A high-density metal-like ABS composite material and its application

Abstract

This invention relates to the field of polymer materials, specifically to a high-density metallic-like ABS composite material and its applications. The high-density metallic-like ABS composite material comprises the following components in parts by weight: ABS resin, polyolefin blend resin, modified iron powder, modified chopped glass fiber, compatibilizer, anti-aging agent, and viscosity reducer. The modified iron powder is spherical atomized iron powder surface-modified with polyether-modified amino silicone oil; the modified chopped glass fiber is chopped glass fiber surface-activated and modified with a silane coupling agent. Through the gradation and surface modification of the modified iron powder, combined with the synergistic effect of the polyolefin blend resin and the viscosity reducer, high density and a metallic appearance are achieved while maintaining good melt flowability and mechanical properties. The application method of the high-density metallic-like ABS composite material is simple, easy to control, and conducive to large-scale industrial production. The resulting high-density metallic-like plastic composite material products exhibit stable yield and superior overall performance.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, specifically to a high-density metal-like ABS composite material and its applications. Background Technology

[0002] In-Mold Decoration (IMD) is a surface decoration technology, also known as in-mold decoration or paint-free technology. It involves embedding a printed decorative film (film) into the mold during the injection molding process, so that the decorative pattern is integrated with the surface of the plastic part and thus achieves a decorative effect with high fidelity and wear resistance.

[0003] IMD technology is widely used in various products requiring aesthetically pleasing and durable surfaces, such as mobile phone screen lenses and casings, home appliance control panels, car dashboards, car body parts, rice cooker control panels, mobile phone cases, and toy car casings. Current technologies generally use ABS, PC, and PMMA plastic materials for IMD injection molding, and the film material is typically PET or PC sheets.

[0004] like Figure 1-2 As shown, some existing simulated car toy car cabinets are made through in-mold injection molding (IMD). To improve the texture, iron sheets are generally added to the injection-molded car cabinet to increase weight. However, adding iron sheets has problems such as complex assembly processes, low bonding strength, easy generation of abnormal noises and local detachment, and difficulty in achieving integrated weight gain for complex curved surfaces. In addition, adding a large amount of iron powder and other metal fillers will significantly reduce the melt flowability and mechanical properties of composite materials, leading to injection molding difficulties, surface fiber floating, and increased brittleness of the product, making it difficult to simultaneously meet the requirements of high density, high flowability, and high mechanical properties. Summary of the Invention

[0005] In order to overcome the shortcomings and deficiencies of the existing technology, the purpose of this invention is to provide a high-density imitation metal ABS composite material with good melt flowability. The high-density imitation metal plastic composite material products made from it have the characteristics of high density, strong metallic texture, excellent mechanical properties and strong bonding with IMD film material, and are suitable for in-mold injection molding.

[0006] The application method of the high-density metal-imitation ABS composite material of the present invention is simple in process, easy to operate and control, which is conducive to large-scale industrial production. The high-density metal-imitation plastic composite material products produced have stable quality and excellent comprehensive performance.

[0007] The objective of this invention is achieved through the following technical solution: a high-density imitation metal ABS composite material, comprising the following components in parts by weight: 80-90 parts ABS resin, 3-8 parts polyolefin blend resin, 15-35 parts modified iron powder, 5-12 parts modified chopped glass fiber, 1-2 parts compatibilizer, 0.4-1 part anti-aging agent, and 0.5-1.2 parts thickener, wherein the modified iron powder is spherical atomized iron powder that has been surface-coated and modified with polyether-modified amino silicone oil; and the modified chopped glass fiber is chopped glass fiber that has been surface-activated and modified with a silane coupling agent.

[0008] This invention relates to a high-density, metal-like ABS composite material. By using polyether-modified amino silicone oil to surface-coat spherical atomized iron powder, the interfacial tension between the iron powder and the ABS resin matrix is ​​significantly reduced, improving the dispersibility and compatibility of the iron powder, while also enhancing the melt flowability of the composite material. Furthermore, by compounding specific proportions of polyolefin blend resin, modified chopped glass fiber, compatibilizer, and viscosity reducer, a high-density, metal-like effect is achieved while ensuring the material's mechanical strength and injection molding performance, making it particularly suitable for IMD (In-Mold Design) processes.

