Personalized matched tough 3D printing resin composition for ear orthopedics as well as preparation method and application of personalized matched tough 3D printing resin composition

Abstract

The invention discloses a personalized matching tough 3D (three-dimensional) printing resin composition for ear orthopaedics as well as a preparation method and application of the personalized matching tough 3D printing resin composition for ear orthopaedics. The medical polyurethane acrylate oligomer is obtained by reacting diisocyanate, polyol, a binary hydroxyl / amino rigid structure chain extender and acrylate containing hydroxyl / amino functional groups according to a molar ratio of (1-5): (1-6): (0.1-5): (1-8). Growth expectation orthopedic design can be achieved through 3D modeling according to the actual conditions of ear malformation of different patients, personalized specific customization is conducted, the synergistic effect of stable orthopedic supporting and wearing comfort can be achieved through the synthesized medical polyurethane acrylate medical material with high elastic modulus and toughness and an optimized formula for debugging, and the medical material is suitable for being applied to the field of ear malformation. An accurate and comfortable precise therapy is provided for a patient, and non-invasive malformation correction is well carried out.

Description

Technical Field

[0001] The present invention relates to the field of ear orthopedic medical materials, and in particular to a personalized tough ear orthopedic 3D printing resin composition, a preparation method and application thereof. Background Art

[0002] Microtia, also known as congenital external and middle ear malformation, is characterized by incomplete development of the auricle, atresia or stenosis of the external auditory canal, and middle ear malformation, while the inner ear is mostly normal and has a certain hearing through bone conduction. It is usually treated through total auricle reconstruction surgery and auricle correction. At the same time, total auricle reconstruction surgery requires two or three step-by-step surgeries to complete. Autologous ribs are generally used as donors. The pain caused by removing the ribs and the postoperative chest deformity and scar shape impose a heavy burden on the patient. Ear orthosis is a medical device specifically used to correct ear deformities, mainly used to correct congenital auricle deformities, including auricle morphological deformities and auricle structural deformities. The shape of the auricle varies from person to person, and for children, the shape of the auricle continues to grow at different ages. At present, most ear orthoses on the market are produced by mold forming. An ear orthosis such as Earwell auricle corrector costs nearly 10,000 yuan. Not only is it expensive, but the orthosis module is solidified, the material mechanics is relatively rigid and poorly matched with different patients, the operation is cumbersome and the wearing comfort is poor. The material has poor affinity with the skin, which can easily lead to traumatic complications such as ear grinding injury and inflammation and infection. The degree of correction can only be adjusted by the card bar, and the patient can only adapt to it step by step. In addition, the device is heavy, personalized adaptation is difficult, the material modulus is single, and the appearance is insufficient, which seriously affects the overall comfort and aesthetics of the patient during the correction process.

[0003] As an emerging rapid additive manufacturing technology, 3D printing technology can produce parts with complex structures compared to traditional subtractive manufacturing methods (such as cutting, grinding, etc.), and there are many types of molding materials, which can greatly reduce R&D costs and reduce material waste. Thanks to the above advantages, 3D printing technology has developed rapidly in recent years, among which photocuring technology is the most widely used. Photocuring 3D printing technology has the advantages of high printing accuracy, high surface smoothness, and fast molding speed. It has broad application prospects in some application fields with significant personalized needs and high precision requirements such as medical devices, medical molds, jewelry design, hand-made figures, and cultural objects. 3D printing technology provides a new personalized solution for the design and manufacture of auricular orthoses. The use of 3D printing technology to prepare auricular orthosis products has the advantages of high personalization, high design freedom, and good product aesthetics. According to the shape of each patient's auricle and the expected correction form, accurate modeling can be carried out to produce orthoses that fully meet their physiological characteristics, improve wearing comfort and correction effect, provide patients with accurate and comfortable precision therapy, and perform non-invasive deformity correction well. Summary of the invention

[0004] The purpose of the present invention is to provide a personalized tough ear orthopedic 3D printing resin composition and a preparation method and application thereof to solve the above-mentioned problems.

