Thermoplastic resin composition, and method for preparing and use thereof

Abstract

The present application provides a kind of thermoplastic resin composition and its preparation method and application.The thermoplastic resin composition includes acrylonitrile-butadiene-styrene resin material 10-40 parts by weight, polymethyl methacrylate 30-70 parts by weight, modified hollow ceramic microbead 1-10 parts and toughening agent 1-20 parts;The modified hollow ceramic microbead includes the hollow ceramic microbead modified by coupling agent and stearate.In the present application, the thermoplastic resin composition has excellent wear resistance, good sound insulation effect, high surface hardness and impact strength.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a thermoplastic resin composition and a preparation method and application thereof. BACKGROUND

[0002] Mahjong is a game of gambling, and its basic playing method is simple and easy to learn, but there are many changes, and the combination varies from person to person, becoming one of the most attractive gambling forms. In April 2017, the International Intellectual Sports Federation announced that mahjong has become a world intellectual sports project. Common mahjong tiles are mainly made of ox bones (bone surface bamboo back), melamine resin, plastic, jade, glass, metal, etc., among which, melamine resin is often used to prepare mahjong tiles for modern automatic mahjong machines due to its high strength, delicate hand feeling and excellent wear resistance.

[0003] The advantages of the automatic mahjong machine mainly lie in high shuffling efficiency, good noise suppression effect and anti-cheating; among them, the mute effect of the mahjong machine is mainly achieved by thickening the sound insulation of the internal velvet of the mahjong machine, and cooperating with the design of the sound insulation cover and the sound insulation anti-collision leaf. However, it cannot solve the noise generated by the collision between the mahjong tiles in the shuffling process or the playing process, and the wear resistance, toughness and surface hardness of the conventional mahjong tiles are low and need to be further improved.

[0004] Therefore, it is an urgent problem in the field to develop a thermoplastic resin material with low noise, high surface hardness, high toughness and high wear resistance. SUMMARY

[0005] In view of the deficiencies in the prior art, the purpose of the present application is to provide a thermoplastic resin composition and a preparation method and application thereof. The thermoplastic resin composition has excellent wear resistance, good sound and heat insulation effect, and high surface hardness and impact strength.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a thermoplastic resin composition, which comprises, by weight, 10-40 parts of acrylonitrile-butadiene-styrene resin material, 30-70 parts of polymethyl methacrylate, 1-10 parts of modified hollow ceramic microbeads and 1-20 parts of toughening agent; the modified hollow ceramic microbeads comprise hollow ceramic microbeads modified by a coupling agent and a stearate.

[0008] Hollow ceramic microspheres are a kind of small spherical ceramic material, the main components are silicon dioxide and aluminum oxide, which has the advantages of light weight, hollow, high strength, wear resistance, high temperature resistance, corrosion resistance and the like; in the application, the hollow ceramic microspheres are modified by using coupling agent and stearate, the coupling agent is subjected to chemical coupling reaction with the silicon dioxide surface of the hollow ceramic microspheres, which is beneficial to preventing the aggregation of the hollow ceramic microspheres in the resin matrix and improving the compatibility of the hollow ceramic microspheres with the resin matrix; and the metal ions in the stearate can be subjected to ion exchange reaction with the metal ions in the hollow ceramic microspheres, thereby effectively reducing the polarity of the metal oxide of the hollow ceramic microspheres, enhancing the interface interaction and compatibility of the hollow ceramic microspheres with the resin matrix, ensuring the impact performance and good appearance of the thermoplastic resin composition, and avoiding the appearance problems such as silver wire or flow mark; meanwhile, the surface hardness and wear resistance of the hollow ceramic microspheres are greatly improved; the acrylonitrile-butadiene-styrene resin material (ABS resin) has high impact strength and good gloss, and low cost; the polymethyl methacrylate (PMMA) is a kind of amorphous transparent material, which has high mechanical strength, surface hardness and good dimensional stability and is easy to be molded, and by compounding the ABS resin with the PMMA, the impact toughness and surface hardness of the material can be improved; therefore, by compounding the modified hollow ceramic microspheres with the acrylonitrile-butadiene-styrene resin material, the polymethyl methacrylate and the toughening agent, the thermoplastic resin composition has excellent wear resistance, sound insulation and heat insulation, high surface hardness and high impact strength.

