A spray-free process for jade patterns

Abstract

The present invention belongs to the technical field of plastic products, and specifically relates to a spray-free process for jade patterns. The spray-free process for jade patterns comprises the following steps: mixing the raw materials evenly, performing injection molding, and polishing the surface. The present invention prepares specific masterbatches, adds functional additives, and combines molding technology to enable the final product to exhibit a natural, smooth, and layered jade texture without the use of an additional spraying process. This method not only greatly simplifies the production process and reduces costs, but also avoids the environmental pollution problems that may arise in the traditional spraying process. In addition, the product prepared by the technical solution provided by the present invention has good mechanical strength, weather resistance, wear resistance, and color durability, and is suitable for use in the fields of high-end decorative materials.

Description

Technical Field

[0001] The invention belongs to the technical field of plastic products, and particularly relates to a spray-free process for producing jade patterns. Background Art

[0002] In the field of plastic product processing, imparting unique decorative effects and textures to product surfaces has always been a key goal of the industry. Traditionally, to achieve an appearance similar to the texture of natural jade, manufacturers typically use a spray coating process. This involves spraying a coating containing specific pigments and additives onto the plastic product after it is formed. This coating is then dried and cured to create the desired texture and color. However, this traditional spray coating process has numerous drawbacks.

[0003] First, the spraying process requires additional equipment and procedures, which increases the complexity and cost of the production process. During the spraying process, paint waste, equipment maintenance, and energy consumption all constitute a considerable economic burden. Secondly, the spraying process may also cause environmental pollution problems. Volatile organic compounds (VOCs) in the paint easily evaporate into the atmosphere during the spraying and drying process, causing adverse effects on the environment. In addition, the adhesion and durability of the spray coating are also key factors that restrict product quality. Once the coating peels or fades, it will seriously affect the appearance and service life of the product.

[0004] In order to solve the above problems, the present invention proposes a spray-free process for jade patterns, which aims to make the final product show a natural, smooth and layered jade texture without using an additional spraying process, while improving the comprehensive performance of the product, providing a better choice for high-end decorative materials and other fields. Summary of the Invention

[0005] The purpose of the present invention is to provide a spray-free process for producing jade patterns. By preparing specific masterbatches and adding functional additives, combined with molding technology, the final product can exhibit a natural, smooth, and layered jade texture without the use of an additional spraying process, while also having good mechanical strength, weather resistance, wear resistance, and color durability.

[0006] A spray-free process for producing jade patterns comprises the following steps: mixing raw materials uniformly, performing injection molding, and polishing the surface to obtain the pattern.

[0007] Preferably, the raw materials include base resin, masterbatch and compatibilizer.

[0008] Preferably, the mass of the masterbatch is 1%-20% of the mass of the base resin.

[0009] Preferably, the added amount of the compatibilizer is 1%-3% of the total mass of the base resin and the masterbatch.

[0010] Preferably, the base resin includes one or more of PA, PP, PC, HIPS, ABS, PMMA, ABS / PMMA, TPU, PBT, and POM; more preferably, it is PP.

[0011] The PP is homopolymer PP, has a melt index of 10-15 g / 10 min at 190° C., an isotacticity of ≥95.5%, and a flexural modulus of ≥1300 MPa.

[0012] In some preferred embodiments, the PP is purchased from Dongguan Weicai Plastic Raw Materials Co., Ltd., PPH-M12.

[0013] The masterbatch is prepared from raw materials including, by weight, 60-120 parts of carrier resin, 0.1-0.5 parts of colorant, 0.5-1 parts of antioxidant, 0.5-1.5 parts of lubricant, 0.5-1 parts of light stabilizer, 2-5 parts of toughening agent and 3-8 parts of inorganic particles.

[0014] Preferably, the carrier resin includes one or more of ABS, PP, PE, PS, and PMMA; more preferably, it is PE, PMMA, and ABS.

[0015] Preferably, the mass ratio of PE, PMMA and ABS is 1:(0.5-2):(0.5-2); more preferably, it is 1:1:1.

[0016] Preferably, the PE includes LLDPE and HDPE.

[0017] Preferably, the mass ratio of LLDPE to HDPE is 1:(0.5-2); more preferably, it is 1:1.

