Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition, which comprises a base resin including recycled resin, a new diene-based graft polymer, and a new vinyl-based non-graft polymer, and an additive including a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00.

Description

[Technical Field]

[0001] This application claims the benefit of priority based on Korean Patent Application No. 10-2022-0134853 filed on October 19, 2022 and Korean Patent Application No. 10-2023-0137677 filed on October 16, 2023, and all contents disclosed in the documents of said Korean patent applications are incorporated herein by reference.

[0002] The present invention relates to a thermoplastic resin composition. [Background technology]

[0003] A diene-based graft polymer comprises a diene-based rubber polymer and a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted onto the diene-based rubber polymer. Compared to conventional high impact polystyrene (HIPS), the diene-based graft polymer has excellent impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity, and processability. Due to these properties, diene-based rubber thermoplastic resin molded products manufactured from the diene-based graft polymer are used as parts for automotive interior and exterior materials, office equipment, and various electrical and electronic products.

[0004] Meanwhile, a thermoplastic resin composition must contain recycled resin in order to be certified as an eco-friendly product. However, because recycled resin has been used before, it has lower impact resistance, tensile strength, chemical resistance, and thermal stability compared to virgin resin. Furthermore, processing it can result in the exposure of foreign matter on the surface of molded products. For these reasons, recycled resin has been used as a raw material for low-grade materials. To address the issues associated with recycled resin, technology has been developed to manufacture eco-friendly products by blending virgin resin in specific ratios. However, thermoplastic resin molded products made from recycled resin still suffer from problems such as poor appearance and reduced chemical resistance due to foreign matter. Summary of the Invention [Problem to be solved by the invention]

[0005] The problem to be solved by the present invention is to provide a thermoplastic resin composition that is excellent in all of appearance properties, impact resistance, tensile strength and chemical resistance. [Means for solving the problem]

[0006] In order to solve the above-mentioned problems, 1) the present invention provides a thermoplastic resin composition comprising a base resin including a recycled resin, a new diene-based graft polymer, and a new vinyl-based non-graft polymer, and an additive including a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00.

[0007] 2) The present invention can provide the thermoplastic resin composition in 1) above, which contains 0.01 to 10.00 parts by weight of the special pigment per 100 parts by weight of the base resin.

[0008] 3) The present invention can provide a thermoplastic resin composition according to 1) or 2), wherein the specialty pigment comprises one or more selected from the group consisting of cellulose, rayon, and silicate minerals.

[0009] 4) In any one of the above 1) to 3), the present invention can provide a thermoplastic resin composition containing 0.10 to 10.00 parts by weight of the inorganic oxide per 100 parts by weight of the base resin.

[0010] 5) The present invention can provide a thermoplastic resin composition according to any one of 1) to 4), wherein the inorganic oxide is at least one selected from the group consisting of titanium dioxide, magnesium oxide, and calcium oxide.

[0011] 6) The present invention can provide a thermoplastic resin composition in any one of 1) to 5) above, wherein the recycled resin contains 8 to 25% by weight of diene monomer units, 15 to 30% by weight of vinyl cyanide monomer units, and the remainder of vinyl aromatic monomer units.

[0012] 7) The present invention, in any one of 1) to 6), can provide a thermoplastic resin composition containing 10.00 to 92.00 parts by weight of the recycled resin per 100 parts by weight of the base resin.

[0013] 8) The present invention can provide a thermoplastic resin composition in any one of 1) to 7) above, wherein the nascent diene graft polymer comprises a diene rubber polymer and a shell containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer.

[0014] 9) In any one of 1) to 8), the present invention can provide a thermoplastic resin composition containing 2.00 to 36.00 parts by weight of the new diene graft polymer per 100 parts by weight of the base resin.

[0015] 10) The present invention can provide a thermoplastic resin composition in any one of 1) to 9), wherein the new vinyl-based non-graft polymer contains vinyl aromatic monomer units and vinyl cyanide monomer units.

