ANTI-FLAME COMPOSITION THEREOF AND METHODS FOR THE PREPARATION THEREOF Field of the Invention The present invention relates to a highly functional polystyrenic resin composition, a anti-flame composition thereof and a methods for the preparation thereof. More particularly, the present invention relates to a resin composition comprising homo- or co-polymer of styrene and styrene derivatives and/or rubber modified resin thereof, and modified polyolefin, having excellently balanced properties between stiffness or rigidity and toughness, good resistance to weathering, gloss and chemical resistance, to a anti-flame composition having anti-flammability as well without deteriorating physical properties of the basic composition, and to methods for the preparation thereof.

Background Art Since thermoplastic polystyrene resin has good processibility, it has been used widely in various industrial fields such as daily necessities, electronics and electric appliances, packaging materials, building materials, etc. Such polystyrene resin includes general purpose polystyrene (GPPS) having good transparency and rigidity, high-impact polystyrene (HIPS) produced to make up for the brittleness of GPPS by adding elastomers such as polybutadiene, styrene-butadiene copolymer rubber, and styrenic resins such as SMA, SAN, ABS, ABS/PC, ABS/PVC, AES, AAS, etc., each being equiped with other required properties through copolymerization and/or blending.

Generally, polystyrene resin refers to general purpose polystyrene (GPPS) and high-impact polystyrene (HIPS). While GPPS has moderate tensile strength but very low impact strength, HIPS has improved impact strength. Such improvement in impact strength, however, sacrifices physical properties such as rigidity, gloss etc., and elastomers and impurities added thereto cause structural deformation, deterioration of other physical properties and yellow change by UV

light. Therefore, the application thereof is significantly limited.

Several methods have been developed to solve the problem: modifying the structure of main chain and elastomers added thereto, introducing various additives such as UV stabilizers, antioxidants, whiteness improving agents etc., forming copolymer resin with second or third monomers, or blending together with polyolefin, enpra resin etc. To improve gloss, the size of dispersed particles was minimized by selecting type of elastomers added and controlling process variables, etc. In most cases, however, desired balanced physical properties have not been achieved. In case where the physical properties are balanced to some extent, it cannot be manufactured and marketed at a commercially acceptable price.

For example, polystyrene prepared by polymerizing styrene monomer in the presence of an EPDM (ethylene-propylene-diene terpolymer) rubber to improve resistance to weathering and tenacity did not show satisfactory properties as expected due to small graft bonding between EPDM rubber and polystyrene chain. Furthermore, dispersed particles therein become bigger (10-- 20in) and make the surface dull and less glossy. Such approaches as blending or, during the polymerization, adding various structures of styrene-butadiene copolymers wherein butadiene double bonds are hydrogenated completely or partially in order to improve impact strength and other physical properties [EP 4,685; 250,970; DE 2,839,357; US 3,810,957 etc.] are not very effective in terms of cost and processibility, because styrene-butadiene copolymer, which is quite expensive, should be added in large amounts to ensure desired impact strength, and tensile strength and other physical properties drop in proportion to the increase of impact strength.

In other approaches, polyolefins such as polyethylene or polypropylene are blended with polystyrene in the presence of compatibilizing agent. (US 3,810, 957; 4,429,323; 4,560,727; 5,278,232; 5,344,869; EP 60, 524; 125,227; 310,015; 329,283; 402,340; 421,359; DE 2,839,357 etc.) The main purpose of these methods is to improve overall physical properties of the resulting blends along with

resistance to weathering. The improvement, however, is not so well balanced that increase in impact strength often accompanies decrease in rigidity, and it is not easy to control the gloss or the melt flow rate of the blends. Furthermore, the physical properties are not stable upon introducing other special additives, which limits various application of the blends. Considering such deterioration of physical properties, most of the blends have been developed as film/sheet (US 902,718; 5,344,714; 5,258,463 etc.) or as adhesive. Molding products made of these blends (US 4,560,727; 5,278,232; 5,344,869 etc.) show significantly lowered mechanical strength, i.e. tensile strength and flexural strength (Yield Stress of the blend is 11.5 to 26.9 N/mm2, while that of polystyrene itself is 25 to 55 N/mm2), little increase in impact strength, and there are no characteristics such as gloss, anti-flammability, etc.

