Thermoplastic Resin Composition

Abstract

Provided is a thermoplastic resin composition comprising polypropylene and a multi-block copolymer. The thermoplastic resin composition including the polypropylene and the multi-block copolymer exhibits excellent scratch resistance, and thus may be usefully used as a resin composition in the manufacturing of products requiring scratch resistance, such as automotive interior materials.

Claims

1. A thermoplastic resin composition comprising polypropylene and a multi-block copolymer, wherein: the multi-block copolymer comprises a polystyrene-based block comprising an aromatic vinyl-based monomer-derived repeating unit and a polyolefin-based block comprising an ethylene-derived repeating unit and an alpha-olefin-derived monomer-derived repeating unit; and the multi-block copolymer satisfies the following conditions when a storage modulus G according to a temperature and a loss modulus G according to a temperature measured by a dynamic mechanical analysis method are plotted as a Y-axis and an X-axis, respectively: a) a slope at 130? C. is 2.00 to 4.00, and b) a slope at 190? C. is 3.00 to 5.00.

2. The thermoplastic resin composition of claim 1, wherein the polypropylene and the multi-block copolymer are included in a weight ratio of 1:0.11 to 1:9.

3. The thermoplastic resin composition of claim 1, wherein a brightness variation is 0.10 to 0.99, and the brightness variation is derived as follows using an Erichsen scratch tester: a) preparing a specimen of 100?100?1 (mm) of the thermoplastic resin composition by a hot press method; b) measuring an initial brightness (L.sub.i) of the specimen; c) forming scratches on a surface of the specimen at an interval of 2 mm with a force of 10 N; d) measuring a brightness (L.sub.f) of the specimen on which the scratches are formed; and e) calculating an amount of change between L.sub.i and L.sub.f.

4. The thermoplastic resin composition of claim 3, wherein the brightness variation is 0.10 to 0.50.

5. The thermoplastic resin composition of claim 1, wherein the alpha-olefin is one or more selected from the group consisting of 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3 -methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, 4,4-dimethyl-1-pentene, 4,4-diethyl-1-hexene, and 3,4-dimethyl-1-hexene.

6. The thermoplastic resin composition of claim 1, wherein the multi-block copolymer further satisfies the condition in which a difference between the slope at 130? C. and the slope at 190? C. is 0.50 to 2.00.

7. The thermoplastic resin composition of claim 6, wherein the multi-block copolymer has the slope at 130? C. which is less than the slope at 190? C.

8. The thermoplastic resin composition of claim 1, wherein the multi-block copolymer further satisfies the slope in the range of 2.00 to 5.00 in the range of 130? C. to 250? C.

9. The thermoplastic resin composition of claim 1, wherein the multi-block copolymer further satisfies the condition in which the slope at 250? C. is 3.00 to 4.80.

10. The thermoplastic resin composition of claim 1, wherein the multi-block copolymer has a molecular weight distribution of 1.5 to 3.0 as measured from gel permeation chromatography (GPC).

Description

EXAMPLES

[0218] Hereinafter, the present invention will be described in detail with reference to examples. However, the following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention.

Reagent and Experiment Condition

[0219] All experiments were performed under an inert atmosphere using a standard glove box and using a Schlenk technique. Toluene, hexane, and tetrahydrofuran (THF) were distilled with benzophenone and used. Methylcyclohexane (anhydrous grade) used in the polymerization reaction was purchased from Tokyo Chemical Industry (TCI) and purified with a Na/K alloy and used. Sublimation grade HfCl.sub.4 was purchased from Streme and used as is. An ethylene-propylene gas mixture was purified with trioctylaluminum (0.6M in a mineral system) in a beam reactor (2.0 L) and used.

[0220] .sup.1H NMR (600 MHz) and .sup.13C NMR (150 Mhz) spectra were recorded using an ECZ 600 instrument (JEOL).

[0221] GPC data were analyzed in 1,2,4-trichlorobenzene at 160? C. using a PL-GPC 220 system equipped with a refractive index detector and two columns (PLarian Mixed-B 7.5?300 mm Varian [Polymer Lab]).

