Thermoplastic resin composition, method for producing same, and molded article including same

Abstract

The present disclosure relates to a thermoplastic resin composition, a method for producing same, and a molded article including same. More specifically, the present disclosure relates to: the thermoplastic resin composition characterized by comprising: 100 parts by weight of a base resin including (A) 79-86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene-based compound, and a vinyl cyanide compound, and (B) 14-21 wt% of at least one graft copolymer selected from the group consisting of (b-1) a graft copolymer in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle size of 200-500 nm and (b-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer containing an alkyl acrylate rubber having an average particle size of 50-400 nm; and (C) 8-21 parts by weight of a thermoplastic polyester elastomer; a method for producing same; and a molded article including same. The present invention has the effect of providing: a thermoplastic resin composition that has excellent mechanical properties and excellent heat resistance and chemical resistance, in particular, excellent sun cream resistance, exhibits high blackness, and can be applied to an uncoated molded article with uniform appearance in injection molding and high quality; a method for producing same; and a molded article including same.

Description

Thermoplastic resin composition, method for producing the same, and molded article comprising the same

[0001] 〔Cross-citation with the applicant(s)〕

[0002] This application claims the benefit of priority from Korean Patent Application No. 10-2023-0146275, filed October 30, 2023, and Korean Patent Application No. 10-2024-0117467, filed August 30, 2024, which is hereby incorporated by reference in its entirety.

[0003] The present invention relates to a thermoplastic resin composition, a method for producing the same, and a molded article comprising the same, and more particularly, to a thermoplastic resin composition having excellent mechanical properties, excellent heat resistance and chemical resistance, particularly excellent sunscreen resistance, high blackness, and a uniform injection-molded appearance, which can be applied to unpainted molded articles, a method for producing the same, and a molded article comprising the same.

[0004] Recently, automakers have been experimenting with various approaches to eliminating the painting process for automotive parts, or "paintless" automotive components, to improve environmental friendliness and cost competitiveness. To achieve this, automotive parts must meet both superior exterior quality and automotive reliability assessments.

[0005] Resin compositions based on PMMA resins, such as acrylate-styrene-acrylonitrile resin (hereinafter referred to as “ASA resin”) / polymethyl methacrylate resin (hereinafter referred to as “PMMA resin”) alloys and acrylonitrile-butadiene-styrene resin (hereinafter referred to as “ABS resin”) resin / PMMA resin alloys, can achieve a high level of blackness, but face many difficulties in product application due to limitations in implementing reliable quality.

[0006] In particular, materials have been developed by adding heat-resistant resins to resin compositions based on PMMA resins to achieve the high level of heat resistance and chemical resistance required for automotive interior parts, especially sun resistance. However, due to poor compatibility between resins, not only is it difficult to obtain the desired level of appearance quality and uniform physical properties, but there is also the problem of insufficient heat resistance and chemical resistance.

[0007] Therefore, there is a need for the development of materials that have excellent heat resistance, chemical resistance, and appearance quality and that can be applied to unpainted molded products.

[0008] [Prior Art Literature]

[0009] [Patent Document]

[0010] Korean Patent No. 10-0417066

[0011] In order to solve the problems of the prior art as described above, the present invention relates to a thermoplastic resin composition that has excellent mechanical properties, excellent heat resistance and sunscreen resistance, high blackness, and a uniform injection-molded appearance, and can be applied to unpainted molded products.

[0012] In addition, the present invention aims to provide a method for producing the above thermoplastic resin composition.

[0013] In addition, the present invention aims to provide a molded product comprising the thermoplastic resin composition described above.

[0014] The above-mentioned and other purposes of this invention can all be achieved by the invention described below.

[0015] In order to achieve the above object, I) the present invention provides a thermoplastic resin composition comprising (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 14 to 21 wt% of a copolymer comprising a rubber component, an aromatic vinyl compound, and a vinyl cyan compound; and (C) 8 to 21 wt% of a thermoplastic polyester elastomer; wherein the thermoplastic resin composition is characterized in that the lightness value (L value) measured using a square disk injection-molded specimen using a colorimeter according to the CIE1976 L*a*b* colorimetric system in a specular component excluded (SCE: SCE) manner is 1.5 or less, and the heat distortion temperature measured under 1.8 MPa according to ISO 75 / Be is 85 ℃ or more.

[0016] II) In the above I), the rubber component may be a conjugated diene rubber, an alkyl acrylate rubber, or a mixture thereof.

[0017]

[0018] In addition, III) the present invention provides a thermoplastic resin composition characterized by comprising: (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, and (B) 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle size of 50 to 400 nm; and (C) 8 to 21 wt% of a thermoplastic polyester elastomer.

[0019] IV) In the above I) to III), the (A) non-graft copolymer may preferably comprise 30 to 60 wt% of alkyl (meth)acrylate, 20 to 50 wt% of alkyl-substituted styrene compound, and 5 to 35 wt% of vinyl cyanide compound based on the total weight thereof.

[0020] V) In the above I) to IV), the graft copolymer (b-1) may preferably comprise 35 to 65 wt% of conjugated diene rubber, 20 to 50 wt% of alkyl (meth)acrylate, 1 to 30 wt% of aromatic vinyl compound, and 1 to 20 wt% of vinyl cyan compound based on the total weight thereof.

[0021] VI) In the above I) to V), the (b-2) graft copolymer may preferably comprise 30 to 70 wt% of alkyl acrylate rubber, 10 to 55 wt% of aromatic vinyl compound, and 1 to 30 wt% of vinyl cyan compound based on the total weight thereof.

[0022] VII) In the above I) to VI), the thermoplastic polyester elastomer (C) may preferably have a melt flow rate of 0.5 to 10 g / 10 min measured at 230°C and 2.16 kg according to ASTM D1238.

[0023] VIII) In the above I) to VII), the thermoplastic polyester elastomer (C) may be an elastomer comprising, preferably, an aromatic dicarboxylic acid or an ester derivative thereof; an aliphatic diol; and a polyalkylene oxide.

[0024] IX) In the above I) to VIII), the aromatic dicarboxylic acid may preferably be at least one selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid.

[0025] X) In the above I) to IX), the aliphatic diol may preferably be at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol.

[0026] XI) In the above I) to X), the polyalkylene oxide may preferably be at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene glycol, and a copolymer of ethylene oxide and tetrahydrofuran.

[0027] XII) In the above I) to XI), the thermoplastic resin composition may preferably include 0.1 to 5 parts by weight of a dye, pigment, or a mixture thereof with respect to 100 parts by weight of the base resin.

[0028] XIII) In the above I) to XII), the thermoplastic resin composition may preferably have a sunscreen resistance of grade 3 or higher on a gray scale.

[0029] XIV) In the above I) to XIII), the thermoplastic resin composition may preferably have a heat distortion temperature of 85°C or higher measured under 1.8 MPa using an injection molded specimen having a thickness of 4 mm according to ISO 75 / Be.

[0030]

[0031] In addition, XV) The present invention provides a base resin comprising 100 parts by weight of (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle size of 50 to 400 nm; And (C) a thermoplastic polyester elastomer 8 to 21 parts by weight; a step of mixing and extruding under conditions of 190 to 280° C. and 100 to 800 rpm is provided.

[0032]

[0033] In addition, XVI) The present invention provides a molded article characterized by including a thermoplastic resin composition of any one of the above I) to XIV).

[0034] According to the present invention, there is provided a thermoplastic resin composition having excellent mechanical properties, heat resistance and chemical resistance, especially sunscreen resistance, high blackness, and uniform injection-molded appearance, which can be applied to unpainted molded products at high quality, a method for producing the same, and a molded product comprising the same.

[0035] In particular, a molded product including a thermoplastic resin composition according to the present invention has a color and uniform appearance quality at the level of a paint job without painting, so that it can be provided as an automobile interior part with a quality higher than that required by the market, and has the advantage of being environmentally friendly and having reduced process costs.

[0036]

[0037] Hereinafter, the thermoplastic resin composition of the present invention, its manufacturing method, and a molded article including the same are described in detail.

[0038] The present inventors have confirmed that when a thermoplastic polyester elastomer is included in a base resin containing at least one graft copolymer selected from the group consisting of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, a graft copolymer in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound are grafted onto a conjugated diene rubber having a predetermined average particle diameter, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having a predetermined average particle diameter, the mechanical properties are excellent, and heat resistance, chemical resistance, sunscreen resistance, blackness, gloss, and appearance quality are all improved, and based on this, they have devoted themselves to further research and completed the present invention.

[0039]

[0040] The thermoplastic resin composition according to this invention is examined in detail as follows.

