Antibacterial Dental Photo-Curable 3D Printing Resin Composition, 3D Printing Product and Application

Abstract

The present invention discloses an antibacterial dental photocurable 3D printing resin composition, a 3D printing product and applications thereof. The antibacterial dental photocurable 3D printing resin composition includes a modified polyurethane acrylate oligomer, a modified epoxy acrylate oligomer and PLA microspheres. The modified polyurethane acrylate oligomer introduces antibacterial groups into the original polyurethane resin, achieving chemical grafting rather than physical mixing. In addition, the modified epoxy acrylate oligomer further improves the strength and wear resistance of the dental resin by introducing a PLA group, while being environmentally friendly and safe. Combining with the PLA microspheres added in the composition, the synergistic effect of the three makes it have excellent, stable and lasting antibacterial properties.

Description

Technical Field

[0001] The present invention relates to the technical field of photosensitive resins, and in particular to antibacterial dental light-cured 3D printing resin compositions, 3D printed products and applications. Background Art

[0002] In recent years, with the widespread application of digital technology and 3D printing technology in the field of oral restoration, oral medicine has entered the digital age, and the application of 3D printing technology in various dental scenarios has been accepted by more and more people. Oral implant guide printing, denture base printing, and temporary crown printing are the most important links in the entire oral restoration. The characteristics of traditional processes are manual manufacturing, long manufacturing cycle, complicated procedures, and low precision. Through 3D printing digitalization, production has greatly simplified the traditional process, reduced the patient's waiting time, improved the patient's comfort, reduced the overall surgical risk, and brought patients a more comfortable, fast, and safe experience.

[0003] The oral cavity is the second most complex microbial community in the human body. It is composed of bacteria, viruses, fungi and protozoa. Dental products such as implant guides and temporary crowns worn in the oral cavity contain bacteria at the interface with the tooth tissue. These bacteria cannot be removed by traditional cleaning methods and will lead to secondary caries and restoration failure. Existing antibacterial dental 3D printing materials, such as Chinese patent documents CN110787066A, CN106038322B, CN109453034B, etc., mainly mix antibacterial agents into the resin. Although they can block the growth of bacteria and reduce the erosion of the restoration to a certain extent, they are short-lived and have poor antibacterial effects. Summary of the invention

[0004] The present invention provides an antibacterial dental light-curing 3D printing resin composition, which is used to solve the defects of the prior art in preparing antibacterial dental 3D printed products, such as short antibacterial maintenance time and poor antibacterial effect.

[0005] In view of this, the scheme of the present invention is:

[0006] The first aspect of the present invention provides an antibacterial dental light-curable 3D printing resin composition, which comprises, by weight: 20-30 parts of modified polyurethane acrylate oligomer, 20-30 parts of modified epoxy acrylate oligomer, 0.5-4 parts of photoinitiator, 40-60 parts of active diluent, 0.2-1 parts of auxiliary agent, and 0.1-2 parts of PLA microspheres;

[0007] The modified polyurethane acrylate oligomer is obtained by respectively subjecting diisocyanate to hinokitiol and bisphenol A glycidyl methacrylate and performing hydroxyl addition blocking.

[0008] The modified epoxy acrylate oligomer is obtained by condensing polylactic acid diol with an acid anhydride to form a carboxylic acid intermediate, and then undergoing a ring-opening esterification reaction with an acrylate containing an epoxy group.

[0009] Furthermore, the preparation method of the modified polyurethane acrylate oligomer is as follows:

[0010] Add a catalyst I to the diisocyanate, heat to 50 - 70 °C, slowly dropwise add hinokitiol, and react until the residual NCO reaches the theoretical NCO to obtain reaction intermediate I;

[0011] Stir and dissolve reaction intermediate I and inhibitor I at 60 - 80 °C, slowly dropwise add glycidyl methacrylate of bisphenol A to intermediate product I, while controlling the temperature at 60 - 80 °C, measure that the residual NCO of the product is less than 0.5%, stop the reaction, and obtain the modified polyurethane acrylate oligomer.

[0012] Preferably, the diisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate.

