A pc / abs alloy, its preparation method and application

Abstract

The application discloses a PC / ABS alloy and a preparation method and application thereof, and belongs to the technical field of high polymer engineering plastics; the PC / ABS alloy provided by the application comprises the following components in parts by mass: 63-78 parts of PC, 8-22 parts of ABS, 5-13 parts of titanium white, 1-6 parts of bisphenol A-bis(diphenyl phosphate), 0.5-5.5 parts of indium tin oxide, 0.1-1.2 parts of carbon black and 0-8 parts of an auxiliary agent; the average particle size of the titanium white is 140-310 nm; and the average particle size of the carbon black is less than or equal to 22 nm. The product prepared by the application has excellent light-shielding high-reflecting white effect and good appearance, and excellent laser welding performance; thereby, the product can be widely applied to the preparation of paint-sprayed parts of automobile interiors and exteriors. Moreover, the preparation method of the PC / ABS alloy is simple in operation and is beneficial to actual production.

Description

Technical Field

[0001] This invention belongs to the field of polymer engineering plastics technology, and particularly relates to a PC / ABS alloy, its preparation method and application. Background Technology

[0002] Polycarbonate / acrylonitrile-butadiene-styrene copolymer alloys (PC / ABS) are widely used in automotive interiors, electronic and electrical housings, and consumer electronics products due to their combination of the excellent impact resistance, heat resistance, and dimensional stability of PC with the good processing flow and cost-effectiveness of ABS. In these applications, PC / ABS components often require excellent structural integrity, airtightness, and a refined appearance.

[0003] To meet the above requirements, especially in the production of components with complex structures, limited space, or requiring clean and seamless connections, laser transmission welding technology has become the preferred process for joining PC / ABS components due to its advantages such as non-contact, high precision, low stress, high degree of automation, and cleanliness and efficiency. However, applying laser welding to light-shielding, high-reflectivity white (hereinafter referred to as "light-shielding high-reflectivity white") appearance parts with stringent aesthetic and functional requirements faces a series of prominent contradictions and technical challenges. Specifically, for common light-colored or white materials, these materials are usually prepared into products with a "light-shielding high-reflectivity white" effect, and their formulations typically require the addition of a high proportion of high-reflectivity pigments (such as titanium dioxide) and light-shielding agents; while these components can give the product excellent appearance coverage and visual whiteness, they will significantly increase the reflectivity and scattering rate of the material to near-infrared lasers. In addition, PC / ABS alloy materials are prone to appearance defects such as "silver streaks" or "air marks" during processing (including injection molding of parts and subsequent laser welding thermal cycling). Especially in light-shielding, high-reflectivity parts, any tiny silver streaks or air marks will be visually magnified, leading to serious appearance defects and significantly reducing product yield and commercial value.

[0004] Therefore, developing a PC / ABS alloy material that can simultaneously achieve excellent laser welding performance (especially for light-shielding, highly reflective parts), effectively suppress silver wire gas marks and appearance defects, and maintain ideal light-shielding properties, high whiteness and high reflectivity has become a key technical problem that urgently needs to be solved in this field. Summary of the Invention

[0005] The purpose of this invention is to overcome the shortcomings of the prior art and provide a PC / ABS alloy that can achieve excellent light-blocking and high reflectivity, as well as good laser welding effect and good appearance, and its preparation method and application.

[0006] To achieve the above objectives, in a first aspect of the present invention, the present invention provides a PC / ABS alloy comprising the following components in parts by weight: 63-78 parts PC, 8-22 parts ABS, 5-13 parts titanium dioxide, 1-6 parts bisphenol A-bis(diphenyl phosphate), 0.5-5.5 parts indium tin oxide, 0.1-1.2 parts carbon black, and 0-8 parts additives; The titanium dioxide has an average particle size of 140-310 nm. The average particle size of the carbon black is ≤22nm.

[0007] The present invention provides a PC / ABS alloy that, by selecting appropriate types of components for compounding, can effectively achieve good welding results, as well as excellent light-blocking and high-reflectivity effects and good appearance.