[0016] 11) The present invention can provide a thermoplastic resin composition according to any one of 1) to 10), wherein the additive comprises an olefin-based non-grafted polymer containing an olefin-based monomer unit and at least one selected from the group consisting of a (meth)acrylate-based monomer unit and a vinyl acetate monomer unit.

[0017] 12) The present invention can provide a thermoplastic resin composition according to the above 11, which contains 1.00 to 10.00 parts by weight of the non-grafted olefin polymer per 100 parts by weight of the base resin. [Effects of the Invention]

[0018] The thermoplastic resin composition according to the present invention can achieve excellent appearance properties, impact resistance, tensile strength and chemical resistance despite containing recycled resin. DETAILED DESCRIPTION OF THE INVENTION

[0019] The present invention will now be described in more detail to aid in understanding the present invention.

[0020] The terms and words used in this specification and claims should not be interpreted as being limited to their ordinary or dictionary meanings, but should be interpreted as having meanings and concepts that are consistent with the technical idea of ​​the present invention, based on the principle that inventors can appropriately define the concepts of terms in order to best explain their inventions.

[0021] In the present invention, the diene monomer may be at least one selected from the group consisting of 1,3-butadiene, isoprene, chloroprene, and piperylene, among which 1,3-butadiene is preferred. In addition, the unit derived from the diene monomer may be a diene monomer unit.

[0022] In the present invention, the vinyl aromatic monomer may be at least one selected from the group consisting of α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene, and p-bromostyrene, among which styrene is preferred. The unit derived from the vinyl aromatic monomer may be a vinyl aromatic monomer unit.

[0023] In the present invention, the vinyl cyanide-based monomer may be at least one selected from the group consisting of acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile, and α-chloroacrylonitrile, among which acrylonitrile is preferred. The unit derived from the vinyl cyanide-based monomer may be a vinyl cyanide-based monomer unit.

[0024] In the present invention, the olefinic monomer may be one or more selected from the group consisting of ethylene, propylene and butylene, and among these, ethylene is preferred.

[0025] In the present invention, the (meth)acrylate monomer may refer to both an acrylate monomer and a methacrylate monomer. The (meth)acrylate monomer is a C1 to C 10 The alkyl (meth)acrylate monomer may be one or more selected from the group consisting 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, and among these, one or more selected from the group consisting of ethyl acrylate and butyl acrylate is preferred.

[0026] In the present invention, the graft ratio of the newly formed diene-based graft polymer can be calculated by the following method.

[0027] First, 2 g of the nascent diene graft polymer powder is dissolved in 300 ml of acetone with stirring for 24 hours, and then separated using a centrifuge to obtain a precipitate. This precipitate is dried at 60 to 120°C to obtain a dried product. The weight of this dried product is then measured. The weight can be measured by substituting the weight of the dried product into the following formula.

[0028] Graft rate (%) = [(weight of new diene graft polymer powder (2 g)) - (weight of dry material) - (weight of diene rubber polymer)] / (weight of diene rubber polymer) x 100

[0029] Weight of diene rubber polymer: Weight of diene rubber polymer theoretically contained in 2 g of nascent diene graft polymer powder; or weight of diene rubber polymer measured by infrared spectroscopy of 2 g of nascent diene graft polymer powder.

[0030] In the present invention, the weight average molecular weight of the shell of the nascent diene graft polymer may refer to the weight average molecular weight of a polymer containing vinyl aromatic monomer units and vinyl cyanide monomer units grafted onto a diene rubber polymer.

[0031] In the present invention, the weight average molecular weight of the shell of the new diene graft polymer can be calculated by the following method.

[0032] The nascent diene-based graft polymer can be dissolved in tetrahydrofuran (THF) solution (concentration: 1 wt%) and then filtered through a 1 μm filter. The material that passes through the 1 μm filter can be subjected to gel permeation chromatography to measure the shell weight average molecular weight relative to a standard polystyrene sample.

[0033] In the present invention, the average particle size of the diene rubber polymer can be measured using a dynamic light scattering method, and more specifically, it can mean the arithmetic average particle size in the particle size distribution measured by the dynamic light scattering method, i.e., the intensity distribution average particle size.