[0009] In the application, the acrylonitrile-butadiene-styrene resin material is 10-40 parts, for example, can be 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts or a range between any of the above values, preferably 15-25 parts.

[0010] In the application, the polymethyl methacrylate is 30-70 parts, for example, can be 30 parts, 32 parts, 34 parts, 36 parts, 38 parts, 40 parts, 42 parts, 44 parts, 46 parts, 48 parts, 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 64 parts, 66 parts, 68 parts, 70 parts or a range between any of the above values, preferably 40-65 parts.

[0011] In the application, the mass percentage content of the polymethyl methacrylate in the thermoplastic resin composition is ≥30%, preferably the mass percentage content of the polymethyl methacrylate is ≥45%, more preferably the mass percentage content of the polymethyl methacrylate is ≥60%.

[0012] In the present application, the modified hollow ceramic microsphere is 1-10 parts, for example, can be 1 part, 1.2 parts, 1.4 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.6 parts, 2.8 parts, 3 parts, 3.2 parts, 3.4 parts, 3.6 parts, 3.8 parts, 4 parts, 4.2 parts, 4.4 parts, 4.6 parts, 4.8 parts, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.6 parts, 6.8 parts, 7 parts, 7.2 parts, 7.4 parts, 7.6 parts, 7.8 parts, 8 parts, 8.2 parts, 8.4 parts, 8.6 parts, 8.8 parts, 9 parts, 9.2 parts, 9.4 parts, 9.6 parts, 9.8 parts, 10 parts or a range between any of the above values, preferably 4-8.5 parts.

[0013] In the present application, the toughening agent is 1-20 parts, for example, can be 1 part, 2 parts, 4 parts, 6 parts, 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts or a range between any of the above values, preferably 2-18 parts, more preferably 5-15 parts.

[0014] The total amount of the coupling agent and the stearate is 0.05-0.85 parts, for example, can be 0.05 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.22 parts, 0.24 parts, 0.26 parts, 0.28 parts, 0.3 parts, 0.32 parts, 0.34 parts, 0.36 parts, 0.38 parts, 0.4 parts, 0.42 parts, 0.44 parts, 0.46 parts, 0.48 parts, 0.5 parts, 0.52 parts, 0.54 parts, 0.56 parts, 0.58 parts, 0.6 parts, 0.62 parts, 0.65 parts, 0.68 parts, 0.7 parts, 0.72 parts, 0.75 parts, 0.78 parts, 0.8 parts, 0.82 parts, 0.84 parts or a range between any of the above values, preferably 0.15-0.65 parts, more preferably 0.2-0.6 parts, based on 100 parts of the hollow ceramic microsphere.

[0015] Preferably, the mass ratio of the coupling agent and the stearate is 1:(0.3-3), wherein the specific value in (0.3-3) can be 0.3, 0.35, 0.4, 0.45, 0.5, 0.52, 0.54, 0.56, 0.58, 0.6, 0.62, 0.64, 0.66, 0.68, 0.7, 0.72, 0.75, 0.78, 0.8, 0.82, 0.85, 0.88, 0.9, 0.92, 0.95, 0.98, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.2, 2.4, 2.6, 2.8, 3 or a range between any of the above values; further preferably 1:(0.5-2.2), more preferably 1:(0.6-2).

[0016] Preferably, the coupling agent comprises a silane coupling agent and / or a titanate coupling agent.

[0017] In the present application, the silane coupling agent comprises, but is not limited to, at least one of vinyltriethoxysilane (A151), vinyltrimethoxysilane (A171), vinyltris(β-methoxyethoxy)silane (A172), γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH-560), γ-methacryloxypropyltrimethoxysilane (KH-570), aminoethylaminopropyltrimethoxysilane, N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane.

[0018] In the present application, the titanate coupling agent comprises, but is not limited to, at least one of isopropyl tri(isostearyl) titanate, isopropyl tri(dioctyl pyrophosphoryl) titanate, bis(dioctyl pyrophosphoryl) ethylene titanate, isopropyl tri(dodecyl benzene sulfonyl) titanate.