[0009] Furthermore, the polyolefin blend resin is a mixture of PP resin and PE resin, wherein the weight ratio of PP resin to PE resin is 1~2:1. The polypropylene PP is selected from Thai Petrochemical 1100PK, and the PE resin is selected from LDPE2426H.

[0010] This invention uses PP resin and PE resin blended in a specific ratio as a polyolefin blend resin. On the one hand, it can improve the interfacial compatibility between ABS resin and modified iron powder, reduce the melt viscosity of the system, and improve injection molding fluidity. On the other hand, the PP / PE blend resin and ABS-g-MAH compatibilizer work synergistically to improve toughness without affecting the overall rigidity of the material, and avoid the increase in brittleness caused by high iron powder content.

[0011] Furthermore, the silane coupling agent is KH-560 or KH-550.

[0012] Furthermore, the anti-aging agent is antioxidant 1010; the viscosity reducer is pentaerythritol stearate.

[0013] Furthermore, the compatibilizer is ABS-g-MAH. The ABS-g-MAH is Shenghao Plastics VE-335K.

[0014] Furthermore, the ABS resin used is from Zhenjiang Chimei, brand name PA-749K.

[0015] Furthermore, the spherical atomized iron powder contains four particle sizes: fine particles with a diameter of 310–330 mesh, fine particles with a diameter of 70–110 mesh, medium particles with a diameter of 40–70 mesh, and coarse particles with a diameter of 26–40 mesh, and the weights are blended in a ratio of 0.5–0.7:2–4:5–7:2–3.

[0016] This invention utilizes four specific particle sizes of spherical atomized iron powder, blended in optimized proportions, to achieve hierarchical nesting and tight packing of particles of different sizes within an ABS matrix. This significantly improves the packing density and metallic-like texture of the composite material. Simultaneously, the coating with polyether-modified amino silicone oil enhances the lubricity of the iron powder, synergistically reducing internal friction and melt viscosity in conjunction with the gradation effect of the different particle sizes. This results in excellent melt flow index while maintaining high filler content, effectively solving the technical challenge of fluidity degradation caused by high-density fillers.

[0017] Furthermore, the polyether-modified amino silicone oil comprises the following components in parts by weight: 60-80 parts of octamethylcyclotetrasiloxane, 15-25 parts of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-8 parts of hexamethyldisiloxane, 0.2-0.5 parts of tetramethylammonium hydroxide, 0.05-0.15 parts of chloroplatinic acid, and 10-20 parts of epoxy-modified polyether acrylate.

[0018] The self-made polyether-modified amino silicone oil of this invention combines the smoothness and lubrication properties of amino silicone oil with the hydrophilicity, oleophilicity, and surface activity of polyether segments. When used to coat iron powder, it can form a dense, flexible organic layer on the surface of the iron powder with good affinity to ABS resin, significantly reducing interfacial defects between iron powder and resin matrix, inhibiting the "fiber floating" phenomenon, and improving the composite material's resistance to heat and oxygen aging and UV aging.

[0019] Furthermore, the preparation method of the polyether-modified amino silicone oil includes the following steps: A1. Octamethylcyclotetrasiloxane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and hexamethyldisiloxane are added sequentially to a reaction vessel, nitrogen gas is introduced and the temperature is raised to 55-65°C, and the mixture is stirred for 10-20 min; then, moisture is removed by vacuuming for 0.8-1.2 h; next, the temperature is raised to 100-120°C and tetramethylammonium hydroxide catalyst is added, and the reaction is carried out for 4-6 h; A2. After the reaction is complete, raise the temperature to 120-170°C and continue the reaction for 25-35 minutes to decompose the tetramethylammonium hydroxide catalyst. Then, perform vacuum treatment again for 0.8-1.2 hours to remove the decomposition products and low-boiling substances of tetramethylammonium hydroxide, and obtain a transparent and clear end-group hydrogen-containing amino silicone oil. A3. Add epoxy-modified polyether acrylate and isopropanol to hydrogen-terminated amino silicone oil, heat to 55-65°C and mix for 10-20 minutes, then add chloroplatinic acid and mix evenly for 0.2-0.8 hours. Finally, remove the solvent by vacuum distillation at 70-80°C to obtain polyether-modified amino silicone oil.

