THERMOPLASTIC RESIN COMPOSITION, METHOD OF PREPARING THE SAME, AND MOLDED ARTICLE MANUFACTURED USING THE SAME

Abstract

A thermoplastic resin composition including an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) including a polymer seed including 70 to 85% by weight of an alkyl (meth)acrylate and 15 to 30% by weight of an aromatic vinyl compound, a rubber core surrounding the polymer seed and including 78 to 90% by weight of an alkyl acrylate and 10 to 22% by weight of an aromatic vinyl compound, and a graft shell surrounding the rubber core and including 65 to 80% by weight of an aromatic vinyl compound, 14 to 25% by weight of a vinyl cyanide compound, and 3 to 15% by weight of an alkyl acrylate; and a non-graft copolymer (B) including an alkyl (meth)acrylate, an aromatic vinyl compound, a vinyl cyanide compound, and an imide-based compound. The present disclosure also relates to a preparation method and a molded article.

Claims

1. A thermoplastic resin composition, comprising: an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) comprising: a polymer seed comprising: 70 to 85% by weight of a first alkyl (meth)acrylate and 15 to 30% by weight of a first aromatic vinyl compound, a rubber core surrounding the polymer seed and comprising: 78 to 90% by weight of a first alkyl acrylate and 10 to 22% by weight of a second aromatic vinyl compound, and a graft shell surrounding the rubber core and comprising: 65 to 80% by weight of a third aromatic vinyl compound, 14 to 25% by weight of a first vinyl cyanide compound, and 3 to 15% by weight of a second alkyl acrylate; and a non-graft copolymer (B) comprising: a second alkyl (meth)acrylate, a fourth aromatic vinyl compound, a second vinyl cyanide compound, and an imide-based compound, wherein the graft copolymer (A) satisfies both Equations 1 and 2 below: $\begin{array}{cc}200?2*r2?300& \left[\left[\left[\right]\right]\mathrm{Equation}1\left[\left[\right]\right]\right]\end{array}$ $\begin{array}{cc}25?r2-r1?45,& \left[\left[\left[\right]\right]\mathrm{Equation}2\left[\left[\right]\right]\right]\end{array}$ wherein: r1 represents an average radius (nm) from a center of the graft copolymer to the polymer seed, and r2 represents an average radius (nm) from the center of the graft copolymer to the rubber core.

2. The thermoplastic resin composition according to claim 1, wherein, in the graft copolymer (A), a difference between a refractive index of the rubber core and a refractive index of the graft shell is 0.08 to 0.09.

3. The thermoplastic resin composition according to claim 1, wherein a difference between a refractive index of the polymer seed of the graft copolymer (A) and a refractive index of the non-graft copolymer (B) is 0.007 or less.

4. The thermoplastic resin composition according to claim 1, wherein, based on 100% by weight in total of the graft copolymer (A), the graft copolymer (A) comprises: 5 to 35% by weight of the polymer seed, 25 to 55% by weight of the rubber core, and 25 to 55% by weight of the graft shell.

5. The thermoplastic resin composition according to claim 1, wherein the non-graft copolymer (B) comprises: 60 to 90% by weight of the second alkyl (meth)acrylate, 3 to 33% by weight of the fourth aromatic vinyl compound, 0.1 to 20% by weight of the second vinyl cyanide compound, and 0.1 to 20% by weight of the imide-based compound.

6. The thermoplastic resin composition according to claim 1, wherein, in the non-graft copolymer (B), the imide-based compound comprises one or more selected from the group consisting of N-phenylmaleimide, maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide.

7. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition comprises: 10 to 90% by weight of the graft copolymer (A), and 10 to 90% by weight of the non-graft copolymer (B), based on a total weight of the graft copolymer (A) and the non-graft copolymer (B).

8. The thermoplastic resin composition according to claim 1, further comprising an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (C) containing a rubber core having an average particle diameter of 50 to 150 nm.

9. The thermoplastic resin composition according to claim 1, wherein a difference between a refractive index of a sol of the thermoplastic resin composition and a refractive index of a gel of the thermoplastic resin composition is 0.005 or less, and the refractive indexes are obtained by adding acetone to the thermoplastic resin composition, performing stirring and centrifugation to obtain an insoluble gel and a soluble sol, and then measuring the refractive indexes of the sol and the gel.

10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition possesses a haze of 5% or less as measured using an injection specimen having a thickness of 3 mm according to ASTM D1003.

11. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition possesses a gloss of 115 or more as measured at 45? using an injection specimen having a thickness of 3 mm according to ASTM D2457.

12. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition possesses an Izod impact strength of 11 kgf.Math.cm/cm or more as measured at room temperature using a specimen having a thickness of ? according to ASTM D256.

13. A method of preparing a thermoplastic resin composition, comprising: kneading and extruding, at 180 to 300? C. and 80 to 400 rpm: an alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) comprising: a polymer seed comprising: 70 to 85% by weight of a first alkyl (meth)acrylate and 15 to 30% by weight of a first aromatic vinyl compound, a rubber core surrounding the polymer seed and comprising: 78 to 90% by weight of a first alkyl acrylate and 10 to 22% by weight of a second aromatic vinyl compound, and a graft shell surrounding the rubber core and comprising: 65 to 80% by weight of a third aromatic vinyl compound, 14 to 25% by weight of a first vinyl cyanide compound, and 3 to 15% by weight of a second alkyl acrylate; and a non-graft copolymer (B) comprising: a second alkyl (meth)acrylate, a fourth aromatic vinyl compound, a second vinyl cyanide compound, and an imide-based compound, wherein the graft copolymer (A) satisfies both Equations 1 and 2 below: $\begin{array}{cc}200?2*r2?300& \left[\left[\left[\right]\right]\mathrm{Equation}1\left[\left[\right]\right]\right]\end{array}$ $\begin{array}{cc}25?r2-r1?45,& \left[\left[\left[\right]\right]\mathrm{Equation}2\left[\left[\right]\right]\right]\end{array}$ wherein: r1 represents an average radius (nm) from a center of the graft copolymer to the polymer seed, and r2 represents an average radius (nm) from the center of the graft copolymer to the rubber core.

14. The method according to claim 13, wherein the kneading and extruding includes kneading and extruding an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (C) containing a rubber core having an average particle diameter of 50 to 150 nm, the graft copolymer (A), and the non-graft copolymer (B).

15. A molded article, comprising the thermoplastic resin composition according to claim 1.

16. The thermoplastic resin composition according to claim 1, wherein: the first alkyl (meth)acrylate includes methyl methacrylate, and the first aromatic vinyl compound includes styrene.

17. The thermoplastic resin composition according to claim 1, wherein: the first alkyl acrylate includes butyl acrylate, and the second aromatic vinyl compound includes styrene.

18. The thermoplastic resin composition according to claim 1, wherein: the third aromatic vinyl compound includes styrene, the first vinyl cyanide compound includes acrylonitrile, and the second alkyl acrylate includes butyl acrylate.

19. The thermoplastic resin composition according to claim 1, wherein: the second alkyl (meth)acrylate includes methyl methacrylate, the fourth aromatic vinyl compound includes styrene, the second vinyl cyanide compound includes acrylonitrile, and the imide-based compound includes N-phenylmaleimide.

Description

EXAMPLES

[0173] Materials used in Examples and Comparative Examples are as follows. [0174] Graft copolymer (A): Prepared in Examples 1 to 10 and Comparative Examples 1 to 11 below. [0175] Phenyl maleimide-transparency-styrene-acrylonitrile (PMI-T-SAN) copolymer (B-1): Non-graft copolymer (weight average molecular weight: 100,000 g/mol, Tg: 120? C.) including 75% by weight of methyl methacrylate, 18% by weight of styrene, 1% by weight of acrylonitrile, and 6% by weight of N-phenylmaleimide [0176] SAMMA copolymer (B-2): Non-graft copolymer including 71% by weight of methyl methacrylate, 22% by weight of styrene, and 7% by weight of acrylonitrile [0177] Graft copolymer (C): Graft copolymer (rubber core: 45% by weight and graft shell: 55% by weight) including a rubber core including 85% by weight of butyl acrylate and 15% by weight of styrene and having an average particle diameter of 90 mm and a graft shell surrounding the rubber core and including 72% by weight of styrene, 20% by weight of acrylonitrile, and 8% by weight of butyl acrylate [0178] Lubricant: SUNLUBE EBS (SUNKOO Co.) [0179] Antioxidant: Songnox 1076 (Songwon Co.) and Irgafos 168 (BASF Co.) [0180] UV absorber: Tinuvin 770 (BASF Co.), Tinuvin P (BASF Co.)

