Thermoplastic resin composition

Abstract

The present invention relates to a thermoplastic resin composition comprising: a base resin comprising a recycled resin, a neodiene-based graft polymer, and a neovinyl-based non-graft polymer; and an additive comprising a special pigment and an inorganic oxide in a weight ratio of 1: 1.10 to 10.00.

Description

Technical Field

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] The present invention claims the benefit of priority of 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, the entire contents of which are incorporated into this specification by reference.

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

[0004] The diene graft polymer comprises a diene rubber polymer and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. Compared with existing high impact polystyrene (HIPS), the diene graft polymer has high impact resistance, chemical resistance, thermal stability, colorability, fatigue resistance, rigidity and processing performance. Due to these properties, diene rubber thermoplastic resin molded products produced from diene graft polymers are used as automotive interior and exterior materials, office supplies and parts of various electrical and electronic products.

[0005] Meanwhile, thermoplastic resin compositions must contain recycled resins certified as environmentally friendly products. However, since recycled resins have been used, the impact resistance, tensile force, chemical resistance and thermal stability of recycled resins are reduced compared to new resins, and foreign matter appears on the surface of molded products when processed. For these reasons, recycled resins have been used for low-grade materials. In order to solve these problems, new technologies are being developed to produce environmentally friendly products by mixing new resins in a certain proportion. However, thermoplastic resin molded products using recycled resins still have problems such as reduced appearance characteristics and reduced chemical resistance due to foreign matter. Summary of the invention

[0006] Technical issues

[0007] The present invention aims to provide a thermoplastic resin composition having excellent appearance characteristics, impact resistance, tensile strength and chemical resistance.

[0008] Technical Solution

[0009] In order to solve the above problems, 1) the present invention provides a thermoplastic resin composition, comprising: a base resin, which comprises a recycled resin, a new diene-based grafted polymer and a new vinyl-based non-grafted polymer; and an additive, which comprises a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00.

[0010] 2) According to 1), the present invention may provide a thermoplastic resin composition comprising 0.01 parts by weight to 10.00 parts by weight of the special pigment based on 100 parts by weight of the base resin.

[0011] 3) According to 1) or 2), the present invention may provide a thermoplastic resin composition, wherein the special pigment comprises one or more selected from cellulose, rayon and silicate minerals.

[0012] 4) According to any one of 1) to 3), the present invention may provide a thermoplastic resin composition comprising 0.10 parts by weight to 10.00 parts by weight of the inorganic oxide based on 100 parts by weight of the base resin.

[0013] 5) According to any one of 1) to 4), the present invention may provide a thermoplastic resin composition, wherein the inorganic oxide is one or more selected from titanium dioxide, magnesium oxide and calcium oxide.

[0014] 6) According to any one of 1) to 5), the present invention can provide a thermoplastic resin composition, wherein the recycled resin contains 8 wt % to 25 wt % of diene monomer units, 15 wt % to 30 wt % of vinyl cyanide monomer units and the remainder of aromatic vinyl monomer units.

[0015] 7) According to any one of 1) to 6), the present invention may provide a thermoplastic resin composition comprising 10.00 parts by weight to 92.00 parts by weight of the recycled resin based on 100 parts by weight of the base resin.

[0016] 8) According to any one of 1) to 7), the present invention may provide a thermoplastic resin composition, wherein the new diene graft polymer comprises a diene rubber polymer and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer.

[0017] 9) According to any one of 1) to 8), the present invention may provide a thermoplastic resin composition comprising 2.00 parts by weight to 36.00 parts by weight of the neodiene-based graft polymer based on 100 parts by weight of the base resin.

[0018] 10) According to any one of 1) to 9), the present invention may provide a thermoplastic resin composition, wherein the neo vinyl-based non-grafted polymer comprises an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit.

[0019] 11) According to any one of 1) to 10), the present invention may provide a thermoplastic resin composition, wherein the additive comprises an olefin non-grafted polymer, which comprises: an olefin monomer unit; and one or more selected from a (meth)acrylate monomer unit and a vinyl acetate monomer unit.