[0018] Preferably, the LLDPE has a melt index of 45-55 g / 10 min at 190°C and a density of 0.9-0.95 g / cm 3 , Izod notch impact strength is 45-50kJ / m 2 .

[0019] In some preferred embodiments, the LLDPE is purchased from ExxonMobil, LL6201XR.

[0020] Preferably, the HDPE has a melt index of 28-32 g / 10 min at 190° C., a tensile yield stress of ≥20 MPa, and a flexural modulus of ≥950 MPa.

[0021] In some preferred embodiments, the HDPE is purchased from ExxonMobil, HDPE HMA 018.

[0022] Preferably, the PMMA has a melt index of 15-20 g / 10 min at 230° C., a total light transmittance of ≥92%, and a Rockwell hardness of ≥84.

[0023] In some preferred embodiments, the PMMA is purchased from Qingdao Zhongxin Huamei Plastic Co., Ltd., China, CM-211.

[0024] Preferably, the ABS has a melt index of 2-5 g / 10 min at 200°C, an elongation of 35%-45%, and a flexural strength of 600-650 kg / cm 3 .

[0025] In some preferred embodiments, the ABS is purchased from Chi Mei in Taiwan, China, PA-726M.

[0026] PP is selected as the main raw material for plastic products. It is not only lightweight, durable and easy to process, but also non-toxic and odorless, with excellent heat resistance and chemical stability, and good transparency, which can maximize the display of the color of the masterbatch. However, its wear resistance is poor, and the addition of masterbatch will affect its mechanical properties. Moreover, the addition of ordinary masterbatch cannot make plastic products show the natural, smooth and layered jade texture without the use of additional spraying process.

[0027] The inventors discovered that by using specific PE and PMMA as carrier resins to prepare masterbatches and applying them in plastic products, they can achieve a texture similar to natural jade without requiring an additional spraying process, while maintaining the color rendering and mechanical properties of the plastic product. This is likely due to the selection of raw materials with different melt indexes and the controlled addition amount, which allows the masterbatch to flow smoothly during the injection molding process, simulating a texture similar to natural jade. PE and PMMA exhibit a synergistic effect. The high strength and rigidity of HDPE provide a solid framework for plastic products, while also imparting high gloss and excellent dimensional stability, making the resulting plastic products suitable for decorative applications. The flexibility and impact resistance of LLDPE enhance the toughness of the plastic products. The combination of these two ensures that the plastic products maintain high strength while also possessing good impact resistance. The high transparency and gloss of PMMA enhance the appearance of the plastic products, improve the transparency of the masterbatch, and achieve clearer colors and a more premium texture. Furthermore, the addition of PMMA improves the surface quality of the plastic products, reducing blemishes and defects. However, the compatibility between PE and PMMA and PP is poor. Direct mixing may cause uneven distribution of the masterbatch in the system, affecting the product effect. In addition, the plastic products prepared from the masterbatch and PP raw materials have limited wear resistance and mechanical properties, which will affect their lifespan.

[0028] Preferably, the colorant includes dye-type color powder, which is not specifically limited and includes but is not limited to organic pigments, inorganic pigments, pearl powder, metal powder, etc.

[0029] Preferably, the antioxidant includes one or more of antioxidant 1010, antioxidant 1076, antioxidant 168, and antioxidant 300; more preferably, antioxidant 1010 and antioxidant 168.

[0030] Preferably, the mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:(0.5-2); more preferably, it is 1:1.

[0031] Preferably, the lubricant includes one or more of oxidized polyethylene wax, paraffin, calcium stearate, silicone oil, fatty acid amide, white mineral oil, barium stearate, magnesium stearate, ethylene bisstearamide, and pentaerythritol stearate; further preferably, oxidized polyethylene wax and calcium stearate.

[0032] Preferably, the mass ratio of the oxidized polyethylene wax to calcium stearate is (1-3):1, and more preferably, 2:1.

[0033] Preferably, the kinematic viscosity of the oxidized polyethylene wax at 140°C is 15 to 25 mm 2 / s, and a softening point of 110-120°C; further preferably, the kinematic viscosity of the oxidized polyethylene wax at 140°C is 20.5 mm 2 / s, softening point is 115℃.

[0034] In some preferred embodiments, the oxidized polyethylene wax is purchased from Henan Yuyang Wax Industry Co., Ltd.