[0041]

[0042] The thermoplastic resin composition of the present invention comprises 100 parts by weight of a base resin comprising (A) 79 to 86 parts by weight of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 14 to 21 parts by weight of a copolymer comprising a rubber component, an aromatic vinyl compound, and a vinyl cyan compound; and (C) 8 to 21 parts by weight of a thermoplastic polyester elastomer; and is characterized in that the lightness value (L value) measured using a square disk injection-molded specimen using a colorimeter according to the CIE1976 L*a*b* colorimetric system in a specular component excluded (SCE) manner is 1.5 or less, and the heat distortion temperature measured under 1.8 MPa according to ISO 75 / Be is 85°C or more. In this case, it has the advantage of being able to be applied to unpainted molded products in high quality, as it has excellent mechanical properties, heat resistance and chemical resistance, especially sun resistance, high blackness, and a uniform injection appearance, realizing a color and appearance at the level of painting.

[0043]

[0044] In addition, the thermoplastic resin composition of the present invention is characterized by comprising 100 parts by weight of a base resin comprising (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm; and (C) 8 to 21 parts by weight of a thermoplastic polyester elastomer. In this case, it has the advantage of being able to be applied to unpainted molded products in high quality, as it has excellent mechanical properties, heat resistance and chemical resistance, especially sun resistance, high blackness, and a uniform injection appearance, realizing a color and appearance at the level of painting.

[0045]

[0046] Hereinafter, the thermoplastic resin composition of the present invention will be described in detail by composition.

[0047]

[0048] (A) Non-graft polymer

[0049] The above (A) non-graft copolymer may be, for example, 79 to 86 wt%, preferably 80 to 85 wt%, and more preferably 80 to 82 wt%, based on 100 wt% of the base resin, and within this range, it has excellent heat resistance and chemical resistance, especially sunscreen resistance, and exhibits high blackness, and has a uniform injection appearance, realizing a color and appearance at the level of painting, so that it has the advantage of being applicable to unpainted molded products in high quality.

[0050] In this description, 'non-graft' means not grafted, and more specifically, not graft polymerized under rubber.

[0051]

[0052] The above (A) non-graft copolymer can be formed by including, for example, an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, and in this case, it has excellent heat resistance and chemical resistance, especially sunscreen resistance, and exhibits high blackness, and has a uniform injection appearance, realizing a color and appearance at the level of painting, so that it has the advantage of being applicable to unpainted molded products in high quality.

[0053] The above (A) non-graft copolymer may preferably comprise 30 to 60 wt% of alkyl (meth)acrylate, 20 to 50 wt% of alkyl-substituted styrene-based compound, and 5 to 35 wt% of vinyl cyanide compound based on the total weight thereof, more preferably 35 to 55 wt% of alkyl (meth)acrylate, 25 to 45 wt% of alkyl-substituted styrene-based compound, and 10 to 30 wt% of vinyl cyanide compound, even more preferably 40 to 50 wt% of alkyl (meth)acrylate, 30 to 40 wt% of alkyl-substituted styrene-based compound, and 15 to 25 wt% of vinyl cyanide compound, and even more preferably 43 to 48 wt% of alkyl (meth)acrylate, 33 to 38 wt% of alkyl-substituted styrene-based compound, and 17 to 22 wt% of vinyl cyanide compound, and within this range, as described below: (B) It has excellent compatibility with copolymers, transparency, gloss, heat resistance and chemical resistance, especially excellent sunscreen resistance, high blackness, and a uniform injection appearance, realizing a color and appearance at the level of painting, so it has the advantage of being applicable to high-quality unpainted molded products.

[0054] Preferably, the above (A) non-graft copolymer may be a methyl methacrylate-α-methyl styrene-acrylonitrile copolymer, in which case it has excellent transparency, heat resistance, and chemical resistance, especially sunscreen resistance, and exhibits high blackness, and has a uniform injection appearance, realizing a color and appearance at the level of painting, so that it has the advantage of being applicable to unpainted molded products in high quality.

[0055]

[0056] The above (A) non-graft copolymer may have a weight average molecular weight of, for example, 50,000 to 200,000 g / mol, preferably 70,000 to 150,000 g / mol, more preferably 80,000 to 120,000 g / mol, and within this range, has excellent mechanical properties such as impact strength and tensile strength and excellent injection moldability.

[0057] In this description, unless otherwise defined, the weight average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, the solvent is THF, the column temperature is 40 ℃, the flow rate is 0.3 ml / min, the sample concentration is 20 mg / ml, the injection amount is 5 ㎕, the column model is 1xPLgel 10 ㎛ MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 ㎛ MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 ㎛ MiniMix-B Guard (50 x 4.6 mm), the measuring device is Agilent 1200 series system, the refractive index detector: Agilent G1362 RID, the RI temperature is 35 ℃, the data processing is Agilent ChemStation S / W, and the test method (Mn, Mw, and PDI) can be measured under OECD TG 118 conditions.

[0058]

[0059] The above (A) non-graft polymer may have a glass transition temperature of 110°C or higher, preferably 115°C or higher, and more preferably 115 to 150°C as measured according to ASTM D3418, for example, and in this case, there is an effect of improving heat resistance.

[0060] In this paper, the glass transition temperature can be measured at a heating rate of 10℃ / min using a TA Instruments Q100 DSC (Differential Scanning Calorimetry) according to ASTM D3418.

[0061] The above (A) non-graft polymer may have a flow index of 8 g / 10 min or more, preferably 10 g / 10 min or more, and more preferably 10 to 20 g / 10 min, as measured at 220°C and under a 10 kg load according to ASTM D1238, and has excellent processability within this range.

[0062] The above (A) non-graft polymer may have a refractive index of 1.52 to 1.55, preferably 1.53 to 1.54, as measured at room temperature using an Abbe refractometer according to ASTM D542, for example, and within this range, it has excellent transparency and gloss and excellent heat resistance and weather resistance.

[0063] In this description, room temperature may be a point within the range of 23 ± 3 ℃.

[0064]

[0065] The above (A) non-graft polymer can be manufactured by, for example, including the steps of: i) introducing a reaction mixture comprising 30 to 60 wt% of an alkyl (meth)acrylate, 20 to 50 wt% of an alkyl-substituted styrene-based compound, 5 to 35 wt% of a vinyl cyanide compound, a solvent, and a multifunctional group-containing organic peroxide initiator into a polymerization device and subjecting the mixture to bulk polymerization to obtain a polymer reaction solution; and ii) introducing the polymer reaction solution of step i) into a volatilization tank and volatilizing unreacted monomers and the solvent to separate the polymer.

[0066]

[0067] The bulk polymerization of step i) above can be preferably carried out under conditions of 100 to 130°C and a residence time in the reactor of 6 to 8 hours, and more preferably can be carried out under conditions of 110 to 120°C and a residence time in the reactor of 7 to 8 hours.

[0068] The polymerization device used in the above polymerization reaction is not particularly limited, but a continuous polymerization device having two or more stirred tank reactors connected in series is preferred. In this case, the reactors are not particularly limited, but the first reactor is preferably a stirred tank with a heat exchanger attached to the front end of the reactor, and the second or more reactors are preferably evaporative stirred tank reactors including a stirred tank, a storage tank, a condenser, and a pressure regulating plate.

[0069] The solvent may be, for example, toluene, methyl ethyl ketone or a mixture thereof, preferably toluene, in which case it is easy to control viscosity and has the effect of suppressing a decrease in polymerization conversion rate.

[0070] The above multifunctional group-containing organic peroxide initiator may be, for example, at least one selected from the group consisting of 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, and 1,1-bis(t-butylperoxy)2-methylcyclohexane, and in this case, there is an advantage of excellent productivity and reduced thermal discoloration.

[0071] The organic peroxide initiator may be, for example, 0.05 to 0.3 parts by weight based on 100 parts by weight of the total of the alkyl-substituted styrene compound, the alkyl (meth)acrylate, and the vinyl cyan compound, and within this range, there is an effect of increasing the polymerization conversion rate and molecular weight.

[0072]

[0073] The above step ii) can be performed in a conventional volatilization tank as a conventional volatilization and separation process, for example, the reaction solution (polymer reaction solution) polymerized and discharged from a continuous polymerization device is introduced into a first volatilization tank equipped with a heat exchanger that maintains a vacuum pressure of 100 to 200°C and 500 to 650 torr, and then the reaction solution discharged from the first volatilization tank is introduced into a second volatilization tank equipped with a heat exchanger that maintains a vacuum pressure of 200 to 250°C and 50 torr or less, preferably 20 to 30 torr, to volatilize unreacted monomers and solvents, and then condense and reintroduce them as raw materials, and the polymer can be manufactured by being processed into a pellet form while passing through a transfer pump and an extruder.