[0020] 12) According to 11), the present invention may provide a thermoplastic resin composition comprising 1.00 to 10.00 parts by weight of the olefin-based non-grafted polymer based on 100 parts by weight of the base resin.

[0021] Beneficial Effects

[0022] The thermoplastic resin composition according to the present invention may exhibit excellent appearance characteristics, impact resistance, tensile strength, and chemical resistance despite the inclusion of recycled resin in the thermoplastic resin composition. DETAILED DESCRIPTION

[0023] Hereinafter, the present invention will be described in more detail to help understanding of the present invention.

[0024] The terms or words in this specification and claims should not be construed as limited to their ordinary meanings or dictionary meanings, but based on the principle that inventors can appropriately define the concepts of the terms in order to interpret their inventions in the best manner, the terms or words should be construed as meanings and concepts consistent with the technical concept of the present invention.

[0025] In the present invention, the diene monomer may be one or more selected from 1,3-butadiene, isoprene, chloroprene and piperylene, preferably 1,3-butadiene. The unit derived from the diene monomer may be a diene monomer unit.

[0026] In the present invention, the aromatic vinyl monomer may be one or more selected from α-methylstyrene, α-ethylstyrene, p-methylstyrene, 2,4-dimethylstyrene, styrene, p-fluorostyrene, p-chlorostyrene and p-bromostyrene, preferably styrene. The unit derived from the aromatic vinyl monomer may be an aromatic vinyl monomer unit.

[0027] In the present invention, the vinyl cyanide monomer may be one or more selected from acrylonitrile, methacrylonitrile, (Z)-3-phenylacrylonitrile and α-chloroacrylonitrile, preferably acrylonitrile. The unit derived from the vinyl cyanide monomer may be a vinyl cyanide monomer unit.

[0028] In the present invention, the olefin monomer may be one or more selected from ethylene, propylene and butene, preferably ethylene.

[0029] In the present invention, the (meth)acrylic acid ester monomer may be a term covering both acrylic acid ester monomers and methacrylic acid ester monomers. The (meth)acrylic acid ester monomer may be a (meth)acrylic acid C1-C 10 The alkyl ester monomer may be one or more selected from methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, heptyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and decyl (meth)acrylate, preferably one or more selected from ethyl acrylate and butyl acrylate.

[0030] In the present invention, the grafting ratio of the new diene-based graft polymer can be calculated by the following method.

[0031] First, 2 g of the new diene graft polymer powder was dissolved in 300 ml of acetone while stirring for 24 hours, and then separated using a centrifuge to obtain a precipitate. The precipitate was dried at 60° C. to 120° C. to obtain a dried product. Then, the weight of the dried product was measured, and the measured value was substituted into the following formula.

[0032] Grafting rate (%) = [(weight of new diene graft polymer powder (2 g)) - (weight of dried product) - (weight of diene rubber polymer)] / (weight of diene rubber polymer) × 100

[0033] Weight of diene rubber polymer: weight of diene rubber polymer theoretically contained in 2 g of the new diene graft polymer powder; or weight of diene rubber polymer measured by analyzing 2 g of the new diene graft polymer powder using infrared spectroscopy.

[0034] In the present invention, the weight average molecular weight of the shell in the new diene-based graft polymer may be a weight average molecular weight of a polymer including an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted to a diene-based rubber polymer.

[0035] In the present invention, the weight average molecular weight of the shell in the neodiene-based graft polymer can be calculated by the following method.

[0036] The neodiene-based graft polymer was dissolved in a tetrahydrofuran (THF) solution (concentration: 1 wt%) and then passed through a 1 μm filter. The weight average molecular weight of the shell can be measured by gel permeation chromatography of the filtered solution as a relative value to a standard polystyrene sample.

[0037] In the present invention, the average particle size of the diene rubber polymer may be measured by dynamic light scattering. Specifically, the average particle size may refer to the arithmetic average particle size in the particle size distribution measured by dynamic light scattering, that is, the average particle size based on the scattering intensity distribution.

