Antibacterial dental photocuring 3D printing resin composition, 3D printing article of manufacture, and use thereof

Abstract

Disclosed are an antibacterial dental photocuring 3D printing resin composition, a 3D printing article of manufacture, and use thereof. The antibacterial dental photocuring 3D printing resin composition comprises a modified polyurethane acrylate oligomer, a modified epoxy acrylate oligomer, and PLA microspheres. The modified polyurethane acrylate oligomer comprises an antibacterial group introduced into the original polyurethane resin, enabling chemical grafting instead of physical mixing. In addition, the modified epoxy acrylate oligomer comprises an introduced PLA group, further improving the strength and wear resistance of dental resin and ensuring environmental friendliness and safety. The modified oligomers and the PLA microspheres added to the composition work synergistically to enable the composition to have excellent, stable, and lasting antibacterial performance.

Description

Antibacterial dental photocurable 3D printing resin composition, 3D printing product and application TECHNICAL FIELD

[0001] The present application relates to the technical field of photosensitive resin, in particular to an antibacterial dental photocurable 3D printing resin composition, a 3D printing product and application. BACKGROUND

[0002] In recent years, with the wide application of digital technology and 3D printing technology in the field of oral repair, oral medicine has entered the digital era, and 3D printing technology has been accepted by more and more people in various dental scenes. Oral implant guide plate printing, denture base printing, and temporary crown printing are the most important links in the entire oral repair. The traditional process is characterized by manual manufacturing, long manufacturing cycle, complex process, and low accuracy. The production of 3D printing digitalization greatly simplifies the traditional process, reduces the waiting time of patients, improves the comfort of patients, reduces the risk of the entire operation, and brings a more comfortable, fast, and safe experience to patients.

[0003] The oral cavity is the second most complex microbial community in the human body. It is composed of bacteria, viruses, fungi, and protozoa. The interface between the implant guide plate, temporary crown, and other dental products worn in the oral cavity and the tooth tissue contains bacteria that cannot be removed by traditional cleaning methods, which can cause secondary caries and repair failure. The existing antibacterial dental 3D printing materials, such as Chinese patent documents CN110787066A, CN106038322B, and CN109453034B, mainly mix antibacterial agents into the resin. Although it can block the growth of bacteria to some extent and reduce the erosion of the prosthesis, the maintenance time is short and the antibacterial effect is poor.

[0004] SUMMARY

[0005] The present application provides an antibacterial dental photocurable 3D printing resin composition to solve the defects of short antibacterial maintenance time and poor antibacterial effect of the existing antibacterial dental 3D printing product.

[0006] Therefore, the present application provides the following solutions:

[0007] In a first aspect, the present application provides an antibacterial dental photocurable 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.

[0008] The modified polyurethane acrylate oligomer is obtained by hydroxyl addition and capping of diisocyanate and thujanol, bisphenol A glycidyl methacrylate, respectively;

[0009] The modified epoxy acrylate oligomer is prepared by condensation of polylactic acid diol with anhydride to form carboxylic acid intermediate, and ring-opening esterification with epoxy group-containing acrylate.

[0010] Further, the preparation method of the modified polyurethane acrylate oligomer is as follows:

[0011] The catalyst I is added to the diisocyanate, heated to 50-70℃, and the thujyl alcohol is slowly added dropwise, and the reaction is carried out until the residual NCO reaches the theoretical NCO, to obtain the reaction intermediate I;

[0012] The reaction intermediate I and the polymerization inhibitor I are stirred and dissolved at 60-80℃, the bisphenol A glycidyl methacrylate is slowly added dropwise into the intermediate I, while the temperature is controlled at 60-80℃, the residual NCO of the product is determined to be less than 0.5%, and the reaction is stopped, to obtain the modified polyurethane acrylate oligomer.

[0013] Preferably, the diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate.

[0014] Preferably, the catalyst I is at least one selected from butyl titanate, stannous octoate, dibutyl tin acetate, dibutyl tin dilaurate, dioctyl tin dilaurate, zinc acetate, zinc isooctoate, zinc isooctoate, bismuth isooctoate, bismuth laurate, bismuth neodecanoate; more preferably, stannous octoate, dibutyl tin dilaurate.

[0015] Preferably, the polymerization inhibitor I is at least one selected from methylhydroquinone, hydroquinone, p-hydroxyanisole, t-butyl hydroquinone; more preferably, p-hydroxyanisole.