(1) Preparation of transition metal compound

##STR00022##

(i) Preparation of Ligand Compound

[0222] ##STR00023##

[0223] 2,6-dicyclohexylaniline (0.772 g, 3.00 mmol) and 6-bromo-2-pyridinecarbox aldehyde (0.558 g, 3.00 mmol) were dissolved in toluene (5 mL) and molecular sieve was added thereto. The mixture was heated to 70? C. overnight while being stirred. After the filtration, the solvent was removed from a rotary evaporator. A yellow solid was obtained (1.07 g, 84%).

[0224] 1H NMR (C.sub.6D.sub.6): ? 8.41(s, 1H, NCH), 8.09 (d, J=7.8 Hz, 1H), 7.53 (m, 3H), 6.85 (d, J=7.8 Hz, 1H), 6.63 (t, J=7.8 Hz, 1H) , 2.74 (m, 2H) , 1.87 (d, J=12 Hz, 4H), 1.64 (d, J=12.6 Hz, 4H), 1.54(d, J=10.8 Hz, 2H), 1.39(quartet, J=10.2 Hz, 4H), 1.11(m, 6H) ppm.

[0225] .sup.13H NMR (C.sub.6D.sub.6): ? 26.55, 27.33, 34.25, 39.30, 119.42, 124.32, 125.21, 129.83, 136.68, 138.82, 142.54, 148.94, 155.95, 162.06 ppm.

[0226] HRMS (EI): m/z calcd ([M.sup.+] C.sub.24H.sub.29BrN.sub.2) 424.1514. Found: 424.1516.

[0227] Under nitrogen, the compound (1.07 g, 2.51 mmol), 1-naphthyl boronic acid (0.453 g, 2.64 mmol), Na.sub.2CO.sub.3 (0.700 g, 6.60 mmol), and toluene (5 mL) filled a Schlenk flask. A solution of (Ph.sub.3P).sub.4Pd(7.83 mg, 0.00678 mmol) was added to degassed H.sub.2O/EtOH(1 mL, v/v, 1:1) and toluene (1 mL). Light yellow oil was obtained by column chromatography on silica gel using ethyl acetate (v/v, 90:3:1) containing hexane and a small amount of triethylamine (0.712 g, 60%).

[0228] .sup.1H NMR (C.sub.6D.sub.6): ? 8.70(s, 1H, NCH), 8.41 (d, J=7.8 Hz, 1H) , 8.31 (d, J=7.8 Hz, 1H) , 7.68 (d, J=7.2 Hz, 1H) , 7.65 (d, J=7.8 Hz, 1H), 7.54(d, J=7.2 Hz, 1H), 7.27(m, 4H), 7.20(m, 4H), 2.93 (m, 2H), 1.90 (d, J=12 Hz, 4H), 1.61 (d, J=13.2 Hz, 4H), 1.50 (d, J=12.6 Hz, 2H), 1.38 (m, 4H), 1.11 (m, 6H), ppm.

[0229] .sup.13C NMR (C.sub.6D.sub.6): ? 26.63, 27.38, 34.35, 39.36, 119.21, 124.32, 124.98, 125.50, 126.15, 126.21, 126.64, 126.75, 128.15, 128.73, 129.38, 131.81, 134.52, 136.94, 137.14, 138.52, 149.48, 155.13, 159.79, 164.05 ppm.

[0230] HRMS (EI): m/z calcd ([M.sup.+] C.sub.34H.sub.36N.sub.2) 472.2878. Found: 472.2878.

[0231] 2-isopropylphenyllithium (0.114 g, 0.904 mmol) dissolved in diethyl ether (8 mL) was added dropwise to a Schlenk flask containing the compound (0.247 g, 0.523 mmol) in diethyl ether (20 mL). Stirring was performed for 3 hours, and then an aqueous solution (10 mL) of ammonium chloride (0.30 g) was added, and the product was extracted with diethyl ether (3?10 mL). The resulting oil was dried at 60? C. overnight at high vacuum. A yellow solid was obtained (0.257 g, 83%).

