PC-ABS composite material and preparation method and application thereof

Abstract

The invention belongs to the technical field of engineering plastics, and particularly relates to a PC-ABS composite material and a preparation method and application thereof. The PC resin is used as a matrix, and the mica powder with a specific diameter-thickness ratio and a specific mesh number is added, so that the shear stress of the matrix and glue can be reduced when the temperature rises; meanwhile, due to the high radius-thickness ratio of the mica powder, the reactivity of the mica powder and the polyurethane adhesive is enhanced, and the bonding force between the base material and the adhesive is further remarkably improved. On the basis, ABS resin with a specific rubber phase particle size is further introduced, so that good mechanical properties of the material can be maintained, shielding on the effect of the mica powder can be avoided, the overall mechanical properties can be synergistically enhanced, and finally, the PC-ABS composite material has high toughness, high stripping force and excellent heat-resistant bonding stability; and the material can be widely applied to automotive interior cladding parts.

Description

Technical Field

[0001] This invention belongs to the field of engineering plastics technology. More specifically, it relates to a PC-ABS composite material, its preparation method, and its application. Background Technology

[0002] Overlay processing, a key post-processing method for automotive interior plastic products, effectively enhances the tactile feel and comfort of the interior by bonding fabrics such as leather and felt to the surface of a plastic substrate, thus gaining widespread favor from OEMs and consumers. Among commonly used interior plastics such as PC / ABS, ABS, and PP, PC / ABS alloy has become the preferred choice for many demanding applications due to its excellent heat resistance and low-temperature impact resistance. However, this type of material also has significant drawbacks: it is prone to significant dimensional changes when subjected to drastic temperature variations, leading to substantial shear stress between the overlay layer and the substrate, which can cause fabric detachment and severely affect product durability and aesthetics.

[0003] Currently, although the commonly used PC / ABS alloy performs well in terms of mechanical strength, its bonding strength with the covering material is still insufficient. Especially under high-temperature conditions, delamination occurs frequently, becoming a key technical bottleneck restricting the quality and reliability of interior materials. Summary of the Invention

[0004] The technical problem to be solved by the present invention is to overcome the shortcomings of the commonly used PC / ABS alloy in the market, which, although it performs well in terms of mechanical strength, still has insufficient bonding strength with the coating material, especially under high temperature conditions, and delamination problems occur frequently. The present invention provides a PC-ABS composite material.

[0005] The purpose of this invention is to provide a method for preparing the PC-ABS composite material.

[0006] Another object of the present invention is to provide the application of the PC-ABS composite material.

[0007] Another object of the present invention is to provide a coated article.

[0008] The above-mentioned objective of this invention is achieved through the following technical solution:

[0009] This invention protects a PC-ABS composite material, which, by weight, comprises the following components: PC resin (polycarbonate) 40-80 parts; ABS resin (acrylonitrile-butadiene-styrene terpolymer) 5-40 parts; mica powder 5-20 parts; The mica powder has a mesh size of 300 or greater. The aspect ratio of the mica powder is greater than or equal to 65:1; The average particle size of the rubber phase of the ABS resin is greater than or equal to 0.5µm.

[0010] This invention uses PC resin as a matrix and adds mica powder with a specific aspect ratio and mesh size. This reduces the shear stress between the substrate and the adhesive when the temperature rises. Simultaneously, thanks to the high aspect ratio of the mica powder, its reactivity with the polyurethane adhesive is enhanced, significantly improving the adhesion between the substrate and the adhesive. Furthermore, the introduction of ABS resin with a specific rubber phase particle size maintains the material's good mechanical properties while avoiding obscuring the effect of the mica powder. This also synergistically enhances the overall mechanical properties, ultimately giving the PC-ABS composite material high toughness, high peel strength, and excellent heat-resistant adhesive stability.

[0011] Preferably, the PC resin accounts for no less than 41% of the mass percentage of the PC-ABS composite material.

[0012] Specifically, the PC resin can be 40, 42, 45, 50, 55, 60, 65, 70, 75, 80 parts, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0013] The system of the present invention does not limit the type of PC. The polycarbonate is preferably bisphenol A type polycarbonate, but self-made PC can also be used.