[0020] Furthermore, the preparation method of the modified iron powder includes the following steps: B1. Mix polyether-modified amino silicone oil and anhydrous ethanol at a mass ratio of 1:2 to 4 and stir until homogeneous to obtain a diluted polyether-modified amino silicone oil solution. B2. Continuously stir the spherical atomized iron powder at high speed, and spray the diluted solution evenly to wet the powder; the mass ratio of spherical atomized iron powder to polyether modified amino silicone oil is 100:1.5~2.5; after spraying, place it in an environment of 80~90℃ to dry for 1~3 hours, completely remove the solvent by rotary evaporation, and let it cool naturally before use.

[0021] Furthermore, the preparation method of the modified chopped glass fiber includes the following steps: C1. Mix the silane coupling agent with an aqueous ethanol solution of 30-40% by mass and stir for 10-20 minutes to prepare an activated silane coupling agent solution. C2. Immerse the chopped glass fibers in the activation solution to fully impregnate and coat them. The mass ratio of glass fiber to silane coupling agent is 100:1 to 1.8. After impregnation, dry the fibers at 90 to 110°C for 1 to 2 hours to obtain modified chopped glass fibers.

[0022] Furthermore, the chopped glass fiber has a length of 3–6 mm and a single filament diameter of 10–13 μm.

[0023] This invention employs a silane coupling agent to surface-activate and coat chopped glass fibers. One end of the silane coupling agent forms a strong chemical bond with the silanol groups on the glass fiber surface, while the other end physically entangles or chemically bonds with the ABS resin matrix, thereby constructing a robust "molecular bridge" between the glass fiber and the resin. This interface design significantly enhances the interfacial bonding strength between the glass fiber and the matrix, enabling the glass fiber to effectively bear and transfer loads, fully exerting its reinforcing effect, and significantly improving the tensile strength and hardness of the composite material. Simultaneously, the excellent interfacial bonding effectively suppresses the "fiber floating" phenomenon during injection molding.

[0024] The present invention also provides an application of the above-mentioned high-density metal-like ABS composite material in in-mold injection molding.

[0025] Furthermore, the application method of the high-density metal-like ABS composite material in in-mold injection molding includes the following steps: S1. Take ABS resin, polyolefin blend resin and ABS-g-MAH compatibilizer according to the ratio and put them into a high-speed mixer. Stir at room temperature for 5 to 10 minutes to mix evenly to obtain a premixed matrix. S2. Add modified iron powder, anti-aging agent, and thickener to the premixed matrix in sequence, and stir at low speed until well mixed; finally, add modified short-cut glass fiber and gently mix for a short time to obtain the mixture. S3. Place the film material into the mold cavity and position the film material on the inner surface of the mold cavity, then close the mold. S4. The mixture obtained in step S2 is fed into the barrel of an injection molding machine. The temperature of the melting section of the injection molding machine is controlled at 200-230℃. The screw is used for low-speed shearing to ensure uniform mixing and plasticization of the material. The temperature of the mold is kept constant at 75-85℃. The molten and plasticized mixture is injected into the mold cavity at high speed through the hot runner. The injection pressure is 100-140MPa and the holding pressure is 40-80MPa. The molten mixture is bonded and composited with the film material in the mold cavity. After heat preservation and pressure holding, it is cooled and shaped. Finally, the mold is opened and demolded to obtain a high-density imitation metal plastic composite material product with integrated in-mold injection molding.

[0026] Furthermore, the film material includes a carrier layer, an ink layer, a white underlayer, and an adhesive layer arranged sequentially from the outside to the inside. In step S3, the adhesive layer of the film material faces into the mold cavity.

[0027] The application method of the high-density imitation metal ABS composite material of this invention is simple in process, easy to operate and control, and conducive to large-scale industrial production. The application method of this invention achieves stable mold filling and integrated composite of the high-filler system and the film material in IMD in-mold injection molding by optimizing the injection molding process parameters to match the flowability of the composite material. The resulting product has no floating fibers or flow marks on the surface, uniform metallic texture, strong film layer adhesion, and high yield.

[0028] The beneficial effects of this invention are as follows: 1. A high-density metal-like ABS composite material is provided. By modifying the gradation and surface of iron powder, combined with the synergistic effect of polyolefin blend resin and anti-tack agent, high density and metal-like appearance are achieved while maintaining good melt flowability and mechanical properties.

[0029] 2. The use of polyether-modified amino silicone oil to coat the iron powder significantly improves the compatibility between the iron powder and the ABS matrix, avoids "floating fiber" and brittle fracture, and enhances the weather resistance and surface quality of the product.