[0034] In the present invention, the average particle size of the diene rubber polymer can be measured using a Nicomp 380 device manufactured by Particle Sizing Systems.

[0035] In the present invention, the weight average molecular weight of the non-grafted polymer can be measured as a relative value to that of a standard polystyrene sample by gel permeation chromatography using tetrahydrofuran as an eluent.

[0036] In the present invention, the length and average diameter of the special pigment and the average particle size of the inorganic oxide can be measured using a nitrogen gas adsorption method, specifically, a BET analyzer, Surface Area and Porosity Analyzer ASAP 2020 manufactured by Micromeritics.

[0037] thermoplastic resin composition A thermoplastic resin composition according to one embodiment of the present invention comprises: 1. a base resin including recycled resin, a new diene-based graft polymer, and a new vinyl-based non-graft polymer; and 2. an additive including a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00.

[0038] The special pigment and inorganic oxide may be contained in a weight ratio of 1:1.10 to 10.00, preferably 1:2.00 to 9.00, more preferably 1:3.00 to 8.50, even more preferably 1:3.00 to 8.00, and most preferably 1:5.00 to 7.00. If the inorganic oxide is contained in an amount less than the above range, the special pigment will not be oriented in the resin flow direction, and the appearance characteristics of the injected product will be deteriorated. If the inorganic oxide is contained in an amount greater than the above range, the impact resistance of the thermoplastic resin composition will be deteriorated.

[0039] The components of the thermoplastic resin composition according to one embodiment of the present invention will be described in detail below.

[0040] 1. Base resin 1) Recycled resin Recycled resin is a component included in a thermoplastic resin composition to be certified as an eco-friendly product. It is a recycled product made by processing and reusing used resin or waste resin. Specifically, the recycled resin may refer to a resin that is collected, crushed, washed, separated, and sorted from waste resin, and then processed and reused according to its intended use. The form of the recycled resin is not particularly limited.

[0041] The recycled resin may be one or more selected from the group consisting of recycled polyethylene, recycled polypropylene, recycled polyester, recycled polystyrene, recycled polyamide, recycled polycarbonate, recycled diene-based graft polymers, and recycled vinyl-based non-graft polymers.

[0042] The recycled resin may include a diene-based monomer unit, a vinyl cyanide-based monomer unit, and a vinyl aromatic-based monomer unit. The diene-based monomer unit may improve the impact resistance of the recycled resin. The vinyl cyanide-based monomer unit may improve the chemical resistance of the recycled resin. In addition, the vinyl aromatic-based monomer unit may improve the processability of the recycled resin.

[0043] Meanwhile, the recycled resin may contain diene monomer units in an amount of 8.00 to 25.00% by weight, preferably 12.00 to 18.00% by weight. If the above conditions are met, the impact resistance of the recycled resin can be further improved.

[0044] The recycled resin may contain 15 to 30% by weight, preferably 18 to 24% by weight, of vinyl cyanide monomer units. If the above conditions are met, the chemical resistance of the recycled resin can be further improved.

[0045] The recycled resin may contain a residual amount of vinyl aromatic monomer units to bring the total weight to 100% by weight.

[0046] The content of the recycled resin can be 10.00 to 92.00 parts by weight, preferably 30.00 to 80.00 parts by weight, based on 100 parts by weight of the base resin. When the above conditions are met, a carbon reduction effect can be obtained and good physical properties can be achieved.

[0047] 2) New diene-based graft polymers The nascent diene graft polymer is a diene graft polymer that has never been used before, and is a component that improves the impact resistance of thermoplastic resin compositions.

[0048] The nascent diene graft polymer may be a graft polymer including a diene rubber polymer and a shell including vinyl aromatic monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. The shell may include vinyl aromatic monomer units and vinyl cyanide monomer units that are not grafted to the diene rubber polymer.

[0049] The diene rubber polymer can be produced by polymerizing, preferably crosslinking, a diene monomer, and has an average particle size of 50 to 600 nm, preferably 150 to 450 nm. When the above conditions are met, the impact resistance and surface properties of the diene graft polymer can be improved.

