Extruded spraying-free ABS alloy material and preparation method thereof

Abstract

The invention relates to an extrusion spraying-free ABS alloy material and a preparation method thereof. The extrusion spraying-free ABS alloy material is prepared from the following components in parts by weight: 70-90 parts of ABS resin, 5-15 parts of spraying-free imitation metal master batches, 2-8 parts of a toughening agent, 1-3 parts of a compatilizer, 0.1-0.5 part of a weather-resistant agent, 0.2-1 part of an antioxidant, 0.2-1 part of a lubricant and 0.5-2 parts of a dispersing agent. The spraying-free imitation metal master batch is added into the ABS alloy material, so that the defects of flow mark weld lines and the like of the ABS alloy material can be overcome, and the mechanical property and the stability of the spraying-free ABS alloy material can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, and particularly relates to an extrusion spray-free ABS alloy material and a preparation method thereof. BACKGROUND

[0002] ABS resin material is a terpolymer of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and the relative content of the three monomers can be arbitrarily changed to form various resins. As one of the five general synthetic plastics, ABS resin has unique properties, such as chemical resistance, low-temperature impact resistance and excellent processing performance, and therefore, ABS resin material can be applied in various industries. At present, most consumer products such as home appliances and electronic appliances still use ABS resin material as the shell of product parts, because ABS resin material has good dimensional stability and high light appearance aesthetic performance. With the gradual upgrading of the aesthetic requirements of home appliances, metallic texture has gradually become the main trend of home appliance appearance design.

[0003] Spray-free metallic texture plastic has been applied in products of home appliances, automobiles, 3C, daily necessities and building materials due to its excellent appearance, economy and environmental protection, and has obtained wide praise in the market. However, as shown in Figure 1 、 Figure 2 , the existing market's imitation metal spray-free material cannot solve the problems of surface flow mark weld line, pitting and the like, and at the same time, the metallic texture is weak and has appearance defects. SUMMARY

[0004] Therefore, the purpose of the present application is to provide an extrusion spray-free ABS alloy material and a preparation method thereof, so as to solve the problems of the existing market's imitation metal spray-free material, and greatly improve the defects of flow mark weld line, pitting, weak metallic texture and the like of the extrusion material.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical scheme: The present application provides an extrusion spray-free ABS alloy material, which is prepared from the following components by weight: 70-90 parts of ABS resin, 5-15 parts of spray-free imitation metal master batch as described above, 2-8 parts of toughening agent, 1-3 parts of compatibility agent, 0.1-0.5 parts of weather-resistant agent, 0.2-1 parts of antioxidant, 0.2-1 parts of lubricant and 0.5-2 parts of dispersing agent.

[0006] As a further improvement of the above-mentioned scheme of the present application, the preparation method of the spray-free imitation metal master batch comprises the following steps: S1. Grinding and sieving atomized aluminum powder to obtain aluminum pigment with a thick cake structure; S2. Stirring and mixing the thick-cake-structure aluminum pigment with anhydrous ethanol, ammonia water under a protective atmosphere, adding tetraethyl orthosilicate, heating reaction, then adding silane coupling agent, stirring at room temperature, post-processing, to obtain modified silica-coated aluminum pigment; S3. The modified silica-coated aluminum pigment is subjected to copolymerization crosslinking reaction with acrylonitrile, and post-processing to obtain a spray-free metal-imitating master batch.

[0007] The spray-free metal-imitating master batch prepared by the present application contains aluminum powder with very strong polarity on the surface, which can be tightly combined with ABS resin, thereby ensuring complete interface compatibility between the aluminum powder and the ABS resin. Meanwhile, the thick-cake-structure aluminum powder contained in the spray-free metal-imitating master batch has a higher thickness-diameter ratio than the traditional flaky aluminum powder, so the light reflection effect of multiple light reflection surfaces of the aluminum powder is closer, which can significantly improve the corner color change problem caused by traditional flaky aluminum powder, fundamentally improve the defects such as flow mark weld line, and eliminate the defects such as flow mark weld line and pitting caused by uneven dispersion of metal powder and agglomeration of melt flow metal powder during the forming injection molding process, thereby improving the metal texture effect of the extruded spray-free ABS alloy material.

[0008] As a further improvement of the above-mentioned scheme of the present application, in step S1, the particle size of the atomized aluminum powder is 10-60 μm; and / or, the grinding and polishing is to put the atomized aluminum powder into a ball mill, use a steel column with a diameter of 1.0-4.0 mm, and grind and polish at a speed of 30 r / min for 300-900 min; and / or, the screening is carried out by a combined screening process of linear vibration screen and lelo screen, to obtain aluminum pigment with a thick-cake-structure, a particle size of 30-100 μm, and a thickness-diameter ratio of 1:3-1:6.

[0009] As a further improvement of the above-mentioned scheme of the present application, in step S2, the silane coupling agent includes methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane, and the mass ratio of methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane is 1-3:1:1; and / or, the amount ratio of the silane coupling agent, anhydrous ethanol, ammonia water, thick-cake-structure aluminum pigment, tetraethyl orthosilicate is 3-8 g:200-550 mL:5-15 mL:5-10 g:4-8 g, and the concentration of the ammonia water is 25%; and / or, the heating reaction is stirring at 40-60℃ for 2-4 h, and the drying is carried out at 80-85℃ in a vacuum environment for 5-7 h.

