Antibacterial light-curing 3D printing material, preparation method thereof and 3D printing device

Abstract

The present invention provides an antibacterial light-curing 3D printing material, which comprises the following components in parts by weight: 100 parts by weight of a biocompatible oligomer / monomer, 0.05-55 parts by weight of a supramolecular photoinitiator system, 5-30 parts by weight of an antibacterial agent, and 1-20 parts by weight of an auxiliary agent, wherein the supramolecular photoinitiator system is a supramolecular compound active under light radiation in the visible light band.

Description

[0001] This application is a divisional application with application number 201811014123.5, application date August 31, 2018, and invention name “An antibacterial photocurable 3D printing material, preparation method thereof, and 3D printing device”. Technical Field

[0002] The present invention relates to an antibacterial light-cured 3D printing material, a preparation method thereof and a 3D printing device, belonging to the technical field of 3D printing applications, and specifically to an antibacterial visible light-cured 3D printing material, a preparation method thereof and a 3D printing device for printing the material. Background Art

[0003] 3D printing, also known as additive manufacturing, is an emerging rapid prototyping manufacturing technology with the advantages of high molding efficiency, low material cost, and the ability to prepare complex structures. Its unique manufacturing advantages have made it extremely popular in various fields and it is known as the symbol of the third industrial revolution. 3D printing technology involves a variety of molding methods. Among them, based on the principle of photocuring molding, the printing technologies using photocuring resin as raw materials mainly include stereolithography (SLA), digital light processing (DLP) and three-dimensional inkjet printing (3DSP). Compared with other molding methods, photocuring 3D printing has the advantages of high molding accuracy, fast printing speed and mature technology. It is currently widely used in many fields such as product design, mold manufacturing, scientific research, cultural creativity, and medical treatment.

[0004] With the continuous expansion of the application of 3D printing technology, 3D printing products have been widely introduced into people's lives. In modern highly civilized society, people attach great importance to whether daily necessities are environmentally friendly and harmful to health. It is very important to develop 3D printing materials with antibacterial properties. In the medical field, many medical supplies and equipment are easily infected with microorganisms. With the increasing number of 3D printed medical aids and medical implants, the demand for antibacterial 3D printing materials has been further intensified. At present, there are a small number of reports on antibacterial photocurable 3D printing materials, but most of these materials require the use of ultraviolet (UV) light curing 3D printing technology. UV curing 3D printing technology has the disadvantages of being environmentally unfriendly, high equipment cost and low curing depth. Especially for the above-mentioned antibacterial photosensitive materials, the antibacterial components contained therein are often inorganic powders or particles, which have a certain absorption of ultraviolet light, which will greatly affect the efficiency of UV 3D printing. As described in patents CN107312133A and CN205668388U, visible light 3D printing technology can effectively solve the problems caused by the above-mentioned UV curing, but there are currently no reports on antibacterial visible light curing 3D printing materials.

[0005] In the prior art, the photoinitiators in the material composition are mostly small molecule compounds. After the printed parts are formed, the small molecule photoinitiators can easily migrate to the surface of the parts, endangering the health of those who come into contact with them. Some researchers have grafted small molecule compounds with polymerizable monomers to synthesize macromolecular photoinitiators, which can effectively reduce the migration of photoinitiators. However, the synthesis process of macromolecular photoinitiators is complicated and not conducive to large-scale preparation.

[0006] Therefore, an urgent problem to be solved is to develop an antibacterial visible light-curing 3D printing material that can reduce or avoid the migration of small molecule photoinitiators to the surface of the workpiece. Summary of the invention

[0007] Technical issues

[0008] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a new type of antibacterial light-curing 3D printing material. The material is cured by visible light, which can solve the safety and printing efficiency problems existing in the prior art using ultraviolet light curing; the material is cured by a supramolecular photoinitiator system, which can solve the problem that the existing conventional photoinitiators easily migrate to the surface of the workpiece and cause health threats; the material has significant antibacterial properties and can solve the problem that the workpiece is easily infected by microorganisms.