[0030] 3. This composite material is particularly suitable for IMD (In-Mold Molding) integrated molding, with a wide process window and strong bonding with the film material. It can replace traditional metal inserts, achieving a balance between lightweight, complex shapes and high-quality surfaces. It is suitable for fields such as simulation toys, home appliance panels, and automotive interiors.

[0031] 4. The preparation method and application process are simple, environmentally friendly, easy to industrialize, have low overall cost, and good product consistency. Attached Figure Description

[0032] Figure 1 The product image of the simulated toy car cabinet (left image) and the exterior view when unfolded (right image); Figure 2 This is an internal view of a simulated toy car cabinet in the prior art when it is unfolded. Figure 3 This is an inner view of the simulated toy car cabinet of the present invention when it is unfolded. Detailed Implementation

[0033] To facilitate understanding by those skilled in the art, the present invention will be further described below with reference to embodiments. The content mentioned in the embodiments is not intended to limit the present invention.

[0034] Example 1 This embodiment provides a high-density metal-like ABS composite material, comprising the following components in parts by weight: 85 parts ABS resin, 6 parts polyolefin blend resin, 25 parts modified iron powder, 8 parts modified chopped glass fiber, 1.5 parts compatibilizer, 0.7 parts anti-aging agent, and 0.8 parts thickener. The modified iron powder is spherical atomized iron powder surface-modified with polyether-modified amino silicone oil; the modified chopped glass fiber is chopped glass fiber surface-activated and modified with a silane coupling agent.

[0035] Furthermore, the polyolefin blend resin is a mixture of PP resin and PE resin, wherein the weight ratio of PP resin to PE resin is 1:1. The polypropylene (PP) is selected from Thai Petrochemical 1100PK, and the PE resin is selected from LDPE 2426H.

[0036] Furthermore, the silane coupling agent is KH-560.

[0037] Furthermore, the anti-aging agent is antioxidant 1010; the viscosity reducer is pentaerythritol stearate.

[0038] Furthermore, the compatibilizer is ABS-g-MAH. The ABS-g-MAH is Shenghao Plastics VE-335K.

[0039] Furthermore, the ABS resin used is from Zhenjiang Chimei, brand name PA-749K.

[0040] Furthermore, the spherical atomized iron powder contains four particle sizes: fine particles with a diameter of 320 mesh, fine particles with a diameter of 90 mesh, medium particles with a diameter of 55 mesh, and coarse particles with a diameter of 35 mesh, and the weights are blended in a ratio of 0.6:3:6:2.5.

[0041] Furthermore, the polyether-modified amino silicone oil comprises the following components in parts by weight: 70 parts of octamethylcyclotetrasiloxane, 20 parts of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 6 parts of hexamethyldisiloxane, 0.3 parts of tetramethylammonium hydroxide, 0.08 parts of chloroplatinic acid, and 15 parts of epoxy-modified polyether acrylate.

[0042] Furthermore, the preparation method of the polyether-modified amino silicone oil includes the following steps: A1. Octamethylcyclotetrasiloxane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and hexamethyldisiloxane were sequentially added to a reaction vessel, nitrogen gas was introduced and the temperature was raised to 60°C, and the mixture was stirred for 15 min; then, the water was removed by vacuuming under reduced pressure for 1 h; then, the temperature was raised to 110°C and tetramethylammonium hydroxide catalyst was added, and the reaction was carried out for 5 h; A2. After the reaction is complete, the temperature is raised to 150°C and the reaction continues for 30 minutes to decompose the tetramethylammonium hydroxide catalyst. Then, vacuum treatment is performed again for 1 hour to remove the decomposition products and low-boiling substances of tetramethylammonium hydroxide, and a transparent and clear end-group hydrogen-containing amino silicone oil is obtained. A3. Epoxy-modified polyether acrylate and isopropanol were added to hydrogen-terminated amino silicone oil, heated to 60°C and mixed for 15 min. Then chloroplatinic acid was added and mixed evenly, and the reaction was carried out for 0.6 h. Finally, the solvent was removed by vacuum distillation at 75°C to obtain polyether-modified amino silicone oil.

