3D printing anti-caries dental appliance and method thereof

Abstract

The invention provides a 3D printing anti-caries dental appliance and a method thereof, and belongs to the field of oral medical treatment, and the method specifically comprises the following steps: S1, combining fluoride ions with crown ether as a carrier through a chemical reaction in a polar aprotic solvent to form a stable subject-object compound; s2, the subject-object compound is purified, and the purified subject-object compound is verified; s3, the checked subject-object compound is mixed with a 3D printing base material, and a 3D printing raw material is obtained; s4, according to design parameters, the raw materials are subjected to 3D printing to manufacture the anti-caries dental appliance. By means of the treatment scheme, the anti-caries component is evenly dispersed in the 3D printing base material, and fluorine ions can be effectively and continuously released in the oral cavity environment for a long time.

Description

Technical Field

[0001] The present invention relates to oral medical treatment, and in particular to a 3D printed caries-preventing dental appliance and a method thereof. Background Art

[0002] Caries prevention is an important topic in the field of oral health. Caries is caused by the acidic substances produced by the metabolism of oral bacteria, which erode the tooth surface. For people who wear braces, although they can effectively improve tooth alignment and bite problems, they may also become a breeding ground for food residues and bacteria during use, thereby increasing the risk of caries. Therefore, the need for caries prevention is more urgent. Effective caries prevention measures are essential to maintaining oral health and ensuring the smooth progress of the correction process.

[0003] In 3D printing technology, how to achieve uniform dispersion of anti-caries ingredients such as fluoride ions in oral appliance materials is a technical challenge. This type of challenge mainly comes from the physical properties of powdered ingredients such as fluoride ions. They tend to aggregate and settle when mixed with 3D printing substrates, similar to the uniform dispersion of salt in water, while sugar has a slightly poorer dispersion and milk is more likely to settle. Fluoride ions also have similar dispersion uniformity problems in the substrate. Even if they can be initially uniformly dispersed in the substrate, the re-aggregation of fluoride ions during processing will lead to uneven anti-caries ingredients in the finished product. Uneven dispersion will lead to inconsistency of effective ingredients in the finished product, affecting the anti-caries effect. In addition, the aggregation of fluoride ions may also cause equipment clogging and uneven product surface during the 3D printing process, reducing product quality. Continuously stirring the substrate to redisperse fluoride ions may introduce bubbles, further affecting the structural integrity and aesthetics of the product. These challenges require the development of new material formulations and process technologies to ensure the effective and uniform distribution of anti-caries ingredients in 3D printed oral appliances.

[0004] In addition, during the manufacturing and use of braces, how to ensure that fluoride ions can be stored in a non-released state and then effectively released during the approximately 2-week wearing period is also an important but challenging task. This requires the development of special packaging technology or materials that can stably encapsulate fluoride ions during the manufacturing and storage of braces to prevent their premature release, while ensuring that fluoride ions can be continuously released at a controlled rate during wearing to achieve an anti-caries effect. At present, there is no effective means to solve this difficulty. Summary of the invention

[0005] Therefore, in order to overcome the shortcomings of the above-mentioned prior art, the present invention provides a 3D printed anti-caries dental appliance in which an anti-caries component is uniformly dispersed in a 3D printed base material and can effectively and continuously release fluoride ions for a long time in an oral environment, as well as a method for 3D printing an anti-caries dental appliance.

[0006] In order to achieve the above-mentioned object, the present invention provides a method for 3D printing an anti-caries dental appliance, comprising: S1, combining fluoride anions in fluoride with a crown ether as a carrier by chemical reaction in a polar aprotic solvent to form a stable host-guest complex; the solubility of the fluoride and the crown ether in the solvent is greater than 10 g / L; S2, purifying the host-guest complex and verifying the purified host-guest complex; S3, mixing the verified host-guest complex with a 3D printing substrate to obtain a raw material for 3D printing; S4, according to design parameters, 3D printing the raw material to manufacture an anti-caries dental appliance, and the viscosity range of the raw material at a printing temperature of 20°C is 200-1000 mPa·s.

[0007] In one embodiment, the fluoride is tetrabutylammonium fluoride.

[0008] In one embodiment, the crown ether is any one of the crown ethers of 15-crown-5 ether, 12-crown-4 ether and 18-crown-6 ether.

[0009] In one embodiment, the weight of the host-guest complex is 0.1% to 1% of the weight of the 3D printing substrate.

[0010] In one embodiment, the fluoride ion and the crown ether are mixed and reacted in a closed environment of ozone to generate a host-guest complex, the reaction temperature is 13° C. to 15° C., and the reaction time is 15 to 18 hours.

[0011] In one embodiment, the solvent is at least one of dimethyl sulfoxide and N,N-dimethylformamide.

[0012] In one embodiment, the 3D printing substrate comprises 55-75 weight percent of urethane (meth) acrylate, 15-25 weight percent of vinyl ester, 5-15 weight percent of di(meth)acrylate, and less than 5 weight percent of photoinitiator.

[0013] In one embodiment, the 3D printing substrate comprises 20 to 80 weight percent of methacrylate, 10 to 35 weight percent of reactive vinyl unsaturated groups, and less than 5 weight percent of a photoinitiator.

[0014] In one of the embodiments, the step further includes S5, post-processing the anti-caries dental appliance, wherein the post-processing comprises at least one of photocuring and heat treatment.

[0015] A 3D printed caries-preventing dental appliance, wherein the 3D printed caries-preventing dental appliance is printed by the above-mentioned method.

