A photosensitive prepolymer, a photosensitive resin composition and its application

Abstract

The present application provides a photosensitive prepolymer, a photosensitive resin composition and its application. The raw materials for preparing the photosensitive prepolymer include a combination of oligomeric polyols, alicyclic diisocyanates, chain extenders and hydroxyl-containing acrylic ester monomers; the chain extender is an organic substance with a molecular weight of less than 800 and containing 3 or more primary hydroxyl groups. The present application improves the compatibility of the components by designing and compounding the raw materials, while retaining the flexibility characteristics of the oligomeric polyol chain segments, and having a suitable viscosity. It is possible to prepare a photosensitive resin composition suitable for 3D printing, and the obtained 3D printing material can be used as an oral support, has excellent mechanical properties, can increase the correction force, and can change and restore the shape under temperature changes, providing excellent correction effects, and has broad application prospects in oral and dental materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, specifically to the technical field of 3D printing materials and oral materials, and in particular relates to a photosensitive prepolymer, a photosensitive resin composition and applications thereof. Background Art

[0002] With the continuous improvement of living standards, people are paying more and more attention to orthodontics. The currently widely used transparent orthodontic device materials are PETG or TPU materials. After scanning the patient's teeth, simulating tooth movement through a program, and making a model of the patient's dentition, the transparent composite resin film is hot-pressed to produce a transparent orthodontic device for each planned tooth movement stage. In order to improve the orthodontic effect, additional accessories need to be attached to the surface of the transparent orthodontic device, but this solution makes the installation and removal of the entire transparent orthodontic device more difficult when multiple accessories are attached to the teeth; at the same time, the installation and removal process of the accessories may also cause deformation, which makes the attachments more likely to fall off, increasing the difficulty of orthodontic treatment.

[0003] The industry is committed to applying 3D printing technology in the field of orthodontics, hoping to use the convenient customization of 3D printing to quickly develop treatment plans to respond to patients. At the same time, it is hoped that the transparent orthodontic devices manufactured by 3D printing can retain the "hard and tough" characteristics of the diaphragm material and provide sufficient correction force. However, due to the requirements of photocuring 3D printing molding on the viscosity of photosensitive resins, it is often difficult to increase the molecular weight of photosensitive prepolymers, which leads to the difficulty of compounding photosensitive resin compositions after photocuring molding. It is difficult to balance hardness and toughness, and cannot match the mechanical properties of hot-pressed diaphragms, which seriously hinders the promotion and application of 3D printing technology in the field of orthodontics. Therefore, the development of photosensitive resin materials that can match the mechanical properties of hot-pressed diaphragms is an urgent problem to be solved in this field. Summary of the invention

[0004] In view of the problems existing in the prior art, the present invention provides a photosensitive prepolymer, a photosensitive resin composition and applications thereof. The photosensitive prepolymer improves the compatibility of the components by designing and compounding the raw materials for preparation, while retaining the flexibility characteristics of the oligomeric polyol chain segments and having suitable viscosity, and can be used to prepare a photosensitive resin composition suitable for 3D printing. The obtained 3D printing material can be used as an oral support, has excellent mechanical properties, can increase the corrective force, and can change and restore the shape under temperature changes, providing excellent corrective effects, and has broad application prospects in oral and dental materials.

[0005] To achieve this object, the present invention adopts the following technical solutions:

[0006] In a first aspect, the present application provides a photosensitive prepolymer, wherein the raw materials for preparing the photosensitive prepolymer include a combination of oligomeric polyols, alicyclic diisocyanates, chain extenders and hydroxyl-containing acrylate monomers; the chain extender is an organic substance having a molecular weight of less than 800 and containing 3 or more primary hydroxyl groups.

[0007] The photosensitive prepolymer provided in the present application is obtained by reacting oligomeric polyols, alicyclic diisocyanates, chain extenders and hydroxyl-containing acrylate monomers; wherein the oligomeric polyols construct the polymer soft segment, and the alicyclic diisocyanates and chain extenders participate in the construction of the polymer hard segment; at the same time, the introduction of the chain extender reduces the entanglement of the prepolymer molecular chains and reduces the viscosity; in addition, the introduction of the chain extender can regulate the glass transition temperature and increase the response temperature of the thermal shape memory; and then by introducing hydroxyl-containing acrylate monomers for end-capping, on the one hand, the photosensitive prepolymer contains a reactive double bond group, which can meet the needs of photocuring and 3D printing, and on the other hand, by end-capping with hydroxyl-containing acrylate monomers, the polyester or polyether segment is connected to the oligomeric polyol segment with poor compatibility (such as hydroxyl-containing liquid rubber, polydimethylsiloxane), so that the prepared prepolymer improves the compatibility of the oligomeric polyol component while retaining the flexibility characteristics of the oligomeric polyol segment.

[0008] Specifically, the photosensitive prepolymer comprises carbamate (obtained by the reaction of alicyclic diisocyanate, oligomeric polyol and chain extender) and acrylate structure as the main chain, the photosensitive group (hydroxyl-containing acrylate) is bonded to the carbamate structure, and comprises a soft segment (oligomeric polyol) and a hard segment (chain extender reacts with alicyclic diisocyanate); the soft segment structure helps the photosensitive prepolymer to show flexibility, and the hard segment gives it strength and heat resistance. The hard carbon skeleton in the photosensitive prepolymer gives the material excellent physical properties such as thermal properties, strength, and elastic modulus, and the soft carbon skeleton allows the material to change shape and suitable tensile elongation by external force after heating. At the same time, the photosensitive prepolymer forms a specific segment structure based on the design of the raw materials for preparation, and there are two incompletely compatible phases in the segment: a stationary phase that maintains the shape of the molded product and a rubber phase; the stationary phase will restore the product to its original shape under the action of the recovery stress, thereby achieving shape memory.

