Halogen-free and fluorine-free PC composite material with matt effect and flame retardancy

Abstract

The present application provides a kind of halogen-free fluorine-free PC composite material with matte effect and flame retardancy, comprising the following components by weight: PC, 39-93.8 parts; matte effect additive, 5-25 parts; toughening agent, 0.5-10 parts; flame retardant, 0.5-20 parts; anti-dripping agent, 0.05-2 parts; antioxidant, 0.05-2 parts; colorant, 0.1-2 parts; the matte effect additive is one or more than two compounds of matting agent, inorganic mineral powder additive, organic additive, high molecular additive, incompatible polymer additive, reactive polymer additive; the anti-dripping agent is a fluorine-free anti-dripping agent. The composite material provided by the present application does not contain halogen and fluorine-containing components, is more environmentally friendly, has good flame retardant effect and mechanical properties, the appearance of the product formed by the composite material is better, the surface matte effect is better, the production cost is saved, and the application range of the composite material is expanded.

Description

[Technical Field]

[0001] This invention relates to the field of composite material technology, and in particular to a halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy. [Background Technology]

[0002] Polycarbonate (PC) possesses excellent mechanical properties, dimensional stability, heat resistance, UV resistance, and electrical properties, making it widely used as an engineering plastic in glass assembly, automotive, and electronics industries. However, PC's inherent flame retardancy rating is UL94 V-2 (it drips when exposed to fire), posing a safety hazard. Therefore, in practical production and applications, PC must be modified to improve its flame retardancy. Currently, the most common method to improve PC's flame retardancy is to combine halogen-free flame retardants with PTFE-containing anti-dripping agents. Among halogen-free flame retardants, perfluorobutyl sulfonate (PFBS) flame retardants are the most effective. Although they offer significant flame retardant improvements with minimal addition, they belong to perfluorinated or polyfluoroalkyl substances (PFAS), posing potential hazards to our health and the environment. While PTFE-containing anti-dripping agents enhance the material's resistance to dripping when exposed to fire, the fluorine they contain also poses a potential threat to our health and the environment.

[0003] With social development and technological advancements, mobile internet, new energy, and related industries have become closely intertwined with our lives. For the appearance of 3C electronic products, mainstream aesthetics have shifted away from high gloss and shine. Matte, frosted, and matte finishes are now considered more practical. These finishes make smooth surfaces less smooth, allowing light to diffuse and reduce glare, providing a more comfortable visual experience. They are also less prone to scratches and easier to carry and store. Currently, methods to achieve matte, frosted, and matte finishes on PC materials include: using matte molding molds to create the surface; and adding auxiliary materials such as silicone microspheres, silicone powder, and square barium sulfate to the PC material. However, the former involves complex molding and mold maintenance processes and high production costs; the latter is difficult to control the particle size of the auxiliary materials, making it difficult to control the material stability and the final matte effect. Furthermore, the cost of these auxiliary materials is high. Additionally, neither of these methods can achieve a combination of matte, frosted, and matte textures with environmentally friendly flame retardancy in PC materials.

[0004] In view of this, the present invention provides a halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy. The resulting composite material does not contain halogens or fluorine-containing components. After molding, the product has a good appearance and matte finish (surface gloss reaches 40-60 GU), while also having good flame retardancy and mechanical properties, saving costs and expanding the application range of the composite material. [Summary of the Invention]

[0005] The technical problem this invention aims to solve is as follows: Currently, when modifying PC to enhance its flame retardancy, it is generally necessary to add halogen-free flame retardants such as perfluorobutyl sulfonate flame retardants (PFBS type) and PTFE-containing anti-dripping agents. However, the fluorine contained in these two additives poses a hazard to human health and the environment. To achieve a matte or frosted finish, products are typically molded using frosted molding dies or by adding auxiliary materials such as organosilicon microspheres, organosilicon powder, or square barium sulfate. The former involves complex processes and high production costs, while the latter suffers from difficulties in controlling the particle size of the auxiliary materials, resulting in uncontrollable frosting effects and composite material stability, as well as high costs. This invention provides a halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy to address these problems.