[0005] According to one aspect of the present invention, a personalized tough ear orthopedic 3D printing resin composition is provided, comprising a class of medical polyurethane acrylate oligomers, wherein the medical polyurethane acrylate oligomers are obtained by reacting diisocyanate, polyol, dibasic hydroxyl / amino rigid structure chain extender and acrylate containing hydroxyl / amino functional groups in a molar ratio of 1-5:1-6:0.1-5:1-8, and the general structural formula thereof is: ; Where m>1,n>1; wherein R1 is at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4-mixtures), and trimethylhexamethylene diisocyanate (2,2,4-, 2,4,4-mixtures); R2 is a diol with a molecular weight of 200 to 2000, at least one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hydroxy silicone oil, polycaprolactone diol, polysuccinate diol, polycarbonate diol and polylactic acid diol; R3 is at least one of a rigid structured diol or diamine / amine chain extender selected from bisphenol A, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-(1,4-phenylene diisopropylidene)diphenylamine, 4,4'-(1,3-phenylene bis(propane-2,2-diyl))diphenylamine, bisphenol A polyoxyethylene ether, tetrabromobisphenol A bis(2-hydroxyethyl) ether, 4,4'-(hexafluoroisopropylidene)diphenol, and 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline; R4 is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate, pentaerythritol triacrylate, and tert-butylaminoethyl methacrylate.

[0006] In some embodiments, the following components are included by weight percentage: 30-70% medical polyurethane acrylate oligomer; 15-45% acrylate monomer diluent; 0.1-5% free radical photoinitiator; 0.1-5% antioxidant; 0.1-10% auxiliary agent, and the sum of the percentage composition of the above components meets 100%.

[0007] In some embodiments, the medical polyurethane acrylate oligomer comprises the following preparation method: S1. Add the polyol into a three-necked flask equipped with a mechanical stirrer, evacuate at 110°C, and remove water for 0.5-3 h; S2, placing in a nitrogen atmosphere at a temperature of 50-100°C, adding dibutyltin dilaurate as a catalyst, and adding diisocyanate dropwise, reacting for 2-10 hours to obtain prepolymer 1; S3, placing the prepolymer 1 in a nitrogen atmosphere at a temperature of 50-100° C., adding dibutyltin dilaurate as a catalyst, and adding a diol or a diamine / amine chain extender dropwise, reacting for 2-10 h, to obtain a prepolymer 2; S4, adding dibutyltin dilaurate and acrylate containing hydroxyl or amino functional groups to the prepolymer 2, and reacting for 2 to 10 to obtain the final product.

[0008] In some embodiments, the diisocyanate is at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicycloethylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4- mixtures), and trimethylhexamethylene diisocyanate (2,2,4-, 2,4,4- mixtures).

[0009] In some embodiments, the polyol is at least one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, polycarbonate glycol, and polylactic acid glycol. The diol or diamine / amine chain extender is at least one of bisphenol A, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-(1,4-phenylene diisopropyl)diphenylamine, 4,4'-(1,3-phenylene bis(propane-2,2-diyl))diphenylamine, bisphenol A polyoxyethylene ether, tetrabromobisphenol A bis(2-hydroxyethyl) ether, 4,4'-(hexafluoroisopropyl)diphenol, and 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline.

[0010] In some embodiments, the acrylate containing a hydroxyl or amino functional group is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate, pentaerythritol triacrylate, and tert-butylaminoethyl methacrylate.

[0011] In some embodiments, the acrylate monomer diluent is at least two of propoxylated neopentyl glycol diacrylate, propoxylated propylene glycol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxyethoxyethyl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, tripropylene glycol diacrylate in dipropylene glycol dimethacrylate, pentaerythritol pentaacrylate, bisphenol A ethoxylated diacrylate, and bisphenol A epoxy acrylate.

