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 (meth)acrylate; and a non-graft copolymer (B) including an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide 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, and a second vinyl cyanide compound, wherein the graft copolymer (A) satisfies both Equations 1 and 2 below: $\begin{array}{cc}2002r2300& \mathrm{Equation}1\end{array}$ $\begin{array}{cc}25r2-r145,& \mathrm{Equation}2\end{array}$ wherein r1 represents an average radius (nm) from a center of the graft copolymer to a surface of the polymer seed facing the rubber core, and r2 represents an average radius (nm) from the center of the graft copolymer to a surface of the rubber core facing the graft shell.

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: 55 to 85% by weight of the second alkyl (meth)acrylate, 10 to 35% by weight of the fourth aromatic vinyl compound, and 1 to 20% by weight of the second vinyl cyanide compound.

6. 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).

7. 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.

8. 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 0.01 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 refractive indexes thereof are measured.

9. 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.

10. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition possesses a gloss of 120 or more as measured at 45 using an injection specimen having a thickness of 3 mm according to ASTM D2457.

11. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin composition possesses an Izod impact strength of 13 kgf.Math.cm/cm or more as measured at room temperature using a specimen having a thickness of according to ASTM D256.

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

13. 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.

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

15. 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.

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

17. 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, 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, the non-graft copolymer (B) comprises: 55 to 85% by weight of the second alkyl (meth)acrylate, 10 to 35% by weight of the fourth aromatic vinyl compound, and 1 to 20% by weight of the second vinyl cyanide compound, and 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 0.01 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 refractive indexes thereof are measured.

18. The thermoplastic resin composition according to claim 17, wherein: the first alkyl (meth)acrylate includes methyl methacrylate, the first aromatic vinyl compound includes styrene, the first alkyl acrylate includes butyl acrylate, the second aromatic vinyl compound includes styrene, the third aromatic vinyl compound includes styrene, the first vinyl cyanide compound includes acrylonitrile, the second alkyl acrylate includes butyl acrylate, the second alkyl (meth)acrylate includes methyl methacrylate, the fourth aromatic vinyl compound includes styrene, and the second vinyl cyanide compound includes acrylonitrile.

19. 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, and a second vinyl cyanide compound, wherein the graft copolymer (A) satisfies both Equations 1 and 2 below: $\begin{array}{cc}2002r2300& \mathrm{Equation}1\end{array}$ $\begin{array}{cc}25r2-r145,& \mathrm{Equation}2\end{array}$ wherein: r1 represents an average radius (nm) from a center of the graft copolymer to a surface of the polymer seed facing the rubber core, and r2 represents an average radius (nm) from the center of the graft copolymer to a surface of the rubber core facing the graft shell.

20. The method according to claim 19, 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).

Description

EXAMPLES

(1) Materials used in Examples and Comparative Examples are as follows. Graft copolymer (A): Prepared in Examples 1 to 10 and Comparative Examples 1 to 11 below. SAMMA copolymer (B-1): Methyl methacrylate-styrene-acrylonitrile non-graft copolymer including 71% by weight of methyl methacrylate, 22% by weight of styrene, and 7% by weight of acrylonitrile SAN copolymer (B-2): Styrene-acrylonitrile non-graft copolymer (90HR, LG Chemical Co.) including 73% by weight of styrene and 27% by weight of acrylonitrile 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 Lubricant: SUNLUBE EBS (SUNKOO Co.) Antioxidant: Songnox 1076 (Songwon Co.) and Irgafos 168 (BASF Co.) UV absorber: Tinuvin 770 (BASF Co.), Tinuvin P (BASF Co.)

Example 1

(2) 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.

(3) 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

(4) 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

(5) 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

(6) 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

(7) 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

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

Comparative Example 12

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

TEST EXAMPLES

(10) 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. The refractive indexes of the seed, core, and shell of the graft copolymer and the refractive index of the non-graft copolymer were calculated by Equation 3 below.

(11) 0$\begin{array}{cc}\mathrm{RI}=.Math.\mathrm{Wti}*\mathrm{RIi}& \left[\mathrm{Equation}3\right]\end{array}$$\mathrm{Wti}=\mathrm{Weight}\mathrm{fraction}\left(\%\right)\mathrm{of}\mathrm{each}\mathrm{component}\mathrm{of}\mathrm{copolymer}$$\mathrm{RIi}=\mathrm{Refractive}\mathrm{index}\mathrm{of}\mathrm{polymer}\mathrm{of}\mathrm{each}\mathrm{component}\mathrm{of}\mathrm{copolymer}$ 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.

(12) 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. 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. 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. Gloss of injection specimen: The gloss of an injection specimen having a thickness of 3 mm was measured at 45 according to ASTM D2457. 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. 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. 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.

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

(14) 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.

(15) 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 refractive 0.089 0.083 0.087 0.082 index of core and refractive index of shell Thermoplastic Graft copolymer (A) 50 50 50 50 resin (% by weight) composition SAMMA copolymer (B-1) 50 50 50 50 (% by weight) Graft copolymer (C) (% by weight) Difference between refractive index of seed 0.004 0.004 0.004 0.004 of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze (%) 4.7 4.5 4.3 4.8 specimen Impact strength 14 15 13 15 (kgf .Math. cm/cm) Gloss 135 132 134 131 Weather resistance 2.6 2.2 2.4 2.2 (E) Extrusion Haze (%) 2.2 2.1 2.3 2.1 specimen Gloss 127 123 123 124 Refractive index difference between sol 0.0034 0.0020 0.0031 0.0024 and gel in thermoplastic resin composition

