Preparation method and application of 3D printing photosensitive material

Abstract

The invention relates to the technical field of 3D printing, in particular to a preparation method and application of a 3D printing photosensitive material, and the preparation method comprises the following steps: weighing the following raw materials in parts by weight: 45-50 parts of acrylic resin oligomer, 20-25 parts of acrylate monomer, 25-30 parts of epoxy resin, 4-6 parts of initiator, 7-11 parts of modified filler and 4-6 parts of nano titanium dioxide doped blending agent. According to the 3D printing photosensitive material disclosed by the invention, the acrylic resin oligomer is matched with the acrylate monomer, the epoxy resin and the initiator, meanwhile, the modified filler and the blending agent doped with the nano titanium dioxide are added, and the impact strength performance effect of the product is remarkable through blending, coordination and joint synergism of the raw materials; the wear resistance and the fracture performance of the product are harmoniously improved, and meanwhile, the product has excellent corrosion resistance and heat change resistance stability effects.

Description

Technical Field

[0001] The present invention relates to the technical field of 3D printing, and particularly to a preparation method and application of a 3D printing photosensitive material. Background Art

[0002] 3D printing technology, also known as "additive manufacturing" technology academically, is also called additive manufacturing or incremental manufacturing. In 3D printing technology, stereolithography is the most common. It mainly uses a laser to irradiate a photosensitive resin, causing the resin to undergo radiation polymerization to form a cross-linked polymer and produce a solid material. The existing photosensitive 3D printing materials have poor impact strength performance, as well as poor wear resistance and fracture performance of the products. It is difficult to achieve coordinated improvement in the performance of the products, and the corrosion resistance and heat distortion stability of the products are poor, which limits the use efficiency of the products. Based on this, the present invention makes further improvement and treatment. Summary of the Invention

[0003] Aiming at the defects of the prior art, the purpose of the present invention is to provide a preparation method and application of a 3D printing photosensitive material to solve the problems raised in the above background art.

[0004] The present invention adopts the following technical solutions to solve the technical problems: The present invention provides a preparation method of a 3D printing photosensitive material, including the following steps: Weigh the raw materials according to parts by weight: 45 - 50 parts of an acrylic resin oligomer, 20 - 25 parts of an acrylate monomer, 25 - 30 parts of an epoxy resin, 4 - 6 parts of an initiator, 7 - 11 parts of a modified filler, and 4 - 6 parts of a formulation agent doped with nano-titanium dioxide; Stir the above raw materials at 50°C for 2 hours until they are uniformly dispersed to obtain a 3D printing photosensitive material.

[0005] Preferably, the acrylic resin oligomer is prepared from aliphatic polyurethane acrylate and polyurethane acrylate according to a weight ratio of 1:1; Aliphatic polyurethane acrylate, model: UO22 - 002, viscosity (cps / 25°C): 60000, Riton Chemical Co., Ltd.; Polyurethane acrylate, model: Laromer PR9000, BASF; The acrylate monomer is prepared from 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate according to a weight ratio of 1:1; The epoxy resin is bisphenol A epoxy resin with an epoxy value of 0.50; The initiator is prepared from a free radical photoinitiator and a cationic initiator according to a weight ratio of 1:1. The free radical photoinitiator is 1-hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

[0006] Preferably, the preparation method of the modified filler is as follows: S01: Place halloysite carbon nanotubes in a sufficient amount of sulfuric acid solution with a mass fraction of 5-8%, mix well, then wash with water and dry; Thermally modify the dried halloysite carbon nanotubes, and after the modification is completed, obtain thermally modified halloysite carbon nanotubes; Specifically, the modification method is as follows: First, heat up at a rate of 4-6 °C / min to 245-255 °C, keep warm for 1 h, then heat up at a rate of 2-3 °C / min to 350 °C, continue to keep warm for 35 min, and finally air-cool to room temperature; S02: Prepare a chitosan solution with a mass fraction of 2-5%, and prepare a nano-bentonite solution by mixing lanthanum oxide, chitosan solution and nano-bentonite according to the weight ratio of (1-3):(5-8):(3-4); Ultrasonically treat the thermally modified halloysite carbon nanotubes and the nano-bentonite solution according to the weight ratio of 3:5. After the ultrasonic treatment is completed, filter and dry to obtain a nano-bentonite / halloysite carbon nanotube composite agent; S03: Add 2-5 parts of zirconia whiskers and 3-4 parts of wood cellulose to 5-8 parts of hydrochloric acid dopamine solution with a mass fraction of 5%, and then add 1-3 parts of silane coupling agent KH550, and stir and blend to obtain a reinforcing liquid; S04: Mix and ball-mill the nano-bentonite / halloysite carbon nanotube composite agent and the reinforcing liquid according to the weight ratio of 5:3. The ball-milling speed is 1000-1500 r / min, and ball-mill for 1 h. After the ball-milling is completed, filter and dry to obtain the modified filler.