[0038] In the present invention, the average particle size of the diene-based rubber polymer can be measured using a Nicomp 380 instrument commercially available from Particle Sizing Systems.

[0039] In the present invention, the weight average molecular weight of the non-grafted polymer can be measured as a relative value with respect to a standard polystyrene sample by gel permeation chromatography using tetrahydrofuran as an eluent.

[0040] In the present invention, nitrogen adsorption can be used to measure the length and average diameter of a specific pigment and the average particle size of an inorganic oxide. Specifically, the measurement can be performed using a BET analysis instrument commercially available from Micromeritics, Surface Area and Porosity Analyzer ASAP 2020.

[0041] Thermoplastic resin composition

[0042] The thermoplastic resin composition according to one embodiment of the present invention comprises: 1) a base resin comprising a recycled resin, a neodiene-based graft polymer and a neovinyl-based non-graft polymer; and 2) an additive comprising a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00.

[0043] The special pigment and the 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. When the content of the inorganic oxide is less than the above conditions, the phenomenon that the special pigment is oriented in the flow direction of the resin cannot be concealed, resulting in a decrease in the appearance characteristics of the injection molded product. When the content of the inorganic oxide is greater than the above conditions, the impact resistance of the thermoplastic resin composition is reduced.

[0044] Hereinafter, components of a thermoplastic resin composition according to one embodiment of the present invention will be described in detail.

[0045] 1. Base resin

[0046] 1) Recycled resin

[0047] The recycled resin is a component contained in a thermoplastic resin composition certified as an environmentally friendly product, and is a recycled product that is reused by processing used resin or resin waste. Specifically, the recycled resin may be resin waste that can be reused after being collected, crushed, washed, separated and classified, and processed for various purposes. There is no particular limitation on the form of the recycled resin.

[0048] The recycled resin may be one or more selected from recycled polyethylene, recycled polypropylene, recycled polyester, recycled polystyrene, recycled polyamide, recycled polycarbonate, recycled diene-based grafted polymers and recycled vinyl-based non-grafted polymers.

[0049] The recycled resin may contain diene monomer units, vinyl cyanide monomer units and aromatic vinyl monomer units. The diene monomer units may improve the impact resistance of the recycled resin. The vinyl cyanide monomer units may improve the chemical resistance of the recycled resin. In addition, the aromatic vinyl monomer units may improve the processing properties of the recycled resin.

[0050] The recycled resin may contain 8.00 wt % to 25.00 wt %, preferably 12.00 wt % to 18.00 wt % of the diene monomer unit. When this condition is met, the impact resistance of the recycled resin may be further improved.

[0051] The recycled resin may contain 15 to 30 wt %, preferably 18 to 24 wt % of vinyl cyanide monomer units. When this condition is met, the chemical resistance of the recycled resin may be further improved.

[0052] The recycled resin may contain the remaining amount of the aromatic vinyl-based monomer unit such that the total weight of the recycled resin becomes 100 weight %.

[0053] The amount of the recycled resin may 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 this condition is met, a carbon reduction effect and an appropriate level of physical properties may be achieved.

[0054] 2) Neodiene graft polymers

[0055] The novel diene-based graft polymer is a never-before-used diene-based graft polymer, which is a component for improving the impact resistance of a thermoplastic resin composition.

[0056] The new diene graft polymer may be a graft polymer comprising a diene rubber polymer and a shell comprising aromatic vinyl monomer units and vinyl cyanide monomer units grafted to the diene rubber polymer. The shell may comprise aromatic vinyl monomer units and vinyl cyanide monomer units not grafted to the diene rubber polymer.

[0057] The diene rubber polymer can be prepared by polymerizing, preferably crosslinking, a diene monomer and has an average particle size of 50 to 600 nm, preferably 150 to 450 nm. When this condition is met, the impact resistance and surface properties of the diene graft polymer can be improved.