[0012] In some embodiments, the free radical photoinitiator is at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate; the auxiliary agent includes at least two of a pigment, an inhibitor, a thixotropic agent, a leveling agent, a defoaming agent, a plasticizer, a stabilizer, and a silane coupling agent.

[0013] A method for preparing a personalized tough ear orthopedic 3D printing resin composition comprises the following steps: weighing each component according to a weight ratio, firstly dissolving the free radical photoinitiator uniformly in the acrylate monomer, then adding the remaining components and stirring uniformly, and then vacuum degassing to obtain a finished product.

[0014] An application of a personalized tough ear orthosis 3D printing resin composition, comprising the application of the personalized tough ear orthosis 3D printing resin composition according to any one of claims 1 to 9 on an SLA, DLP or LCD light-curing 3D printer with a curing wavelength of 380 to 420 nm.

[0015] Compared with the prior art, the beneficial effects of this application are: This application can realize growth-anticipated orthopedic design through 3D modeling according to the actual condition of ear deformity of different patients, and carry out personalized and customized design. Through the synthesis of high elastic modulus and toughness medical polyurethane acrylate medical materials, supplemented by optimal formula adjustment, it can achieve the synergistic effect of stable orthopedic support and wearing comfort, help patients provide accurate and comfortable precision therapy, and perform non-invasive deformity correction well; This application solves the problems of the existing technical solutions, such as the curing of the module of the medical ear orthosis, the rigid mechanics of the material and the poor matching with different patients, the cumbersome operation and poor wearing comfort, which can easily lead to trauma such as ear grinding injury and inflammatory infection, as well as the heavy reliance on a single material leading to insufficient material performance. Through the pre-3D modeling, the deformed ear is scanned and the expected orthodontic design is carried out, combined with the molecular structure design of the material, the accuracy of the photosensitive resin material required for formula adjustment and optimization is carried out, and the mechanical properties are adjusted to match the modulus range of human cartilage tissue. On the basis of achieving effective correction, the stability and comfort of wearing are greatly improved, meeting the application field of high-performance ear orthosis materials, and further expanding the application scope of 3D casting photosensitive resin in medical materials. DETAILED DESCRIPTION

[0016] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0017] The present invention also provides a method for preparing a personalized tough ear orthosis 3D printing resin composition, comprising the following steps: weighing each component according to a weight ratio, first dissolving a free radical photoinitiator evenly in an acrylate monomer, then adding the remaining components and stirring evenly, and then vacuum degassing to obtain a personalized tough ear orthosis 3D printing resin composition.

[0018] Embodiment 1: Preparation of medical polyurethane acrylate oligomers: Weigh 50 parts by weight of 1000 molecular weight polyethylene glycol and 50 parts by weight of 1000 molecular weight polypropylene glycol into a 1000 ml flask and remove water under vacuum at 110°C for 0.5 to 3 h.

[0019] The temperature was lowered to 60°C, and 0.2 parts by weight of dibutyltin dilaurate was added and stirred evenly. 49 parts by weight of IPDI was weighed and added dropwise into the flask, and the reaction was timed for 5 hours to obtain a mixture.

[0020] The reaction temperature was maintained at 60° C., 0.3 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 20 parts by weight of tetrabromobisphenol A bis(2-hydroxyethyl) ether were weighed and the reaction was further timed for 4 hours to obtain a chain extension prepolymer.

[0021] 0.3 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 60 parts by weight of 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate was weighed, and then the temperature was slowly raised to 80° C. and the reaction was timed for 6 hours to obtain the final product.

[0022] Preparation method of 3D printing resin composition for personalized tough ear correction: 6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 100 parts by weight of ethoxylated trimethylolpropane triacrylate and 100 parts by weight of diethylene glycol dimethacrylate were weighed and mixed in a beaker, and stirred and dispersed until 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was completely dissolved.