[0009] In addition, another object of the present invention is to provide a method for preparing the above-mentioned antibacterial light-curing 3D printing material, by which the antibacterial light-curing 3D printing material with the above-mentioned excellent properties can be prepared, and the preparation method is simple and easy. At the same time, in this method, the photoinitiator is prepared into a supramolecule through the host-guest interaction, the preparation method is simple, and the anti-migration effect is significant.

[0010] In addition, another object of the present invention is to provide a 3D printing device for printing the above-mentioned antibacterial light-curing 3D printing material, wherein the 3D printing device can use a visible light laser light source for printing, and the container for holding the material can heat the material, thereby improving the fluidity of the material. The 3D printing device can print the above-mentioned antibacterial light-curing 3D printing material into a product having antibacterial properties and good mechanical properties, with a fast molding speed, a layer can be cured in 0.5 to 5 seconds, and the printing efficiency is high, overcoming the problem of long curing time of similar UV products.

[0011] To achieve the above object, the present invention adopts the following technical solutions:

[0012] An antibacterial light-curing 3D printing material, comprising the following components in parts by weight:

[0013] Biocompatible oligomers / monomers 100 parts by weight,

[0014] Supramolecular photoinitiator system 0.05-5 parts by weight,

[0015] 5-30 parts by weight of antibacterial agent,

[0016] 1-20 parts by weight of auxiliary agent,

[0017] The supramolecular photoinitiator system is a supramolecular compound that is active under light radiation in the visible light band.

[0018] According to the present invention, the biocompatible oligomer / monomer is one or more of biocompatible epoxy acrylate, biocompatible polyurethane acrylate, biocompatible polyester acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and polypropylene glycol dimethacrylate.

[0019] According to the present invention, the supramolecular photoinitiator system is formed by a host compound encapsulating a guest photoinitiator; the host compound is one or more of cucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril, cucurbit[8]uril, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, calixarene, and crown ether; the guest photoinitiator is one or more of the following compounds active under visible light radiation: dye / borate compounds, camphorquinone, fluorinated diphenyl titanocene, bis(pentafluorinated phenyl) titanocene, and organic peroxide compounds.

[0020] According to the present invention, the addition ratio of the host compound of the supramolecular photoinitiator system to the guest photoinitiator of the supramolecular photoinitiator system is 1.1-1.5:1, and more preferably 1.2-1.3:1.

[0021] According to the present invention, the content of the supramolecular photoinitiator system is preferably 0.5-2 parts by weight, and more preferably 0.5-1 part by weight.

[0022] According to the present invention, the antibacterial agent is one or more of silver (Ag) nanoparticles, cuprous oxide (Cu2O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyapatite, and quaternized mercaptosilicon dioxide hybrid particles.

[0023] According to the present invention, the auxiliary agent includes one or more of a pigment, a filler, an antioxidant, a defoamer, a wetting agent, and an inhibitor.

[0024] According to the present invention, the pigment includes at least one of cadmium yellow, cadmium red, chrome green and iron blue; the filler includes at least one of calcium carbonate, barium sulfate, montmorillonite and talc; the defoamer includes at least one of ethanol, n-butanol, silicone ester and mineral oil; the wetting agent includes at least one of lecithin, polyamino salt and polyvalent carboxylate; and the inhibitor includes at least one of hydroxyanisole and hydroquinone.

[0025] According to the present invention, the viscosity of the antibacterial light-curing 3D printing material at room temperature is 20-5000 cps, preferably 100-1000 cps.