[0008] Specifically, in the first aspect, the present invention selects to add titanium dioxide and carbon black in the above-mentioned mass proportions and with an average particle size within a certain range. The two can synergistically improve the appearance yield and light-shielding high reflectivity of the alloy, while also having good welding effect. More specifically, the addition of titanium dioxide gives the material a light-shielding high reflectivity effect, which can strongly scatter and reflect incident light back, thereby providing basic whiteness, brightness and hiding power. At the same time, carbon black has a high light absorption effect and can act as a laser absorption layer during laser welding to ensure energy absorption and thus ensure welding effect. In addition, the average particle size of the two is within a certain range, which can effectively improve the appearance yield. Secondly, this invention adds bisphenol A-bis(diphenyl phosphate) (BDP) within a specific mass range, which can interact well with titanium dioxide and carbon black, improving the appearance yield. Simultaneously, BDP can reduce shear forces and minimize the damage of titanium dioxide to PC resin, preventing the formation of tiny silver-white streaks (silver threads) or gas marks inside or on the surface of the part due to side reactions during resin degradation. This effectively improves the product's appearance yield. Furthermore, BDP promotes the function of titanium dioxide and carbon black, achieving excellent laser welding results. Thirdly, this invention adds indium tin oxide within a specific mass range, which not only regulates laser absorption / transmission characteristics, helping to achieve more controllable and uniform laser energy absorption, thus improving the product's laser welding performance, but also works synergistically with BDP to help achieve good dispersion of titanium dioxide and carbon black and optical control, further enhancing the product's appearance and excellent light-blocking and high-reflectivity effect.

[0009] For example, the mass fraction of PC can be any point value or any two-point range between 63 and 78 parts, such as 63 parts, 65 parts, 68 parts, 70 parts, 72 parts, 75 parts, 78 parts, or any two-point range such as 65-75 parts; the mass fraction of ABS can be 8 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts, 22 parts, or any two-point range such as 10-20 parts; the mass fraction of bisphenol A-bis(diphenyl phosphate) can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, or any two-point range such as 2- 5 parts; the indium tin oxide can be any point value or any two-point range value between 0.5 and 5.5 parts, for example, it can be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 5.5 parts or any two-point range value such as 1-5 parts; the carbon black can be 0.1 parts, 0.2 parts, 0.4 parts, 0.6 parts, 0.8 parts, 1 part, 1.2 parts or any two-point range value such as 0.3-1 parts; the additive can be 0.5 parts, 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts or any two-point range value such as 0.5-7 parts.

[0010] Preferably, in the PC / ABS alloy, the mass percentage of PC is ≥50%.

[0011] More preferably, in the PC / ABS alloy, the mass percentage of PC is 58-80%.

[0012] It should be noted that the average particle size of the titanium dioxide is tested using the dynamic light scattering method in ISO 22412:2024; the average particle size of the carbon black is tested using the electron microscopy method in ASTM D3849-22.

[0013] For example, the average particle size of the titanium dioxide can be any point value or a range between any two points between 140-310nm, such as 146-300nm, 146-175nm, 146-234nm, 175-234nm, 175-300nm, 234-300nm, etc., or it can be 140nm, 160nm, 180nm, 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 310nm, etc.

[0014] In a preferred embodiment of the PC / ABS alloy of the present invention, the average particle size of the titanium dioxide is 170-240 nm. For example, it can be 175-234 nm, or it can be 170 nm, 175 nm, 180 nm, 185 nm, 190 nm, 195 nm, 200 nm, 205 nm, 210 nm, 215 nm, 220 nm, 225 nm, 230 nm, 235 nm, 240 nm, etc.

[0015] This invention has found that the average particle size of titanium dioxide affects its interaction with carbon black, BDP, and indium tin oxide, thereby affecting the product's light-shielding, high-reflectivity, and appearance, as well as its solderability. When the average particle size of titanium dioxide is selected within the above-mentioned range, especially within a further preferred range, the overall performance of the obtained product is better.