[0010] As a further improvement of the above-mentioned scheme of the present application, in step S3, the copolymerization and crosslinking reaction comprises the following steps: uniformly mixing the modified silica-coated aluminum pigment, the surfactant and deionized water, adding acrylonitrile, heating and stirring, then adding initiator and crosslinking agent and continuously stirring, after the reaction is completed, cooling to room temperature, filtering, washing, drying, and granulating to obtain the spray-free metal-imitating masterbatch.

[0011] As a further improvement of the above-mentioned scheme of the present application, the modified silica-coated aluminum pigment, the surfactant, the acrylonitrile, the initiator and the crosslinking agent are used in a ratio of 1-2 g: 0.05-0.1 g: 3-6 mL: 0.06-0.12 g: 0.025-0.05 g; and / or, the surfactant is sodium dodecyl sulfate, the initiator is potassium persulfate, and the crosslinking agent is N,N'-methylene bisacrylamide; and / or, the heating and stirring is performed at 80-95°C for 2-4 h, and the drying is performed at 80-85°C under vacuum for 5-7 h.

[0012] As a further improvement of the above-mentioned scheme of the present application, the ABS resin is acrylonitrile-butadiene-styrene copolymer, and the acrylonitrile-butadiene-styrene copolymer is obtained by blending emulsion-prepared acrylonitrile-butadiene-styrene copolymer and bulk-prepared acrylonitrile-butadiene-styrene copolymer in a mass ratio of 3:1.

[0013] As a further improvement of the above-mentioned scheme of the present application, the toughening agent is styrene-ethylene-butylene-styrene block copolymer; and / or, the compatibilizer is carboxylic acid grafted compatibilizer; and / or, the antioxidant is hindered phenolic antioxidant; and / or, the lubricant is lubricant TAS-2A; and / or, the dispersant is polymethacrylic acid derivative dispersant; and / or, the light stabilizer is benzotriazole light stabilizer.

[0014] The present application also provides a method for preparing the extruded spray-free ABS alloy material as described above, which comprises the following steps: uniformly mixing ABS resin, toughening agent, compatibilizer, weathering agent, antioxidant, lubricant and dispersant in a proportion, then adding them into the main feeding port of an extruder, adding the spray-free metal-imitating masterbatch into the side feeding port of the extruder, and then performing melt blending and extrusion granulation to obtain the extruded spray-free ABS alloy material.

[0015] As a further improvement of the above-mentioned scheme of the present application, the ABS resin, the toughening agent, the compatibilizer, the weathering agent, the antioxidant, the lubricant and the dispersant are mixed at a temperature of 80-100 DEG C for 2-4 hours; and / or, the extruder is a double-screw extruder, the barrel temperature of the extruder is 200-230 DEG C, the screw rotation speed is 200-300 rpm, and the vacuum degree is 0.06-0.1 MPa; and / or, the TME element and the ZME element are arranged at the middle position of the extruder, and the toothed disc is arranged at the head position of the extruder.

[0016] Compared with the prior art, the present application has the following beneficial effects: 1. The present application adds the spray-free metal-imitating master batch into the ABS alloy material, which can solve the defects such as flow mark and weld line of the ABS alloy material, and can improve the mechanical properties and stability of the spray-free ABS alloy material.

[0017] 2. In the preparation of the spray-free metal-imitating master batch, the atomized aluminum powder is ground and screened to obtain aluminum pigments with a thick cake structure, then tetraethyl orthosilicate (TEOS) is hydrolyzed on the surface of the aluminum pigments under alkaline conditions to form a silica coating layer, the silica is modified using a silane coupling agent to obtain thick cake structure aluminum pigments coated with modified silica, and then the thick cake structure aluminum pigments coated with modified silica are copolymerized and crosslinked with acrylonitrile to form a network structure on the surface of the aluminum pigments, which is interwoven with O-Si-O functional groups and cyano groups, thereby obtaining a thick cake spray-free metal-imitating master batch with very strong polarity on the surface and high dispersibility in resin, and the thick cake structure (thickness-diameter ratio 1:3-6) has more reflective surfaces than the traditional lamellar structure (thickness-diameter ratio 1:20-100) of aluminum pigments.

[0018] 3. The prepared spray-free imitation metal master batch is introduced into the extrusion spray-free ABS alloy material, the surface of the spray-free imitation metal master batch has very strong polarity, can be combined with the ABS resin, so that the interface compatibility between the spray-free imitation metal master batch and the ABS resin is ensured, the spray-free imitation metal master batch can be uniformly dispersed in the material, and the thick cake structure has multiple reflective surfaces, the reflective situation of the spray-free imitation metal master batch after turning is basically the same as that before turning in the injection molding process of the spray-free material, so that the color change problem of the corner can be avoided, the defects such as flow mark weld line are fundamentally improved, the defects such as flow mark weld line and pitting caused by uneven dispersion of metal powder and agglomeration of the melt flow metal powder in the injection molding process are eliminated, and the metal texture effect of the extrusion spray-free ABS alloy material is improved. In addition, due to the network structure of the O-Si-O functional group and the cyano group in the spray-free imitation metal master batch, the reaction between the chemical reagents such as oil stains and the rubber molecules can be effectively prevented to cause aging, the mechanical properties and stability of the extrusion spray-free ABS alloy material can be improved, and the Si-O in the spray-free imitation metal master batch has high bond energy and large chemical inertness, so that the high and low temperature deformation resistance of the extrusion spray-free ABS alloy material can be improved.