[0006] The solution to the technical problem of this invention is: a halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy, comprising the following components in parts by weight:

[0007] PC, 39–93.8 copies;

[0008] Matte finish additive, 5-25 parts;

[0009] Toughening agent, 0.5–10 parts;

[0010] Flame retardant, 0.5–20 parts;

[0011] Anti-dripping agent, 0.05–2 parts;

[0012] Antioxidant, 0.05–2 parts;

[0013] Colorant, 0.1 to 2 parts;

[0014] The matte finish additive is one or more of the following: matting agent, inorganic mineral powder additive, organic additive, polymer additive, incompatible polymer additive, and additive reactive polymer additive;

[0015] The anti-drip agent is a fluorine-free anti-drip agent, and the anti-drip agent is one or more of the following: silicon-based anti-drip agent, carbon-based anti-drip agent, whisker-based anti-drip agent, and inorganic clay-based anti-drip agent.

[0016] Preferably, the PC is virgin PC or recycled PC (PCR PC).

[0017] Preferably, the PC is one or more of the following: bisphenol A type PC, polyester type PC, organosilicon copolymer PC, cyclohexane bisphenol A type PC, and high-temperature resistant PC synthesized from bisphenol TMC. The melt flow rate MI of the PC is (4-70) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20,000-50,000, and the molecular weight distribution is 1-2.5.

[0018] Preferably, the matting agent comprises one or more of titanium dioxide, silica, silicates, or aluminates; the inorganic mineral powder additive comprises one or more of inorganic silica microspheres (average particle size 15-50 μm), nano-barium sulfate (average particle size 1-3 μm), and surface-modified talc; the organic additive comprises organosilicon microspheres (average particle size 4-8 μm); the polymer additive comprises polymethyl methacrylate (PMMA) microspheres (average particle size 5-15 μm); the incompatible polymer additive comprises one or more of ultra-high molecular weight styrene-acrylonitrile copolymer, ultra-high molecular weight polystyrene, ultra-high molecular weight acrylics, and ultra-high molecular weight polyethylene; and the added reactive polymer additive comprises one or more of maleic anhydride grafts and epoxy graft polymers.

[0019] Preferably, the toughening agent is one or more of the following: unsaturated rubber toughening agent, saturated rubber toughening agent, styrene-based thermoplastic elastomer toughening agent, polyurethane-based thermoplastic elastomer toughening agent, polyolefin-based thermoplastic elastomer toughening agent, polyamide-based thermoplastic elastomer toughening agent, high-rubber powder toughening agent, acrylate copolymer toughening agent, silicone / acrylic composite rubber toughening agent, ethylene-methyl acrylate copolymer, or n-butyl acrylate-glycidyl ester toughening agent.

[0020] Preferably, the flame retardant is one or more of the following: hypophosphite flame retardants, phosphate ester flame retardants, sulfonate flame retardants, phosphazene flame retardants, organosilicon flame retardants, and silane coupling agent flame retardants.

[0021] Preferably, the silicon-based anti-drip agent comprises one or more of silicon nanotubes, wollastonite, and talc; the carbon-based anti-drip agent comprises one or two of single-walled carbon nanotubes and multi-walled carbon nanotubes; the whisker-based anti-drip agent comprises one or two of calcium sulfate whiskers and magnesium sulfate whiskers; and the inorganic clay-based anti-drip agent comprises montmorillonite.

[0022] Preferably, the antioxidant is one or more of hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, and amine antioxidants.

[0023] Preferably, the colorant is one or more of the following: pure powder colorant, colored sand colorant, and color masterbatch colorant.

[0024] A method for preparing a halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy is characterized in that the components are mixed evenly and then fed into an extruder for extrusion granulation. The extruder is a twin-screw extruder, the processing temperature range of the extruder is set to 260℃~270℃, and the screw speed of the extruder is 480~500RPM.

[0025] The beneficial effects of this invention are that it provides a halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy. The resulting composite material does not contain halogens or fluorine-containing components, making it relatively environmentally friendly. At the same time, it can have good flame retardancy and mechanical properties. After the composite material is molded, the product has a good appearance and a good matte finish (surface gloss reaches 40-60 GU), which saves production costs and expands the application range of the composite material. [Attached Image Description]

[0026] Figure 1 This is a schematic diagram of the appearance of the product injection molded from the particles obtained in Embodiment 1 of the present invention.