Example 1

[0181] An acrylate-styrene-acrylonitrile graft copolymer (A) including a polymer seed including methyl methacrylate (hereinafter referred to as MMA) and styrene (hereinafter referred to as SM) in a weight ratio of 72/28, a rubber core including butyl acrylate (hereinafter referred to as BA) and SM in a weight ratio of 85/15, and a graft shell including SM, acrylonitrile (hereinafter referred to as AN), and BA in a weight ratio of 76/16/8 was prepared. In this case, in the graft copolymer (A), 20% by weight of the polymer seed, 40% by weight of the rubber core, and 40% by weight of the graft shell were included.

[0182] 1 part by weight of a lubricant, 1 part by weight of an antioxidant, and 0.6 parts by weight of an UV absorber were added to 50 parts by weight of the prepared graft copolymer (A) and 50 parts by weight of the non-graft copolymer (B), and kneading and extrusion were performed at 220? C. and 200 rpm to prepare pellets. The prepared pellets were injected at a molding temperature of 220? C. to prepare an injection specimen for measuring physical properties. In addition, the prepared pellets were extruded at 220? C. and 200 rpm using a single-screw film extruder to prepare an extrusion specimen for measuring physical properties.

Examples 2 to 8

[0183] The same procedure as in Example 1 was performed except that, instead of the graft copolymer (A) of Example 1, the graft copolymer (A) polymerized according to the components and contents shown in Tables 1 and 2 was used.

Example 9

[0184] The same procedure as in Example 7 was performed except that, instead of 50 parts by weight of the graft copolymer (A) prepared in Example 7, 30 parts by weight of the graft copolymer (A) and 20 parts by weight of the graft copolymer (C) were used.

Example 10

[0185] The same procedure as in Example 7 was performed except that, instead of 50 parts by weight of the graft copolymer (A) prepared in Example 7, 35 parts by weight of the graft copolymer (A) and 15 parts by weight of the graft copolymer (C) were used.

Comparative Examples 1 to 10

[0186] The same procedure as in Example 1 was performed except that, instead of the ASA graft copolymer (A) of Example 1, the ASA graft copolymer (A) polymerized according to the components and contents shown in Tables 3 and 4 below was used.

Comparative Example 11

[0187] The same procedure as in Example 5 was performed except that, instead of the PMI-T-SAN copolymer (B-1) of Example 5, the SAMMA copolymer (B-2) was used.

Comparative Example 12

[0188] A transparent acrylonitrile-butadiene-styrene resin (TR557, LG Chemical Co.) was injected to prepare an injection specimen for measuring physical properties.

Test Examples

[0189] The properties of the pellets and specimens prepared in Examples 1 to 10 and Comparative Examples 1 to 12 were measured by the following methods, and the results are shown in Tables 1 to 4 below. [0190] The refractive indexes of the seed, rubber core, and graft shell of the graft copolymer and the refractive index of the non-graft copolymer were calculated by Equation 3 below.

[00010]$\begin{array}{cc}\mathrm{RI}=.Math.\mathrm{Wti}*\mathrm{RIi}& \left[\mathrm{Equation}3\right]\end{array}$ [0191] Wti=Weight fraction (%) of each component of copolymer [0192] RIi=Refractive index of polymer of each component of copolymer [0193] Average particle diameters (nm) of polymer seed, rubber core, and graft shell: For each of the polymer seed, the rubber core, and the graft shell, upon completion of preparation thereof, a sample was obtained, and the average particle diameter of the sample was measured by dynamic light scattering. Specifically, the average particle diameter was measured as an intensity value using a Nicomp 380 particle size analyzer (manufacturer: PSS) in a Gaussian mode. As a specific measurement example, a sample was prepared by diluting 0.1 g of latex (total solids content: 35 to 50 wt %) 1,000 to 5,000-fold with distilled water. Then, the average particle diameter of the sample was measured using a flow cell in auto-dilution in a measurement mode of dynamic light scattering/intensity 300 kHz/intensity-weight Gaussian analysis. At this time, setting values were as follows: temperature: 23? C. and measurement wavelength: 632.8 nm.