[0009] Furthermore, the present invention introduces alicyclic diisocyanate and organic small molecule polyol as chain extenders to construct the hard segment. The two are compounded with each other. On the one hand, the photosensitive prepolymer and the photosensitive resin composition containing the same have excellent mechanical properties. On the other hand, compared with aromatic diisocyanates, the alicyclic structure has better stability and is not prone to yellowing. At the same time, it also avoids material degradation to produce aromatic diamine substances that are carcinogenic to the human body; at the same time, the introduction of the organic small molecule polyol chain extender allows the prepolymer molecules to form a dendritic segment structure, reducing the entanglement of the prepolymer molecular chain. Compared with straight-chain prepolymer molecules of the same molecular weight, the dendritic prepolymer has lower viscosity and reduces the use of diluent monomers; in addition, the introduction of the chain extender can regulate (improve) the shape memory response temperature of the photosensitive prepolymer.

[0010] In summary, the present invention improves the compatibility of the oligomeric polyol components through the design and mutual compounding and synergy of the preparation raw materials such as oligomeric diols, alicyclic diisocyanates, chain extenders, and hydroxyl-containing acrylic ester monomers, while retaining the flexibility characteristics of the oligomeric polyol chain segments, and having appropriate viscosity, and can prepare a photosensitive resin composition suitable for 3D printing. The obtained 3D printing material can be used as an oral support, has excellent mechanical properties, can increase the corrective force, and can change and restore the shape under temperature changes, providing excellent corrective effects, and has broad application prospects in oral and dental materials.

[0011] As a preferred technical solution of the present invention, the oligomeric polyol includes any one of hydroxyl-containing liquid rubber, alcohol-based double-terminated silicone oil, polyester polyol, and polyether polyol, or a combination of at least two thereof. Preferably, the number average molecular weight of the oligomeric polyol is 500-5000, for example, 800, 1000, 1200, 1500, 1800, 2000, 2200, 2500, 2800, 3000, 3200, 3500, 3800, 4000, 4200, 4500 or 4800, and the hydroxyl content is 0.4-4.0 mmol / g, for example, 0.6 mmol / g, 1.0 mmol / g, 1.5 mmol / g, 2.0 mmol / g, 2.5 mmol / g, 3.0 mmol / g, 3.5 mmol / g or 3.8 mmol / g, etc.

[0012] Further preferably, the hydroxyl-containing liquid rubber comprises any one of hydroxyl-terminated polybutadiene, hydroxyl-terminated polyisoprene, and hydroxyl-terminated butadiene-pentadiene rubber, or a combination of at least two thereof, and is obtained by polymerization of butadiene and / or isoprene through one or more addition modes of 1,2-addition, trans-1,4-addition, and cis-1,4-addition; the alcohol-based double-terminated silicone oil is preferably hydroxypropyl double-terminated polydimethylsiloxane; the polyester polyol is preferably polycaprolactone diol and polybutylene adipate; the polyether polyol is preferably polytetramethylene glycol and polypropylene glycol.

[0013] Preferably, the alicyclic diisocyanate includes any one of 1,4-cyclohexane diisocyanate, 1,3-diisocyanate-2-methylcyclohexane, 2,4-diisocyanate-1-methylcyclohexane, isophorone diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, or a combination of at least two thereof.

[0014] Preferably, the chain extender is any one of trimethylolpropane, triethylolpropane, pentaerythritol, polycaprolactone triol, tetraethylolmethane, trimethylolpropane, and pentaerythritol, or a combination of at least two thereof; or, the chain extender is a urea-based condensate of an alicyclic diisocyanate and two diethanolamine molecules, such as a urea-based condensate of isophorone diisocyanate (IPDI for short) and two diethanolamines.

[0015] Preferably, the hydroxyl-containing acrylate monomer is a mono(meth)acrylate of a polyether or polyester having a number average molecular weight of 200-800, and the number average molecular weight may be, for example, 300, 350, 400, 450, 500, 550, 600, 650, 700 or 750, and more preferably polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, polycaprolactone diol monoacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, polycaprolactone diol monomethacrylate.

[0016] As a preferred technical solution of the present invention, the total molar number of hydroxyl groups in the oligomeric polyol and the chain extender is n1, the molar number of NCO groups in the alicyclic diisocyanate is n2, and n1:n2=1:(1.1-3), for example, it can be 1:1.15, 1:1.2, 1:1.25, 1:1.3, 1:1.35, 1:1.4, 1:1.45, 1:1.5, 1:1.6, 1:1.7, 1:1.8, 1:1.9, 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.4, 1:2.5, 1:2.6, 1:2.7, 1:2.8 or 1:2.9, etc.

[0017] Preferably, the molar ratio of the oligomeric polyol to the chain extender is 1:(0.1-1), for example, it can be 1:0.1, 1:0.3, 1:0.5, 1:0.6, 1:0.8 or 1:1, etc.

[0018] Preferably, the number average molecular weight of the photosensitive prepolymer is 2000-20000, for example, 3000, 5000, 8000, 10000, 13000, 15000, 17000 or 18000.

[0019] In a second aspect, the present application provides a method for preparing the photosensitive prepolymer as described in the first aspect, the preparation method comprising:

[0020] The oligomeric polyol, alicyclic diisocyanate and chain extender are polymerized to obtain a polyurethane intermediate terminated with an NCO group; the polyurethane intermediate is terminated with a hydroxyl-containing acrylic ester monomer to obtain the photosensitive prepolymer.

[0021] Preferably, the oligomeric polyols, chain extenders and other components are dehydrated to prevent moisture from affecting the polymerization reaction.

[0022] Preferably, the polymerization reaction is carried out in the presence of a solvent.