[0027] Figure 2 This is a schematic diagram of the appearance of the product obtained by particle injection molding in Embodiment 2 of the present invention.

[0028] Figure 3 This is a schematic diagram of the appearance of the product injection molded from the particles obtained in Comparative Example 1 of the present invention.

[0029] Figure 4 This is a schematic diagram of the appearance of the product injection molded from the particles obtained in Comparative Example 2 of the present invention.

Detailed Implementation Methods

[0030] To further illustrate the technical means and effects of the present invention, the following detailed description is provided in conjunction with the embodiments of the present invention and their accompanying drawings.

[0031] This invention provides a halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy, comprising the following components in parts by weight:

[0032] PC, 39–93.8 copies;

[0033] Matte finish additive, 5-25 parts;

[0034] Toughening agent, 0.5–10 parts;

[0035] Flame retardant, 0.5–20 parts;

[0036] Anti-dripping agent, 0.05–2 parts;

[0037] Antioxidant, 0.05–2 parts;

[0038] Colorant, 0.1 to 2 parts;

[0039] The matte finish additive is one or more of the following: matting agent, inorganic mineral powder additive, organic additive, polymer additive, incompatible polymer additive, and additive reactive polymer additive;

[0040] The anti-drip agent is a fluorine-free anti-drip agent, and the anti-drip agent is one or more of the following: silicon-based anti-drip agent, carbon-based anti-drip agent, whisker-based anti-drip agent, and inorganic clay-based anti-drip agent.

[0041] The PC referred to herein is either virgin PC or recycled PC (PCR PC).

[0042] The PC is one or more of the following: bisphenol A type PC, polyester type PC, organosilicon copolymer PC, cyclohexane bisphenol A type PC, and high-temperature resistant PC synthesized from bisphenol TMC. The melt flow rate MI of the PC is (4-70) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20,000-50,000, and the molecular weight distribution is 1-2.5.

[0043] The matting agent comprises one or more of titanium dioxide, silica, silicates, or aluminates; the inorganic mineral powder additive comprises one or more of inorganic silica microspheres (average particle size 15-50 μm), nano-barium sulfate (average particle size 1-3 μm), and surface-modified talc; the organic additive comprises organosilicon microspheres (average particle size 4-8 μm); the polymer additive comprises polymethyl methacrylate (PMMA) microspheres (average particle size 5-15 μm); the incompatible polymer additive comprises one or more of ultra-high molecular weight styrene-acrylonitrile copolymer, ultra-high molecular weight polystyrene, ultra-high molecular weight acrylics, and ultra-high molecular weight polyethylene; and the added reactive polymer additive comprises one or more of maleic anhydride grafts and epoxy graft polymers.

[0044] The toughening agent is one or more of the following: unsaturated rubber toughening agent, saturated rubber toughening agent, styrene thermoplastic elastomer toughening agent, polyurethane thermoplastic elastomer toughening agent, polyolefin thermoplastic elastomer toughening agent, polyamide thermoplastic elastomer toughening agent, high-rubber powder toughening agent, acrylate copolymer toughening agent, silicone / acrylic composite rubber toughening agent, ethylene-methyl acrylate copolymer, or n-butyl acrylate-glycidyl ester toughening agent.

[0045] The unsaturated rubber toughening agent includes one or more blends of nitrile rubber (NBR), natural rubber (NR), styrene-butadiene rubber (SBR), and butadiene rubber (BR); the saturated rubber toughening agent includes one or more blends of butyl rubber (IIR), ethylene propylene rubber (EPR), ethylene propylene diene monomer (EPDM), and halogenated butyl rubber; the styrene-based thermoplastic elastomer toughening agent includes methyl methacrylate-butadiene-styrene terpolymer (MBS), styrene-butadiene-styrene copolymer (SBS), and hydrogenated SBS (SEBS). The toughening agent comprises one or more of the following: styrene-isoprene-styrene (SIS); the polyamide thermoplastic elastomer toughening agent includes TPU; the polyolefin thermoplastic elastomer toughening agent comprises one or more of the following: chlorinated polyethylene (CPE), ethylene-octene copolymer (POE), thermoplastic dynamic vulcanizate (TPV), and ethylene-vinyl acetate copolymer (EVA); the polyamide thermoplastic elastomer toughening agent includes polyamide thermoplastic elastomer (TPAE); and the acrylate copolymer toughening agent includes acrylic copolymer modified resin (ACR).

