A hybrid modified photosensitive resin, its preparation method, a 3D printing photosensitive resin and a dental appliance made therefrom

Abstract

The present invention relates to the technical field of polymer materials, and particularly relates to a hybrid modified photosensitive resin, a preparation method thereof, a 3D printing photosensitive resin and an orthodontic appliance made therefrom. The hybrid modified photosensitive resin provided by the present invention comprises the following components in parts by weight: 30-50 parts of polyurethane acrylate prepolymer, 50-70 parts of silver-doped epoxy acrylate prepolymer, 0.02-0.05 part of p-methoxyphenol, 0.02-0.05 part of dibutyltin dilaurate, 1-3 parts of surface-modified nano-TiO 2 powder, and 20-40 parts of ethyl acetate. The hybrid modified photosensitive resin provided by the present invention has high strength, high toughness, good wear resistance and antibacterial property; the 3D printing photosensitive resin provided by the present invention uses the above hybrid modified photosensitive resin as a raw material, and the orthodontic appliance prepared by using the 3D printing photosensitive resin has high strength, good wear resistance, high toughness, can ensure the orthodontic effect, has good antibacterial property, and can protect dental health.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and particularly relates to a hybrid modified photosensitive resin, a preparation method thereof, a 3D printing photosensitive resin and an orthodontic appliance made of the 3D printing photosensitive resin. Background Art

[0002] With the continuous improvement of people's living standards, people's requirements for beauty are also getting higher and higher. Therefore, the orthodontics industry has developed rapidly. The existing orthodontic correction methods are roughly divided into two categories. One is the traditional orthodontic means represented by metal arch wires, and the other is the invisible correction means represented by resin orthodontic appliances. The resin orthodontic appliances are favored by more and more young patients due to their convenient wearing and aesthetic features. According to the general orthodontic procedure, patients will wear orthodontic appliances of different shapes at different treatment stages, so that the teeth gradually move according to the predetermined designed shape, and finally achieve neat arrangement of the teeth.

[0003] At present, most of the commercially available resin orthodontic appliances are made of plastics. However, the strength of this plastic material is limited, and it is easy to deform under strong force, resulting in a decrease in the corrective force exerted by the orthodontic appliance on the teeth and affecting the orthodontic effect. Summary of the Invention

[0004] The purpose of the present invention is to provide a hybrid modified photosensitive resin, a preparation method thereof, a 3D printing photosensitive resin and an orthodontic appliance made of the 3D printing photosensitive resin. The hybrid modified photosensitive resin provided by the present invention has the characteristics of high strength, and also has high toughness, good wear resistance and antibacterial and bactericidal properties.

[0005] The 3D printing photosensitive resin provided by the present invention uses the above-mentioned hybrid modified photosensitive resin as a raw material, and an orthodontic appliance is prepared by using the 3D printing photosensitive resin. The obtained orthodontic appliance has high strength, good wear resistance, high toughness, can ensure the orthodontic effect of teeth, and has good antibacterial and bactericidal properties, and can protect the dental health.

[0006] In order to achieve the above purpose, the present invention provides the following technical solutions:

[0007] The present invention provides a hybrid modified photosensitive resin, which comprises the following components in parts by weight: 30-50 parts of polyurethane acrylate prepolymer, 50-70 parts of silver-doped epoxy acrylate prepolymer, 0.02-0.05 part of p-methoxyphenol, 0.02-0.05 part of dibutyltin dilaurate, 1-3 parts of surface-modified nano-TiO 2 powder and 20-40 parts of ethyl acetate.

[0008] Preferably, the silver-doped epoxy acrylate prepolymer comprises the following raw materials for preparation in parts by weight: 30-50 parts of epoxy acrylate, 0.5-2 parts of tin ethylhexanoate, 0.02-0.05 parts of p-methoxyphenol, 10-20 parts of caprolactone, and 2-5 parts of an organic acid silver salt solution; the concentration of the organic acid silver salt solution is 5-15 wt%.

[0009] Preferably, the polyurethane acrylate prepolymer comprises the following raw materials for preparation in parts by weight: 30-50 parts of isophorone diisocyanate, 0.1-0.4 parts of dibutyltin dilaurate, 0.01-0.03 parts of p-methoxyphenol, and 15-25 parts of hydroxy acrylate.

[0010] Preferably, the surface-modified nano-TiO 2 powder comprises silane coupling agent-modified nano-TiO 2 .

[0011] The present invention also provides a preparation method of the hybrid-modified photosensitive resin described in the above technical solution, comprising the following steps:

[0012] Mix the polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate for in-situ polymerization reaction, and remove the solvent in the obtained reaction solution to obtain the hybrid-modified photosensitive resin.

[0013] The present invention also provides a 3D printing photosensitive resin, comprising the following components in parts by weight: 1-3 parts of photoinitiator, 50-100 parts of hybrid-modified photosensitive resin, 15-40 parts of solubilizer, 0.05-1 part of leveling agent, and 0.05-1 part of defoaming agent; the hybrid-modified photosensitive resin is the hybrid-modified photosensitive resin described in the above technical solution or the hybrid-modified photosensitive resin prepared by the preparation method described in the above technical solution.

[0014] Preferably, the photoinitiator comprises one or more of 2-isopropylthioxanthone, benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,4,6-trimethylbenzoyl diphenylphosphine oxide, and 2-benzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl) butanone;

[0015] Preferably, the leveling agent comprises one or more of organosilicon-ethylene oxide copolymer, organosilicon-propylene oxide copolymer, organosilicon-polyacrylate copolymer, and polyether-modified silicone;

[0016] Preferably, the defoaming agent comprises one or more of ethylene oxide copolymer ether, propylene oxide copolymer ether, and polyether siloxane copolymer.