[0043] Furthermore, the preparation method of the modified iron powder includes the following steps: B1. Mix polyether-modified amino silicone oil and anhydrous ethanol at a mass ratio of 1:3 and stir evenly to obtain a diluted polyether-modified amino silicone oil solution. B2. Continuously stir the spherical atomized iron powder at high speed, and spray the diluted solution evenly to wet the powder; the mass ratio of spherical atomized iron powder to polyether modified amino silicone oil is 100:2; after spraying, place it in an environment of 85℃ to dry for 2 hours, completely remove the solvent by rotary evaporation, and let it cool naturally before use.

[0044] Furthermore, the preparation method of the modified chopped glass fiber includes the following steps: C1. Mix the silane coupling agent with a 35% (w / w) aqueous ethanol solution and stir for 15 min to prepare the silane coupling agent activation solution. C2. Immerse the chopped glass fibers in the activation solution to fully impregnate and coat them. The mass ratio of glass fiber to silane coupling agent is 100:1.4. After impregnation, dry the fibers at 100°C for 1.5 hours to obtain modified chopped glass fibers.

[0045] Furthermore, the chopped glass fiber has a length of 5 mm and a single filament diameter of 12 μm.

[0046] This embodiment also provides the application of the above-mentioned high-density metal-like ABS composite material in in-mold injection molding, and the application method includes the following steps: S1. Take ABS resin, polyolefin blend resin and ABS-g-MAH compatibilizer according to the ratio and put them into a high-speed mixer. Stir at room temperature for 8 minutes to mix evenly to obtain a premixed matrix. S2. Add modified iron powder, anti-aging agent, and thickener to the premixed matrix in sequence, and stir at low speed until well mixed; finally, add modified short-cut glass fiber and gently mix for a short time to obtain the mixture. S3. Place the film material into the mold cavity and position the film material on the inner surface of the mold cavity, then close the mold. S4. The mixture obtained in step S2 is fed into the injection molding machine barrel. The temperature of the melting section of the injection molding machine is controlled at 220°C. The screw is used for low-speed shearing to ensure uniform mixing and plasticization of the material. The temperature of the constant mold is 80°C. The molten and plasticized mixture is injected into the mold cavity at high speed through the hot runner. The injection pressure is 120MPa and the holding pressure is 60MPa. The molten mixture is bonded and composited with the film material in the mold cavity. After heat preservation and pressure holding, it is cooled and shaped. Finally, the mold is opened and demolded to obtain a high-density imitation metal plastic composite material product with integrated in-mold injection molding.

[0047] Furthermore, the film material includes a carrier layer, an ink layer, a white underlayer, and an adhesive layer arranged sequentially from the outside to the inside. In step S3, the adhesive layer of the film material faces into the mold cavity.

[0048] Example 2 This embodiment provides a high-density metal-like ABS composite material, comprising the following components in parts by weight: 80 parts ABS resin, 3 parts polyolefin blend resin, 15 parts modified iron powder, 5 parts modified chopped glass fiber, 1 part compatibilizer, 0.4 parts anti-aging agent, and 0.5 parts thickener. The modified iron powder is spherical atomized iron powder that has undergone surface modification treatment with polyether-modified amino silicone oil; the modified chopped glass fiber is chopped glass fiber that has undergone surface activation and modification with a silane coupling agent.

[0049] This embodiment also provides the application of the above-mentioned high-density metal-like ABS composite material in in-mold injection molding, and the application method includes the following steps: S1. Take ABS resin, polyolefin blend resin and ABS-g-MAH compatibilizer according to the ratio and put them into a high-speed mixer. Stir at room temperature for 8 minutes to mix evenly to obtain a premixed matrix. S2. Add modified iron powder, anti-aging agent, and thickener to the premixed matrix in sequence, and stir at low speed until well mixed; finally, add modified short-cut glass fiber and gently mix for a short time to obtain the mixture. S3. Place the film material into the mold cavity and position the film material on the inner surface of the mold cavity, then close the mold. S4. The mixture obtained in step S2 is fed into the injection molding machine barrel. The temperature of the melting section of the injection molding machine is controlled at 220°C. The screw is used for low-speed shearing to ensure uniform mixing and plasticization of the material. The temperature of the constant mold is 80°C. The molten and plasticized mixture is injected into the mold cavity at high speed through the hot runner. The injection pressure is 120MPa and the holding pressure is 60MPa. The molten mixture is bonded and composited with the film material in the mold cavity. After heat preservation and pressure holding, it is cooled and shaped. Finally, the mold is opened and demolded to obtain a high-density imitation metal plastic composite material product with integrated in-mold injection molding.