[0016] Further, the preparation method of the modified epoxy acrylate oligomer is as follows:

[0017] The polylactic acid diol and the anhydride are mixed and heated to 80-170℃, after the anhydride is completely melted, the catalyst II and the polymerization inhibitor II are added, and the reaction is carried out until the acid value reaches the theoretical acid value of the reaction completion, to obtain the reaction intermediate II;

[0018] The epoxy group-containing acrylate is slowly added dropwise into the obtained reaction intermediate II, and the reaction is carried out by heating to 90-110℃, the acid value of the product is determined to be less than 5mg KOH / g, and the epoxy value is less than 0.1mol / 100g, to obtain the modified epoxy acrylate oligomer.

[0019] Preferably, the acrylate containing an epoxy group is a methacrylic acid-2,3- epoxypropyl ester homologous compound, including esters of acrylic acid and epoxypropyl.

[0020] Preferably, the polylactic acid diol has a molecular weight of 500-2000.

[0021] Preferably, the acid anhydride is at least one selected from phthalic anhydride, maleic anhydride, fumaric anhydride, acetic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride.

[0022] Preferably, the catalyst II is at least one selected from tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, dimethyldioctylammonium bromide, trimethylpropylammonium bromide, triphenylphosphine, N,N-dimethylbenzylamine.

[0023] Preferably, the polymerization inhibitor II is at least one selected from methylhydroquinone, hydroquinone, p-hydroxyanisole, t-butyl hydroquinone, and more preferably p-hydroxyanisole.

[0024] Further, the reactive diluent is at least one selected from hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl acrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane formal acrylate, 4-t-butylcyclohexyl acrylate, triethylene glycol dimethacrylate, acryloyl morpholine, tripropylene 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.

[0025] Further, the assistant is at least one selected from a leveling agent, a defoaming agent, or a wet dispersing agent.

[0026] Further, the photoinitiator is at least one selected from phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide, poly(ethylene glycol) bis(p-dimethylaminobenzoate), methyl o-benzoylbenzoate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, isopropyl thioxanthone.

[0027] Further, the PLA microspheres have a particle size of 100-1000 nm, preferably 100-300 nm.

[0028] In the preparation of the modified polyurethane acrylate oligomer described above, taking isophorone diisocyanate as an example, the preparation route is as follows:

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

[0030] In the second aspect of the present application, the preparation method of the antibacterial dental photocurable 3D printing resin of the first aspect is proposed, and each component is heated to 40-60℃ and stirred and mixed for more than 0.5h to obtain the antibacterial dental photocurable 3D printing resin.

[0031] In the third aspect of the present application, the 3D printing product is obtained by mixing the antibacterial dental photocurable 3D printing resin composition of the first aspect and performing photocuring printing.

[0032] Further, the photocuring condition is 385-405nm waveband photocuring.

[0033] Further, the printing mode includes SLA, DLP and LCD printing.

[0034] In the fourth aspect of the present application, the antibacterial dental photocurable 3D printing resin composition of the first aspect or the 3D printing product of the third aspect is used in the preparation of dental products; the dental products include but are not limited to oral implant guide plates, denture bases, temporary crown teeth and other products.

[0035] Compared with the prior art, the present application has the following beneficial effects:

[0036] 1. The antibacterial dental photocurable 3D printing resin composition provided by the present application comprises a modified polyurethane acrylate oligomer, a modified epoxy acrylate oligomer and PLA microspheres; the modified polyurethane acrylate oligomer introduces an antibacterial group in the original polyurethane resin, realizes chemical grafting instead of 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, and is environmentally friendly and safe. Combined with the addition of PLA microspheres in the composition, the synergistic effect of the three makes it have excellent, stable and durable antibacterial performance.

[0037] 2. The antibacterial dental photocurable 3D printing resin composition provided by the present application improves the resin sedimentation, improves the storage stability and stability during the printing process by adding PLA microspheres. At the same time, the weather resistance of the resin is improved, and the shrinkage rate during curing is reduced, meeting 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 a bacteriostatic effect. DETAILED DESCRIPTION

[0038] The technical solutions of the present application will be described clearly and completely below in combination with preferred embodiments. Obviously, the described embodiments are only part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor fall within the protection scope of the present application.

[0039] In the following examples, the polylactic acid diol is produced by Xiaogan Yisheng New Material Co., Ltd., and the molecular weight is 500-2000; the PLA microspheres are prepared according to the patent publication CN116473927B, and the rest of the reagents are standard products on the market. Unless otherwise specified, the operations described in the experimental process are basic means mastered by those skilled in the art.

