Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising: a base resin comprising a diene-based graft polymer and a vinyl-based non-graft polymer, the vinyl-based non-graft polymer comprising an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit; and an additive including an olefin-based non-graft polymer, the olefin-based non-graft polymer including an olefin-based monomer unit, a (meth) acrylate-based monomer unit, and a maleic acid monomer unit.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present invention claims priority to and the benefit of Korean Patent Application No. 10-2022-0136421, filed on October 21, 2022, which is hereby incorporated by reference in its entirety. Technical Field

[0003] The present invention relates to thermoplastic resin compositions. Background Art

[0004] Diene graft polymers include diene rubber polymers and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. Compared with high impact polystyrene (HIPS), diene graft polymers have excellent physical properties such as high impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity and processability. Due to these physical properties, diene graft polymers have been used as parts for automotive interior and exterior materials, office supplies and various electrical and electronic products or toys.

[0005] However, despite these excellent physical properties, cracks occurred when strong solvents were used to evaluate the chemical resistance of the diene-based graft polymers.

[0006] In order to solve the above problems, research has been conducted to adjust the rubber content in the diene graft polymer or to increase the size of the diene graft polymer. However, in this case, the fluidity of the diene graft polymer is reduced, and the degree to which chemical resistance can be improved is limited due to the increased residual stress in the thermoplastic resin molded product.

[0007] [Related technical literature]

[0008] [Patent Document]

[0009] (Patent Document 1) KR2011-0061303A Summary of the invention

[0010] [Technical issues]

[0011] The present invention is directed to providing a thermoplastic resin composition having excellent processability, impact resistance, heat resistance and chemical resistance.

[0012] [Technical solution]

[0013] In order to solve the above problems, 1) the present invention provides a thermoplastic resin composition, which comprises: a base resin, wherein the base resin comprises a diene grafted polymer and a vinyl non-grafted polymer, wherein the vinyl non-grafted polymer comprises an aromatic vinyl monomer unit and a vinyl cyanide monomer unit; and an additive comprising an olefin non-grafted polymer, wherein the olefin non-grafted polymer comprises an olefin monomer unit, a (meth)acrylate monomer unit and a maleic acid monomer unit.

[0014] 2) According to 1), the present invention provides a thermoplastic resin composition comprising 0.5 to 5.0 parts by weight of the olefin-based non-grafted polymer based on 100 parts by weight of the base resin.

[0015] 3) According to 1) or 2), the present invention provides a thermoplastic resin composition, wherein the olefinic non-grafted polymer is a terpolymer consisting of an olefinic monomer unit, a (meth)acrylic acid ester monomer unit and a maleic acid monomer unit.

[0016] 4) According to any one of 1) to 3), the present invention provides a thermoplastic resin composition, wherein the olefinic non-grafted polymer is an ethylene / ethyl acrylate / maleic anhydride terpolymer.

[0017] 5) According to any one of 1) to 4), the present invention provides a thermoplastic resin composition, wherein the diene-based graft polymer comprises a diene-based rubber polymer and a shell, the shell comprising an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted to the diene-based rubber polymer.

[0018] 6) According to any one of 1) to 5), the present invention provides a thermoplastic resin composition comprising 10.0 to 40.0 parts by weight of the diene-based graft polymer based on 100 parts by weight of the base resin.

[0019] 7) According to any one of 1) to 6), the present invention provides a thermoplastic resin composition, wherein the base resin comprises a maleimide-based non-grafted polymer, and the maleimide-based non-grafted polymer comprises a maleimide-based monomer unit, an aromatic vinyl-based monomer unit and a maleic acid-based monomer unit.

[0020] 8) According to 7), the present invention provides a thermoplastic resin composition comprising 10.0 to 50.0 parts by weight of the maleimide-based non-grafted polymer based on 100 parts by weight of the base resin.

[0021] 9) According to 7) or 8), the present invention provides a thermoplastic resin composition, wherein the maleimide-based non-grafted polymer is a terpolymer composed of maleimide-based monomer units, aromatic vinyl-based monomer units and maleic acid-based monomer units.