[0050] The rest of this embodiment is the same as that in Embodiment 1.

[0051] Example 3 This embodiment provides a high-density metal-like ABS composite material, comprising the following components in parts by weight: 90 parts ABS resin, 8 parts polyolefin blend resin, 35 parts modified iron powder, 12 parts modified chopped glass fiber, 2 parts compatibilizer, 1 part anti-aging agent, and 1.2 parts thickener. The modified iron powder is spherical atomized iron powder that has undergone surface modification treatment with polyether-modified amino silicone oil; the modified chopped glass fiber is chopped glass fiber that has undergone surface activation and modification with a silane coupling agent.

[0052] This embodiment also provides the application of the above-mentioned high-density metal-like ABS composite material in in-mold injection molding, and the application method includes the following steps: S1. Take ABS resin, polyolefin blend resin and ABS-g-MAH compatibilizer according to the ratio and put them into a high-speed mixer. Stir at room temperature for 8 minutes to mix evenly to obtain a premixed matrix. S2. Add modified iron powder, anti-aging agent, and thickener to the premixed matrix in sequence, and stir at low speed until well mixed; finally, add modified short-cut glass fiber and gently mix for a short time to obtain the mixture. S3. Place the film material into the mold cavity and position the film material on the inner surface of the mold cavity, then close the mold. S4. The mixture obtained in step S2 is fed into the injection molding machine barrel. The temperature of the melting section of the injection molding machine is controlled at 220°C. The screw is used for low-speed shearing to ensure uniform mixing and plasticization of the material. The temperature of the constant mold is 80°C. The molten and plasticized mixture is injected into the mold cavity at high speed through the hot runner. The injection pressure is 120MPa and the holding pressure is 60MPa. The molten mixture is bonded and composited with the film material in the mold cavity. After heat preservation and pressure holding, it is cooled and shaped. Finally, the mold is opened and demolded to obtain a high-density imitation metal plastic composite material product with integrated in-mold injection molding.

[0053] The rest of this embodiment is the same as that in Embodiment 1.

[0054] Comparative Example 1 The difference between this comparative example and Example 1 is that the modified iron powder is spherical atomized iron powder that has been surface-activated and coated with a silane coupling agent.

[0055] Furthermore, the silane coupling agent is KH-560.

[0056] Furthermore, the preparation method of the modified iron powder includes the following steps: D1. Mix the silane coupling agent with a 35% (w / w) aqueous ethanol solution and stir for 15 min to prepare the silane coupling agent activation solution. D2. Continuously stir the spherical atomized iron powder at high speed, and spray the silane coupling agent activation solution evenly to wet the powder; the mass ratio of spherical atomized iron powder to silane coupling agent is 100:2; after spraying, place it in an environment of 85℃ to dry for 2 hours, completely remove the solvent by rotary evaporation, and let it cool naturally before use.

[0057] Comparative Example 2 The difference between this comparative example and Example 1 is that the modified chopped glass fiber is chopped glass fiber that has undergone surface coating modification treatment with polyether-modified amino silicone oil.

[0058] Furthermore, the preparation method of the modified chopped glass fiber includes the following steps: E1. Mix polyether-modified amino silicone oil and anhydrous ethanol at a mass ratio of 1:3 and stir evenly to obtain a diluted polyether-modified amino silicone oil solution. E2. Immerse the chopped glass fibers in a diluted solution of polyether-modified amino silicone oil to fully impregnate and coat them. The mass ratio of glass fiber to polyether-modified amino silicone oil is 100:1.4. After impregnation, dry the fibers at 100°C for 1.5 hours to obtain modified chopped glass fibers.

[0059] Comparative Example 3 The difference between this comparative example and Example 1 is that the spherical atomized iron powder contains three particle sizes: fine particles with a diameter of 320 mesh, fine particles with a diameter of 90 mesh, and coarse particles with a diameter of 35 mesh, and they are blended in a weight ratio of 0.6:3:2.5.

[0060] Performance testing 1. Melt Flow Rate (MFR) of the high-density metallic-like ABS composite materials prepared in Example 1 and Comparative Examples 1-3: The test was conducted at 260°C; the number of grams of fluid flowing out of the circular tube within 10 minutes was recorded. The test data are shown in Table 1 below: Table 1

[0061] 2. Performance tests were conducted on the high-density metal-like plastic composite materials prepared in Example 1 and Comparative Examples 1-3. Their density, tensile strength, hardness, and weather resistance were tested. The test data are shown in Table 2 below: Table 2

[0062] Tensile strength test: Tensile strength shall be tested in accordance with GB / T 1040.2-2022.