[0232] .sup.1H NMR (C.sub.6D.sub.6): ? 8.24 (m, 1H), 7.90 (m, 1H), 7.64 (m, 1H), 7.62 (d, J=7.8 Hz, 1H), 7.56 (d, J=7.2 Hz, 1H), 7.26 (m, 3H), 7.22 (m, 4H), 7.11 (m, 5H), 5.62 (d, J=5.4 Hz, 1H, NCH), 4.59 (d, J=5.4 Hz, 1H, NH), 3.31(septet, J=7.2 Hz, 1H, CH), 2.74 (m, 2H), 1.79 (d, J=7.8 Hz, 2H), 1.64 (m, 4H), 1.54 (m, 4H), 1.32 (m, 4H), 1.08 (m, 2H), 1.03 (d, J=6.6 Hz, 3H, CH.sub.3), 1.00 (m, 1H), 0.980 (d, J=6.6 Hz, 3H, CH.sub.3), 0.921 (m, 3H) ppm.

[0233] .sup.13C NMR (C.sub.6D.sub.6): ? 23.78, 24.45, 26.63, 27.42, 27.54, 28.96, 34.77, 35.08, 39.01, 67.64, 119.99, 122.89, 124.13, 124.80, 125.36, 125.77, 126.08, 126.46, 126.56, 126.71, 127.58, 128.55, 129.35, 131.84, 134.64, 136.94, 138.77, 141.88, 142.24, 144.97, 146.32, 159.28, 163.74 ppm.

[0234] HRMS (EI): m/z calcd ([M.sup.+] C.sub.43H.sub.48N.sub.2) 592.3817. Found: 592.3819.

(ii) Preparation of Transition Metal Compound

[0235] To a Schlenk flask was filled with the ligand compound (0.150 g, 0.253 mmol) in toluene (1.5 g), and n-BuLi (0.17 mL, 1.6 M solution in hexane, 0.27 mmol) was added dropwise at room temperature. Stirring was performed for 1 hour, and then HfCl.sub.4(0.0814 g, 0.254 mmol) was added as a solid. The reaction mixture was heated at 100? C., and stirred for 2 hours. After cooling was performed, MeMgBr (0.29 mL, 3.1 M solution in diethyl ether, 0.89 mmol) was added thereto, and stirred at room temperature overnight. After a volatile material was removed with a vacuum line, the product was extracted with toluene (1.5 g). The extract was obtained through cellite filtration. After the solvent was removed through a vacuum line, the residue was softened in hexane (2 mL) to obtain a yellow solid (0.128 g, 63%).

[0236] .sup.1H NMR (C.sub.6D.sub.6): ? 8.58(d, J=7.8 Hz, 1H), 8.29 (d, J=8.4 Hz, 1H), 7.79 (d, J=7.8 Hz, 1H), 7.71 (d, J=7.2 Hz, 1H), 7.54(d, J=7.8 Hz, 1H), 7.46 (m, 1H), 7.30(m, 2H), 7.15 (m, 3H), 7.09 (m, 3H), 6.88 (t, J=7.8 Hz, 1H), 6.62(d, J=8.4 Hz, 1H), 6.48 (s, 1H, NCH), 3.39(m, 1H), 2.92 (m, 2H), 2.15 (d, J=13.8 Hz, 1H), 2.10 (d, J=13.8 Hz, 2H), 1.80 (m, 2H), 1.65 (m, 3H), 1.29 (m, 6H), 1.17 (d, J=7.2 Hz, 3H, CH.sub.3), 1.07 (m, 3H), 0.99 (s, 3H, HfCH.sub.3), 0.95 (m, 2H), 0.73 (d, J=7.2 Hz, 3H, CH.sub.3), 0.70 (s, 3H, HfCH.sub.3), 0.23 (m, 1H) ppm.