[0074]

[0075] The above (A) non-graft copolymer can be produced by, for example, solution polymerization, bulk polymerization, emulsion polymerization, or suspension polymerization, and preferably bulk polymerization. The solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization are not particularly limited as long as they are each a solution polymerization, bulk polymerization, emulsion polymerization, and suspension polymerization method commonly practiced in the technical field to which the present invention pertains.

[0076]

[0077] In this description, a polymer comprising a compound means a polymer polymerized including the compound, and the units within the polymer are derived from the compound.

[0078]

[0079] In this description, alkyl (meth)acrylate may be defined to include both alkyl acrylate and alkyl methacrylate.

[0080] In the present invention, the alkyl acrylate may be, for example, an alkyl acrylate having 1 to 15 carbon atoms in the alkyl group, and preferably may be at least one selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylbutyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, hexyl acrylate, heptyl acrylate, n-pentyl acrylate, and lauryl acrylate, and more preferably may be an alkyl acrylate including a chain alkyl group having 1 to 4 or 8 carbon atoms, and even more preferably may be n-butyl acrylate or 2-ethylhexyl acrylate.

[0081] In the present invention, the alkyl methacrylate may be, for example, an alkyl methacrylate having an alkyl group having 1 to 15 carbon atoms, preferably at least one selected from the group consisting of methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylbutyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate, more preferably an alkyl methacrylate including a chain alkyl group having 1 to 4 carbon atoms, and even more preferably methyl methacrylate.

[0082]

[0083] In the present invention, the alkyl-substituted styrene compound is at least one selected from the group consisting of, for example, α-methyl styrene, ρ-methyl styrene, ο-ethyl styrene, m-ethyl styrene, ρ-ethyl styrene, ρ-t-butyl styrene, and 2,4-dimethyl styrene, and is preferably α-methyl styrene, in which case excellent heat resistance is effective.

[0084]

[0085] In the present invention, the vinyl cyanide compound may be, for example, at least one selected from the group consisting of acrylonitrile, methacrylonitrile, ethylacrylonitrile, and isopropylacrylonitrile, and preferably acrylonitrile.

[0086]

[0087] (B) A copolymer comprising a rubber component, an aromatic vinyl compound, and a vinyl cyan compound.

[0088] The above (B) copolymer may be, for example, 14 to 21 wt%, preferably 15 to 20 wt%, and more preferably 18 to 20 wt%, based on 100 wt% of the base resin, and within this range, it has the advantage of excellent mechanical properties, heat resistance and chemical resistance, and especially excellent sunscreen resistance.

[0089]

[0090] The above rubber component may be, for example, conjugated diene rubber, alkyl acrylate rubber, or a mixture thereof, in which case it has the advantage of excellent mechanical properties, heat resistance, chemical resistance, and especially sunscreen resistance.

[0091]

[0092] The above aromatic vinyl compound and vinyl cyan compound may be within the same range as the types of aromatic vinyl compound and vinyl cyan compound included in the (A) non-graft copolymer of the present invention.

[0093]

[0094] The above (B) copolymer may be preferably a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound; a copolymer comprising conjugated diene rubber, an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound; or a mixture thereof, more preferably a copolymer comprising alkyl acrylate rubber, an aromatic vinyl compound, and a vinyl cyan compound, and a mixture of a copolymer comprising conjugated diene rubber, an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound, and specifically a mixture of a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer and an alkyl acrylate-styrene-acrylonitrile copolymer, and in this case, there is an advantage of having excellent mechanical properties, heat resistance, chemical resistance, and, in particular, excellent sunscreen resistance.

[0095]

[0096] The above (B) copolymer may be more preferably at least one selected from the group consisting of (b-1) a graft copolymer in which an alkyl (meth)acrylate, an aromatic vinyl compound and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and (b-2) an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer including an alkyl acrylate rubber having an average particle size of 50 to 400 nm, and more preferably, it may include both the (b-1) graft copolymer and the (b-2) graft copolymer, in which case there is an advantage of excellent mechanical properties as well as excellent heat resistance and chemical resistance, particularly excellent sunscreen resistance.

[0097] When both the above (b-1) graft copolymer and (b-2) graft copolymer are included, the weight ratio of the (b-1) graft copolymer and the (b-2) graft copolymer may be, for example, 9:1 to 1:9, preferably 7:3 to 5:5, and within this range, there is an advantage of excellent mechanical properties, heat resistance and chemical resistance, and especially excellent sunscreen resistance.

[0098]

[0099] (b-1) A graft copolymer in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm.

[0100] The above (b-1) graft copolymer may be, for example, composed of 35 to 65 wt% of conjugated diene rubber, 20 to 50 wt% of alkyl (meth)acrylate, 1 to 30 wt% of aromatic vinyl compound and 1 to 20 wt% of vinyl cyan compound based on the total weight thereof, preferably 40 to 60 wt% of conjugated diene rubber, 25 to 45 wt% of alkyl (meth)acrylate, 1 to 25 wt% of aromatic vinyl compound and 1 to 15 wt% of vinyl cyan compound, more preferably 45 to 55 wt% of conjugated diene rubber, 30 to 40 wt% of alkyl (meth)acrylate, 5 to 20 wt% of aromatic vinyl compound and 1 to 10 wt% of vinyl cyan compound, even more preferably 47 to 52 wt% of conjugated diene rubber, 33 to 38 wt% of alkyl (meth)acrylate, It can be made by including 10 to 15 wt% of an aromatic vinyl compound and 1 to 5 wt% of a vinyl cyan compound, and within this range, it has the advantages of excellent mechanical properties, transparency, glossiness, and colorability.

[0101]

[0102] The average particle diameter of the above conjugated diene rubber may be preferably 200 to 450 nm, preferably 250 to 400 nm, more preferably 250 to 350 nm, and even more preferably 270 to 320 nm, and within this range, it has the advantages of excellent mechanical properties, transparency, glossiness, and colorability.

[0103]

[0104] In this paper, the average particle size can be measured using dynamic light scattering, and specifically, it is measured as an intensity value in Gaussian mode using a particle measuring device (product name: Nicomp 380, manufacturer: PSS). As a specific measurement example, the sample is prepared by diluting 0.1 g of latex with a total solid content of 35 to 50 wt% with distilled water 1,000 to 5,000 times, and the measurement method is measured using a flow cell through auto-dilution. The measurement mode is dynamic light scattering / Intensity 300 KHz / Intensity-weight Gaussian Analysis, and the setting values ​​are temperature 23 ℃, measurement wavelength 632.8 nm, and channel width 10 μsec.

[0105]

[0106] The above conjugated diene rubber can be manufactured by, for example, adding 100 parts by weight of a conjugated diene compound, 0.2 to 4 parts by weight of an emulsifier, 0.02 to 1.5 parts by weight of a polymerization initiator, 0.5 parts by weight of an electrolyte, 0.1 to 0.5 parts by weight of a molecular weight regulator, and 90 to 130 parts by weight of ion-exchanged water, and subjecting the mixture to an emulsion polymerization reaction at 65 to 85°C for 25 to 50 hours.

[0107]

[0108] The above conjugated diene rubber may have a gel content of, for example, 50 to 99 wt%, preferably 60 to 99 wt%, more preferably 70 to 95 wt%, and even more preferably 80 to 95 wt%, and within this range, graft copolymerization is effectively formed on the outside of the rubber particles, thereby providing excellent mechanical properties, transparency, gloss, colorability, and processability.

[0109] In this description, the gel content can be calculated by adding 1 g of graft copolymer to 30 ml of acetone, stirring at room temperature for 12 hours, centrifuging the mixture to collect only the insoluble matter that is not dissolved in acetone, drying it for 12 hours, and measuring the weight, using the following mathematical formula 1. As a specific measurement example, the gel content is obtained by adding 1 g of the graft copolymer to 30 ml of acetone, stirring the mixture at room temperature for 12 hours at 210 rpm using a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075), centrifuging the mixture at 18,000 rpm at 0°C for 3 hours using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble matter that has not dissolved in acetone, drying the mixture at 85°C for 12 hours using a forced convection oven (Equipment name: Lab companion OF-12GW) using a forced circulation drying method, and then measuring the weight using the following mathematical formula 1.

[0110] [Mathematical Formula 1]

[0111] Gel content (wt%) = [Weight of insoluble matter (gel) (g) / Weight of sample (g)] * 100

[0112]

[0113] The conjugated diene rubber used in the above emulsion polymerization reaction may be, for example, a polybutadiene rubber latex having a swelling index of 12 to 40, and preferably a polybutadiene rubber latex having a swelling index of 20 to 35, in which case the mechanical properties and processability are excellent.