[0019] 4. In the preparation of the extrusion spray-free ABS alloy material, the double screw extruder is provided with a TME element and a ZME element at the middle position and a toothed disc at the head position, so that the dispersion effect is greatly improved, the pitting problem of the traditional extrusion spray-free material is solved, the yield of the production is improved, and the production efficiency is improved. BRIEF DESCRIPTION OF DRAWINGS

[0020] Figure 1 The electron microscope image of the existing extrusion spray-free material on the market; Figure 2 The appearance picture of the existing extrusion spray-free material product on the market; Figure 3 The electron microscope image of the thick cake structure aluminum pigment prepared in Example 2; Figure 4 The appearance picture of the product made of the extrusion spray-free ABS alloy material prepared by using Example 2. DETAILED DESCRIPTION

[0021] In order to facilitate the understanding of the present application, the present application will be described more fully below with specific examples. However, the present application can be realized in many different forms, and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0023] The raw materials used in the following examples and comparative examples of the present application are as follows: ABS resin: mixed by Qimei 749SK (emulsion method), Takahashi 725 (bulk method) according to the mass ratio of 3:1; Toughening agent: G1650MU, produced by Kraton, USA; Compatibilizer: CMG7000, produced by Jia Yirong; Weathering agent: 384-2, produced by BASF; Antioxidant: antioxidant 1010, produced by Ji Yixi; Lubricant: TAS-2A, produced by Suzhou Xingtai Guoguang; Dispersant: EFKA-4401, produced by Evonik; Methyl triethoxysilane: YJ-69, produced by Shandong Yuanjin; Vinyl triethoxysilane: A-151, produced by Shandong Yuanjin; Dimethyl dimethoxysilane: YJ-1101, produced by Shandong Yuanjin; Deionized water: prepared by RO reverse osmosis method; Ammonia water: concentration of 25%, commercially available; Atomized aluminum powder: FLPG25, produced by Henan Yuanyang Powder; Tetraethyl orthosilicate: analytical pure, produced by Shantou Guanghua Chemical Factory; Anhydrous ethanol: produced by Shandong Mingxin Chemical Industry; Acrylonitrile: chemically pure, produced by Shandong Jinyueyuan; Initiator: potassium persulfate, produced by Shandong Shijitongda; Surfactant: sodium dodecyl sulfate, VT859, produced by Hebei Pinke Research Institute; Crosslinking agent: N,N'-methylene bisacrylamide, produced by Hubei Yongqi Chemical Industry; Commercially available metal masterbatch: PE1106, produced by Jingcheng.

[0024] The above raw materials are only for the purpose of illustrating the source and composition of reagents used in the experiments of the present application, in order to fully disclose, and do not mean that other similar reagents or reagents provided by other suppliers cannot achieve the present application.

[0025] Unless otherwise specified, the reagents, methods and equipment used in the present application are conventional reagents, methods and equipment in the technical field.

[0026] Example 1 The present example provides an extruded spray-free ABS alloy material, which comprises the following components by weight: ABS resin 70 parts, spray-free metal-imitating masterbatch 5 parts, toughening agent 2 parts, compatibilizer 1 part, weathering agent 0.1 part, antioxidant 0.2 part, lubricant 0.2 part, and dispersant 0.5 part.

[0027] The preparation method of the extruded spray-free ABS alloy material of the present example comprises the following steps: under a nitrogen atmosphere, the ABS resin, toughening agent, compatibilizer, weathering agent, antioxidant, lubricant, and dispersant are mixed uniformly at 80°C for 4h, then added from the main feeding port of the twin-screw extruder, the spray-free metal-imitating masterbatch is added from the side feeding port of the twin-screw extruder, the barrel temperature of the twin-screw extruder is controlled at 200°C, the screw rotation speed is 200rpm, and the vacuum degree is 0.1MPa, then melt blending and extrusion granulation are performed to obtain the extruded spray-free ABS alloy material. In the present example, a TME element and a ZME element are arranged at the middle position of the twin-screw extruder, and a toothed disc is arranged at the head position.

[0028] The preparation method of the spray-free metal-imitating masterbatch of the present example comprises the following three steps S1-S3: S1. The atomized aluminum powder with a particle size of 10-60μm is put into a ball mill, a steel column with a diameter of 1.0-4.0mm is used for grinding at a speed of 30r / min for 600min, then the combined screening process of linear vibration screen and Roto screen is used for screening to obtain aluminum pigment with a thick cake structure with a particle size of 30-100μm and a thickness-diameter ratio of 1:3-6; S2. The thick cake structure aluminum pigment obtained in step S1, anhydrous ethanol, and ammonia water (concentration 25%) are stirred and mixed under a protective atmosphere, tetraethyl orthosilicate is added, the temperature is raised to 60°C for reaction for 3h, then silane coupling agent (obtained by mixing methyl triethoxysilane, vinyl triethoxysilane, and dimethyl dimethoxysilane at a mass ratio of 1:1:1) is added, stirring at room temperature for 48h, after the reaction is completed, the product is filtered, washed with anhydrous ethanol three times, then dried at 80°C under vacuum for 6h to obtain modified silica-coated aluminum pigment, wherein the amount ratio of silane coupling agent, anhydrous ethanol, ammonia water, thick cake structure aluminum pigment, and tetraethyl orthosilicate is 3g:200mL:5mL:5g:4g; S3. The modified silica-coated aluminum pigment obtained in step S2 is subjected to a copolymerization cross-linking reaction with acrylonitrile to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres, and after treatment, a spray-free metal-imitating masterbatch is obtained. The specific process is as follows: the modified silica-coated aluminum pigment, a surfactant and deionized water are uniformly mixed, acrylonitrile is added, stirring is carried out at 85℃ for 3h, and then an initiator and a cross-linking agent are added and continuous stirring is carried out. The amount ratio of the modified silica-coated aluminum pigment, the surfactant, the acrylonitrile, the initiator and the cross-linking agent is 1g:50mg:3mL:60mg:25mg. After the reaction is completed, the reaction system is cooled to room temperature to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres. After the reaction is completed, the product is filtered and washed with anhydrous ethanol three times. After drying at 80℃ for 6h, the product is granulated to obtain a spray-free metal-imitating masterbatch.