[0237] .sup.13H NMR (C.sub.6D.sub.6): ? 23.31, 25.04, 26.63, 26.74, 27.70, 27.76, 27.81, 28.29, 28.89, 35.00, 35.66, 36.62, 37.02, 38.13, 40.88, 62.53, 67.00, 77.27, 119.30, 120.30, 124.29, 125.52, 125.60, 125.97, 126.95, 127.06, 127.73, 129.91, 130.00, 130.09, 130.85, 134.36, 135.80, 140.73, 140.89, 144.02, 145.12, 146.31, 146.38, 146.49, 164.46, 170.79, 206.40 ppm.

[0238] Anal. calcd. (C.sub.45H.sub.52HfN.sub.2): C, 67.61; H, 6.56; N, 3.50%. Found: C, 67.98; H, 6.88; N, 3.19%.

(2) Preparation of Organozinc Compound

[0239] 15.0 g (98.3 mmol) of 4-vinylbenzyl chloride and 2.628 g (108.1 mmol) of a magnesium metal were added to 78 ml of diethyl ether and stirred at 0? C. for 1.0 hour, and then filtered on cellite to remove magnesium added in excess. 19.2 g (81.9 mmol) of p-tosyl-OCH.sub.2CH.sub.2Cl dissolved in 27 ml of diethyl ether was added dropwise to the prepared 4-vinylbenzyl-magnesium chloride (4-vinylbenzyl-MgCl) Grignard reagent. Stirring was performed overnight, and then filtration on cellite was performed to remove magnesium chloride tosylate (MgCl (OTs)), which is an insoluble salt. The filtered filter cake was washed three times with 70 ml of hexane, and the solvent was removed with a rotary evaporator to obtain 14.2 g of a crude product. 43 mg (3,000 ppm) of t-butylcatechol was added as a radical remover, and under full vacuum, vacuum distillation was performed at 85? C. to obtain a compound represented by Formula 8-4-1 below. As a result of measuring the weight of the obtained compound, the yield was obtained at 81 wt %, and .sup.1H NMR and .sup.13C NMR spectra were measured.

##STR00024##

[0240] .sup.1H NMR (C.sub.6D.sub.6): ? 7.20 (d, J=8.4 Hz, 2H), 6.88 (d, J=8.4 Hz, 2H), 6.61 (dd, J=16, 9.6 Hz, 1H, ?CH), 5.63 (d, J=16 Hz, 1H, ?CH.sub.2), 5.09 (d, J=9.6 Hz, 1H, ?CH.sub.2), 3.04 (t, J=6.6 Hz, 2H, CH.sub.2), 2.42 (t, J=6.6 Hz, 2H, CH.sub.2), 1.64 (quintet, J=6.6 Hz, 2H, CH.sub.2Cl) ppm.

[0241] .sup.13C NMR (C.sub.6D.sub.6): ? 32.61, 34.12, 44.07, 113.13, 126.74, 128.97, 135.99, 137.11, 140.63 ppm.

[0242] Thereafter, 10.0 g (55.3 mmol) of the prepared compound (4-(3-chloropropyl)styrene) represented by Formula 8-4-1 above was dissolved in a mixed solvent of 20 ml of toluene and 7.98 g (111 mmol) of tetrahydrofuran (THF), and was added dropwise at room temperature to a suspension in which 2.02 g (83.0 mmol) of magnesium powder was stirred in 40 mL of toluene. After stirring was performed for 5.0 hours, a slight heat was gradually generated, and then the reaction mixture was filtered on celite to remove magnesium added in excess. 6.94 g (55.3 mmol, 1 equivalent to Grignard reagent) of ethyl zinc methoxide produced by reacting 6.83 g (55.3 mmol) of diethyl zinc (Et.sub.2Zn) and 1.78 g (55.3 mmol) of methanol in-situ in 30 ml of toluene at room temperature for 1.0 hour was added to the filtrate. Thereafter, 60 ml of toluene was added thereto, followed by stirring at room temperature for 1.0 hour, and then the solvent was removed using a high vacuum line. Thereafter, 96 g of hexane was added thereto, and magnesium chloridemethoxide (MgCl(OMe)), which is an insoluble salt, was removed on cellite. The filtrate was stored at ?30? C. to deposit a compound represented by Formula 5-4 as a white crystalline solid. As a result of measuring the weight, the yield was obtained at 56 wt % (7.28 g), and .sup.1H NMR and .sup.13C NMR were measured.