[0023] Weigh 120 parts by weight of the synthesized acrylic polyamine and 4 parts by weight of the additive in a beaker, disperse at high speed at room temperature for 0.5 to 3 hours, and then vacuum degassing to obtain the finished product.

[0024] When in use, the ultraviolet light wavelength required for printing and curing of the resin is 350~450 nm, and the applicable 3D printers are LCD-3D printers, SLA-3D printers and DLP-3D printers.

[0025] Embodiment 2: Preparation of medical polyurethane acrylate oligomers: Weigh 30 parts by weight of 600 molecular weight polyethylene glycol and 70 parts by weight of 2000 molecular weight polycaprolactone diol into a 1000 ml flask and remove water under vacuum at 110°C for 0.5-3 h.

[0026] The temperature was lowered to 70°C, and 0.4 parts by weight of dibutyltin dilaurate was added and stirred evenly. 60 parts by weight of IPDI was weighed and added dropwise into the flask, and the reaction was timed for 8 hours to obtain a mixture.

[0027] The reaction temperature was maintained at 70°C, and 0.3 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 30 parts by weight of bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate was weighed and the reaction was further timed for 5 hours to obtain a chain extension prepolymer.

[0028] 0.3 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 80 parts by weight of 3-(acryloyloxy)-2-hydroxypropyl methacrylate was weighed, and then the temperature was slowly raised to 80° C. and the reaction was timed for 7 hours to obtain the final product.

[0029] Preparation method of 3D printing resin composition for personalized tough ear correction: 6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 100 parts by weight of ethoxylated trimethylolpropane triacrylate and 100 parts by weight of diethylene glycol dimethacrylate were weighed and mixed in a beaker, and stirred and dispersed until 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was completely dissolved.

[0030] 120 parts by weight of the synthesized medical polyurethane acrylate oligomer and 4 parts by weight of the auxiliary agent were weighed into a beaker and dispersed at high speed for 15 to 30 minutes at room temperature. Subsequently, vacuum degassing was performed to obtain the finished product.

[0031] When in use, the ultraviolet light wavelength required for printing and curing of the resin is 300~450nm, and the applicable 3D printers are LCD-3D printers and DLP-3D printers.

[0032] Embodiment 3: Preparation of medical polyurethane acrylate oligomers: Weigh 30 parts by weight of aliphatic polycarbonate diol with a molecular weight of 1000 and 60 parts by weight of polypropylene glycol with a molecular weight of 2000 into a 1000 ml flask and remove water under vacuum at 110° C. for 0.5 to 3 h.

[0033] The temperature was lowered to 80°C, and 0.2 parts by weight of dibutyltin dilaurate was added and stirred evenly. 80 parts by weight of IPDI was weighed and added dropwise into the flask, and the reaction was timed for 5 hours to obtain a mixture.

[0034] The reaction temperature was lowered to 70°C, and 0.6 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 40 parts by weight of 4,4′-(1,4-phenylenediisopropylidene)diphenylamine was weighed and the reaction was further timed for 6 hours to obtain a chain extension prepolymer.

[0035] 0.2 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 80 parts by weight of propoxylated neopentyl glycol diacrylate was weighed, and then the temperature was slowly raised to 80° C. and the reaction was timed for 3 hours to obtain the final product.

[0036] Preparation method of 3D printing resin composition for personalized tough ear correction: 6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 100 parts by weight of ethoxylated trimethylolpropane triacrylate and 100 parts by weight of diethylene glycol dimethacrylate were weighed and mixed in a beaker, and stirred and dispersed until 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was completely dissolved.

[0037] 120 parts by weight of the synthesized medical polyurethane acrylate oligomer and 4 parts by weight of the auxiliary agent were weighed into a beaker and dispersed at high speed for 15 to 30 minutes at room temperature. Subsequently, vacuum degassing was performed to obtain the finished product.

[0038] When in use, the ultraviolet light wavelength required for printing and curing of the resin is 300~450nm, and the applicable 3D printers are LCD-3D printers and DLP-3D printers.

