature of 215 ° C. in a volatilizer, and pellet-shaped transparent A styrene-acrylonitrile-methylmethacrylate (SANMMA) terpolymer, a copolymer resin, was prepared.

(III) SAN-based copolymer

As the copolymer resin, SAN (product name 96HC, manufactured by LG Chemical) manufactured by continuous bulk polymerization was used as it is without purification.

High viscosity silicone resin

As the high viscosity silicone resin, MB50-007 (manufactured by Dow Corning Co., Ltd.) was used as it is without purification.

Example 1

As the base resin, 100 parts by weight of a resin including (I) 40 parts by weight of an ABS graft copolymer and (II) 60 parts by weight of a SANMMA terpolymer, 0.2 parts by weight of a high viscosity silicone resin, 1.0 part by weight of lubricant EBA, and 0.8 parts by weight of antioxidant IR1076 (manufactured by Ciba Geige) was added thereto to prepare pellets at 230 ° C. using a twin screw extruder.

Example 2

In Example 1, 100 parts by weight of a resin including (I) ABS based graft copolymer 40 parts by weight, (II) 30 parts by weight of SANMMA terpolymer and (III) 30 parts by weight of SAN based copolymer was used as the base resin. Except that was carried out in the same manner as in Example 1.

Example 3

Except for the use of 100 parts by weight of a resin including 20 parts by weight of (I) ABS graft copolymer and 80 parts by weight of (II) SANMMA terpolymer, and 0.3 parts by weight of a high viscosity silicone resin as the base resin in Example 1 And the same method as in Example 1.

Example 4

Except for the use of 100 parts by weight of a resin comprising (I) 30 parts by weight of ABS-based graft copolymer and (II) 70 parts by weight of SANMMA terpolymer, and 0.4 parts by weight of a high viscosity silicone resin as the base resin in Example 1 Was carried out in the same manner as in Example 1.

Example 5

Except for the use of 100 parts by weight of a resin comprising (I) 50 parts by weight of ABS-based graft copolymer and (II) 50 parts by weight of SANMMA terpolymer, and 0.4 parts by weight of a high viscosity silicone resin as the base resin in Example 1 Was carried out in the same manner as in Example 1.

Example 6

In Example 1, 100 parts by weight of a resin including (I) 50 parts by weight of ABS-based graft copolymer, (II) 25 parts by weight of SANMMA terpolymer and (III) 25 parts by weight of SAN-based copolymer was used. , The same procedure as in Example 1 was carried out except that 0.7 parts by weight of a high viscosity silicone resin was used.

Comparative Example 1

In Example 1, 100 parts by weight of a resin including (I) 40 parts by weight of ABS-based graft copolymer and (II) 60 parts by weight of SANMMA terpolymer was used, except that high viscosity silicone resin was not used. And the same method as in Example 1.

Comparative Example 2

In Example 1, as the basic resin, (I) ABS based graft copolymer 40 parts by weight, (II) SANMMA terpolymer 100 parts by weight of the resin containing 10 parts by weight and (III) SAN-based copolymer 50 parts by weight , The same procedure as in Example 1 was carried out except that no high viscosity silicone resin was used.

Comparative Example 3

In Example 1, 100 parts by weight of a resin including (I) 60 parts by weight of ABS-based graft copolymer, (II) 40 parts by weight of SANMMA terpolymer and (III) 50 parts by weight of SAN-based copolymer was used. , Except that 0.4 parts by weight of the high viscosity silicone resin was used in the same manner as in Example 1.

Comparative Example 4

In Example 1, 100 parts by weight of a resin including (I) 50 parts by weight of ABS-based graft copolymer, (II) 25 parts by weight of SANMMA terpolymer and (III) 25 parts by weight of SAN-based copolymer was used. , Except that 1.5 parts by weight of a high viscosity silicone resin was used.

[Test Example]

Physical properties of the thermoplastic resin compositions prepared in Examples and Comparative Examples were measured by the following methods, and the results are shown in Table 1 below.

A) Flowability (MI)-measured under conditions of 220 ° C., 10 kg load and g / 10 min, according to ASTM D1238.

B) Tensile strength (TS)-measured according to ASTM D638.

E) Elongation (TE)-measured according to ASTM D638.

D) Pencil Hardness-After fixing the pencil with a load of 0.3 kg and an angle of 45˚, it was determined whether the surface of the specimen was scratched by the naked eye by the pencil hardness.

ㅁ) Weather resistance (ΔE)-Measured by a weather resistance measuring device (QUV). The measurement conditions were UV LAMP roughness 0.77 W / m ² , humidity 50%, BLACK PANEL temperature 60 ℃, after 20 hours of discoloration was measured by a color meter.