[0063] Hardness testing: The Shore hardness tester was used for testing.

[0064] Weather resistance test: The sample was placed under a UV lamp for 36 hours. The UV lamp had a power of 60 W, a wavelength of 340 nm, and an irradiance of 0.68 W / m². 2 ·nm, temperature is 60°C.

[0065] As can be seen from Tables 1 and 2, Example 1 achieves the best balance between density, mechanical properties, flowability and weather resistance, which is superior to the comparative examples.

[0066] Comparative Example 1, which uses iron powder modified with a silane coupling agent, exhibits inferior flowability, density, mechanical properties, and weather resistance compared to Example 1, particularly with a significant decrease in hardness. Both Comparative Example 1 and Example 1 demonstrate that the long-chain macromolecules of the polyether-modified amino silicone oil form a flexible, low-friction physical coating on the iron powder surface, facilitating easy sliding of iron powder particles within the melt and thus significantly increasing the melt flow index. This flexible coating also prevents hard-on-hard contact between the iron powder and the resin, thereby improving tensile strength and weather resistance. In contrast, Comparative Example 1, which uses iron powder modified with a silane coupling agent, while the silane coupling agent can form chemical bonds with the iron powder, may result in a significant decrease in hardness and weather resistance because it may fix the iron powder within the resin. Furthermore, the silane coupling agent, being a small molecule, cannot provide the necessary lubrication effect for the iron powder, resulting in a lower density as the iron powder cannot be sufficiently tightly packed.

[0067] Comparative Example 2, which used polyether-modified amino silicone oil to modify glass fiber, showed an abnormally high density, and its flowability and strength were inferior to those of Example 1. As a reinforcing material, glass fiber needs to form a strong chemical bond with the resin matrix to effectively transfer loads and improve tensile strength and hardness. Comparative Example 1 and Example 1 show that Example 1 used a silane coupling agent for modification. The silane oxygen group at one end of the silane coupling agent reacts with the silanol groups on the glass fiber surface to form a covalent bond, while the organic functional groups at the other end react with or entangle with the ABS resin, resulting in significant product reinforcement. In contrast, Comparative Example 2 used polyether-modified amino silicone oil. The polyether-modified amino silicone oil forms a lubricating and flexible physical coating on the glass fiber surface. While this allows the glass fiber to flow more easily during injection molding, it also hinders the formation of a strong bond between the glass fiber and the resin. In Comparative Example 2, the glass fiber not only failed to provide reinforcement but, due to its smooth surface and large aspect ratio, was prone to excessive sliding, breakage, or agglomeration during mixing and injection molding. This could lead to an abnormally high density in Comparative Example 2, which is likely due to the irregular, loose accumulation of broken glass fiber fragments; it also results in lower tensile strength and hardness compared to Example 1.

[0068] Comparative Example 3 used a three-size blend of iron powder. Due to the lack of medium-sized particles, the gaps between coarse particles were too large, and they could not be effectively separated or stably supported by fine particles. This caused isolated large particles to easily rotate or shift under stress, failing to effectively bear and transfer stress. At the same time, a large number of fine and tiny particles, lacking the interspersing of medium-sized particles, tended to aggregate and settle, forming localized loose agglomerates. These factors combined resulted in increased friction within the system, the worst fluidity, and the inability to form a coherent rigid framework, thus leading to the lowest hardness and tensile strength. This fully demonstrates that the continuous blending of four size grades is the key to achieving a synergistic effect of high fluidity and high mechanical properties in a highly filled system.

[0069] The above embodiments are preferred implementations of the present invention. In addition, the present invention can be implemented in other ways. Any obvious substitutions without departing from the concept of the present invention are within the protection scope of the present invention.

Claims

1. A high-density, metal-like ABS composite material, characterized in that: The product comprises the following components in parts by weight: 80-90 parts ABS resin, 3-8 parts polyolefin blend resin, 15-35 parts modified iron powder, 5-12 parts modified chopped glass fiber, 1-2 parts compatibilizer, 0.4-1 part anti-aging agent, and 0.5-1.2 parts thickener. The modified iron powder is spherical atomized iron powder that has undergone surface coating modification with polyether-modified amino silicone oil; the modified chopped glass fiber is chopped glass fiber that has undergone surface activation modification with a silane coupling agent.