[0029] Example 2 The present example provides an extrusion spray-free ABS alloy material, which comprises the following components in parts by weight: ABS resin 75 parts, spray-free metal-imitating masterbatch 8 parts, toughening agent 4.5 parts, compatibilizer 1.5 parts, weathering agent 0.2 parts, antioxidant 0.3 parts, lubricant 0.3 parts and dispersant 1 part.

[0030] The preparation method of the extrusion spray-free ABS alloy material of the present example comprises the following steps: under a nitrogen atmosphere, the ABS resin, the toughening agent, the compatibilizer, the weathering agent, the antioxidant, the lubricant and the dispersant are uniformly mixed at 85℃ for 2.5h, and then added from the main feeding port of the twin-screw extruder. The spray-free metal-imitating masterbatch is added from the side feeding port of the twin-screw extruder. The barrel temperature of the twin-screw extruder is controlled at 210℃, the screw rotation speed is 220rpm, and the vacuum degree is 0.08MPa. After melt blending and extrusion granulation, the extrusion spray-free ABS alloy material is obtained. In the present example, a TME element and a ZME element are arranged at the middle position of the twin-screw extruder, and a toothed disc is arranged at the head position.

[0031] The preparation method of the spray-free metal-imitating masterbatch of the present example comprises the following three steps S1-S3: S1. The atomized aluminum powder with a particle size of 10-60μm is put into a ball mill, and a steel cylinder with a diameter of 1.0-4.0mm is used to grind at a speed of 30r / min for 600min. Then, the combined screening process of a linear vibrating screen and a Roto screen is used for screening to obtain an aluminum pigment with a thick cake structure, a particle size of 30-100μm and a thickness-diameter ratio of 1:3-6. Figure 3 The electron microscope image of the aluminum pigment obtained in the present step is shown in Figure 1. Figure 3 It can be seen from the electron microscope image that the aluminum pigment obtained in the present step has a thick cake structure. S2. The thick-cake-structure aluminum pigment obtained in step S1, anhydrous ethanol, ammonia water (25% concentration) were stirred and mixed under a protective atmosphere, tetraethyl orthosilicate was added, the temperature was raised to 60°C and reacted for 3 hours, then silane coupling agent (obtained by mixing methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane in a mass ratio of 2:1:1) was added, and stirred at room temperature for 48 hours. After the reaction was completed, the product was filtered, washed with anhydrous ethanol three times, and then dried at 80°C under vacuum for 6 hours to obtain a modified silica-coated aluminum pigment. The amount ratio of silane coupling agent, anhydrous ethanol, ammonia water, thick-cake-structure aluminum pigment, tetraethyl orthosilicate was 6g: 300mL: 8mL: 7g: 6g; S3. The modified silica-coated aluminum pigment obtained in step S2 was subjected to copolymerization and crosslinking reaction with acrylonitrile to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres, and after treatment, a spray-free metal-imitating master batch was obtained. The specific process was as follows: the modified silica-coated aluminum pigment, a surfactant and deionized water were uniformly mixed, acrylonitrile was added, and stirred at 85°C for 3h. After the addition of an initiator and a crosslinking agent, the stirring was continued. The amount ratio of modified silica-coated aluminum pigment, surfactant, acrylonitrile, initiator and crosslinking agent was 1.5g: 80mg: 5mL: 100mg: 40mg. After the reaction was completed, the reaction system was cooled to room temperature to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres. After the reaction was completed, the product was filtered, washed with anhydrous ethanol three times, and then granulated after drying at 80°C for 6 hours to obtain a spray-free metal-imitating master batch.

[0032] Figure 4 The product appearance picture of the extrusion spray-free ABS alloy material prepared by using the embodiment is shown in Figure 1. Figure 4 It can be seen that the product surface appearance is bright and has no defects.

[0033] Example 3 The embodiment provides an extrusion spray-free ABS alloy material, which comprises the following components in parts by weight: ABS resin 80 parts, spray-free metal-imitating master batch 10 parts, toughening agent 5 parts, compatibility agent 2 parts, weather-resistant agent 0.3 parts, antioxidant 0.5 parts, lubricant 0.5 parts and dispersing agent 1.2 parts.