[0114] In this description, the swelling index can be calculated by adding 1 g of graft copolymer to 30 ml of acetone, stirring at room temperature for 12 hours, centrifuging the mixture to collect only the insoluble portion that is not dissolved in acetone, drying it for 12 hours, and measuring the weight, using the following mathematical formula 2. As a specific measurement example, the swelling index is obtained by adding 1 g of the graft copolymer to 30 ml of acetone, stirring the mixture at room temperature for 12 hours at 210 rpm using a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075), centrifuging the mixture at 18,000 rpm at 0 ℃ for 3 hours using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble matter that has not dissolved in acetone, drying the mixture at 85 ℃ for 12 hours using a forced convection oven (Equipment name: Lab companion OF-12GW) using a forced circulation drying method, and measuring the weight, using the following mathematical formula 2.

[0115] [Equation 2]

[0116] Swelling index = Weight before drying after centrifugation / Weight after drying after centrifugation

[0117]

[0118] The above conjugated diene rubber may preferably be at least one selected from the group consisting of butadiene, polybutadiene, styrene-butadiene, polyisoprene and butadiene-isoprene, and in this case, it has excellent mechanical properties and processability.

[0119] The above emulsifier may be, for example, at least one selected from the group consisting of alkyl aryl sulfonates, alkali methyl alkyl sulfates, sulfonated alkyl esters, soaps of fatty acids, and alkali salts of rosin acids.

[0120] The emulsifier may be, for example, 0.2 to 1.5 parts by weight, preferably 0.5 to 1.0 parts by weight, based on 100 parts by weight of the monomer mixture.

[0121]

[0122] The polymerization initiator may be, for example, at least one selected from the group consisting of water-soluble persulfates, fat-soluble peroxy compounds, and oxidation-reduction polymerization initiators.

[0123] The above water-soluble persulfate may be, for example, at least one selected from the group consisting of persulfate, sodium persulfate, and potassium persulfate.

[0124] The above-mentioned lipid-soluble peroxy compound may be, for example, at least one selected from the group consisting of cumene hydroperoxide, diisopropyl benzene hydroperoxide, azobisisobutyl nitrile, tertiary butyl hydroperoxide, paramethane hydroperoxide, and benzoyl peroxide.

[0125] The above-mentioned oxidation-reduction polymerization initiator may be, for example, at least one selected from the group consisting of sodium formaldehyde sulfoxylate, sodium ethylenediamine tetraacetate, ferrous sulfate, dextrose, sodium pyrophosphate, and sodium sulfite.

[0126] The above polymerization initiator can be used in an amount of, for example, 0.02 to 0.3 parts by weight, preferably 0.1 to 0.2 parts by weight, per 100 parts by weight of the monomer mixture.

[0127]

[0128] The electrolyte may be, for example, at least one selected from the group consisting of KCl, NaCl, KHCO3, NaHCO3, K2CO3, Na2CO3, KHSO3, K4P2O7, K3PO4, Na3PO4, K2HPO4, and Na2HPO4.

[0129] The above molecular weight regulator may be, for example, a mercaptan, and preferably, a tertiary dodecyl mercaptan.

[0130] The above emulsion polymerization can be performed, for example, at 65 to 85°C, preferably 70 to 80°C, and has the advantage that the gel content and swelling index of the rubber latex can be easily controlled within this range.

[0131] As an example, a monomer mixture including an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound can be grafted onto the conjugated diene rubber latex manufactured as described above through emulsion polymerization to manufacture a graft copolymer (b-1) according to the present invention.

[0132] The above emulsion polymerization can be carried out, for example, at a temperature of 65 to 85°C for 3 to 10 hours, and preferably at a temperature of 70 to 80°C for 4 to 9 hours.

[0133]

[0134] The above (b-1) graft copolymer may be, for example, present in an amount of 0 to 21 wt%, preferably 0 to 18 wt%, more preferably 3 to 18 wt%, even more preferably 5 to 18 wt%, even more preferably 5 to 14 wt%, particularly preferably 5 to 11 wt%, even more preferably 7 to 11 wt%, and most preferably 8 to 10 wt%, based on the total weight of the base resin, and within this range, it has the advantages of excellent mechanical properties, transparency, glossiness, and colorability.

[0135]

[0136] In the present invention, the conjugated diene compound may be, for example, at least one selected from the group consisting of 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, and piperylene, and preferably 1,3-butadiene.

[0137] In the present invention, the aromatic vinyl compound may be, for example, at least one selected from the group consisting of styrene, α-methyl styrene, ο-methyl styrene, ρ-methyl styrene, m-methyl styrene, ethyl styrene, isobutyl styrene, t-butyl styrene, ο-brobo styrene, ρ-bromostyrene, m-bromostyrene, ο-chloro styrene, ρ-chloro styrene, m-chloro styrene, vinyltoluene, vinylxylene, fluorostyrene, and vinylnaphthalene, preferably at least one selected from the group consisting of styrene and α-methyl styrene, more preferably styrene, and in this case, there is an effect of having appropriate fluidity, excellent processability, and excellent mechanical properties such as impact resistance.

[0138]

[0139] The types of alkyl (meth)acrylate and vinyl cyan compound included in the above (b-1) graft copolymer may be within the same category as the types of alkyl (meth)acrylate and vinyl cyan compound included in the (A) non-graft copolymer of the present invention.

[0140]

[0141] (b-2) Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising alkyl acrylate rubber having an average particle diameter of 50 to 400 nm

[0142] The above (b-2) graft copolymer may be formed by, for example, including an alkyl acrylate rubber (core) and an aromatic vinyl compound-vinyl cyan compound copolymer (shell) surrounding the core.

[0143] The above (b-2) graft copolymer may be, for example, composed of 30 to 70 wt% of alkyl acrylate rubber, 10 to 55 wt% of aromatic vinyl compound, and 1 to 30 wt% of vinyl cyan compound based on the total weight thereof, preferably 40 to 60 wt% of alkyl acrylate rubber, 20 to 45 wt% of aromatic vinyl compound, and 5 to 20 wt% of vinyl cyan compound, more preferably 45 to 55 wt% of alkyl acrylate rubber, 30 to 40 wt% of aromatic vinyl compound, and 10 to 15 wt% of vinyl cyan compound, and within this range, it has the advantages of excellent mechanical properties, processability, weather resistance, transparency, gloss, and colorability.

[0144]

[0145] The above alkyl acrylate rubber may preferably have an average particle size of 80 to 400 nm, more preferably 100 to 400 nm, even more preferably 100 to 150 nm or 300 to 400 nm, and within this range, has excellent physical property balance while exhibiting excellent mechanical properties, gloss, transparency, and colorability.

[0146]

[0147] The above alkyl acrylate rubber can be manufactured, for example, by emulsion polymerization of alkyl acrylate, and preferably by emulsion polymerization by mixing alkyl acrylate, an emulsifier, an initiator, a grafting agent, a crosslinking agent, an electrolyte, and a solvent. In this case, the grafting efficiency is excellent, and thus the mechanical properties are excellent.

[0148] The above alkyl acrylate rubber may be formed by including, for example, a seed, and preferably may be formed by including a rubber seed.

[0149] The above seed can be manufactured by polymerizing, for example, 1 to 20 wt%, preferably 2 to 15 wt%, more preferably 3 to 10 wt% of one or more monomers selected from the group consisting of aromatic vinyl compounds, vinyl cyan compounds, and alkyl acrylates, based on 100 wt% of the above (b-2) graft copolymer, and within this range, excellent effects such as impact strength, weather resistance, and physical property balance are achieved.

[0150]

[0151] The above aromatic vinyl compound-vinyl cyan compound copolymer (shell) may have, for example, a weight average molecular weight of 40,000 to 120,000 g / mol, preferably 50,000 to 110,000 g / mol, more preferably 60,000 to 110,000 g / mol, and within this range, has excellent impact strength, tensile strength, and processability.

[0152]

[0153] The above (b-2) graft copolymer can be produced, for example, by emulsion polymerization, and in this case, it has the advantages of excellent mechanical properties, processability, weather resistance, transparency, gloss, and colorability.

[0154] The above emulsion polymerization is not particularly limited to an emulsion polymerization method commonly practiced in the technical field to which the present invention belongs, and may be performed using an emulsion graft polymerization method, for example.

[0155]

[0156] The above (b-2) graft copolymer may have a graft ratio calculated by the following mathematical formula 3 of, for example, 25% or more, preferably 30% or more, more preferably 30 to 70%, even more preferably 30 to 60%, and even more preferably 30 to 50%, and has the advantage of excellent mechanical properties and processability within this range.

[0157] [Equation 3]

[0158] Grafting ratio (%) = [Weight of grafted monomer (g) / Weight of rubber (g)] * 100

[0159] (In the above mathematical expression 3, the weight (g) of the grafted monomer is the weight obtained by subtracting the rubber weight (g) from the weight of the insoluble substance (gel) after dissolving the graft copolymer in acetone and centrifuging it, and the rubber weight (g) is the weight (g) of the rubber component theoretically added in the graft copolymer powder.)