[0019] Preferably, the stearate comprises at least one of zinc stearate, calcium stearate or magnesium stearate.

[0020] Preferably, the average particle size of the hollow ceramic microsphere is 5-30 μm, for example, can be 5 μm, 6 μm, 8 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, etc.

[0021] In the present application, the average particle size of the hollow ceramic microsphere is tested by a laser particle size analyzer.

[0022] Preferably, the apparent density of the hollow ceramic microsphere is 0.2-1.2 g / cm 3 , for example, can be 0.2 g / cm 3 , 0.3 g / cm 3 , 0.4 g / cm 3 , 0.5 g / cm 3 , 0.6 g / cm 3 , 0.7 g / cm 3 , 0.8 g / cm 3 , 0.9 g / cm 3 , 1 g / cm 3 , 1.1 g / cm 3 , 1.2 g / cm 3 , etc.

[0023] In the present application, the apparent density of the hollow ceramic microsphere is measured according to the GB / T 1636-2008 "Determination of apparent density of materials that can flow from a specified funnel" standard.

[0024] In the present application, the modified hollow ceramic microsphere is prepared by the following method, which comprises:

[0025] The hollow ceramic microsphere, stearate, coupling agent and solvent are mixed and reacted to obtain the modified hollow ceramic microsphere; the solvent comprises water; the reaction temperature is 50-55℃, and the reaction time is 20-60min; after the reaction, the steps of washing, filtering and drying are further included.

[0026] Preferably, the acrylonitrile-butadiene-styrene resin material comprises acrylonitrile-butadiene-styrene resin, or a mixture of acrylonitrile-styrene copolymer and butadiene-acrylonitrile-styrene graft copolymer.

[0027] In the present application, the melt flow rate of the acrylonitrile-butadiene-styrene resin, acrylonitrile-styrene copolymer and butadiene-acrylonitrile-styrene graft copolymer is independently 3-60g / 10min, for example, it can be 3g / 10min, 3.5g / 10min, 4g / 10min, 4.5g / 10min, 5g / 10min, 5.5g / 10min, 6g / 10min, 6.5g / 10min, 7g / 10min, 7.5g / 10min, 8g / 10min, 8.5g / 10min, 9g / 10min, 9.5g / 10min, 10g / 10min, 15g / 10min, 20g / 10min, 25g / 10min, 30g / 10min, 35g / 10min, 40g / 10min, 45g / 10min, 50g / 10min, 55g / 10min, 60g / 10min or a range between any of the above values, according to the standard GB / T 3682.1-2018 at 220℃, 10kg.

[0028] In the present application, the mass percentage of styrene structural unit in the acrylonitrile-styrene copolymer is 5-55%, for example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or a range between any of the above values, and the balance is acrylonitrile structural unit.

[0029] In the present application, the mass percentage content of styrene structural units in the acrylonitrile-butadiene-styrene resin and the butadiene-acrylonitrile-styrene graft copolymer is independently 5-55%, for example, it can be 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or a range between any of the above values; the mass percentage content of butadiene structural units is independently 10-65%, for example, it can be 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or a range between any of the above values; the balance is acrylonitrile structural units.

[0030] Preferably, the melt flow rate of the polymethyl methacrylate is 1-17 g / 10 min at 230°C, 3.8 kg, for example, it can be 1 g / 10 min, 1.5 g / 10 min, 2 g / 10 min, 2.5 g / 10 min, 3 g / 10 min, 3.5 g / 10 min, 4 g / 10 min, 4.5 g / 10 min, 5 g / 10 min, 5.5 g / 10 min, 6 g / 10 min, 6.5 g / 10 min, 7 g / 10 min, 7.5 g / 10 min, 8 g / 10 min, 8.5 g / 10 min, 9 g / 10 min, 9.5 g / 10 min, 10 g / 10 min, 12 g / 10 min, 14 g / 10 min, 15 g / 10 min, 16 g / 10 min, 17 g / 10 min or a range between any of the above values.

[0031] In the present application, the melt flow rate of the polymethyl methacrylate is tested according to the GB / T 3682-2000 standard.