[0046] The flame retardant is one or more of the following: hypophosphite flame retardants, phosphate ester flame retardants, sulfonate flame retardants, phosphazene flame retardants, organosilicon flame retardants, and silane coupling agent flame retardants.

[0047] The hypophosphite-based flame retardant includes one or a combination of vinyl aluminum hypophosphite and vinyl phosphoric acid; the phosphate ester-based flame retardant includes one or more of 1,3-phenylene phosphate (2,6-tolyl) tetraester, tetraphenyl bisphenol A diphosphate and its derivatives (BDP), tetraphenyl resorcinol diphosphate and its derivatives (RDP), and triphenyl phosphate (TPP); the sulfonate-based flame retardant includes one or a combination of potassium benzenesulfonylbenzenesulfonate (KSS), sodium 2,4,5-trichlorobenzenesulfonate (STB), and sodium toluenesulfonate (NATS). The flame retardant comprises one or more of the following: the phosphazene flame retardant includes one or two of hexaphenoxycyclotriphosphazene and hexachlorocyclotriphosphazene; the organosilicon flame retardant includes one or more of the following: polysiloxane and its derivative flame retardants, cross-linked polydimethylsiloxane (PDMS) and its derivative flame retardants, polysilane flame retardants, polysiloxane and its derivative flame retardants, polysilsesquioxane and its derivative flame retardants, and silane or siloxane and its derivative flame retardants containing functional groups such as amino, hydroxyl, and carboxyl groups; the silane coupling agent flame retardant includes one or two of the following: vinyltrimethoxysilane and titanate coupling agent.

[0048] The silicon-based anti-drip agent comprises one or more of silicon nanotubes, wollastonite, and talc; the carbon-based anti-drip agent comprises one or two of single-walled carbon nanotubes and multi-walled carbon nanotubes; the whisker-based anti-drip agent comprises one or two of calcium sulfate whiskers and magnesium sulfate whiskers; and the inorganic clay-based anti-drip agent comprises montmorillonite.

[0049] The antioxidant is one or more of the following: hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, and amine antioxidants.

[0050] The hindered phenolic antioxidants include one or more of the following: (β-3,5-di-tert-butyl-4-hydroxyphenyl) octadecyl acrylate, 2,6-di-tert-butyl-4-cresol (antibiotic 264), and β-(4-hydroxy-3,5-di-tert-butylphenyl) propionic acid; the phosphite antioxidants include one or more of the following: tris(2,4-di-tert-butylphenyl) phosphite, pentaerythritol diphosphite, triphenyl phosphite, and tributyl phosphite; the thiolated antioxidants include thiodicarboxylic acid esters; and the amine antioxidants include one or more of the following: naphthylamine, diphenylamine, and p-phenylenediamine.

[0051] The colorant is one or more of the following: pure carbon black type colorant, oil-based black type colorant, dye type colorant, manganese iron black type colorant, chromium copper black type colorant, colorant with added lubricant powder carrier, colorant with added resin powder carrier, and dispersant colorant.

[0052] The colorant is one or more of the following: pure powder colorant, colored sand colorant, and color masterbatch colorant.

[0053] Example 1

[0054] A halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy comprises the following components in parts by weight: 66.2 parts PC, 17 parts matte finish additive, 5 parts toughening agent, 9.9 parts flame retardant, 0.6 parts fluorine-free anti-dripping agent, 0.3 parts antioxidant, and 1 part colorant.

[0055] The 66.2 PC samples were all PCR PCs, specifically a mixture of 30 MITEK 10040 PCR PCs and 36.2 MITEK 20050 PCR PCs. The MITEK 10040 PCR PC had a melt flow rate (MI) of 65.6 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 25,000–30,000, and a molecular weight distribution of 1.5–2.0. The MITEK 20050 PCR PC had a melt flow rate (MI) of 6.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 47,000–50,000, and a molecular weight distribution of 1.5–2.0.