[0035] Preferably, the light stabilizer comprises bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0036] Preferably, the toughening agent includes one or more of ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, ethylene-vinyl acetate copolymer, and ethylene-acrylate-glycidyl methacrylate terpolymer; further preferably, it is ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, and ethylene-vinyl acetate copolymer.

[0037] Preferably, the mass ratio of the ethylene-octene copolymer, the methyl methacrylate-butadiene-styrene copolymer, and the ethylene-vinyl acetate copolymer is (1-3):(1-3):1; more preferably, it is 2:2:1.

[0038] Preferably, the ethylene-octene copolymer has a melt index of 28-32 g / 10 min at 190° C., is preheated using a large rotor for 1 minute, and rotated at 121° C. for 4 minutes, and has a Mooney viscosity of 1-3 MU.

[0039] In some preferred embodiments, the ethylene-octene copolymer is purchased from Dow Chemical, USA, 8400.

[0040] Preferably, the methyl methacrylate-butadiene-styrene copolymer has a rubber content of 58%-62%, a hydroxyl value of 4-6 phr, and an impact strength of 73-75 kJ / m at a thickness of 1 / 8 inch. 2 .

[0041] In some preferred embodiments, the methyl methacrylate-butadiene-styrene copolymer is purchased from Kanebuchi, Japan, M521.

[0042] Preferably, the melt index of the ethylene-vinyl acetate copolymer at 190°C is 2-3 g / 10 min, the vinyl acetate content is 16%-20%, and the elongation at break is 750-850 MPa; further preferably, the melt index of the ethylene-vinyl acetate copolymer at 190°C is 2.5 g / 10 min, the vinyl acetate content is 18%, and the elongation at break is 800 MPa.

[0043] In some preferred embodiments, the ethylene-vinyl acetate copolymer is purchased from Formosa Plastics Corporation in Taiwan, China, and is designated as EVA SF45TAISOX.

[0044] The inventors discovered that the use of specific ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, and ethylene-vinyl acetate copolymer as toughening agents can enhance impact resistance and wear resistance while maintaining good weather resistance and jade-like effects. This may be due to the synergistic effect of the three. Ethylene-octene copolymer, with its high elasticity and toughness, builds an energy absorption network in plastic products, effectively dispersing and absorbing external impact energy, while optimizing the internal structure, reducing defects, and laying the foundation for improved wear resistance. Methyl methacrylate-butadiene-styrene copolymer, through its unique microphase separation structure, not only maintains the transparency of plastic products, but also enhances their impact resistance, and can also form a protective film on the surface to improve wear resistance. Ethylene-vinyl acetate copolymer, with its good weather resistance and softness, absorbs and disperses ultraviolet rays, reduces aging, and maintains the softness and ease of processing of plastic products. These three toughening agents are intertwined in plastic products to form a multi-layered toughening network. Through their interaction, they enhance the overall performance of plastic products, enhancing impact resistance and abrasion resistance while maintaining good weather resistance and jade-like effects. This synergistic mechanism makes plastic products more durable and practical while maintaining their aesthetics, providing strong support for applications in high-end decorative applications.

[0045] Preferably, the inorganic particles include one or more of modified graphene oxide, talc, montmorillonite, kaolin, titanium dioxide, silicon dioxide, and calcium carbonate; further preferably, they are modified graphene oxide.

[0046] Preferably, the preparation method of the modified graphene oxide comprises the following steps: hydrolyzing the coupling agent in an ethanol aqueous solution, adding graphene oxide, stirring at 55-65° C. for 1-3 hours, vacuum filtering, taking out the powder, heating and drying to obtain the modified graphene oxide.

[0047] Preferably, the mass fraction of ethanol in the ethanol aqueous solution is 10%-20%; more preferably, it is 15%.

[0048] Preferably, the volume ratio of the coupling agent to the ethanol aqueous solution is 1:30-50; more preferably, it is 1:40.

[0049] Preferably, the coupling agent is one or more of N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, and 3-aminopropyltriethoxysilane; further preferably, it is N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane.

[0050] Preferably, the mass ratio of the N-(β-aminoethyl)-γ-aminopropyltriethoxysilane to 3-mercaptopropyltriethoxysilane is 1:(0.5-2); more preferably, it is 1:1.

[0051] Preferably, the graphene oxide includes a first graphene oxide and a second graphene oxide.