[0017] The present invention also provides a method for preparing the 3D printing photosensitive resin described in the above technical solution, which includes the following steps:

[0018] Mix a photoinitiator, a hybrid-modified photosensitive resin, a solubilizer, a leveling agent, and an antifoaming agent under light-shielded conditions to obtain the 3D printing photosensitive resin.

[0019] The present invention also provides a wear-resistant, high-strength, and antibacterial orthodontic dental appliance, which is prepared by using the 3D printing photosensitive resin described in the above technical solution or the 3D printing photosensitive resin prepared by the preparation method described in the above technical solution as a raw material.

[0020] The present invention also provides a method for preparing the wear-resistant, high-strength, and antibacterial orthodontic dental appliance described in the above technical solution, which includes the following steps:

[0021] Perform 3D laser printing on the raw material to obtain the dental appliance; the raw material includes the 3D printing photosensitive resin described in the above technical solution or the 3D printing photosensitive resin prepared by the preparation method described in the above technical solution;

[0022] Perform shaping baking on the dental appliance to obtain the wear-resistant, high-strength, and antibacterial orthodontic dental appliance; the baking temperature is 60-90°C.

[0023] The present invention provides a hybrid-modified photosensitive resin, which includes the following components in parts by weight: 30-50 parts of polyurethane acrylate prepolymer, 50-70 parts of silver-doped epoxy acrylate prepolymer, 0.02-0.05 parts of p-methoxyphenol, 0.02-0.05 parts of dibutyltin dilaurate, 1-3 parts of surface-modified nano-TiO 2 powder, and 20-40 parts of ethyl acetate. In the hybrid-modified photosensitive resin provided by the present invention, nano-silver particles are uniformly distributed in its structure, which not only has a certain strengthening effect on the hybrid-modified photosensitive resin, improves the strength of the hybrid-modified photosensitive resin, but also endows the hybrid-modified photosensitive resin with stronger antibacterial and bactericidal properties; the hybrid-modified photosensitive resin is obtained by in-situ polymerization of epoxy acrylate and polyurethane acrylate, and the hard and soft chain segments in the molecular chain are organically combined, so that the obtained hybrid-modified photosensitive resin not only has high strength, but also has high toughness; the hybrid-modified photosensitive resin also adds surface-modified nano-TiO 2 powder, and the surface-modified nano-TiO 2 powder is uniformly dispersed in the resin. The addition of two nano-fillers, nano-TiO 2 and nano-silver, can enhance the mechanical properties of the hybrid-modified photosensitive resin to a certain extent; under ultraviolet light irradiation, nano-TiO 2 can generate free radicals with very strong chemical activity, and then kill bacteria in a short time; and, nano-TiO 2 will also be combined with nano-silver particles to produce a synergistic effect, further improving the antibacterial and bactericidal effects.

[0024] The present invention also provides a preparation method of the hybrid-modified photosensitive resin described in the above solution, including the following steps: Mix polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate for in-situ polymerization reaction, and remove the solvent in the obtained reaction solution to obtain the hybrid-modified photosensitive resin. The present invention in-situ modifies the epoxy acrylate prepolymer and adds an organic silver salt as an antibacterial factor. The silver ions are reduced to uncharged nano silver particles by the free radicals generated during the polymerization reaction, so that the generated nano silver particles are evenly distributed in the structure of the silver-doped epoxy acrylate prepolymer; at the same time, through in-situ polymerization, the soft and hard segments in the molecular chain segments of the hybrid-modified photosensitive resin are organically combined, achieving high strength and high toughness at the same time, meeting the requirements of the resin performance for the dental appliance, and further evenly distributing the nano silver particles in the hybrid-modified photosensitive resin.

[0025] The present invention also provides a 3D printing photosensitive resin, including the following components in parts by weight: 1-3 parts of photoinitiator, 50-100 parts of hybrid-modified photosensitive resin, 15-40 parts of solubilizer, 0.05-1 part of leveling agent, and 0.05-1 part of defoaming agent. The 3D printing photosensitive resin provided by the present invention uses the above hybrid-modified photosensitive resin as the basic component, and adds specific contents of solubilizer, leveling agent, defoaming agent and photoinitiator. The obtained 3D printing photosensitive resin can carry out polymerization reaction under the action of ultraviolet light, is suitable for 3D printing, and has high strength, high toughness and good wear resistance, excellent mechanical properties, and also has an antibacterial and bactericidal effect.

[0026] The present invention also provides a preparation method of the 3D printing photosensitive resin described in the above solution. The preparation method provided by the present invention has simple process, easy-to-realize conditions, low cost, is green and environmentally friendly, and has broad industrial application prospects.

[0027] The present invention also provides a wear-resistant, high-strength and antibacterial orthodontic dental appliance, which is prepared from the 3D printing photosensitive resin described in the above solution. The wear-resistant, high-strength and antibacterial orthodontic dental appliance provided by the present invention not only has high strength and fully meets the strength requirements of dental orthodontics for materials, but also has good wear resistance and toughness, is convenient for patients to wear, and also has good antibacterial and bactericidal properties, avoiding hurting the patient's teeth during dental orthodontics and protecting the oral health of the patient.