In the history of development of the polystyrenic resin composition, general purpose polystyrene (GPPS), which is transparent, glossy and has good rigidity but low impact strength, has been changed to opaque high impact polystyrene (HIPS) having improved impact resistance and elastic property provided by adding elastomers such as various rubbers, which is still not sufficient in resistance to weathering, rigidity and gloss. To overcome the drawbacks in high impact polystyrene such as loss of transparency, low rigidity and low resistance to heat and weathering, several methods have been proposed: reducing the diameter or the content of dispersed particles to improve gloss; introducing monomer for copolymerization such as MMA, BA to improve transparency; introducing other specific elastomers or blending with polyolefin derivatives in the presence of various compatability agent to improve rigidity or resistance to weathering. However, none of the methods can make satisfactory and commercially available processes to effectively overcome the shortcomings without deteriorating well established other physical properties thereof until now.

Therefore, there have been needs for polystyrenic resin compositions having both the rigidity of general purpose polystyrene and the impact resistance of high impact polystyrene at the same time, said resin

composition being easily processed and handled, controllable in other specific physical properties such as gloss, weatherability, chemical resistance and flammability with little or no dropping other good physical properties, which often occurred in prior methods, and still remaining competitive in manufacturing cost that it could be commercialized.

Under the circumstances, the inventors have investigated various combinations of matrix phase, dispersion phase and compatibility agent, and prepared low price blends of polystyrenic resin composition having effectively dispersed phase and high stability, by using dispersion phase of modified polyolefin copolymer produced in the presence of metallocene catalyst, compatibility agents comprising a certain amount of styrene-olefin block copolymer and suitable polystyrene resin matrix phase. The inventors also found that the polystyrenic resin composition having substantially same physical properties can be prepared through mass or mass-suspension polymerization by using conventional facilities which have been used for manufacturing HIPS. Further, the inventors found that adding various additives such as anti-flame agent to the composition hardly deteriorates other physical properties thereof, and the resulting anti-flame composition showed even better physical properties than ABS resin.

Brief Description of the Drawings Figure 1 shows the change of Izod impact strength of the composition according to the present invention and conventional resin with the lapse of tinke; and Figure 2 shows the change of tensile impact strength of the composition according to the present invention and conventional resin with the lapse of time.

Disclosure of the Invention Therefore, it is an object of the present invention to provide a highly functional polystyrenic resin composition solving the problems

of conventional polystyrene resin and the improvement thereof, having remarkably balanced rigidity and impact resistance, excellent resistance to weathering and high gloss, which are controllable, being easily processed, handled and equipped with additional characteristics such as anti-flammability, etc., and methods for the preparation thereof Another object of the present invention, is to provide a polystyrenic resin composition having anti-flame characteristic as well as other good physical properties described above and methods for the preparation thereof.

Further, the object of the present invention is to use a polystyrenic resin composition according to the invention to manufacture various molding products in a cost effective way, replacing ABS or blends thereof which have been used in the fields where conventional general purpose polystyrene and high impact polystyrene could not make use.

Thus, in the first aspect of the invention, there is provided a polystyrenic resin composition comprising; (A) 30--96 wt% of homo- or co-polymer of styrene and styrene derivatives and/or rubber modified resin thereof; (B) 3.8 ~ 55 wt% of a modified olefin copolymer produced in the presence of metallocene catalyst, or a mixture of the modified copolymer and other olefin polymers; (C) 0.2 15 wt% of block copolymer of polystyrene and polyolefin, wherein one or more polystyrene block is separated by one or more polyolefin block.

Besides (A), (B) and (C), the polystyrenic resin composition of the second aspect of the invention further comprises (D) one or more additives selected from the group consisting of anti-flame agents, lubricants, heat resistance improvers, plasticizers, light stabilizers, antioxidants, mold release agents, anti-static agents, conductive additives, impact reinforcing agents, colorants such as dyes and pigments, glass fiber, foaming agents, organic or inorganic fillers.

In the third aspect of the invention, there is provided a method for preparing blends of the polystyrenic resin composition comprising said (A), (B) and (C) components and optionally one or more additives of (D) by using a known melting extruder.

In the forth aspect, there is provided a method for preparing polymerized reaction products of the polystyrenic resin composition comprising said (A), (B) and (C) components and/or optionally one or more additives of (D) by using known polymerizing facilities.

In the fifth aspect, there are provided various molding products such as injection molding products, extrusion molding products made of the polystyrenic resin composition.