[0034] The preparation method of the extruded spray-free ABS alloy material of the embodiment comprises the following steps: under a nitrogen atmosphere, uniformly mixing ABS resin, toughening agent, compatibilizer, weather-resistant agent, antioxidant, lubricant and dispersant at 90℃ for 3h, then adding from the main feeding port of the twin-screw extruder, adding spray-free metal-imitating masterbatch from the side feeding port of the twin-screw extruder in proportion, controlling the barrel temperature of the twin-screw extruder to be 220℃, the screw rotation speed to be 250rpm, and the vacuum degree to be 0.08MPa, and then carrying out melt blending and extruding and granulating to obtain the extruded spray-free ABS alloy material. In the embodiment, the middle position of the twin-screw extruder is provided with a TME element and a ZME element, and the head position is provided with a toothed disc.

[0035] The preparation method of the spray-free metal-imitating masterbatch of the embodiment comprises the following three steps S1-S3: S1. Put the atomized aluminum powder with a particle size of 10-60μm into a ball mill, use a steel column with a diameter of 1.0-4.0mm to grind at a speed of 30r / min for 600min, then screen by the combined screening process of linear vibration screen and Roto screen to obtain aluminum pigment with a thick-cake structure, a particle size of 30-100μm and a thickness-diameter ratio of 1:3-6; S2. Under a protective atmosphere, stir and mix the thick-cake structure aluminum pigment obtained in step S1, anhydrous ethanol and ammonia water (concentration of 25%), then gradually add tetraethyl orthosilicate, heat to 60℃ and react for 3h, then add silane coupling agent (obtained by mixing methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane in a mass ratio of 3:1:1), stir at room temperature for 48h, filter after the reaction is completed, wash the product with anhydrous ethanol three times, then dry at 80℃ in a vacuum environment for 6h to obtain modified silica-coated aluminum pigment, wherein the amount ratio of silane coupling agent, anhydrous ethanol, ammonia water, thick-cake structure aluminum pigment and tetraethyl orthosilicate is 8g:550mL:15mL:10g:8g; S3. Carry out copolymerization and crosslinking reaction of the modified silica-coated aluminum pigment obtained in step S2 and acrylonitrile to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres, and then carry out post-treatment to obtain spray-free metal-imitating masterbatch. The specific process is as follows: uniformly mix the modified silica-coated aluminum pigment and surfactant in deionized water, add acrylonitrile, stir at 85℃ for 3h, continuously stir after adding initiator and crosslinking agent, and the amount ratio of modified silica-coated aluminum pigment, surfactant, acrylonitrile, initiator and crosslinking agent is 2g:80mg:6mL:120mg:50mg; after the reaction is completed, cool to room temperature to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres; filter after the reaction is completed, wash the product with anhydrous ethanol three times, granulate after drying at 80℃ for 6h to obtain spray-free metal-imitating masterbatch.

[0036] Example 4 The present example provides an extruded spray-free ABS alloy material, which comprises the following components in parts by weight: ABS resin 85 parts, spray-free metal-imitating masterbatch 12 parts, toughening agent 6.5 parts, compatibilizer 2.5 parts, weathering agent 0.4 parts, antioxidant 0.8 parts, lubricant 0.8 parts, and dispersant 1.5 parts.

[0037] The preparation method of the extruded spray-free ABS alloy material of the present example comprises the following steps: under a nitrogen atmosphere, the ABS resin, toughening agent, compatibilizer, weathering agent, antioxidant, lubricant, and dispersant are mixed uniformly at a ratio of 95°C for 3.5h, then added to the main feeding port of the twin-screw extruder, the spray-free metal-imitating masterbatch is added from the side feeding port of the twin-screw extruder at a ratio, the barrel temperature of the twin-screw extruder is controlled at 230°C, the screw speed is 300rpm, and the vacuum degree is 0.06MPa, and after melting blending and extrusion granulation, the extruded spray-free ABS alloy material is obtained. In the present example, a TME element and a ZME element are arranged at the middle position of the twin-screw extruder, and a toothed disc is arranged at the head position.

[0038] The preparation method of the spray-free metal-imitating masterbatch of the present example comprises the following three steps S1-S3: S1. The atomized aluminum powder with a particle size of 10-60μm is put into a ball mill, a steel column with a diameter of 1.0-4.0mm is used for grinding at a speed of 30r / min for 600min, and then the combined screening process of linear vibration screen and lelo screen is used for screening to obtain aluminum pigment with a thick cake structure with a particle size of 30-100μm and a thickness-diameter ratio of 1:3-6; S2. The thick cake structure aluminum pigment obtained in step S1, anhydrous ethanol, and ammonia water (concentration 25%) are stirred and mixed under a protective atmosphere, tetraethyl orthosilicate is gradually added, the temperature is raised to 60°C and reacted for 3 hours, then silane coupling agent (obtained by mixing methyl triethoxysilane, vinyl triethoxysilane, and dimethyl dimethoxysilane at a mass ratio of 1:1:1) is added, and stirred at room temperature for 48 hours. After the reaction is completed, the product is filtered, washed with anhydrous ethanol three times, and then dried at 80°C in a vacuum environment for 6h to obtain modified silica-coated aluminum pigment. The amount ratio of silane coupling agent, anhydrous ethanol, ammonia water, thick cake structure aluminum pigment, and tetraethyl orthosilicate is 7g:400mL:10mL:10g:6g; S3. The modified silica-coated aluminum pigment obtained in step S2 is subjected to a copolymerization crosslinking reaction with acrylonitrile to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres, and after treatment, a spray-free metal-imitating masterbatch is obtained. The specific process is as follows: the modified silica-coated aluminum pigment, a surfactant and deionized water are uniformly mixed, acrylonitrile is added, stirring is carried out at 85℃ for 3h, an initiator and a crosslinking agent are added, and continuous stirring is carried out. The amount ratio of the modified silica-coated aluminum pigment, the surfactant, the acrylonitrile, the initiator and the crosslinking agent is 1.5g: 100mg: 4mL: 80mg: 30mg. After the reaction is completed, the reaction system is cooled to room temperature to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres. After the reaction is completed, the product is filtered, washed with anhydrous ethanol three times, and granulated after drying at 80℃ for 6h to obtain a spray-free metal-imitating masterbatch.