[0194] Note that, r1 was a value obtained by dividing the average particle diameter of the seed by 2, and r2 was a value obtained by dividing the average particle diameter of the seed-containing core by 2. [0195] Izod impact strength (IMP; kgf.Math.cm/cm): Izod impact strength was measured at room temperature using an injection specimen having a thickness of ? according to ASTM D256. [0196] Haze (%): The haze of an injection specimen having a thickness of 3 mm and the haze of an extrusion specimen having a thickness of 0.15 mm were measured according to ASTM D1003. As haze decreases, transparency increases. [0197] Gloss of injection specimen: The gloss of an injection specimen having a thickness of 3 mm was measured at 45? according to ASTM D2457. [0198] Gloss of extrusion specimen: The gloss of an extrusion specimen having a thickness of 0.15 mm was measured at 60? according to ASTM D2457. [0199] Difference in refractive index between sol and gel in thermoplastic resin composition: 30 g of acetone was added to 0.5 g of thermoplastic resin composition pellets, stirring was performed at 210 rpm and room temperature for 12 hours using a shaker (SKC-6075, Lab Companion Co.), and centrifugation was performed at 18,000 rpm and 0? C. for 3 hours using a centrifuge (Supra R30, Hanil Science Co.) to separate a gel insoluble in acetone and a sol soluble in acetone. Then, the gel and the sol were dried via forced circulation at 85? C. for 12 hours using a forced convection oven (OF-12GW, Lab Companion Co.), and the refractive indexes of the gel and the sol were measured at room temperature using an Abbe refractometer according to ASTM D542. Then, difference in refractive indexes was calculated. [0200] Heat deflection temperature (HDT, ? C.): Heat deflection temperature was measured under a load of 18.5 kgf according to ASTM D648. [0201] Vicat softening temperature (Vicat, ? C.): Vicat softening temperature was measured at a heating rate of 50? C./h under a load of 50 N according to ASTM D1525. [0202] Weather resistance (?E): After leaving an specimen for 3,000 hours in an accelerated weather resistance tester (Weather-O-Meter, Ci4000, ATLAS Co., xenon arc lamp, Quartz (inner)/S.Boro (outer) filters, irradiance of 0.55 W/m.sup.2 at 340 nm) according to SAE J1960, the degree of discoloration was measured using a color difference meter, and weather resistance (?E) was calculated by Equation 7 below. ?E below is an arithmetic mean value of L, a, and b values of the specimen measured by the CIE LAB color coordinate system before and after the accelerated weather resistance test. Weather resistance increases as the value of ?E approaches zero.

[00011]$\begin{array}{cc}?E=\sqrt{{\left(L^{}-L_0\right)}^2+{\left(a^{}-a_0\right)}^2+{\left(b^{}-b_0\right)}^2}& \left[\mathrm{Equation}7\right]\end{array}$

[0203] In Equation 7, L, a, and b are respectively L, a, and b values measured using the CIE LAB color coordinate system after leaving a specimen for 3,000 hours according to SAE J1960, and L.sub.0, a.sub.0, and b.sub.0 are respectively L, a, and b values measured using the CIE LAB color coordinate system before leaving the specimen.

TABLE-US-00001 TABLE 1 Example Example Example Example Classification 1 2 3 4 Graft Seed MMA/SM 72/28 72/28 72/28 72/28 copolymer (% by weight) (A) Core BA/SM 85/15 85/15 85/15 85/15 (% by weight) Shell SM/AN/BA 76/16/8 71/18/11 71/24/5 68/22/10 (% by weight) 2*r2 (nm) 240 240 240 240 r2 ? r1 (nm) 35 35 35 35 Difference between 0.089 0.083 0.087 0.082 refractive index of core and refractive index of shell Thermoplastic Graft copolymer 50 50 50 50 resin (A) composition (% by weight) PMI-T-SAN 50 50 50 50 copolymer (B-1) (% by weight) Graft copolymer (C) (% by weight) Difference between refractive 0.004 0.004 0.004 0.004 index of seed of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze (%) 4.7 4.3 4.4 4.6 specimen Impact 12 13 11 13 strength (kgf .Math. cm/ cm) Gloss 126 122 128 123 HDT (? C.) 93.3 92.1 94 92.5 Vicat (? C.) 101.3 100.5 102.4 100.8 Weather 2.6 2.3 2.5 2.4 resistance (?E) Extrusion Haze (%) 2.3 2.2 2.4 2.2 specimen Gloss 120 115 121 117 Refractive index difference 0.0038 0.0023 0.0033 0.0028 between sol and gel in thermoplastic resin composition