[0022] 10) According to any one of 7) to 9), the present invention provides a thermoplastic resin composition, wherein the maleimide-based non-grafted polymer is an N-phenylmaleimide / styrene / maleic anhydride polymer.

[0023] [Beneficial Effects]

[0024] The thermoplastic resin composition according to an embodiment of the present invention exhibits excellent processability, impact resistance, heat resistance, and chemical resistance. DETAILED DESCRIPTION

[0025] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0026] The terms and words in this specification and claims should not be construed as limited to their ordinary or dictionary meanings, but should be construed as meanings and concepts consistent with the technical idea of ​​the present invention based on the principle that inventors can appropriately define the concepts of the terms in order to describe their invention in the best manner.

[0027] In the present invention, the diene rubber polymer can be prepared by polymerizing, especially crosslinking, a diene monomer or a monomer mixture having a diene monomer as a main component. The diene monomer can be one or more of 1,3-butadiene, isoprene, chloroprene and piperylene, preferably 1,3-butadiene.

[0028] In the present invention, the aromatic vinyl monomer may be one or more of α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene and p-bromostyrene, preferably styrene. The unit derived from the aromatic vinyl monomer may be an aromatic vinyl monomer unit.

[0029] In the present invention, the vinyl cyanide monomer may be one or more of acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, preferably acrylonitrile. The unit derived from the vinyl cyanide monomer may be a vinyl cyanide monomer unit.

[0030] In the present invention, the olefin monomer may be one or more of ethylene, propylene and butene, preferably ethylene. The unit derived from the olefin monomer may be an olefin monomer unit.

[0031] In the present invention, (meth)acrylate monomers may be terms including acrylate monomers and methacrylate monomers. (Meth)acrylate monomers may be monomers based on (meth)acrylic acid C1-C10 alkyl esters and one or more of methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and decyl (meth)acrylate, preferably one or more of ethyl acrylate and butyl acrylate. The unit derived from the (meth)acrylate monomer may be a (meth)acrylate monomer unit.

[0032] In the present invention, the maleimide monomer can be one or more of maleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-laurylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(4-chlorophenyl)maleimide, 2-methyl-N-phenylmaleimide, N-(4-bromophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-(4-hydroxyphenyl)maleimide, N-(4-methoxyphenyl)maleimide, N-(4-carboxyphenyl)maleimide and N-benzylmaleimide, preferably N-phenylmaleimide. The unit derived from a maleimide-based monomer may be a maleimide-based monomer unit.

[0033] In the present invention, the maleic acid monomer may be one or more of maleic anhydride, maleic acid, maleic acid monoester and maleic acid diester, preferably maleic anhydride. The unit derived from the maleic acid monomer may be a maleic acid monomer unit.

[0034] In the present invention, the grafting ratio of the diene-based graft polymer can be calculated by the following method.

[0035] First, 2 g of diene graft polymer powder was dissolved in 300 ml of acetone while stirring for 24 hours, and then separated using a centrifuge to obtain a precipitate. The precipitate was dried at 60° C. to 120° C. to obtain a dry product. Then, the weight of the dry product was measured, and the measured value was substituted into the following equation.

[0036] Grafting rate (%) = [(weight of diene graft polymer powder (2 g)) - (weight of dried product) - (weight of diene rubber polymer)] / (weight of diene rubber polymer) × 100

[0037] Weight of diene rubber polymer: the weight of the diene rubber polymer theoretically contained in 2 g of the diene graft polymer powder; or the weight of the diene rubber polymer measured by analyzing 2 g of the diene graft polymer powder using infrared spectroscopy.

[0038] In the present invention, the weight average molecular weight of the shell in the diene-based graft polymer may be a weight average molecular weight of a polymer including an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted to a diene-based rubber polymer.

[0039] In the present invention, the weight average molecular weight of the shell in the diene-based graft polymer can be calculated by the following method.