[0007] Preferably, the ultrasonic power of the ultrasonic treatment in S02 is 350-400 W, and ultrasonic for 30-40 min.

[0008] Preferably, the stirring speed of the stirring and blending treatment in S03 is 750-850 r / min, and stir for 1 h.

[0009] Preferably, the length of the wood cellulose is 3-5 µm, and the diameter of the zirconia whiskers is 2-4 µm.

[0010] Preferably, the preparation method of the doping nano-titanium dioxide formulation agent is as follows: S101: Blend and mix nano-silica sol, sodium silicate solution and Tris-HCl buffer solution evenly according to the weight ratio of (2-4):3:(5-8) to obtain a nano-silica sol solution; Add 1-3 parts of hydroxyethyl cellulose and 1-2 parts of sodium stearate to 4-7 parts of the nano-silica sol solution and stir evenly to obtain a formulated nano-silica sol colloid; S102: Blend 2 - 5 parts of nano - titanium dioxide and 1 - 3 parts of nano - calcium carbonate into 5 - 8 parts of yttrium nitrate solution, stir well, then filter by suction and dry to obtain a modifier doped with nano - titanium dioxide; S103: Mix the modifier doped with nano - titanium dioxide and the formulated nano - silicon sol colloid in a weight ratio of 3:5, perform ball - milling treatment at a ball - milling speed of 1500 r / min for 1 h. After the ball - milling is completed, filter by suction and dry to obtain a formulation doped with nano - titanium dioxide.

[0011] Preferably, the mass fraction of the sodium silicate solution is 2 - 5%; the pH value of the Tris - HCl buffer solution is 8 - 9.

[0012] Preferably, the mass fraction of the yttrium nitrate solution is 4 - 6%.

[0013] The present invention also provides an application of a preparation method of a 3D - printing photosensitive material in 3D - printing materials.

[0014] Compared with the prior art, the present invention has the following beneficial effects: The 3D - printing photosensitive material of the present invention uses an acrylic resin oligomer in combination with an acrylate monomer, an epoxy resin, and an initiator. At the same time, a modified filler and a formulation doped with nano - titanium dioxide are added. Through the coordination of raw materials, they work together to enhance the efficiency. The impact strength performance of the product is remarkable, and the wear resistance and fracture performance of the product are coordinately improved. At the same time, the product has excellent corrosion resistance and heat - distortion stability; the modified filler uses halloysite carbon nanotubes, which are activated and improved by an acid solution, and then thermally improved. The thermal improvement is carried out in a step - by - step and segmented manner to further optimize the activity of halloysite carbon nanotubes. At the same time, it is combined with ultrasonic treatment of nano - bentonite solution. The lanthanum oxide, chitosan solution, and nano - bentonite in the nano - bentonite solution are coordinated. The lamellar nano - bentonite penetrates into the system, further combined with the tubular structure with a high specific surface area to optimize the performance coordination of the system. At the same time, an enhancing liquid is used to further enhance the synergistic effect. The zirconia whiskers in the enhancing liquid are coordinated with lignocellulose in a whisker - like structure and incorporated into the system, and then adjusted with dopamine hydrochloride solution and silane coupling agent KH550, so that the performance of the product is further improved; the formulation doped with nano - titanium dioxide is prepared by co - formulating and co - adjusting nano - silicon sol, sodium silicate solution, and Tris - HCl buffer solution into a nano - silicon sol liquid, and then further coordinating with auxiliary hydroxyethyl cellulose and sodium stearate, so that the performance of the product is coordinated. The nano - titanium dioxide and nano - calcium carbonate are co - combined and adjusted with yttrium nitrate solution, and then further coordinated with the formulated nano - silicon sol colloid. The obtained formulation doped with nano - titanium dioxide can reinforce the system, further adjust the modified filler, and work together synergistically to further improve the performance of the product. Detailed implementation manners

[0015] The following describes the technical solutions in the embodiments of the present invention clearly and completely in conjunction with specific embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0016] A preparation method of a 3D printing photosensitive material in this embodiment includes the following steps: Weigh raw materials by weight: 45-50 parts of acrylic resin oligomer, 20-25 parts of acrylate monomer, 25-30 parts of epoxy resin, 4-6 parts of initiator, 7-11 parts of modified filler, and 4-6 parts of a blending agent doped with nano-titanium dioxide; Stir the above raw materials at 50°C for 2 h until they are evenly dispersed to obtain a 3D printing photosensitive material.