[0023] In the preparation method of the photosensitive prepolymer of the present invention, as the polymerization reaction proceeds, the molecular weight of the product increases continuously and the viscosity increases. As the viscosity increases, the heat of reaction generated by the polymerization reaction is not easy to diffuse, resulting in a rapid increase in the system temperature, which accelerates the polymerization reaction, and will cause the oligomer to gel before reaching a sufficient molecular weight, and cannot be used as a material. Therefore, in the preparation process of the photosensitive prepolymer, in order to avoid the polyurethane intermediate from gelling before reaching a sufficient molecular weight, it is preferred to react in a solvent. The solvent does not participate in the reaction (the solvent must not have functional groups such as hydroxyl, amino, isocyanate, etc. that can react with carbamate), and is used to control the reaction rate of the material to prevent the viscosity from increasing rapidly and gelling due to the increase in molecular weight.

[0024] Preferably, the solvent may be a conventional organic solvent, such as any one of ketone solvents (such as acetone, butanone), ester solvents (such as ethyl acetate, butyl acetate), and aromatic solvents (such as toluene, xylene), or a combination of at least two thereof; however, such organic solvents need to be removed when preparing the photosensitive resin composition or the 3D printing material.

[0025] In order to facilitate the application of the photosensitive prepolymer and the preparation of the photosensitive resin composition, the solvent used in the polymerization reaction is preferably a diluent monomer, thereby avoiding the need for an additional step of removing the organic solvent before compounding the photosensitive resin composition.

[0026] Preferably, the diluent monomer includes a monofunctional monomer and / or a crosslinking monomer. For example, preferably, the monofunctional monomer includes acrylate and / or methacrylate, and more preferably, cyclotrimethylolpropane methyl acetal methacrylate, benzyl methacrylate, 2-tetrahydropyranyl methacrylate, menthyl methacrylate, acetone glycerol methacrylate, acryloyl morpholine, fenchyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 1-adamantane acrylate, 1-adamantane methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, any one or a combination of at least two of them; for example, preferably, the crosslinking monomer is an acrylate compound having at least two unsaturated double bonds in its molecular structure. The compound includes any one of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, propoxylated 1,6-hexanediol diacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trihydroxyethyl isocyanurate triacrylate, and trihydroxyethyl isocyanurate trimethacrylate, or a combination of at least two thereof.

[0027] Preferably, the amount of the solvent (diluting the monomer) used in the polymerization reaction is sufficient to regulate the reaction rate and control the photosensitive prepolymer product to have a suitable viscosity.

[0028] Preferably, the mass ratio of the oligomeric polyol to the solvent is 1:(0.2-5), for example, it can be 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.8, 1:2, 1:2.2, 1:2.5, 1:2.8, 1:3, 1:3.2, 1:3.5, 1:3.8, 1:4, 1:4.2, 1:4.5 or 1:4.8, etc.

[0029] Preferably, the viscosity of the photosensitive prepolymer (at room temperature / normal temperature) is 5000-50000 mPa·s.

[0030] In order to prevent the diluent monomer used as a solvent from being polymerized, the polymerization reaction is preferably carried out in the presence of a polymerization inhibitor.

[0031] Preferably, the inhibitor comprises a phenolic compound, illustratively including but not limited to: any one or a combination of at least two of hydroquinone, p-methoxyphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-p-methylphenol, vitamin E, tea polyphenols, tert-butyl-4-hydroxyanisole, and N,N'-bis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hydrazine (antioxidant 1024).

[0032] Preferably, based on the mass of the oligomeric polyol as 100%, the mass of the inhibitor is ≤2%, for example, it can be 0, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5% or 1.8%, etc., and more preferably 0-1%.

[0033] Preferably, the polymerization reaction is carried out in the presence of a catalyst.

[0034] Preferably, the catalyst includes any one of an amine catalyst, a tin catalyst, a titanium catalyst, a zinc catalyst, and a bismuth catalyst, or a combination of at least two of them.

[0035] Preferably, the amine catalyst includes any one of triethylamine, triethylenediamine, N-ethylmorpholine, triethylenediamine, N,N-dimethylcyclohexylamine, and pentamethyldiethylenetriamine, or a combination of at least two thereof.

[0036] Preferably, the tin-based catalyst includes any one of trimethyltin laurate, dibutyltin dilaurate, and stannous octoate, or a combination of at least two thereof.

[0037] Preferably, the titanium-based catalyst is a titanium-based organic metal salt, such as tetrabutyl titanate and / or tetraisopropyl titanate.

[0038] Preferably, the zinc-based catalyst is a zinc-based organic metal salt, such as any one of zinc octoate, zinc isooctanoate, and zinc 2-ethylhexanoate, or a combination of at least two thereof.

[0039] Preferably, the bismuth-based catalyst is a bismuth-based organic metal salt, such as bismuth isooctanoate and / or bismuth 2-ethylhexanoate.

[0040] As a preferred technical solution of the present invention, the catalyst is added to make the polymerization reaction proceed faster. Even without the catalyst, the polymerization reaction can proceed. From the perspective of the application safety of dental / oral materials, it is preferred not to add a catalyst.

[0041] Preferably, based on the mass of the oligomeric polyol as 100%, the mass of the catalyst is ≤2%, for example, it can be 0, 0.01%, 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.2%, 1.5% or 1.8%, etc., and more preferably 0-1%.

[0042] Preferably, the polymerization reaction temperature is 20-100°C, for example, it can be 30°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C, 58°C, 60°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 90°C or 95°C, etc.

[0043] In order to avoid the polymerization of the diluent monomer used as a solvent and to prevent the system from gelling, the polymerization temperature is preferably ≤ 60°C, more preferably 30-60°C.