[0026] On the other hand, the present invention also provides a method for preparing the above-mentioned antibacterial light-curing 3D printing material, the method comprising the following steps:

[0027] S1: preparing a supramolecular photoinitiator system: weighing a certain amount of a small molecule photoinitiator as a guest photoinitiator, dissolving it in an organic solvent, adjusting its pH value to 2-5, and then adding a macrocyclic molecule as a main compound in batches while stirring at a speed of 500-2000 r / min, continuing to stir for 60-100 min after adding the main compound, and then using a rotary evaporator to evaporate the solvent and dry to obtain the supramolecular photoinitiator system;

[0028] S2: preparing antibacterial light-curing 3D printing material: uniformly mixing 100 parts by weight of biocompatible oligomer / monomer, 0.05-5 parts by weight of the supramolecular photoinitiator system prepared in the above step S1, 5-30 parts by weight of antibacterial agent, and 1-20 parts by weight of auxiliary agent by mechanical stirring at room temperature, wherein the stirring speed is 500-2000 r / min, thereby obtaining a homogeneous mixture, and the mixture is stored in a light-shielded manner, thereby obtaining the antibacterial light-curing 3D printing material.

[0029] Wherein in the step S1, the pH value is preferably 2 to 3, and

[0030] In step S2, the mixture is preferably stored in a light-proof manner using tin foil.

[0031] On the other hand, the present invention further provides a 3D printing device for printing the above-mentioned antibacterial light-curing 3D printing material, the 3D printing device comprising a light source, a mechanical motion device, a software control system and a container for accommodating the antibacterial light-curing 3D printing material. The light source, in cooperation with the mechanical motion device and the software control system, solidifies the antibacterial light-curing 3D printing material provided by the container while accumulating it layer by layer to form a product.

[0032] According to the present invention, the light source is a visible laser light source with a light emission wavelength of 415 nm-750 nm.

[0033] According to the present invention, the container is capable of heating the contained antibacterial light-curing 3D printing material in a range of room temperature to 70°C to improve the fluidity of the antibacterial light-curing 3D printing material.

[0034] Beneficial effects of the present invention:

[0035] According to the above technical solution of the present invention, an antibacterial light-curable 3D printing material is provided. The antibacterial light-curable 3D printing material is cured by visible light, which solves the safety and printing efficiency problems existing in the prior art of ultraviolet light curing. The printing speed is fast, and a layer can be cured in 0.5~5s, which overcomes the problem of long curing time of similar UV products. The material is cured by a supramolecular photoinitiator system, which solves the problem that the existing conventional photoinitiator easily migrates to the surface of the workpiece and causes a health threat to the person who contacts the workpiece. The material has significant antibacterial properties, which solves the problem that the workpiece is easily infected with microorganisms.

[0036] In addition, the present invention also provides a method for preparing the above-mentioned antibacterial light-cured 3D printing material, by which the antibacterial light-cured 3D printing material with the above-mentioned excellent properties is prepared, and the preparation method is simple and easy. At the same time, in the method, the photoinitiator is prepared into a supramolecule through the host-guest interaction, the preparation method is simple, and the anti-migration effect is significant.

[0037] In addition, the present invention also provides a 3D printing device for printing the above-mentioned antibacterial light-curing 3D printing material. The 3D printing device uses a visible light laser light source for printing, and the container for holding the material can heat the material, thereby improving the fluidity of the material. The 3D printing device can print the above-mentioned antibacterial light-curing 3D printing material into a product with antibacterial properties and good mechanical properties, with high printing efficiency and fast molding speed. DETAILED DESCRIPTION

[0038] Below, more fully illustrate one or more exemplary embodiments of the present invention.As those skilled in the art will appreciate, as long as do not depart from the spirit or scope of the present invention, the exemplary embodiments can be modified in various ways, and the spirit or scope of the present invention is not limited to the exemplary embodiments described herein.

[0039] As described above, the present invention creatively proposes for the first time a visible light-curable 3D printing material with antibacterial properties. The material comprises the following components in parts by weight: 100 parts by weight of a biocompatible oligomer / monomer, 0.05-5 parts by weight of a supramolecular photoinitiator system, 5-30 parts by weight of an antibacterial agent, and 1-20 parts by weight of an auxiliary agent, wherein the supramolecular photoinitiator system is a supramolecular compound that is active under light radiation in the visible light band.