[0058] The amount of the diene rubber polymer in the diene graft polymer may be 40 to 80 wt%, preferably 50 to 70 wt%. When this condition is met, the impact resistance of the diene graft polymer can be further improved.

[0059] The amount of the aromatic vinyl monomer unit in the diene graft polymer may be 10 to 50 wt %, preferably 20 to 40 wt %. When this condition is met, the processability of the diene graft polymer can be further improved.

[0060] The amount of the vinyl cyanide monomer unit in the diene graft polymer may be 1 to 30 wt %, preferably 5 to 25 wt %. When this condition is met, the chemical resistance of the diene graft polymer can be further improved.

[0061] The grafting rate of the neodiene-based graft polymer may be 25.0% to 70.0%, preferably 30.0% to 65.0%, more preferably 30.0% to 50.0%. When this condition is satisfied, a sufficient level of impact resistance can be achieved without reducing the fluidity of the thermoplastic resin composition.

[0062] The weight average molecular weight of the shell in the neodiene-based graft polymer may be 50,000 to 200,000 g / mol, preferably 65,000 to 180,000 g / mol, more preferably 65,000 to 75,000 g / mol. When this condition is met, a sufficient level of impact resistance can be achieved without reducing the fluidity of the thermoplastic resin composition.

[0063] The amount of the neodiene-based graft polymer may be 2.00 to 36.00 parts by weight, preferably 10.00 to 28.00 parts by weight, based on 100 parts by weight of the base resin. When this condition is met, the impact resistance and surface properties of the thermoplastic resin composition may be further improved.

[0064] 3) New vinyl non-grafted polymers

[0065] The novel vinyl-based non-grafted polymer is a vinyl-based non-grafted polymer that has never been used, and is a component for improving the processability of the thermoplastic resin composition.

[0066] The vinyl-based non-grafted polymer may include an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit.

[0067] The vinyl-based non-grafted polymer may include an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit in a weight ratio of 90:10 to 60:40, preferably 85:15 to 65:35. When this condition is met, a vinyl-based non-grafted polymer having improved processability and chemical resistance may be prepared.

[0068] The weight average molecular weight of the vinyl-based non-grafted polymer may be 70,000 to 200,000 g / mol, preferably 90,000 to 200,000 g / mol, more preferably 90,000 to 160,000 g / mol. When this condition is met, a sufficient level of impact resistance can be achieved without reducing the fluidity of the thermoplastic resin composition.

[0069] The vinyl-based non-graft polymer may be contained in a balance such that the total amount of components of the base resin becomes 100 parts by weight.

[0070] 2. Additives

[0071] 1) Special pigments

[0072] The special pigment is a component included in order to hide foreign matters resulting from recycled resin, which appear on the surface of a molded article produced from the thermoplastic resin composition.

[0073] Due to the special pigment, a molded article produced from the thermoplastic resin composition can have an irregular pattern such as granite or marble on the surface, and thus foreign matter generated due to recycled resin can be effectively concealed.

[0074] The special pigment can be a fiber-type pigment or a plate-type pigment. When the special pigment is in the form of a fiber, the length of the special pigment can be 0.1 mm to 5.0 mm, preferably 0.2 mm to 1.0 mm. When the special pigment is in the form of a plate, the average diameter of the special pigment can be 0.1 mm to 5.0 mm, preferably 0.3 mm to 1.0 mm. When the above conditions are met, the impact resistance of the thermoplastic resin composition can be minimized while effectively covering foreign matter on the surface of the molded article produced by the thermoplastic resin composition.

[0075] The special pigment may be one or more selected from cellulose, rayon and silicate minerals. The silicate mineral may be mica.

[0076] The amount 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 this condition is met, the reduction in impact resistance of the thermoplastic resin composition can be minimized while effectively covering foreign matter on the surface of a molded article produced from the thermoplastic resin composition.

[0077] 2) Inorganic oxides

[0078] The inorganic oxide is a component that can mask weld lines due to the orientation of a specific pigment, which appear on a molded article produced from the thermoplastic resin composition.