[0039] Embodiment 4: Preparation of medical polyurethane acrylate oligomers: 33 parts by weight of polyethylene glycol with a molecular weight of 1000, 33 parts by weight of polycaprolactone diol with a molecular weight of 800 and 33 parts by weight of aliphatic polycarbonate diol with a molecular weight of 1000 were weighed into a 1000 ml flask and vacuum-dried at 110° C. for 0.5 to 3 h.

[0040] The temperature was lowered to 60°C, and 0.5 parts by weight of dibutyltin dilaurate was added and stirred evenly. 78 parts by weight of IPDI was weighed and added dropwise into the flask, and the reaction was timed for 10 hours to obtain a mixture.

[0041] The reaction temperature was raised to 70°C, and 0.6 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 30 parts by weight of 4,4′-(1,4-phenylene diisopropylidene) diphenylamine was weighed and the reaction was further timed for 4 hours to obtain a chain extension prepolymer.

[0042] 0.8 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 60 parts by weight of 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate was weighed, and then the temperature was slowly raised to 80° C. and the reaction was timed for 6 hours to obtain the final product.

[0043] Preparation method of 3D printing resin composition for personalized tough ear correction: 6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 100 parts by weight of ethoxylated trimethylolpropane triacrylate and 100 parts by weight of diethylene glycol dimethacrylate were weighed and mixed in a beaker, and stirred and dispersed until 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was completely dissolved.

[0044] 120 parts by weight of the synthesized medical polyurethane acrylate oligomer and 4 parts by weight of the auxiliary agent were weighed into a beaker and dispersed at high speed for 15 to 30 minutes at room temperature. Subsequently, vacuum degassing was performed to obtain the finished product.

[0045] When in use, the ultraviolet light wavelength required for printing and curing of the resin is 300~450nm, and the applicable 3D printers are LCD-3D printers and DLP-3D printers.

[0046] Embodiment 5: Preparation of medical polyurethane acrylate oligomers: Weigh 40 parts by weight of 1000 molecular weight polypropylene glycol, 30 parts by weight of 1000 molecular weight polylactic acid diol and 30 parts by weight of 1000 molecular weight hydroxy silicone oil in a 1000 ml flask and remove water under vacuum at 110°C for 0.5 to 3 h.

[0047] The temperature was lowered to 80°C, and 0.5 parts by weight of dibutyltin dilaurate was added and stirred evenly. 78 parts by weight of IPDI was weighed and added dropwise into the flask, and the reaction was timed for 10 hours to obtain a mixture.

[0048] The reaction temperature was maintained at 80°C, and 11.0 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 20 parts by weight of 4,4′-(1,4-phenylene diisopropylidene) diphenylamine was weighed and the reaction was further timed for 4 hours to obtain a chain extension prepolymer.

[0049] 1.2 parts by weight of dibutyltin dilaurate was added to the flask and stirred evenly. 80 parts by weight of 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate was weighed, and then the temperature was slowly raised to 90° C. and the reaction was timed for 4 hours to obtain the final product.

[0050] Preparation method of 3D printing resin composition for personalized tough ear correction: 6 parts by weight of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 100 parts by weight of ethoxylated trimethylolpropane triacrylate, 100 parts by weight of acryloylmorpholine and 60 parts by weight of neopentyl glycol dimethacrylate were weighed and mixed in a beaker, and stirred and dispersed until 2,4,6-trimethylbenzoyl-diphenylphosphine oxide was completely dissolved.

[0051] 120 parts by weight of the synthesized medical polyurethane acrylate oligomer and 10 parts by weight of the auxiliary agent were weighed into a beaker and dispersed at high speed for 20 to 60 minutes at room temperature. Subsequently, vacuum degassing was performed to obtain the finished product.

[0052] When in use, the ultraviolet light wavelength required for printing and curing of the resin is 300~450nm, and the applicable 3D printers are LCD-3D printers and DLP-3D printers.