[0044] Preferably, the polymerization reaction time is 1-8 h, for example, it can be 1.5 h, 2 h, 2.5 h, 3 h, 3.5 h, 4 h, 4.5 h, 5 h, 5.5 h, 6 h, 6.5 h, 7 h or 7.5 h, and more preferably 2-6 h.

[0045] In the present invention, the polyurethane intermediate can be prepared by a one-step method or a two-step method. Specifically, the one-step method comprises: putting oligomeric polyol, alicyclic diisocyanate and chain extender into a reaction device, and performing polymerization reaction in the presence of an optional solvent, an optional inhibitor and an optional catalyst to obtain the polyurethane intermediate. The two-step method comprises: putting oligomeric polyol and alicyclic diisocyanate into a reaction device, and performing a first stage reaction in the presence of an optional solvent, an optional inhibitor and an optional catalyst, and then adding a chain extender to perform a second stage reaction to obtain the polyurethane intermediate.

[0046] Preferably, the temperature of the end-capping reaction is 20-100°C, for example, it can be 30°C, 35°C, 38°C, 40°C, 42°C, 45°C, 48°C, 50°C, 52°C, 55°C, 58°C, 60°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C, 80°C, 90°C or 95°C, etc., more preferably 30-60°C.

[0047] Preferably, the end-capping reaction time is 0.5-12 h, for example, it can be 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h, 10 h or 11 h, and more preferably 1-8 h.

[0048] In addition, the polymerization reaction and the end-capping reaction are carried out under stirring conditions, and the stirring speeds of the polymerization reaction and the end-capping reaction are each independently 100-600 rpm, for example, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm, 500 rpm or 550 rpm, etc.

[0049] In a third aspect, the present application provides a photosensitive resin composition, which includes a combination of a photosensitive prepolymer and an initiator; the photosensitive prepolymer is the photosensitive prepolymer described in the first aspect, or the photosensitive prepolymer is a photosensitive prepolymer prepared by the preparation method described in the second aspect.

[0050] Preferably, the mass percentage of the photosensitive prepolymer in the photosensitive resin composition is 15%-65%, for example, it can be 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55% or 60%.

[0051] Preferably, the mass percentage of the initiator in the photosensitive resin composition is 0.5%-5%, for example, it can be 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%.

[0052] Preferably, the initiator is a free radical initiator.

[0053] Preferably, the initiator comprises a photoinitiator and optionally a thermal initiator.

[0054] Preferably, the mass percentage of the photoinitiator in the photosensitive resin composition is 0.5%-5%, for example, it can be 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%.

[0055] Preferably, the photoinitiator includes 2-hydroxy-2-methylpropiophenone (photoinitiator 184), 1-hydroxycyclohexyl phenyl ketone (photoinitiator 1173), methyl benzoylformate (photoinitiator MBF), benzoin dimethyl ether (photoinitiator 651), 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl-1-propanone (photoinitiator 2959), 4,4'-bis(diethylamino)benzophenone (photoinitiator EAB), difunctional ketone sulfone (photoinitiator 1001M), 2,4-diethylthiazolone (photoinitiator DETX) , 2-methyl-2-(4-morpholinyl)-1-(4-(methylthio)phenyl)-1-propanone (photoinitiator 907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (photoinitiator 369), ethyl 2,4,6-trimethylbenzoylphenylphosphonate (photoinitiator TPO-L), diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator TPO), phenyl bis (2,4,6-trimethylbenzoyl)phosphine oxide (photoinitiator 819), any one or a combination of at least two thereof.

[0056] Preferably, the thermal initiator includes any one of dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile, or a combination of at least two thereof.

[0057] Preferably, the photosensitive resin composition further comprises a diluent monomer, and the diluent monomer comprises a monofunctional monomer and / or a cross-linking monomer.

[0058] Preferably, the mass percentage of the diluent monomer in the photosensitive resin composition is 30%-80%, for example, it can be 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70% or 75%.

[0059] Preferably, the monofunctional monomer is preferably an acrylate and / or methacrylate whose homopolymer Tg is above 50°C, preferably 50-150°C, such as 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C or 140°C, and further preferably cyclotrimethylolpropane formal methacrylate, benzyl methacrylate, 2-tetrahydropyranyl methacrylate, menthyl methacrylate, acetone glycerol methacrylate, acryloyl morpholine, fenchyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 1-adamantane acrylate, 1-adamantane methacrylate, dicyclopentenyl acrylate, and any one or a combination of at least two of dicyclopentenyl methacrylate.

[0060] As a preferred technical solution of the present invention, the monofunctional monomer is more preferably cyclotrimethylolpropane methyl methacrylate, menthyl methacrylate, acetone glycerol methacrylate, dicyclopentenyl acrylate, acryloyl morpholine, etc., and a diluent monomer with low odor or no irritating odor is selected to avoid the strong irritating odor caused by the selection of diluent monomers such as isobornyl acrylate and / or isobornyl methacrylate, thereby improving the user experience of the photosensitive resin composition during the printing process.

[0061] Preferably, the cross-linking monomer is an acrylate compound containing at least two unsaturated double bonds in its molecular structure, including any one or a combination of at least two of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, propoxylated 1,6-hexanediol diacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trihydroxyethyl isocyanurate triacrylate, and trihydroxyethyl isocyanurate trimethacrylate.

[0062] Preferably, the photosensitive resin composition further comprises additives, and the additives include any one or a combination of at least two of a polymerization inhibitor, an ultraviolet absorber, a defoamer, a thickener, a leveling agent, and a stabilizer.

[0063] Preferably, the mass percentage of the additive in the photosensitive resin composition is ≤5%, for example, it can be 0, 0.1%, 0.2%, 0.5%, 0.6%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4% or 4.5%, etc.