[0028] The present invention also provides a preparation method of the wear-resistant, high-strength and antibacterial orthodontic dental appliance described in the above solution. The preparation method provided by the present invention is not only convenient to operate, but also green and environmentally friendly, avoiding pollution of the dental appliance during the production process and ensuring the cleanliness and safety of the dental appliance. Detailed embodiments

[0029] The present invention provides a hybrid modified photosensitive resin, which comprises the following components in parts by weight: 30-50 parts of polyurethane acrylate prepolymer, 50-70 parts of silver-doped epoxy acrylate prepolymer, 0.02-0.05 part of p-methoxyphenol, 0.02-0.05 part of dibutyltin dilaurate, 1-3 parts of surface-modified nano-TiO 2 powder and 20-40 parts of ethyl acetate.

[0030] Unless otherwise specified, all components used in the present invention are commercially available.

[0031] In parts by weight, the hybrid modified photosensitive resin provided by the present invention comprises 30-50 parts of polyurethane acrylate prepolymer, preferably 35-45 parts, more preferably 37-42 parts. In the present invention, the polyurethane acrylate prepolymer preferably comprises the following raw materials for preparation in parts by weight: 30-50 parts of isophorone diisocyanate, preferably 35-45 parts, 0.1-0.4 part of dibutyltin dilaurate, preferably 0.2-0.3 part, 0.01-0.03 part of p-methoxyphenol, preferably 0.02-0.03 part, and 15-25 parts of hydroxy acrylate, preferably 18-22 parts. In the present invention, the hydroxy acrylate preferably comprises one or more of hydroxyethyl acrylate (HEA), hydroxypropyl acrylate (HPA), hydroxyethyl methacrylate (HEMA) and hydroxypropyl methacrylate (HPMA).

[0032] In the present invention, the preparation method of the polyurethane acrylate prepolymer preferably comprises the following steps: mixing isophorone diisocyanate, dibutyltin dilaurate, p-methoxyphenol and hydroxy acrylate for a nucleophilic reaction. When the content of -NCO groups in the reactants reaches 1 / 2-1 / 3 of the initial value, the reactants are cooled to obtain the polyurethane acrylate prepolymer. The mixing is preferably as follows: first mix isophorone diisocyanate, dibutyltin dilaurate and p-methoxyphenol, then raise the temperature of the obtained mixture to 40-60 °C, and then dropwise add hydroxy acrylate; the mixing is preferably carried out by stirring; after the dropwise addition of hydroxy acrylate is completed, the reaction is preferably continued under the conditions of heat preservation and stirring until the content of -NCO groups in the reactants reaches 1 / 2-1 / 3 of the initial value and then stopped; the cooling is preferably to room temperature.

[0033] Based on the parts by weight of the polyurethane acrylate prepolymer, the hybrid modified photosensitive resin comprises 50 - 70 parts, preferably 55 - 65 parts, more preferably 57 - 63 parts of silver-doped epoxy acrylate prepolymer. The silver-doped epoxy acrylate prepolymer preferably comprises the following raw materials for preparation in parts by weight: 30 - 50 parts, preferably 35 - 45 parts of epoxy acrylate, 0.5 - 2 parts, preferably 1 - 1.5 parts of tin ethylhexanoate, 0.02 - 0.05 parts, preferably 0.03 - 0.04 parts of p-hydroxyanisole, 10 - 20 parts, preferably 14 - 16 parts of caprolactone, 2 - 5 parts, preferably 3 - 4 parts of organic acid silver salt solution; the concentration of the organic acid silver salt solution is 5 - 15 wt%. The organic acid silver salt in the organic acid silver salt solution preferably comprises one or more of silver 2-ethylhexanoate, silver picolinate and silver cyclohexanebutyrate; the solvent of the organic acid silver salt solution preferably comprises ethyl acetate.

[0034] In the present invention, the preparation method of the silver-doped epoxy acrylate prepolymer preferably comprises the following steps: mixing epoxy acrylate, tin ethylhexanoate, p-hydroxyanisole and caprolactone for nucleophilic reaction, adding the organic acid silver salt solution for ripening after the reaction solution is cooled, and removing the solvent to obtain the silver-doped epoxy acrylate prepolymer. In the present invention, the temperature of the nucleophilic reaction is preferably 105 - 115 °C, and the time is preferably 8 - 10 h. In the present invention, epoxy acrylate, tin ethylhexanoate and p-hydroxyanisole are preferably mixed first, and the obtained mixture is heated to 105 - 115 °C and then caprolactone is added dropwise. The time of the nucleophilic reaction is counted from the completion of the dropwise addition of caprolactone; the mixing is preferably carried out by stirring. After the nucleophilic reaction is completed, the present invention preferably cools the obtained reaction solution to room temperature, and then adds the organic silver salt solution under stirring conditions. The temperature of the ripening is preferably 35 - 45 °C, and the time is preferably 30 - 60 min; the method of removing the solvent is preferably low-pressure distillation; in the present invention, the polyurethane acrylate prepolymer and the silver-doped epoxy acrylate prepolymer are in-situ polymerized, so that the hard and soft segments in the molecular chain segments of the prepared hybrid photosensitive resin are organically combined, having high strength and high toughness at the same time, meeting the requirements of the resin performance for the dental appliance.

[0035] Based on the parts by weight of the polyurethane acrylate prepolymer, the hybrid modified photosensitive resin comprises 0.02 - 0.05 parts, preferably 0.03 - 0.04 parts, more preferably 0.04 parts of p-hydroxyanisole.

[0036] Based on the parts by weight of the polyurethane acrylate prepolymer, the hybrid modified photosensitive resin comprises 0.02 - 0.05 parts, preferably 0.03 - 0.04 parts, more preferably 0.04 parts of dibutyltin dilaurate.