[0017] The acrylic resin oligomer in this embodiment is prepared from aliphatic polyurethane acrylate and polyurethane acrylate according to a weight ratio of 1:1; Aliphatic polyurethane acrylate, model: UO22-002, viscosity (cps / 25°C): 60000, Riton Chemical Co., Ltd.; Polyurethane acrylate, model: Laromer PR9000, BASF; The acrylate monomer is prepared from 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate according to a weight ratio of 1:1; The epoxy resin is bisphenol A epoxy resin with an epoxy value of 0.50; The initiator is prepared from a free radical photoinitiator and a cationic initiator according to a weight ratio of 1:1. The free radical photoinitiator is 1-hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

[0018] The preparation method of the modified filler in this embodiment is as follows: S01: Mix halloysite carbon nanotubes in a sufficient amount of sulfuric acid solution with a mass fraction of 5-8% until they are fully mixed, then wash with water and dry; Thermally improve the dried halloysite carbon nanotubes. After the improvement is completed, thermally improved halloysite carbon nanotubes are obtained; The specific improvement method is as follows: First, heat up at a rate of 4-6°C / min to 245-255°C, hold for 1 h, then heat up at a rate of 2-3°C / min to 350°C, continue to hold for 35 min, and finally air-cool to room temperature; S02: preparing a chitosan solution with a mass fraction of 2-5%, and preparing a nano-bentonite solution by mixing lanthanum oxide, chitosan solution and nano-bentonite in a weight ratio of (1-3): (5-8): (3-4); The heat-modified halloysite carbon nanotubes and nano-bentonite liquid are ultrasonically treated in a weight ratio of 3:5, and after the ultrasonic treatment, the mixture is filtered and dried to obtain a nano-bentonite / haloysite carbon nanotube compound; S03: adding 2-5 parts of zirconium oxide whiskers and 3-4 parts of wood cellulose to 5-8 parts of 5% by mass dopamine hydrochloride solution, and then adding 1-3 parts of silane coupling agent KH550, stirring and blending to obtain a reinforcing solution; S04: The nano-bentonite / halloysite carbon nanotube compound and the reinforcing liquid are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1000-1500 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a modified filler.

[0019] The ultrasonic power of the ultrasonic treatment in S02 of this embodiment is 350-400W, and the ultrasonic treatment is performed for 30-40 minutes.

[0020] The stirring speed of the stirring and blending process in S03 of this embodiment is 750~850r / min, and the stirring is for 1h.

[0021] The length of the wood cellulose in this embodiment is 3-5 μm, and the diameter of the zirconium oxide whisker is 2-4 μm.

[0022] The preparation method of the formulation of doped nano titanium dioxide in this embodiment is: S101: uniformly mixing the nano-silica sol, the sodium silicate solution and the Tris-HCl buffer solution in a weight ratio of (2-4):3:(5-8) to obtain a nano-silica sol solution; Add 1-3 parts of hydroxyethyl cellulose and 1-2 parts of sodium stearate to 4-7 parts of nano-silica sol solution and stir evenly to obtain a prepared nano-silica sol; S102: 2-5 parts of nano titanium dioxide and 1-3 parts of nano calcium carbonate are mixed and added into 5-8 parts of yttrium nitrate solution, and stirred sufficiently, and then filtered and dried to obtain a modifier doped with nano titanium dioxide; S103: The modifier doped with nano-titanium dioxide and the prepared nano-silica sol are mixed in a weight ratio of 3:5, and the mixture is ball-milled at a speed of 1500 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the prepared agent doped with nano-titanium dioxide.

[0023] The mass fraction of the sodium silicate solution in this embodiment is 2-5%; the pH value of the Tris-HCl buffer solution is 8-9.

[0024] The mass fraction of the yttrium nitrate solution in this embodiment is 4-6%.

[0025] The application of a preparation method of a 3D printing photosensitive material in this embodiment in 3D printing materials.

[0026] Example 1: A preparation method of a 3D printing photosensitive material in this embodiment includes the following steps: Weigh the raw materials according to parts by weight: 45 parts of acrylic resin oligomer, 20 parts of acrylate monomer, 25 parts of epoxy resin, 4 parts of initiator, 7 parts of modified filler, and 4 parts of a blending agent doped with nano-titanium dioxide; Stir the above raw materials at 50 °C for 2 h until they are evenly dispersed to obtain a 3D printing photosensitive material.