[0040] It should be pointed out that the supramolecular photoinitiator system in the present invention is a molecular complex system formed by the self-assembly of a host compound and a guest compound through non-chemical bonds. That is to say, the supramolecular photoinitiator system in the present invention is a molecular complex system formed by the self-assembly of a macrocyclic molecule and a small molecule photoinitiator through non-chemical bonds. Specifically, the supramolecular photoinitiator system of the present invention is formed by the inclusion of a guest photoinitiator in a host compound. The photoinitiator is a key component for initiating the polymerization reaction of oligomers / monomers. When conventional small molecule initiators are used, there is a difference in the compatibility between the small molecule photoinitiator and the polymer in the obtained printed product, which is easy to migrate to the surface, thereby bringing certain chemical pollution and affecting the antibacterial properties of the product. Introducing a supramolecular system initiator into a 3D printing material can effectively prevent the migration of the initiator component to the surface of the product, avoid chemical pollution, and reduce the impact on the antibacterial properties of the product. In the present invention, by making a supramolecular photoinitiator system with a macrocyclic molecule and a small molecule photoinitiator, the strong movement of the photoinitiator molecules is suppressed, and the surface migration phenomenon of the small molecule photoinitiator can be effectively reduced, thereby avoiding health problems for those who come into contact with the product.

[0041] It should be noted that the theoretical ratio of the host compound and the guest compound in the supramolecular photoinitiator system is 1:1, but considering the reversibility of the reaction and the integrity of the reaction, the present invention slightly overdosed the host compound, and excessive addition would result in waste and increase costs. Therefore, in order to prepare the above supramolecular photoinitiator system with suitable performance, the addition ratio of the host compound and the guest compound can be 1.1~1.5:1, and more preferably 1.2~1.3:1. According to the present invention, the pH value required for the coordination of the host compound and the guest compound is 2~5, and more preferably 2~3. Too low or too high a pH is not conducive to the coordination of the host compound and the guest compound. For example, the host compound can be one or more of cucurbituril, cyclodextrin, calixarene, and crown ether, and the guest compound can be one or more of the following compounds that are active under visible light radiation: dye / borate compounds, quinone compounds, titanocene compounds, and organic peroxide compounds.

[0042] For example, the cyclodextrin may be one or more of α-cyclodextrin, β-cyclodextrin, and γ-cyclodextrin, and the quinone compound may be, for example, camphorquinone (CQ); the titanocene compound may be fluorinated diphenyl titanocene (Irgacure 784), bis(pentafluorophenyl) titanocene, etc.

[0043] It should be further pointed out that the content of the supramolecular photoinitiator system contained in the above-mentioned visible light-curable 3D printing material with antibacterial properties of the present invention is preferably 0.5-2 parts by weight, and more preferably 0.5-1 parts by weight to achieve a good photoinitiator effect. When the initiator content is too little, the initiation speed is slow, and when it is too much, waste is generated and the initiation speed is no longer increased.

[0044] It should be pointed out that the biocompatible oligomer / monomer refers to an oligomer / monomer that does not produce rejection, stimulation, toxicity, etc. when in contact with biological tissue. Antibacterial light-cured 3D printing materials are generally used to print three-dimensional structures in contact with biological tissue. Therefore, it is necessary to select oligomers and monomers with good biocompatibility to reduce the rejection of printed parts and biological tissue. According to the present invention, for the convenience of measurement, the biocompatible oligomer / monomer is taken as the reference weight part, which is taken as 100 weight parts as mentioned above. The biocompatible oligomer / monomer can be one or more of biocompatible epoxy acrylate, biocompatible polyurethane acrylate, biocompatible polyester acrylate, polyethylene glycol diacrylate (PEGDA), polyethylene glycol dimethacrylate (PEGDMA), polypropylene glycol diacrylate (PPGDA), and polypropylene glycol dimethacrylate (PEGDA).

[0045] In order to make the antibacterial light-cured 3D printing material of the present invention have good antibacterial properties, the above-mentioned antibacterial agent can be one or more of silver (Ag) nanoparticles, cuprous oxide (Cu2O) nanoparticles, zinc oxide (ZnO) nanoparticles, magnesium-doped hydroxyapatite, and quaternized mercaptosilica hybrid particles.