[0040] The diene-based graft polymer was dissolved in a tetrahydrofuran (THF) solution (concentration: 1 wt%) and then passed through a 1 μm filter. The weight average molecular weight of the shell can be measured as a relative value relative to a standard polystyrene sample by gel permeation chromatography of the material that has passed through the 1 μm filter.

[0041] In the present invention, the weight average molecular weight can be measured by gel permeation chromatography using tetrahydrofuran as an eluent as a relative value with respect to a standard polystyrene sample.

[0042] In the present invention, the glass transition temperature can be measured by differential scanning calorimetry.

[0043] In the present invention, the average particle size can be measured by dynamic light scattering, specifically, using a Nicomp 380 instrument commercially available from ParticleSizing Systems. In the present invention, the average particle size may refer to the arithmetic mean particle size in the particle size distribution measured by dynamic light scattering, that is, the average particle size based on the scattered intensity distribution.

[0044] 1. Thermoplastic resin composition

[0045] The thermoplastic resin composition according to an embodiment of the present invention includes: 1) a base resin including a diene-based grafted polymer and a vinyl-based non-grafted polymer, wherein the vinyl-based non-grafted polymer includes an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit; and 2) an additive including an olefin-based non-grafted polymer, wherein the olefin-based non-grafted polymer includes an olefin-based monomer unit, a (meth)acrylate-based monomer unit, and a maleic acid-based monomer unit.

[0046] The base resin may include a maleimide-based non-grafted polymer including a maleimide-based monomer unit, an aromatic vinyl-based monomer unit, and a maleic acid-based monomer unit.

[0047] Hereinafter, components of the thermoplastic resin composition according to an embodiment of the present invention will be described in detail.

[0048] 1) Base resin

[0049] (1) Diene graft polymer

[0050] The diene-based graft polymer is a component that improves the impact resistance, tensile force and stress of the thermoplastic resin composition.

[0051] The diene graft polymer may include a diene rubber polymer and a shell including aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. The shell may also include aromatic vinyl monomer units and vinyl cyanide monomer units not grafted to the diene rubber polymer.

[0052] The diene-based rubber polymer may have an average particle size of 50 nm to 500 nm, preferably 70 nm to 470 nm. When this condition is satisfied, the impact resistance and surface characteristics of the diene-based graft polymer may be improved.

[0053] The amount of the diene rubber polymer in the diene graft polymer may be 40.0 wt % to 80.0 wt %, preferably 50.0 wt % to 70.0 wt %. When this condition is met, the impact resistance of the diene graft polymer can be further improved.

[0054] The amount of the aromatic vinyl monomer unit in the diene graft polymer may be 10.0 to 50.0 wt %, preferably 20.0 to 40.0 wt %. When this condition is met, the processability of the diene graft polymer may be further improved.

[0055] The amount of the vinyl cyanide monomer unit in the diene graft polymer may be 1.0 wt % to 30.0 wt %, preferably 5.0 wt % to 25.0 wt %. When this condition is met, the chemical resistance of the diene graft polymer can be further improved.

[0056] The grafting rate of the diene-based graft polymer may be 10.0% to 50.0%, preferably 20.0% to 45.0%. When this condition is satisfied, excellent impact resistance and tensile properties may be achieved.

[0057] The weight average molecular weight of the shell in the diene-based graft polymer may be 50,000 g / mol to 130,000 g / mol, preferably 60,000 g / mol to 100,000 g / mol. When this condition is met, excellent impact resistance and tensile properties may be achieved.

[0058] Based on 100 parts by weight of the base resin, the amount of the diene graft polymer may be 10.0 to 40.0 parts by weight, preferably 15.0 to 35.0 parts by weight, and more preferably 20.0 to 30.0 parts by weight. When this condition is met, the impact resistance, tensile force, and stress of the thermoplastic resin composition can be further improved.

[0059] (2) Vinyl non-grafted polymers

[0060] The vinyl-based non-grafted polymer is a component for improving the processability of the thermoplastic resin composition.

[0061] The vinyl-based non-grafted polymer includes an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit, and may preferably be a binary polymer composed of an aromatic vinyl-based monomer unit and a vinyl cyan-based monomer unit.