[0027] The acrylic resin oligomer in this embodiment is prepared from aliphatic polyurethane acrylate and polyurethane acrylate according to a weight ratio of 1:1; Aliphatic polyurethane acrylate, model: UO22-002, viscosity (cps / 25 °C): 60000, Riteng Chemical Co., Ltd.; Polyurethane acrylate, model: Laromer PR9000, BASF; The acrylate monomer is prepared from 2-hydroxyethyl methacrylate and hydroxypropyl methacrylate according to a weight ratio of 1:1; The epoxy resin is bisphenol A type epoxy resin with an epoxy value of 0.50; The initiator is prepared from a free radical photoinitiator and a cationic initiator according to a weight ratio of 1:1. The free radical photoinitiator is 1-hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

[0028] The preparation method of the modified filler in this embodiment is as follows: S01: Place halloysite carbon nanotubes in a sufficient amount of 5% sulfuric acid solution, mix well, then wash with water and dry; Perform thermal improvement treatment on the dried halloysite carbon nanotubes. After the improvement is completed, obtain thermally improved halloysite carbon nanotubes; The specific improvement method is as follows: First, heat up at a rate of 4 °C / min to 245 °C, keep warm for 1 h, then heat up at a rate of 2 °C / min to 350 °C, continue to keep warm for 35 min, and finally air-cool to room temperature; S02: Prepare a 2% chitosan solution, and prepare a nano-bentonite solution by mixing lanthanum oxide, chitosan solution and nano-bentonite according to a weight ratio of 1:5:3; The heat-improved halloysite carbon nanotubes and nano-bentonite liquid are ultrasonically treated according to a weight ratio of 3:5. After the ultrasonic treatment is completed, filtration and drying are carried out to obtain a nano-bentonite / halloysite carbon nanotube compounding agent; S03: Add 2 parts of zirconia whiskers and 3 parts of wood cellulose to 5 parts of a 5% hydrochloric acid dopamine solution by mass, and then add 1 part of silane coupling agent KH550, and carry out stirring and blending treatment to obtain a reinforcing liquid; S04: The nano-bentonite / halloysite carbon nanotube compounding agent and the reinforcing liquid are mixed and ball-milled according to a weight ratio of 5:3. The ball-milling speed is 1000 r / min, and ball-milling is carried out for 1 h. After the ball-milling is completed, filtration and drying are carried out to obtain a modified filler agent.

[0029] In S02 of this example, the ultrasonic power of the ultrasonic treatment is 350 W, and ultrasonic treatment is carried out for 30 min.

[0030] In S03 of this example, the stirring speed of the stirring and blending treatment is 750 r / min, and stirring is carried out for 1 h.

[0031] In this example, the length of the wood cellulose is 3 µm, and the diameter of the zirconia whiskers is 2 µm.

[0032] The preparation method of the doping nano-titanium dioxide dispensing agent in this example is as follows: S101: Mix nano-silica sol, sodium silicate solution and Tris-HCl buffer solution evenly according to a weight ratio of 2:3:5 to obtain a nano-silica sol liquid; Add 1 part of hydroxyethyl cellulose and 1 part of sodium stearate to 4 parts of the nano-silica sol liquid and stir evenly to obtain a dispensed nano-silica sol colloid; S102: Blend 2 parts of nano-titanium dioxide and 1 part of nano-calcium carbonate and add them to 5 parts of yttrium nitrate solution and stir well, then carry out filtration and drying to obtain a modified agent of doped nano-titanium dioxide; S103: Mix the modified agent of doped nano-titanium dioxide and the dispensed nano-silica sol colloid according to a weight ratio of 3:5 and carry out ball-milling treatment. The ball-milling speed is 1500 r / min, and ball-milling is carried out for 1 h. After the ball-milling is completed, filtration and drying are carried out to obtain a dispensing agent of doped nano-titanium dioxide.

[0033] In this example, the mass fraction of the sodium silicate solution is 2%; the pH value of the Tris-HCl buffer solution is 8.

[0034] In this example, the mass fraction of the yttrium nitrate solution is 4%.

[0035] The application of the preparation method of a 3D printing photosensitive material in this example in 3D printing materials.

[0036] Example 2: The preparation method of a 3D printing photosensitive material in this example includes the following steps: Weigh the raw materials according to parts by weight: 50 parts of acrylic resin oligomer, 25 parts of acrylate monomer, 30 parts of epoxy resin, 6 parts of initiator, 11 parts of modified filler, and 6 parts of doping nano-titanium dioxide preparation agent; Stir the above raw materials at 50 °C for 2 h until evenly dispersed to obtain a 3D printing photosensitive material.

[0037] The acrylic resin oligomer in this example is prepared from aliphatic polyurethane acrylate and polyurethane acrylate according to a weight ratio of 1:1; Aliphatic polyurethane acrylate, model: UO22-002, viscosity (cps / 25 °C): 60000, Riton Chemical Co., Ltd.; Polyurethane acrylate, model: Laromer PR9000, BASF; The acrylate monomer is prepared from 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate according to a weight ratio of 1:1; The epoxy resin is bisphenol A type epoxy resin with an epoxy value of 0.50; The initiator is prepared from a free radical photoinitiator and a cationic initiator according to a weight ratio of 1:1. The free radical photoinitiator is 1-hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