Suitable polystyrene of the invention includes homo- or co-polymer of styrene and styrene derivatives, and/or rubber modified resin thereof, having average molecular weight of from 100,000 to 500,000, preferably from 150,000 to 350,000. The amount of polystyrene in the composition is preferably from 30 to 96 wt%, more preferably from 60 to 85 wt%.

As a dispersion phase, a modified olefin copolymer prepared through polymerization using metallocene based single site catalyst, having general formula (I) wherein n and m are integers of from 1 to 500, X is hydrogen, aromatic or aliphatic hydrocarbon, or copolymer thereof having from C 1 to C950, Y is (CH2)wCH3, W is an integer of from 0 to 1000. or a mixture of the modified copolymer and other olefin polymers is used in an amount of 3.8 ~ 55 wt%, preferably 7 ~ 30 30 wt%. The average molecular weight is from 40,000 to 300,000.

The other olefin copolymers to be mixed with the modified olefin copolymer may be, for example, polyethylene (HDPE, LDPE, LLDPE, VLDPE, ULDPE etc.), polypropylene, ethyl-vinyl based copolymer (EVA), polyethylene-propylene (EPM) and polyethylene-propylene-diene copolymer (EPDM), and acryl based copolymer (EAA), etc. The copolymer of ethylene and other alkene

compound produced in the presence of metallocene catalyst, containing alkene from 5 to 50 wt% is most preferable.

Styrene-olefin block copolymer is added as compatibility agent, and has one or more polystyrene block(S) separated by one or more polyolefin block(O). Suitable block copolymers have general formulae (II) or (III): SI-O1-(S2)n (Il) wherein n is 0 or 1, S1-O1-O2-(S2)m (III) wherein m is an integer not less than 0.

The polystyrene block is 13 70 wt% of the total block copolymer, and molecular weight thereof is from 5,000 to 500,000.

Block copolymers represented by general formulae (IIIa) or (IIIb) are particularly preferable.

SmtEn--PwfySx (IIIa) Sm(En-Bw)ySx (IIIb) wherein S is polystyrene block, EP is polyethylene-polypropylene block, EB is polyethylene-polybutylene block, m is from 30 to 350, n and w are independently from 200 to 900, x is from 0 to 350, and y is an integer of from 1 to 100. The content of polystyrene block is 13 70 wt% in each case.

The amount of styrene-olefin block copolymer is 0.215 wt%, preferably 2 10 wt% by the total composition.

Various additives can be added to polystyrenic resin composition according to the invention without dropping impact strength, tensile strength and other physical properties of the basic composition. Such additives include anti-flame agents, lubricants, heat resistance improvers, plasticizers, light stabilizers, antioxidants, mold release agent, anti-static agents, conductive additives, impact reinforcing agents, colorants such as dyes and pigments, glass fiber, foaming agents, organic or inorganic fillers.

Anti-flame agents, even added in a large amount, do not cause any substantial deterioration of physical properties. The anti-flame agents may be added up to 5 35 wt%, depending on anti-flammability required in the final molding products. The term "anti-flame agent" used herein has the widest meaning including anti-flame supporting agents such as antimony trioxide, chlorinated polyethylene, as well as halogen-based and non-halogen-based anti-flame agent.

Blends of the polystyrenic resin composition according to the present invention can be prepared by mixing the components in a mixing device equipped with rotating means, such as ribbon blender, V-shaped blender and Henchel mixer under the condition of hundreds or thousands rpm at room temperature, and then melt-extruding by using a melting extruder such as conventional extruder, Brabender plasticorder, Banbury mixer, mixing roll, kneader, etc. Preferably, the melt-extruding is carried out at 170--260"C, and rotating velocity of screw is 180--350rpm.

The polystyrenic resin composition of the invention may be prepared by using polymerization facilities conventionally employed in manufacturing polystyrene-based resin. In this case, the mixture of styrene and/or the derivatives thereof, if necessary, other monomers which may be incorporated into copolymer, modified polyolefins, rubbers, additives, etc is subjected to mass or mass-suspension polymerization as in HIPS production.

The physical properties of resulting polymerization products are substantially same with those of blending products, and may be controlled as in HIPS production. Thus, the physical properties of the final products vary depending on property control of HIPS such as the average molecular weight of matrix phase PS, existence of initiator, type and amount of additives, stirring speed in processing steps, etc.

Therefore, general factors relating to conventional HIPS production may be considered in polymerization of the composition according to the invention.