[0056] The matte finish additive is an inorganic mineral powder additive, specifically talc powder that has undergone surface grafting modification using long-chain silanes. Its fineness is 2000 mesh and its aspect ratio is 5:1, which can improve the compatibility and surface bonding with PC. Under the condition of meeting the high flexural modulus, the composite material can have a matte frosted effect directly after injection molding in a mirror mold.

[0057] The toughening agent is a styrene-based thermoplastic elastomer, specifically a core-shell methyl methacrylate-butadiene-styrene terpolymer (MBS), with a rubber core and a grafted methyl methacrylate (MMA) shell. It can significantly improve the impact resistance of resins and engineering plastics, while also exhibiting good high-temperature molding resistance (heat aging resistance, hydrolysis resistance), chemical resistance, and durability.

[0058] The 9.9 parts of flame retardant are a compound of 0.4 parts of sulfonate flame retardant and 9.5 parts of phosphate flame retardant. The sulfonate flame retardant is potassium benzenesulfonylbenzenesulfonate (KSS), which is characterized by low addition amount, halogen-free and fluorine-free, and can be combined with other types of flame retardants. The phosphate flame retardant is tetraphenylbisphenol A diphosphate and its derivative flame retardant (BDP), which is a pale yellow liquid with high viscosity at room temperature (25℃) and good fluidity after heating to above 70℃. The content of phosphorus element in the component that plays a key role in flame retardancy is ≥8.9%.

[0059] The fluorine-free anti-dripping agent is a silicon-based anti-dripping agent, specifically a surface-modified silicon nanowire. The S891 type anti-dripping agent produced by Dongguan Sanhe Chemical is selected, which has the characteristics of low addition amount and significant anti-dripping effect.

[0060] The 0.3 parts of antioxidant are a compound of 0.24 parts of hindered phenolic antioxidant and 0.06 parts of phosphite antioxidant. The hindered phenolic antioxidant is selected from octadecyl acrylate (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, i.e., antioxidant 1076, and the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite, i.e., antioxidant 168. The two have a significant synergistic effect and are characterized by low addition amount and significant antioxidant and anti-yellowing effects.

[0061] The colorant is carbon black-based black sand coated with a flow dispersant material. The flow dispersant is Kao EB-FF type flow dispersant, accounting for 50%. It ensures that the carbon black can be dispersed and does not agglomerate, while having little impact on the performance of the resin material and minimal environmental pollution.

[0062] To prepare this halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy, the corresponding weight parts of the components are weighed according to the above proportions, and the components are mixed evenly and then fed into an extruder. The mixture of the components is sheared, mixed and conveyed by the extruder screw, and fully melted and compounded. Then it is extruded through the die head, drawn into strips, cooled and pelletized to finally obtain finished particles. The extruder is a twin-screw extruder, the processing temperature range of the extruder is set to 260℃~270℃, and the screw speed of the extruder is 480~500RPM.

[0063] Example 2

[0064] A halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy comprises the following components in parts by weight: 65.2 parts PC, 17 parts matte finish additive, 6 parts toughening agent, 9.9 parts flame retardant, 0.6 parts fluorine-free anti-dripping agent, 0.3 parts antioxidant, and 1 part colorant.

[0065] The 65.2 PC samples were all PCR PCs, specifically a mixture of 30 MITEK 10040 PCR PCs and 35.2 MITEK 20050 PCR PCs. The MITEK 10040 PCR PC had a melt flow rate (MI) of 65.6 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 25,000–30,000, and a molecular weight distribution of 1.5–2.0. The MITEK 20050 PCR PC had a melt flow rate (MI) of 6.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 47,000–50,000, and a molecular weight distribution of 1.5–2.0.

[0066] The matte finish additive is an inorganic mineral powder additive, specifically talc powder that has undergone surface grafting modification using long-chain silanes. Its fineness is 2000 mesh and its aspect ratio is 5:1, which can improve the compatibility and surface bonding with PC. Under the condition of meeting the high flexural modulus, the composite material can have a matte frosted effect directly after injection molding in a mirror mold.

[0067] The toughening agent is a styrene-based thermoplastic elastomer, specifically a core-shell methyl methacrylate-butadiene-styrene terpolymer (MBS), with a rubber core and a grafted methyl methacrylate (MMA) shell. It can significantly improve the impact resistance of resins and engineering plastics, while also exhibiting good high-temperature molding resistance (heat aging resistance, hydrolysis resistance), chemical resistance, and durability.