[0160] The weight of the above insoluble substance (gel) is the weight measured after adding 0.5 g of the graft copolymer dry powder to 50 ml of acetone, stirring at room temperature for 12 hours, centrifuging the mixture to collect only the insoluble matter that did not dissolve in acetone, drying it for 12 hours, and the rubber weight (g) is the weight (g) of the theoretical rubber component added to 0.5 g of the graft copolymer dry powder.

[0161] As a specific measurement example at this time, the weight of the insoluble substance (gel) is measured by adding 0.5 g of the graft copolymer dry powder to 50 ml of acetone, stirring at 210 rpm for 12 hours at room temperature with a stirrer (Orbital Shaker, equipment name: Lab companion SKC-6075), centrifuging at 18,000 rpm at 0 ℃ for 3 hours using a centrifuge (Supra R30 of Hanil Science Co., Ltd.), collecting only the insoluble substance that has not dissolved in acetone, and drying it at 85 ℃ for 12 hours using a forced convection drying method in an oven (Forced Convection Oven; equipment name: Lab companion OF-12GW).

[0162]

[0163] The above (b-2) graft copolymer may have, for example, a weight average molecular weight of 60,000 to 200,000 g / mol, preferably 70,000 to 180,000 g / mol, more preferably 80,000 to 170,000 g / mol, and even more preferably 100,000 to 160,000 g / mol, and within this range, has the advantages of excellent mechanical properties, processability, weather resistance, transparency, gloss, and colorability.

[0164]

[0165] The above (b-2) graft copolymer may be, for example, present in an amount of 0 to 21 wt%, preferably 0 to 18 wt%, more preferably 3 to 18 wt%, even more preferably 5 to 18 wt%, even more preferably 5 to 14 wt%, particularly preferably 5 to 11 wt%, even more preferably 7 to 11 wt%, and most preferably 8 to 10 wt%, based on the total weight of the base resin, and within this range, it has the advantages of excellent mechanical properties, processability, weather resistance, transparency, gloss, and colorability.

[0166]

[0167] The types of alkyl acrylate, aromatic vinyl compound and vinyl cyan compound included in the above (b-2) graft copolymer may be within the same category as the types of alkyl acrylate, aromatic vinyl compound and vinyl cyan compound included in the (A) non-graft copolymer of the present invention.

[0168]

[0169] (C) Thermoplastic polyester elastomer

[0170] The above (C) thermoplastic polyester elastomer may be, for example, 8 to 21 parts by weight, preferably 9 to 21 parts by weight, more preferably 10 to 21 parts by weight, and even more preferably 13 to 21 parts by weight, based on 100 parts by weight of the base resin, and within this range, the mechanical properties and weather resistance are excellent, while transparency, low whitening characteristics, and thin film processing are excellent, thereby improving the appearance quality and emotional quality.

[0171]

[0172] The above (C) thermoplastic polyester elastomer may be an elastomer comprising, for example, an aromatic dicarboxylic acid or an ester derivative thereof; an aliphatic diol; and a polyalkylene oxide; and in this case, it may provide advantages such as high flexibility, mechanical strength, and heat resistance, and excellent balance.

[0173] A crystalline hard segment is formed from the aromatic dicarboxylic acid or its ester derivative and an aliphatic diol, and a soft soft segment is formed from a polyalkylene oxide, and the crystalline hard segment and the soft soft segment can be arranged randomly, for example.

[0174]

[0175] The above aromatic dicarboxylic acid may be, for example, at least one selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid, and preferably, terephthalic acid, isophthalic acid, or a mixture thereof.

[0176] The ester derivative of the above aromatic dicarboxylic acid may be, for example, at least one selected from the group consisting of dimethyl terephthalate, dimethyl isophthalate, 2,6-dimethyl naphthalene dicarboxylate, dimethyl 1,5-naphthalene dicarboxylic acid, and dimethyl 1,4-cyclohexane dicarboxylate, and preferably dimethyl terephthalate, dimethyl isophthalate, or a mixture thereof.

[0177] The aromatic dicarboxylic acid or its ester derivative may be included in an amount of 25 to 70 wt%, preferably 30 to 65 wt%, and more preferably 35 to 60 wt%, based on the total weight of the thermoplastic polyester elastomer, and provides the advantage of easy reaction within this range.

[0178]

[0179] The above aliphatic diol may have, for example, a number average molecular weight of 300 g / mol or less, preferably 60 to 300 g / mol.

[0180] In this paper, unless otherwise defined, the number average molecular weight can be measured using GPC (Gel Permeation Chromatography, waters breeze), and as a specific example, it can be measured as a relative value to a standard PS (standard polystyrene) sample through GPC (Gel Permeation Chromatography, waters breeze) using THF (tetrahydrofuran) as an eluent. At this time, as a specific measurement example, solvent: THF, column temperature: 40 ℃, flow rate: 0.3 ml / min, sample concentration: 20 mg / ml, injection volume: 5 ㎕, column model: 1xPLgel 10 μm MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 μm MiniMix-B (250 x 4.6 mm) + 1xPLgel 10 μm MiniMix-B Guard (50 x 4.6 mm), equipment name: Agilent 1200 series system, refractive index detector: Agilent G1362 RID, RI temperature: 35 ℃, data processing: Agilent ChemStation S / W, test method (Mn, Mw and PDI): OECD TG 118 conditions can be measured.

[0181]

[0182] The above aliphatic diol may preferably be at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol and 1,4-cyclohexanedimethanol, and more preferably 1,4-butanediol.

[0183] The aliphatic diol may be included, for example, in an amount of 15 to 45 wt%, preferably 20 to 40 wt%, and more preferably 25 to 40 wt%, based on the total weight of the thermoplastic polyester elastomer, and within this range, the reaction can proceed smoothly and the balance of physical properties such as flexibility and mechanical strength is excellent.

[0184]

[0185] The above polyalkylene oxide is a soft segment of an aliphatic polyester, and may be at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, a copolymer of ethylene oxide and propylene oxide, an ethylene oxide addition polymer of polypropylene glycol, and a copolymer of ethylene oxide and tetrahydrofuran, and preferably polytetramethylene glycol.

[0186] The polyalkylene oxide may be included, for example, in an amount of 5 to 50 wt%, preferably 10 to 45 wt%, and more preferably 15 to 40 wt%, based on the total weight of the thermoplastic polyester elastomer, and within this range, the thermoplastic polyester elastomer has excellent flexibility, mechanical strength, and heat resistance, resulting in an excellent balance of physical properties.

[0187] The above polyalkylene oxide may have a number average molecular weight of, for example, 600 to 3,000 g / mol, preferably 1,000 to 2,000 g / mol, and within this range, a thermoplastic polyester elastomer having a stable polymerization reaction and excellent physical property balance can be obtained.

[0188] The above polyalkylene oxide may preferably be polypropylene glycol whose terminals are capped with ethylene oxide, in which case there is an advantage of excellent polymerization reactivity.

[0189]

[0190] The above (C) thermoplastic polyester elastomer may preferably include a branching agent, in which case the melt viscosity and melt strength of the elastomer can be increased.

[0191] The branching agent may be, for example, at least one selected from the group consisting of glycerol, pentaerythritol, trimellitic anhydride, trimellitic acid, trimethylol propane, and neopentyl glycol, preferably trimellitic anhydride, and in this case, it has the effect of increasing the melt viscosity and melt tension of the elastomer.

[0192] The above branching agent may be, for example, present in an amount of 0.05 to 0.1 wt%, preferably 0.05 to 0.09 wt%, and more preferably 0.06 to 0.09 wt%, based on 100 wt% of the total thermoplastic polyester elastomer, and has the effect of increasing melt strength within this range.

[0193]

[0194] The above (C) thermoplastic polyester elastomer may be, for example, manufactured by melt polymerizing an aromatic dicarboxylic acid or an ester derivative thereof, an aliphatic diol, and a polyalkylene oxide, in which case it provides the advantage of having an excellent balance of physical properties such as flexibility, mechanical strength, and heat resistance, while also having better moldability.

[0195] The above (C) thermoplastic polyester elastomer may preferably be manufactured by further solid-state polymerization of a resin manufactured by the above melt polymerization, in which case it provides the advantage of excellent balance of physical properties such as flexibility, mechanical strength, and heat resistance, while also having better moldability.

[0196] Preferably, the thermoplastic polyester elastomer (C) may be manufactured by producing a BHBT (bis(4-hydroxy) butyl terephthalate) oligomer by a transesterification reaction of an aromatic dicarboxylic acid, an aliphatic diol, and a polyalkylene oxide in the presence of a titanium butoxide (TBT) catalyst at 140 to 215°C for 110 to 130 minutes, then reintroducing the TBT catalyst and conducting a melt polymerization reaction at 215 to 245°C for 110 to 130 minutes while stepwise reducing the pressure from 760 torr to 0.3 torr.