[0037] Based on the parts by weight of the polyurethane acrylate prepolymer, the hybrid modified photosensitive resin comprises surface-modified nano-TiO2 1 to 3 parts of powder, preferably 2 to 3 parts, more preferably 2 parts. In the present invention, the surface-modified nano-TiO 2 powder preferably comprises nano-TiO modified with a silane coupling agent 2 ; the silane coupling agent preferably comprises KH570.

[0038] In the present invention, the preparation method of the surface-modified nano-TiO 2 powder preferably comprises the following steps: mixing nano-TiO 2 powder and a silane coupling agent solution and then drying to obtain surface-modified nano-TiO 2 powder; the mass ratio of the nano-TiO 2 powder to the silane coupling agent is 100:3 to 8; the concentration of the silane coupling agent solution is preferably 15 to 20 wt%, and the solvent is preferably ethanol; the particle size of the nano-TiO 2 powder is preferably less than 900 nm, more preferably 100 to 900 nm. During the mixing process, the silane coupling agent chemically bonds with the surface of nano-TiO 2 to adsorb the silane coupling agent on the surface of nano-TiO 2 to form a certain steric hindrance, which can effectively prevent agglomeration between nano-TiO 2 particles, and further enable nano-TiO 2 to be uniformly and stably dispersed in the resin. In the present invention, the nano-TiO 2 powder is preferably dried before mixing, the drying temperature is preferably 105 to 130 °C, and the time is preferably 1 to 2 h; the mixing temperature is preferably 105 to 120 °C; the mixing is preferably carried out by stirring, and the stirring preferably includes first high-speed stirring, medium-speed stirring, and second high-speed stirring in sequence; the rotation speed of the first high-speed stirring is preferably 1500 to 2000 r / min, and the time of the first high-speed stirring is preferably 5 min; the rotation speed of the medium-speed stirring is preferably 300 to 600 r / min; the rotation speed of the second high-speed stirring is preferably 1500 to 2000 r / min, and the time is preferably 15 to 30 min; the silane coupling agent solution is preferably added in a spray form during medium-speed stirring; the drying temperature is preferably 80 to 100 °C. By modifying the nano-TiO 2 powder in the present invention, the nano-TiO 2 powder is fully and uniformly dispersed in the hybrid-modified photosensitive resin, ensuring the uniformity of the material properties. In the present invention, the nano-TiO 2 powder can generate highly chemically active free radicals under ultraviolet light irradiation, which can kill bacteria in a short time; nano-TiO 2 will also have a synergistic effect when compounded with nano-silver particles, further improving nano-TiO2 The antibacterial, bacteriostatic and bactericidal effects result in the obtained hybrid modified photosensitive resin having good antibacterial and bactericidal properties; moreover, the addition of two kinds of nano-fillers, nano-TiO 2 and nano-silver particles can, to a certain extent, improve the mechanical properties of the hybrid modified photosensitive resin.

[0039] Based on the parts by weight of the polyurethane acrylate prepolymer, the hybrid modified photosensitive resin comprises 20-40 parts of ethyl acetate, preferably 25-35 parts, and more preferably 28-32 parts.

[0040] The present invention also provides a preparation method of the hybrid modified photosensitive resin described in the above technical solution, comprising the following steps:

[0041] Mix the polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate for in-situ polymerization reaction, and remove the solvent in the obtained reaction solution to obtain the hybrid modified photosensitive resin.

[0042] In the present invention, the polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate are mixed for in-situ polymerization reaction to obtain a reaction solution. In the present invention, the temperature of the in-situ polymerization reaction is preferably 60-75 °C; the present invention preferably first stirs and mixes the polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate at room temperature for 10-30 min, and then raises the temperature to the in-situ polymerization reaction temperature at a constant rotation speed for reaction; the rotation speed of the stirring and mixing at room temperature is preferably 2000-2500 r / min; the present invention has no special requirements for the time of the in-situ polymerization reaction, and the reaction ends when all the -NCO groups in the reactants are reacted. In the present invention, through the above in-situ polymerization reaction, the hard and soft segments in the molecular chain segments of the hybrid modified photosensitive resin are organically combined, achieving high strength and high toughness at the same time, meeting the requirements of the resin performance for the dental appliance, and further uniformly distributing the nano-silver particles in the hybrid modified photosensitive resin.

[0043] After obtaining the reaction solution, the present invention removes the solvent in the obtained reaction solution to obtain the hybrid modified photosensitive resin. In the present invention, the method for removing the solvent is preferably distillation, and more preferably low-pressure distillation.

[0044] The present invention also provides a 3D printing photosensitive resin, which comprises the following components in parts by weight: 1-3 parts of a photoinitiator, 50-100 parts of a hybrid-modified photosensitive resin, 15-40 parts of a solubilizer, 0.05-1 part of a leveling agent, and 0.05-1 part of an antifoaming agent; the hybrid-modified photosensitive resin is the hybrid-modified photosensitive resin described in the above solution or the hybrid-modified photosensitive resin prepared by the preparation method described in the above solution.

[0045] In parts by weight of the photoinitiator, the 3D printing photosensitive resin provided by the present invention comprises 1-3 parts of a photoinitiator, preferably 2-3 parts, more preferably 2 parts. In the present invention, the photoinitiator preferably comprises one or more of 2-isopropylthioxanthone, benzoin dimethyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, ethyl 2,4,6-trimethylbenzoyl phenylphosphinate, and 2-benzyl-2-dimethylamino-1-(4-morpholinobenzylphenyl) butanone.