[0013] Preferably, the catalyst I is selected from at least one of tetrabutyl titanate, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, zinc acetate, zinc isooctoate, zinc isooctoate, bismuth isooctoate, bismuth laurate, bismuth neodecanoate; more preferably stannous octoate, dibutyltin dilaurate.

[0014] Preferably, the inhibitor I is selected from at least one of methylhydroquinone, hydroquinone, p - methoxyphenol, tert - butylhydroquinone; more preferably p - methoxyphenol.

[0015] Furthermore, the preparation method of the modified epoxy acrylate oligomer is as follows:

[0016] Mix polylactic acid diol and acid anhydride and heat to 80 - 170 °C. After the acid anhydride is completely melted, add catalyst II and inhibitor II, and react until the acid value reaches the theoretical acid value at the end of the reaction to obtain reaction intermediate II;

[0017] Slowly dropwise add the acrylate containing an epoxy group to the obtained reaction intermediate II, heat to 90 - 110 °C for reaction, measure that the acid value of the product is less than 5 mg KOH / g and the epoxy value is less than 0.1 mol / 100 g to obtain the modified epoxy acrylate oligomer.

[0018] Preferably, the acrylate containing an epoxy group is a homologue of 2,3 - epoxypropyl methacrylate, including esters of acrylic acid and epoxypropyl.

[0019] Preferably, the molecular weight of the polylactic acid diol is 500 - 2000.

[0020] Preferably, the acid anhydride is selected from at least one of phthalic anhydride, maleic anhydride, fumaric anhydride, acetic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and nadic anhydride.

[0021] Preferably, the catalyst II is selected from at least one of tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetraamylammonium bromide, dimethyldioctylammonium bromide, trimethylpropylammonium bromide, triphenylphosphine, and N,N - dimethylbenzylamine.

[0022] Preferably, the inhibitor II is selected from at least one of methylhydroquinone, hydroquinone, p - methoxyphenol, and tert - butylhydroquinone, and more preferably p - methoxyphenol.

[0023] Further, the reactive diluent is selected from at least one of 2 - hydroxyethyl acrylate, 2 - hydroxypropyl acrylate, 4 - hydroxybutyl acrylate, 2 - hydroxyethyl methacrylate, 2 - hydroxypropyl methacrylate, lauryl acrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane methylal acrylate, 4 - tert - butylcyclohexyl acrylate, triethylene glycol dimethacrylate, acryloylmorpholine, dipropylene glycol diacrylate, 1,6 - hexanediol diacrylate, neopentyl glycol propoxylate diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol(200) diacrylate, dimethylaminoethyl methacrylate, pentaerythritol triacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, and dipentaerythritol hexaacrylate.

[0024] Further, the auxiliary agent is selected from at least one of a leveling agent, a defoaming agent, or a wetting and dispersing agent.

[0025] Further, the photoinitiator is selected from at least one of phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide, poly(ethylene glycol) bis(p - dimethylaminobenzoate), methyl o - benzoylbenzoate, 2 - benzyl - 2 - dimethylamino - 1 - (4 - morpholinophenyl)butanone, and isopropylthioxanthone.

[0026] Further, the particle size of the PLA microspheres is 100 - 1000 nm, preferably 100 - 300 nm.

[0027] In the preparation of the above - mentioned modified polyurethane acrylate oligomer, taking isophorone diisocyanate as an example, its preparation route is as follows:

[0028]

[0029] In the preparation of the modified epoxy acrylate oligomer described above, taking maleic anhydride as an example, its preparation route is as follows:

[0030]

[0031] In the second aspect of the present invention, a preparation method of the antibacterial dental photocurable 3D printing resin described in the first aspect is proposed. Heat each component to 40 - 60 °C and stir and mix for more than 0.5 h to obtain it.

[0032] In the third aspect of the present invention, a 3D printed product is proposed, which is obtained by mixing and photocuring the antibacterial dental photocurable 3D printing resin composition described in the first aspect.

[0033] Furthermore, the photocuring condition is photocuring with light in the 385 - 405 nm band.