[0197] The above melt polymerization reaction can be performed until the melt flow rate (MFR) measured at 230°C and a load of 2.16 kg reaches 20 g / 10 min according to ASTM D1238. After completion of the reaction, the strands can be pelletized by discharging them from the reactor under nitrogen pressure.

[0198] Then, the pellets can be subjected to solid-state polymerization in a solid-state polymerization reactor or a rotary vacuum dryer at a temperature ranging from 140 to 200°C for 10 to 24 hours under an inert gas stream such as nitrogen.

[0199] The above solid-state polymerization can be carried out until the melt flow rate measured under 230°C and 2.16 kg load according to ASTM D1238 becomes 10 g / 10 min or less, preferably 0.5 to 10 g / 10 min, more preferably 1 to 10 g / 10 min, and even more preferably 3 to 8 g / 10 min.

[0200] The vacuum applied during the above solid polymerization is not particularly limited as long as it is the degree of vacuum generally applied in the technical field to which the present invention belongs.

[0201] The above solid-state polymerization reactor may be a vessel vacuum dryer or the like connected to a rotatable high vacuum pump, and the inert gas stream may be a nitrogen gas stream or the like.

[0202] In this description, the content of monomer in the polymer may mean the weight % of monomer introduced during polymer production or the weight % of units derived from the monomer (based on monomer).

[0203]

[0204] The above (C) thermoplastic polyester elastomer may have a melt flow rate of 0.5 to 10 g / 10 min, preferably 1 to 10 g / 10 min, and more preferably 3 to 8 g / 10 min, measured at 230° C. and under a load of 2.16 kg according to ASTM D1238, and has the advantage of excellent moldability within this range.

[0205] The above (C) thermoplastic polyester elastomer may have, for example, a Shore hardness of 30D to 50D, preferably 35D to 47D, more preferably 35D to 40D, and within this range, the flexibility and mechanical strength of the composition are excellent.

[0206] Unless otherwise specified in this document, Shore hardness may be measured according to the method specified in ISO 868 (Type D).

[0207]

[0208] In this description, elastomer may also be referred to as an elastic polymer or elastic rubber, as in the technical field to which the present invention pertains, and a commercially available product may be used as long as it follows the definition of the present invention.

[0209]

[0210] thermoplastic resin composition

[0211] The thermoplastic resin composition may contain, for example, 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 0.5 to 2 parts by weight of a dye, pigment, or a mixture thereof, based on 100 parts by weight of the base resin, and within this range, it has the advantage of excellent mechanical properties, processability, weather resistance, transparency, gloss, heat resistance, and chemical resistance, as well as excellent colorability.

[0212]

[0213] The thermoplastic resin composition may have, for example, a sunscreen resistance of grade 3 or higher on a gray scale as measured by the following method, preferably grade 3 or higher on a gray scale and 'no swelling or cracking', and within this range, the composition has excellent physical property balance and excellent chemical resistance, thereby improving the appearance quality and providing high-quality automobile parts.

[0214] In this paper, the method for measuring sunscreen resistance is as follows: First, 100 mg of SPF 50+ sunscreen is applied to a white cotton cloth for sunscreen testing, measuring 3 cm x 3 cm or more, preferably 5 cm x 5 cm. The sunscreen is applied evenly to the entire surface of the white cotton cloth, and can be applied using a hand wearing chemical-resistant latex gloves. The white cotton cloth, on which the sunscreen is evenly applied, is placed on a disk test piece measuring 10 cm x 10 cm x 2 mm and left in a constant temperature chamber at 80 ± 2 ℃ for 1 hour. Then, the white cotton cloth is removed, the disk test piece is washed with a neutral detergent, and dried. Thereafter, the surface condition of the dried disk test piece is examined, and an evaluation is made with reference to the ISO 105 (Textile - Test for color fastness) gray scale for contamination. The sunscreen resistance evaluation for the same composition is performed at least twice, and preferably three times or more. Here, the size of the disk specimen must be larger than the white cotton cloth and must be flat.

[0215] In this description, room temperature may be a point within the range of 23 ± 3 ℃.

[0216]

[0217] The thermoplastic resin composition may have a heat distortion temperature of 85°C or higher, preferably 85 to 100°C, measured under 1.8 MPa according to ISO 75 / Be, for example, and has an excellent balance of physical properties and excellent heat resistance within this range, thereby providing a high-quality automobile interior material.

[0218]

[0219] The thermoplastic resin composition may have a lightness value (L value) of, for example, 1.5 or less, preferably 1.3 or less, more preferably 1.2 or less, and even more preferably 0.1 to 1.2, as measured using a square disk injection molded specimen using a colorimeter according to the CIE1976 L*a*b* colorimetric system using a specular component excluded (SCE) method, and within this range, the composition has an excellent balance of physical properties and an excellent black feel, thereby providing an effect of providing a beautiful appearance by having a color at the level of a paint job. In this case, a lower lightness value (L value) means an excellent black feel.

[0220] In this description, the colorimeter is not particularly limited as long as it is an extrusion mixer commonly used in the technical field to which the present invention belongs, and specifically, it may be Ci7800 from X-rite.

[0221]

[0222] The thermoplastic resin composition may have a gloss of 90 or more, preferably 93 or more, more preferably 95 or more, and even more preferably 95 to 120, as measured at 60° in accordance with ASTM D523 using, for example, a square disk injection molded specimen, and within this range, it has the advantage of exhibiting excellent physical property balance while exhibiting high gloss and excellent colorability.

[0223]

[0224] The thermoplastic resin composition may have the advantage of excellent appearance quality, in which no flow marks or fogging occur when observing with the naked eye a square disk injection molded specimen, for example, under conditions of an injection temperature of 270°C and an injection speed of 70 mm / min.

[0225]

[0226] The thermoplastic resin composition may further preferably include at least one selected from the group consisting of a heat stabilizer, a light stabilizer, a colorant, a lubricant, a release agent, an antistatic agent, an antibacterial agent, a processing aid, a metal deactivator, a flame retardant, a flame suppressor, an anti-drip agent, an anti-friction agent, and an anti-wear agent, in an amount of 0.01 to 5 parts by weight, 0.05 to 3 parts by weight, 0.1 to 2 parts by weight, or 0.5 to 1 part by weight, based on 100 parts by weight of the base resin, and within this range, the thermoplastic resin composition of the present invention has the effect of well implementing the required properties without lowering the original properties.

[0227]

[0228] The above heat stabilizer may preferably include a primary heat stabilizer and a secondary heat stabilizer.

[0229] The above primary heat stabilizer may be, for example, a phenol-based heat stabilizer, preferably 2-t-butyl-6-(3-t-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy-3,5-di-t-pentylphenyl)ethyl]-4,6-di-t-pentylphenyl acrylate, 1,6-hexanediolbis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-thiodiethylenebis-[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, Tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate, tris[(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, 2,2'-methylenebis(4-methyl-6-t-butylphenol)terephthalate, 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 3,9-bis[1,1-dimethyl-2-{β-(3-t-butyl-4-hydroxy-5-methyl-phenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, It may be at least one selected from the group consisting of 2,2-bis[4-(2-3,5-di-t-butyl-4-hydroxyhydrocinnamoyloxy)ethoxyphenyl]propane, and β-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, and more preferably octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate (IR1076).

[0230] The above secondary heat stabilizer may be, for example, a phosphorus-based heat stabilizer, and preferably, bis(dialkylphenyl)pentaerythritol diphosphite ester, phosphite ester, trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, (octyl)diphenyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearylpentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-t-butyl-4-hydroxy-phenyl)butane diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidenediphenyl diphosphite, Tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-t-butylphenol)diphosphite, tris(mono- and di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidenediphenol polyphosphite, phenyl(4,4'-isopropylidenediphenol)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, tris[4,4'-isopropylidenebis(2-t-butylphenol)] phosphite, di(isodecyl)phenyl phosphite, 4,4'-isopropylidenebis(2-t-butylphenol)bis(nonylphenyl) phosphite, bis(2,4-di-t-butyl-6-methylphenyl)ethyl phosphite, It may be at least one selected from the group consisting of 2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxa-phosphepine-6-yl}oxy]-N,N-bis[2-[{2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine-6-yl}oxy]ethyl]-ethanamine, and 6-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-t-butyldibenz[d,f][1.3.2]-dioxaphosphepine, and more preferably, it may be tris(2,4-di-tert-butylphenyl) phosphite (IF168). there is.