[0050] The diene graft polymer may have a diene rubber polymer content of 40 to 80% by weight, preferably 50 to 70% by weight. When the above conditions are satisfied, the impact resistance of the diene graft polymer can be further improved.

[0051] The content of the vinyl aromatic monomer unit in the diene graft polymer may be 10 to 50% by weight, preferably 20 to 40% by weight. When the above conditions are satisfied, the processability of the diene graft polymer can be further improved.

[0052] The content of vinyl cyanide monomer units in the diene graft polymer may be 1 to 30% by weight, preferably 5 to 25% by weight. When the above conditions are satisfied, the chemical resistance of the diene graft polymer can be further improved.

[0053] The graft ratio of the newly formed diene graft polymer may be 25.0 to 70.0%, preferably 30.0 to 65.0%, and more preferably 30.0 to 50.0%. When the above conditions are satisfied, the flowability of the thermoplastic resin composition is not reduced, and a good level of impact resistance can be achieved.

[0054] The weight-average molecular weight of the shell of the nascent diene graft polymer may be 50,000 to 200,000 g / mol, preferably 65,000 to 180,000 g / mol, and more preferably 65,000 to 75,000 g / mol. When the above conditions are satisfied, the flowability of the thermoplastic resin composition is not reduced, and a good level of impact resistance can be achieved.

[0055] The content of the new diene graft polymer can be 2.00 to 36.00 parts by weight, preferably 10.00 to 28.00 parts by weight, per 100 parts by weight of the base resin. When the above conditions are met, the impact resistance and surface properties of the thermoplastic resin composition can be further improved.

[0056] 3) New vinyl non-graft polymers The nascent vinyl-based non-grafted polymer is a vinyl-based non-grafted polymer that has never been used before, and is a component that improves the processability of the thermoplastic resin composition.

[0057] The vinyl-based non-graft polymer may include a vinyl aromatic monomer unit and a vinyl cyanide monomer unit.

[0058] The vinyl-based non-graft polymer may contain vinyl aromatic monomer units and vinyl cyanide monomer units in a weight ratio of 90:10 to 60:40, preferably 85:15 to 65:35. By satisfying the above conditions, a vinyl-based non-graft polymer with improved processability and chemical resistance can be produced.

[0059] The weight-average molecular weight of the non-grafted vinyl polymer is 70,000 to 200,000 g / mol, preferably 90,000 to 200,000 g / mol, and more preferably 90,000 to 160,000 g / mol. When the above conditions are satisfied, the flowability of the thermoplastic resin composition is not reduced, and a good level of impact resistance can be achieved.

[0060] The vinyl-based non-graft polymer may be included as the remainder so that the total of the constituent elements of the base resin is 100 parts by weight.

[0061] 2. Additives 1) Special pigments The special pigment is a component contained to conceal foreign matter generated by the recycled resin from appearing on the surface of a molded article produced from the thermoplastic resin composition.

[0062] The special pigment allows the molded product made from the thermoplastic resin composition to have an irregular pattern on the surface, resembling granite or marble, which can effectively hide impurities generated by the recycled resin.

[0063] The special pigment may be in the form of a fiber or a plate. If the special pigment is in the form of a fiber, it may have a length of 0.1 to 5.0 mm, preferably 0.2 to 1.0 mm. If the special pigment is in the form of a plate, it may have an average diameter of 0.1 to 5.0 mm, preferably 0.3 to 1.0 mm. If the above conditions are met, it is possible to minimize a decrease in the impact resistance of the thermoplastic resin composition and effectively conceal foreign matter on the surface of a molded article produced from the thermoplastic resin composition.

[0064] The special pigment may be one or more selected from the group consisting of cellulose, rayon, and silicate minerals, and the silicate minerals may be mica.

[0065] The content of the special pigment may be 0.01 to 10.00 parts by weight, preferably 0.10 to 5.00 parts by weight, based on 100 parts by weight of the base resin. When the above conditions are met, the decrease in impact resistance of the thermoplastic resin composition can be minimized and foreign matter on the surface of a molded article produced from the thermoplastic resin composition can be effectively concealed.