TABLE-US-00002 TABLE 2 Exam- Exam- Exam- Exam- Exam- Exam- Classification ple 5 ple 6 ple 7 ple 8 ple 9 ple 10 Graft Seed MMA/SM 72/28 76/24 78/22 82/18 78/22 78/22 copolymer (% by weight) (A) Core BA/SM 85/15 87/13 85/15 85/15 85/15 85/15 (% by weight) Shell SM/AN/BA 72/20/8 72/20/8 72/20/8 72/20/8 72/20/8 72/20/8 (% by weight) 2*r2 (nm) 240 240 240 240 240 240 r2 ? r1 (nm) 35 35 35 35 35 35 Difference between 0.086 0.088 0.086 0.086 0.086 0.086 refractive index of core and refractive index of shell Thermoplastic Graft 50 50 50 50 30 35 resin copolymer (A) composition (% by weight) PMI-T-SAN 50 50 50 50 50 50 copolymer (B-1) (% by weight) Graft 20 15 copolymer (C) (% by weight) Difference between 0.004 0.000 0.002 0.006 0.002 0.002 refractive index of seed of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze 4 3.8 3.6 3.8 2.5 2.7 specimen (%) Impact 12 14 13 13 13 12 strength (kgf .Math. cm/cm) Gloss 125 129 130 132 131 133 HDT 93.1 92.9 93.2 93 93 93.1 (? C.) Vicat 101.2 100.9 101.1 101.5 100.9 101.1 (? C.) Weather 2.3 2.6 2.4 2.4 2.1 2.2 resistance (?E) Extrusion Haze 2.1 2 1.7 1.6 1.4 1.5 specimen (%) Gloss 118 119 119 122 120 121 Refractive index 0.0019 0.0027 0.0029 0.0031 0.0026 0.0028 difference between sol and gel in thermoplastic resin composition

TABLE-US-00003 TABLE 3 Compar- Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Classification ple 1 ple 2 ple 3 ple 4 ple 5 ple 6 Graft Seed MMA/SM 92/8 68/32 72/28 72/28 72/28 72/28 copolymer (% by (A) weight) Core BA/SM 85/15 85/15 95/5 70/30 85/15 85/15 (% by weight) Shell SM/AN/BA 72/20/8 72/20/8 72/20/8 72/20/8 72/8/20 75/25/0 (% by weight) 2*r2 (nm) 240 240 240 240 240 240 r2 ? r1 (nm) 35 35 35 35 35 35 Difference between 0.086 0.086 0.099 0.066 0.079 0.093 refractive index of core and refractive index of shell Thermoplastic Graft 50 50 50 50 50 50 resin copolymer (A) composition (% by weight) PMI-T-SAN 50 50 50 50 50 50 copolymer (B-1) (% by weight) Graft copolymer (C) (% by weight) Difference between 0.016 0.008 0.004 0.004 0.004 0.004 refractive index of seed of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze 40.5 17.2 55.3 30.7 46.2 20.9 specimen (%) Impact 6 8 15 4 5 11 strength (kgf .Math. cm/cm) Gloss 90 93 85 87 79 94 HDT 93.5 93.1 92.5 93.6 90.9 95.1 (? C.) Vicat 102 101.1 100.7 102.1 100.1 103.4 (? C.) Weather 2.5 2.3 2.4 2.1 2.7 2.6 resistance (?E) Extrusion Haze 5.3 4.1 6.6 4.3 5.5 4.5 specimen (%) Gloss 89 90 85 83 70 88 Refractive index 0.0070 0.0087 0.0131 0.0082 0.0129 0.0136 difference between sol and gel in thermoplastic resin composition

TABLE-US-00004 TABLE 4 Compar- Compar- Compar- Compar- Compar- Compar- ative ative ative ative ative ative Exam- Exam- Exam- Exam- Exam- Exam- Classification ple 7 ple 8 ple 9 ple 10 ple 11 ple 12 Graft Seed MMA/SM 72/28 72/28 0/100 100/0 72/28 copolymer (% by (A) weight) Coe BA/SM 85/15 85/15 100/0 81/19 85/15 (% by weight) Shell SM/AN/BA 72/20/8 72/20/8 75/25/0 100 (MMA) 72/20/8 (% by weight) 2*r2 (nm) 360 160 230 240 240 r2 ? r1 (nm) 52 23 40 35 35 Difference between 0.086 0.086 0.112 0.005 0.086 refractive index of core and refractive index of shell Thermoplastic Graft 50 50 50 50 50 resin copolymer (A) composition (% by weight) PMI-T-SAN 50 50 50 50 copolymer (B-1) (% by weight) SAMMA 50 copolymer (B-2) (% by weight) Graft copolymer (C) (% by weight) Difference between 0.004 0.004 0.076 0.024 0.004 refractive index of seed of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze 23.5 2.1 71.4 45.1 4.2 2 specimen (%) Impact 15 3 16 5 13 17 strength (kgf .Math. cm/cm) Gloss 92 133 82 90 129 150 HDT 92.7 93.4 94.8 95.3 80.5 81 (? C.) Vicat 101.2 101.8 103 103.5 92.3 89 (? C.) Weather 2.9 2.3 2.8 2.3 2.5 8.8 resistance (?E) Extrusion Haze 5.1 1.3 5.4 4.1 2.1 specimen (%) Gloss 87 119 85 86 125 Refractive index 0.0037 0.0013 0.0100 0.0245 0.0018 difference between sol and gel in thermoplastic resin composition