[0046] It should be noted that the absorption of ultraviolet light by nanoparticles is related to the particle size. As long as it is nano-level particles, they will inevitably absorb ultraviolet light. Experiments show that if you want to significantly reduce UV absorption, you can only increase the particle size until the particle is no longer a nanoparticle, and then loses the performance of the nanoparticle and has no antibacterial effect. In addition, adjusting the intensity of ultraviolet light and the irradiation time can solve the problem of photocuring antibacterial, but it cannot be used for 3D printing. The reason is that, first of all, if the intensity of ultraviolet light increases, the heat will increase. On the one hand, it is difficult for 3D printed products to withstand such a large amount of heat, and on the other hand, it is difficult to find high-power UV equipment for 3D printing. Secondly, if the irradiation time is increased, it will only be useful under a certain curing thickness. As the thickness of the printing layer increases, increasing the UV light exposure time has little effect. Simply increasing the time will also not complete 3D printing. In other words, using UV curing for 3D printing cannot achieve the molding of highly doped antibacterial materials.

[0047] It can be seen that for 3D printing technology, if UV curing is used, the antibacterial nanoparticles have a strong absorption of UV light, so in order to complete 3D printing, the added content of antibacterial nanoparticles is very limited. In other words, the antibacterial properties of the printed products obtained by 3D printing using UV curing will not be excellent.

[0048] In view of this, the present invention proposes a method of using visible light curing, because the visible light curing depth is much higher than that of ultraviolet light, and the antibacterial nanoparticles do not have the above-mentioned problems when curing with visible light as when curing with ultraviolet light. Therefore, by introducing visible light as a 3D printing light source, the present invention can greatly increase the amount of antibacterial agent added and achieve excellent antibacterial effect.

[0049] Adding antibacterial components to a polymer system by co-doping is the simplest, most direct and most efficient way to prepare antibacterial materials. Generally, the antibacterial property of a polymer product is proportional to the content of the antibacterial component added, that is, the higher the content of the antibacterial agent, the better the antibacterial property. However, excessive addition of antibacterial components will affect the curing depth of the material, thereby affecting the printing efficiency. Using visible light as a curing light source can significantly improve the curing depth of the material, thereby supporting a higher amount of antibacterial components added. In the prior art, ultraviolet light is used for curing. Since the antibacterial photosensitive material has a certain absorption of ultraviolet light, it will greatly affect the efficiency of UV 3D printing, so its addition amount is limited. Relatively speaking, the present invention uses visible light curing, and there is no problem in the prior art. Therefore, the content of the above-mentioned antibacterial agent in the present invention can be 5-30 parts by weight, preferably 20-30 parts by weight, which is much larger than the amount added in UV curing. Therefore, compared with the UV curing 3D printing material in the prior art, better antibacterial effect can be achieved.

[0050] According to the present invention, the above-mentioned auxiliary agent may include one or more of pigment (such as cadmium yellow, cadmium red, chrome green, iron blue, etc.), filler (such as calcium carbonate, barium sulfate, montmorillonite, talcum powder, etc.), antioxidant, defoamer (such as ethanol, n-butanol, silicone ester, mineral oil, etc.), wetting agent (such as lecithin, polyamino salt, polyvalent carboxylate, etc.), inhibitor (such as hydroxyanisole, hydroquinone, etc.). In addition, the content of the above-mentioned auxiliary agent is 1-20 parts by weight, preferably 2-5 parts by weight.

[0051] It should be pointed out that the above antibacterial light-curing 3D printing material has a viscosity of 20-5000 cps at room temperature, preferably 100-1000 cps, and a moderate surface tension, and is suitable for visible light 3D printing.

[0052] According to the present invention, the antibacterial light-curable 3D printing material has a fast curing speed under visible light conditions, and a layer can be cured in 0.5 to 5 seconds.