[0034] Furthermore, the printing methods include SLA, DLP, and LCD printing.

[0035] In the fourth aspect of the present invention, an application of the antibacterial dental photocurable 3D printing resin composition described in the first aspect, or the 3D printed product described in the third aspect, in the preparation of dental products is proposed; the dental products include but are not limited to oral implant guides, denture bases, temporary crowns, and other products.

[0036] Compared with the prior art, the present invention has the following beneficial effects:

[0037] 1. The antibacterial dental photocurable 3D printing resin composition provided by the present invention includes a modified polyurethane acrylate oligomer, a modified epoxy acrylate oligomer, and PLA microspheres; the modified polyurethane acrylate oligomer introduces antibacterial groups into the original polyurethane resin, realizing chemical grafting rather than physical mixing; in addition, the modified epoxy acrylate oligomer further improves the strength and wear resistance of the dental resin by introducing a PLA group, while being environmentally friendly and safe. Combining with the PLA microspheres added in the composition, the synergistic effect of the three makes it have excellent, stable, and lasting antibacterial properties.

[0038] 2. The antibacterial dental photocurable 3D printing resin composition provided by the present invention effectively improves resin sedimentation by adding PLA microspheres, improves its storage stability and stability during the printing process. At the same time, it increases the weather resistance of the resin, reduces the curing shrinkage rate, and meets the requirements of dental 3D printing. On the other hand, the PLA microspheres have biocompatibility and permeability, can penetrate the cell membrane of bacteria, and destroy the structure and function of bacteria, thereby playing an antibacterial role. Specific Embodiments

[0039] The technical solutions of the present invention will be clearly and completely described below in conjunction with preferred embodiments. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the protection scope of the present invention.

[0040] In the following examples, the polylactic acid diol was produced by Xiaogan Yisheng New Materials Co., Ltd., with a molecular weight of 500 - 2000; the PLA microspheres were prepared according to the patent publication CN116473927B, and the rest of the reagents were commercially available standard products. Unless otherwise specified, the operations described in the experimental process are basic means mastered by those skilled in the art.

[0041] Example 1

[0042] Add 1 mol of isophorone diisocyanate and 0.056 g of stannous octoate into a container equipped with a stirring device and a temperature measuring device, heat to 60 °C, and slowly dropwise add 1 mol of hinokitiol thereto. React until the residual NCO reaches the theoretical NCO to obtain reaction intermediate I.

[0043] Dissolve reaction intermediate I and 0.24 g of inhibitor methylhydroquinone by stirring at 70 °C, and slowly drop the mixture into 1 mol of bisphenol A glycidyl methacrylate (Bis - GMA), while controlling the temperature at 70 °C. Measure that the residual NCO of the product is less than 0.5%, and stop the reaction to obtain a modified polyurethane acrylate oligomer.

[0044] Add 1 mol of phthalic anhydride and 0.5 mol of polylactic acid diol (molecular weight 500) into a container equipped with a stirring device and a temperature measuring device, heat to 100 °C. After the phthalic anhydride is completely melted, add 1.99 g of catalyst tetramethylammonium bromide and 0.1 g of inhibitor hydroquinone, and react until the acid value reaches the theoretical acid value to obtain reaction intermediate II.

[0045] Slowly drop 1 mol of glycidyl methacrylate into the obtained reaction intermediate II, heat to 110 °C for reaction, measure that the acid value of the product is less than 5 mg KOH / g and the epoxy value is less than 0.1 mol / 100 g to obtain a modified epoxy acrylate oligomer.

[0046] 25 parts of the modified polyurethane acrylate oligomer, 25 parts of the modified epoxy acrylate oligomer, 4 parts of phenylbis(2,4,6 - trimethylbenzoyl)phosphine oxide, 50 parts of polyethylene glycol(200) diacrylate, 0.2 part of wetting and dispersing agent, 1 part of PLA microspheres (particle size 200 nm). Heat and stir - mix in a 60 °C water bath for 30 min to obtain photocurable resin A.