[0038] The preparation method of the modified filler in this example is as follows: S01: Place halloysite carbon nanotubes in a sufficient amount of 8% sulfuric acid solution, mix well, then wash with water and dry; Thermally improve the dried halloysite carbon nanotubes. After the improvement is completed, thermally improved halloysite carbon nanotubes are obtained; The specific improvement method is as follows: First, heat up at a rate of 6 °C / min to 255 °C, hold for 1 h, then heat up at a rate of 3 °C / min to 350 °C, continue to hold for 35 min, and finally air-cool to room temperature; S02: Prepare a 5% chitosan solution, and prepare a nano-bentonite solution by mixing lanthanum oxide, chitosan solution and nano-bentonite according to a weight ratio of 3:8:4; Ultrasonically treat the thermally improved halloysite carbon nanotubes and the nano-bentonite solution according to a weight ratio of 3:5. After the ultrasonic treatment is completed, filter and dry to obtain a nano-bentonite / halloysite carbon nanotube compound agent; S03: Add 5 parts of zirconia whiskers and 4 parts of wood cellulose to 8 parts of 5% hydrochloric acid dopamine solution, and then add 3 parts of silane coupling agent KH550, and stir and blend to obtain a reinforcing liquid; S04: The nano-bentonite / halloysite carbon nanotube compound and the reinforcing liquid are mixed in a weight ratio of 5:3 and ball-milled at a speed of 1500 r / min for 1 h. After the ball milling is completed, the mixture is filtered and dried to obtain a modified filler.

[0039] The ultrasonic power of the ultrasonic treatment in S02 of this embodiment is 400W, and the ultrasonic treatment is performed for 40 minutes.

[0040] The stirring speed of the stirring and blending process in S03 of this embodiment is 850r / min, and the stirring is for 1h.

[0041] In this embodiment, the length of the wood cellulose is 5 μm, and the diameter of the zirconium oxide whisker is 4 μm.

[0042] The preparation method of the formulation of doped nano titanium dioxide in this embodiment is: S101: Evenly mixing the nano-silica sol, the sodium silicate solution and the Tris-HCl buffer solution in a weight ratio of 4:3:8 to obtain a nano-silica sol solution; Add 3 parts of hydroxyethyl cellulose and 2 parts of sodium stearate to 7 parts of nano-silica sol solution and stir evenly to obtain a prepared nano-silica sol; S102: 5 parts of nano titanium dioxide and 3 parts of nano calcium carbonate are mixed and added into 8 parts of yttrium nitrate solution, and stirred thoroughly, and then filtered and dried to obtain a modifier doped with nano titanium dioxide; S103: The modifier doped with nano-titanium dioxide and the prepared nano-silica sol are mixed in a weight ratio of 3:5, and the mixture is ball-milled at a speed of 1500 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the prepared agent doped with nano-titanium dioxide.

[0043] The mass fraction of the sodium silicate solution in this embodiment is 5%; the pH value of the Tris-HCl buffer solution is 9.

[0044] The mass fraction of the yttrium nitrate solution in this embodiment is 6%.

[0045] The present embodiment provides an application of a method for preparing a 3D printing photosensitive material in 3D printing materials.

[0046] Embodiment 3: A method for preparing a 3D printing photosensitive material in this embodiment comprises the following steps: Weigh the raw materials according to weight: 47.5 parts of acrylic resin oligomer, 22.5 parts of acrylate monomer, 27.5 parts of epoxy resin, 5 parts of initiator, 9 parts of modified filler and 5 parts of nano-titanium dioxide doped formulation; The above raw materials were stirred at 50° C. for 2 h until they were evenly dispersed to obtain a 3D printing photosensitive material.

[0047] The acrylic resin oligomer in this embodiment is prepared by mixing aliphatic polyurethane acrylate and polyurethane acrylate in a weight ratio of 1:1; Aliphatic polyurethane acrylate, model: UO22 - 002, viscosity (cps / 25℃): 60000, Riton Chemical Co., Ltd.; Polyurethane acrylate, model: Laromer PR9000, BASF; The acrylate monomer is prepared by mixing 2 - hydroxyethyl methacrylate and 2 - hydroxypropyl methacrylate in a weight ratio of 1:1; The epoxy resin is bisphenol A type epoxy resin with an epoxy value of 0.50; The initiator is prepared by mixing a free radical photo - initiator and a cationic initiator in a weight ratio of 1:1. The free radical photo - initiator is 1 - hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