[0062] The vinyl-based non-grafted polymer may include an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit in a weight ratio of 90:10 to 60:40, preferably 85:15 to 65:35. When this condition is met, a vinyl-based non-grafted polymer having improved processability and chemical resistance may be prepared.

[0063] The vinyl-based non-graft polymer may be contained as the balance such that the total amount of the components of the base resin becomes 100 parts by weight.

[0064] (3) Maleimide non-grafted polymers

[0065] The maleimide-based non-grafted polymer is a component that improves the heat resistance of the thermoplastic resin composition.

[0066] The maleimide non-grafted polymer includes maleimide monomer units, aromatic vinyl monomer units and maleic acid monomer units, and may preferably be a terpolymer composed of maleimide monomer units, aromatic vinyl monomer units and maleic acid monomer units, and more preferably is an N-phenylmaleimide / styrene / maleic anhydride terpolymer.

[0067] The maleimide-based non-grafted polymer may include 40.0 to 60.0 wt %, preferably 45.0 to 55.0 wt % of a maleimide-based monomer unit. When this condition is satisfied, heat resistance may be improved.

[0068] The maleimide-based non-grafted polymer may include 35.0 to 55.0 wt %, preferably 40.0 to 50.0 wt % of an aromatic vinyl-based monomer unit. When this condition is satisfied, impact resistance may be improved.

[0069] The maleimide-based non-grafted polymer may contain 0.01 to 10.0 wt %, preferably 0.50 to 7.0 wt % of a maleic acid-based monomer unit. When this condition is met, heat resistance may be improved.

[0070] The glass transition temperature of the maleimide-based non-grafted polymer may be 175° C. to 210° C., preferably 180° C. to 205° C., and more preferably 182° C. to 320° C. When this condition is satisfied, the heat resistance of the thermoplastic resin composition may be further improved.

[0071] The weight average molecular weight of the maleimide-based non-grafted polymer may be 75000 g / mol to 150000 g / mol, preferably 80000 g / mol to 130000 g / mol. When this condition is met, the impact resistance, processability and heat resistance of the thermoplastic resin composition may be improved.

[0072] Based on 100 parts by weight of the base resin, the amount of the maleimide-based non-grafted polymer may be 10.0 to 50.0 parts by weight, preferably 15.0 to 45.0 parts by weight, and more preferably 20.0 to 40.0 parts by weight. When this condition is met, the heat resistance of the thermoplastic resin composition can be significantly improved while minimizing the reduction in impact resistance and processability.

[0073] 2) Additives

[0074] (1) Olefin non-grafted polymers

[0075] The olefin-based non-grafted polymer is a component for improving the chemical resistance of the thermoplastic resin composition.

[0076] The olefinic non-grafted polymer includes olefinic monomer units, (meth)acrylic acid ester monomer units and maleic acid monomer units, and may preferably be a terpolymer composed of olefinic monomer units, (meth)acrylic acid ester monomer units and maleic acid monomer units, more preferably an ethylene / ethyl acrylate / maleic anhydride polymer.

[0077] The amount of the olefin-based monomer unit may be 60.0 to 80.0 wt%, preferably 65.0 to 75.0 wt%, based on the total weight of the olefin-based non-grafted polymer. When this condition is satisfied, the chemical resistance of the thermoplastic resin composition may be improved.

[0078] The amount of the (meth)acrylate monomer unit may be 19.0 to 39.0 wt %, preferably 24.0 to 34.0 wt %, based on the total weight of the olefin non-grafted polymer. When this condition is met, the chemical resistance of the thermoplastic resin composition may be improved.

[0079] The amount of the maleic acid monomer unit may be 0.1 wt % to 5.0 wt %, preferably 0.1 wt % to 3.0 wt %, based on the total weight of the olefin non-grafted polymer. When this condition is met, chemical resistance can be improved while maintaining basic physical properties of the thermoplastic resin composition such as impact resistance, etc.