[0032] Preferably, the toughening agent includes at least one of acrylonitrile-butadiene-styrene rubber powder, acrylate rubber or silicone rubber.

[0033] In the present application, the mass percentage content of butadiene in the acrylonitrile-butadiene-styrene rubber powder is 55-70%, for example, it can be 55%, 56%, 58%, 60%, 62%, 64%, 66%, 68%, 70% or a range between any of the above values.

[0034] Preferably, the thermoplastic resin composition further includes other auxiliary agents 0.5-6 parts by weight, for example, it can be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts or a range between any of the above values.

[0035] Preferably, the other auxiliary agent includes at least one of an antioxidant, a lubricant or a weather-resistant agent.

[0036] In the present application, the antioxidant includes, but is not limited to, hindered phenolic antioxidant, phosphite antioxidant, etc.; the hindered phenolic antioxidant includes, but is not limited to, tetra[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (antioxidant 1010), β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl ester (antioxidant 1076), N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (antioxidant 1098), etc.; the phosphite antioxidant includes, but is not limited to, tris(2,4-di-tert-butylphenyl)phosphite (antioxidant 168), bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite (antioxidant 626), etc.

[0037] In the present application, the lubricant includes, but is not limited to, at least one of vinyl bis-stearamide, erucamide or stearate, preferably erucamide.

[0038] In the present application, the weathering agent includes, but is not limited to, one or several of hindered amine light stabilizer, benzotriazole light stabilizer, benzophenone light stabilizer or triazine light stabilizer.

[0039] In the present application, the hindered amine light stabilizer includes, but is not limited to, bis-2,2,6,6-tetramethylpiperidine-4-yl sebacate (light stabilizer 770), polymer of succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinol (light stabilizer 622), poly-{[6-[(1,1,3,3-tetramethylbutyl)-imino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidyl)-amino]-hexylene-[4-(2,2,6,6-tetramethylpiperidyl)-amino]} (light stabilizer 944), etc.

[0040] The benzotriazole light stabilizer includes, but is not limited to, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-3',5'-dicumylphenyl)benzotriazole, etc.

[0041] The benzophenone light stabilizer includes, but is not limited to, 2-hydroxy-4-n-octyloxybenzophenone (UV531).

[0042] The triazine light stabilizer includes, but is not limited to, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol (UV1164).

[0043] As a preferred technical scheme of the present application, the thermoplastic resin composition comprises, in parts by weight, 10-40 parts of acrylonitrile-butadiene-styrene resin material, 30-70 parts of polymethyl methacrylate, 1-10 parts of modified hollow ceramic microbeads, 1-20 parts of toughening agent, 0.3-3 parts of lubricant, 0.2-1.2 parts of antioxidant, and 0.5-1.5 parts of weather-resistant agent.

[0044] In the present application, the thermoplastic resin composition can also be added with other auxiliary agents as needed, exemplarily including but not limited to coloring agents, antistatic agents (such as ethoxylated lauric acid amine, dilauryl phosphate, glycerol monostearate, etc.), coupling agents (such as silane coupling agent, titanate coupling agent, etc.), compatibilizers (such as maleic anhydride grafted acrylonitrile-butadiene-styrene polymer, etc.), flame retardants (such as aluminum hydroxide, magnesium hydroxide, ammonium polyphosphate, melamine derivative, brominated triazine, decabromodiphenyl ethane, brominated epoxy, etc.), and the like.

[0045] In a second aspect, the present application provides a preparation method of the thermoplastic resin composition according to the first aspect, comprising the following steps:

[0046] The acrylonitrile-butadiene-styrene resin material, the polymethyl methacrylate, the modified hollow ceramic microbeads, and the toughening agent are mixed and extruded to obtain the thermoplastic resin composition.

[0047] Preferably, the mixed material further comprises at least one of the lubricant, the antioxidant, or the weather-resistant agent.

[0048] Preferably, the mixing comprises premixing the acrylonitrile-butadiene-styrene resin material, the polymethyl methacrylate, and the toughening agent, and optionally the antioxidant and the lubricant in a formulation amount of 40-60%, and then mixing the modified hollow ceramic microbeads and the remaining lubricant.