[0064] Preferably, the inhibitor comprises a phenolic compound, and further preferably any one or a combination of at least two of hydroquinone, p-methoxyphenol, 6-tert-butyl-2,4-dimethylphenol, 2,6-di-tert-butyl-p-methylphenol, vitamin E, tea polyphenols, tert-butyl-4-hydroxyanisole, and N,N'-bis(β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hydrazine (antioxidant 1024).

[0065] In the present application, the ultraviolet absorber is not particularly limited, and any conventional ultraviolet absorber that can be used in a polymer system is applicable to the present invention.

[0066] Preferably, the ultraviolet absorber includes any one of UV-1, UV-O, UV-9, BP-6, BP-4, UV-531, UV-P, UVP-327, UV-328, UV-329, UV-360, UV-571, triazine-5, UV-1164, UV-1577, UV-627, and UV-1600, or a combination of at least two thereof.

[0067] In the present application, the defoamer, thickener, and leveling agent are not particularly limited, and conventional defoamers, thickeners, leveling agents, etc. that can be used in polymer systems are applicable to the present invention. Exemplarily, the defoamer includes an organosilicon defoamer; and / or, the thickener includes silicon dioxide (e.g., fumed silica); and / or, the leveling agent includes a polyether-modified polysiloxane leveling agent.

[0068] Preferably, the stabilizer includes any one of free tertiary amine, hindered amine, and organic phosphate, or a combination of at least two or three thereof, to stabilize the photosensitive resin composition. Exemplarily, the free tertiary amine includes diethylethanolamine and / or trihexylamine.

[0069] In the present application, the introduction of the additives (such as inhibitors, UV absorbers, defoamers, thickeners, leveling agents, stabilizers) can improve the thermal stability, oxidation stability, storage stability, surface properties, flow properties and processing properties of the photosensitive resin composition.

[0070] In addition, the photosensitive resin composition may further include other additives that may be added by those skilled in the art, such as any one of a pigment, a filler, and an organic solvent, or a combination of at least two of them.

[0071] In the present application, the photosensitive resin composition is in a liquid state and can be cured by light exposure; the light exposure includes UV (ultraviolet) light exposure, but it is not limited to UV light and can also be applied to other light exposures. The photosensitive resin composition is in a liquid state before light exposure and initiates a curing cross-linking reaction under light exposure to form a polymer system with a network structure.

[0072] In the present invention, the preparation method of the photosensitive resin composition comprises: uniformly mixing a photosensitive prepolymer, an initiator, a diluent monomer, an optional cross-linking monomer and an optional additive to obtain the photosensitive resin composition.

[0073] In a fourth aspect, the present application provides an application of the photosensitive resin composition as described in the third aspect in biomedical materials.

[0074] Preferably, the photosensitive resin composition is applied to oral materials.

[0075] On the other hand, the present application provides a 3D printing material, the raw materials for preparing the 3D printing material include the photosensitive resin composition as described in the third aspect.

[0076] In this application, the term "3D printing" refers to the process of using 3D digital data to create a three-dimensional object by layering materials. In this specification, 3D printing technology is mainly described as digital light processing (DLP), stereolithography equipment (SLA) and PolyJet technology, but it is understood that it also includes other 3D printing technologies.

[0077] Preferably, the method for preparing the 3D printing material comprises: placing the photosensitive resin composition in a 3D printer for 3D printing to obtain the 3D printing material.

[0078] Preferably, the 3D printing further includes a secondary curing step.

[0079] Preferably, the secondary curing is performed under conditions of light (eg UV light) and / or heating.

[0080] Preferably, the heating temperature is 40-100°C, for example, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C or 95°C, etc., more preferably 50-80°C.

[0081] Preferably, the secondary curing time is 5-30 min, for example, it can be 6 min, 8 min, 10 min, 12 min, 15 min, 18 min, 20 min, 22 min, 25 min or 28 min.

[0082] In a fifth aspect, the present application provides an oral support, wherein the raw materials for preparing the oral support include the photosensitive resin composition as described in the third aspect.

[0083] Preferably, the cured product of the photosensitive resin composition and the 3D printing material (oral support) have excellent mechanical properties, and the right-angle tear strength thereof is ≥160 kN / m, and may be 160-200 kN / m; the yield strength is ≥25 MPa, and may be 25-35 MPa; the tensile elastic modulus is ≥800 MPa, and may be 800-1200 MPa; and the elongation at break is ≥50%, and may be 50-80%.

[0084] Preferably, the oral support comprises any one of an artificial tooth, a transparent orthodontic device, a surgical guide, and a splint.

[0085] In the present application, the photosensitive resin composition can be used to prepare oral supports through 3D printing technology, and can output transparent orthodontic devices that conform to the patient's oral structure style, such as orthodontic braces, orthodontic retainers, dental arch expanders, etc., which have excellent mechanical properties, can improve the correction force, and can change and restore the shape when heated, thereby improving the user's comfort. At the same time, a variety of customized dental products (such as artificial teeth, surgical guides, and splints) can also be provided.

[0086] Specifically, the photosensitive resin composition can be used to print a transparent orthodontic device customized according to the patient's oral structure, which can increase the correction force. At a higher temperature (50-100°C, such as immersed in warm water or boiling water), the transparent orthodontic device is easily deformed after being subjected to force, and the shape automatically returns to its original state after the external force is removed; but when the transparent orthodontic device immersed in warm water or boiling water and deformed by force is placed in the oral environment for use, due to the change in body temperature (body temperature is lower than the temperature at which it can be deformed), its shape is fixed and can exert a correction force. Further, because it has plasticity under the condition of 50-100°C, that is, under the condition of 50-60°C hot water (the temperature that the oral cavity can withstand), the transparent orthodontic device can be shaped and easy to remove; such as in warm boiled water, the external force is removed, and the shape returns to the original printed shape; such as the deformed resin is kept under external force and cooled to room temperature, the shape remains unchanged in the stressed shape, and has shape memory characteristics. After the transparent orthodontic device is cleaned with warm water and placed in the mouth, the temperature of the device gradually drops to body temperature. During this process, the device spontaneously returns to its original shape (3D printed shape suitable for orthodontics). After it is completely fixed, it gradually exerts its orthodontic effect.