[0079] The inorganic oxide may be one or more selected from titanium dioxide, magnesium oxide and calcium oxide, preferably titanium dioxide, which can easily mask the weld line generated due to the orientation of the specific pigment.

[0080] The average particle size of the inorganic oxide may be 50 nm to 400 nm, preferably 150 nm to 350 nm, and more preferably 200 nm to 300 nm. When this condition is met, the reduction in impact resistance of the thermoplastic resin composition can be minimized, while foreign matter generated by recycled resin and weld lines generated during injection molding can be effectively concealed.

[0081] The amount of the inorganic oxide may be 0.1 to 10.0 parts by weight, preferably 0.5 to 8.0 parts by weight, based on 100 parts by weight of the base resin. When this condition is satisfied, weld lines generated due to orientation of the special pigment may be masked without reducing impact resistance.

[0082] 3) Olefin non-grafted polymers

[0083] The olefin-based non-grafted polymer is a component that improves the chemical resistance of the thermoplastic resin composition, can effectively mask foreign matter generated by recycled resin through a synergistic effect with a special pigment, and minimizes the reduction in impact resistance.

[0084] The olefinic non-grafted polymer may include: an olefinic monomer unit; and one or more selected from (meth) acrylic acid ester monomer units and vinyl acetate monomer units. The olefinic non-grafted polymer may include 5 to 50 wt%, preferably 15 to 35 wt%, of one or more selected from (meth) acrylic acid ester monomer units and vinyl acetate monomer units to minimize the reduction in tensile strength of the thermoplastic resin composition and further improve chemical resistance.

[0085] The olefinic non-grafted polymer may be one or more selected from ethylene / vinyl acetate polymer, ethylene / ethyl acrylate polymer and ethylene / butyl acrylate polymer.

[0086] Based on 100 parts by weight of the base resin, the amount of the olefinic non-grafted 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. When this condition is met, the chemical resistance and impact resistance of the thermoplastic resin composition can be improved while minimizing the reduction in tensile force.

[0087] Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention can be implemented in many different forms and is not limited to the embodiments described in this specification.

[0088] Examples and Comparative Examples

[0089] Descriptions of components used in the following Examples and Comparative Examples are as follows.

[0090] 1. Base resin

[0091] 1) Recycled resin: containing 15 wt% butadiene monomer units, 22 wt% acrylonitrile monomer units and 63 wt% styrene monomer units

[0092] 2) Neodiene graft polymers

[0093] 2-1) Neodiene-based graft polymer 1: comprising a butadiene rubber polymer having an average particle size of 320 nm and a shell comprising styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a grafting rate of 35.0% and a weight average molecular weight of the shell of 75,000 g / mol.

[0094] 2-2) Neodiene-based graft polymer 2: comprising a butadiene rubber polymer having an average particle size of 340 nm and a shell comprising styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a grafting rate of 30.0% and a weight average molecular weight of the shell of 65,000 g / mol.

[0095] 2-3) Neodiene-based graft polymer 3: comprising a butadiene rubber polymer having an average particle size of 110 nm and a shell comprising styrene units and acrylonitrile units grafted to the butadiene rubber polymer, with a grafting rate of 65.0% and a weight average molecular weight of the shell of 65,000 g / mol.

[0096] 3) New vinyl non-grafted polymers

[0097] 3-1) New vinyl-based non-grafted polymer 1: a styrene / acrylonitrile non-grafted polymer having a weight average molecular weight of 100,000 g / mol prepared by polymerization of 75.0 wt % of styrene and 25.0 wt % of acrylonitrile

[0098] 3-2) New vinyl-based non-grafted polymer 2: a styrene / acrylonitrile non-grafted polymer having a weight average molecular weight of 130,000 g / mol prepared by polymerization of 78.0 wt% of styrene and 22.0 wt% of acrylonitrile

[0099] 3-3) Neovinyl non-grafted polymer: a styrene / acrylonitrile non-grafted polymer having a weight average molecular weight of 200,000 g / mol prepared by polymerization of 70 wt% styrene and 30 wt% acrylonitrile