[0066] 2) Inorganic oxides The inorganic oxide is a component that can shield weld lines that occur due to the orientation of special pigments in molded articles made from thermoplastic resin compositions.

[0067] The inorganic oxide may be one or more selected from the group consisting of titanium dioxide, magnesium oxide, and calcium oxide, and titanium dioxide is preferred as it can easily shield weld lines that occur due to the orientation of special pigments.

[0068] The inorganic oxide may have an average particle size of 50 to 400 nm, preferably 150 to 350 nm, and more preferably 200 to 300 nm. When the above conditions are satisfied, the decrease in impact resistance of the thermoplastic resin composition can be minimized, and foreign matter generated by the recycled resin and weld lines generated during injection molding can be effectively concealed.

[0069] The content of the inorganic oxide can be 0.1 to 10.0 parts by weight, preferably 0.5 to 8.0 parts by weight, per 100 parts by weight of the base resin. When the above conditions are met, weld lines generated by the orientation of the special pigment can be shielded without reducing impact resistance.

[0070] 3) Olefin-based non-graft polymers The non-grafted olefin polymer is a component that improves the chemical resistance of the thermoplastic resin composition. In addition, the non-grafted olefin polymer is a component that can effectively hide impurities generated by recycled resins and minimize degradation of impact resistance through synergy with the special pigment.

[0071] The non-grafted olefin polymer may include an olefin monomer unit and at least one selected from the group consisting of a (meth)acrylate monomer unit and a vinyl acetate monomer unit. Here, the non-grafted olefin polymer may include 5 to 50 wt %, preferably 15 to 35 wt %, of at least one selected from the group consisting of a (meth)acrylate monomer unit and a vinyl acetate monomer unit in order to minimize a decrease in tensile strength of the thermoplastic resin composition and further improve chemical resistance.

[0072] The non-grafted olefin polymer may be at least one selected from the group consisting of ethylene / vinyl acetate polymer, ethylene / ethyl acrylate polymer, and ethylene / butyl acrylate polymer.

[0073] The content of the non-grafted olefin polymer may be 1.00 to 10.00 parts by weight, preferably 1.50 to 8.00 parts by weight, and more preferably 2.00 to 4.00 parts by weight, relative to 100 parts by weight of the base resin. When the above conditions are met, the decrease in tensile strength of the thermoplastic resin composition can be minimized and the chemical resistance and impact resistance can be improved.

[0074] While the present invention may be embodied in various different forms, it is to be understood that the invention is not limited to the specific embodiments set forth herein, and that the invention may be embodied in various different forms without departing from the spirit or scope of the present invention.

[0075] Examples and Comparative Examples The components used in the following examples and comparative examples are described below.

[0076] 1. Base resin 1) Recycled resin: Recycled resin containing 15% by weight of butadiene monomer units, 22% by weight of acrylonitrile monomer units, and 63% by weight of styrene monomer units.

[0077] 2) New diene-based graft polymers 2-1) New diene graft polymer 1: A butadiene rubber polymer having an average particle size of 320 nm and a shell containing styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a graft ratio of 35.0% and a weight average molecular weight of the shell of 75,000 g / mol.

[0078] 2-2) New diene graft polymer 2: A butadiene rubber polymer having an average particle size of 340 nm and a shell containing styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a graft ratio of 30.0% and a weight average molecular weight of the shell of 65,000 g / mol.

[0079] 2-3) New diene graft polymer 3: A butadiene rubber polymer having an average particle size of 110 nm and a shell containing styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a graft ratio of 65.0% and a weight average molecular weight of the shell of 65,000 g / mol.

[0080] 3) New vinyl non-graft polymers 3-1) New vinyl non-graft polymer 1: A styrene / acrylonitrile non-graft polymer having a weight average molecular weight of 100,000 g / mol and prepared by polymerizing 75.0% by weight of styrene and 25.0% by weight of acrylonitrile.

[0081] 3-2) New vinyl non-graft polymer 2: A styrene / acrylonitrile non-graft polymer having a weight average molecular weight of 130,000 g / mol, prepared by polymerizing 78.0% by weight of styrene and 22.0% by weight of acrylonitrile.