I) Color-After adding black pigment to 1 part by weight with respect to 100 parts by weight of the base resin and coloring, ΔL and ΔE were measured using a colorimeter as Example 5 under CIE D65 conditions.

division Example Comparative example One 2 3 4 5 6 One 2 3 4 Composition (parts by weight) ABS copolymer 40 40 20 30 50 50 40 40 60 50 SANMMA copolymer 60 30 80 70 50 25 0 10 0 25 SAN-based resin 0 30 0 0 0 25 60 50 40 25 High viscosity silicone resin 0.2 0.2 0.3 0.4 0.4 0.7 0 0 0.4 1.5 Black Pigment - - - - 1.0 1.0 - - - 1.0 Properties MI (220 ℃ / 10㎏) 6.5 7.1 6.8 6.6 5.2 5.5 6.8 9.3 3.2 5.9 TS 380 385 510 440 320 330 400 390 300 330 TE 31 45 31 35 33 38 38 42 59 35 Pencil hardness 2B 3B HB B 3B 3B 4B 4B 4B 2B Weather Resistance (△ E) 1.5 3.8 1.2 2.1 - - 4.9 5.6 5.5 - color △ L - - - - Standard 1.34 - - - 1.93 △ E - - - - Standard 1.36 - - - 1.94

Through Table 1, the thermoplastic resin composition of Examples 1 to 6 including the base resin and the high viscosity silicone resin of the present invention includes Comparative Example 1, high viscosity silicone resin not containing the ASA terpolymer and high viscosity silicone resin It was confirmed that the Comparative Example 2 and the ABS-based graft copolymer that do not have excellent weather resistance and scratch resistance compared to Comparative Example 3 outside the scope of the present invention.

In addition, the thermoplastic resin compositions of Examples 5 and 6, which were colored by adding black pigment, could not observe color change within 20 hours of weathering analysis time including black pigment, and the color analysis results under CIE D65 conditions. Including a high viscosity silicone resin in excess, the scratch resistance is somewhat improved, but the color was confirmed to be excellent compared to Comparative Example 4, the color is significantly reduced.

As described above, according to the present invention, while maintaining physical properties such as fluidity, tensile strength, color, and thermal stability, the weather resistance and scratch resistance are greatly improved, and thus are suitable for application to extrusion sheets and building materials that are left outdoors. In particular, it is possible to implement improved weather resistance and scratch resistance through a single extrusion without co-extrusion, thereby providing an economical and recyclable thermoplastic resin composition.

Claims (10)

A base resin including 20 to 50 parts by weight of acrylonitrile-butadiene-styrene graft copolymer and 10 to 80 parts by weight of acrylate-styrene-acrylonitrile terpolymer, and a high viscosity based on 100 parts by weight of the base resin. Characterized in that it comprises 0.2 to 1.0 parts by weight of silicone resin Thermoplastic resin composition. The method of claim 1, The base resin further comprises 30 parts by weight or less of the styrene-acrylonitrile copolymer in 100 parts by weight of the base resin  Thermoplastic resin composition. The method of claim 2, The styrene-acrylonitrile copolymer is characterized in that it comprises 30 to 90 parts by weight of styrene monomer, and 10 to 70 parts by weight of acrylonitrile monomer. Thermoplastic resin composition. The method of claim 2, The styrene monomer is at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, ο-ethylstyrene, p-ethylstyrene, and vinyltoluene, The acrylonitrile-based monomer is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile Thermoplastic resin composition. The method according to claim 1 or 2, The acrylonitrile-butadiene-styrene graft copolymer comprises 100 parts by weight of a conjugated diene rubber polymer, 30 to 60 parts by weight of styrene monomer, and 10 to 30 parts by weight of acrylonitrile monomer. Thermoplastic resin composition. The method according to claim 1 or 2, The acrylate-styrene-acrylonitrile terpolymer may include 40 to 60 parts by weight of acrylate monomer, 10 to 40 parts by weight of styrene monomer, and 3 to 30 parts by weight of acrylonitrile monomer. doing Thermoplastic resin composition. The method of claim 5, The conjugated diene rubber polymer is at least one selected from the group consisting of butadiene, isoprene, and chloroisoprene rubber polymers, The styrene monomer is at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, ο-ethylstyrene, p-ethylstyrene, and vinyltoluene, The acrylonitrile-based monomer is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile Thermoplastic resin composition. The method of claim 6, The acrylate monomer is selected from the group consisting of methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate, methyl acrylate, and ethyl acrylate; The styrene monomer is at least one selected from the group consisting of styrene, α-methylstyrene, p-methylstyrene, ο-ethylstyrene, p-ethylstyrene, and vinyltoluene, The acrylonitrile-based monomer is at least one member selected from the group consisting of acrylonitrile, methacrylonitrile, and ethacrylonitrile Thermoplastic resin composition. The method according to claim 1 or 2, The high viscosity silicone resin is characterized in that the viscosity is 100,000 to 200,000 cst at 25 ℃ Thermoplastic resin composition. The method according to claim 1 or 2, The high viscosity silicone resin is selected from the group consisting of polydimethylsiloxanes, and silicone resins in the form of a master batch thereof. Thermoplastic resin composition.