[0047] Example 2

[0048] Add 1 mol of toluene diisocyanate and 0.056 g of dioctyltin dilaurate into a container equipped with a stirring device and a temperature measuring device, heat it to 70 °C, slowly dropwise add 1 mol of hinokitiol thereto, and react until the residual NCO reaches the theoretical NCO to obtain reaction intermediate I.

[0049] Stir and dissolve reaction intermediate I and 0.24 g of inhibitor p-methoxyphenol at 80 °C, slowly dropwise add the mixture into 1 mol of bisphenol A glycidyl methacrylate (Bis-GMA), while controlling the temperature at 80 °C, measure that the residual NCO of the product is less than 0.5%, and stop the reaction to obtain a modified polyurethane acrylate oligomer.

[0050] Add 1 mol of maleic anhydride and 0.5 mol of polylactic acid diol (molecular weight 500) into a container equipped with a stirring device and a temperature measuring device, heat it to 90 °C, until maleic anhydride is completely melted, add 1.99 g of catalyst tetraethylammonium bromide and 0.1 g of inhibitor p-methoxyphenol, and react until the acid value reaches the theoretical acid value to obtain reaction intermediate II.

[0051] Slowly dropwise add 1 mol of glycidyl methacrylate into the obtained reaction intermediate II, heat it to 100 °C for reaction, measure that the acid value of the product is less than 5 mg KOH / g and the epoxy value is less than 0.1 mol / 100 g to obtain a modified epoxy acrylate oligomer.

[0052] 20 parts of modified polyurethane acrylate oligomer, 30 parts of modified epoxy acrylate oligomer, 2 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 55 parts of polyethylene glycol (200) diacrylate, 0.2 part of wetting and dispersing agent, 2 parts of PLA microspheres (particle size 300 nm), heat and stir and mix in a 60 °C water bath for 30 min to obtain photocurable resin B.

[0053] Example 3

[0054] Add 1 mol of hexamethylene diisocyanate and 0.056 g of dioctyltin dilaurate into a container equipped with a stirring device and a temperature measuring device, heat it to 50 °C, slowly dropwise add 1 mol of hinokitiol thereto, and react until the residual NCO reaches the theoretical NCO to obtain reaction intermediate I.

[0055] Stir and dissolve reaction intermediate I and 0.24 g of inhibitor p-methoxyphenol at 60 °C, slowly dropwise add the mixture into 1 mol of bisphenol A glycidyl methacrylate (Bis-GMA), while controlling the temperature at 60 °C, measure that the residual NCO of the product is less than 0.5%, and stop the reaction to obtain a modified polyurethane acrylate oligomer.

[0056] Add 1 mol of phthalic anhydride and 0.5 mol of polylactic acid diol (molecular weight 1000) into a container equipped with a stirring device and a temperature measuring device. Heat it to 90 °C. After the phthalic anhydride is completely melted, add 1.99 g of catalyst tetramethylammonium bromide and 0.1 g of inhibitor p-hydroxyanisole. React until the acid value reaches the theoretical acid value to obtain reaction intermediate II.

[0057] Slowly drop 1 mol of glycidyl methacrylate into the obtained reaction intermediate II. Heat it to 100 °C for reaction. Measure that the acid value of the product is less than 5 mg KOH / g and the epoxy value is less than 0.1 mol / 100 g to obtain a modified epoxy acrylate oligomer.

[0058] 30 parts of modified polyurethane acrylate oligomer, 20 parts of modified epoxy acrylate oligomer, 3 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 45 parts of polyethylene glycol (200) diacrylate, 0.2 part of wetting and dispersing agent, 0.5 part of PLA microspheres (particle size 100 nm). Heat and stir in a water bath at 60 °C for 30 min to obtain photocurable resin C.

[0059] Comparative Example 1

[0060] Photocurable resin D, which is different from Example 1 in that no modified epoxy acrylate oligomer is added.

[0061] Comparative Example 2

[0062] Photocurable resin E, which is different from Example 1 in that no modified polyurethane acrylate oligomer is added.

[0063] Comparative Example 3

[0064] Photocurable resin F, which is different from Example 1 in that no PLA microspheres are added.