[0082] 3-3) New vinyl non-graft polymer: A styrene / acrylonitrile non-graft polymer with a weight average molecular weight of 200,000 g / mol, produced by polymerizing 70% by weight of styrene and 30% by weight of acrylonitrile.

[0083] 2. Additives 1) Special pigments 1-1) Cellulose: Illumi Yarn No. 25-05 (average length: 0.5 mm) from Daiya Kogyo Co., Ltd.

[0084] 2) Inorganic oxide: Titanium dioxide (average particle size: 250 nm)

[0085] 3) Olefin-based non-graft polymer: EVEA28025 from LG Chemical Co., Ltd. (flow index (190°C, 2.16 kg): 25 g / 10 min, ethylene / vinyl acetate non-graft polymer produced by polymerizing 72 wt% ethylene and 28 wt% vinyl acetate)

[0086] The above-mentioned components were mixed in the amounts shown in Tables 1 to 4 below and stirred to produce thermoplastic resin compositions.

[0087] Experimental Example 1 The thermoplastic resin compositions of the examples and comparative examples were extruded to produce pellets, and the pellets were evaluated by the methods described below. The results are shown in Tables 1 to 4 below.

[0088] 1) Melt Flow Index (g / 10 min): Measured under conditions of 220°C and 10 kg in accordance with ASTM D1238. In the present invention, a melt flow index of 20.0 g / 10 min or more was determined to be excellent in processability.

[0089] Experimental Example 2 The thermoplastic resin compositions of the examples and comparative examples were extruded and injected to prepare test pieces, which were then evaluated by the methods described below. The results are shown in Tables 1 to 4 below.

[0090] 1) Izod impact strength (kg·cm / cm, 3.2 mm): Measured according to ASTM D 256. In the present invention, an Izod impact strength of 18.0 kg·cm / cm or more was determined to be excellent in impact resistance.

[0091] 2) Tensile strength (kg / cm 2): Measured in accordance with ASTM D638. In the present invention, the tensile strength is 380.0 kg / cm 2 If the value was equal to or greater than this, it was determined that the tensile strength was excellent.

[0092] 3) Chemical resistance (time): A test piece manufactured in accordance with ASTM D638 was fixed to a jig with a deformation rate of 1%, and then laundry detergent (Nanox) was applied to the surface. The time required for the test piece to completely break was measured. In the present invention, if the time required for breakage was 30.0 hours or more, the test piece was determined to have excellent chemical resistance.

[0093] 4) Number of foreign particles: One surface of the test piece (10 cm x 10 cm x 3 mm) was observed under an optical microscope (KEYENCE CORPORATION VHX-500) at 100x magnification, and the number of foreign particles of different colors with a diameter of 200 μm or more was counted.

[0094] Here, the term "impurities" refers to opaque particles that are not only generated by the special pigment but can be confirmed with an optical microscope, have a diameter of 200 μm or more, and have a hue different from the background color (resin hue). Also, if the number of impurities is 10 or less, the product is deemed to have excellent appearance characteristics.

[0095] 5) Number of weld lines: When a test piece with a total of seven holes of 8.5 mm in diameter was injected, the number of weld lines that were generated by the orientation of the special pigment and where the resin that had separated and flowed through the holes reunited was counted. If the number of weld lines was three or less, it was determined that the weld line shielding effect was excellent.

[0096] [Table 1]

[0097] [Table 2]

[0098] [Table 3]

[0099] [Table 4]

[0100] Tables 1 to 4 show that Examples 1 to 5, which are thermoplastic resin compositions containing a special pigment and inorganic oxide in a weight ratio of 1:1.10 to 10:00, exhibited excellent flow index, impact strength, tensile strength, chemical resistance, appearance, and weld seam shielding. Furthermore, comparing Examples 3, 6, and 7, which varied the types of new diene-based graft polymers, revealed that the graft ratio and shell weight-average molecular weight of the new diene-based graft polymer significantly affected the flow index, impact strength, tensile strength, chemical resistance, and appearance of the thermoplastic resin composition. Furthermore, comparing Examples 3, 8, and 9, which varied the types of new vinyl-based non-graft polymers, revealed that the composition and weight-average molecular weight of the new vinyl-based graft polymer significantly affected the flow index, impact strength, tensile strength, chemical resistance, and appearance of the thermoplastic resin composition.