[0049] Preferably, the extrusion is performed at a temperature of 200-260°C, a rotation speed of 300-500 rpm, and a pressure of 1-5 MPa.

[0050] In the present application, the extrusion is performed in a twin-screw extruder; the length-diameter ratio of the twin-screw extruder is (40-44):1.

[0051] In a third aspect, the present application provides a mahjong tile shell, wherein the material of the mahjong tile shell comprises the thermoplastic resin composition according to the first aspect.

[0052] In a fourth aspect, the present application provides a mahjong tile, wherein the mahjong tile comprises the thermoplastic resin composition according to the first aspect or the mahjong tile shell according to the second aspect.

[0053] In the present application, the mahjong tile can be a hand-wound mahjong tile, a machine-washed mahjong tile, or the like.

[0054] The numerical ranges recited herein include all values from and including the lower and upper values. This is true even if the upper and lower values are stated to be limited. Rounding off any value to the nearest integer is understood to be encompassed by this application. The present application is not to be limited in scope by the exemplified range or test conditions disclosed herein. Functionally equivalent products, having both the same functional aim and the same functional result are equivalent discipline of the application. Equivalent values allow for a number of variations and modifications as long as the desired end result is achieved.

[0055] Compared with the prior art, the present application has the beneficial effects of:

[0056] The thermoplastic resin composition provided by the present application has excellent wear resistance, sound insulation and heat insulation, high surface hardness and high impact strength by adding hollow ceramic microbeads modified by a coupling agent and a stearate, and compounding the modified hollow ceramic microbeads with acrylonitrile-butadiene-styrene resin material, polymethyl methacrylate and toughening agent in specific contents. DETAILED DESCRIPTION

[0057] The technical solutions of the present application will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only to help understand the present application and should not be regarded as specific limitations of the present application.

[0058] Unless otherwise specified, the materials used in the present application can be purchased on the market or prepared by conventional methods; the materials used in the present application are as follows:

[0059] ABS resin: ABS PA-757K, Zhenjiang Qimei;

[0060] AS resin: SAN NF2200 AK, Taiwan Chemical of Taiwan Province, China;

[0061] PMMA-1: PMMASX-304, Suzhou Shuangxiang, 230℃, 3.8kg, melt flow rate is 2g / 10min;

[0062] PMMA-2: PMMACM-207, Taiwan Chemical of Taiwan Province, China, 230℃, 3.8kg, melt flow rate is 8g / 10min;

[0063] PMMA-3: PMMALG2, Japan Sumitomo Chemical, 230℃, 3.8kg, melt flow rate is 15g / 10min;

[0064] Toughening agent

[0065] Silicone rubber: MR502, Japan Zhong Yuan;

[0066] Acrylate rubber: EM500, LG Chemical of South Korea;

[0067] Antioxidant: a composite antioxidant composed of tetrakis[β-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate]pentaerythritol ester and tris(2,4-di-tert-butylphenyl) phosphite at a mass ratio of 1:1;

[0068] Hollow ceramic microbeads: Shanghai Gruen Nanometer Material Co., Ltd.; average particle size: 20 μm, apparent density: 0.8 g / cm 3 .

[0069] Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 3

[0070] Preparation Examples 1 to 10 and Comparative Preparation Examples 1 to 3 each provide a modified hollow ceramic microbead, wherein the raw material for preparing the modified hollow ceramic microbead comprises hollow ceramic microbeads and a modifier; the weight fraction of the modifier, and the type and ratio of the modifier are shown in Table 1, based on 100 parts by weight of the hollow ceramic microbeads; wherein " / " indicates that the component is not present in the formulation; "-" indicates that the component is present in the formulation.

[0071] The method for preparing the modified hollow ceramic microbead comprises:

[0072] The hollow ceramic microbeads, the stearate and the coupling agent are placed in a reaction kettle in the amount according to the formulation, 0.2% of distilled water by weight of the hollow ceramic microbeads is added, and after being raised to 55°C, the mixture is fully stirred in a magnetic stirrer for 40 min, then washed with deionized water, filtered, and vacuum dried at 60°C to obtain the modified hollow ceramic microbead.