[0016] For example, the average particle size of the carbon black can be any point value between ≤22nm or a range between any two points, such as 10-20nm, 10-13nm, 10-17nm, 13-17nm, 13-20nm, 17-20nm, etc., or 5nm, 6nm, 7nm, 8nm, 9nm, 10nm, 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm, 19nm, 20nm, 21nm, 22nm, etc.

[0017] In a preferred embodiment of the PC / ABS alloy of the present invention, the carbon black has an average particle size of 8-22 nm.

[0018] Preferably, the average particle size of the carbon black is 13-17 nm.

[0019] This invention has found that the average particle size of carbon black affects laser absorption. It also influences its interaction with BDP and indium tin oxide (ITO). When the average particle size of the carbon black is further selected within the aforementioned range, and especially within a more preferred range, the overall performance of the resulting product is superior.

[0020] As a preferred embodiment of the PC / ABS alloy of the present invention, the PC / ABS alloy comprises the following components in parts by weight: 68-72 parts PC, 13-18 parts ABS, 8-11 parts titanium dioxide, 3-5 parts bisphenol A-bis(diphenyl phosphate), 2-4 parts indium tin oxide, 0.3-0.5 parts carbon black, and 0-8 parts additives.

[0021] This invention has found that the mass fraction of components in a PC / ABS alloy affects the overall performance of the composite material. When the mass fraction of components in the composite material is further selected within the above-mentioned range, the overall performance of the resulting composite material is even better.

[0022] As a preferred embodiment of the PC / ABS alloy of the present invention, the PC has a melt flow index of 8-62 g / 10 min under the test conditions of 300℃ / 1.2 kg.

[0023] It should be noted that the melt flow index of the PC under the test conditions of 300℃ / 1.2kg was obtained with reference to ISO 1133-2011.

[0024] For example, the melt flow index of the PC under the test conditions of 300℃ / 1.2kg can be any point value or any two-point range value between 8-62g / 10min, such as 10-60g / 10min, 20-60g / 10min, 10-20g / 10min, or 8g / 10min, 10g / 10min, 20g / 10min, 30g / 10min, 40g / 10min, 50g / 10min, 60g / 10min, 62g / 10min, etc.

[0025] Preferably, the melt flow index of the PC under the test conditions of 300℃ / 1.2kg is 15-25g / 10min.

[0026] The present invention has found that when the melt flow index of PC is further selected within the above range under the test conditions of 300℃ / 1.2kg, the overall performance of the obtained product is better.

[0027] As a preferred embodiment of the PC / ABS alloy of the present invention, the melt flow index of the ABS under the test conditions of 220℃ / 10kg is 6-17g / 10min.

[0028] It should be noted that the melt flow index of the ABS under the test conditions of 220℃ / 10kg was obtained with reference to ISO 1133-2011.

[0029] For example, the melt flow index of the ABS under the test condition of 220℃ / 10kg can be any point value or any two-point range value between 6-17g / 10min, such as 7-15g / 10min, or 6g / 10min, 7g / 10min, 8g / 10min, 10g / 10min, 12g / 10min, 14g / 10min, 16g / 10min, 17g / 10min, etc.

[0030] The present invention has found that further selecting the melt flow index of ABS under the test conditions of 220℃ / 10kg within the above range can better help improve the overall performance of the product.

[0031] In a preferred embodiment of the PC / ABS alloy of the present invention, the indium tin oxide has an average particle size of 60-180 nm.

[0032] It should be noted that the average particle size of the indium tin oxide was tested using the transmission electron microscopy method as described in ISO 21363:2021.

[0033] For example, the average particle size of the indium tin oxide can be any point value or any two-point range value between 60-180nm, such as 65-172nm, 65-100nm, 100-172nm, etc., or 60nm, 62nm, 65nm, 68nm, 70nm, 80nm, 90nm, 100nm, 120nm, 140nm, 160nm, 180nm, etc.