[0101] However, Comparative Example 1, which is a thermoplastic resin composition that does not contain any special pigments or inorganic oxides, had a large number of foreign matters, and therefore the appearance properties were deteriorated.

[0102] Furthermore, Comparative Example 2, which is a thermoplastic resin composition containing an inorganic oxide but not a special pigment, also had a large number of foreign matters, and therefore the appearance properties were deteriorated.

[0103] Furthermore, in Comparative Example 3, which is a thermoplastic resin composition containing a special pigment but not an inorganic oxide, the number of weld lines was large, and therefore the shielding effect for the weld lines was reduced.

[0104] In addition, Comparative Example 4, which is a thermoplastic resin composition containing a special pigment and an inorganic oxide in a weight ratio of 1:0.05, had a large number of weld lines, and therefore the shielding effect for the weld lines was reduced.

[0105] In addition, Comparative Example 5, which is a thermoplastic resin composition containing a special pigment and an inorganic oxide in a weight ratio of 1:1.00, had a large number of foreign objects and weld lines, resulting in a decrease in appearance characteristics and weld line shielding effect.

[0106] In addition, Comparative Example 6, which is a thermoplastic resin composition containing a special pigment and an inorganic oxide in a weight ratio of 1:10.50, and Comparative Example 7, which is a thermoplastic resin composition containing a special pigment and an inorganic oxide in a weight ratio of 1:13.33, showed reduced impact resistance.

Claims

1. a base resin including recycled resin, a nascent diene-based graft polymer, and a nascent vinyl-based non-graft polymer; A thermoplastic resin composition comprising a special pigment and an additive comprising an inorganic oxide in a weight ratio of 1:1.10 to 10.

00.

2. The thermoplastic resin composition according to claim 1, wherein the special pigment is contained in an amount of 0.01 to 10.00 parts by weight per 100 parts by weight of the base resin.

3. The thermoplastic resin composition according to claim 1, wherein the specialty pigment comprises at least one selected from the group consisting of cellulose, rayon, and silicate minerals.

4. 2. The thermoplastic resin composition according to claim 1, wherein the inorganic oxide is contained in an amount of 0.10 to 10.00 parts by weight per 100 parts by weight of the base resin.

5. 2. The thermoplastic resin composition according to claim 1, wherein the inorganic oxide is at least one selected from the group consisting of titanium dioxide, magnesium oxide, and calcium oxide.

6. 2. The thermoplastic resin composition according to claim 1, wherein the recycled resin comprises 8 to 25% by weight of diene monomer units, 15 to 30% by weight of vinyl cyanide monomer units, and the remainder of vinyl aromatic monomer units.

7. The thermoplastic resin composition according to claim 1, comprising 10.00 to 92.00 parts by weight of the recycled resin relative to 100 parts by weight of the base resin.

8. 2. The thermoplastic resin composition of claim 1, wherein the nascent diene-based graft polymer comprises a diene-based rubber polymer and a shell comprising vinyl aromatic-based monomer units and vinyl cyanide-based monomer units grafted to the diene-based rubber polymer.

9. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 1, comprising 2.00 to 36.00 parts by weight of the nascent diene graft polymer.

10. 2. The thermoplastic resin composition of claim 1, wherein the nascent vinyl-based non-grafted polymer comprises vinyl aromatic-based monomer units and vinyl cyanide-based monomer units.

11. 2. The thermoplastic resin composition according to claim 1, wherein the additive comprises an olefin-based non-grafted polymer containing an olefin-based monomer unit and at least one selected from the group consisting of a (meth)acrylate-based monomer unit and a vinyl acetate monomer unit.

12. For 100 parts by weight of the base resin, The thermoplastic resin composition according to claim 11, comprising 1.00 to 10.00 parts by weight of the non-grafted olefin polymer.

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