[0204] As shown in Tables 1 to 4, it can be confirmed that the thermoplastic resin compositions (Examples 1 to 10) according to the present invention have heat deflection temperature and Vicat softening temperature, equal to or superior to those of the thermoplastic resin compositions of Comparative Examples 1 to 12. In addition, the thermoplastic resin compositions according to the present invention have excellent impact strength, haze, gloss, and weather resistance. Note that, in terms of haze and gloss, Examples 9 and 10 including the graft copolymer (A) and the graft copolymer (C) are superior.

[0205] On the other hand, in the case of Comparative Examples 1 and 2 in which the composition ratio of the polymer seed of the graft copolymer (A) is out of the range of the present invention, since difference in refractive index between a sol and a gel in a thermoplastic resin composition is large, the haze and gloss of both injection and extrusion specimens, and impact strength are poor.

[0206] In addition, in the case of Comparative Examples 3 and 4 in which the composition of the rubber core of the graft copolymer (A) is out of the range of the present invention, the difference in refractive index between the rubber core and shell of the graft copolymer (A) is out of the range of 0.8 to 0.9. In addition, since the refractive index difference between a sol and a gel in a thermoplastic resin composition increases, the haze and gloss of both injection and extrusion specimens are poor. In particular, in the case of Comparative Example 4, impact strength is very low.

[0207] In addition, in the case of Comparative Examples 5 and 6 in which the composition of the graft shell of the graft copolymer (A) is out of the range of the present invention, the difference in refractive index between the rubber core and shell of the graft copolymer (A) is out of the range of 0.8 to 0.9. In addition, since the refractive index difference between a sol and a gel in a thermoplastic resin composition increases, the haze and gloss of both injection and extrusion specimens are poor. In the case of Comparative Example 5, impact strength is also low.

[0208] In addition, in the case of Comparative Example 7 in which 2*r2 and r2-r1 of the rubber core of the graft copolymer (A) exceed the range of the present invention, haze, gloss, and weather resistance are poor. In the case of Comparative Example 8 in which 2*r2 and r2-r1 of the rubber core of the graft copolymer (A) are less than the range of the present invention, impact strength is very poor.

[0209] In addition, in the case of Comparative Example 9 including only styrene in the seed and only butyl acrylate in the rubber core as in the prior art, the difference between the refractive index of the rubber core of the graft copolymer (A) and the refractive index of the shell is out of the range of 0.8 to 0.9. The difference in refractive index between the polymer seed of the graft copolymer (A) and the non-graft copolymer (B) and the refractive index difference between a sol and a gel in a thermoplastic resin composition increase, resulting in deterioration of haze, gloss, and weather resistance.

[0210] In addition, in the case of Comparative Example 10 in which only methyl methacrylate is included in a seed and a shell, respectively, the difference between the refractive index of the rubber core of the graft copolymer (A) and the refractive index of the shell is out of the range of 0.8 to 0.9, and the difference in refractive index between the polymer seed of the graft copolymer (A) and the non-graft copolymer (B) increases, resulting in decrease in haze, gloss, and impact strength.

[0211] In addition, in the case of Comparative Example 11 in which the SAMMA copolymer (B-2) is used instead of the PMI-T-SAN copolymer (B-1), heat deflection temperature and Vicat softening temperature are reduced, resulting in decrease in heat resistance.

[0212] In addition, in the case of Comparative Example 12 in which the transparent acrylonitrile-butadiene-styrene resin is used, weather resistance is very poor.

[0213] In conclusion, when the composition and composition ratio of the polymer seed, core, and shell of the alkyl (meth)acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (A) are adjusted within a predetermined range according to the present invention, and the difference between the refractive index of the core and the refractive index of the shell and the difference between the refractive index of the polymer seed of the graft copolymer (A) and the refractive index of the non-graft copolymer (B) are reduced, impact resistance, transparency, gloss, heat resistance, and weather resistance may be excellent.