Scratch-resistant PC and ABS composite material, preparation method thereof and automobile interior trim strip

Abstract

The invention relates to the technical field of automobile parts, in particular to an anti-scratch PC (polycarbonate) and ABS (acrylonitrile butadiene styrene) composite material, a preparation method of the anti-scratch PC and ABS composite material and an automobile interior trim strip. The scratch-resistant PC and ABS composite material is prepared from the following raw materials in parts by mass: 50 to 70 parts of PC resin, 15 to 45 parts of ABS resin, 1 to 2 parts of compatilizer, 4 to 6 parts of color master batch and 10 to 14 parts of scratch-resistant master batch, the scratch-resistant master batch is polyamide master batch doped with fluorine-containing alkyl-vinyl POSS (Polyhedral Oligomeric Silsesquioxane), and the fluorine-containing alkyl-vinyl POSS is connected to the polyamide master batch through vinyl. The scratch-resistant PC and ABS composite material, the preparation method thereof and the automobile interior trim strip have excellent scratch resistance and sunscreen cream resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of automobile parts, and more particularly to an anti-scratch PC and ABS composite material, a preparation method thereof, and an automobile interior trim strip. Background Art

[0002] Polycarbonate (PC) is a commonly used engineering plastic with excellent mechanical, heat resistance, and electrical properties. However, due to its molecular rigidity and steric hindrance, PC has a high melting temperature, difficult processing, and is prone to stress cracking. When PC is blended with acrylonitrile / butadiene / styrene copolymer (ABS) resin, it combines the heat resistance, dimensional stability, and mechanical properties of PC with low melt viscosity and good processing fluidity. Consequently, ABS-PC composites are widely used in the production of automotive interior trim.

[0003] However, with the improvement of people's living standards, while meeting their material needs, girls' demand for decoration and beauty has gradually increased, among which hand care is also extremely important. For example, in order to improve the beauty of nails, girls usually decorate their hands with manicures, and in order to reduce the damage of the sun to their hands, they will use sunscreen to protect them. However, the above operations will cause damage to the car's interior trim.

[0004] Specifically, after women apply manicures to their nails, the spiked nails can easily scratch the interior trim. Furthermore, after women apply sunscreen to their hands, the sunscreen can easily remain on the surface of the trim. Prolonged sunscreen contact can cause discoloration, bubbles, and wrinkles on the trim. Therefore, there is an urgent need for a PC / ABS composite material with both excellent scratch and sunscreen resistance for the production of automotive interior trim. Summary of the Invention

[0005] In order to improve the defects of conventional PC and ABS composite materials, such as poor scratch resistance and sunscreen resistance, the present application provides a scratch-resistant PC and ABS composite material, a preparation method thereof, and an automotive interior trim strip.

[0006] In the first aspect, the present application provides a scratch-resistant PC and ABS composite material, which adopts the following technical solution: A scratch-resistant PC and ABS composite material comprises the following raw materials in parts by mass: 50-70 parts of PC resin, 15-45 parts of ABS resin, 1-2 parts of a compatibilizer, 4-6 parts of a masterbatch, and 10-14 parts of an anti-scratch masterbatch; the anti-scratch masterbatch is a polyamide masterbatch doped with a fluoroalkyl-vinyl POSS, and the fluoroalkyl-vinyl POSS is connected to the polyamide masterbatch via a vinyl group.

[0007] The erosion of sunscreen on PC and ABS composite materials is mainly caused by the penetration of solvents or lipid substances. The polyamide molecular chain contains a large number of amide groups, which can form hydrogen bonds between these amide groups, thereby enhancing the interaction between the polyamide molecular chains, making the molecular chains more tightly arranged, and making it more difficult for solvent molecules to penetrate into the interior of the polymer. In other words, polyamide has extremely excellent solvent resistance. When polyamide is added to PC and ABS composite materials, while retaining the original excellent comprehensive performance of PC and ABS composite materials, its sunscreen resistance can also be improved.

[0008] As for the scratch resistance of PC and ABS composite materials, nanoparticles are usually added at present. Nanoparticles have a high specific surface area and can significantly enhance the interaction between the particle surface and PC and ABS composite materials, thereby significantly improving the ability of PC and ABS composite materials to resist mechanical deformation. However, the high specific surface area of ​​nanoparticles also makes them prone to agglomeration and difficult to disperse in polymers.

[0009] POSS (polyhedral oligomeric silsesquioxane) is an organic-inorganic hybrid nanomaterial whose molecules possess a rigid inorganic core formed by Si-O-Si. This inorganic core structure, similar to silica, possesses high hardness and can effectively resist scratches from external objects. Furthermore, the chemical structure present on the POSS surface can reduce surface friction, allowing scratching objects to slide across the surface, thereby reducing scratch damage. Furthermore, the organic groups present on the POSS surface can also improve the compatibility between its polymers. In other words, POSS combines the rigidity of inorganic nanomaterials with the flexibility of organic polymers. Therefore, when added to PC and ABS composites, it can effectively enhance the scratch resistance of these composites while also effectively avoiding the adverse effects of agglomeration.