[0039] Example 5 The present example provides a kind of extrusion spray-free ABS alloy material, which includes the following components by weight: ABS resin 90 parts, spray-free metal-imitating masterbatch 15 parts, toughening agent 8 parts, compatibility agent 3 parts, weathering agent 0.5 parts, antioxidant 1 part, lubricant 1 part and dispersant 2 parts.

[0040] The preparation method of the extrusion spray-free ABS alloy material of the present example includes the following steps: under nitrogen atmosphere, proportionally mix ABS resin, toughening agent, compatibility agent, weathering agent, antioxidant, lubricant and dispersant uniformly at 100℃ for 2h, then add them from the main feeding port of double screw extruder, proportionally add spray-free metal-imitating masterbatch from the side feeding port of double screw extruder, control the barrel temperature of double screw extruder at 230℃, screw rotation speed at 300rpm and vacuum degree at 0.06MPa, and then melt blend and extrude and granulate to obtain the extrusion spray-free ABS alloy material. In the present example, TME element and ZME element are arranged at the middle position of double screw extruder, and toothed disc is arranged at the head position.

[0041] The preparation method of the spray-free metal-imitating masterbatch of the present example includes the following three steps S1-S3: S1. Put atomized aluminum powder with particle size of 10-60μm into a ball mill, grind with steel column with diameter of 1.0-4.0mm at a speed of 30r / min for 600min, and then screen by combined screening process of linear vibration screen and lelo screen to obtain aluminum pigment with thick cake structure with particle size of 30-100μm and thickness-diameter ratio of 1:3-6; S2. The thick-cake-structure aluminum pigment obtained in step S1, anhydrous ethanol, ammonia water (25% concentration), and tetraethyl orthosilicate were stirred and mixed under a protective atmosphere, and the temperature was raised to 60°C for reaction for 3 hours. Then, a silane coupling agent (obtained by mixing methyl triethoxysilane, vinyl triethoxysilane, and dimethyl dimethoxysilane at a mass ratio of 2:1:1) was added, and stirring was performed at room temperature for 48 hours. After the reaction was completed, the product was filtered, washed with anhydrous ethanol three times, and then dried at 80°C under vacuum for 6 hours to obtain the modified silica-coated aluminum pigment. The amount ratio of the silane coupling agent, anhydrous ethanol, ammonia water, thick-cake-structure aluminum pigment, and tetraethyl orthosilicate was 5 g: 300 mL: 9 mL: 7 g: 6 g. S3. The modified silica-coated aluminum pigment obtained in step S2 was subjected to copolymerization and crosslinking reaction with acrylonitrile to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres, and post-treatment was performed to obtain a spray-free metal-imitating master batch. The specific process was as follows: the modified silica-coated aluminum pigment and a surfactant were uniformly mixed in deionized water, and acrylonitrile was added. Stirring was performed at 85°C for 3 hours, and then an initiator and a crosslinking agent were added and stirring was continuously performed. The amount ratio of the modified silica-coated aluminum pigment, surfactant, acrylonitrile, initiator, and crosslinking agent was 1.2 g: 80 mg: 4 mL: 70 mg: 35 mg. After the reaction was completed, the reaction system was cooled to room temperature to obtain aluminum pigment-silica-polyacrylonitrile composite microspheres. After the reaction was completed, the product was filtered, washed with anhydrous ethanol three times, and then dried at 80°C for 6 hours to obtain a spray-free metal-imitating master batch.

[0042] Comparative Example 1 The present comparative example provides a spray-free metal-imitating master batch prepared by the same method as in Example 1. The difference between the present comparative example and Example 1 is that, in the preparation of the spray-free metal-imitating master batch of the present comparative example, only dimethyl dimethoxysilane was used as the silane coupling agent in step S2, and the amount ratio of the dimethyl dimethoxysilane, anhydrous ethanol, ammonia water, thick-cake-structure aluminum pigment, and tetraethyl orthosilicate was 1 g: 200 mL: 5 mL: 5 g: 4 g.

[0043] Comparative Example 2 The present comparative example provides a spray-free metal-imitating master batch prepared by the same method as in Example 1. The difference between the present comparative example and Example 1 is that, in the preparation of the spray-free metal-imitating master batch of the present comparative example, no initiator was added in step S2.

[0044] Comparative Example 3 The present comparative example provides an extruded spray-free ABS alloy material, which adopts the same implementation as Example 1, and the difference from Example 1 is that the spray-free metal-imitating master batch of the present comparative example is prepared by the following steps S1: the atomized aluminum powder with a particle size of 10-60 μm is put into a ball mill, a steel column with a diameter of 10-20 mm is used to grind at a speed of 150 r / min for 2000 min, and then the linear vibration screen and the lelo screen are combined for screening, so that the aluminum pigment with a flaky structure, a particle size of 30-100 μm and a thickness-diameter ratio of 1:20-100 is obtained.