[0100] 2. Additives

[0101] 1) Special pigments

[0102] 1-1) Cellulose: Illumi Yarn No. 25-05 commercially available from Daiya Kogyo Co., Ltd (average length: 0.5 mm)

[0103] 2) Inorganic oxide: titanium dioxide (average particle size: 250nm)

[0104] 3) Olefin non-grafted polymer: EVEA28025 commercially available from LG Chemical (melt flow index (190° C., 2.16 kg): 25 g / 10 min, ethylene / vinyl acetate non-grafted polymer prepared by polymerization of 72 wt % ethylene and 28 wt % vinyl acetate)

[0105] The above components were mixed in the amounts shown in Table 1 to Table 4 below and stirred to prepare a thermoplastic resin composition.

[0106] Experimental Example 1

[0107] Each of the thermoplastic resin compositions of Examples and Comparative Examples was extruded to prepare pellets. The pellets were evaluated using the method described below, and the results thereof are shown in Tables 1 to 4 below.

[0108] 1) Melt flow index (g / 10 min): The melt flow index is measured under the conditions of 220° C. and 10 kg according to ASTM D1238. In the present invention, when the melt flow index is 20.0 g / 10 min or more, the processability is judged to be excellent.

[0109] Experimental Example 2

[0110] Each of the thermoplastic resin compositions of Examples and Comparative Examples was extruded and injection molded to prepare a sample. The sample was evaluated using the method described below, and the results thereof are shown in Tables 1 to 4 below.

[0111] 1) Izod impact strength (kg·cm / cm, 3.2 mm): The Izod impact strength was measured according to ASTM D 256. In the present invention, when the Izod impact strength is 18.0 kg·cm / cm or more, the impact resistance is judged to be excellent.

[0112] 2) Tensile strength (kg / cm 2 ): The tensile strength is measured according to ASTM D638. In the present invention, when the tensile strength is 380.0 kg / cm 2 When the value is greater than or equal to 0.05, the tensile force is judged to be excellent.

[0113] 3) Chemical resistance (hours): A sample prepared according to ASTM D638 was fixed on a fixture at a strain rate of 1%, and washing powder Nanox was applied to the surface of the sample, and then the time required for the sample to be completely broken was measured. In the present invention, when the measurement time is 30.0 hours or more, the chemical resistance is judged to be excellent.

[0114] 4) Number of foreign matters: One surface of a sample (10 cm×10 cm×3 mm) was observed at 100-fold magnification using an optical microscope (VHX-500 commercially available from Keyence Corporation), and the number of foreign matters of different colors having a diameter of 200 μm or more was counted.

[0115] Foreign matter refers to an opaque particle, excluding particles formed by special pigments, with a diameter of 200 μm or more, a color different from the background color (resin color), and can be observed with an optical microscope. When the number of foreign matter is 10 or less, the appearance characteristics are judged to be excellent.

[0116] 5) Number of weld lines: When a sample having a total of 7 holes with a diameter of 8.5 mm was injected, the number of weld lines that appeared due to the orientation of the special pigment when the resin recombined after flowing through the holes was counted. When the number of weld lines was 3 or less, the effect of masking the weld lines was judged to be excellent.

[0117] [Table 1]

[0118]

[0119]

[0120] [Table 2]

[0121]

[0122] [Table 3]

[0123]

[0124] [Table 4]

[0125]

[0126]

[0127] Referring to Tables 1 to 4, each thermoplastic resin composition in Examples 1 to 5, which contains a special pigment and an inorganic oxide in a weight ratio of 1:1.10 to 10.00, has excellent melt flow index, excellent impact strength, tensile strength, chemical resistance, appearance characteristics, and excellent effect of hiding weld lines. In addition, when comparing Examples 3, 6, and 7 in which the type of the new diene grafted polymer is changed, it can be seen that the grafting rate of the new diene grafted polymer and the weight average molecular weight of the shell in the new diene grafted polymer significantly affect the melt flow index, impact strength, tensile strength, chemical resistance, and appearance characteristics of the thermoplastic resin composition. On the other hand, when comparing Examples 3, 8, and 9 in which the type of the new vinyl non-grafted polymer is changed, it can be seen that the composition and weight average molecular weight of the new vinyl grafted polymer significantly affect the melt flow index, impact strength, tensile strength, chemical resistance, and appearance characteristics of the thermoplastic resin composition.