[0052] Preferably, the weight ratio of the first graphene oxide to the second graphene oxide is 1:(0.5-2); more preferably, it is 2:3.

[0053] Preferably, the first graphene oxide has an average thickness of 0.5 to 1.2 nm, a diameter of 4 to 7 μm, and one layer.

[0054] Preferably, the second graphene oxide has an average thickness of 1 to 3 nm, a diameter of 4 to 7 μm, and 2 to 5 layers.

[0055] In some preferred embodiments, the first graphene oxide and the second graphene oxide are both purchased from Zhejiang Zhiti Nano Micro New Materials Co., Ltd.

[0056] Preferably, the added amount of the coupling agent is 1%-2% of the mass of graphene oxide.

[0057] The inventors discovered that by using modified graphene oxide as inorganic particles, the wear resistance and impact resistance of plastic products can be improved without affecting their jade-like effect, making them more suitable for use in high-end decorative applications. This may be because, on the one hand, by compounding a first graphene oxide and a second graphene oxide with different numbers of layers and sizes, the first graphene oxide has a single-layer structure, a small average thickness, and a suitable diameter, which can effectively fill the voids in the polymer matrix as a nanofiller, reducing defects and improving the material's density and overall strength. On the other hand, although the second graphene oxide has slightly more layers, its larger interlayer spacing and better dispersibility help form more physical crosslinks in the polymer, improving the material's toughness and impact resistance. The compounding of the two graphene oxides not only leverages their respective advantages, but also achieves complementary performance through a synergistic effect, thereby producing a modified graphene oxide with better overall performance. On the other hand, by selecting N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane as coupling agents, their unique functional groups chemically react with functional groups on the surface of graphene oxide, thereby introducing new active groups on the graphene oxide surface. This significantly enhances the interfacial interaction between graphene oxide and the polymer matrix, improving their compatibility and interfacial bonding. This modification not only enhances the dispersion stability of graphene oxide in the polymer but also promotes the uniform transmission of stress within the material, thereby significantly improving the wear resistance and mechanical properties of the plastic products. When this modified graphene oxide is added as an inorganic particle to a masterbatch and further used in the preparation of PP plastic products, its excellent dispersibility and interfacial bonding enable the plastic products to maintain a good jade-like effect while significantly improving wear resistance, scratch resistance, aging resistance, and mechanical properties. This broadens the application areas of plastic products, especially their competitiveness in the high-end decoration field.

[0058] The method for preparing the masterbatch comprises the following steps: mixing the raw materials for preparing the masterbatch, adding the raw materials into a twin-screw extruder, and performing melt extrusion to form granules.

[0059] The temperatures of zones 1 to 5 of the twin-screw extruder are 200-210° C., 210-220° C., 220-230° C., 220-230° C., and 230-240° C., respectively; and the rotation speed is 400-500 r / min.

[0060] Preferably, the compatibilizer includes MAH-g-PP and SMA.

[0061] Preferably, the mass ratio of MAH-g-PP to SMA is (1-3):1; more preferably, it is 2:1.

[0062] Preferably, the MAH-g-PP has a melt index of 30-40 g / 10 min at 190° C., and an MAH graft content of 0.8%-1.2%.

[0063] In some preferred embodiments, the MAH-g-PP is purchased from Dongguan Kangjin New Material Technology Co., Ltd.

[0064] Preferably, the maleic anhydride content in the SMA is 23%-27%, the weight average molecular weight is 7000-8000, the molar ratio of St to MAH is 2:1, and the acid value is 270-305 mgKOH / g.

[0065] In some preferred embodiments, the SMA is purchased from Guangdong Dingxin Polymer Technology Co., Ltd.

[0066] The inventors discovered that using specific MAH-g-PP and SMA as compatibilizers can improve the compatibility between PE, PMMA, and PP, thereby enhancing the jade-like effect and mechanical properties of the plastic products. This may be due to the synergistic effect of MAH-g-PP and SMA. On the one hand, the maleic anhydride functional groups of MAH-g-PP and SMA interact with the polar groups in the polymer to form a multi-point cross-linked structure, which not only enhances the interfacial bonding between the polymers but also promotes the uniform distribution of stress within the material. On the other hand, the styrene in SMA is highly compatible with the non-polar parts of PE and PP, further enhancing the stability and uniformity of the system. This synergistic effect makes the masterbatch blend prepared from PE and PMMA and PP easier to plasticize and form during processing, while also improving the mechanical properties, heat resistance, and chemical resistance of the product.