[0053] As described above, the antibacterial light-curing 3D printing material of the present invention has good antibacterial properties and is suitable for the preparation of parts in technical fields with relatively high antibacterial requirements such as medical and food fields. In addition, the antibacterial light-curing 3D printing material of the present invention can be cured by visible light, avoiding the problems of poor safety caused by the use of ultraviolet light for curing, and has a fast printing speed, and a layer can be cured in 0.5~5s, overcoming the problem of long curing time of similar UV products. In addition, the antibacterial light-curing 3D printing material of the present invention uses a supramolecular photoinitiator system instead of the small molecule photoinitiator in the prior art, overcoming the problem that the small molecule photoinitiator can easily migrate to the surface of the part and endanger the health of the contactor.

[0054] In addition, the present invention also provides a method for preparing the above-mentioned antibacterial light-curing 3D printing material, comprising the following steps:

[0055] S1: Preparation of supramolecular photoinitiator system: Weigh a certain amount of guest compound, i.e., small molecule photoinitiator, and dissolve it in an organic solvent (preferably a low boiling point solvent such as dichloromethane, methanol, ethyl acetate, etc.), adjust the system pH to 2-5, preferably 2-3, add the main compound, i.e., macrocyclic molecule, in batches under stirring at a speed of 500-2000 r / min, continue stirring for 60-100 min after the addition is completed, use a rotary evaporator, maintain the temperature at 30-50°C under reduced pressure to evaporate the solvent, take out the sample and dry it in a vacuum drying oven at 60-80°C for 8-12h to obtain the supramolecular photoinitiator system. It should be pointed out that in this step, the order of adding the components cannot be changed, otherwise it will affect the formation of the supramolecular photoinitiator system and affect the final anti-migration.

[0056] S2: Preparation of 3D printing materials: 100 parts by weight of biocompatible oligomers / monomers, 0.05-5 parts by weight of the supramolecular photoinitiator system prepared in step S1, 5-30 parts by weight of antibacterial agents, and 1-20 parts by weight of auxiliary agents are mixed evenly by mechanical stirring at room temperature, wherein the stirring speed is 500-2000 r / min to obtain a homogeneous mixture, and the mixture is stored in a light-proof manner, preferably in a light-proof manner with tin foil, thereby obtaining the antibacterial light-curable 3D printing material. It should be pointed out that in this step, the change in the order of adding the above components will not affect the material properties.

[0057] By using the above method, the visible light-curable 3D printing material with antibacterial properties of the present invention can be prepared, and the preparation method is simple and easy. At the same time, in the method, the photoinitiator is prepared into a supramolecule through the host-guest interaction, the preparation method is simple, and the anti-migration effect is significant.

[0058] In addition, the present invention also proposes a device for printing the above-mentioned antibacterial light-curing 3D printing material, which includes a light source, a mechanical motion device, a software control system and a container for the antibacterial light-curing 3D printing material of the present invention, wherein the light source, in cooperation with the mechanical motion device and the software control system, solidifies the antibacterial light-curing 3D printing material provided by the container while accumulating layer by layer to form a product. According to the present invention, the light source is a visible laser light source with a light emission wavelength of 415 nm-750 nm. It should be pointed out that the light source must be a pure color laser light source, such as a blue laser light source. According to the present invention, the container for 3D printing material has the ability to heat the contained material, and the heating range is from room temperature to 70°C, and the fluidity of the printing material is significantly improved under heating. In the present invention, room temperature refers to a temperature range of 23°C to 30°C.

[0059] According to the present invention, the antibacterial light-curing 3D printing material of the present invention can be printed into a product having antibacterial properties and good mechanical properties by using the above-mentioned 3D printing device, with high printing efficiency and fast molding speed.

[0060] Hereinafter, the present invention will be described in detail with reference to specific embodiments.

[0061] Example 1

[0062] In this example, cucurbitacin [8] uril and camphorquinone (CQ) were weighed in a ratio of 1.2:1 and added and mixed in this order, ethyl acetate was selected as the solvent, stirred for 45 minutes, the solvent was evaporated, dried, and set aside.