[0068] The 9.9 parts of flame retardant are a compound of 0.4 parts of sulfonate flame retardant and 9.5 parts of phosphate flame retardant. The sulfonate flame retardant is potassium benzenesulfonylbenzenesulfonate (KSS), which is characterized by low addition amount, halogen-free and fluorine-free, and can be combined with other types of flame retardants. The phosphate flame retardant is tetraphenylbisphenol A diphosphate and its derivative flame retardant (BDP), which is a pale yellow liquid with high viscosity at room temperature (25℃) and good fluidity after heating to above 70℃. The content of phosphorus element in the component that plays a key role in flame retardancy is ≥8.9%.

[0069] The fluorine-free anti-dripping agent is a silicon-based anti-dripping agent, specifically a surface-modified silicon nanowire. The S891 type anti-dripping agent produced by Dongguan Sanhe Chemical is selected, which has the characteristics of low addition amount and significant anti-dripping effect.

[0070] The 0.3 parts of antioxidant are a compound of 0.24 parts of hindered phenolic antioxidant and 0.06 parts of phosphite antioxidant. The hindered phenolic antioxidant is selected from octadecyl acrylate (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, i.e., antioxidant 1076, and the phosphite antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite, i.e., antioxidant 168. The two have a significant synergistic effect and are characterized by low addition amount and significant antioxidant and anti-yellowing effects.

[0071] The colorant is carbon black-based black sand coated with a flow dispersant material. The flow dispersant is Kao EB-FF type flow dispersant, accounting for 50%. It ensures that the carbon black can be dispersed and does not agglomerate, while having little impact on the performance of the resin material and minimal environmental pollution.

[0072] To prepare this halogen-free and fluorine-free PC composite material that combines a matte finish and flame retardancy, the corresponding weight parts of the components are weighed according to the above proportions, and the components are mixed evenly and then fed into an extruder. The mixture of the components is sheared, mixed and conveyed by the extruder screw, and fully melted and compounded. Then it is extruded through the die head, drawn into strips, cooled and pelletized to finally obtain finished particles. The extruder is a twin-screw extruder, the processing temperature range of the extruder is set to 260℃~270℃, and the screw speed of the extruder is 480~500RPM.

[0073] Comparative Example 1

[0074] A PC composite material comprises the following components in parts by weight: 66.8 parts PC, 17 parts matte finish additive, 5 parts toughening agent, 9.9 parts flame retardant, 0.3 parts antioxidant, and 1 part colorant.

[0075] The 66.8 PC samples were all PCR PCs, specifically a mixture of 30 MITEK 10040 PCR PCs and 36.8 MITEK 20050 PCR PCs. The MITEK 10040 PCR PC had a melt flow rate (MI) of 65.6 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 25,000–30,000, and a molecular weight distribution of 1.5–2.0. The MITEK 20050 PCR PC had a melt flow rate (MI) of 6.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 47,000–50,000, and a molecular weight distribution of 1.5–2.0.

[0076] The matte finish additive is an inorganic mineral powder additive, specifically talc powder that has undergone surface grafting modification using long-chain silanes. The fineness of the talc powder is 2000 mesh, and the aspect ratio is 5:1.

[0077] The toughening agent is a styrene-based thermoplastic elastomer, specifically a core-shell structured methyl methacrylate-butadiene-styrene terpolymer (MBS), with a rubber core and a grafted methyl methacrylate (MMA) shell.

[0078] The 9.9 parts of flame retardant are a compound of 0.4 parts of sulfonate flame retardant and 9.5 parts of phosphate flame retardant. The sulfonate flame retardant is potassium benzenesulfonylbenzenesulfonate (KSS), and the phosphate flame retardant is tetraphenylbisphenol A diphosphate and its derivative flame retardant (BDP).

[0079] The 0.3 parts of antioxidant are a compound of 0.24 parts of hindered phenolic antioxidant and 0.06 parts of phosphite antioxidant. The hindered phenolic antioxidant is octadecyl acrylate (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, i.e., antioxidant 1076, and the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, i.e., antioxidant 168.