2. The high-density metal-like ABS composite material according to claim 1, characterized in that: The polyolefin blend resin is a mixture of PP resin and PE resin, wherein the weight ratio of PP resin to PE resin is 1 to 2:

1.

3. The high-density metal-like ABS composite material according to claim 1, characterized in that: The compatibilizer is ABS-g-MAH.

4. The high-density metal-like ABS composite material according to claim 1, characterized in that: The polyether-modified amino silicone oil comprises the following components in parts by weight: 60-80 parts of octamethylcyclotetrasiloxane, 15-25 parts of N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-8 parts of hexamethyldisiloxane, 0.2-0.5 parts of tetramethylammonium hydroxide, 0.05-0.15 parts of chloroplatinic acid, and 10-20 parts of epoxy-modified polyether acrylate.

5. The high-density metal-like ABS composite material according to claim 4, characterized in that: The preparation method of the polyether-modified amino silicone oil includes the following steps: A1. Octamethylcyclotetrasiloxane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane and hexamethyldisiloxane are added sequentially to a reaction vessel, nitrogen gas is introduced and the temperature is raised to 55-65°C, and the mixture is stirred for 10-20 min; then, moisture is removed by vacuuming for 0.8-1.2 h; next, the temperature is raised to 100-120°C and tetramethylammonium hydroxide catalyst is added, and the reaction is carried out for 4-6 h; A2. After the reaction is complete, raise the temperature to 120-170°C and continue the reaction for 25-35 minutes to decompose the tetramethylammonium hydroxide catalyst. Then, perform vacuum treatment again for 0.8-1.2 hours to remove the decomposition products and low-boiling substances of tetramethylammonium hydroxide, and obtain a transparent and clear end-group hydrogen-containing amino silicone oil. A3. Add epoxy-modified polyether acrylate and isopropanol to hydrogen-terminated amino silicone oil, heat to 55-65°C and mix for 10-20 minutes, then add chloroplatinic acid and mix evenly for 0.2-0.8 hours. Finally, remove the solvent by vacuum distillation at 70-80°C to obtain polyether-modified amino silicone oil.

6. The high-density metal-like ABS composite material according to claim 1, characterized in that: The spherical atomized iron powder contains four particle sizes: fine particles with a diameter of 310–330 mesh, fine particles with a diameter of 70–110 mesh, medium particles with a diameter of 40–70 mesh, and coarse particles with a diameter of 26–40 mesh. The weights are blended in a ratio of 0.5–0.7:2–4:5–7:2–3.

7. The high-density metal-like ABS composite material according to claim 1, characterized in that: The silane coupling agent is KH-560 or KH-550.

8. The high-density metal-like ABS composite material according to claim 1, characterized in that: The anti-aging agent is antioxidant 1010; the viscosity reducer is pentaerythritol stearate.

9. The application of the high-density metal-like ABS composite material according to any one of claims 1-8 in in-mold injection molding.

10. The application according to claim 9, characterized in that: Includes the following steps: S1. Take ABS resin, polyolefin blend resin and ABS-g-MAH compatibilizer according to the ratio and put them into a high-speed mixer. Stir at room temperature for 5 to 10 minutes to mix evenly to obtain a premixed matrix. S2. Add modified iron powder, anti-aging agent, and thickener to the premixed matrix in sequence, and stir at low speed until well mixed; finally, add modified short-cut glass fiber and gently mix for a short time to obtain the mixture. S3. Place the film material into the mold cavity and position the film material on the inner surface of the mold cavity, then close the mold. S4. The mixture obtained in step S2 is fed into the barrel of an injection molding machine. The temperature of the melting section of the injection molding machine is controlled at 200-230℃. The screw is used for low-speed shearing to ensure uniform mixing and plasticization of the material. The temperature of the mold is kept constant at 75-85℃. The molten and plasticized mixture is injected into the mold cavity at high speed through the hot runner. The injection pressure is 100-140MPa and the holding pressure is 40-80MPa. The molten mixture is bonded and composited with the film material in the mold cavity. After heat preservation and pressure holding, it is cooled and shaped. Finally, the mold is opened and demolded to obtain a high-density imitation metal plastic composite material product with integrated in-mold injection molding.

Images