[0046] In parts by weight of the photoinitiator, the 3D printing photosensitive resin comprises 50-100 parts of a hybrid-modified photosensitive resin, preferably 60-90 parts, more preferably 70-80 parts, and further preferably 74-77 parts. In the present invention, the hybrid-modified photosensitive resin is the hybrid-modified photosensitive resin described in the above solution or the hybrid-modified photosensitive resin prepared by the preparation method described in the above solution. In the present invention, the hybrid-modified photosensitive resin, as the main component of the 3D printing photosensitive resin, endows the 3D printing photosensitive resin with high strength, high toughness, and good wear resistance, and enables the 3D printing photosensitive resin to have antibacterial and bactericidal properties.

[0047] In parts by weight of the photoinitiator, the 3D printing photosensitive resin comprises 15-40 parts of a solubilizer, preferably 20-35 parts, more preferably 25-30 parts. In the present invention, the solubilizer preferably comprises an acrylic acid derivative, and the acrylic acid derivative preferably comprises tripropylene glycol diacrylate.

[0048] In parts by weight of the photoinitiator, the 3D printing photosensitive resin comprises 0.05-1 part of a leveling agent, preferably 0.06-0.09 part, more preferably 0.07-0.08 part. In the present invention, the leveling agent preferably comprises one or more of an organosilicon-ethylene oxide copolymer, an organosilicon-propylene oxide copolymer, an organosilicon-polyacrylate copolymer, and a polyether-modified silicone. In the examples of the present invention, the leveling agent used is BYK-354.

[0049] Based on the parts by weight of the photoinitiator, the 3D printing photosensitive resin comprises 0.05 to 1 part of an antifoaming agent, preferably 0.1 to 0.8 part, more preferably 0.2 to 0.5 part, and further preferably 0.3 to 0.4 part. In the present invention, the antifoaming agent preferably comprises one or more of ethylene oxide copolymer ether, propylene oxide copolymer ether, and polyether silicone copolymer. In the examples of the present invention, the antifoaming agent used is BYK-1790.

[0050] The present invention also provides a preparation method of the 3D printing photosensitive resin described in the above solution, comprising the following steps:

[0051] Mix the photoinitiator, the hybrid-modified photosensitive resin, the solubilizer, the leveling agent, and the antifoaming agent under light-shielded conditions to obtain the 3D printing photosensitive resin.

[0052] In the present invention, the temperature of the mixing is preferably room temperature; the mixing time is preferably 20 to 30 min; the mixing is preferably stirring, and the rotation speed of the stirring is preferably 1000 to 2000 r / min. The preparation method provided by the present invention has simple process, easy-to-realize conditions, low cost, and is green and environmentally friendly.

[0053] The present invention also provides a wear-resistant, high-strength, and antibacterial orthodontic dental appliance, which is prepared by using the 3D printing photosensitive resin described in the above solution or the 3D printing photosensitive resin prepared by the preparation method described in the above solution as a raw material. The wear-resistant, high-strength, and antibacterial orthodontic dental appliance provided by the present invention not only has high strength and fully meets the strength requirements of dental orthodontics for materials, but also has good wear resistance and toughness, is convenient for patients to wear, and also has good antibacterial and bactericidal properties, avoiding harming the teeth of patients during dental orthodontics and protecting the oral health of patients.

[0054] The present invention also provides a preparation method of the wear-resistant, high-strength, and antibacterial orthodontic dental appliance described in the above solution, comprising the following steps:

[0055] Perform 3D laser printing on the raw material to obtain a dental appliance; the raw material comprises the 3D printing photosensitive resin described in the above technical solution or the 3D printing photosensitive resin prepared by the preparation method described in the above technical solution;

[0056] Perform shaping baking on the dental appliance to obtain the wear-resistant, high-strength, and antibacterial orthodontic dental appliance; the baking temperature is 60 to 90 °C.

[0057] In the present invention, the conditions for laser printing are preferably a DLP laser 3D printer with a laser wavelength of 380 - 420 nm. The printing wavelength is preferably 380 nm, the light source power is preferably 15 w, the printing accuracy is preferably 25 microns, and the printing rate is preferably 15 s per layer. The baking is preferably carried out by fitting the dental appliance onto a dental mold with a fixed shape. The baking time is preferably 1 - 2 h. The baking is preferably carried out in an incubator. The preparation method provided by the present invention has a simple process, is green and environmentally friendly, and has the prospect of large-scale industrial application.

[0058] In order to further illustrate the present invention, the 3D printing photosensitive resin and its preparation method provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the protection scope of the present invention.

[0059] The specifications and sources of each component in the embodiments of the present invention: 2 - phenylbenzyl - 2 - dimethylamine - 1 - (4 - morpholinobenzylphenyl) butanone (photoinitiator), Jiangsu Guangxin Photo - sensitive New Materials Co., Ltd.; epoxy acrylate, Jiangsu KaiLing RuiYang Chemical Co., Ltd.; tin ethylhexanoate, Shanghai Aladdin Reagent Co., Ltd.; dibutyltin dilaurate, Shanghai Aladdin Reagent Co., Ltd.; caprolactone, Sinopharm Chemical Reagent Co., Ltd.; silver 2 - ethylhexanoate, Shanghai Aladdin Reagent Co., Ltd.; isophorone diisocyanate, Dongrun Chemical Materials Co., Ltd.; p - methoxyphenol, Tianjin Fuyu Fine Chemical Co., Ltd.; 2 - hydroxyethyl methacrylate, Tianjin Tianjiao Radiation Curing Materials Co., Ltd.; nano - TiO 2 powder, Shandong Yousuo Chemical Technology Co., Ltd.; KH570, Guangzhou Suixin Chemical Co., Ltd.; BYK - 354 (flow leveling agent), Foshan Qianyou Chemical Co., Ltd.; BYK - 1790 (defoaming agent), Foshan Qianyou Chemical Co., Ltd.; tripropylene glycol diacrylate (solubilizer), Jiangsu KaiLing RuiYang Chemical Co., Ltd.; polyurethane acrylate oligomer, Yixing Yanglin New Materials Co., Ltd.