[0040] Example 1

[0041] In a container equipped with stirring device and temperature measuring device, 1 mol of isophorone diisocyanate and 0.056 g of stannous octoate were added and heated to 60°C, and then 1 mol of cypress alcohol was slowly added dropwise, and the reaction was continued until the residual NCO reached the theoretical NCO to obtain reaction intermediate I.

[0042] Reaction intermediate I and 0.24 g of polymerization inhibitor methylhydroquinone were dissolved by stirring at 70°C, and then the mixture was slowly added dropwise into 1 mol of bisphenol A glycidyl methacrylate (Bis-GMA), while the temperature was controlled at 70°C, and the residual NCO of the product was determined to be less than 0.5%, and the reaction was stopped to obtain a modified polyurethane acrylate oligomer.

[0043] In a container equipped with stirring device and temperature measuring device, 1 mol of phthalic anhydride and 0.5 mol of polylactic acid diol (molecular weight 500) were added and heated to 100°C, and then 1.99 g of tetramethylammonium bromide and 0.1 g of polymerization inhibitor hydroquinone were added after the phthalic anhydride was completely melted, and the reaction was continued until the acid value reached the theoretical acid value to obtain reaction intermediate II.

[0044] 1 mol of glycidyl methacrylate was slowly added dropwise into the obtained reaction intermediate II, and the reaction was carried out by heating to 110°C, and the acid value of the product was determined to be less than 5 mg KOH / g, and the epoxy value was less than 0.1 mol / 100 g, to obtain a modified epoxy acrylate oligomer.

[0045] Modified polyurethane acrylate oligomer 25 parts, modified epoxy acrylate oligomer 25 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 4 parts, polyethylene glycol (200) diacrylate 50 parts, wetting dispersant 0.2 parts, PLA microspheres (particle size 200 nm) 1 part, 60°C water bath heating and stirring for 30 min to obtain photocuring resin A.

[0046] Example 2

[0047] In a container equipped with stirring device, temperature measuring device, 1 mol of toluene diisocyanate and dioctyltin dilaurate 0.056 g were added and heated to 70°C, 1 mol of cypress alcohol was slowly added dropwise, and the reaction was continued until the residual NCO reached the theoretical NCO to obtain reaction intermediate I.

[0048] Reaction intermediate I and 0.24 g of polymerization inhibitor p-hydroxyanisole were dissolved by stirring at 80°C, and the mixture was slowly added dropwise to 1 mol of bisphenol A glycidyl methacrylate (Bis-GMA) while controlling the temperature at 80°C. The residual NCO of the product was determined to be less than 0.5%, and the reaction was stopped to obtain a modified polyurethane acrylate oligomer.

[0049] In a container equipped with stirring device, temperature measuring device, 1 mol of maleic anhydride and 0.5 mol of polylactic acid diol (molecular weight 500) were added and heated to 90°C. After the maleic anhydride was completely melted, 1.99 g of tetraethylammonium bromide and 0.1 g of polymerization inhibitor p-hydroxyanisole were added as catalysts, and the reaction was continued until the acid value reached the theoretical acid value to obtain reaction intermediate II.

[0050] 1 mol of glycidyl methacrylate was slowly added dropwise to the obtained reaction intermediate II, and the reaction was carried out by heating to 100°C. The acid value of the product was determined to be less than 5 mg KOH / g, and the epoxy value was less than 0.1 mol / 100 g to obtain a modified epoxy acrylate oligomer.

[0051] Modified polyurethane acrylate oligomer 20 parts, modified epoxy acrylate oligomer 30 parts, phenyl bis(2,4,6-trimethylbenzoyl) phosphine oxide 2 parts, polyethylene glycol (200) diacrylate 55 parts, wetting dispersant 0.2 parts, PLA microspheres (particle size 300 nm) 2 parts, 60°C water bath heating and stirring for 30 min to obtain photocuring resin B.

[0052] Example 3

[0053] In a container equipped with stirring device, temperature measuring device, 1 mol of hexamethylene diisocyanate and dioctyltin dilaurate 0.056 g were added and heated to 50°C, 1 mol of cypress alcohol was slowly added dropwise, and the reaction was continued until the residual NCO reached the theoretical NCO to obtain reaction intermediate I.

[0054] Reaction intermediate I and 0.24 g of polymerization inhibitor p-hydroxyanisole were dissolved by stirring at 60°C, and the mixture was slowly added dropwise to 1 mol of bisphenol A glycidyl methacrylate (Bis-GMA) while controlling the temperature at 60°C. The residual NCO of the product was determined to be less than 0.5%, and the reaction was stopped to obtain a modified polyurethane acrylate oligomer.