[0048] The preparation method of the modified filler in this embodiment is as follows: S01: Place halloysite carbon nanotubes in a sufficient amount of sulfuric acid solution with a mass fraction of 5 - 8%, mix well, then wash with water and dry; Thermally modify the dried halloysite carbon nanotubes. After the modification is completed, thermally modified halloysite carbon nanotubes are obtained; The specific modification method is as follows: First, heat up at a rate of 5℃ / min to 250℃, hold for 1 h, then heat up at a rate of 2.5℃ / min to 350℃, continue to hold for 35 min, and finally air - cool to room temperature; S02: Prepare a chitosan solution with a mass fraction of 3.5%. Mix lanthanum oxide, the chitosan solution and nanobentonite in a weight ratio of 2:6.5:3.5 to form a nanobentonite solution; Ultrasonically treat the thermally modified halloysite carbon nanotubes and the nanobentonite solution in a weight ratio of 3:5. After the ultrasonic treatment is completed, filter by suction and dry to obtain a nanobentonite / halloysite carbon nanotube compound; S03: Add 3.5 parts of zirconia whiskers and 3.5 parts of wood cellulose to 6.5 parts of hydrochloric acid dopamine solution with a mass fraction of 5%, and then add 2 parts of silane coupling agent KH550, and stir and blend to obtain a strengthening liquid; S04: Mix the nanobentonite / halloysite carbon nanotube compound and the strengthening liquid in a weight ratio of 5:3, perform ball - milling treatment at a ball - milling speed of 1250 r / min for 1 h. After the ball - milling is completed, filter by suction and dry to obtain the modified filler.

[0049] In S02 of this embodiment, the ultrasonic power of the ultrasonic treatment is 375 W, and the ultrasonic treatment lasts for 35 min.

[0050] The stirring speed of the stirring and blending process in S03 of this embodiment is 800 r / min, and the stirring is for 1 hour.

[0051] In this embodiment, the length of the wood cellulose is 4 μm, and the diameter of the zirconium oxide whisker is 3 μm.

[0052] The preparation method of the formulation of doped nano titanium dioxide in this embodiment is: S101: Evenly mixing the nano-silica sol, the sodium silicate solution and the Tris-HCl buffer solution in a weight ratio of 3:3:6.5 to obtain a nano-silica sol solution; Add 2 parts of hydroxyethyl cellulose and 1.5 parts of sodium stearate to 5.5 parts of nano-silica sol solution and stir evenly to obtain a prepared nano-silica sol; S102: 3.5 parts of nano titanium dioxide and 2 parts of nano calcium carbonate are mixed and added into 6.5 parts of yttrium nitrate solution, and stirred thoroughly, and then filtered and dried to obtain a modifier doped with nano titanium dioxide; S103: The modifier doped with nano-titanium dioxide and the prepared nano-silica sol are mixed in a weight ratio of 3:5, and the mixture is ball-milled at a speed of 1500 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the prepared agent doped with nano-titanium dioxide.

[0053] The mass fraction of the sodium silicate solution in this embodiment is 3.5%; the pH value of the Tris-HCl buffer solution is 8.5.

[0054] The mass fraction of the yttrium nitrate solution in this embodiment is 5%.

[0055] The present embodiment provides an application of a method for preparing a 3D printing photosensitive material in 3D printing materials.

[0056] Comparative Example 1: The difference from Example 3 is that no modified filler is added.

[0057] Comparative Example 2: The difference from Example 3 is that no nano-bentonite / halloysite carbon nanotube compounding agent is added to the modified filler.

[0058] Comparative Example 3: The difference from Example 3 is that no thermally modified halloysite carbon nanotubes are added in the preparation of the nano-bentonite / halloysite carbon nanotube compound.

[0059] Comparative Example 4: The difference from Example 3 is that the thermally modified halloysite carbon nanotubes are not subjected to thermal modification treatment.

[0060] Comparative Example 5: The difference from Example 3 is that no nano-bentonite liquid is added in the preparation of the nano-bentonite / halloysite carbon nanotube compound.

[0061] Comparative Example 6: The difference from Example 3 is that no nano-bentonite is added to the nano-bentonite liquid.

[0062] Comparative Example 7: Different from Example 3, the reinforcing liquid was not added to the modified filler.

[0063] Comparative Example 8: Different from Example 3, zirconia whiskers and wood cellulose were not added to the reinforcing liquid.

[0064] Comparative Example 9: Different from Example 3, the formulation containing doped nano-titanium dioxide was not added.

[0065] Comparative Example 10: Different from Example 3, the modifier for doping nano-titanium dioxide was not added during the preparation of the formulation containing doped nano-titanium dioxide.

[0066] Comparative Example 11: Different from Example 3, nano-titanium dioxide was not added during the preparation of the modifier for doping nano-titanium dioxide.

[0067] Comparative Example 12: Different from Example 3, the formulated nano-silica sol was not added during the preparation of the formulation containing doped nano-titanium dioxide.

[0068] Comparative Example 13: Different from Example 3, hydroxyethyl cellulose and sodium stearate were not added to the formulated nano-silica sol.

[0069] Comparative Example 14: Different from Example 3, the nano-silica sol liquid was not added to the formulated nano-silica sol.