[0045] Comparative Example 4 The present comparative example provides an extruded spray-free ABS alloy material, which adopts the same implementation as Example 1, and the difference from Example 1 is that the spray-free metal-imitating master batch of the present comparative example is prepared by the following steps S2: no crosslinking agent is added.

[0046] Comparative Example 5 The present comparative example provides an extruded spray-free ABS alloy material, which adopts the same implementation as Example 1, and the difference from Example 1 is that the spray-free metal-imitating master batch of the present comparative example is prepared by the following steps S2: no crosslinking agent is added.

[0047] Test Example The extruded spray-free ABS alloy materials of Examples 1-5 and Comparative Examples 1-5 above are subjected to high-low temperature deformation test (low temperature is -40°C and high temperature is 70°C), low temperature (-40°C) cantilever beam notched impact strength test, washing-up liquid resistance test, and appearance test, and the test results are shown in Table 1. Among them: (1) The washing-up liquid resistance test method is as follows: 1A type tensile sample (total length 150 mm) specified in GB / T1040.2 is prepared from the extruded spray-free ABS alloy material, a total of 10 samples are prepared and placed on a jig with a length of 145 mm, keeping the sample in a bending stress state; then washing-up liquid is applied to the bending part of 5 of the stress samples, and the other 5 are not applied as a control, then wrapped with a wrapping film, after 48 hours of test, the electronic tensile testing machine is used to test the tensile strength T0 of the ABS sample without washing-up liquid and the tensile strength T1 of the ABS sample with washing-up liquid, and the tensile strength retention rate of the 5 ABS samples with washing-up liquid is calculated according to the formula T1*100 / T0; (2) Appearance test: ① The extrusion spray-free ABS alloy materials of Examples 1-5 and Comparative Examples 1-5 were made into standard samples (30 cm*50 cm), and then the number of pits ≥0.1 mm on the samples was counted under an environmental scanning electron microscope and a microscope; ② The extrusion spray-free ABS alloy materials of Examples 1-5 and Comparative Examples 1-5 were made into 100 standard samples (30 cm*90 cm*0.25 mm), and then the number of flow mark weld lines on each standard sample was counted under a daylight lamp to obtain the flow mark weld line rejection rate; (3) High and low temperature deformation test: The extrusion spray-free ABS alloy materials of Examples 1-5 and Comparative Examples 1-5 were made into standard samples (30 cm*50 cm), and then the samples were stored at low temperature (-40℃) and high temperature (70℃) for 72 hours, respectively, and the gap change of the samples was observed.

[0048] Table 1 Performance test results

[0049] According to the results in Table 1, it can be seen that: Examples 1-5 compared with Comparative Example 5: The extrusion spray-free ABS alloy materials prepared by Examples 1-5 have lower flow mark weld line rejection rate and pit number, which shows that the spray-free metal-imitating master batch of the application can solve the defects such as flow mark weld line and pit of ABS alloy materials; The extrusion spray-free ABS alloy materials prepared by Examples 1-5 can still maintain a high tensile retention rate after the dishwashing detergent corrosion test, and the high and low temperature deformation gap is not obvious, which shows that the spray-free metal-imitating master batch of the application can prevent the reaction between oil stains and rubber molecules and aging, can improve the mechanical properties and stability of the spray-free ABS alloy materials, and improve the high and low temperature deformation resistance of the materials; Example 1 compared with Comparative Example 1, Comparative Example 2, Comparative Example 4: Comparative Example 1 is not enough to modify the silicon dioxide on the surface of the aluminum pigment when preparing the spray-free metal-imitating master batch due to the use of a small amount of silane coupling agent, and when cross-linking with acrylonitrile, the complete network structure of O-Si-O functional groups and cyano groups interwoven on the surface of the aluminum pigment cannot be formed, which leads to a significant increase in the scrap rate of the flow mark weld line, a significant decrease in the tensile retention rate after the washing-up liquid corrosion test, and a significant increase in the number of pits; Comparative Example 2 is not copolymerized with acrylonitrile when preparing the spray-free metal-imitating master batch, and Comparative Example 4 is not cross-linked with acrylonitrile when preparing the spray-free metal-imitating master batch, and Comparative Example 2 and Comparative Example 4 cannot form the network structure of O-Si-O functional groups and cyano groups interwoven on the surface of the aluminum pigment, which leads to a large increase in the scrap rate of the flow mark weld line, a large decrease in the tensile retention rate after the washing-up liquid corrosion test, a significant increase in the number of pits, and a significant increase in the high-low temperature deformation gap; this shows that the acrylonitrile grafted aluminum powder coating layer can improve the compatibility of ABS resin and aluminum powder, reduce the appearance defects such as flow mark weld line and pitted pit, and the like; Example 1 compared with Comparative Example 3: the aluminum pigment in Comparative Example 3 is in a sheet structure, which leads to a significant increase in the scrap rate of the flow mark weld line; this shows that the thick cake structure of the spray-free metal-imitating master batch plays a key role in eliminating the appearance defects such as pits, flow mark weld lines, and the like of the material.

[0050] The technical features of the above-described embodiments can be combined in any manner, and to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, however, as long as the combinations of the technical features do not exist, they should be considered as the scope of the description.