##STR00025##

[0243] .sup.1H NMR (C.sub.6D.sub.6): ? 7.24 (d, J=7.8 Hz, 2H), 6.90 (d, J=7.8 Hz, 2H), 6.64 (dd, J=17, 11 Hz, 1H, ?CH), 5.66 (d, J=17 Hz, 1H, ?CH.sub.2), 5.11 (d, J=11 Hz, 1H, ?CH.sub.2), 2.43 (t, J=7.2 Hz, 2H, CH.sub.2), 1.80 (quintet, J=7.2 Hz, 2H, CH.sub.2), ?0.19 (t, J=7.2 Hz, 2H, CH.sub.2Zn) ppm.

[0244] .sup.13C NMR (C.sub.6D.sub.6) : ? 12.66, 28.82, 40.09, 113.15, 127.31, 129.23, 136.05, 137.10, 142.91 ppm.

(3) Preparation of Anionic Polymerization Initiator

[0245] ##STR00026##

[0246] n-BuLi (0.14 mg, 2.2 mmol) was added dropwise to pentamethyldiethylenetriamine (PMDTA, 0.37 g, 2.2 mmol) in 1-octene (13.0 g). Stirring was performed overnight at room temperature, a yellow solution (0.16 mmol-Li/g) of pentylallyl-Li(PMDTA) was obtained. The aliquot was analyzed by .sup.1H NMR spectroscopy. .sup.1H NMR spectrum was recorded, and then a solution of C.sub.6D.sub.6 was quenched with H.sub.2O (or D.sub.2O) and filtered in a pipette with a short pad of anhydrous MgSO4 to record .sup.1H NMR spectrum again.

(4) Preparation of Multi-Block Copolymer

Preparation Example 1

[0247] A Parr reactor (3.785 L) was vacuum dried at 120? C. for 2 hours. As a scavenger, a solution of MMAO (0.6 mg, 1,000 ?mol-Al) in methylcyclohexane (1,200 g) was introduced into the reactor, and then the mixture was stirred at 120? C. for 1 hour using a heating jacket, and thereafter, the solution was removed using a cannula.

[0248] The reactor was filled with methylcyclohexane (1,200 g) containing MMAO (1,000 ?mol-Al) as a scavenger, and filled with 1-hexene (560 g) as an alpha-olefin monomer, and then the temperature was set to 90? C. A solution of the organozinc compound (3,720 ?mol) of Formula 5-4 above in methylcyclohexane (5 g) was filled as a chain transfer agent, and then a methylcyclohexane solution containing the transition metal compound (12 ?mol-Hf) activated with [(C.sub.18H.sub.37).sub.2N(H)Me].sup.+[B(C.sub.6F.sub.5).sub.4].sup.? (1.0 eq) in methylcyclohexane was injected. Polymerization was performed within the range of 90 to 120? C. for 40 minutes while maintaining the pressure in the reactor at 25 bar by opening a valve of an ethylene tank.

[0249] After the polymerization, ethylene gas was discharged and then the temperature of the reactor was adjusted to back to 90? C.

[0250] When the temperature reached 90? C., pentylallyl-Li-(PMDTA) (3,125 ?mol) in methylcyclohexane (10 g) was added. The temperature was maintained at 90? C. for 30 minutes during stirring, and then styrene (109 g) was injected. The temperature was adjusted in the range of 90 to 100? C. using a heating jacket. The viscosity increased gradually and reached nearly non-visible conditions within 5 hours. An aliquot was taken for analysis by .sup.1H NMR spectroscopy. From the .sup.1H NMR analysis of an aliquot, complete conversion of styrene was confirmed. After the complete conversion of styrene, 2-ethylhexanoic acid and ethanol were continuously injected. An obtained polymer mass was dried overnight in a vacuum oven at 80? C.