[0080] The amount of the olefinic non-grafted polymer may be 0.5 to 5.0 parts by weight, preferably 0.5 to 3.0 parts by weight, based on 100 parts by weight of the base resin. When this condition is met, chemical resistance can be improved while minimizing the reduction in impact resistance, processability, and heat resistance.

[0081] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in several different forms and is not limited to the embodiments described herein.

[0082] Examples and Comparative Examples

[0083] Descriptions of components used in the following Examples and Comparative Examples are as follows.

[0084] 1) Base resin

[0085] (1) Diene grafted polymer: comprising 60.0 wt% of a butadiene rubber polymer having an average particle size of 300 nm and a shell, wherein the shell comprises 30.0 wt% of styrene units and 10.0 wt% of acrylonitrile units grafted to the butadiene rubber polymer, and the weight average molecular weight of the shell is 80,000 g / mol and the grafting rate is 35%.

[0086] (2) Vinyl-based non-grafted polymer: a styrene / acrylonitrile binary polymer having a weight average molecular weight of 130,000 g / mol prepared by polymerization of 73 wt % of styrene and 27 wt % of acrylonitrile.

[0087] (3) Maleimide-based non-grafted polymer: N-phenylmaleimide / styrene / maleic anhydride terpolymer having a weight average molecular weight of 125,000 g / mol and a glass transition temperature of 185° C. prepared by polymerization of 52.0 wt % of N-phenylmaleimide, 46.0 wt % of styrene and 2.0 wt % of maleic anhydride.

[0088] 2) Additives

[0089] (1) Olefin-based non-grafted polymer: an ethylene / ethyl acrylate / maleic anhydride terpolymer having a melting point of 79° C. prepared by polymerization of 69.7 wt % of ethylene, 29 wt % of ethyl acrylate and 1.3 wt % of maleic anhydride.

[0090] (2) Ethylene / methyl acrylate binary polymer: has a melting point of 91° C. and is prepared by polymerization of 76% by weight of ethylene and 24% by weight of methyl acrylate.

[0091] The above components were mixed in the amounts shown in Table 1 and Table 2 below and stirred to prepare a thermoplastic resin composition.

[0092] Experimental Example 1

[0093] Each of the thermoplastic resin compositions of Examples and Comparative Examples was extruded to prepare pellets, and the pellets were evaluated using the method described below, and the results are shown in Tables 1 and 2 below.

[0094] (1) Melt flow index (g / 10 min): The melt flow index was measured under the conditions of 220° C. and 10 kg according to ASTM D1238. In the present invention, when the melt flow index is 4.0 g / 10 min or more, the processability is judged to be excellent.

[0095] Experimental Example 2

[0096] Each of the thermoplastic resin compositions of Examples and Comparative Examples was extruded and injection molded to prepare a sample, and the sample was evaluated using the method described below, and the results thereof are shown in Tables 1 to 4 below.

[0097] (2) Izod impact strength (kg·cm / cm, 1 / 4 inch): The Izod impact strength was measured according to ASTM D 256. In the present invention, when the Izod impact strength is 10.0 kg·cm / cm or more, the impact resistance is judged to be excellent.

[0098] (3) Heat deflection temperature (°C): The heat deflection temperature was measured in an unannealed condition according to ASTM D648. In the present invention, when the heat deflection temperature is 90.0°C or more, the heat resistance is judged to be excellent.

[0099] (4) Chemical resistance: Each sample (200 mm×12.7 mm×3.2 mm) was fixed to a bending jig with a stress of 1.1%, and 1 cc of a thinner (T803, commercially available from NOROO BEE Chemical Co.) was applied, and the time until cracks occurred in each sample was measured.

[0100] ○: No cracks occurred within 600 seconds after the application of the diluent.

[0101] ×: Cracks occurred within 600 seconds after the thinner was applied.