[0014] Specifically, the ABS resin can be 5, 10, 15, 20, 23, 25, 30, 35, 40 parts, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0015] Specifically, the mica powder can be 5, 10, 13, 15, 20 parts, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0016] Furthermore, the mica powder includes at least one of the following (1) to (2): (1) The mica powder has a mesh size of 300~1000 mesh; (2) The diameter-to-thickness ratio of the mica powder is (65~120):1.

[0017] Specifically, the mesh size of the mica powder can be 300, 325, 350, 375, 400, 500, 550, 600, 700, 750, 800, 900, 1000 mesh, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0018] Preferably, the mica powder has a mesh size of 300-600 mesh, and more preferably 300-400 mesh.

[0019] The mesh size described in this invention is determined by a grid sieving method.

[0020] Specifically, the aspect ratio of the mica powder can be 65:1, 70:1, 75:1, 78:1, 80:1, 85:1, 90:1, 95:1, 100:1, 105:1, 110:1, 120:1, etc., or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0021] The aspect ratio of the mica powder is (65~100):1, more preferably (90~100):1.

[0022] The diameter-to-thickness ratio refers to the ratio of diameter to thickness. The method for testing the diameter-to-thickness ratio is as follows: the diameter (particle size) and thickness of 1000 mica powder particles are measured using equipment such as an optical microscope, and the average diameter value is divided by the average thickness value to obtain the diameter-to-thickness ratio.

[0023] Further, the ABS resin includes at least one of the following (1) to (2): (1) The average particle size of the rubber phase of the ABS resin is 0.5~1.5 µm.

[0024] (2) The melt flow rate at 220℃ and 10kg is 2~30g / 10min.

[0025] Specifically, the average particle size of the rubber phase of the ABS resin can be 0.5, 0.6, 0.7, 0.8, 0.85, 0.9, 1, 1.2, 1.3, 1.4, 1.5 µm, or any specific point value between these values, or any range of these values. For the sake of simplicity, not all possible point values ​​or ranges are listed here.

[0026] Preferably, the average particle size of the rubber phase of the ABS resin is 0.7~1µm.

[0027] The average particle size of the rubber phase was determined in accordance with the test standard GB / T 42208-2022. The specific test conditions were as follows: ABS frozen sections were stained with transition metal oxides, and the phases were visualized under a transmission electron microscope. The average particle size of the rubber phase was measured and statistically analyzed.

[0028] Furthermore, the melt flow rate of the PC resin at 300°C and 1.2 kg is 8~32, preferably 10~30 g / 10 min, and more preferably 10~20 g / 10 min.

[0029] Specifically, the melt flow rate of the PC resin at 300°C and 1.2 kg can be 8, 9, 10, 15, 20, 25, 30, 32 g / 10 min, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0030] Furthermore, the ABS resin, in accordance with ISO 1133-1:2022 standard, has a melt flow rate of 2~30 g / 10 min at 220°C and 10 kg, preferably 6~30 g / 10 min, and more preferably 20~30 g / 10 min.

[0031] Specifically, the melt flow rate of the ABS resin, according to ISO 1133-1:2022 standard at 220℃ and 10kg, can be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 25, 28, 30 g / 10min, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or ranges are listed here.

[0032] Furthermore, the PC-ABS composite material also includes 1 to 5 parts of MBS resin (methyl methacrylate-butadiene-styrene terpolymer). Adding MBS resin to the above components can further improve the mechanical properties of the material.

[0033] Furthermore, the MBS resin, in a formulation system of PC:MBS=100:5 (mass ratio) according to ISO 1133-1:2022, has a melt flow rate of 10~20g / 10min at 300℃ and 1.2kg, preferably 13~17g / 10min, and more preferably 13~15g / 10min.

[0034] Specifically, in a formulation system of PC:MBS=100:5 (mass ratio) according to ISO 1133-1:2022 standard, the melt flow rate of the MBS resin at 300℃ and 1.2kg can be 10, 12, 13, 13.2, 14, 14.8, 15, 16, 16.8, 17, 18, 19, 20 g / 10min, or any specific point value between the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or ranges are listed here.

[0035] Preferably, the MBS resin, in a formulation system of PC:MBS=100:5 (mass ratio) according to ISO 1133-1:2022, has a melt flow rate of 13~17 g / 10 min at 300°C and 1.2 kg, more preferably 14~15 g / 10 min.