Preparation Examples 2 to 4

[0251] A multi-block copolymer was prepared in the same manner as in Preparation Example 1 except that the reaction conditions were changed as shown in Table 1 below.

Comparative Preparation Example 1

[0252] G1651, which is an SEBS of Kraton Inc., was set as Comparative Preparation Example 1.

Comparative Preparation Example 2

[0253] A multi-block copolymer was prepared in the same manner as in Preparation Example 1 except that diethyl zinc was used instead of the organozinc compound of Formula 5-4 above in Preparation Example 1.

Comparative Preparation Example 3

[0254] Me.sub.3SiCH.sub.2Li (2,600 ?mol, 291.4 mg) and PMDETA (2,600 ?mol, 537.3 mg) were mixed with methylcyclohexane (20.7 g) and then stirred at room temperature for 30 minutes to prepare a polymerization initiator.

[0255] A multi-block copolymer was prepared in the same manner as in Example 1 except that Me.sub.3SiCH.sub.2Li.Math.(PMDETA) prepared above was used instead of pentylallyl-Li.Math.(PMDTA) as the anionic initiator in Example 1, and that the reaction conditions were changed as shown in Table 1 below.

Comparative Preparation Example 4

[0256] A multi-block copolymer was prepared in the same manner as in Example 1 except that Oc.sub.3Al (1976.7 mg, 1,348 ?mol-Al/25 wt % in hexane) was used instead of MMAO as the scavenger in Example 1, and that the reaction conditions were changed as shown in Table 1 below.

Comparative Preparation Example 5

[0257] A transition metal compound, a co-catalyst, and an organozinc compound were prepared according to the preparation of a transition metal compound, preparation of a co-catalyst, and preparation of an organozinc compound described in Korean Patent Publication 2020-0132635, and then a polyolefin-polystyrene-based multi-block copolymer was prepared according to a method described in Example 1 of the Korean Patent Publication 2020-0132635.

TABLE-US-00001 TABLE 1 Catalyst Organic Alpha-olefin Polymerization initiator Input zinc Input Input amount Scavenger compound amount Styrene amount (?mol) Type (?mol) (?mol) Type (g) (g) Type (?mol) Preparation 12 MMAO 1000 3100 1-hexene 560 104 Allyl-based 2600 Example 1 Preparation 12 MMAO 1000 3100 1-hexene 560 104 Allyl-based 2600 Example 2 Preparation 12 MMAO 1000 3720 1-hexene 560 109 Allyl-based 3125 Example 3 Preparation 12 MMAO 2020 3100 1-hexene 560 104 Allyl-based 3410 Example 4 Comparative Kraton G1651 Preparation Example 1 Comparative 10 MMAO 749 3000 1-hexene 430 100 Allyl-based 2600 Preparation Example 2 Comparative 12 MMAO 1000 3100 1-octene 560 98 Silyl-based 2600 Preparation Example 3 Comparative 20 TOA 1348 2496 1-octene 229 61 Allyl-based 2746 Preparation Example 4 Comparative 10 TOA 238 640 1-hexene 34 12 Silyl-based 988 Preparation Example 5

Experimental Example 1

[0258] The physical properties of the multi-block copolymer of each of Examples and Comparative Examples were measured as follows.

(1) Measurement of Contents of Ethylene, Alpha-Olefin, and Styrene

[0259] The measurement was performed through nuclear magnetic resonance (NMR). Using Bruker 600 MHz AVANCE III HD NMR device, .sup.1H NMR was measured under the condition of ns=16, d1=3s, solvent=TCE-d2, and 373K, and then the TCE-d2 solvent peak was calibrated to 6.0 ppm. CH.sub.3 of 1-propylene was confirmed at 1 ppm and a CH.sub.3-related peak (triplet) of a butyl branch by 1-hexene was confirmed near 0.96 ppm to calculate the contents.