[0073] Table 1

[0074]

[0075] Table 2

[0076]

[0077]

[0078] Examples 1 to 15 and Comparative Examples 1 to 8

[0079] Examples 1 to 15 and Comparative Examples 1 to 8 each provide a thermoplastic resin composition, wherein the formulation of the thermoplastic resin composition is shown in Table 3, based on parts by weight; wherein " / " indicates that the component is not present in the formulation; and the method for preparing the thermoplastic resin composition comprises:

[0080] The acrylonitrile-butadiene-styrene resin material, polymethyl methacrylate and toughening agent, antioxidant and 50% of the formula amount of lubricant are premixed for 2 min to obtain mixture A; the modified hollow ceramic microbead and the remaining lubricant are premixed for 5 min to obtain mixture B, then mixture A is fed into the main feeding port of the twin-screw extruder, and mixture B is fed into the side feeding port of the twin-screw extruder, and the hot melt, extrusion and granulation are carried out to obtain the thermoplastic resin composition; the temperature of the twin-screw extruder from the feeding port to the die is 160℃, 210℃, 220℃, 220℃, 230℃, 230℃, 240℃, 240℃, 230℃, 230℃, 230℃ in turn, the rotating speed of the twin-screw extruder is 400 rpm, and the pressure is 3 MPa; the length-diameter ratio of the twin-screw extruder is 44:1, and the side feeding port is located at the position of 3-4 screw cylinders before the die.

[0081] Table 3

[0082]

[0083]

[0084] Table 4

[0085]

[0086]

[0087] Table 5

[0088]

[0089]

[0090] Performance test

[0091] (1) Izod notched impact strength: the Izod notched impact strength of the thermoplastic resin composition provided by Examples 1-15 and Comparative Examples 1-8 is tested according to GB / T 1843-2008, "Determination of Izod Impact Strength of Plastics".

[0092] (2) Hardness: the hardness of the thermoplastic resin composition provided by Examples 1-15 and Comparative Examples 1-8 is determined according to Rockwell hardness HRA.

[0093] (3) Wear resistance: the thermoplastic resin composition provided by Examples 1-15 and Comparative Examples 1-8 was injection molded to obtain a square plate of 3mm x 100mm x 100mm, and the mass change before and after wear of the square plate was tested by using a wear tester, and the test parameters of the wear tester were as follows: single arm load: 500g; grinding wheel type: H-18; sample rotation speed: 60r / min; rotation friction frequency: 5000 revolutions; the smaller the mass change before and after wear, the better the wear resistance.

[0094] (4) Sound insulation: the thermoplastic resin composition was injection molded into mahjong, and was repeatedly shuffled in a mahjong machine, and the noise of the mahjong within 30min was tested by using a noise decibel meter, and the maximum noise value was recorded, and the smaller the value, the better the sound insulation effect.

[0095] The specific test results are shown in Table 6.

[0096] Table 6

[0097]

[0098] As can be seen from Table 6, the thermoplastic resin composition provided by the present application has excellent wear resistance, sound insulation, high surface hardness and high impact strength by adding hollow ceramic microbeads modified by a coupling agent and a stearate, and the modified hollow ceramic microbeads are compounded with acrylonitrile-butadiene-styrene resin material, polymethyl methacrylate and toughening agent at specific contents. It is especially suitable for the shell of injection-grade mahjong, and can effectively improve the problems of scratching and noise caused by the collision of mahjong during shuffling and dealing. The cantilever beam notched impact strength of the thermoplastic resin composition is ≥4.5kJ / m 2 , the Rockwell hardness is ≥109, the mass change before and after wear is ≤0.48mg, and the sound insulation effect is ≤59 decibels.

[0099] As can be seen from the comparison of Example 1 and Comparative Examples 1-6, the toughness or wear resistance of the thermoplastic resin composition is poor, and the sound insulation effect of the mahjong is poor if the specific modified hollow ceramic microbeads or the content of the modified hollow ceramic microbeads is not within a specific range.

[0100] As can be seen from Example 1 and Comparative Examples 7 and 8, the ABS and PMMA are compounded at specific contents, and the thermoplastic resin composition can have good toughness and wear resistance.