[0060] In the embodiments of the present invention, the silver - doped epoxy acrylate prepolymer, polyurethane acrylate prepolymer, and surface - modified nano - TiO 2 powder are prepared by the following methods:

[0061] 1. Preparation of silver - doped epoxy acrylate prepolymer

[0062] Weigh 500 g of epoxy acrylate, 10 g of tin 2-ethylhexanoate, and 0.5 g of p-hydroxyanisole, and put them into a heating and stirring reaction kettle. Heat up to 110 °C. After the temperature stabilizes, gradually add 180 g of caprolactone drop by drop. Stir and react at a constant temperature for 10 h. Cool the reactant to room temperature. While stirring continuously, add 50 g of an ethyl acetate solution of silver 2-ethylhexanoate with a concentration of 10 wt%. Heat up to 45 °C and stir and cure for 60 min. Remove the solvent by low-pressure distillation to obtain a silver-doped epoxy acrylate prepolymer.

[0063] 2. Preparation of polyurethane acrylate prepolymer

[0064] Weigh 500 g of isophorone diisocyanate, 2 g of dibutyltin dilaurate, and 0.2 g of p-hydroxyanisole, and put them into a heating and stirring reaction kettle. Heat up to 60 °C. After the temperature stabilizes, gradually add 250 g of 2-hydroxyethyl methacrylate drop by drop. Stir and react at a constant temperature until the content of -NCO groups in the reactant is 1 / 2 of the initial value. Cool the reactant to room temperature to obtain a polyurethane acrylate prepolymer.

[0065] 3. Preparation of surface-modified nano-TiO 2 powder

[0066] Dry 1000 g of nano-TiO 2 powder in an oven at 110 °C for 2 h to remove the absorbed moisture. Then add it to a high-speed mixer at 110 °C and stir at a high speed of 1500 r / min for 5 min. Then stir at a medium speed of 500 r / min. At the same time, spray 250 g of an ethanol solution of KH570 with a concentration of 20 wt% in a spray manner. Stir at a high speed of 1500 r / min for a second time for 15 min. Then dry in an oven at 80 °C to obtain surface-modified nano-TiO 2 powder.

[0067] The component ratios in Examples 1 to 6 and Comparative Example 1 are shown in Table 1.

[0068] Table 1 Component ratios of Examples 1 to 6 and Comparative Example 1 (unit: g)

[0069]

[0070] Example 1

[0071] (A) Preparation of hybrid-modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 2 g of surface-modified nano-TiO 2Put 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 3 g of surface-modified nano-TiO

[0072] (B) Preparation of 3D printing photosensitive resin: Put 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid-modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354, and 0.2 g of BYK-1790 into a stainless-steel reaction kettle in the dark at room temperature and stir and mix them at high speed for 20 min, then let it stand for 10 min to obtain 3D printing photosensitive resin.

[0073] Example 2

[0074] (A) Preparation of hybrid-modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 3 g of surface-modified nano-TiO 2 Put 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 3 g of surface-modified nano-TiO

[0075] (B) Preparation of 3D printing photosensitive resin: Put 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid-modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354, and 0.2 g of BYK-1790 into a stainless-steel reaction kettle in the dark at room temperature and stir and mix them at high speed for 20 min, then let it stand for 10 min to obtain 3D printing photosensitive resin.

[0076] Example 3

[0077] (A) Preparation of hybrid-modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 4 g of surface-modified nano-TiO 2 Put 50 g of polyurethane acrylate prepolymer, 50 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-hydroxyanisole, 0.02 g of dibutyltin dilaurate, 4 g of surface-modified nano-TiO

[0078] (B) Preparation of 3D printing photosensitive resin: 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354 and 0.2 g of BYK-1790 were stirred and mixed at high speed in a stainless steel reaction kettle in the dark at room temperature for 20 min, and then left standing for 10 min to obtain 3D printing photosensitive resin.

[0079] Example 4

[0080] (A) Preparation of hybrid modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 60 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-methoxyphenol, 0.02 g of dibutyltin dilaurate, 2 g of surface-modified nano-TiO 2 powder and 30 g of ethyl acetate were put into a heating and stirring reaction kettle, stirred and dispersed at 2000 r / min at room temperature for 15 min, then heated to 70 °C, and when the temperature was stable, the reaction was stirred at a constant temperature until all the -NCO groups in the reactants reacted, and the reaction was terminated. Ethyl acetate was removed by low-pressure distillation to obtain hybrid modified photosensitive resin.

[0081] (B) Preparation of 3D printing photosensitive resin: 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354 and 0.2 g of BYK-1790 were stirred and mixed at high speed in a stainless steel reaction kettle in the dark at room temperature for 20 min, and then left standing for 10 min to obtain 3D printing photosensitive resin.