(16) TABLE-US-00002 TABLE 2 Example Example Example Example Example Example Classification 5 6 7 8 9 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 refractive 0.086 0.088 0.086 0.086 0.086 0.086 index of core and refractive index of shell Thermoplastic Graft copolymer (A) 50 50 50 50 30 35 resin (% by weight) composition SAMMA copolymer (B-1) 50 50 50 50 50 50 (% by weight) Graft copolymer (C) 20 15 (% by weight) Difference between refractive index of seed 0.004 0.000 0.002 0.006 0.002 0.002 of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze (%) 4.1 3.7 3.5 3.6 2.2 2.6 specimen Impact strength 14 16 16 15 16 15 (kgf .Math. cm/cm) Gloss 131 135 137 138 137 138 Weather resistance 2.4 2.5 2.3 2.6 2 2 (E) Extrusion Haze (%) 2 1.8 1.6 1.6 1.5 1.5 specimen Gloss 126 123 125 126 123 122 Refractive index difference between sol 0.0016 0.0025 0.0030 0.0034 0.0025 0.0027 and gel in thermoplastic resin composition

(17) TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Comparative Comparative Comparative Classification Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Graft Seed MMA/SM 92/8 68/32 72/28 72/28 72/28 72/28 copolymer (% by weight) (A) 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 refractive 0.086 0.086 0.099 0.066 0.079 0.093 index of core and refractive index of shell Thermoplastic Graft copolymer (A) 50 50 50 50 50 50 resin (% by weight) composition SAMMA copolymer (B-1) 50 50 50 50 50 50 (% by weight) Graft copolymer (C) (% by weight) Difference between refractive index of seed 0.016 0.008 0.004 0.004 0.004 0.004 of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze (%) 43 15 50 32 41 18 specimen Impact strength 8 9 16 6 7 12 (kgf .Math. cm/cm) Gloss 94 98 91 95 86 99 Weather resistance 2.6 2.2 2.2 2.2 2.4 2.8 (E) Extrusion Haze (%) 5.1 4.2 6.5 4.3 5.6 4.8 specimen Gloss 98 102 95 90 79 95 Refractive index difference between sol 0.0071 0.0085 0.0093 0.0080 0.0131 0.0137 and gel in thermoplastic resin composition

(18) TABLE-US-00004 TABLE 4 Comparative Comparative Comparative Comparative Comparative Comparative Classification Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Graft Seed MMA/SM 72/28 72/28 0/100 100/0 72/28 copolymer (% by weight) (A) Core 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 72/20/8 (% by weight) (MMA) 2*r2 (nm) 360 160 230 240 240 r2 r1 (nm) 52 23 40 35 35 Difference between refractive 0.086 0.086 0.112 0.005 0.086 index of core and refractive index of shell Thermoplastic Graft copolymer (A) 50 50 50 50 50 resin (% by weight) composition SAMMA copolymer (B-1) 50 50 50 50 (% by weight) SAN copolymer (B-2) 50 (% by weight) Graft copolymer (C) (% by weight) Difference between refractive index of seed 0.004 0.004 0.076 0.024 0.052 of graft copolymer (A) and refractive index of non-graft copolymer (B) Injection Haze (%) 22 2 65 42 85 2 specimen Impact strength 18 4.2 18 6.5 13 17 (kgf .Math. cm/cm) Gloss 101 141 91 95 89 150 Weather resistance 3 2.2 2.9 2.2 3.1 8.5 (E) Extrusion Haze (%) 5.2 1.4 5.2 3.9 15 specimen Gloss 95 126 92 95 92 Refractive index difference between sol 0.0039 0.0012 0.0105 0.0248 0.0460 and gel in thermoplastic resin composition

(19) As shown in Tables 1 to 4, it can be confirmed that, compared to Comparative Examples 1 to 12, the thermoplastic resin compositions (Examples 1 to 10) according to the present invention have excellent impact strength, haze, gloss, and weather resistance. Note that, in terms of haze and weather resistance, Examples 9 and 10 including the graft copolymer (A) and the graft copolymer (C) are superior. 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 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) is large, the haze and gloss of both injection and extrusion specimens, and impact strength are poor.

(20) 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, since the difference in refractive index between the rubber core and graft shell of the graft copolymer (A) is out of the range of 0.08 to 0.09, the haze and gloss of both injection and extrusion specimens are reduced. In particular, in the case of Comparative Example 4, impact strength is also low.

(21) 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, since the difference in refractive index between the rubber core and graft shell of the graft copolymer (A) is out of the range of 0.08 to 0.09, the haze and gloss of both injection and extrusion specimens are reduced, and impact strength is also low.

(22) In addition, in the case of Comparative Example 7 in which 2*r2 and r2r1 of the rubber core of the graft copolymer (A) exceed the range of the present invention, haze, gloss, and weather resistance are reduced. In the case of Comparative Example 8 in which 2*r2 and r2r1 of the rubber core of the graft copolymer (A) are less than the range of the present invention, impact strength is very poor.

(23) In addition, in the case of Comparative Example 9 including only styrene in the seed and only butyl acrylate in the core as in the prior art, since the refractive index difference between the core and seed of the graft copolymer (A) is out of the range of 0.08 to 0.09, and the difference in refractive index between the 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, the haze and gloss of both injection and extrusion specimens are poor, and weather resistance and impact resistance are reduced.

(24) In addition, in the case of Comparative Example 10 in which only methyl methacrylate is included in the seed and shell of the graft copolymer (A), respectively, since the difference between the refractive index of the seed of the graft copolymer (A) and the refractive index of the non-graft copolymer (B) and the refractive index difference between a sol and a gel in a thermoplastic resin composition are large, haze, gloss, and impact strength are poor.

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

(26) 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, and weather resistance may be excellent.