[0102] [Table 1]

[0103]

[0104] [Table 2]

[0105]

[0106] Referring to Tables 1 and 2, the thermoplastic resin composition of Example 1, which includes a diene-based graft polymer and a vinyl-based non-graft polymer as a base resin and includes an olefin-based non-graft polymer as an additive, has excellent melt flow index, excellent impact strength and chemical resistance, and a sufficient level of heat deflection temperature. Examples 2 to 6 include a diene-based graft polymer, a vinyl-based non-graft polymer and a maleimide-based non-graft polymer as a base resin and include an olefin-based non-graft polymer as an additive, and have excellent melt flow index, excellent impact strength and chemical resistance, and high heat deflection temperature.

[0107] When comparing Example 2 and Example 3, it can be seen that as the content of the olefinic non-grafted polymer increases, the melt flow index and impact strength increase, but the heat deflection temperature decreases.

[0108] When comparing Example 1, Example 2, and Example 6, it can be seen that the maleimide-based non-grafted polymer increases the heat deflection temperature but decreases the melt flow index and impact strength.

[0109] When comparing Examples 4 to 6, it can be seen that the content of the olefinic non-grafted polymer affects the heat deflection temperature.

[0110] When Example 1 and Comparative Example 1 are compared, Example 1 has remarkable chemical resistance compared to Comparative Example 1 which does not include the olefin-based non-grafted polymer.

[0111] When comparing Examples 4 to 6 and Comparative Example 2, Examples 4 to 6 have excellent impact strength and chemical resistance compared to Comparative Example 2 which does not include the olefin-based non-grafted polymer, but have a decreased heat deflection temperature.

[0112] When Example 5 and Comparative Example 3 are compared, Example 5 has remarkably high impact strength and chemical resistance compared to Comparative Example 3 including an ethylene / methyl acrylate binary polymer instead of an olefin-based non-grafted polymer.

[0113] When comparing Example 6 and Comparative Example 4, Example 5 has remarkably high impact strength and chemical resistance compared to Comparative Example 4 including an ethylene / methyl acrylate binary polymer instead of an olefin-based non-grafted polymer.

Claims

1. A thermoplastic resin composition comprising: A base resin comprising a diene-based grafted polymer and a vinyl-based non-grafted polymer, wherein the vinyl-based non-grafted polymer comprises an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit; and The additive comprises an olefinic non-grafted polymer, wherein the olefinic non-grafted polymer comprises an olefinic monomer unit, a (meth)acrylic acid ester monomer unit and a maleic acid monomer unit.

2. The thermoplastic resin composition according to claim 1, in, The thermoplastic resin composition includes 0.5 parts by weight to 5.0 parts by weight of the olefin-based non-graft polymer based on 100 parts by weight of the base resin.

3. The thermoplastic resin composition according to claim 1, in, The olefin non-grafted polymer is a terpolymer composed of olefin monomer units, (meth) acrylic acid ester monomer units and maleic acid monomer units.

4. The thermoplastic resin composition according to claim 1, in, The olefin non-grafted polymer is an ethylene / ethyl acrylate / maleic anhydride terpolymer.

5. The thermoplastic resin composition according to claim 1, in, The diene-based graft polymer includes a diene-based rubber polymer and a shell, and the shell includes an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted onto the diene-based rubber polymer.

6. The thermoplastic resin composition according to claim 1, in, The thermoplastic resin composition includes 10.0 parts by weight to 40.0 parts by weight of the diene-based graft polymer based on 100 parts by weight of the base resin.

7. The thermoplastic resin composition according to claim 1, in, The base resin includes a maleimide-based non-grafted polymer, and the maleimide-based non-grafted polymer includes a maleimide-based monomer unit, an aromatic vinyl-based monomer unit, and a maleic acid-based monomer unit.

8. The thermoplastic resin composition according to claim 7, in, The thermoplastic resin composition includes 10.0 parts by weight to 50.0 parts by weight of the maleimide-based non-grafted polymer based on 100 parts by weight of the base resin.

9. The thermoplastic resin composition according to claim 7, in, The maleimide non-grafted polymer is a terpolymer composed of maleimide monomer units, aromatic vinyl monomer units and maleic acid monomer units.

10. The thermoplastic resin composition according to claim 7, in, The maleimide-based non-grafted polymer is N-phenylmaleimide / styrene / maleic anhydride polymer.

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