[0034] Preferably, the average particle size of the indium tin oxide is 90-110 nm.

[0035] The present invention has found that further selecting the average particle size of indium tin oxide within the above-mentioned range can better achieve the overall performance of the product.

[0036] In a preferred embodiment of the PC / ABS alloy of the present invention, the additives include at least one of toughening agents, antioxidants, or lubricants.

[0037] In a preferred embodiment of the PC / ABS alloy of the present invention, the toughening agent includes at least one of MBS, EBA, and EMA.

[0038] In a preferred embodiment of the PC / ABS alloy of the present invention, the antioxidant includes at least one of hindered phenolic antioxidants, thioester antioxidants, phosphite antioxidants, and hindered amine antioxidants.

[0039] For example, the hindered phenolic antioxidant may be antioxidant 1010, antioxidant 1076, etc.; the thioester antioxidant may be antioxidant 168, antioxidant TNP, etc.; the phosphite antioxidant may be antioxidant DLTDP, antioxidant DSTDP, etc.; and the hindered amine antioxidant may be antioxidant 770, antioxidant 944, etc.

[0040] In a preferred embodiment of the PC / ABS alloy of the present invention, the lubricant includes at least one of magnesium stearate, pentaerythritol stearate, ethylene bis-stearamide, and polyethylene wax.

[0041] In a second aspect, the present invention provides a method for preparing the PC / ABS alloy, the method comprising the following steps: The dried raw materials are mixed in proportion and fed into an extruder. After melt extrusion, drawing, cooling, pelletizing and drying, PC / ABS alloy is obtained.

[0042] In a preferred embodiment of the preparation method described in this invention, the extruder is a co-rotating twin-screw extruder with a screw length-to-diameter ratio of 46-52, an extrusion temperature of 190-270℃, and a screw speed of 400-600 rpm. In a third aspect, the present invention provides the application of the PC / ABS alloy in the preparation of automotive interior trim.

[0043] For example, the automotive interior includes ambient lighting, etc.

[0044] In a fourth aspect, the present invention provides an article of manufacture made of the PC / ABS alloy described herein.

[0045] Compared with the prior art, the beneficial effects of the present invention are as follows: This invention provides a PC / ABS alloy that, by selecting appropriate mass proportions of components, exhibits excellent interactions between the components, resulting in a product with superior light-shielding and high-reflectivity properties, a pleasant appearance, and excellent laser welding performance. Therefore, it can be widely used in the fabrication of automotive interior trim. Furthermore, the preparation method of the PC / ABS alloy provided by this invention is simple to operate and beneficial for practical production. Detailed Implementation

[0046] To better illustrate the purpose, technical solution, and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0047] Unless otherwise specified, the reagents, methods and equipment used in this invention are all conventional reagents, methods and equipment in the field.

[0048] PC1: Melt index of 20 g / 10 min under test conditions of 300℃ / 1.2 kg, PC 2220, Wanhua Chemical; PC2: Melt index of 10g / 10min under test conditions of 300℃ / 1.2kg, PC S-2000F, Mitsubishi, Japan; PC3: Melt index of 60 g / 10 min under test conditions of 300℃ / 1.2 kg, PC 2600, Wanhua Chemical.

[0049] ABS1: Melt index of 7 g / 10 min under test conditions of 220℃ / 10 kg, ABS 275, Gaoqiao Petrochemical; ABS2: Melt index of 15g / 10min under test conditions of 220℃ / 10kg, ABS 8434, Gaoqiao Petrochemical.

[0050] Titanium dioxide 1: Average particle size is 175nm; Titanium dioxide 2: average particle size is 234nm; Titanium dioxide 3: average particle size is 146nm; Titanium dioxide 4: average particle size is 300nm; Titanium dioxide 5: average particle size is 120nm; Titanium dioxide 6: average particle size is 350nm, TYR-569, Yibin Tianyuan Haifeng Hetai; Titanium dioxide 1-5 are obtained by grinding, pulverizing and sieving titanium dioxide 6.