[0010] Specifically, the present application specifically selects fluoroalkyl-vinyl POSS, in which the vinyl group can be in situ polymerized during the preparation of polyamide masterbatch, and the carbon-fluorine bond in the fluoroalkyl group has high bond energy, short bond distance, and low surface energy, making it difficult for oil molecules to adhere to the polymer surface, exhibiting extremely excellent oleophobic properties. Therefore, it can further improve the solvent resistance of PC and ABS composite materials.

[0011] In summary, when polyamide masterbatch doped with fluoroalkyl-vinyl POSS is added to PC and ABS composite materials, the prepared PC and ABS composite materials will have excellent scratch resistance and sunscreen resistance.

[0012] Preferably, the anti-scratch masterbatch comprises the following raw materials in parts by mass: 10-16 parts of fluorinated alkyl-vinyl POSS, 10-20 parts of acrylamide monomer, 10-15 parts of acrylate monomer, 40-60 parts of polyamide resin, 4-6 parts of dispersant, 1-2 parts of initiator, 2-4 parts of caprolactam and 10-20 parts of solvent.

[0013] Preferably, the acrylamide monomer is one of N-isopropyl acrylamide, N-isopropyl methacrylamide, N-hydroxymethyl acrylamide, N,N-dimethyl acrylamide and dimethylaminopropyl (meth) acrylamide; and / or; The acrylic acid ester monomer is one of butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, amyl methacrylate, dimethylaminomethyl (meth)acrylate and cyclohexyl acrylate; and / or; The dispersant is one of ethylene bisstearamide and calcium stearate; and / or; The initiator is one of azobisisobutyronitrile, sodium persulfate and dibenzoyl peroxide; and / or; The solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and xylene.

[0014] Preferably, the anti-scratch masterbatch is prepared by the following preparation method: In-situ polymerization: First, mix fluoroalkyl-vinyl POSS, caprolactam and 1 / 2 solvent, then add acrylamide monomer and acrylate monomer in sequence, mix them evenly under ultrasonication for 20-40 minutes, add initiator, introduce nitrogen, heat to 60-80°C, and react for 4-8 hours to obtain a prepolymer; Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 20-40 minutes, then add polyamide resin and 1 / 2 solvent and mix well. Transfer to a banbury mixer and mix for 30-60 minutes at a mixing temperature of 140-180°C to obtain a banbury product. Extrusion granulation: transfer the mixed product to a twin-screw extruder for extrusion granulation, with a feeding temperature of 180-200°C, a melting temperature of 220-240°C, and an extrusion temperature of 210-230°C.

[0015] Preferably, the fluorinated alkyl-vinyl POSS is prepared by reacting methacryloxypropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane, and the mass ratio of methacryloxypropyltrimethoxysilane to tridecafluorooctyltrimethoxysilane is 1:(6-8).

[0016] Preferably, the fluorinated alkyl-vinyl POSS is prepared by the following preparation method: First, 900-1100 mL of dichloromethane, 600-800 g of tridecafluorooctyltrimethoxysilane and 90-110 g of methacryloyloxypropyltrimethoxysilane were mixed, stirred, heated to 40°C and refluxed, and then 90-110 mL of potassium hydroxide aqueous solution was added dropwise. The concentration of the potassium hydroxide aqueous solution was 30-40 g / L, and the reaction was stirred again for 72 hours. Finally, the reaction solution was adjusted to neutrality with acetic acid and washed with water. The lower layer of liquid was removed and the dichloromethane was removed by rotary evaporation at a temperature of 30-40°C to obtain fluorinated alkyl-vinyl POSS.

[0017] Preferably, the anti-scratch masterbatch further comprises 20-30 parts of self-repairing capsules, and the self-repairing capsules are prepared by the following steps: S1. Deionized water, urea, and 37% formaldehyde aqueous solution are first mixed in a mass ratio of 2:1:(2-3), and then the pH value is adjusted to 8-9 with triethanolamine. The mixture is then heated at a temperature of 70-80° C. for 1 hour, during which 1% by weight of ammonium chloride and 0.5% by weight of resorcinol are added. Finally, the product is cooled to room temperature to obtain a urea-formaldehyde resin prepolymer. S2, deionized water and dealkalized lignin are mixed in a mass ratio of 1000: (2-4), the pH value is then adjusted to 10-11 with ammonia water, and the pH value is then adjusted to 2-3 with hydrochloric acid, and finally methylene diphenyl diisocyanate and isophorone diisocyanate are added to the solution in a mass ratio of (3-5) : 1, with methylene diphenyl diisocyanate and isophorone diisocyanate accounting for 50-70% of the total mass, and then stirred at high speed to obtain a polyurea microsphere emulsion containing a self-healing medium; S3. Add urea-formaldehyde resin prepolymer and polyurea microsphere emulsion containing self-healing medium to 0.1% PVA solution in a mass ratio of 1:1 until an emulsion is formed, and then adjust the pH value of the solution to 8-9 with triethanolamine. Stir for 3-5 hours at a water bath temperature of 70-80°C. After the reaction is completed, remove the precipitate, wash and dry to obtain self-healing capsules.