[0070] Comparative Example 15: Different from Example 3, nano-silica sol and sodium silicate solution were not added to the nano-silica sol liquid.

[0071] The photosensitive resin was formed by stereolithography printing. The process parameters were: main emission wavelength 405 mm, printing layer thickness 5 mm, ultraviolet laser power 58 W, printing speed 40 mm / h. The prepared samples were cut into a size of 80 mm × 10 mm × 5 mm, and the properties of Examples 1 - 3 and Comparative Examples 1 - 15 were tested, including impact strength, wear resistance and fracture properties. The test results are as follows: The impact strength performance is poor, and the wear resistance and fracture properties of the product are poor. It is difficult to achieve coordinated improvement of the product's properties, as well as the corrosion resistance and heat distortion stability of the product

[0072] It can be seen from Comparative Examples 1 - 15 and Examples 1 - 3; The product of Example 3 has excellent notched impact strength, and at the same time has excellent wear resistance and elongation at break properties. The product can achieve coordinated improvement.

[0073] Test Examples 1-3 and Comparative Examples 1-15 for the corrosion resistance and heat distortion stability of the products (the products were placed under 5% sodium hydroxide alkali mist conditions for 24 h, then placed at 50 °C for 12 h, and then placed at 70 °C for 12 h. The above was one cycle, and the cycle was repeated 10 times to test the corrosion resistance and heat distortion stability of the products), and the test results are as follows;

[0074] It can be seen from Comparative Examples 1-15 and Example 3 that the product of Example 3 still has corrosion resistance and heat distortion stability, and the product stability effect is remarkable; It can be seen from Comparative Example 1, Comparative Example 9 and Example 3 that when one of the modified filler and the formulation doped with nano-titanium dioxide is not added to the product, the performance of the product deteriorates significantly. By using the synergistic combination of the two, the product performance effect is remarkable; It can be seen from Comparative Examples 1-8 and Example 3 that when the nano-bentonite / halloysite carbon nanotube compounding agent is not added to the modified filler, the heat-improved halloysite carbon nanotube is not added during the preparation of the nano-bentonite / halloysite carbon nanotube compounding agent, and the heat-improved halloysite carbon nanotube is not subjected to heat improvement treatment, the performance of the product shows a deteriorating trend; When the nano-bentonite liquid is not added during the preparation of the nano-bentonite / halloysite carbon nanotube compounding agent, the nano-bentonite is not added to the nano-bentonite liquid, the reinforcing liquid is not added to the modified filler, the zirconia whiskers and wood cellulose are not added to the reinforcing liquid, the performance of the product shows a deteriorating trend to varying degrees. By using the reinforcing liquid, nano-bentonite liquid and specific nano-bentonite / halloysite carbon nanotube compounding agent obtained by the specific method of the present invention, the performance effect of the nano-bentonite / halloysite carbon nanotube compounding agent obtained by the specific method of the present invention is the most remarkable. Using other methods instead is not as obvious as the effect of the present invention; It can be seen from Comparative Examples 10-15 and Example 3 that when the modifier doped with nano-titanium dioxide is not added during the preparation of the formulation doped with nano-titanium dioxide, the nano-titanium dioxide is not added during the preparation of the modifier doped with nano-titanium dioxide, and the nano-silica sol colloid is not added during the preparation of the formulation doped with nano-titanium dioxide, the performance of the product shows a deteriorating trend. By using the modifier doped with nano-titanium dioxide obtained by a specific method, the product performance effect is the most remarkable; When hydroxyethyl cellulose and sodium stearate are not added to the nano-silica sol colloid, the nano-silica sol liquid is not added to the nano-silica sol colloid, and the nano-silica sol and sodium silicate solution are not added to the nano-silica sol liquid, the performance of the product shows a deteriorating trend to varying degrees. Only by using the nano-silica sol colloid obtained by the specific method of the present invention, the product performance effect is the most remarkable.

[0075] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above-described exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the present invention. Therefore, in any aspect, the embodiments should be regarded as exemplary and non-restrictive. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be embraced within the present invention.

[0076] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A preparation method of a 3D printing photosensitive material, characterized in that, The following steps are included: Weigh the raw materials by weight parts: 45 - 50 parts of acrylic resin oligomer, 20 - 25 parts of acrylate monomer, 25 - 30 parts of epoxy resin, 4 - 6 parts of initiator, 7 - 11 parts of modified filler, and 4 - 6 parts of a formulation agent doped with nano - titanium dioxide; Stir the above - mentioned raw materials at 50 °C for 2 h until evenly dispersed to obtain a 3D - printing photosensitive material.