[0080] The colorant is carbon black-based black sand coated with a flow dispersant material, and the flow dispersant is Kao EB-FF type flow dispersant, accounting for 50%.

[0081] To prepare the PC composite material, the corresponding weight parts of the components are weighed according to the above proportions, and the components are mixed evenly and then fed into an extruder. After the mixture of the components is sheared, mixed and conveyed by the extruder screw, it is fully melted and compounded. Then it is extruded through the die head, drawn into strips, cooled and pelletized to finally obtain finished particles. The extruder is a twin-screw extruder, the processing temperature range of the extruder is set to 260℃~270℃, and the screw speed of the extruder is 480~500RPM.

[0082] Comparative Example 2

[0083] A PC composite material comprises the following components in parts by weight: 66.5 parts PC, 17 parts matte finish additive, 5 parts toughening agent, 9.9 parts flame retardant, 0.3 parts fluorine-containing anti-dripping agent, 0.3 parts antioxidant, and 1 part colorant.

[0084] The 66.5 PC samples were all PCR PCs, specifically a mixture of 30 MITEK 10040 PCR PCs and 36.5 MITEK 20050 PCR PCs. The MITEK 10040 PCR PC had a melt flow rate (MI) of 65.6 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 25,000–30,000, and a molecular weight distribution of 1.5–2.0. The MITEK 20050 PCR PC had a melt flow rate (MI) of 6.2 g / 10 min (300℃ / 1.2 kg), a weight-average molecular weight of 47,000–50,000, and a molecular weight distribution of 1.5–2.0.

[0085] The matte finish additive is an inorganic mineral powder additive, specifically talc powder that has undergone surface grafting modification using long-chain silanes. The fineness of the talc powder is 2000 mesh, and the aspect ratio is 5:1.

[0086] The toughening agent is a styrene-based thermoplastic elastomer, specifically a core-shell structured methyl methacrylate-butadiene-styrene terpolymer (MBS), with a rubber core and a grafted methyl methacrylate (MMA) shell.

[0087] The 9.9 parts of flame retardant are a compound of 0.4 parts of sulfonate flame retardant and 9.5 parts of phosphate flame retardant. The sulfonate flame retardant is potassium benzenesulfonylbenzenesulfonate (KSS), and the phosphate flame retardant is tetraphenylbisphenol A diphosphate and its derivative flame retardant (BDP).

[0088] The fluorinated anti-dripping agent is a non-coated polytetrafluoroethylene (PTFE) material, which is a white powder and does not easily adhere.

[0089] The 0.3 parts of antioxidant are a compound of 0.24 parts of hindered phenolic antioxidant and 0.06 parts of phosphite antioxidant. The hindered phenolic antioxidant is octadecyl acrylate (β-3,5-di-tert-butyl-4-hydroxyphenyl) acrylate, i.e., antioxidant 1076, and the phosphite antioxidant is tris(2,4-di-tert-butylphenyl) phosphite, i.e., antioxidant 168.

[0090] The colorant is carbon black-based black sand coated with a flow dispersant material, and the flow dispersant is Kao EB-FF type flow dispersant, accounting for 50%.

[0091] To prepare the PC composite material, the corresponding weight parts of the components are weighed according to the above proportions, and the components are mixed evenly and then fed into an extruder. After the mixture of the components is sheared, mixed and conveyed by the extruder screw, it is fully melted and compounded. Then it is extruded through the die head, drawn into strips, cooled and pelletized to finally obtain finished particles. The extruder is a twin-screw extruder, the processing temperature range of the extruder is set to 260℃~270℃, and the screw speed of the extruder is 480~500RPM.

[0092] The particles from Examples 1-2 and Comparative Examples 1-2 were directly injection molded into color slabs using a 3000# mirror-finish mold core. A schematic diagram of the appearance is shown below. Figure 1-4 As shown, the particles from Examples 1-2 and Comparative Examples 1-2 were injection molded into standard test strips on an injection molding machine. The test strips were then subjected to relevant physical property tests according to the standard. The test results are shown in Table 1.

[0093] Table 1 Test Results

[0094]

[0095] The test results above show that this invention has achieved the preparation of a halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy. The resulting composite material does not contain halogen compounds or fluorine substances, making it more environmentally friendly. It also has good flame retardancy and mechanical properties. The composite material products have a beautiful appearance (uniform appearance, no defects such as material spots or silver streaks) and a good matte finish (appearance gloss reaches 40-60 GU), saving production costs and expanding the application range of composite materials.