[0018] Even though the scratch resistance of automotive interior parts has been improved, there is still a possibility of scratches on automotive interior parts. Since the shell of the self-repairing capsule is made of urea-formaldehyde resin and polyurea, it has a certain brittleness. When external force damages the automotive interior parts, the self-repairing capsule will break first, causing the self-repairing media methylene diphenyl diisocyanate and isophorone diisocyanate in the self-repairing capsule to flow out and fill the scratch gaps. The isocyanate groups of methylene diphenyl diisocyanate and isophorone diisocyanate can react with water molecules, thereby playing a role in scratch repair.

[0019] Preferably, the anti-scratch masterbatch is prepared by the following preparation method: Modification of self-repairing capsules: First, the self-repairing capsules are dispersed in caprolactam, and then fluorinated alkyl-vinyl POSS is added and mixed to obtain modified self-repairing capsules; In-situ polymerization: First, the modified self-healing capsules and 1 / 2 of the solvent are mixed, and then acrylamide monomers and acrylate monomers are added in sequence. Ultrasonic mixing is performed for 20-40 minutes to mix evenly. An initiator is added, nitrogen is introduced, and the temperature is raised to 60-80°C. The reaction is carried out for 4-8 hours to obtain a prepolymer. Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 20-40 minutes, then add polyamide resin and 1 / 2 solvent and mix well. Transfer to a banbury mixer and mix for 30-60 minutes at a mixing temperature of 140-180°C to obtain a banbury product. Extrusion granulation: transfer the mixed product to a twin-screw extruder for extrusion granulation, with a feeding temperature of 180-200°C, a melting temperature of 220-240°C, and an extrusion temperature of 210-230°C.

[0020] In this application, the surface of the self-repairing capsules is first modified by silanization, thereby effectively improving the dispersion of the self-repairing capsules in the PC and ABS composite materials, and then promoting the self-repairing capsules to be evenly anchored in various areas of the PC and ABS composite materials, further improving the repair stability of the self-repairing capsules.

[0021] In a second aspect, the present application provides a preparation method, which adopts the following technical solution: A preparation method for preparing the above-mentioned scratch-resistant PC and ABS composite material comprises the following steps: (1) Adding the masterbatch and the compatibilizer into the injection molding machine, and then mixing and granulating to obtain the color base material; (2) adding the coloring base material, anti-scratch masterbatch, PC resin and ABS resin into an injection molding machine, and then injection molding to obtain an anti-scratch PC and ABS composite material; The specific process parameters of the above-mentioned injection molding machine are: the temperature of zone 1 is 235℃, the temperature of zone 2 is 250℃, the temperature of zone 3 is 255℃, the temperature of zone 4 is 260℃, the temperature of zone 5 is 265℃, the temperature of zone 6 is 270℃, the temperature of zone 7 is 265℃, the temperature of zone 8 is 260℃, the temperature of zone 9 is 260℃, the temperature of zone 10 is 260℃, and the screw speed is 400r / min.

[0022] In a third aspect, the present application provides an automotive interior trim strip, which adopts the following technical solution: An automobile interior trim strip is prepared from the above-mentioned anti-scratch PC and ABS composite material.

[0023] In summary, this application has the following beneficial effects: 1. The erosion of sunscreen on PC and ABS composite materials is mainly caused by the penetration of solvents or lipid substances. The polyamide molecular chain contains a large number of amide groups, which can form hydrogen bonds between these amide groups, thereby enhancing the interaction between the molecular weights of polyamide, making the molecular weight arrangement more compact, and making it more difficult for solvent molecules to penetrate into the interior of the polymer. In other words, polyamide has extremely good solvent resistance. When polyamide is added to PC and ABS composite materials, while retaining the original excellent comprehensive performance of PC and ABS composite materials, its sunscreen resistance can also be improved.

[0024] 2. POSS (polyhedral oligomeric silsesquioxane) is an organic-inorganic hybrid nanomaterial whose molecules have a rigid inorganic core formed by Si-O-Si. This inorganic core structure is similar to silica and has high hardness, which can effectively resist scratches from external objects. At the same time, the chemical structure on the surface of POSS can also reduce the friction on the surface of the material, allowing the scratching object to slide on the surface of the material, thereby reducing scratch damage. In addition, the organic groups on the surface of POSS can also improve the compatibility between its polymers. In other words, POSS combines the rigidity of inorganic nanomaterials with the flexibility of organic polymers. Therefore, when it is added to PC and ABS composite materials, it can effectively improve the scratch resistance of PC and ABS composite materials while effectively avoiding the adverse effects of agglomeration.