[0087] Compared with the prior art, the present invention has the following beneficial effects:

[0088] (1) In the photosensitive prepolymer provided in the present application, the compatibility of oligomeric polyol components with poor compatibility (such as hydroxyl-containing liquid rubber and polydimethoxysiloxane) is improved by designing and compounding the raw materials for preparing the oligomeric polyol, alicyclic diisocyanate, chain extender, hydroxyl-containing acrylic ester monomer, etc., while retaining the flexibility characteristics of such oligomeric polyol chain segments, and having appropriate viscosity, and being able to prepare a photosensitive resin composition suitable for 3D printing. The obtained 3D printing material can be used as an oral support, has excellent mechanical properties, can increase the corrective force, and can change and restore the shape under temperature changes, providing an excellent corrective effect.

[0089] (2) The photosensitive resin composition provided in this application can be cured and molded using 3D printing technology to output orthodontic products that conform to the oral structure style, so that the right-angle tear strength of the product is ≥160kN / m, the yield strength is ≥25MPa, the tensile elastic modulus is ≥800MPa, and the elongation at break is ≥50%. It has excellent mechanical properties, increases the correction force, and has thermal shape memory characteristics to improve the user's comfort. The photosensitive prepolymer and photosensitive resin composition provided in this application can provide a variety of customized dental products and have broad application prospects. DETAILED DESCRIPTION

[0090] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0091] In the following specific embodiments of the present invention, the materials, reagents, etc. used can all be conventional commercially available raw materials obtained from commercial channels. Among them, the material information of the oligomeric polyol is as follows:

[0092] Hydroxyl-terminated polybutadiene: number average molecular weight 1350, hydroxyl value 1.61-2.00mmol / g, brand HTPB HF-III, purchased from Tianyuan Aerospace Materials;

[0093] Hydroxypropyl di-terminated silicone oil: number average molecular weight 2000, hydroxyl value 56 mg KOH / g, brand TEGO PROTECT 5001, purchased from Evonik Degussa;

[0094] Polycaprolactone diol: number average molecular weight of 1000, hydroxyl value of 107-117 mg KOH / g, brand PCL210N, purchased from Daicel Japan;

[0095] Polytetrahydrofuran diol: number average molecular weight of 2000, hydroxyl value of 54.7-57.5 mg KOH / g, brand PTMG2000, purchased from Hyosung, South Korea;

[0096] Polypropylene glycol: number average molecular weight of 600, hydroxyl value of 170-208 mg KOH / g, brand PPG-600, purchased from Shandong Dongda Chemical;

[0097] Polybutylene adipate: number average molecular weight of 5000, hydroxyl value of 20-24 mg KOH / g, brand T-5044, purchased from Huada Chemical;

[0098] Example 1

[0099] A photosensitive prepolymer, the preparation raw materials include terminal hydroxyl polybutadiene, alicyclic diisocyanate (isophorone diisocyanate, IPDI), a chain extender (pentaerythritol) and a hydroxyl-containing acrylic ester monomer (polycaprolactone diol monoacrylate), the molar ratio of the terminal hydroxyl polybutadiene, isophorone diisocyanate, pentaerythritol and polycaprolactone diol monoacrylate is 1:2:0.25:1; the specific preparation method includes the following steps:

[0100] (1) After nitrogen replacement of the reaction apparatus, hydroxyl-terminated polybutadiene and chain extender were added according to the above molar ratio, and solvent (polypropylene glycol diacrylate, PPG400DA) and polymerization inhibitor (p-methoxyphenol) were added at the same time, so that the mass ratio of hydroxyl-terminated polybutadiene, solvent and polymerization inhibitor was 1:1:0.003, and the above materials were mixed and dispersed uniformly under stirring conditions, and vacuum dehydrated for 1 hour;

[0101] (2) adding alicyclic diisocyanate to the reaction system of step (1), heating to 45° C. with stirring at 300 rpm, adding a catalyst (dibutyltin dilaurate, the mass ratio of which to terminal hydroxyl polybutadiene is 0.003:1), reacting for 4 h, and obtaining a polyurethane intermediate terminated with an NCO group;

[0102] (3) maintaining the temperature and stirring rate of step (2) unchanged, adding a hydroxyl-containing acrylic ester monomer to carry out a capping reaction, cooling to 25° C. after 6 hours, discharging the material, and obtaining the photosensitive prepolymer.

[0103] Examples 2-7, Comparative Examples 1-5

[0104] A photosensitive prepolymer, which differs from Example 1 only in that the raw materials for preparation are different, as shown in Table 1; in Table 1, "molar ratio" represents the molar ratio of oligomeric polyol, alicyclic diisocyanate, chain extender and hydroxyl-containing acrylate monomer; in Table 1, the usage ratio of catalyst, inhibitor and solvent is the same as that in Example 1; the preparation method is the same as that in Example 1.

[0105] Table 1

[0106]

[0107]

[0108] The number average molecular weight of the photosensitive prepolymers provided in the above embodiments and comparative examples was tested by gel chromatography (GPC) with tetrahydrofuran as the mobile phase. The rotational viscosity of the photosensitive prepolymer (containing solvent) was tested according to the method in standard GB / T 22235. The obtained data are shown in Table 2.