[0260] In addition, the content of styrene was calculated using an aromatic peak near 6.5 to 7.5 ppm.

(2) Weight Average Molecular Weight (Mw, g/mol) and Polydispersity Index (PDI)

[0261] The weight average molecular weight (Mw, g/mol) and the number average molecular weight (Mn, g/mol) were measured by gel permeation chromatography (GPC), respectively, and the weight average molecular weight was divided by the number average molecular weight to calculate the polydispersity index (PDI). [0262] Column: PL Olexis [0263] Solvent: TCB(trichlorobenzene) [0264] Flow rate: 1.0 ml/min [0265] Sample concentration: 1.0 mg/ml [0266] Injection amount: 200 ? [0267] Column temperature: 160? C. [0268] Detector: Agilent High Temperature RI detector [0269] Standard: Polystyrene [0270] Calculate molecular weight by Universal calibration using the Mark-Houwink equation (K=40.8?10.sup.?5, ?=0.7057)
(3) Measurement of slope of G-G plot

[0271] A storage modulus G according to temperatures and a loss modulus G according to temperatures were obtained by raising the temperature by 5? C. per minute from 130? C. to 250? C. with a frequency of 1 Hz and a strain of 0.5% using a dynamic mechanical analysis (DMA) device, and then the storage modulus

[0272] G according to temperatures and the loss modulus G according to temperatures were respectively plotted as a y-axis and an x-axis.

TABLE-US-00002 TABLE 2 NMR (wt %) GPC Alpha- Mw Slope of G-G plot Ethylene olefin Styrene (g/mol) PDI @130? C. @150? C. @190? C. @200? C. @250? C. Preparation 42.5 32.1 25.4 180236 1.79 2.93 3.36 3.83 3.80 3.47 Example 1 Preparation 43.3 31.1 25.6 144188 1.67 2.84 3.27 4.45 4.47 4.28 Example 2 Preparation 43.6 31.9 24.5 160889 1.77 2.94 3.37 4.04 4.01 3.52 Example 3 Preparation 45.0 28.3 26.7 145506 1.86 2.58 2.87 3.15 3.16 3.16 Example 4 Comparative 43.4 24.8 31.8 139261 1.13 2.88 4.52 6.39 7.43 10.14 Preparation Example 1 Comparative 42.8 32.4 24.8 113012 1.49 1.85 1.71 1.61 1.55 1.24 Preparation Example 2 Comparative 40.2 23.1 36.7 113379 1.56 2.28 2.30 2.29 2.30 2.16 Preparation Example 3 Comparative 42.3 22.7 34.9 61310 1.71 0.87 0.78 0.71 0.73 0.88 Preparation Example 4 Comparative 49.1 25.3 25.5 98042 1.87 2.55 2.63 2.93 2.90 2.49 Preparation Example 5

Preparation of Resin Composition

Example 1

[0273] To 0.25 parts by weight of the multi-block copolymer prepared in Preparation Example 1 above, 1 parts by weight of highly crystalline polypropylene (CB5230, product of Korea Petrochemical Ind. Co., LTD) having a melt index (230? C., 2.16 kg) of 30 g/10 min was added, and then solution blending was performed in xylene using a reactor to prepare a resin composition compound. At the time, the temperature was 200? C. to 230? C., the impeller rotation speed was 400 rpm, and the blending time was 4 hours. After the blending was finished, the compound was recovered and then dried overnight in a vacuum oven of 100? C.

Example 2

[0274] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Example 2 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Example 3

[0275] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Example 3 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Example 4

[0276] A resin composition compound was prepared in the same manner as Example 3 except that the content of the multi-block copolymer prepared in Preparation Example 3 and the content of the polypropylene were respectively changed to 0.67 parts by weight and 1 part by weight.