[0065] Comparative Example 4

[0066] Photocurable resin G, the preparation method of the modified polyurethane acrylate oligomer uses isophorone diisocyanate and bisphenol A glycidyl methacrylate (Bis-GMA) in Example 1 to react directly, the difference is that no hinokitiol is added.

[0067] Comparative Example 5

[0068] Photocurable resin H, the preparation method of the modified epoxy acrylate oligomer uses phthalic anhydride and glycidyl methacrylate in Example 1 to react directly, the difference is that no polylactic acid diol is added.

[0069] Experimental Example

[0070] The antibacterial material is printed into shape by using DLP digital light processing technology, and then post-cured in a curing box with a light source in the wavelength range of 385 - 405 nm to obtain the finished temporary crowns, all of which are milky yellow.

[0071] An LCD printer, a DLP printer, or an SLA printer is used to print the antibacterial dental materials of Examples 1 - 3 and Comparative Examples 1 - 5 into standard splines. The mechanical properties of the obtained splines are tested with reference to ASTM D638, ASTM D790, ASTM D256, and ASTM D2240 respectively, and the antibacterial properties against Escherichia coli and the stability test are carried out with reference to GB / B 31402 - 2015. The results are shown in Table 1 and Table 2 below.

[0072] Table 1: Performance test data of comparative examples and examples

[0073]

[0074] It is not difficult to see from Table 1 that by comparing the results of Photo-curing Resins A - C, it can be shown that excellent antibacterial properties are produced under the action of modified polyurethane acrylate oligomer, modified epoxy acrylate oligomer, and PLA microspheres. When Resins D - H lack specific modified polymers or specific components respectively, their bactericidal rates all decrease significantly, indicating that the modified polyurethane acrylate oligomer, modified epoxy acrylate oligomer, and PLA microspheres have a synergistic effect.

[0075] Table 2: Stability test data of comparative examples and examples

[0076]

[0077]

[0078] It is not difficult to see from Table 2 that by comparing the results of A - C, it can be shown that stable antibacterial properties are produced under the action of modified polyurethane acrylate oligomer, modified epoxy acrylate oligomer, and PLA microspheres. When Resins D - H lack specific modified polymers or specific components respectively, their bactericidal stability decreases significantly, indicating that the modified polyurethane acrylate oligomer, modified epoxy acrylate oligomer, and PLA microspheres have a synergistic effect.

[0079] Shrinkage rate test: The shrinkage rates of the above-mentioned photo-curing resins in the printed and photo-cured state of examples and comparative examples are tested, and the results are shown in Table 3.

[0080] Table 3: Curing shrinkage rate test data of examples and comparative examples

[0081]

[0082] As can be seen from Table 3, the resin obtained in the examples has a low curing shrinkage rate. However, the shrinkage rate of Resin F decreased significantly because no PLA microspheres were added. The main reason for the volume shrinkage is that the resin changes from a liquid state to a solid state during printing, and the acrylate changes from van der Waals force to covalent bond connection, resulting in a shortened distance between the corresponding atoms and thus volume shrinkage. The PLA microspheres are perfectly and uniformly filled into the resin through parameter adjustment, playing a good role in skeleton support and effectively reducing the resin curing shrinkage rate, meeting the requirements of dental 3D printing resin.