[0025] 3. This application specifically uses fluoroalkyl-vinyl POSS, in which the vinyl group can be in situ polymerized during the preparation of polyamide masterbatch, and the carbon-fluorine bond in the fluoroalkyl group has high bond energy, short bond distance, and low surface energy, making it difficult for oil molecules to adhere to the polymer surface, exhibiting extremely excellent oleophobic properties. Therefore, it can further improve the solvent resistance of PC and ABS composite materials. DETAILED DESCRIPTION

[0026] PC resin 303-10; ABS resin PA-758; polyamide resin GV-5H; Dongguan Caijian black masterbatch; compatibilizer: maleic anhydride grafted styrene CAS: 9011-13-6; The acrylamide monomer is a mixture of N-isopropylacrylamide and N-hydroxymethylacrylamide, and the mass ratio of N-isopropylacrylamide to N-hydroxymethylacrylamide is 2:1; N-isopropylacrylamide CAS: 2210-25-5; N-hydroxymethylacrylamide CAS: 924-42-5; The acrylate monomer is 2-ethylhexyl acrylate CAS: 103-11-17; the dispersant is ethylene bisstearamide CAS: 110-30-50; the antioxidant is hindered phenol antioxidant 1010; the initiator is azobisisobutyronitrile CAS: 78-67-1; the solvent is selected from N,N-dimethylformamide CAS: 68-12-2; methacryloxypropyltrimethoxysilane CAS: 2530-85-0; tridecafluorooctyltrimethoxysilane CAS: 3069-40-7; phenyltrimethylsilane CAS: 766-08-5; dichloromethane CAS: 75-09-2; potassium hydroxide CAS: 1310-58-3; acetic acid CAS: 64-19-7; urea CAS: 57-13-6; 37% methyl Aldehyde aqueous solution (Merck); triethanolamine (CAS: 102-71-6); ammonium chloride (CAS: 12125-02-9); resorcinol (CAS: 108-46-3); dealkalized lignin (CAS: 9005-53-2); ammonia (CAS: 1336-21-6); hydrochloric acid (CAS: 7647-01-0); methylene diphenyl diisocyanate (CAS: 2536-05-2); isophorone diisocyanate (CAS: 4098-71-9); PVA (CAS: 9002-89-5).

[0027] Example 1

[0028] A scratch-resistant PC and ABS composite material, comprising the following raw materials in parts by weight: 60 kg PC resin, 30 kg ABS resin, 1.5 kg compatibilizer, 5 kg color masterbatch, and 12 kg anti-scratch masterbatch; The preparation method of the scratch-resistant PC and ABS composite material comprises the following steps: (1) Adding the masterbatch and the compatibilizer into the injection molding machine, and then mixing and granulating to obtain the color base material; (2) Adding the coloring base material, anti-scratch masterbatch, PC resin and ABS resin into the injection molding machine, and then injection molding to obtain the anti-scratch PC and ABS composite material; The specific process parameters of the above injection molding machine are: zone 1 temperature is 235°C, zone 2 temperature is 250°C, zone 3 temperature is 255°C, zone 4 temperature is 260°C, nozzle temperature is 250°C, and screw speed is 400r / min.

[0029] Scratch-resistant PC and ABS composite materials are used to prepare automotive interior parts.

[0030] The anti-scratch masterbatch includes the following raw materials in parts by mass: 13 kg of fluoroalkyl-vinyl POSS, 15 kg of acrylamide monomer, 13 kg of acrylate monomer, 50 kg of polyamide resin, 5 kg of dispersant, 1.5 kg of initiator, 3 kg of caprolactam and 15 kg of solvent; The anti-scratch masterbatch is prepared by the following steps: In situ polymerization: First, fluorinated alkyl-vinyl POSS, caprolactam, and 1 / 2 solvent were mixed, followed by the addition of acrylamide monomers and acrylate monomers, followed by ultrasonic mixing for 30 minutes, the addition of initiator, the introduction of nitrogen, the heating to 70°C, and the reaction for 6 hours to obtain a prepolymer; Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 30 minutes, then add polyamide resin and mix evenly. Transfer to an internal mixer and mix for 40 minutes at a mixing temperature of 160°C to obtain a mixed product. Extrusion granulation: The mixed product was transferred to a twin-screw extruder for extrusion granulation, with a feeding temperature of 190°C, a melting temperature of 230°C, and an extrusion temperature of 220°C.

[0031] Fluoroalkyl-vinyl POSS is prepared by reacting methacryloxypropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane, and the mass ratio of methacryloxypropyltrimethoxysilane to tridecafluorooctyltrimethoxysilane is 1:7. Fluorinated alkyl-vinyl POSS is prepared by the following preparation method: First, 1000 mL of dichloromethane, 700 g of tridecafluorooctyltrimethoxysilane and 100 g of methacryloyloxypropyltrimethoxysilane were mixed, stirred, heated to 40°C and refluxed, and then 100 mL of potassium hydroxide aqueous solution was added dropwise. The concentration of the potassium hydroxide aqueous solution was 35 g / L. The reaction was stirred again for 72 hours. Finally, the reaction solution was adjusted to neutrality with acetic acid and washed with water. The lower layer of liquid was removed and the dichloromethane was removed by rotary evaporation at 35°C to obtain fluorinated alkyl-vinyl POSS.