The polystyrenic resin composition of the present invention may be injection molded to injection molding products, being anti-flame or

not, or extrusion molded with suitable additives to extrusion molding products such as film, sheet, etc.

The following non-limiting examples are given to illustrate the present invention.

EXAMPLE 1 The following components are used for the preparation of blends of polystyrenic resin composition (DH 1 DH22) in amounts as indicated in Table 1a Component (A) : Solarene polystyrene grade, pellet type Component (B) : polyolefin copolymer grade modified by metallocene based single site catalyst Component (C) : S tyrene-poly (ethylene-propylene)-styrene block copolymer and Styrene-poly(ethylene-butylene)-styrene block copolymer The components were mechanically mixed in a Henchel mixer at a room temperature, under 1000 rpm for 5 minutes. Then, the mixture was melt and mixed in a twin-screw extruder (L/D=25) at a <BR> <BR> <BR> <BR> temperature ranging from 170 to 250 C under 200 to 300 rpm of the screw, pelletized in a strand cutting way. To measure mechanical properties thereof, test samples were prepared from the resulting polystyrene blends by using a injection molding machine under the conditions as follows: Temperature of the injection molding machine = 210°C; Temperature of the metallic mold = 50or; Molding cycle = 35 sec.

Tensile strength, Izod impact strength and flexural strength of each test sample were measured in accordance with ASTM D638 and ASTM D256. Measurement of gloss was effected on a test sample of 56.0mm in diameter and 1.6mm in thickness in accordance with ASTM D523 by using Gloss meter (angle of incident = 60 ) The results are shown in Table 1.

Table 1A example Al A2 A3 A4 A5 A6 B1 B2 B3 B4 B5 DH 1 77 19 DH 2 65 15 DH 3 55 20 20 DH 4 83 15 DH 5 60 5 29 DH 6 86 10 DH 7 65 19 DH 8 50 9 39 DH 9 76 19 DH 10 77 14 DH 11 57 38 DH 12 49 32 10 DH 13 57 29 10 DH 14 65 7 20 DH 15 69 11 DH 16 55 17 DH 17 78 19 DH 18 50 DH 19 69 10 11 DH 20 78 DH 21 68 10 DH 22 57 6 20 DH 23 86 12 DH 24 73 17 DH 25 84 10

Table 1B example B6 B7 B8 B9 C1 C2 C3 C4 C5 C6 DI D2 D3 DH 1 4 DH 2 14 3 3 DII 3 0.5 4.5 DH 4 2 DH 5 4 2 DH 6 5 DH 7 13 3 DII 8 2 DH 9 5 DH 10 9 DH 11 5 DH 12 2 7 DH 13 4 DH 14 8 DH 15 17 3 DH 16 25 3 DII 17 3 DH 18 40 6 4 DH 19 10 DH 20 19 3 DH 21 19 3 DH 22 5 15 DH 23 2 DH 24 5 5 DH 25 3 3

Table 1C Tensile Izod impact Flexural Flexural strength Gloss example strength strength modulus (#y) 2 2 (%) (kg/cm ) (kg O cm/cm) (kg/cm ) (kg/cm ) DH 1 376 12.7 521 18100 92 DH 2 417 32.6 545 21300 80 DH 3 376 20.2 540 20400 86 DH 4 440 22.4 650 21000 101 DH 5 410 20.8 610 20500 90 DH 6 480 8.5 690 22000 115 DH 7 410 9.4 620 21000 81 DH 8 310 30.5 500 17000 72 DH 9 430 19.4 632 20900 98 DH 10 460 22.5 683 23100 90 DH 11 290 38.2 421 15900 74 DH 12 321 24.1 493 17200 75 DH 13 410 15.4 604 20100 80 DH 14 358 14.5 537 18300 84 DH 15 369 22.1 510 20,000 68 DH 16 380 23.8 540 20,900 70 DH 17 444 19.0 660 23,000 89 DH 18 305 45.8 502 18,900 68 DH 19 406 29.9 522 20,100 71 DH 20 438 47.0 633 23,700 95 DH 21 407 25.7 600 21,000 88 DH 22 320 - 45.7 511 19,700 76 DH 23 420 12.3 608 21,500 86 DH 24 381 23.4 524 20,700 78 DH 25 395 15.2 562 21,000 83