[0051] The above-described embodiments only express several embodiments of the present application, the description is more specific and detailed, but it cannot be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. An extruded, spray-free ABS alloy material, characterized in that, It is prepared from the following components by weight: ABS resin 70~90 parts, spray-free metal-imitating masterbatch 5~15 parts, toughening agent 2~8 parts, compatibility agent 1~3 parts, weathering agent 0.1~0.5 parts, antioxidant 0.2~1 parts, lubricant 0.2~1 parts, dispersing agent 0.5~2 parts.

2. The extruded, spray-freeze ABS alloy material of claim 1, wherein, The preparation method of the spray-free metal-imitating masterbatch comprises the following steps: S1. Atomized aluminum powder is ground and sieved to obtain aluminum pigment with thick cake structure; S2. The thick cake structure aluminum pigment is mixed with anhydrous ethanol and ammonia water under a protective atmosphere, tetraethyl orthosilicate is added, heated and reacted, then silane coupling agent is added, stirred at room temperature, and post-treated to obtain modified silica-coated aluminum pigment; S3. The modified silica-coated aluminum pigment is subjected to copolymerization crosslinking reaction with acrylonitrile, post-treated to obtain spray-free metal-imitating masterbatch.

3. The extruded, spray-freeze ABS alloy material of claim 2, wherein, In step S1, the particle size of the atomized aluminum powder is 10~60μm; and / or, the grinding is to put the atomized aluminum powder into a ball mill, use steel columns with a diameter of 1.0~4.0mm, and grind at a speed of 30r / min for 300~900min; and / or, the sieving is to sieve by combined sieving process of linear vibration sieve and lelo sieve to obtain aluminum pigment with thick cake structure with a particle size of 30~100μm and a thickness-diameter ratio of 1:3~6.

4. The extruded, spray-freeze ABS alloy material of claim 2, wherein, In step S2, the silane coupling agent comprises methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane, and the mass ratio of methyl triethoxysilane, vinyl triethoxysilane and dimethyl dimethoxysilane is 1~3:1:1; and / or, the amount ratio of the silane coupling agent, anhydrous ethanol, ammonia water, thick cake structure aluminum pigment, tetraethyl orthosilicate is 3~8g:200~550mL:5~15mL:5~10g:4~8g, and the concentration of the ammonia water is 25%; and / or, the heating reaction is stirring at 40~60℃ for 2~4h, and the drying is drying at 80~85℃ in a vacuum environment for 5~7h.

5. The extruded, spray-freeze-dried ABS alloy material of claim 2, wherein, In step S3, the copolymerization crosslinking reaction comprises the following steps: the modified silica-coated aluminum pigment, a surfactant and deionized water are uniformly mixed, acrylonitrile is added, heated and stirred, then an initiator and a crosslinking agent are added and continuously stirred, after the reaction is completed, the mixture is cooled to room temperature, filtered, washed, dried and granulated to obtain spray-free metal-imitating masterbatch.

6. The extruded, spray-freeze-dried ABS alloy material of claim 5, wherein, The amount ratio of the modified silica-coated aluminum pigment, the surfactant, acrylonitrile, the initiator and the crosslinking agent is 1~2g:0.05~0.1g:3~6mL:0.06~0.12g:0.025~0.05g; and / or, the surfactant is sodium dodecyl sulfate, the initiator is potassium persulfate, and the crosslinking agent is N,N'-methylene bisacrylamide; and / or, the heating and stirring is stirring at 80~95℃ for 2~4h, and the drying is drying at 80~85℃ in a vacuum environment for 5~7h.

7. The extruded, spray-freeze-dried ABS alloy material of claim 1, wherein, The ABS resin is acrylonitrile-butadiene-styrene copolymer, and the acrylonitrile-butadiene-styrene copolymer is obtained by mixing emulsion method prepared acrylonitrile-butadiene-styrene copolymer and body method prepared acrylonitrile-butadiene-styrene copolymer in a mass ratio of 3:

1.

8. The extruded, spray-freeze-dried ABS alloy material of claim 1, wherein, The toughening agent is styrene-ethylene-butylene-styrene block copolymer; and / or, the compatilizer is carboxylic acid graft compatilizer; and / or, the antioxidant is hindered phenolic antioxidant; and / or, the lubricant is lubricant TAS-2A; and / or, the dispersant is poly methacrylic acid derivative dispersant; and / or, the light stabilizer is benzotriazole light stabilizer.

9. A method of making the extruded, spray-freeze-dried ABS alloy material of any one of claims 1-8, characterized in that, It comprises the following steps: After the ABS resin, the toughening agent, the compatilizer, the weathering agent, the antioxidant, the lubricant and the dispersant are mixed uniformly in a protective atmosphere, they are added into the main feeding port of the extruder, the paint-free metal-imitating master batch is added into the side feeding port of the extruder, and then the melt blending and extrusion granulation are carried out, so that the paint-free ABS alloy material is obtained.

10. The method of making an extruded, spray-freeze ABS alloy material of claim 9, wherein, The mixing temperature of the ABS resin, the toughening agent, the compatilizer, the weathering agent, the antioxidant, the lubricant and the dispersant is 80-100 DEG C, and the mixing time is 2-4 h; and / or, the extruder is a double screw extruder, the barrel temperature of the extruder is 200-230 DEG C, the screw rotating speed is 200-300 rpm, and the vacuum degree is 0.06-0.1 MPa; and / or, the TME element and the ZME element are arranged at the middle position of the extruder, and the toothed disc is arranged at the head position of the extruder.

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