[0032] Example 2

[0033] The difference from Example 1 is that the anti-scratch masterbatch is also added with 25 kg of self-repairing capsules; The self-repairing capsule is prepared by the following steps: S1. Deionized water, urea, and 37% formaldehyde aqueous solution were first mixed in a mass ratio of 2:1:2.7, and then the pH value was adjusted to 8 with triethanolamine. The mixture was then heated at 75° C. for 1 hour, during which 1% of the total mass of ammonium chloride and 0.5% of resorcinol were added. Finally, the product was cooled to room temperature to obtain a urea-formaldehyde resin prepolymer. S2. Deionized water and dealkalized lignin are mixed in a mass ratio of 1000:3, and then the pH value is adjusted to 11 with ammonia water, and then the pH value is adjusted to 3 with hydrochloric acid. Finally, methylene diphenyl diisocyanate and isophorone diisocyanate are added to the solution in a mass ratio of 4:1, and methylene diphenyl diisocyanate and isophorone diisocyanate account for 60% of the total mass. Then, the mixture is stirred at a high speed to obtain a polyurea microsphere emulsion containing a self-healing medium; S3. Add urea-formaldehyde resin prepolymer and polyurea microsphere emulsion containing self-healing medium to 0.1% PVA solution in a mass ratio of 1:1 until an emulsion is formed, and then adjust the pH value of the solution to 9 with triethanolamine. Stir in a water bath at 75°C for 4 hours. After the reaction is completed, remove the precipitate, wash and dry it to obtain self-healing capsules.

[0034] The anti-scratch masterbatch is prepared by the following steps: In situ polymerization: First, fluorinated alkyl-vinyl POSS, caprolactam, and 1 / 2 solvent were mixed, followed by the addition of acrylamide monomers and acrylate monomers, followed by ultrasonic mixing for 30 minutes, the addition of initiator, the introduction of nitrogen, the heating to 70°C, and the reaction for 6 hours to obtain a prepolymer; Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 30 minutes, then add polyamide resin, self-repairing capsules and 1 / 2 solvent and mix well. Transfer to an internal mixer and mix for 40 minutes at a mixing temperature of 160°C to obtain a mixed product. Extrusion granulation: The mixed product was transferred to a twin-screw extruder for extrusion granulation, with a feeding temperature of 190°C, a melting temperature of 230°C, and an extrusion temperature of 220°C.

[0035] Example 3

[0036] The difference from Example 2 is that the timing of adding the self-repairing capsules is different, as follows: The anti-scratch masterbatch is prepared by the following steps: Modification of self-repairing capsules: First, the self-repairing capsules are dispersed in caprolactam, and then fluorinated alkyl-vinyl POSS is added and mixed to obtain modified self-repairing capsules; In-situ polymerization: First, the modified self-healing capsules and 1 / 2 of the solvent were mixed, and then acrylamide monomers and acrylate monomers were added in sequence. The mixture was ultrasonically mixed for 30 minutes, and then an initiator was added. Nitrogen was introduced, and the temperature was raised to 70°C. The reaction was carried out for 6 hours to obtain a prepolymer. Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 30 minutes, then add polyamide resin and 1 / 2 solvent and mix well. Transfer to an internal mixer and mix for 45 minutes at 160°C to obtain a mixed product. Extrusion granulation: The mixed product was transferred to a twin-screw extruder for extrusion granulation, with a feeding temperature of 190°C, a melting temperature of 230°C, and an extrusion temperature of 220°C.

[0037] Example 4-Example 5 The difference from Example 3 is that the addition amounts of the components of the anti-scratch masterbatch are different, as shown in Table 1.

[0038] Table 1 Addition amount of each component of the anti-scratch masterbatch of Example 3 to Example 5

[0039] Comparative Example 1 A PC and ABS composite material, comprising the following raw materials in parts by weight: 60 kg PC resin, 30 kg ABS resin, 1.5 kg compatibilizer and 5 kg masterbatch; The preparation method of the scratch-resistant PC and ABS composite material comprises the following steps: (1) Adding the masterbatch and the compatibilizer into the injection molding machine, and then mixing and granulating to obtain the color base material; (2) Adding the coloring base material, PC resin and ABS resin into the injection molding machine, and then injection molding to obtain the anti-scratch PC and ABS composite material; The specific process parameters of the above injection molding machine are: zone 1 temperature is 235°C, zone 2 temperature is 250°C, zone 3 temperature is 255°C, zone 4 temperature is 260°C, nozzle temperature is 250°C, and screw speed is 400r / min.

[0040] Comparative Example 2 The difference from Example 1 is that no fluorinated alkyl-vinyl POSS is added to the anti-scratch masterbatch.

[0041] Comparative Example 3 The difference from Example 1 is that the fluorinated alkyl-vinyl POSS is prepared by reacting methacryloxypropyltrimethoxysilane and phenyltrimethylsilane, and the mass ratio of methacryloxypropyltrimethoxysilane to phenyltrimethylsilane is 1:7.