Table 1D Comparison of Tensile physical properties Izod impact Flexural Flexural strength Gloss of polystyrene, strength strength strength modulus (#y) (%) ABS resin and (kg . cm/cm (kg/cm²) (kg/cm²) (kg/cm²) commercial blends (kg/cm ) 1 460 1.5 700 32,000 - 2 500 1.2 550 32,000 - 3 320 10.0 470 23,000 40 4 340 8.3 560 - 45 5 5 480 18.0 750 24,000 96 6 480 20 700 - 95 7 290 6.4 - - - 8 240 14.5 Al, A2, A3 : Polymer of styrene monomer Dongbu Hannong Chemical Co., Ltd., SolareneR GPPS grade 144, 126, 116 A4, A5, A6 : Copolymer of styrene monomer and rubber Dongbu Hannong Chemical Co., Ltd., SolareneR HIPS grade 616, 724, 334 B1, B2, B3 : metallocene-based polyethylene octene copolymer Engage grade (Dupont Dow), Densities are 0.870, 0.868, 0.902, respectively B4 : metallocene-based polyethylene hexene copolymer ExactR grade (Exxon), density is 0.880 B5, B6, B7 : metallocene-based alpha-olefin copolymer TafmerR grade (Mitsui sekiyu Kagaku, Japan), A0586X, PO480, PO775 grade, respectively B8 : EPDM 520P (Kumho Petrochemical) grade B9 : metallocene based EPDM Elastomer Nodel IPO 4725P grade (Dupont Dow)

C1, C2, C3 : styrene-ethylene-propylene or styrene-ethylene-propylene-styrene block copolymer content of styrene is 35, 65, 13 wt%, respectively (Kuraray, Septon C1, C2, C3 : styrene-ethylene-propylene-styrene block copolymer melt flow indexes are 3.5, 0.7, 9.5g/lOmin, respectively (Asahi, TuftecR) D1, D2, D3 : Impact modifier (Rubber or elastomer), styrene-butadiene copolymer, T-168 (Enichem, EuropreneO, Tufprene 125 (Asahi), Stereon 840A (Firestone) grade 1,2 : Polymer of styrene monomer Jeil Industries Inc. (Korea) HF-2660 grade and Asahi Chem. (Japan) 666R grade 3,4 : Copolymer of styrene monomer and rubber, Jeil Worsted (Korea) HR-1360 grade and Hyosung BASF (Korea) 432 grade 5,6 : AB S (A crylonitrile -butadiene-styrene) ter-polymer LG Chem. (Korea) HF380 grade and Hyosung BASF (Korea) 857N grade 7,8 : Blends of linear low density polyethylene(LLDPE) and polystyrene (KR Patent 95-2888) EXAMPLE 2 Anti-flame agents (D) are further added to the composition of Example 1 as shown in Table 2 and test samples were prepared according to the process of Example 1. Halogen-based and non-halogen-based anti-flame agents, and anti-flame supporting agents such as antimony trioxide, chlorinated polyethylene are used herein as the components (D).

Flammability and other physical properties of the test samples were measured and shown in Table 2. Table 2 shows that impact strength and tensile strength are not dropped by adding the anti-flame agents.

Table 2A example DH 4 DH 9 DH 12 D1 D4 D5 D6 D7 D8 D9 D10 DHF 1 80 13 2 5 DHF 2 81 7 7 5 DHF 3 80 15 1 4 DHF 4 81 16 3 DHF 5 80 3 8 9 DHF 6 83 13 4 DHF 7 79 14 2 5 DHF 8 84 12 4 DHF 9 86 5 4.5 4.5 DHF 10 82 11 2 5 DHF 11 79 8 8 5 DHF 12 80 1 8 6 5 DHF 13 83 4 8 5 DHF 14 79 14 2 5 DHF 15 79 8 8 5