[0051] Barium sulfate: with an average particle size of 175nm, obtained by grinding, crushing and sieving barium sulfate (HD-800, Yichang Hengda Chemical, with an average particle size of 1850nm).

[0052] BDP: Commercially available.

[0053] TPP: Triphenyl phosphate, commercially available.

[0054] Indium tin oxide 1: average particle size is 100 nm; Indium tin oxide 2: average particle size is 65 nm; Indium tin oxide 3: average particle size is 172 nm; Indium tin oxide 1-3 were obtained by grinding, pulverizing and sieving indium tin oxide (ITO TARGET, Umicore, Belgium, with an average particle size of 15000nm).

[0055] Carbon black 1: average particle size is 13 nm; Carbon black 2: average particle size is 17nm; Carbon black 3: average particle size is 20nm; Carbon black 4: average particle size is 10 nm; Carbon Black 5: Average particle size 26nm, MagiCab 1013F, Anhui Heiyu; Carbon black 1-4 are obtained by grinding, pulverizing and sieving carbon black 5.

[0056] Toughening agent: ABS POW HR181, Kumho Petrochemical, South Korea; Antioxidant: A mixture of antioxidant 1010 and antioxidant 168 in a 1:1 mass ratio; Lubricant: Pentaerythritol stearate, commercially available.

[0057] Examples 1-14 and Comparative Examples 1-8 The present invention provides a PC / ABS alloy in embodiments and comparative examples, wherein the component content (parts by weight) of the PC / ABS alloy is shown in Tables 1-3; Table 1 Table 2 Table 3 The preparation methods for the examples and comparative examples are as follows: After drying, the raw materials are mixed in proportion and added to a mixer for uniform mixing. Then, the mixture is fed into a twin-screw extruder. The feed rate of the twin-screw extruder (screw diameter of 35mm) is adjusted to 80kg / kg. After extrusion, stranding, cooling, pelletizing, and drying, PC / ABS alloy is obtained. The parameters of the twin-screw extruder are as follows: the temperature of each screw section from the feed port to the die head is 190℃, 240℃, 250℃, 260℃, 260℃, 265℃, and 270℃, respectively; the twin-screw speed is 500rpm; and the length-to-diameter ratio is 48.