[0082] Example 5

[0083] (A) Preparation of hybrid modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 60 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-methoxyphenol, 0.02 g of dibutyltin dilaurate, 3 g of surface-modified nano-TiO 2 powder and 30 g of ethyl acetate were put into a heating and stirring reaction kettle, stirred and dispersed at 2000 r / min at room temperature for 15 min, then heated to 70 °C, and when the temperature was stable, the reaction was stirred at a constant temperature until all the -NCO groups in the reactants reacted, and the reaction was terminated. Ethyl acetate was removed by low-pressure distillation to obtain hybrid modified photosensitive resin.

[0084] (B) Preparation of 3D printing photosensitive resin: 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354 and 0.2 g of BYK-1790 were stirred and mixed at high speed in a stainless steel reactor in the dark at room temperature for 20 min, and then left standing for 10 min to obtain 3D printing photosensitive resin.

[0085] Example 6

[0086] (A) Preparation of hybrid modified photosensitive resin: Weigh 50 g of polyurethane acrylate prepolymer, 70 g of silver-doped epoxy acrylate prepolymer, 0.02 g of p-methoxyphenol, 0.02 g of dibutyltin dilaurate, 3 g of surface-modified nano-TiO 2 powder and 30 g of ethyl acetate were put into a heating and stirring reactor, stirred and dispersed at 2000 r / min at room temperature for 15 min, then heated to 70 °C. When the temperature was stable, the reaction was stirred at a constant temperature until all -NCO groups in the reactants reacted, and the reaction was ended. Ethyl acetate was removed by low-pressure distillation to obtain hybrid modified photosensitive resin.

[0087] (B) Preparation of 3D printing photosensitive resin: 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 100 g of hybrid modified photosensitive resin, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354 and 0.2 g of BYK-1790 were stirred and mixed at high speed in a stainless steel reactor in the dark at room temperature for 20 min, and then left standing for 10 min to obtain 3D printing photosensitive resin.

[0088] Comparative Example 1

[0089] (A) Preparation of 3D printing photosensitive resin: 2 g of 2-phenylbenzyl-2-dimethylamine-1-(4-morpholinobenzylphenyl)butanone (photoinitiator 369), 40 g of polyurethane acrylate oligomer, 60 g of epoxy acrylate oligomer, 20 g of tripropylene glycol diacrylate, 0.5 g of BYK-354 and 0.2 g of BYK-1790 were stirred and mixed at high speed in a stainless steel reactor in the dark at room temperature for 20 min, and then left standing for 10 min to obtain 3D printing photosensitive resin.

[0090] The 3D printing photosensitive resins prepared in Examples 1-6 and Comparative Example 1 were used to print the shapes required for testing with a Sprintray-Pro S type 3D printer produced by Zhejiang Xunshi Technology Co., Ltd.: For the tensile test specimen, according to GB / T 1040.2-2006, it was printed into a dumbbell-shaped specimen of 115 mm × 25 mm × 4 mm; for other tests, it was printed into a test piece of 50 mm × 50 mm × 1 mm.

[0091] The performance test method is as follows:

[0092] 1. Tensile strength and elongation at break are tested in accordance with GB / T 1040.3-2006, the measurement temperature is 25 °C, and the tensile rate is 10 mm / min.

[0093] 2. Antibacterial test: Take 3 specimens from each group for direct contact antibacterial experiment. Among them, 3 specimens are soaked in saliva for 1 day, and the other 3 specimens are soaked in saliva for 1 week; place the soaked specimens in a 24-well culture plate (with the adhesive layer facing up uniformly), take 10 μl of bacterial suspension and inoculate it on the surface of the specimens, and then cover the surface of the specimens with a polyester film of the same size to reduce the volatilization of the bacterial liquid. Incubate at a constant temperature of 37 °C and 0.5% CO 2 in the darkroom for 24 h; then place the specimens in 9.99 ml of fresh BHI and shake for 2 min to completely elute the bacteria attached to the surface of the specimens, perform gradient dilution and then plate colony counting, repeat each concentration 3 times, and take the average value of the results.

[0094] 3. Wear rate test: Conduct friction and wear tests on the specimens on a pin-on-disc friction and wear testing machine, record the wear amount, and detect the wear resistance performance. Repeat each test 3 times and take the average value of the results.

[0095] The test results of the above tests are shown in Table 2.

[0096] Table 2 Performance test results of 3D printing photosensitive resins in Examples 1-6 and Comparative Example 1

[0097]

[0098] From the test results in Table 2, it can be seen that the tensile strength of the 3D printing photosensitive resins provided in Examples 1-6 of the present invention can reach more than 34.6 MPa, which is significantly better than that of the 3D printing photosensitive resin in Comparative Example 1, which is 27.2 MPa; the elongation at break of the 3D printing photosensitive resins provided in Examples 1-6 of the present invention is not less than 2.85%, which is much higher than that of the 3D printing photosensitive resin in Comparative Example 1, which is 2.23%; the antibacterial rate of the 3D printing photosensitive resins provided in Examples 1-6 of the present invention after being soaked in saliva for 1 day all reaches more than 97.04%, and the antibacterial rate of Example 6 can reach 99.85%. The antibacterial rate of the 3D printing photosensitive resins provided in Examples 1-6 of the present invention after being soaked in saliva for 1 week is not less than 98.33%, and can even reach 99.96%; the wear rate of the 3D printing photosensitive resins provided in Examples 1-6 of the present invention is not higher than 23.9×10 -2 g, which is significantly better than that of the 3D printing photosensitive resin in Comparative Example 1, which is 30.8×10 -2 g.