[0231] The above-mentioned active agent may preferably be at least one selected from the group consisting of aliphatic amide active agents, fatty acid ester active agents, and olefin waxes.

[0232] The above-mentioned aliphatic amide-based active agent may preferably be at least one selected from the group consisting of stearamide, oleamide, erucamide, ethylene bis stearamide, and ethylene bis oleamide.

[0233] The fatty acid ester-based lubricant may preferably be at least one selected from the group consisting of fatty acid esters of mono- or polyhydric alcohols, hydrogenated oils, butyl stearate, stearic acid monoglyceride, pentaerythritol tetrastearate, stearyl stearate, ester wax, and alkyl phosphate esters.

[0234] The above olefin wax may preferably be a polyethylene wax.

[0235]

[0236] Method for producing a thermoplastic resin composition

[0237] The method for producing a thermoplastic resin composition of the present invention comprises: (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 100 parts by weight of a base resin comprising 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle size of 50 to 400 nm; And (C) 8 to 21 parts by weight of thermoplastic polyester elastomer; characterized by including a step of mixing and extruding under conditions of 190 to 280° C. and 100 to 800 rpm. In this case, it has excellent mechanical properties, heat resistance and chemical resistance, especially excellent sunscreen resistance, and high blackness, and has a uniform injection appearance, realizing a color and appearance at the level of painting, so that it has the advantage of being applicable to unpainted molded products in high quality.

[0238]

[0239] The method for manufacturing the above thermoplastic resin composition shares all the technical characteristics of the thermoplastic resin composition described above. Therefore, a description of the overlapping portions will be omitted.

[0240]

[0241] The above mixing and extrusion can preferably be performed using an extruder at a temperature of 190 to 280°C, more preferably 200 to 260°C, and even more preferably 220 to 250°C, and within this range, stable extrusion is possible and the mixing effect is excellent. At this time, the temperature is the temperature set in the cylinder.

[0242] The above mixing and extrusion can be performed under conditions where the screw rotation speed is, for example, 100 to 800 rpm, preferably 200 to 700 rpm, and more preferably 300 to 600 rpm, in which case the processing amount per unit time is appropriate, resulting in excellent process efficiency.

[0243]

[0244] The thermoplastic resin composition obtained through the above extrusion can be manufactured into pellets using, for example, a pelletizer.

[0245]

[0246] The above extruder is not particularly limited as long as it is an extruder commonly used in the technical field to which the present invention belongs, and may preferably be a twin-screw extruder.

[0247]

[0248] molded products

[0249] The molded article of the present invention is characterized by including the thermoplastic resin composition, and in this case, it has excellent mechanical properties, heat resistance and chemical resistance, especially excellent sunscreen resistance, high blackness, and a uniform injection appearance, realizing a color and appearance at the level of painting, so that it has the advantage of being applicable to unpainted molded articles in high quality.

[0250] The above injection molded product may be, for example, an automobile interior / exterior part or an electrical / electronic product part, and specifically, may be a garnish or cover for an automobile door or center console part.

[0251]

[0252] The method for manufacturing the above molded product preferably comprises: (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 100 parts by weight of a base resin comprising 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyan compound are grafted onto a conjugated diene rubber having an average particle diameter of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyan compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle diameter of 50 to 400 nm; And (C) a step of mixing and extruding under the conditions of 190 to 280° C. and 100 to 800 rpm, including 8 to 21 parts by weight of a thermoplastic polyester elastomer; and a step of molding the extrudate to produce a molded product. In this case, the mechanical properties are excellent, and heat resistance and chemical resistance, especially sunscreen resistance, are excellent, and a high blackness is expressed, and the color and appearance at the level of painting are realized with a uniform injection appearance, so that there is an advantage that it can be applied to an unpainted molded product in high quality.

[0253] The extrudate may be, for example, in the form of pellets or plates.

[0254] In this description, the plate shape is not particularly limited as long as it is defined as a plate shape commonly in the technical field to which the present invention belongs, and may include, for example, a flat shape, a sheet shape, a film shape, a foil shape, etc.

[0255]

[0256] In describing the thermoplastic resin composition, the manufacturing method thereof, and the molded product of the present invention, it is stated that other conditions or equipment, etc. that are not explicitly described can be appropriately selected within the range commonly practiced in the art and are not particularly limited.

[0257]

[0258] Hereinafter, preferred examples are presented to help understand the present disclosure; however, the following examples are merely illustrative of the present disclosure, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and technical idea of ​​the present disclosure, and it is also natural that such changes and modifications fall within the scope of the appended patent claims.

[0259]

[0260] [Example]

[0261] The materials used in the following examples and comparative examples are as follows.

[0262] * (A-1) MMA-α-methyl styrene-acrylonitrile copolymer: a non-graft copolymer comprising alkyl (meth)acrylate, alkyl-substituted styrene compound, and vinyl cyanide compound (290UH from LG Chemical)

[0263] * (A-2) PMMA resin: Polymethyl methacrylate resin (IH830 from LX MMA)

[0264] * (b-1) MABS graft copolymer: A graft copolymer in which alkyl (meth)acrylate, aromatic vinyl compound, and vinyl cyan compound are grafted onto conjugated diene rubber with a particle size of 250 to 350 nm (TR550 of LG Chemical)

[0265] * (b-2) ASA graft copolymer: Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with a particle size of 100 to 150 nm (SA130 of LG Chemical)

[0266] * (b-3) ABS graft copolymer: Acrylonitrile-butadiene-styrene graft copolymer containing butadiene rubber with a particle size of 250 to 350 nm (DP270 of LG Chemical)

[0267] * (b-4) SAN copolymer: styrene-acrylonitrile copolymer (81HF from LG Chemical)

[0268] * (b-5) ASA graft copolymer: Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with a particle size of 450 to 550 nm (SA927 of LG Chemical)

[0269] * (b-6) ASA graft copolymer: Alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer containing alkyl acrylate rubber with a particle size of 300 to 400 nm (SA928 of LG Chemical)

[0270] * (C) TPEE: Thermoplastic polyester elastomer (KEYFLEX BT2140D (LG Chemical) with a melt flow rate of 5 g / 10 min (230 ℃, 2.16 kg) and a Shore D hardness of 40D)

[0271] * (D) Black dye: Sumiplast Black HLC from Sumitomo Chemical Co., Ltd.

[0272] Here, MMA stands for methyl methacrylate, PMMA stands for polymethyl methacrylate, MABS stands for methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer, and TPEE stands for thermoplastic polyester elastomer.

[0273]

[0274] Examples 1 to 10 and Comparative Examples 1 to 12

[0275] The ingredients and contents described in Tables 1 and 2 below were each fed into a twin-screw extruder (25Φ), melted, mixed, and extruded to produce pellets. The produced pellets were used to produce injection molded specimens.

[0276] Additionally, specimens for measuring gloss, brightness, and appearance quality were produced using a high-gloss mold in an injection molding machine using the manufactured pellets. The high-gloss mold refers to a mold with a smoothly processed mold surface.

[0277]

[0278] [Example Exam]

[0279] The properties of the pellets or specimens manufactured 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 and 2 below.

[0280]

[0281] measurement method

[0282] * Sunscreen resistance: 100 mg of SPF 50+ sunscreen was applied to a 5 cm x 5 cm white cotton cloth for sunscreen testing. The sunscreen was applied evenly over the entire surface of the white cotton cloth using hands wearing chemical-resistant latex gloves. The white cotton cloth with the sunscreen evenly applied was placed on a 10 cm x 10 cm x 2 mm disk test piece and left in a constant temperature chamber at 80 ± 2 ℃ for 1 hour. After taking it out, the white cotton cloth was removed, and the disk test piece was washed with a neutral detergent and dried. The surface condition of the dried disk test piece was examined and evaluated with reference to the gray scale for contamination of ISO 105 (Textile - Test for color fastness). In addition, the presence of swelling or cracking on the disk test piece was also evaluated. At this time, the sunscreen resistance was evaluated three times for the same composition, and the results were indicated. Here, a higher gray scale means better sunscreen properties.

[0283] * Heat deflection temperature (HDT, ℃): Measured under 1.8 MPa according to ISO 75 / Be.

[0284] * Brightness value (L value): The L value was measured using a colorimeter (X-rite Ci7800) based on the CIE1976 L*a*b* colorimetric system by removing the specular component (SCE) from a square disk injection molded specimen. For black color, a lower L value indicates better blackness.

[0285] * Gloss: Measured at 60° using square disk injection molded specimens according to ASTM D523.

[0286] * Appearance quality: The presence of flow marks and fogging was visually assessed on square disk injection molded specimens and indicated as follows.