[0036] Furthermore, the PC-ABS composite material also includes 0.05 to 1.5 parts of other additives.

[0037] Specifically, the other additives may be 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.8, 1, 1.2, 1.5 parts, or specific point values ​​between any of the above values, or any range of these values. For the sake of simplicity, not all possible point values ​​or range values ​​are listed here.

[0038] Furthermore, the other additives include antioxidants.

[0039] Preferably, the antioxidant includes at least one of hindered phenolic antioxidants and phosphite antioxidants.

[0040] Furthermore, the hindered phenolic antioxidant is selected from one or more of antioxidant 1010, antioxidant 2246, and antioxidant 1076.

[0041] Furthermore, the phosphite antioxidant is selected from one or more of antioxidant 168, triphenyl phosphite, and antioxidant 626.

[0042] Preferably, the antioxidant is a combination of hindered phenolic antioxidants and phosphite antioxidants.

[0043] Furthermore, the mass ratio of the hindered phenolic antioxidant to the phosphite antioxidant is 1:(0.5~2), preferably 1:(1~2), and more preferably 1:1.

[0044] The present invention protects a method for preparing the PC-ABS composite material, comprising the following steps: mixing the components uniformly, melt extruding, and granulating to obtain the PC-ABS composite material.

[0045] Preferably, the melt extrusion and granulation are carried out using a twin-screw extruder.

[0046] Preferably, the temperature of the twin-screw extruder is 250~280℃.

[0047] This invention protects the application of the PC-ABS composite material in the preparation of automotive interior parts.

[0048] The present invention also protects a coated article, comprising a coated part, wherein the outer surface of the part is bonded with a coating layer by an adhesive, and the part comprises the PC-ABS composite material.

[0049] Compared with the prior art, the present invention has the following beneficial effects: (1) This invention uses PC resin as the matrix and adds mica powder with a specific aspect ratio and mesh size, which can reduce the shear stress between the substrate and the adhesive when the temperature rises. At the same time, thanks to the high aspect ratio of the mica powder, its reactivity with the polyurethane adhesive is enhanced, thereby significantly improving the adhesion between the substrate and the adhesive. On this basis, ABS resin with a specific rubber phase particle size is further introduced, which can maintain the good mechanical properties of the material while avoiding the obscuring of the effect of the mica powder, and can also synergistically enhance the overall mechanical properties. In the end, the PC-ABS composite material has high toughness, high peel strength and excellent heat-resistant adhesive stability, and can be widely used in automotive interior covering parts.

[0050] (2) Adding MBS resin to the above components can further improve the mechanical properties of the material. Detailed Implementation

[0051] The present invention will be further illustrated below with reference to specific embodiments, but the embodiments do not limit the present invention in any way. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in this technical field.

[0052] The raw materials for the examples and comparative examples are as follows: 1. PC resin: PC Resin-1 (PC-1): POLYCARBONATE RESIN TARFLON FN2200, melt index is 10 g / 10min, test standard ISO 1133-1: 2022, test conditions 300℃, 1.2kg; manufacturer: Formosa Plastics Idemitsu.

[0053] PC Resin-2 (PC-2): PC H-3000, melt flow rate is 30 g / 10min, test standard ISO 1133-1:2022, test conditions 300℃, 1.2kg; manufacturer: Mitsubishi Chemical, Japan.

[0054] 2. ABS resin: ABS Resin-1 (ABS-1): ABS 8391, melt flow rate is 27 g / 10 min, test standard ISO 1133-1:2022, test conditions 220 ℃, 10 kg; average particle size of rubber phase: 0.7 µm, test standard GB / T 42208-2022, test conditions: ABS frozen sections, stained with transition metal oxides, phased under transmission electron microscopy, and the average particle size of rubber phase was measured and statistically analyzed; manufacturer: Shanghai Gaoqiao Petrochemical Co., Ltd.

[0055] ABS Resin-2 (ABS-2): ABS 3513, melt flow rate is 6 g / 10min, test standard ISO 1133-1:2022, test conditions 220 ℃, 10kg; average particle size of rubber phase: 1.0 µm, test standard GB / T 42208-2022, test conditions: ABS frozen sections, stained with transition metal oxides, phased under transmission electron microscopy, and the average particle size of rubber phase was measured and statistically analyzed; manufacturer: Shanghai Gaoqiao Petrochemical Co., Ltd.