[0109] Table 2

[0110] project Photosensitive prepolymer number Number average molecular weight Viscosity (mPa·s) Example 1 A1 9600 10000 Example 2 A2 8000 15000 Example 3 A3 16000 40000 Example 4 A4 19000 45000 Example 5 A5 12000 32000 Example 6 A6 18000 38000 Example 7 A7 17000 48000 Comparative Example 1 D1 12000 320000 Comparative Example 2 D2 12000 11000 Comparative Example 3 D3 8000 90000 Comparative Example 4 D4 6000 6000 Comparative Example 5 D5 10000 260000

[0111] The photosensitive resin composition and 3D printing material of the present invention will be described in detail below using multiple application examples.

[0112] Application Example 1-7, Comparison Application Example 1-5

[0113] A photosensitive resin composition, the types and amounts of each component are shown in Table 3 below; the photosensitive resin composition is used to prepare a 3D printing material, and the method includes:

[0114] Mix the components evenly according to the formula shown in Table 3 to obtain the photosensitive resin composition; pour the photosensitive resin composition into the resin tank of the 3D printer (model CPD-100, light source wavelength 405nm), set the layer thickness to 0.1mm, and the exposure time of each layer to 8s. After printing, place it in an ultrasonic cleaner, clean the uncured resin on the surface with anhydrous ethanol, and blow dry the residual ethanol with a high-pressure air gun, and then place the printed model in a UV curing light box for secondary curing. The temperature in the UV curing light box is 80°C, and the secondary curing time is 15min. The 3D printing material is obtained as a test sample for subsequent performance testing.

[0115] Table 3

[0116]

[0117]

[0118] The following performance tests were performed on the aforementioned 3D printing materials:

[0119] (1) Right-angle tear strength: tested according to the method in standard GB / T 529;

[0120] (2) Yield strength, tensile modulus strength and elongation at break: tested according to the method in standard ASTM D638;

[0121] (3) Shape memory performance: The shape of the transparent orthodontic appliance is formed by a computer program, and the corresponding transparent orthodontic appliance is printed using a 3D printer. In order to confirm its shape memory properties, thermal deformation and shape recovery experiments were carried out. Specifically, the sample to be tested was immersed in 80°C water, and then an external force was applied to change the shape to determine whether the deformation was fixed at 37°C. The deformed shape was then immersed in 60°C water to determine whether it could be restored to its original shape. If deformation, fixation and recovery can be achieved, it means that the shape memory property is present.

[0122] The test results are shown in Table 4:

[0123] Table 4

[0124]

[0125] According to the above performance test results, the photosensitive prepolymer provided by the present invention is used to prepare a photosensitive resin composition, which can meet the requirements of 3D printing and obtain a 3D printing material with excellent mechanical properties, wherein the right-angle tear strength is ≥160kN / m, the yield strength is ≥25MPa, the tensile elastic modulus is ≥800MPa, and the elongation at break is ≥50%; the excellent mechanical properties exhibited by the 3D printing material enable it to fully meet the performance requirements of dental / oral products such as transparent orthodontic devices and increase the correction force.

[0126] Furthermore, the 3D printed material (transparent orthodontic appliance) sample can change its shape when an external force is applied at a temperature of 50-100°C, and can be fixed in the deformed shape in cold water; the shape can be restored when immersed in an environment of 50-100°C again, thereby exhibiting shape memory characteristics; the photosensitive resin composition can be used to 3D print a transparent orthodontic appliance through DLP, and the orthodontic device can be attached to the surface of the patient's teeth during treatment to exert an orthodontic retention effect.

[0127] The photosensitive resin composition prepared using the photosensitive resin D1 of Comparative Example 1 exhibits shape memory characteristics under the set conditions, but the viscosity of D1 is too large. In order to facilitate 3D printing, too much dilution monomer is introduced into the composition, which reduces the mechanical properties of the material. The photosensitive resin composition prepared using the photosensitive resin D2 of Comparative Example 2 also exhibits shape memory characteristics and similar mechanical properties under the set conditions, but the introduction of aromatic isocyanates such as MDI makes the material prone to produce carcinogenic substances such as aromatic amines during degradation, and it is not recommended for use in oral materials. The photosensitive resin composition prepared using the photosensitive resin D3 of Comparative Example 3 has poor compatibility, and the printed material is whitish and has poor transparency, which affects the appearance of orthodontic materials. The photosensitive resin compositions prepared using the photosensitive resin D4 of Comparative Example 4 and the photosensitive resin D5 of Comparative Example 5 cannot have shape memory under the set conditions, and their mechanical properties are relatively poor, which cannot meet the basic performance requirements of orthodontic materials.

[0128] The present invention illustrates the detailed process equipment and process flow of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed process equipment and process flow, that is, it does not mean that the present invention must rely on the above-mentioned detailed process equipment and process flow to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A photosensitive prepolymer, characterized in that: The raw materials for preparing the photosensitive prepolymer include a combination of oligomeric polyols, alicyclic diisocyanates, chain extenders and hydroxyl-containing acrylic ester monomers; the chain extender is an organic substance with a molecular weight of less than 800 and containing 3 or more primary hydroxyl groups.

2. The photosensitive prepolymer according to claim 1, characterized in that: The oligomeric polyol comprises any one or a combination of at least two of hydroxyl-containing liquid rubber, alcohol-based double-terminated silicone oil, polyester polyol, and polyether polyol. Preferably, the number average molecular weight of the oligomeric polyol is 500-5000, and the hydroxyl content is 0.4-4.0 mmol / g; Preferably, the alicyclic diisocyanate includes any one of 1,4-cyclohexane diisocyanate, 1,3-diisocyanate-2-methylcyclohexane, 2,4-diisocyanate-1-methylcyclohexane, isophorone diisocyanate, 1,4-cyclohexane dimethyl diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, or a combination of at least two thereof; Preferably, the chain extender is any one of trimethylolpropane, triethylolpropane, pentaerythritol, polycaprolactone triol, tetraethylolmethane, trimethylolpropane, and pentaerythritol, or a combination of at least two thereof; or, the chain extender is a urea condensate of alicyclic diisocyanate and two diethanolamine molecules; Preferably, the hydroxyl-containing acrylate monomer is a monoacrylate and / or monomethacrylate of a polyether or polyester with a number average molecular weight of 200-800, preferably polypropylene glycol monoacrylate, polybutylene glycol monoacrylate, polycaprolactone diol monoacrylate, polypropylene glycol monomethacrylate, polybutylene glycol monomethacrylate, polycaprolactone diol monomethacrylate.