[0063] Then, 30 parts by weight of biocompatible bisphenol A epoxy acrylate, 70 parts by weight of polyethylene glycol diacrylate (PEGDA), 1 part by weight of a supramolecular photoinitiator system assembled from cucurbit[8]uril and camphorquinone (CQ), 10 parts by weight of silver nanoparticles, and 2 parts by weight of an auxiliary agent were stirred and mixed uniformly at room temperature to obtain a homogeneous mixture, which was then stored in a dark place for later use.

[0064] The above mixture was added into the material container of the visible light 3D printing device, and the printing was maintained at room temperature (25°C), with a printing speed of 2 s per layer, and finally the product was printed.

[0065] The following method can be used to detect whether the surface of the product in this embodiment contains a photoinitiator: (1) using high performance liquid chromatography (HPLC) to determine the characteristic retention time of the photoinitiator, preparing a series of samples of different concentrations, and generating a standard curve; (2) after printing is completed, washing the surface of the product with an organic solvent, concentrating the washing liquid and then calibrating it quantitatively with a volumetric flask; (3) taking a sample from the solution obtained in the above (2) for HPLC detection, and comparing it with the HPLC characteristic peak of the standard, and calculating the photoinitiator content with reference to the standard curve of the sample; (4) after the product is stored for 10 days (days) and 30 days, washing the surface of the product with an organic solvent, concentrating the washing liquid and then calibrating it quantitatively with a volumetric flask; (5) taking a sample from the solution obtained in the above (4) for HPLC detection, and comparing it with the HPLC characteristic peak of the standard, and calculating the photoinitiator content with reference to the standard curve of the sample; (6) comparing the residual initiator content on the surface of the product at 0 days, 10 days, and 30 days.

[0066] According to the test, no small molecule photoinitiator was detected on the surface of the printed product of this embodiment from 0 day to 30 days. At the same time, the printed product of this embodiment has good antibacterial properties.

[0067] Example 2

[0068] In this embodiment, cyclodextrin and camphorquinone (CQ) are weighed in a ratio of 1.3:1 and added and mixed in this order, ethanol is selected as the solvent, stirred for 50 minutes, and the solvent is evaporated and dried for later use.

[0069] 50 parts by weight of biocompatible aliphatic polyurethane acrylate, 50 parts by weight of polyethylene glycol dimethacrylate (PEGDMA), 2 parts by weight of a supramolecular photoinitiator system assembled from cyclodextrin and camphorquinone (CQ), 15 parts by weight of cuprous oxide nanoparticles, and 2 parts by weight of an auxiliary agent were stirred and mixed uniformly at room temperature to obtain a homogeneous mixture, which was then shielded from light and stored for later use.

[0070] The above mixture was added into the material container of the visible light 3D printing device, and the material temperature was adjusted to 35°C before printing, with a printing speed of one layer of 2 s, and finally the product was printed.

[0071] The detection method in Example 1 can also be used to detect whether the surface of the product in this example contains a photoinitiator, and the specific detection method will not be described in detail.

[0072] According to the test, no small molecule photoinitiator was detected on the surface of the printed product of this embodiment from 0 day to 30 days. At the same time, the printed product of this embodiment has good antibacterial properties.

[0073] Example 3

[0074] In this example, calixarene and diphenyl titanocene fluoride (Irgacure 784) were weighed in a ratio of 1.5:1 and added and mixed in this order, acetone was selected as the solvent, stirred for 55 minutes, the solvent was evaporated, dried, and set aside.

[0075] 70 parts by weight of biocompatible polyester acrylate, 30 parts by weight of polypropylene glycol diacrylate (PPGDA), 1.5 parts by weight of calixarene and fluorinated diphenyl titanocene (Irgacure 784), 10 parts by weight of zinc oxide nanoparticles, and 2 parts by weight of an auxiliary agent are stirred and mixed uniformly at room temperature to obtain a homogeneous mixture, which is then stored in a dark place for later use.