[0058] Example of effect The performance tests of the PC / ABS alloys prepared in the examples and comparative examples included the following aspects: 1. Appearance Test: Twenty 100*100*3mm square plates were continuously injection molded from the PC / ABS alloys prepared in the examples and comparative examples using a high-gloss mold. Ten of these plates were randomly selected and visually inspected under a D65 light source at a distance of approximately 20cm. The surface of the square plates was checked for silver streaks or air marks, and the number of plates with abnormal appearance (silver streaks or air marks) was recorded. The appearance evaluation criteria are shown in Table 4 below. Table 4 2. Laser welding performance test: 20 laser-welded specimens of PC / ABS alloy were continuously injection molded using a high-gloss mold. Welding strength evaluation: The PC / ABS alloy specimens to be tested were injection molded using a mold (the injection molded specimens were made according to ISO 527-1:2019, and the specimen size was 140mm×20mm×3mm). Then, a laser welding experiment was conducted. The tensile testing machine was used to test the force required for the welded specimen to be re-destructed. The test standard was ISO 527-2:2025. The results are shown in Table 5. Table 5 As can be seen from Table 5, when the technical solution of the present invention is adopted, the obtained product has good appearance and good welding effect; specifically, the appearance grade of the obtained product is between 1 and 3, and the welding strength is above 43.4 MPa; and by referring to DIN 5033-9-2018 part 7, the reflectivity of the product prepared in the example is tested, and the reflectivity of the obtained product is between 80.0 and 89.4%, that is, the obtained product has excellent light-blocking and high white reflection effect; As can be seen from Examples 1, 7-9 and Comparative Examples 1-2, the average particle size of titanium dioxide affects the overall performance of the product. When the average particle size of titanium dioxide in Comparative Examples 1-2 is outside the range, the appearance of the obtained product deteriorates significantly, and the welding strength also decreases significantly. As can be seen from Examples 1 and Comparative Example 3, when barium sulfate is used to replace titanium dioxide in Comparative Example 3, the appearance of the obtained product deteriorates, and the welding strength also shows a downward trend. As can be seen from Examples 1, 12-14 and Comparative Example 4, the average particle size of carbon black also affects the overall performance of the product. When the average particle size of carbon black in Comparative Example 4 is outside the range, the overall performance of the obtained product decreases significantly. As can be seen from Examples 1 and Comparative Example 5, when no carbon black is added in Comparative Example 5, the welding strength decreases significantly, and the appearance also decreases to a certain extent. As can be seen from Example 1 and Comparative Example 6, when BDP is not added, the appearance of the product is poor and the welding strength also tends to decrease. As can be seen from Examples 1 and 10-11, the average particle size of nano-indium tin oxide affects the overall performance of the product; as can be seen from Examples 1 and Comparative Example 7, when nano-indium tin oxide is not added, the appearance and welding strength of the obtained product are significantly worse. As can be seen from Examples 1, 2-3 and Comparative Example 8, the mass fraction of the components also affects the overall performance of the product. When the mass fraction of titanium dioxide in Comparative Example 8 is not within the range given in this invention, the appearance and welding strength of the obtained product decrease to a certain extent. As can be seen from Example 1 and Comparative Example 9, the excellent overall effect of the present invention cannot be achieved when other components are used to replace BDP.

[0059] Finally, it should be noted that the above embodiments are used to illustrate the technical solutions of the present invention and not to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the essence and scope of the technical solutions of the present invention.

Claims

1. A PC / ABS alloy, characterized in that, The PC / ABS alloy comprises the following components in parts by weight: 63-78 parts PC, 8-22 parts ABS, 5-13 parts titanium dioxide, 1-6 parts bisphenol A-bis(diphenyl phosphate), 0.5-5.5 parts indium tin oxide, 0.1-1.2 parts carbon black, 0-8 parts additives; The titanium dioxide has an average particle size of 140-310 nm. The average particle size of the carbon black is ≤22nm.

2. The PC / ABS alloy according to claim 1, characterized in that, The PC / ABS alloy comprises the following components in parts by weight: 68-72 parts PC, 13-18 parts ABS, 8-11 parts titanium dioxide, 3-5 parts bisphenol A-bis(diphenyl phosphate), 2-4 parts indium tin oxide, 0.3-0.5 parts carbon black, and 0-8 parts additives.

3. The PC / ABS alloy according to claim 1, characterized in that, The titanium dioxide has an average particle size of 170-240 nm. And / or, the average particle size of the carbon black is 8-22 nm.

4. The PC / ABS alloy according to claim 1, characterized in that, The melt flow index of the PC under the test conditions of 300℃ / 1.2kg was 8-62g / 10min.

5. The PC / ABS alloy according to claim 1, characterized in that, The melt flow index of the ABS under the test conditions of 220℃ / 10kg is 6-17g / 10min.

6. The PC / ABS alloy according to claim 1, characterized in that, The average particle size of the indium tin oxide is 60-180 nm.

7. The PC / ABS alloy according to claim 1, characterized in that, The additives include at least one toughening agent, antioxidant, or lubricant.

8. The method for preparing the PC / ABS alloy according to any one of claims 1-7, characterized in that, The preparation method includes the following steps: the dried raw materials are mixed in proportion and fed into an extruder, and then melt-extruded, stretched, cooled, pelletized and dried to obtain PC / ABS alloy.

9. The application of the PC / ABS alloy as described in any one of claims 1-7 in the preparation of automotive interior trim.

10. An article characterized in that, The article is made of PC / ABS alloy as described in any one of claims 1-7.

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