2. The preparation method of a 3D printing photosensitive material according to claim 1, wherein The acrylic resin oligomer is prepared by mixing aliphatic polyurethane acrylate and polyurethane acrylate at a weight ratio of 1:1; aliphatic polyurethane acrylate, model: UO22 - 002, viscosity (cps / 25 °C): 60000, Ritek Chemical Co., Ltd.; polyurethane acrylate, model: Laromer PR9000, BASF; the acrylate monomer is prepared by mixing hydroxyethyl methacrylate and hydroxypropyl methacrylate at a weight ratio of 1:1; the epoxy resin is bisphenol A type epoxy resin with an epoxy value of 0.50; the initiator is prepared by mixing a free - radical photo - initiator and a cationic initiator at a weight ratio of 1:1, the free - radical photo - initiator is 1 - hydroxycyclohexyl phenyl ketone, and the cationic initiator is BASF 784.

3. The preparation method of a 3D printing photosensitive material according to claim 1, characterized in that, The preparation method of the modified filler is as follows: S01: Place halloysite carbon nanotubes in a sufficient amount of sulfuric acid solution with a mass fraction of 5 - 8%, mix well, then wash with water and dry; subject the dried halloysite carbon nanotubes to thermal modification treatment, and after the modification is completed, obtain thermally modified halloysite carbon nanotubes; The specific modification method is: First, heat up at a rate of 4 - 6 °C / min to 245 - 255 °C, hold for 1 h, then heat up at a rate of 2 - 3 °C / min to 350 °C, continue to hold for 35 min, and finally air - cool to room temperature; S02: Prepare a chitosan solution with a mass fraction of 2 - 5%, and prepare a nano - bentonite solution by mixing lanthanum oxide, the chitosan solution, and nano - bentonite according to a weight ratio of (1 - 3):(5 - 8):(3 - 4); Ultrasonically treat the thermally modified halloysite carbon nanotubes and the nano - bentonite solution according to a weight ratio of 3:

5. After the ultrasonic treatment is completed, filter by suction and dry to obtain a nano - bentonite / halloysite carbon nanotube compounding agent; S03: Add 2 - 5 parts of zirconia whiskers and 3 - 4 parts of wood cellulose to 5 - 8 parts of a hydrochloric acid dopamine solution with a mass fraction of 5%, and then add 1 - 3 parts of silane coupling agent KH550, and perform stirring and blending treatment to obtain a reinforcing liquid; S04: Mix and ball - mill the nano - bentonite / halloysite carbon nanotube compounding agent and the reinforcing liquid according to a weight ratio of 5:3, with a ball - milling speed of 1000 - 1500 r / min and ball - milling for 1 h. After the ball - milling is completed, filter by suction and dry to obtain the modified filler.

4. The preparation method of a 3D printing photosensitive material according to claim 3, characterized in that, The ultrasonic power of the ultrasonic treatment in S02 is 350 - 400 W, and the ultrasonic treatment is carried out for 30 - 40 min.

5. The preparation method of a 3D printing photosensitive material according to claim 3, characterized in that, The stirring speed of the stirring and blending treatment in S03 is 750 - 850 r / min, and the stirring is carried out for 1 h.

6. The preparation method of a 3D printing photosensitive material according to claim 3, characterized in that, The length of the wood cellulose is 3 - 5 µm, and the diameter of the zirconia whiskers is 2 - 4 µm.

7. The preparation method of a 3D printing photosensitive material according to claim 1, characterized in that, The preparation method of the formulation agent doped with nano - titanium dioxide is: S101: uniformly mixing the nano-silica sol, the sodium silicate solution and the Tris-HCl buffer solution in a weight ratio of (2-4):3:(5-8) to obtain a nano-silica sol solution; Add 1-3 parts of hydroxyethyl cellulose and 1-2 parts of sodium stearate to 4-7 parts of nano-silica sol solution and stir evenly to obtain a prepared nano-silica sol; S102: 2-5 parts of nano titanium dioxide and 1-3 parts of nano calcium carbonate are mixed and added into 5-8 parts of yttrium nitrate solution, and stirred sufficiently, and then filtered and dried to obtain a modifier doped with nano titanium dioxide; S103: The modifier doped with nano-titanium dioxide and the prepared nano-silica sol are mixed in a weight ratio of 3:5, and the mixture is ball-milled at a speed of 1500 r / min for 1 h. After the ball-milling is completed, the mixture is filtered and dried to obtain the prepared agent doped with nano-titanium dioxide.

8. The preparation method of a 3D printing photosensitive material according to claim 7, characterized in that, The mass fraction of the sodium silicate solution is 2-5%; the pH value of the Tris-HCl buffer solution is 8-9.

9. The preparation method of a 3D printing photosensitive material according to claim 7, wherein The mass fraction of the yttrium nitrate solution is 4-6%.

10. Application of the method for preparing a 3D printing photosensitive material according to any one of claims 1 to 9 in 3D printing materials.

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