Example 5

[0277] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Example 4 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Comparative Example 1

[0278] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Comparative Preparation Example 1 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Comparative Example 2

[0279] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Comparative Preparation Example 1 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Comparative Example 3

[0280] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Comparative Preparation Example 2 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Comparative Example 4

[0281] A resin composition compound was prepared in the same manner as Example 2 except that the multi-block copolymer prepared in Comparative Preparation Example 3 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Comparative Example 5

[0282] A resin composition compound was prepared in the same manner as Example 1 except that the multi-block copolymer prepared in Comparative Preparation Example 4 was used instead of the multi-block copolymer prepared in Preparation Example 1.

Experimental Example 2

Measurement of Bright VarianceEvaluation of Scratch Resistance

[0283] Using each of the resin compositions of Examples and Comparative Examples, a specimen of 100?100?1 (mm) was produced by a hot press method under the conditions of 200? C. and 20 bar. Thereafter, using an Erichsen scratch tester 430P, the initial brightness (L.sub.i) of the specimen was measured. Then, for the specimen, scratches were formed on the surface at an interval of 2 mm with a force of 10 N using an Eriksen scratch tester, and then a brightness (L.sub.f) of the specimen on which the scratches are formed was measured, and an amount of change between L.sub.i and L.sub.f was calculated.

TABLE-US-00003 TABLE 3 Mixing ratio Brightness variation (PP:Multi-block (Scratch resistance Resin copolymer) properties) composition (Weight ratio) (?L) Example 1 PP/Preparation 1:0.25 0.47 Example 1 Example 2 PP/Preparation 1:0.25 0.36 Example 2 Example 3 PP/Preparation 1:0.25 0.20 Example 3 Example 4 PP/Preparation 1:0.67 0.14 Example 3 Example 5 PP/Preparation 1:0.25 0.48 Example 4 Comparative PP/Comparative 1:0.25 0.99 Example 1 Preparation Example 1 Comparative PP/Comparative 1:0.67 0.60 Example 2 Preparation Example 1 Comparative PP/Comparative 1:0.25 0.57 Example 3 Preparation Example 2 Comparative PP/Comparative 1:0.25 0.51 Example 4 Preparation Example 3 Comparative PP/Comparative 1:0.25 0.60 Example 5 Preparation Example 4

[0284] As can be confirmed from Table 3 above, the resin compositions of Examples 1 to 5 showed a small bright variance compared to the resin compositions of Comparative Examples 1 to 5.

[0285] As such, the resin compositions of Examples 1 to 5 according to one example of the present invention had a small brightness variation value which indicates that the brightness variation caused by the scratches formed on the surface is small, so that it was confirmed that the scratch resistance of the surface was significantly excellent.

[0286] In addition, when examining Examples 3 and 4 and Comparative Examples 1 and 2, it was confirmed that the larger amount of multi-block copolymers were mixed with respect to the polypropylene, the further decreased the brightness variation of the resin composition. However, typically, as the content of a block copolymer is increased in a resin composition comprising polypropylene and the block copolymer, the flow flowability (flow rate, melt flow rate) of the resin composition decreases, so that the processability is lowered. The resin composition of Example 4 comprised a block copolymer in less than half the ratio of the resin composition of Comparative Example 2, but exhibited a very small brightness variation value, so that it can be confirmed the resin composition of Example 4 has significantly excellent scratch resistance while exhibiting relatively excellent processability.

[0287] The resin compositions of Examples 1 to 3 and 5 also comprised a block copolymer in less than half the ratio of the resin composition of Comparative Example 2, but exhibited a very small brightness variation value, and also exhibited a low brightness variation compared to the resin compositions of Comparative Examples 1 to 3 and 5.

[0288] From the above results, it can be seen that the resin composition according to one example of the present invention may achieve excellent scratch resistance even with a small content of block copolymers, so that it can be confirmed that the present technology may provide a resin composition exhibiting excellent scratch resistance while maintaining flow flowability. In addition, when the resin composition according to one example of the present invention comprises a relatively large amount of block copolymers, the resin composition may exhibit further excellent scratch resistance, so that it has been confirmed that the amount of the resin composition may be properly adjusted according to required scratch resistance.