[0056] ABS Resin-3 (ABS-3): ABS 745, melt flow rate is 10 g / 10 min, test standard ISO 1133-1:2022, test conditions 220 ℃, 10 kg; average particle size of rubber phase: 0.2 µm, test standard GB / T 42208-2022, test conditions: ABS frozen sections, stained with transition metal oxides, phased under transmission electron microscopy, and the average particle size of rubber phase was measured and statistically analyzed; manufacturer: Kumho Petrochemical Co., Ltd., South Korea.

[0057] 3. Mineral powder: Mica-1: Suzorite 60-S, 400 mesh, aspect ratio 100:1, IMERYS.

[0058] Mica-2: WG-160, 300 mesh, aspect ratio 90:1, IMERYS.

[0059] Mica-3: Suzorite150 NY, 600, aspect ratio 65:1, IMERYS.

[0060] Mica-4: Mica, 4-K, 400 mesh, aspect ratio 50:1, IMERYS.

[0061] Mica-5: Suzorite 325-S, 200 mesh, aspect ratio 80:1, IMERYS.

[0062] Talc: Talc, WG-325, 325 mesh, Imerys Mica Kings Mountain, In. (Manufacturer).

[0063] 4. Other resins: MBS Resin-1 (MBS-1): M-732, melt flow rate is 14.8 g / 10 min, test standard ISO1133 1:2022, test conditions 300℃, 1.2kg, test formulation system PC-1 / MBS=100:5 (mass ratio); manufacturer: Kanekachi, Japan.

[0064] MBS Resin-2 (MBS-2): M-521, melt flow rate is 16.8 g / 10 min, test standard ISO1133 1:2022, test conditions 300℃, 1.2kg, test formulation system PC-1 / MBS=100:5 (mass ratio); manufacturer: LG Korea.

[0065] MBS Resin-3 (MBS-3): M-701, melt flow rate is 13.2 g / 10 min, test standard ISO1133 1:2022, test conditions 300℃, 1.2kg, test formulation system PC-1 / MBS=100:5 (mass ratio); manufacturer: Kanekachi, Japan.

[0066] 5. Other additives Compound antioxidant: Antioxidant-1 and antioxidant-2 are used in combination at a mass ratio of 1:1.

[0067] Antioxidant-1: Hindered phenolic antioxidant, Antioxidant 1010, commercially available; Antioxidant-2: Phosphite antioxidant, Antioxidant 168, commercially available.

[0068] Unless otherwise specified, all components used in the parallel embodiments and comparative examples are the same commercially available products.

[0069] Example 1: A mineral powder-filled PC-ABS composite material with high peel strength The weight proportions of the raw materials used in Example 1 are shown in Table 1.

[0070] A method for preparing a high peel strength mineral powder-filled PC-ABS composite material includes the following steps: weighing the raw materials according to the amounts of each component in Table 1, mixing the components evenly, and then melting and extruding the mixture through a twin-screw extruder at a temperature of 250~280℃ and granulating it to obtain the PC-ABS composite material.

[0071] Examples 2-11: High peel strength mineral powder-filled PC-ABS composite materials The weight proportions of the raw materials used in the following embodiments are shown in Table 1.

[0072] The specific preparation steps of the other embodiments are the same as those in Embodiment 1.

[0073] Table 1. Weight parts of raw materials used in Examples 1-11

[0074] Comparative Examples 1-5: A PC-ABS composite material The weight proportions of raw materials used in each of the following comparative examples are shown in Table 2.

[0075] The specific preparation steps for each comparative example are the same as those in Example 1.

[0076] Table 2. Weight parts of raw materials used in Comparative Examples 1-5

[0077] Performance determination of experimental examples The PC-ABS composite materials prepared in the above embodiments and comparative examples were tested using the following test methods.

[0078] 1. Initial peel force test method: PC-ABS composite material particles were added to an injection molding machine and melted at 260℃ to form 130*13*2mm sample strips. The sample strips were then coated with a one-component polyurethane adhesive (120g / m²). 2 The carpet surface was heated and bonded, and the bonded sample was left at room temperature for 4 days to cure. The peel force of the bonded sample was tested according to GB / T 2792-2014 standard.