Table 2B Tensile Izod impact Flexural Flexural Flammability strength example strength strength modulus (UL94, (#y) (kg . cm/cm) (kg/cm²) (kg/cm²) 3.2mmt) (kg/cm²) DHF 1 352 16.1 521 20100 5VA DHF 2 427 19.1 545 21000 VO DHF 3 401 15.0 577 20000 V0 DHF 4 304 19.4 650 16900 VO DIIF 5 371 20.4 610 20000 V2 DHF 6 354 17.5 690 19700 V2 DHF 7 397 12.0 620 19800 5VA DIIF 8 297 15.6 500 16600 V2 DHF 9 317 23.8 632 16900 V2 DIIF 10 405 14.7 683 20400 V1 DHF 11 360 18.4 421 19900 VO DHF 12 384 20.3 493 21100 VO DHF 13 441 18.3 604 21400 V2 DHF 14 263 10.4 537 16300 VO DHF 15 302 20.8 510 16700 V2 D4, D6, D7 : Halogen-based anti-flame agent Brome contents are 67.2, 83, 69.5~70.5%, respectively (Albemarle, SaytexR) D5 : Brome-based low toxic anti-flame agent S8010 Grade (Albemarle, SaytexR) D8 : Halogen-based anti-flame agent Brome content is 66~68% (Flamecut 121k) D9 : Chlorinated polyethylene (CPE)

D10 : Antimony trioxide(Sb203) EXAMPLE 3 Styrenes were subjected to mass polymerization in the presence of components (B), (C) and (D) by using conventional HIPS polymerization facilities. The overall characteristics containing average molecular weight, melt flow rate, etc., of the matrix polystyrene were <BR> <BR> <BR> controlled just as each Solarene GPPS grade. From the resulting products [the compostions thereof are shown in Table 1; DH23, DH24, DH25], test samples were prepared and the mechanical properties thereof were measured according to the process of Example 1. The results are shown in Table 1(do23, DH24, DH25).

Therefore, the polystyrenic resin composition according to the invention can be prepared by using conventional polystyrene polymerization facilities as well as melting extruder.

COMPARATIVE EXAMPLE Blends of Component (A) : Solarene polystyrene grade (Dongbu Hannong Chemical Co., Ltd, Korea), pellet type Component (B) : A high density polyethylene (HDPE) and a linear low density polyethylene(LLDPE); and Component (C) : Olefin grafted polystyrene copolymer shown in Table 3 were prepared and the physical properties thereof were measured according to the process of Example 1. The results are shown in Table 3. In contrast to the blends of the present invention, the blends of the comparative examples did not show balanced physical properties.

Table 3A example Al A2 A3 B1 B2 C1 C2 C3 DH 1 67 26 7 DH 2 67 26 7 DH 3 64 22 14 DH 4 69 25 6 DH 5 66 24 10 DH 6 58 29 13 DH 7 69 24 7 DH 8 71 19 10 DH 9 70 30 DH 10 64 27 9 Table 3B Tensile Izod impact Flexural Flexural example strength(#y) strength strength modulus (kg/cm²) (kg . cm/cm) (kg/cm²) (kg/cm²) DH 1 438 1.5 664 20570 DH 2 441 1.7 642 20100 DH 3 191 4.7 311 15800 DH 4 390 2.4 550 19100 DH 5 230 3.8 320 11800 DH 6 380 2.5 509 16400 DH 7 197 10.4 320 10100 DH 8 390 2.5 540 19000 DH 9 305- 1.5 467 17300 DH 10 348 4.5 498 18300 Al, A2 : Polymer of styrene monomer, Dongbu Hannong Chemical Co., Ltd., Solarene GPPS grade 144, 126 A3 : Copolymer of styrene monomer and rubber Dongbu Hannong Chemical Co., Ltd., Solarene3 HIPS grade 616

B1 : High density polyethylene(HDPE), Korea Petrochemical Ind., Co., Ltd., E308 grade, density 0.956 B2 : Linear low density polyethylene(LLDPE) Hyundai Petrochemical Co., Ltd.

SF318 grade, density 0.920 C 1 : low density polyethylene grafted polystyrene (LDPE-g-PS,70/30 wt%) (Japan oil and fat) C2 : polypropylene grafted polystyrene (PP-g-PS, 70/30 wt%) (Japan oil and fat) C3 : ethyleneglycol metacrylate grafted polystyrene (EGMA-g-PS, 70/30 wt%) (Japan oil and fat) PHYSICAL PROPERTY TEST The resistance to weathering of the samples prepared in Example 1 (DH4, DH9, DH12) is evaluated. The test was carried out according to ASTM D1435-85 through outdoor exposure in 15 weeks, and the change of impact strength and tensile strength in ABS, HIPS and the test samples of Example 1 were measured and shown in Figs. 1 and 2. The ABS test sample was HF 380 grade (Kumho Chem., Korea), and the HIPS test sample was Solarene H724 grade (Dongbu Hannong Chemical Co., Ltd.).