[0101] The above specific embodiments further illustrate the purpose, technical solutions and advantages of the present application, and it should be understood that the above description is only a specific embodiment of the present application and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. A thermoplastic resin composition, characterized by, The thermoplastic resin composition comprises 10-40 parts by weight of acrylonitrile-butadiene-styrene resin material, 30-70 parts by weight of polymethyl methacrylate, 1-10 parts by weight of modified hollow ceramic microbeads, and 1-20 parts by weight of toughening agent; The modified hollow ceramic microbeads comprise hollow ceramic microbeads modified by a coupling agent and a stearate; The mass ratio of the coupling agent to the stearate is 1:(0.3-3); The coupling agent comprises a silane coupling agent and / or a titanate coupling agent; The toughening agent comprises at least one selected from acrylonitrile-butadiene-styrene rubber powder, acrylate rubber, and silicone rubber.

2. The thermoplastic resin composition according to claim 1, characterized by The total amount of the coupling agent and the stearate is 0.05-0.85 parts by weight based on 100 parts by weight of the hollow ceramic microbeads.

3. The thermoplastic resin composition according to claim 2, characterized by The total amount of the coupling agent and the stearate is 0.15-0.65 parts by weight based on 100 parts by weight of the hollow ceramic microbeads.

4. The thermoplastic resin composition according to claim 1, characterized by The mass ratio of the coupling agent to the stearate is 1:(0.5-2.2).

5. The thermoplastic resin composition according to claim 1, wherein The stearate comprises at least one selected from zinc stearate, calcium stearate, and magnesium stearate.

6. The thermoplastic resin composition according to claim 1, characterized by The average particle size of the hollow ceramic microbeads is 5-30 μm.

7. The thermoplastic resin composition according to claim 1, wherein The apparent density of the hollow ceramic microbeads is 0.2-1.2 g / cm 3 .

8. The thermoplastic resin composition according to Claim 1, characterized by The acrylonitrile-butadiene-styrene resin material comprises acrylonitrile-butadiene-styrene resin.

9. The thermoplastic resin composition according to Claim 1, characterized by The acrylonitrile-butadiene-styrene resin material comprises a mixture of acrylonitrile-styrene copolymer and butadiene-acrylonitrile-styrene graft copolymer.

10. The thermoplastic resin composition according to Claim 1, characterized by The polymethyl methacrylate has a melt flow rate of 1-17 g / 10 min at 230 °C under a load of 3.8 kg.

11. The thermoplastic resin composition according to claim 1, characterized by The thermoplastic resin composition further comprises 0.5-6 parts by weight of other auxiliary agents.

12. The thermoplastic resin composition according to claim 11, characterized by The other auxiliary agents comprise at least one selected from antioxidants, lubricants, and light stabilizers.

13. The thermoplastic resin composition according to claim 12, characterized by The thermoplastic resin composition comprises 0.3-3 parts by weight of lubricant, 0.2-1.2 parts by weight of antioxidant, and 0.5-1.5 parts by weight of light stabilizer.

14. A method for producing the thermoplastic resin composition according to any one of claims 1 to 13, characterized by, The preparation method comprises the following steps: The acrylonitrile-butadiene-styrene resin material, the polymethyl methacrylate, the modified hollow ceramic microbeads, and the toughening agent are mixed and extruded to obtain the thermoplastic resin composition.

15. The preparation method according to claim 14, characterized in that The mixing comprises premixing the acrylonitrile-butadiene-styrene resin material, the polymethyl methacrylate, and the toughening agent, and optionally the antioxidant and 40-60% of the lubricant by formula amount, and then mixing the modified hollow ceramic microbeads and the remaining lubricant.

16. The method of claim 14, wherein, The temperature for the extrusion is 200-260 °C, the rotation speed is 300-500 rpm, and the pressure is 1-5 MPa.

17. A mahjong case, characterized by, The material of the mahjong tile shell comprises the thermoplastic resin composition according to any one of claims 1-13.

18. A set of mahjong tiles, characterized in that, The mahjong tile comprises the thermoplastic resin composition according to any one of claims 1-13 or the mahjong tile shell according to claim 17.

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