[0083] Although the embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the present invention. The scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. An antibacterial dental light-curing 3D printing resin composition, characterized in that, The components by weight parts include: 20 - 30 parts of modified polyurethane acrylate oligomer, 20 - 30 parts of modified epoxy acrylate oligomer, 0.5 - 4 parts of photoinitiator, 40 - 60 parts of reactive diluent, 0.2 - 1 part of additive, and 0.1 - 2 parts of PLA microspheres; The modified polyurethane acrylate oligomer is obtained by hydroxy - addition capping of diisocyanate with hinokitiol and glycidyl methacrylate of bisphenol A; The modified epoxy acrylate oligomer is obtained by condensation of polylactic acid diol and acid anhydride to generate a carboxylic acid intermediate, and then by ring - opening esterification reaction with an acrylate containing an epoxy group; 2. The composition according to claim 1, wherein The preparation method of the modified polyurethane acrylate oligomer is as follows: Add catalyst I to diisocyanate, heat to 50 - 70 °C, slowly drop - wise add hinokitiol, and react until the residual NCO reaches the theoretical NCO to obtain reaction intermediate I; Stir and dissolve reaction intermediate I and inhibitor I at 60 - 80 °C, slowly drop - wise add glycidyl methacrylate of bisphenol A to intermediate product I, while controlling the temperature at 60 - 80 °C, stop the reaction when the residual NCO of the product is less than 0.5%, and obtain the modified polyurethane acrylate oligomer; 3. The composition according to claim 2, characterized in that, The diisocyanate is selected from at least one of toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate; and / or, The catalyst I is selected from at least one of tetrabutyl titanate, stannous octoate, dibutyltin diacetate, dibutyltin dilaurate, dioctyltin dilaurate, zinc acetate, zinc isooctanoate, zinc isooctanoate, bismuth isooctanoate, bismuth laurate, and bismuth neodecanoate; and / or, The inhibitor I is selected from at least one of methylhydroquinone, hydroquinone, p - methoxyphenol, and tert - butylhydroquinone; 4. The composition according to claim 1, wherein The preparation method of the modified epoxy acrylate oligomer is as follows: Mix polylactic acid diol and acid anhydride and heat to 80 - 170 °C until the acid anhydride is completely melted, then add catalyst II and inhibitor II, and react until the acid value reaches the theoretical acid value at the end of the reaction to obtain reaction intermediate II; Slowly drop - wise add the acrylate containing an epoxy group to the obtained reaction intermediate II, heat to 90 - 110 °C for reaction, and stop the reaction when the acid value of the product is less than 5 mg KOH / g and the epoxy value is less than 0.1 mol / 100 g to obtain the modified epoxy acrylate oligomer; 5. The composition according to claim 4, wherein The molecular weight of the polylactic acid diol is 500 - 2000; and / or, The acid anhydride is selected from at least one of phthalic anhydride, maleic anhydride, fumaric anhydride, acetic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and nadic anhydride; and / or, The catalyst II is selected from at least one of tetra - methylammonium bromide, tetra - ethylammonium bromide, tetra - butylammonium bromide, tetra - pentylammonium bromide, dimethyldioctylammonium bromide, trimethylpropylammonium bromide, triphenylphosphine, and N,N - dimethylbenzylamine; and / or, The inhibitor II is selected from at least one of methylhydroquinone, hydroquinone, p - methoxyphenol, and tert - butylhydroquinone; 6. The composition according to claim 1, wherein The active diluent is selected from at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl acrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane methylal acrylate, 4-tert-butylcyclohexyl acrylate, triethylene glycol dimethacrylate, acryloylmorpholine, dipropylene glycol diacrylate, 1,6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol (200) diacrylate, dimethylaminoethyl methacrylate, pentaerythritol triacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; and / or, The auxiliary agent is selected from at least one of a leveling agent, an antifoaming agent or a wetting and dispersing agent; and / or, The photoinitiator is selected from at least one of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, poly(ethylene glycol) bis(p-dimethylaminobenzoate), methyl o-benzoylbenzoate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, isopropylthioxanthone; and / or, The particle size of the PLA microspheres is 100-1000 nm.

7. The preparation method of the antibacterial dental light-curing 3D printing resin according to any one of claims 1-6, characterized in that, Each component is heated to 40-60 °C and stirred and mixed for more than 0.5 h to obtain the product.

8. 3D printed article, characterized in that, It is obtained by mixing the antibacterial dental photocurable 3D printing resin composition according to any one of claims 1-6 and subjecting it to photocuring printing.

9. The 3D printed article according to claim 8, wherein, The printing method is selected from SLA, DLP or LCD printing.

10. Use of the antibacterial dental photocurable 3D printing resin composition according to any one of claims 1-6 or the 3D printing product according to any one of claims 8-9 in the preparation of dental products.

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