[0053] Mechanical property testing method: The above-mentioned embodiments 1 to 5 are printed on a light-curing 3D printer using SLA, DLP or LCD and a curing wavelength of 300 to 450 nm to print test specimens and models, and the corresponding mechanical performance indicators and wearing comfort are tested. The test results are shown in Table 1.

[0054] Table 1 The orthosis printed in the above-mentioned Example 5 is relatively comfortable to wear because its elastic modulus is closer to the modulus of human cartilage and its texture is softer, so it is more comfortable to wear. Of course, it is directly related to the degree of size matching of personalized customization. Subsequent designs will formulate appropriate printing compositions according to the actual usage of patients to meet the requirements of good comfortable wearing and successful non-invasive correction.

[0055] This application can realize growth-anticipated orthopedic design through 3D modeling according to the actual condition of ear deformity of different patients, and carry out personalized and customized design. Through the synthesis of high elastic modulus and toughness medical polyurethane acrylate medical materials, supplemented by optimal formula adjustment, it can achieve the synergistic effect of stable orthopedic support and wearing comfort, help patients provide accurate and comfortable precision therapy, and perform non-invasive deformity correction well; This application solves the problems of the existing technical solutions, such as the curing of the module of the medical ear orthosis, the rigid mechanics of the material and the poor matching with different patients, the cumbersome operation and poor wearing comfort, which can easily lead to trauma such as ear grinding injury and inflammatory infection, as well as the heavy reliance on a single material leading to insufficient material performance. Through the pre-3D modeling, the deformed ear is scanned and the expected orthodontic design is carried out, combined with the molecular structure design of the material, the accuracy of the photosensitive resin material required for formula adjustment and optimization is carried out, and the mechanical properties are adjusted to match the modulus range of human cartilage tissue. On the basis of achieving effective correction, the stability and comfort of wearing are greatly improved, meeting the application field of high-performance ear orthosis materials, and further expanding the application scope of 3D casting photosensitive resin in medical materials.

[0056] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A personalized tough ear orthopedic 3D printing resin composition, characterized in that: A class of medical polyurethane acrylate oligomers is included, wherein the medical polyurethane acrylate oligomer is obtained by reacting diisocyanate, polyol, dibasic hydroxyl / amino rigid structure chain extender and acrylate containing hydroxyl / amino functional groups in a molar ratio of 1-5:1-6:0.1-5:1-8, and the general structural formula is: ； Where m > 1, n > 1; wherein R1 is at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4-mixtures), and trimethylhexamethylene diisocyanate (2,2,4-, 2,4,4-mixtures); R2 is a diol with a molecular weight of 200 to 2000, at least one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, hydroxy silicone oil, polycaprolactone diol, polysuccinate diol, polycarbonate diol and polylactic acid diol; R3 is at least one of a rigid structured diol or diamine / amine chain extender selected from bisphenol A, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-(1,4-phenylene diisopropylidene)diphenylamine, 4,4'-(1,3-phenylene bis(propane-2,2-diyl))diphenylamine, bisphenol A polyoxyethylene ether, tetrabromobisphenol A bis(2-hydroxyethyl) ether, 4,4'-(hexafluoroisopropylidene)diphenol, and 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline; R4 is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate, pentaerythritol triacrylate, and tert-butylaminoethyl methacrylate.

2. The personalized tough ear orthopedic 3D printing resin composition according to claim 1, characterized in that: The following components are included by weight percentage: The medical polyurethane acrylate oligomer 30-70%; Acrylate monomer diluent 15~45%; Free radical photoinitiator 0.1~5%; Antioxidant 0.1~5%; Additives 0.1~10%; The sum of the percentages of the above components satisfies 100%.