[0042] Comparative Example 4 The difference from Example 1 is that the fluorinated alkyl-vinyl POSS is prepared by reacting phenyltrimethylsilane and tridecafluorooctyltrimethoxysilane, and the mass ratio of phenyltrimethylsilane to tridecafluorooctyltrimethoxysilane is 1:7.

[0043] 1. Scratch resistance test Ten samples were taken from each of Examples 1 to 5 and Comparative Examples 1 to 4, and the hardness of the samples was tested according to ASTM 3633-00 "Method for Determination of Paint Film Hardness by Pencil Test". The test results were taken as the mode, and the hardness levels from soft to hard were 6B, 5B, 4B, 3B, 2B, 1B, HB, F, 1H, 2H, 3H, 4H, 5H and 6H.

[0044] The test data are shown in Table 2.

[0045] 2. Sunscreen resistance test Ten samples were taken from each of Examples 1 to 5 and Comparative Examples 1 to 4, and then a layer of special gauze was covered on the surface of the samples, and sunscreen (Chando Refreshing Sport Sunscreen) was evenly applied. The samples were placed at 80°C for 24 hours, taken out and cooled to room temperature, and graded according to the discoloration, bubbles, and wrinkles on the surface of the samples. No discoloration, bubbles, or wrinkles on the surface - Level 1; Surface discoloration, no bubbles, no wrinkles - Level 2; Surface discoloration, slight bubbles or slight wrinkles - Level 3; Surface discoloration, slight bubbles, and slight wrinkling - Level 4; Surface discoloration, numerous bubbles, and extensive wrinkling - Level 5.

[0046] The test data are shown in Table 2.

[0047] Table 2 Scratch resistance and sunscreen resistance test table of Examples 1 to 5 and Comparative Examples 1 to 4

[0048] 3. Self-repair performance test Three samples were taken out from Examples 1 to 5 respectively, and then the sample surfaces were scratched using a cone-angle diamond indenter, a normal load of 500 mN, a scratching speed of 100 μm / s, and a scratching time of 1 minute. Then all the samples were immersed in deionized water for 24 hours. After that, the samples were taken out to observe the surface repair conditions and graded. The repair conditions were ranked from low to high as E, D, C, B and A.

[0049] The test data are shown in Table 3.

[0050] Table 3 Self-repairing performance test table of Example 1 to Example 5

[0051] With reference to Comparative Examples 1-2 and in combination with Table 2, it can be seen that the sunscreen resistance of Comparative Example 2 is significantly improved relative to Comparative Example 1, which shows that the sunscreen resistance of PC and ABS composite materials can be improved without adding fluorinated alkyl-vinyl POSS to the friction-resistant masterbatch.

[0052] The reason is that the erosion of sunscreen on PC and ABS composite materials is mainly caused by the penetration of solvents or lipid substances, and the polyamide molecular chain contains a large number of amide groups, which can form hydrogen bonds between these amide groups, thereby enhancing the interaction between the molecular weights of polyamide, the molecular weight arrangement is more compact, and it is more difficult for solvent molecules to penetrate into the interior of the polymer. In other words, polyamide has extremely good solvent resistance. When polyamide is added to PC and ABS composite materials, while retaining the original excellent comprehensive performance of PC and ABS composite materials, its sunscreen resistance can also be improved.

[0053] With reference to Comparative Examples 2-4 and Example 1 and in combination with Table 2, it can be seen that, relative to Comparative Example 2, the scratch resistance of Comparative Examples 3-4 and Example 1 is significantly improved, among which Example 1 has the largest improvement, Example 4 has the smallest improvement, and Example 3 has a medium improvement.

[0054] Meanwhile, compared with Comparative Example 2, the sunscreen resistance of Comparative Example 3 was substantially unchanged, but the sunscreen resistance of Comparative Example 4 was significantly improved, and the sunscreen resistance of Example 1 was further improved.

[0055] This demonstrates that the addition of POSS can effectively improve the scratch resistance of PC and ABS composites. The scratch resistance of PC and ABS composites is particularly outstanding when methacryloyloxypropyltrimethoxysilane is used as one of the raw materials. When POSS is used with tridecafluorooctyltrimethoxysilane as one of the raw materials, the sunscreen resistance of PC and ABS composites is particularly outstanding. Furthermore, when tridecafluorooctyltrimethoxysilane and methacryloyloxypropyltrimethoxysilane are used in combination, the sunscreen resistance of PC and ABS composites is further enhanced.

[0056] The reason is that POSS (polyhedral oligomeric silsesquioxane) is an organic-inorganic hybrid nanomaterial whose molecules have a rigid inorganic core formed by Si-O-Si. This inorganic core structure is similar to silica and has high hardness, which can effectively resist scratches from external objects. At the same time, the chemical structure on the surface of POSS can also reduce the friction on the surface of the material, allowing the scratching object to slide on the surface of the material, thereby reducing scratch damage. In addition, the organic groups on the surface of POSS can also improve the compatibility between its polymers.