[0287] ○: Excellent appearance due to no flow marks or fogging

[0288] X: Flow marks or fogging occur, resulting in poor appearance

[0289]

[0290] In case of loss of the old example 12345678910(A-1)82828282828085828282(A-2)(b-1)999181071269(b-2)99918108612(b-3)(b-4)(b-5)(b-6)9(C)10152015151515101015(D)1111111111Water quality sunscreen grade 3~4 grade 4 grade 3~4 grade 3~4 grade 3~4 grade 3~4 grade 3~4 grade 3~4 grade HDT(℃)87868586868587878786 Brightness Value (L value) 1.01.01.00.91.11.00.91.01.01.2 Gloss 95959596949595959594 Appearance Quality ○○○○○○○○○○

[0291] Water content in water 123456789101112(A-1)828282758290828082(A-2)808080(b-1)18925109109(b-2)18920209(b-3)1820(b-4)10(b-5)9(b-6)(C)51510101010301010(D)111111111111Water content in water 2nd grade 2nd grade 2~3rd grade 3~4th grade 3rd grade 2~3rd grade 2nd grade 4th grade 2nd grade 3HDT(℃)888887838580807888828787Brightness Value (L value) 0.9 1.1 1.0 1.2 3.5 2.8 0.9 3.5 0.7 1.5 5.0 2.6 Glossiness 96 94 95 94 90 87 88 94 95 90 92 93 Appearance Quality ○○○○XX○X○XXX

[0292] (In the above Tables 1 and 2, each content of (A-1), (A-2), (b-1), (b-2), (b-3), (b-4), (b-5), and (b-6) is weight % based on the total weight thereof, and each content of (C) and (D) is weight part based on 100 weight parts of the total weight of (A-1), (A-2), (b-1), (b-2), (b-3), (b-4), (b-5), and (b-6).)

[0293] As shown in Tables 1 to 2 above, the thermoplastic resin compositions of Examples 1 to 10 according to the present invention were superior to Comparative Examples 1 to 12 in terms of sunscreen resistance, heat distortion temperature, brightness value, gloss, and appearance quality.

[0294] On the other hand, Comparative Examples 1 to 3, which did not include (C) TPEE or included a small amount of TPEE, had poor sunscreen resistance, and Comparative Example 10, which included an excessive amount of (C) TPEE, had poor heat distortion temperature and appearance quality.

[0295] In addition, Comparative Example 4, which included (A) a non-graft copolymer below the scope of the present invention and (B) a graft copolymer exceeding the scope of the present invention, had a low heat distortion temperature and thus poor heat resistance, and Comparative Example 9, which included (A) a non-graft copolymer above the scope of the present invention and (B) a graft copolymer below the scope of the present invention, had poor sunscreen resistance.

[0296] In addition, Comparative Example 5 including (b-3) graft copolymer and Comparative Example 6 including (A-2) non-graft copolymer and (b-3) graft copolymer had poor appearance quality and high brightness value, resulting in poor colorability.

[0297] In addition, Comparative Example 7, which included (A-2) a non-graft copolymer and did not include (C) TPEE, had poor sunscreen resistance, heat distortion temperature, and gloss.

[0298] In addition, Comparative Examples 8, 11 and 12 including (A-2) non-graft copolymer, (b-4) SAN copolymer or (b-5) ASA graft copolymer had poor sunscreen resistance, heat distortion temperature, brightness value or appearance quality.

[0299]

[0300] In conclusion, it was confirmed that the thermoplastic resin composition comprising a thermoplastic polyester elastomer in a predetermined amount in a base resin including at least one graft copolymer selected from the group consisting of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, a graft copolymer in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound are grafted onto a conjugated diene rubber having a predetermined average particle diameter, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer comprising an alkyl acrylate rubber having a predetermined average particle diameter has excellent mechanical properties, excellent heat resistance and sun resistance, high blackness, and a uniform injection appearance, and has the advantage of being applicable to unpainted molded products in high quality.

Claims

1. 100 parts by weight of a base resin comprising (A) 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyan compound, and (B) 14 to 21 wt% of a copolymer comprising a rubber component, an aromatic vinyl compound, and a vinyl cyan compound; and (C) 8 to 21 parts by weight of a thermoplastic polyester elastomer; The brightness value (L value) measured with a square disk injection molded specimen using a colorimeter according to the CIE1976 L*a*b* colorimetric system using the specular component excluded (SCE) method is 1.5 or less. Characterized by a heat distortion temperature of 85 ℃ or higher measured under 1.8 MPa according to ISO 75 / Be Thermoplastic resin composition.

2. In paragraph 1, The above rubber component is characterized in that it is a conjugated diene rubber, an alkyl acrylate rubber, or a mixture thereof. Thermoplastic resin composition.

3. 100 parts by weight of a base resin comprising 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, and (B) 14 to 21 wt% of at least one graft copolymer selected from the group consisting of a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle size of 50 to 400 nm; and (C) characterized by comprising 8 to 21 parts by weight of a thermoplastic polyester elastomer; Thermoplastic resin composition.

4. In paragraph 1 or paragraph 3, The above (A) non-graft copolymer is characterized in that it comprises 30 to 60 wt% of alkyl (meth)acrylate, 20 to 50 wt% of alkyl-substituted styrene compound, and 5 to 35 wt% of vinyl cyanide compound based on the total weight thereof. Thermoplastic resin composition.

5. In paragraph 3, The above (b-1) graft copolymer is characterized in that it comprises 35 to 65 wt% of conjugated diene rubber, 20 to 50 wt% of alkyl (meth)acrylate, 1 to 30 wt% of aromatic vinyl compound, and 1 to 20 wt% of vinyl cyan compound based on the total weight thereof. Thermoplastic resin composition.

6. In paragraph 3, The above (b-2) graft copolymer is characterized in that it comprises 30 to 70 wt% of alkyl acrylate rubber, 10 to 55 wt% of aromatic vinyl compound, and 1 to 30 wt% of vinyl cyan compound based on the total weight thereof. Thermoplastic resin composition.

7. In paragraph 1 or paragraph 3, The above (C) thermoplastic polyester elastomer is characterized in that the melt flow rate measured at 230°C and 2.16 kg according to ASTM D1238 is 0.5 to 10 g / 10 min. Thermoplastic resin composition.

8. In paragraph 1 or 3, The above (C) thermoplastic polyester elastomer is characterized in that it is an elastomer comprising an aromatic dicarboxylic acid or an ester derivative thereof; an aliphatic diol; and a polyalkylene oxide. Thermoplastic resin composition.

9. In paragraph 8, The above aromatic dicarboxylic acid is characterized in that it is at least one selected from the group consisting of terephthalic acid, isophthalic acid, 2,6-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid, and 1,4-cyclohexane dicarboxylic acid. Thermoplastic resin composition.

10. In paragraph 8, The above aliphatic diol is characterized in that at least one selected from the group consisting of ethylene glycol, propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 1,4-cyclohexanedimethanol. Thermoplastic resin composition.

11. In paragraph 8, The polyalkylene oxide is characterized in that it is at least one selected from the group consisting of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol, copolymers of ethylene oxide and propylene oxide, ethylene oxide addition polymers of polypropylene glycol, and copolymers of ethylene oxide and tetrahydrofuran. Thermoplastic resin composition.

12. In paragraph 1 or paragraph 3, The thermoplastic resin composition is characterized in that it contains 0.1 to 5 parts by weight of a dye, pigment, or a mixture thereof based on 100 parts by weight of the base resin. Thermoplastic resin composition.

13. In paragraph 1 or paragraph 3, The thermoplastic resin composition is characterized in that it has a sunscreen resistance of grade 3 or higher on a gray scale. Thermoplastic resin composition.

14. In paragraph 3, The thermoplastic resin composition is characterized in that the heat distortion temperature measured under 1.8 MPa according to ISO 75 / Be is 85 ℃ or higher. Thermoplastic resin composition.

15. 100 parts by weight of a base resin comprising 79 to 86 wt% of a non-graft copolymer comprising an alkyl (meth)acrylate, an alkyl-substituted styrene compound, and a vinyl cyanide compound, and 14 to 21 wt% of at least one graft copolymer selected from the group consisting of (A) a graft copolymer (b-1) in which an alkyl (meth)acrylate, an aromatic vinyl compound, and a vinyl cyanide compound are grafted onto a conjugated diene rubber having an average particle size of 200 to 500 nm, and (B) an alkyl acrylate-aromatic vinyl compound-vinyl cyanide compound graft copolymer (b-2) comprising an alkyl acrylate rubber having an average particle size of 50 to 400 nm; And (C) a thermoplastic polyester elastomer 8 to 21 parts by weight; characterized by including a step of mixing and extruding under conditions of 190 to 280° C. and 100 to 800 rpm. A method for producing a thermoplastic resin composition.

16. Characterized in that it comprises a thermoplastic resin composition of any one of claims 1 to 14. Molded product.