3. The personalized tough ear orthopedic 3D printing resin composition according to claim 2, characterized in that: The medical polyurethane acrylate oligomer comprises the following preparation method: S1. Add the polyol into a three-necked flask equipped with a mechanical stirrer, evacuate at 110°C, and remove water for 0.5-3 h; S2, placing in a nitrogen atmosphere at a temperature of 50-100°C, adding dibutyltin dilaurate as a catalyst, and adding diisocyanate dropwise, reacting for 2-10 hours to obtain prepolymer 1; S3, placing the prepolymer 1 in a nitrogen atmosphere at a temperature of 50-100° C., adding dibutyltin dilaurate as a catalyst, and adding a diol or a diamine / amine chain extender dropwise, reacting for 2-10 h, to obtain a prepolymer 2; S4, adding dibutyltin dilaurate and acrylate containing hydroxyl or amino functional groups to the prepolymer 2, and reacting for 2 to 10 to obtain the final product.

4. The personalized tough ear orthopedic 3D printing resin composition according to claim 3, characterized in that: The diisocyanate is at least one of isophorone diisocyanate (IPDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), trimethylhexamethylene diisocyanate (2,2,4- and 2,4,4- mixture), and trimethylhexamethylene diisocyanate (2,2,4-, 2,4,4- mixture).

5. The personalized tough ear orthopedic 3D printing resin composition according to claim 3, characterized in that: The polyol is at least one of polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polycaprolactone glycol, polycarbonate glycol, and polylactic acid glycol. The diol or diamine / amine chain extender is at least one of bisphenol A, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 4,4'-diaminodiphenylmethane, 2,2-bis(4-aminophenyl)propane, 4,4'-(1,4-phenylene diisopropyl)diphenylamine, 4,4'-(1,3-phenylene bis(propane-2,2-diyl))diphenylamine, bisphenol A polyoxyethylene ether, tetrabromobisphenol A bis(2-hydroxyethyl) ether, 4,4'-(hexafluoroisopropyl)diphenol, and 4-(4-amino-3,5-dimethylbenzyl)-2,6-dimethylaniline.

6. The personalized tough ear orthopedic 3D printing resin composition according to claim 3, characterized in that: The acrylate containing hydroxyl or amino functional groups is at least one of hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 3-(acryloyloxy)-2-hydroxypropyl methacrylate, 2-[2-[2-(2-hydroxyethoxy)ethoxy]ethoxy]ethyl acrylate, pentaerythritol triacrylate, and tert-butylaminoethyl methacrylate.

7. The personalized tough ear orthopedic 3D printing resin composition according to claim 3, characterized in that: The acrylate monomer diluent is at least two of propoxylated neopentyl glycol diacrylate, propoxylated propylene glycol triacrylate, ethoxylated trimethylolpropane triacrylate, ethoxylated pentaerythritol tetraacrylate, ethoxyethoxyethyl acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, tripropylene glycol diacrylate in dipropylene glycol dimethacrylate, pentaerythritol pentaacrylate, bisphenol A ethoxylated diacrylate, and bisphenol A epoxy acrylate.

8. The personalized tough ear orthopedic 3D printing resin composition according to claim 3, characterized in that: The free radical photoinitiator is at least one of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, and ethyl 2,4,6-trimethylbenzoylphenylphosphonate; the auxiliary agent includes at least two of a pigment, an inhibitor, a thixotropic agent, a leveling agent, a defoamer, a plasticizer, a stabilizer, and a silane coupling agent.

9. A method for preparing a personalized tough ear orthopedic 3D printing resin composition according to claims 1-8, characterized in that: The method comprises the following steps: weighing each component according to the weight ratio, firstly dissolving the free radical photoinitiator uniformly in the acrylate monomer, then adding the remaining components and stirring them uniformly, and then vacuum degassing to obtain the finished product.

10. An application of a personalized tough ear orthopedic 3D printing resin composition, characterized in that: The personalized tough ear orthosis 3D printing resin composition according to any one of claims 1 to 9 is applied on a SLA, DLP or LCD light-curing 3D printer with a curing wavelength of 380 to 420 nm.

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