[0057] In other words, POSS combines the rigidity of inorganic nanomaterials and the flexibility of organic polymers. Therefore, when it is added to PC and ABS composite materials, it can effectively improve the scratch resistance of PC and ABS composite materials while effectively avoiding the adverse effects of agglomeration.

[0058] Specifically, vinyl groups can be polymerized in situ during the preparation of polyamide masterbatches, and the carbon-fluorine bonds in the fluoroalkyl groups have high bond energy, short bond distances, and low surface energy, making it difficult for oil molecules to adhere to the polymer surface, resulting in extremely good oleophobic properties. Therefore, they can further enhance the solvent resistance of PC and ABS composite materials.

[0059] With reference to Examples 1 to 3 and in combination with Table 3, it can be seen that compared with Example 1, the self-repairing performance of Example 2 is significantly improved, and the self-repairing performance of Example 3 is further improved. This shows that the addition of self-repairing capsules can effectively improve the self-repairing performance of PC and ABS composite materials. Moreover, after first dispersing the self-repairing capsules in caprolactam and then adding fluorinated alkyl-vinyl POSS to mix to obtain modified self-repairing capsules, the prepared PC and ABS composite materials will have better self-repairing performance.

[0060] The reason is that when external forces damage the interior parts of the car, the addition of self-repairing capsules can cause the self-repairing capsules to break first because the shell of the self-repairing capsules is made of urea-formaldehyde resin and polyurea, so it has a certain brittleness, causing the self-repairing capsules to break first, thereby causing the self-repairing media methylene diphenyl diisocyanate and isophorone diisocyanate in the self-repairing capsules to flow out and fill the scratch gaps. The isocyanate groups of methylene diphenyl diisocyanate and isophorone diisocyanate can react with water molecules, thereby playing a role in scratch repair.

[0061] First, silanization modification of the surface of the self-repairing capsules can effectively improve the dispersion of the self-repairing capsules in PC and ABS composite materials, thereby prompting the self-repairing capsules to be evenly anchored in various areas of the PC and ABS composite materials, further improving the repair stability of the self-repairing capsules.

[0062] With reference to Example 1 and Example 4-Example 5 and in combination with Table 2-Table 3, it can be seen that compared with Example 1, the scratch resistance, sunscreen resistance and self-repair performance of Example 4-Example 5 are significantly worse. This shows that when the components of the anti-scratch masterbatch are added in the amounts of Example 1, the prepared PC and ABS composite materials will have better scratch resistance, sunscreen resistance and self-repair performance.

[0063] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make non-creative modifications to the present embodiment as needed, but as long as they are within the scope of the claims of the present application, they are protected by the patent law.

Claims

1. A scratch-resistant PC and ABS composite material, characterized in that: The invention comprises the following raw materials in parts by weight: 50-70 parts of PC resin, 15-45 parts of ABS resin, 1-2 parts of compatibilizer, 4-6 parts of masterbatch and 10-14 parts of anti-scratch masterbatch; the anti-scratch masterbatch is a polyamide masterbatch doped with fluoroalkyl-vinyl POSS, and the fluoroalkyl-vinyl POSS is connected to the polyamide masterbatch through vinyl group.

2. The anti-scratch PC and ABS composite material according to claim 1, characterized in that: The anti-scratch masterbatch comprises the following raw materials in parts by mass: 10-16 parts of fluorinated alkyl-vinyl POSS, 10-20 parts of acrylamide monomers, 10-15 parts of acrylate monomers, 40-60 parts of polyamide resins, 4-6 parts of dispersants, 1-2 parts of initiators, 2-4 parts of caprolactam and 10-20 parts of solvents.

3. The anti-scratch PC and ABS composite material according to claim 2, characterized in that: The acrylamide monomer is one of N-isopropyl acrylamide, N-isopropyl methacrylamide, N-hydroxymethyl acrylamide, N,N-dimethyl acrylamide and dimethylaminopropyl (meth) acrylamide; and / or; The acrylic acid ester monomer is one of butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl methacrylate, amyl methacrylate, dimethylaminomethyl (meth)acrylate and cyclohexyl acrylate; and / or; The dispersant is one of ethylene bisstearamide and calcium stearate; and / or; The initiator is one of azobisisobutyronitrile, sodium persulfate and dibenzoyl peroxide; and / or; The solvent is one of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and xylene.

4. The anti-scratch PC and ABS composite material according to claim 2, characterized in that: The anti-scratch masterbatch is prepared by the following preparation method: In-situ polymerization: First, mix fluoroalkyl-vinyl POSS, caprolactam and 1 / 2 solvent, then add acrylamide monomer and acrylate monomer in sequence, mix them evenly under ultrasonication for 20-40 minutes, add initiator, introduce nitrogen, heat to 60-80°C, and react for 4-8 hours to obtain a prepolymer; Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 20-40 minutes, then add polyamide resin and 1 / 2 solvent and mix well. Transfer to a banbury mixer and mix for 30-60 minutes at a mixing temperature of 140-180°C to obtain a banbury product. Extrusion granulation: transfer the mixed product to a twin-screw extruder for extrusion granulation, with a feeding temperature of 180-200°C, a melting temperature of 220-240°C, and an extrusion temperature of 210-230°C.