[0067] During the injection molding, the temperatures of each section of the injection molding machine are: barrel temperature: 220-240°C, nozzle temperature: 230-250°C, mold temperature: 50-70°C; injection pressure is 80-120 MPa, injection speed is 50-70 mm / s, holding time is 10-20s, and cooling time is 20-30s.

[0068] The second aspect of the present invention provides a product prepared by the spray-free process for the jade pattern.

[0069] Compared with the prior art, the advantages and beneficial effects of the present invention are:

[0070] 1. The present invention provides a jade pattern with stable contact properties. By preparing a specific masterbatch, adding functional additives, and combining it with molding technology, the final product exhibits a natural, smooth, and layered jade texture without the need for an additional spraying process. This method not only greatly simplifies the production process and reduces costs, but also avoids the environmental pollution problems that may arise from traditional spraying processes. Furthermore, the product produced using the technical solution provided by the present invention exhibits excellent mechanical strength, weather resistance, wear resistance, and color durability, making it suitable for use in high-end decorative materials and other fields.

[0071] 2. The present invention prepares masterbatches by selecting specific PE and PMMA as carrier resins and applies them in the field of plastic products. It can achieve an effect similar to the texture of natural jade without using an additional spraying process, while ensuring the color presentation effect and the mechanical properties of the plastic products.

[0072] 3. The present invention uses specific MAH-g-PP and SMA as compatibilizers to improve the compatibility between PE and PMMA and PP, thereby improving the jade-like effect and mechanical properties of plastic products.

[0073] 4. The present invention uses specific ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, and ethylene-vinyl acetate copolymer as toughening agents, which can enhance impact resistance and wear resistance while maintaining good weather resistance and jade-like effects.

[0074] 5. By selecting modified graphene oxide as inorganic particles, the present invention can improve the wear resistance and impact resistance of plastic products without affecting the jade-like effect of the plastic products, making the plastic products more suitable for application in the field of high-end decoration. DETAILED DESCRIPTION

[0075] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0076] The raw materials used in the present invention are all commercially available, specifically:

[0077] PP is homopolymer PP with a melt index of 10-15 g / 10 min at 190° C., an isotacticity of ≥95.5%, and a flexural modulus of ≥1300 MPa. It was purchased from Dongguan Weicai Plastic Raw Materials Co., Ltd., PPH-M12.

[0078] The melt index of LLDPE at 190°C is 45-55g / 10min and the density is 0.9-0.95g / cm 3 , Izod notch impact strength is 45-50kJ / m 2 , purchased from ExxonMobil, LL6201XR.

[0079] HDPE has a melt index of 28-32 g / 10 min at 190° C., a tensile yield stress ≥ 20 MPa, and a flexural modulus ≥ 950 MPa and is purchased from ExxonMobil as HDPE HMA018.

[0080] PMMA has a melt index of 15-20 g / 10 min at 230° C., a total light transmittance of ≥92%, and a Rockwell hardness of ≥84. It was purchased from Qingdao Zhongxin Huamei Plastic Co., Ltd., CM-211.

[0081] The melt index of ABS at 200°C is 2-5g / 10min, the elongation is 35%-45%, and the flexural strength is 600-650kg / cm 3 , purchased from Chi Mei, Taiwan, China, PA-726M.

[0082] The kinematic viscosity of oxidized polyethylene wax at 140°C is 20.5 mm 2 / s, softening point is 115℃, purchased from Henan Yuyang Wax Industry Co., Ltd.

[0083] The melt index of the ethylene-octene copolymer at 190° C. is 28-32 g / 10 min. The material is preheated for 1 minute using a large rotor and rotated at 121° C. for 4 minutes. The Mooney viscosity of the material is 1-3 MU and is purchased from Dow Chemical, USA, 8400.

[0084] The rubber content of methyl methacrylate-butadiene-styrene copolymer is 58%-62%, the hydroxyl value is 4-6phr, and the impact strength at 1 / 8 inch thickness is 73-75kJ / m 2 , purchased from Japan, M521.