[0099] Example 7

[0100] The dental braces are prepared using the 3D printing photosensitive resin in Example 6. The laser printing conditions are as follows: using a Sprintray-Pro S type DLP laser 3D printer, preferably with a printing wavelength of 380 nm, a light source power of 15 w, a printing accuracy of 25 microns, and a printing rate of 15 s per layer, to obtain the dental braces;

[0101] The obtained dental braces are put on a dental mold with a fixed shape and baked for shaping at 70 °C for 2 h to obtain the wear-resistant, high-strength, and antibacterial orthodontic dental braces. The obtained wear-resistant, high-strength, and antibacterial orthodontic dental braces have good wear resistance and toughness, are convenient for patients to wear, and also have good antibacterial and bactericidal properties, avoiding harm to the patients' teeth during orthodontics and protecting the oral health of the patients.

[0102] As can be seen from the above examples, the 3D printing photosensitive resin provided by the embodiments of the present invention has high tensile strength, high toughness, good wear resistance, and excellent mechanical properties; in addition, the antibacterial rates of the 3D printing photosensitive resin provided by the embodiments of the present invention after being soaked in saliva for 1 day and 1 week both reach more than 97%, indicating that its antibacterial, bacteriostatic, and bactericidal effects are prominent and meet the requirements of the dental braces for the antibacterial and bactericidal properties of the resin.

[0103] Although the above embodiments have made a detailed description of the present invention, they are only a part of the embodiments of the present invention, rather than all embodiments. Other embodiments can also be obtained based on these embodiments without creative efforts, and these embodiments all fall within the protection scope of the present invention.

Claims

1. A 3D printing photosensitive resin, comprising the following components in parts by weight: 1 - 3 parts of photoinitiator, 50 - 100 parts of hybrid - modified photosensitive resin, 15 - 40 parts of solubilizer, 0.05 - 1 part of leveling agent, and 0.05 - 1 part of defoaming agent; The hybrid modified photosensitive resin comprises the following components in parts by weight: 30-50 parts of polyurethane acrylate prepolymer, 50-70 parts of silver-doped epoxy acrylate prepolymer, 0.02-0.05 part of p-hydroxyanisole, 0.02-0.05 part of dibutyltin dilaurate, 1-3 parts of surface-modified nano-TiO 2 powder and 20-40 parts of ethyl acetate; The silver - doped epoxy acrylate prepolymer comprises the following raw materials for preparation in parts by weight: 30 - 50 parts of epoxy acrylate, 0.5 - 2 parts of tin ethylhexanoate, 0.02 - 0.05 parts of p - methoxyphenol, 10 - 20 parts of caprolactone, and 2 - 5 parts of organic acid silver salt solution; the concentration of the organic acid silver salt solution is 5 - 15 wt%; The polyurethane acrylate prepolymer comprises the following raw materials for preparation in parts by weight: 30 - 50 parts of isophorone diisocyanate, 0.1 - 0.4 parts of dibutyltin dilaurate, 0.01 - 0.03 parts of p - methoxyphenol, and 15 - 25 parts of hydroxy acrylate; The surface-modified nano-TiO 2 powder includes silane coupling agent-modified nano-TiO 2 .

2. The 3D printing photosensitive resin according to claim 1, characterized in that, The preparation method of the hybrid - modified photosensitive resin comprises the following steps: Mix polyurethane acrylate prepolymer, silver-doped epoxy acrylate prepolymer, p-methoxyphenol, dibutyltin dilaurate, surface-modified nano-TiO 2 powder and ethyl acetate to carry out an in-situ polymerization reaction, remove the solvent in the resulting reaction solution, and obtain a hybrid-modified photosensitive resin.

3. The 3D printing photosensitive resin according to claim 1, characterized in that, The photoinitiator includes one or more of 2 - isopropylthioxanthone, benzoin dimethyl ether, 1 - hydroxycyclohexyl phenyl ketone, 2 - hydroxy - 2 - methyl - 1 - phenyl - 1 - propanone, ethyl 2,4,6 - trimethylbenzoyl phenylphosphinate, and 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinobenzylphenyl) butanone; The leveling agent includes one or more of silicone - ethylene oxide copolymer, silicone - propylene oxide copolymer, silicone - polyacrylate copolymer, and polyether - modified silicone; The defoaming agent includes one or more of ethylene oxide copolymer ether, propylene oxide copolymer ether, and polyether - silicone copolymer.

4. The preparation method of the 3D printing photosensitive resin according to any one of claims 1 - 3, comprises the following steps: Mix the photoinitiator, hybrid - modified photosensitive resin, solubilizer, leveling agent, and defoaming agent under light - shielding conditions to obtain the 3D printing photosensitive resin.

5. An orthodontic appliance with wear - resistance, high strength, and antibacterial properties, which is prepared from the 3D printing photosensitive resin according to any one of claims 1 - 3 or the 3D printing photosensitive resin prepared by the preparation method according to claim 4.

6. The preparation method of the orthodontic appliance with wear - resistance, high strength, and antibacterial properties according to claim 5, comprises the following steps: Perform 3D laser printing on the raw material to obtain the orthodontic appliance; the raw material includes the 3D printing photosensitive resin according to any one of claims 1 - 3 or the 3D printing photosensitive resin prepared by the preparation method according to claim 4; Perform shaping baking on the orthodontic appliance to obtain the orthodontic appliance with wear - resistance, high strength, and antibacterial properties; the baking temperature is 60 - 90 °C.

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