[0128] However, the thermoplastic resin composition of Comparative Example 1 not including both the special pigment and the inorganic oxide had a large amount of foreign matter, and thus, Comparative Example 1 had degraded appearance characteristics.

[0129] In addition, the thermoplastic resin composition of Comparative Example 2 including the inorganic oxide but not the special pigment has a large amount of foreign matter, and therefore, Comparative Example 2 has degraded appearance characteristics.

[0130] The thermoplastic resin composition of Comparative Example 3, which contains the special pigment but does not contain the inorganic oxide, has a large number of weld lines, and therefore, the effect of masking the weld lines of Comparative Example 3 is reduced.

[0131] The thermoplastic resin composition of Comparative Example 4 including the special pigment and the inorganic oxide in a weight ratio of 1:0.05 has a large number of weld lines, and therefore, the effect of masking the weld lines of Comparative Example 4 is reduced.

[0132] The thermoplastic resin composition of Comparative Example 5 including the special pigment and the inorganic oxide at a weight ratio of 1:1.00 had a large amount of foreign matter and weld lines, and therefore, the appearance characteristics of Comparative Example 5 and the effect of masking the weld lines were reduced.

[0133] The thermoplastic resin composition of Comparative Example 6 including the special pigment and the inorganic oxide in a weight ratio of 1:10.50, and the thermoplastic resin composition of Comparative Example 7 including the special pigment and the inorganic oxide in a weight ratio of 1:13.33, had reduced impact resistance.

Claims

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

00. 2 . The thermoplastic resin composition according to claim 1 , comprising 0.01 parts by weight to 10.00 parts by weight of the special pigment based on 100 parts by weight of the base resin.

3. The thermoplastic resin composition according to claim 1, wherein The special pigments include one or more selected from cellulose, rayon and silicate minerals. 4 . The thermoplastic resin composition according to claim 1 , comprising 0.10 parts by weight to 10.00 parts by weight of the inorganic oxide based on 100 parts by weight of the base resin.

5. The thermoplastic resin composition according to claim 1, wherein The inorganic oxide includes one or more selected from titanium dioxide, magnesium oxide and calcium oxide.

6. The thermoplastic resin composition according to claim 1, wherein The recycled resin contains 8 to 25 wt % of diene monomer units, 15 to 30 wt % of vinyl cyanide monomer units, and the remainder of aromatic vinyl monomer units. 7 . The thermoplastic resin composition according to claim 1 , comprising 10.00 parts by weight to 92.00 parts by weight of the recycled resin based on 100 parts by weight of the base resin.

8. The thermoplastic resin composition according to claim 1, wherein The novel diene-based graft polymer includes a diene-based rubber polymer and a shell including an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit grafted to the diene-based rubber polymer. 9 . The thermoplastic resin composition according to claim 1 , comprising 2.00 parts by weight to 36.00 parts by weight of the neodiene-based graft polymer based on 100 parts by weight of the base resin.

10. The thermoplastic resin composition according to claim 1, wherein The novel vinyl-based non-grafted polymer comprises an aromatic vinyl-based monomer unit and a vinyl cyanide-based monomer unit.

11. The thermoplastic resin composition according to claim 1, wherein The additive comprises an olefinic non-grafted polymer, wherein the olefinic non-grafted polymer comprises: an olefinic monomer unit; and one or more selected from (meth)acrylic acid ester monomer units and vinyl acetate monomer units. 12 . The thermoplastic resin composition according to claim 11 , comprising 1.00 parts by weight to 10.00 parts by weight of the olefin-based non-graft polymer based on 100 parts by weight of the base resin.

Images