[0085] The ethylene-vinyl acetate copolymer has a melt index of 2.5 g / 10 min at 190° C., a vinyl acetate content of 18%, and an elongation at break of 800 MPa. It was purchased from Formosa Plastics Corporation in Taiwan, China, and is EVA SF45TAISOX.

[0086] The average thickness of the first graphene oxide is 0.5-1.2 nm, the diameter is 4-7 μm, and the number of layers is 1; the average thickness of the second graphene oxide is 1-3 nm, the diameter is 4-7 μm, and the number of layers is 2-5; both are purchased from Zhejiang Zhiti Nano Micro New Materials Co., Ltd.

[0087] MAH-g-PP has a melt index of 30-40 g / 10 min at 190° C. and an MAH graft content of 0.8%-1.2%, and was purchased from Dongguan Kangjin New Material Technology Co., Ltd.

[0088] The maleic anhydride content in SMA is 23%-27%, the weight average molecular weight is 7000-8000, the molar ratio of St and MAH is 2:1, and the acid value is 270-305 mgKOH / g. It was purchased from Guangdong Dingxin Polymer Technology Co., Ltd.

[0089] Example 1

[0090] This embodiment provides a spray-free process for producing jade patterns, comprising the following steps: uniformly mixing the raw materials, performing injection molding, and polishing the surface.

[0091] The raw materials are base resin, masterbatch and compatibilizer.

[0092] The mass of the masterbatch is 10% of the mass of the base resin.

[0093] The added amount of the compatibilizer is 2% of the total mass of the base resin and the masterbatch.

[0094] The base resin is PP.

[0095] The raw materials for preparing the masterbatch include, by weight, 90 parts of carrier resin, 0.3 parts of colorant, 0.8 parts of antioxidant, 1 part of lubricant, 0.8 parts of light stabilizer, 4 parts of toughening agent, and 5 parts of inorganic particles.

[0096] The carrier resin is PE, PMMA and ABS in a mass ratio of 1:1:1.

[0097] The PE is LLDPE and HDPE, with a mass ratio of 1:1.

[0098] The colorant is phthalocyanine blue B.

[0099] The antioxidants are antioxidant 1010 and antioxidant 168, with a mass ratio of 1:1.

[0100] The lubricant is oxidized polyethylene wax and calcium stearate, with a mass ratio of 2:1.

[0101] The light stabilizer is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate.

[0102] The toughening agent is ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, and ethylene-vinyl acetate copolymer, with a mass ratio of 2:2:1.

[0103] The inorganic particles are modified graphene oxide.

[0104] The preparation method of the modified graphene oxide comprises the following steps: hydrolyzing a coupling agent in an ethanol aqueous solution, adding graphene oxide, stirring at 60° C. for 2 hours, vacuum filtering, taking out the powder, heating and drying the powder, and obtaining the modified graphene oxide.

[0105] The mass fraction of ethanol in the ethanol aqueous solution is 15%.

[0106] The volume ratio of the coupling agent to the ethanol aqueous solution is 1:40.

[0107] The coupling agent is N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane, and the mass ratio is 1:1.

[0108] The graphene oxide includes a first graphene oxide and a second graphene oxide, with a weight ratio of 2:3.

[0109] The added amount of the coupling agent is 1.5% of the mass of the graphene oxide.

[0110] The preparation method of the masterbatch comprises the following steps: mixing the raw materials for preparing the masterbatch, adding the raw materials into a twin-screw extruder, and performing melt extrusion and granulation to obtain the masterbatch.

[0111] The temperatures of zones 1 to 5 of the twin-screw extruder are 205° C., 215° C., 225° C., 225° C., and 235° C., respectively; and the rotation speed is 450 r / min.

[0112] The compatibilizers are MAH-g-PP and SMA, with a mass ratio of 2:1.

[0113] During the injection molding, the temperatures of each section of the injection molding machine are: barrel temperature: 230°C, nozzle temperature: 240°C, mold temperature: 60°C; injection pressure is 100 MPa, injection speed is 60 mm / s, holding time is 15 s, and cooling time is 25 s.

[0114] Example 2

[0115] The difference between this embodiment and embodiment 1 is that the mass of the masterbatch is 20% of the mass of the base resin.

[0116] Example 3

[0117] The difference between this embodiment and embodiment 1 is that the raw materials for preparing the masterbatch, calculated by weight, include 120 parts of carrier resin, 0.3 parts of colorant, 0.8 parts of antioxidant, 1 part of lubricant, 0.8 parts of light stabilizer, 4 parts of toughening agent, and 6 parts of inorganic particles.