[0055] In a container equipped with stirring device, temperature measuring device, 1 mol phthalic anhydride and 0.5 mol polylactic diol (molecular weight 1000) were added, heated to 90℃, until the phthalic anhydride was completely melted, then 1.99 g of catalyst tetramethylammonium bromide and 0.1 g of polymerization inhibitor p-hydroxyanisole were added, and the reaction was carried out until the acid value reached the theoretical acid value, to obtain reaction intermediate II.

[0056] 1 mol glycidyl methacrylate was slowly added to the obtained reaction intermediate II, heated to 100℃ for reaction, and the product acid value was less than 5 mg KOH / g, and the epoxy value was less than 0.1 mol / 100g, to obtain modified epoxy acrylate oligomer.

[0057] Modified polyurethane acrylate oligomer 30 parts, modified epoxy acrylate oligomer 20 parts, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide 3 parts, polyethylene glycol (200) diacrylate 45 parts, wet dispersing agent 0.2 parts, PLA microspheres (particle size 100 nm) 0.5 parts, 60℃ water bath heating and stirring for 30 min, to obtain photocuring resin C.

[0058] Comparative example 1

[0059] Photocuring resin D, different from example 1 is that no modified epoxy acrylate oligomer is added.

[0060] Comparative example 2

[0061] Photocuring resin E, different from example 1 is that no modified polyurethane acrylate oligomer is added.

[0062] Comparative example 3

[0063] Photocuring resin F, different from example 1 is that no PLA microspheres are added.

[0064] Comparative example 4

[0065] Photocuring resin G, the preparation method of modified polyurethane acrylate oligomer uses isophorone diisocyanate and bisphenol A glycidyl methacrylate (Bis-GMA) direct reaction to obtain, the difference lies in that no hinokitiol is added.

[0066] Comparative example 5

[0067] Photocuring resin H, the preparation method of modified epoxy acrylate oligomer uses phthalic anhydride and glycidyl methacrylate direct reaction to obtain in example 1, the difference lies in that no polylactic diol is added.

[0068] Experimental example

[0069] The antibacterial material was printed and formed by DLP data light processing technology, and then post-cured in a curing box with a light source in the 385-405 nm wave band to obtain a temporary crown product, which was all milky yellow.

[0070] The antibacterial dental materials of Examples 1-3 and Comparative Examples 1-5 were printed into standard samples by using an LCD printer or a DLP printer or an SLA printer, the mechanical properties of the prepared samples were tested according to ASTM D638, ASTM D790, ASTM D256 and ASTM D2240, respectively, and the antibacterial performance test and stability test of E. coli were carried out according to GB / B 31402-2015. The results are shown in Tables 1 and 2.

[0071] Table 1: Performance test data of comparative examples and examples

[0072] As can be seen from Table 1, the comparison of the results of A-C shows that the modified polyurethane acrylate oligomer, the modified epoxy acrylate oligomer, and the PLA microspheres have a synergistic effect and produce excellent antibacterial performance.

[0073] Table 2: Stability test data of comparative examples and examples

[0074] As can be seen from Table 2, the comparison of the results of A-C shows that the modified polyurethane acrylate oligomer, the modified epoxy acrylate oligomer, and the PLA microspheres have a synergistic effect and produce stable antibacterial performance.

[0075] Shrinkage test: The shrinkage of the above examples and comparative examples of light-cured resin after printing and light curing was tested, and the results are shown in Table 3.

[0076] Table 3: Curing shrinkage test data of examples and comparative examples

[0077] As can be seen from Table 3, the resin obtained by the example has a low curing shrinkage, and the addition of PLA microspheres in resin F leads to a significant decrease in shrinkage. The main reason for volume shrinkage is that the resin changes from a liquid to a solid state during printing, and the acrylate changes from van der Waals force to covalent bond connection. The corresponding interatomic distance is shortened, resulting in volume shrinkage. The PLA microspheres are perfectly and uniformly filled into the resin by parameter adjustment, and play a good skeleton supporting role, effectively reducing the resin curing shrinkage, and meeting the requirements of dental 3D printing resin.

[0078] Although embodiments of the present application have been shown and described, it is to be understood that various modifications, substitutions, replacements and changes can be made to these embodiments without departing from the principles and spirit of the present application, and the scope of the present application is defined by the appended claims and their equivalents.