3. The photosensitive prepolymer according to claim 1 or 2, characterized in that: The total number of moles of hydroxyl groups in the oligomeric polyol and the chain extender is n1, the number of moles of NCO groups in the alicyclic diisocyanate is n2, and n1:n2=1:(1.1-3); Preferably, the molar ratio of the oligomeric polyol to the chain extender is 1:(0.1-1); Preferably, the number average molecular weight of the photosensitive prepolymer is 2000-20000.

4. A method for preparing a photosensitive prepolymer according to any one of claims 1 to 3, characterized in that: The preparation method comprises: The oligomeric polyol, alicyclic diisocyanate and chain extender are polymerized to obtain a polyurethane intermediate terminated with an NCO group; the polyurethane intermediate is terminated with a hydroxyl-containing acrylic ester monomer to obtain the photosensitive prepolymer.

5. The preparation method according to claim 4, characterized in that: The polymerization reaction is carried out in the presence of a solvent; Preferably, the polymerization reaction is carried out in the presence of a catalyst; Preferably, the catalyst comprises any one or a combination of at least two of an amine catalyst, a tin catalyst, a titanium catalyst, a zinc catalyst, and a bismuth catalyst; Preferably, the polymerization reaction temperature is 20-100°C, more preferably 30-60°C; Preferably, the polymerization reaction time is 1-8h, more preferably 2-6h; Preferably, the temperature of the end-capping reaction is 20-100°C, more preferably 30-60°C; Preferably, the end-capping reaction time is 0.5-12 h, more preferably 1-8 h.

6. A photosensitive resin composition, characterized in that: The photosensitive resin composition comprises a combination of a photosensitive prepolymer and an initiator; the photosensitive prepolymer is the photosensitive prepolymer described in any one of claims 1 to 3, or the photosensitive prepolymer is a photosensitive prepolymer prepared by the preparation method described in claim 4 or 5.

7. The photosensitive resin composition according to claim 6, characterized in that: The mass percentage of the photosensitive prepolymer in the photosensitive resin composition is 15%-65%; Preferably, the mass percentage of the initiator in the photosensitive resin composition is 0.5%-5%; Preferably, the initiator comprises a photoinitiator and optionally a thermal initiator; Preferably, the photoinitiator includes any one of 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, methyl benzoylformate, benzoin dimethyl ether, 2-hydroxy-2-methyl-p-hydroxyethyl ether phenyl-1-propanone, 4,4'-bis(diethylamino)benzophenone, difunctional ketone sulfone, 2,4-diethylthiazolone, 2-methyl-2-(4-morpholinyl)-1-(4-(methylthio)phenyl)-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone, ethyl 2,4,6-trimethylbenzoylphenylphosphonate, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, or a combination of at least two thereof; Preferably, the thermal initiator includes any one of dicumyl peroxide, benzoyl peroxide, and azobisisobutyronitrile, or a combination of at least two thereof.

8. The photosensitive resin composition according to claim 6 or 7, characterized in that: The photosensitive resin composition further includes a diluent monomer, and the diluent monomer includes a monofunctional monomer and / or a cross-linking monomer; Preferably, the mass percentage of the diluent monomer in the photosensitive resin composition is 30%-80%; Preferably, the monofunctional monomer is preferably an acrylate and / or methacrylate whose homopolymer Tg is above 50°C, and further preferably any one or a combination of at least two of cyclotrimethylolpropane methylal methacrylate, benzyl methacrylate, 2-tetrahydropyranyl methacrylate, menthyl methacrylate, acetone glycerol methacrylate, acryloyl morpholine, fenchyl acrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 4-tert-butylcyclohexyl acrylate, 4-tert-butylcyclohexyl methacrylate, 1-adamantane acrylate, 1-adamantane methacrylate, dicyclopentenyl acrylate, and dicyclopentenyl methacrylate; Preferably, the cross-linking monomer includes any one of triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, polyethylene glycol diacrylate, polypropylene glycol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, propoxylated 1,6-hexanediol diacrylate, 1,10-decanediol dimethacrylate, tricyclodecane dimethanol diacrylate, tricyclodecane dimethanol dimethacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, ethoxylated trimethylolpropane triacrylate, ditrimethylolpropane tetraacrylate, trihydroxyethyl isocyanurate triacrylate, and trihydroxyethyl isocyanurate trimethacrylate, or a combination of at least two thereof; Preferably, the photosensitive resin composition further comprises an additive, wherein the additive comprises any one or a combination of at least two of an inhibitor, an ultraviolet absorber, a defoamer, a thickener, a leveling agent, and a stabilizer; Preferably, the mass percentage of the additive in the photosensitive resin composition is ≤5%.

9. Use of the photosensitive resin composition according to any one of claims 6 to 8 in biomedical materials; Preferably, the photosensitive resin composition is applied to oral materials.

10. An oral support, characterized in that: The raw material for preparing the oral support comprises the photosensitive resin composition according to any one of claims 6 to 8; Preferably, the oral support comprises any one of an artificial tooth, a transparent orthodontic device, a surgical guide, and a splint.

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