[0118] Comparative Example 1

[0119] The difference between this comparative example and Example 1 is that the mass of the masterbatch is 25% of the mass of the base resin.

[0120] Comparative Example 2

[0121] The difference between this comparative example and Example 1 is that the carrier resins are PE and ABS, with a mass ratio of 1:1.

[0122] Comparative Example 3

[0123] The difference between this comparative example and Example 1 is that the PE is LLDPE.

[0124] Comparative Example 4

[0125] The difference between this comparative example and Example 1 is that the toughening agent is ethylene-octene copolymer and methyl methacrylate-butadiene-styrene copolymer, and the mass ratio is 1:1.

[0126] Comparative Example 5

[0127] The difference between this comparative example and Example 1 is that the coupling agent is N-(β-aminoethyl)-γ-aminopropyltriethoxysilane.

[0128] Comparative Example 6

[0129] The difference between this comparative example and Example 1 is that the graphene oxide is the first graphene oxide.

[0130] Comparative Example 7

[0131] The difference between this comparative example and Example 1 is that the compatibilizer is MAH-g-PP.

[0132] Performance Testing

[0133] The plastic products were tested for room-temperature notched Izod impact strength using the method in ASTM D256-10 (2018). The jade-like effect was rated using the method in patent CN 117866374A, with 1 being the worst and 5 being the best. Ten ratings were performed, and the average value was taken. A colorimeter was used to measure surface color uniformity; a color difference ΔE < 0.5 indicated good color uniformity. Weather resistance was tested by placing the products in a xenon lamp aging chamber, simulating natural light conditions, and measuring color change after 1000 hours. A color difference ΔE < 1.0 indicated good color durability and excellent weather resistance. Rockwell hardness was also tested; higher hardness indicates better abrasion resistance. The results are shown in Table 1.

[0134] Table 1 Measurement results

[0135] Impact strength J / m Imitation jade pattern Color difference ΔE Weather resistance ΔE hardness Example 1 748 4.8 0.42 0.76 88 Example 2 739 4.5 0.50 0.93 84 Example 3 742 4.6 0.38 0.77 86 Comparative Example 1 614 3.9 0.88 1.92 80 Comparative Example 2 645 3.6 0.95 1.84 81 Comparative Example 3 672 4.0 0.66 1.61 82 Comparative Example 4 701 4.3 0.77 1.86 78 Comparative Example 5 725 4.5 0.68 1.57 77 Comparative Example 6 722 4.4 0.62 1.46 79 Comparative Example 7 584 3.8 0.97 2.28 75

[0136] According to statistics, the plastic products prepared by Examples 1 to 3 of the present invention have high impact strength, imitation jade texture on the surface, high color rendering and color durability, and excellent weather resistance and wear resistance. In Comparative Example 1, excessive masterbatch was added, Comparative Example 2 did not add PMMA as a carrier, Comparative Example 3 did not add HDPE as a carrier, Comparative Example 4 did not add ethylene-vinyl acetate copolymer as a toughening agent, Comparative Example 5 did not add 3-mercaptopropyltriethoxysilane as a coupling agent, Comparative Example 6 did not add a second graphene oxide, and Comparative Example 7 did not add SMA as a compatibilizer. The mechanical properties, color rendering effect, imitation jade effect, weather resistance, and hardness of the prepared plastic products were all poor. Therefore, the plastic products prepared using the raw materials and methods described in this application can exhibit a natural, smooth, and layered jade texture without using an additional spraying process, while having good mechanical strength, weather resistance, wear resistance, and color durability.