[0079] 2. Peel strength test method after heat storage: The bonded strips were placed in an environmental chamber at 85℃ for 500 hours, and then the peel strength was tested according to GB / T 2792-2014 standard.

[0080] 3. Test method for notched impact strength of simply supported beams: PC-ABS composite material particles were added to an injection molding machine and melted at 260℃ to form 80*10*4mm specimens. After being conditioned at room temperature for 24 hours, the notched impact strength of a simply supported beam was tested according to GB / T 1043.1-2018 standard.

[0081] Table 3 shows the performance test results of each embodiment and comparative example.

[0082] Table 3 Performance test results of each embodiment and comparative example

[0083] As can be seen from the test results in Table 3, the mineral powder-filled PC / ABS composite material of the present invention exhibits excellent hot peel strength, with an initial peel strength of not less than 5000 N / m and a peel strength of not less than 4000 N / m after hot storage, and an impact strength of not less than 40 kJ / m. 2 Further addition of MBS resin does not negatively impact peel strength but instead enhances the material's impact strength, resulting in a PC / ABS composite material with high hot peel strength and good impact resistance. Furthermore, the addition of other additives, such as antioxidants, does not produce negative effects.

[0084] Compared to Example 1, in Comparative Example 1, the use of mica with a diameter-to-thickness ratio of less than 65:1 resulted in poor peel strength and mechanical properties of the PC / ABS composite material. In Comparative Example 2, the addition of lower mesh mica significantly reduced peel strength and mechanical properties before and after heat storage. In Comparative Example 3, the talc powder provided a slippery effect, making the adhesive difficult to bond and severely reducing the adhesion between the PC / ABS resin and the adhesive, resulting in performance even worse than Comparative Example 4 without fillers. Furthermore, its mechanical properties were also poor. In Comparative Example 4, the absence of mica increased the impact strength, but its peel strength was severely deteriorated. In Comparative Example 5, the added ABS resin had excessively small rubber particle size, resulting in severely deteriorated peel strength and poor mechanical properties.

[0085] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A PC-ABS composite material, characterized in that, By weight, it includes the following components: 40-80 parts PC resin; 5-40 parts ABS resin; 5-20 parts mica powder; The mica powder has a mesh size of 300 or greater. The aspect ratio of the mica powder is greater than or equal to 65:1; The average particle size of the rubber phase of the ABS resin is greater than or equal to 0.5 µm.

2. The PC-ABS composite material according to claim 1, characterized in that, The mica powder includes at least one of the following (1) to (2): (1) The mica powder has a mesh size of 300~1000 mesh; (2) The diameter-to-thickness ratio of the mica powder is (65~120):

1.

3. The PC-ABS composite material according to claim 1, characterized in that, The melt flow rate of the PC resin at 300°C and 1.2 kg is 8~32 g / 10 min.

4. The PC-ABS composite material according to claim 1, characterized in that, The ABS resin includes at least one of the following (1) to (2): (1) The average particle size of the rubber phase of the ABS resin is 0.5~1.5µm. (2) The melt flow rate at 220℃ and 10kg is 2~30g / 10min.

5. The PC-ABS composite material according to claim 1, characterized in that, The PC-ABS composite material also includes 1 to 5 parts of MBS resin.

6. The PC-ABS composite material according to claim 4, characterized in that, The melt flow rate of the MBS resin at 300℃ and 1.2kg load is 10~20g / 10min.

7. The PC-ABS composite material according to claim 1, characterized in that, The PC-ABS composite material also includes 0.05 to 1.5 parts of other additives.

8. A method for preparing the PC-ABS composite material according to any one of claims 1 to 7, characterized in that, The process includes the following steps: mixing the components evenly, melt extruding, and granulating to obtain the PC-ABS composite material.

9. Claim 1 The application of any one of the 7 PC-ABS composite materials in the preparation of automotive interior parts.

10. A coated article, comprising a coated part, wherein the outer surface of the part is adhesively bonded with a coating layer, characterized in that, The component includes the features described in claim 1.

7. The PC-ABS composite material described in any one of the above.

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