Claims

1. An antibacterial dental photocurable 3D printing resin composition, characterized by, The components include, by weight parts: modified polyurethane acrylate oligomer 20-30 parts, modified epoxy acrylate oligomer 20-30 parts, photoinitiator 0.5-4 parts, active diluent 40-60 parts, auxiliary 0.2-1 part, PLA microspheres 0.1-2 parts; The modified polyurethane acrylate oligomer is obtained by hydroxyl addition termination of diisocyanate with thujanol and bisphenol A glycidyl methacrylate, respectively; The modified epoxy acrylate oligomer is obtained by condensation of polylactic acid diol with acid anhydride to form carboxylic acid intermediate, and then ring-opening esterification reaction with epoxy group-containing acrylate.

2. The composition of claim 1, wherein, The preparation method of the modified polyurethane acrylate oligomer is as follows: Add catalyst I to diisocyanate, heat to 50-70℃, slowly drop thujanol, react to residual NCO reaching theoretical NCO, obtain reaction intermediate I; Stir and dissolve reaction intermediate I and polymerization inhibitor I at 60-80℃, slowly drop bisphenol A glycidyl methacrylate into intermediate product I, control temperature at 60-80℃ at the same time, measure product residual NCO less than 0.5%, stop reaction, obtain modified polyurethane acrylate oligomer.

3. The composition of claim 2, wherein, The diisocyanate is at least one selected from toluene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate; and / or, The catalyst I is at least one selected from butyl titanate, stannous octoate, dibutyl tin acetate, dibutyl tin dilaurate, dioctyl tin dilaurate, zinc acetate, zinc isooctoate, zinc isooctoate, bismuth isooctoate, bismuth laurate, bismuth neodecanoate; and / or, The polymerization inhibitor I is at least one selected from methylhydroquinone, hydroquinone, p-hydroxyanisole, tert-butyl hydroquinone.

4. The composition of claim 1, wherein, The preparation method of the modified epoxy acrylate oligomer is as follows: Mix polylactic acid diol and acid anhydride, heat to 80-170℃, after complete melting of the acid anhydride, add catalyst II and polymerization inhibitor II, react to acid value reaching theoretical acid value of reaction completion, obtain reaction intermediate II; Slowly drop epoxy group-containing acrylate into obtained reaction intermediate II, heat to 90-110℃ for reaction, measure product acid value less than 5mg KOH / g, epoxy value less than 0.1mol / 100g, obtain modified epoxy acrylate oligomer.

5. The composition of claim 4, wherein, The polylactic acid diol has a molecular weight of 500-2000; and / or, The acid anhydride is at least one selected from phthalic anhydride, maleic anhydride, fumaric anhydride, acetic anhydride, methylhexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride; and / or, The catalyst II is at least one selected from tetramethylammonium bromide, tetraethylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, dimethyldioctylammonium bromide, trimethylpropylammonium bromide, triphenylphosphine, N,N-dimethylbenzylamine; and / or, The polymerization inhibitor II is at least one selected from methylhydroquinone, hydroquinone, p-hydroxyanisole, tert-butyl hydroquinone.

6. The composition of claim 1, wherein, the active diluent is at least one of hydroxyethyl acrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, lauryl acrylate, isobornyl acrylate, isobornyl methacrylate, trimethylolpropane methylal acrylate, 4-tert-butylcyclohexyl acrylate, triethylene glycol dimethacrylate, acryloyl morpholine, tripropylene glycol diacrylate, 1,6-hexanediol diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, polyethylene glycol (200) diacrylate, dimethylaminoethyl methacrylate urethane, pentaerythritol triacrylate, dipropylene glycol diacrylate, ethoxylated trimethylolpropane triacrylate, propoxylated glycerol triacrylate, ethoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate; and / or, the assistant is at least one of a leveling agent, a defoaming agent, or a wetting dispersant; and / or, the photoinitiator is at least one of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, poly(ethylene glycol) bis(p-dimethylaminobenzoate), methyl o-benzoylbenzoate, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, isopropyl thioxanthone; and / or, the PLA microspheres have a particle size of 100-1000 nm.

7. The method of producing an antibacterial dental photocurable 3D printing resin according to any one of claims 1 to 6, characterized in that, The components are heated to 40-60°C and mixed under stirring for 0.5 h or more.

8. A 3D printed article characterized by, The antibacterial dental photocured 3D printing resin composition of any one of claims 1-6 is mixed and printed by photocuring.

9. The 3D printed article of claim 7, wherein, The printing method includes SLA, DLP, and LCD printing.

10. Use of the antibacterial dental photocured 3D printing resin composition of any one of claims 1-6 or the 3D printed product of any one of claims 8-9 in the preparation of a dental product.

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