[0137] The above is a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A spray-free process for jade patterns, characterized in that: The steps include: uniformly mixing the base resin, masterbatch and compatibilizer, then injection molding, and polishing the surface; The mass of the masterbatch is 1%-20% of the mass of the base resin; the amount of the compatibilizer added is 1%-3% of the total mass of the base resin and the masterbatch; The base resin is PP; The masterbatch is prepared from the following raw materials, calculated by weight: 60-120 parts of carrier resin, 0.1-0.5 parts of colorant, 0.5-1 parts of antioxidant, 0.5-1.5 parts of lubricant, 0.5-1 parts of light stabilizer, 2-5 parts of toughening agent, and 3-8 parts of modified graphene oxide; the carrier resin is PE, PMMA, and ABS in a mass ratio of 1:(0.5-2):(0.5-2); the PE is LLDPE and HDPE in a mass ratio of 1:(0.5-2); The preparation method of the modified graphene oxide comprises the following steps: taking a coupling agent of N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and 3-mercaptopropyltriethoxysilane in a mass ratio of 1:(0.5-2), hydrolyzing the solution in an ethanol aqueous solution, adding graphene oxide, stirring at 55-65° C. for 1-3 hours, vacuum filtering, removing the powder, heating and drying, and obtaining the modified graphene oxide, wherein the amount of the coupling agent added is 1%-2% of the mass of the graphene oxide; The toughening agent is ethylene-octene copolymer, methyl methacrylate-butadiene-styrene copolymer, and ethylene-vinyl acetate copolymer in a mass ratio of (1-3): (1-3): 1; The compatibilizer is MAH-g-PP and SMA in a mass ratio of (1-3):

1.

2. the spray-free process of jade lines according to claim 1, is characterized in that, The LLDPE has a melt index of 45-55 g / 10 min at 190° C., a density of 0.9-0.95 g / cm 3 , and an Izod notched impact strength of 45-50 kJ / m 2 ; The HDPE has a melt index of 28-32 g / 10 min at 190° C., a tensile yield stress ≥ 20 MPa, and a flexural modulus ≥ 950 MPa; The PMMA has a melt index of 15-20 g / 10 min at 230° C., a total light transmittance of ≥92%, and a Rockwell hardness of ≥84; The PP is homopolymer PP, and has a melt index of 10-15 g / 10 min at 190° C., an isotacticity of ≥95.5%, and a flexural modulus of ≥1300 MPa.

3. The spray-free process of jade lines according to claim 1, wherein The MAH-g-PP has a melt index of 30-40 g / 10 min at 190° C., and an MAH graft content of 0.8%-1.2%. The SMA has a maleic anhydride content of 23%-27%, a weight-average molecular weight of 7,000-8,000, a molar ratio of St to MAH of 2:1, and an acid value of 270-305 mgKOH / g. The MAH-g-PP has a melt index of 30-40 g / 10 min at 190° C. and an MAH graft content of 0.8%-1.2%; The SMA has a maleic anhydride content of 23%-27%, a weight-average molecular weight of 7000-8000, a molar ratio of St to MAH of 2:1, and an acid value of 270-305 mgKOH / g.

4. The spray-free process of jade lines according to claim 1, wherein The mass ratio of PE, PMMA and ABS is 1:1:1; The mass ratio of the LLDPE to the HDPE is 1:

1.

5. The spray-free process of jade lines according to claim 1, wherein The antioxidants are antioxidant 1010 and antioxidant 168 in a mass ratio of 1:(0.5-2).

6. The spray-free process of jade lines according to claim 1, wherein The mass ratio of the antioxidant 1010 to the antioxidant 168 is 1:

1.

7. The spray-free process of jade lines according to claim 1, wherein The mass ratio of the ethylene-octene copolymer, the methyl methacrylate-butadiene-styrene copolymer, and the ethylene-vinyl acetate copolymer is 2:2:

1.

8. The spray-free process of jade lines according to claim 1, wherein The mass ratio of MAH-g-PP and SMA is 2:1; The mass ratio of the N-(β-aminoethyl)-γ-aminopropyltriethoxysilane to 3-mercaptopropyltriethoxysilane is 1:1; The mass fraction of ethanol in the ethanol aqueous solution is 10%-20%; The volume ratio of the coupling agent to the ethanol aqueous solution is 1:30-50; The graphene oxide comprises a first graphene oxide and a second graphene oxide in a weight ratio of 1:(0.5-2).

9. The spray-free process of jade lines according to claim 8, wherein The weight ratio of the first graphene oxide to the second graphene oxide is 2:3; the average thickness of the first graphene oxide is 0.5-1.2 nm, the diameter is 4-7 μm, and the number of layers is 1; the average thickness of the second graphene oxide is 1-3 nm, the diameter is 4-7 μm, and the number of layers is 2-5.

10. A product prepared by the spray-free process for producing jade patterns according to any one of claims 1 to 9.