[0096] It should be noted that the present invention is not limited to the above embodiments. Any simple modifications, equivalent changes and alterations made by those skilled in the art to the above embodiments based on the technical solutions of the present invention shall fall within the protection scope of the present invention.

Claims

1. A halogen-free and fluorine-free PC composite material that combines a matte finish with flame retardancy, characterized in that, The components include the following parts by weight: PC, 39–93.8 copies; Matte finish additive, 5-25 parts; Toughening agent, 0.5–10 parts; Flame retardant, 0.5–20 parts; Anti-dripping agent, 0.05–2 parts; Antioxidant, 0.05–2 parts; Colorant, 0.1 to 2 parts; The matte finish additive is one or more of the following: matting agent, inorganic mineral powder additive, organic additive, polymer additive, incompatible polymer additive, and additive reactive polymer additive; The anti-drip agent is a fluorine-free anti-drip agent, and the anti-drip agent is one or more of the following: silicon-based anti-drip agent, carbon-based anti-drip agent, whisker-based anti-drip agent, and inorganic clay-based anti-drip agent.

2. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The PC is either virgin PC or recycled PC.

3. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The PC is one or more of the following: bisphenol A type PC, polyester type PC, organosilicon copolymer PC, cyclohexane bisphenol A type PC, and high-temperature resistant PC synthesized from bisphenol TMC. The melt flow rate MI of the PC is (4-70) g / 10 min (300℃ / 1.2 kg), the weight average molecular weight is 20,000-50,000, and the molecular weight distribution is 1-2.

5.

4. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The matting agent comprises one or more of titanium dioxide, silica, silicates, or aluminates; the inorganic mineral powder additive comprises one or more of inorganic silica microspheres, nano-barium sulfate, and surface-modified talc; the organic additive comprises organosilicon microspheres; the polymeric additive comprises polymethyl methacrylate; the incompatible polymeric additive comprises one or more of ultra-high molecular weight styrene-acrylonitrile copolymer, ultra-high molecular weight polystyrene, ultra-high molecular weight acrylics, and ultra-high molecular weight polyethylene; and the added reactive polymeric additive comprises one or more of maleic anhydride grafts and epoxy graft polymers.

5. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The toughening agent is one or more of the following: unsaturated rubber toughening agents, saturated rubber toughening agents, styrene-based thermoplastic elastomer toughening agents, polyurethane-based thermoplastic elastomer toughening agents, polyolefin-based thermoplastic elastomer toughening agents, polyamide-based thermoplastic elastomer toughening agents, high-rubber powder toughening agents, acrylate copolymer toughening agents, silicone / acrylic composite rubber toughening agents, ethylene-methyl acrylate copolymers, or n-butyl acrylate-glycidyl ester toughening agents.

6. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The flame retardant is one or more of the following: hypophosphite flame retardants, phosphate ester flame retardants, sulfonate flame retardants, phosphazene flame retardants, organosilicon flame retardants, and silane coupling agent flame retardants.

7. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The silicon-based anti-drip agent comprises one or more of silicon nanotubes, wollastonite, and talc; the carbon-based anti-drip agent comprises one or two of single-walled carbon nanotubes and multi-walled carbon nanotubes; the whisker-based anti-drip agent comprises one or two of calcium sulfate whiskers and magnesium sulfate whiskers; and the inorganic clay-based anti-drip agent comprises montmorillonite.

8. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The antioxidant is one or more of the following: hindered phenolic antioxidants, phosphite antioxidants, thiolated antioxidants, and amine antioxidants.

9. The halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in claim 1, characterized in that: The colorant is one or more of the following: pure powder colorant, colored sand colorant, and masterbatch colorant.

10. A method for preparing a halogen-free and fluorine-free PC composite material with both matte finish and flame retardancy as described in any one of claims 1-9, characterized in that: After the components are mixed evenly, they are fed into an extruder for granulation. The extruder is a twin-screw extruder, and the processing temperature range of the extruder is set to 260℃~270℃. The screw speed of the extruder is 480~500RPM.

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