[0076] The above mixture was added into the material container of the visible light 3D printing device, and the material temperature was adjusted to 55°C before printing, with a printing speed of one layer of 2 s, and finally the product was printed.

[0077] The detection method in Example 1 can also be used to detect whether the surface of the product in this example contains a photoinitiator, and the specific detection method will not be described in detail.

[0078] According to the test, no small molecule photoinitiator was detected on the surface of the printed product of this embodiment from 0 day to 30 days. At the same time, the printed product of this embodiment has good antibacterial properties.

[0079] It can be seen that in each of the above embodiments, the antibacterial photocurable 3D printing material according to the present invention is prepared, and the antibacterial photocurable 3D printing material of the present invention is used to prepare 3D printed products with good antibacterial properties under a visible light environment. No environmentally unfriendly ultraviolet light is required during the preparation of the product. There is no small molecule photoinitiator on the surface of the product, which avoids health problems for people who come into contact with the product, thus providing a great improvement over the prior art.

[0080] While exemplary embodiments of the present inventive concept have been particularly shown and described, it will be understood by those skilled in the art that changes in form and details may be made therein without departing from the spirit and scope of the following claims.

Claims

1. An antibacterial light-curing 3D printing material, comprising the following components in parts by weight: Biocompatible oligomers / monomers 100 parts by weight, Supramolecular photoinitiator system 0.05-5 parts by weight, 5-30 parts by weight of antibacterial nanoparticles, 1-20 parts by weight of auxiliary agent, The supramolecular photoinitiator system is a supramolecular compound active under light radiation in the visible light band, and is a molecular complex system formed by self-assembly of macrocyclic molecules and small molecule photoinitiators through non-chemical bonds.

2. The antibacterial light-curing 3D printing material according to claim 1, characterized in that: The antibacterial nanoparticles are one or more of silver nanoparticles, cuprous oxide nanoparticles, and zinc oxide nanoparticles.

3. The antibacterial light-curing 3D printing material according to claim 1, characterized in that: The macrocyclic molecule is a main compound, the small molecule photoinitiator is a guest photoinitiator, and the supramolecular photoinitiator system is formed by the main compound encapsulating the guest photoinitiator.

4. The antibacterial light-curing 3D printing material according to claim 1, characterized in that: The biocompatible oligomer / monomer is one or more of biocompatible epoxy acrylate, biocompatible polyurethane acrylate, biocompatible polyester acrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, polypropylene glycol diacrylate, and polypropylene glycol dimethacrylate.

5. The antibacterial light-curable 3D printing material according to claim 3, characterized in that: The main compound is one or more of cucurbituril [5] uril, cucurbituril [6] uril, cucurbituril [7] uril, cucurbituril [8] uril, α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, calixarene, and crown ether.

6. The antibacterial light-curable 3D printing material according to claim 3, characterized in that: The guest photoinitiator is one or more of the following compounds active under visible light radiation: dye / borate compounds, camphorquinone, fluorinated diphenyl titanocene, bis(pentafluorinated phenyl) titanocene, and organic peroxide compounds.

7. The antibacterial light-curable 3D printing material according to claim 1, characterized in that: The addition ratio of the host compound of the supramolecular photoinitiator system to the guest photoinitiator of the supramolecular photoinitiator system is 1.1-1.5:

1.

8. The antibacterial light-curable 3D printing material according to claim 1, characterized in that: The wavelength range of the visible light is 415nm-750nm.

9. The antibacterial light-curable 3D printing material according to claim 1, characterized in that: The auxiliary agent includes one or more of a pigment, a filler, an antioxidant, a defoamer, a wetting agent, and an inhibitor; the pigment includes at least one of cadmium yellow, cadmium red, chrome green, and iron blue; the filler includes at least one of calcium carbonate, barium sulfate, montmorillonite, and talcum powder; the defoamer includes at least one of ethanol, n-butanol, silicone ester, and mineral oil; the wetting agent includes at least one of lecithin, polyamino salts, and polyvalent carboxylates; and the inhibitor includes at least one of hydroxyanisole and hydroquinone.