5. The anti-scratch PC and ABS composite material according to claim 1, characterized in that: The fluorinated alkyl-vinyl POSS is prepared by reacting methacryloxypropyltrimethoxysilane and tridecafluorooctyltrimethoxysilane, and the mass ratio of methacryloxypropyltrimethoxysilane to tridecafluorooctyltrimethoxysilane is 1:(6-8).

6. The anti-scratch PC and ABS composite material according to claim 5, characterized in that: The fluorinated alkyl-vinyl POSS is prepared by the following preparation method: First, 900-1100 mL of dichloromethane, 600-800 g of tridecafluorooctyltrimethoxysilane and 90-110 g of methacryloyloxypropyltrimethoxysilane were mixed, stirred, heated to 40°C and refluxed, and then 90-110 mL of potassium hydroxide aqueous solution was added dropwise. The concentration of the potassium hydroxide aqueous solution was 30-40 g / L, and the reaction was stirred again for 72 hours. Finally, the reaction solution was adjusted to neutrality with acetic acid and washed with water. The lower layer of liquid was removed and dichloromethane was removed by rotary evaporation at a temperature of 30-40°C to obtain fluorinated alkyl-vinyl POSS.

7. The scratch-resistant PC and ABS composite material according to claim 2, characterized in that: The anti-scratch masterbatch also includes 20-30 parts of self-repairing capsules; The self-repairing capsule is prepared by the following steps: S1. Deionized water, urea, and 37% formaldehyde aqueous solution are first mixed in a mass ratio of 2:1:(2-3), and then the pH value is adjusted to 8-9 with triethanolamine. The mixture is then heated at a temperature of 70-80° C. for 1 hour, during which 1% by weight of ammonium chloride and 0.5% by weight of resorcinol are added. Finally, the product is cooled to room temperature to obtain a urea-formaldehyde resin prepolymer. S2, deionized water and dealkalized lignin are mixed in a mass ratio of 1000: (2-4), the pH value is then adjusted to 10-11 with ammonia water, and the pH value is then adjusted to 2-3 with hydrochloric acid, and finally methylene diphenyl diisocyanate and isophorone diisocyanate are added to the solution in a mass ratio of (3-5) : 1, with methylene diphenyl diisocyanate and isophorone diisocyanate accounting for 50-70% of the total mass, and then stirred at high speed to obtain a polyurea microsphere emulsion containing a self-healing medium; S3. Add urea-formaldehyde resin prepolymer and polyurea microsphere emulsion containing self-healing medium to 0.1% PVA solution in a mass ratio of 1:1 until an emulsion is formed, and then adjust the pH value of the solution to 8-9 with triethanolamine. Stir for 3-5 hours at a water bath temperature of 70-80°C. After the reaction is completed, remove the precipitate, wash and dry it to obtain self-healing capsules.

8. The anti-scratch PC and ABS composite material according to claim 7, characterized in that: The anti-scratch masterbatch is prepared by the following preparation method: Modification of self-repairing capsules: First, the self-repairing capsules are dispersed in caprolactam, and then fluorinated alkyl-vinyl POSS is added and mixed to obtain modified self-repairing capsules; In-situ polymerization: First, the modified self-healing capsules and 1 / 2 of the solvent are mixed, and then acrylamide monomers and acrylate monomers are added in sequence. Ultrasonic mixing is performed for 20-40 minutes to mix evenly. An initiator is added, nitrogen is introduced, and the temperature is raised to 60-80°C. The reaction is carried out for 4-8 hours to obtain a prepolymer. Mixing: Add dispersant to the prepolymer, ultrasonically disperse for 20-40 minutes, then add polyamide resin and 1 / 2 solvent and mix well. Transfer to a banbury mixer and mix for 30-60 minutes at a mixing temperature of 140-180°C to obtain a banbury product. Extrusion granulation: transfer the mixed product to a twin-screw extruder for extrusion granulation, with a feeding temperature of 180-200°C, a melting temperature of 220-240°C, and an extrusion temperature of 210-230°C.

9. A preparation method for preparing the anti-scratch PC and ABS composite material according to any one of claims 1 to 8, characterized in that: The following steps are involved: (1) Adding the masterbatch and the compatibilizer into the injection molding machine, and then mixing and granulating to obtain the color base material; (2) Add the coloring base material, anti-scratch masterbatch, PC resin and ABS resin into the injection molding machine, and then injection mold to obtain the anti-scratch PC and ABS composite material.

10. An automobile interior trim strip, characterized in that: The anti-scratch PC and ABS composite material is prepared from the anti-scratch PC and ABS composite material according to any one of claims 1 to 8.

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