[0016] Compared with the prior art, the advantages of the present invention are: the specific interaction between crown ethers and fluoride ions is determined by using supramolecular chemistry principles and host-guest interaction screening, so as to achieve successful encapsulation of fluoride ions in polar aprotic solvents, and the generated host-guest complex has extremely high stability during the manufacturing process and the storage process, and can slowly release fluoride ions in the oral wearing environment (37°C water bath), providing a continuous oral protection effect, thereby achieving the encapsulation and controlled release of fluoride ions in the orthodontic material. BRIEF DESCRIPTION OF THE DRAWINGS

[0017] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0018] Figure 1 The process steps of the method for 3D printing an anti-caries dental appliance in an embodiment of the present invention;

[0019] Figure 2 whether the preparation steps of the 3D printed anti-caries dental appliance in the embodiments of the present invention are carried out in an ozone-enclosed environment, and the effect on the fluorine content during the storage of the product; and

[0020] Figure 3 1 is the fluoride ion release curve of the anti-caries dental appliance under different environments in the embodiment of the present invention. DETAILED DESCRIPTION

[0021] The embodiments of the present application are described in detail below with reference to the accompanying drawings.

[0022] The following describes the implementation methods of the present application through specific examples, and those skilled in the art can easily understand other advantages and effects of the present application from the contents disclosed in this specification. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. The present application can also be implemented or applied through other different specific implementation methods, and the details in this specification can also be modified or changed in various ways based on different viewpoints and applications without departing from the spirit of the present application. It should be noted that, in the absence of conflict, the following embodiments and the features in the embodiments can be combined with each other. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in the field without making creative work belong to the scope of protection of the present application.

[0023] It should be noted that various aspects of the embodiments within the scope of protection of the present invention are described below. It should be apparent that the aspects described herein can be embodied in a wide variety of forms, and any specific structure and / or function described herein is merely illustrative. Based on the present application, it should be understood by those skilled in the art that an aspect described herein can be implemented independently of any other aspect, and two or more of these aspects can be combined in various ways. For example, any number and aspect described herein can be used to implement the device and / or practice the method. In addition, other structures and / or functionalities other than one or more of the aspects described herein can be used to implement this device and / or practice this method.

[0024] It should also be noted that the illustrations provided in the following embodiments are only schematic illustrations of the basic concept of the present application. The drawings only show components related to the present application rather than being drawn according to the number, shape and size of components in actual implementation. In actual implementation, the type, quantity and proportion of each component may be changed arbitrarily, and the component layout may also be more complicated.

[0025] Additionally, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects described may be practiced without these specific details.

[0026] In chemistry, there is a special class of compounds designed to specifically bind to particular guest molecules or ions through molecular recognition. Such compounds are called host molecules. When they bind to specific guests (such as fluoride ions), they can form stable host-guest complexes. This blocking can be based on different interaction mechanisms, such as hydrogen bonding, electrostatic interactions, or hydrophobic interactions. This type of research has a wide range of applications in the fields of chemical sensing, ion transport, drug delivery, and molecular switches.

[0027] A well-known example of this type of "supramolecular compound" is a supramolecular host molecule based on cyclodextrin or similar structures, which can specifically bind and block small molecules or ions through molecular recognition. However, in general, they are usually used to block larger organic molecules, and their affinity for metal ions and certain small molecules is relatively low.

[0028] This application utilizes the chemical properties of crown ethers as "supramolecular compounds" and uses them to seal fluoride ions. The resulting host-guest complex has extremely high stability during the manufacturing process and storage process. At the same time, it can slowly release fluoride ions in the intraoral wearing environment (37°C water bath), providing a continuous oral protection effect, thereby achieving the sealing and controlled release of fluoride ions in the orthodontic material.

[0029] like Figure 1As shown, the embodiment of the present application provides a method for 3D printing an anti-caries dental appliance, comprising:

[0030] S1, combining the fluoride anion in the fluoride with the crown ether as a carrier through a chemical reaction in a polar aprotic solvent to form a stable host-guest complex; the solubility of the fluoride and the crown ether in the solvent is greater than 10g / L.

[0031] Polar aprotic solvents have the advantages of good solubility for fluoride anions of fluoride and being chemically inert (not reacting with reactants or products); they also have good solubility for crown ethers; and they are easy to operate (such as low volatility and low recovery difficulty). The screening criteria for polar aprotic solvents are that the dielectric constant is greater than 30 and the dipole moment is greater than 3.5 Debye.

[0032] Crown ethers are a class of ring-shaped molecules containing multiple oxygen atoms, which can form coordination bonds with positively charged metal ions or other small molecules through the lone pair of electrons on the oxygen atoms. When applied to fluoride ions, this interaction can allow the crown ether to "enclose" or "wrap" the fluoride ions in its ring structure, which can have a high affinity for it. For example, crown ether compounds with a specific cavity size can specifically bind and enclose fluoride ions through electrostatic interactions and hydrogen bonding with fluoride ions.

[0033] In the process of applying crown ethers to block fluoride ions, the crown ether selected should match the size and shape of the fluoride ions to ensure maximum blocking efficiency and stability of the complex under manufacturing and storage conditions.

[0034] Fluoride ions are anions formed when fluoride is dissolved in a solvent. Under normal conditions, their decomposition temperature is >300°C (the maximum printing temperature is generally between 50°C and 250°C), and they are less sensitive to light for 3D printing.

[0035] The diameter of the crown ether cavity needs to be moderate, which can accommodate fluoride ions and form sufficient interaction force with them to achieve effective sealing. For example, when the diameter of the fluoride ion is about (angstroms), the diameter of all crown ether cavities must be larger than the diameter of the fluoride ion. For example, the diameter of the crown ether cavity can be selected to be Then determine the corresponding crown ether component.

[0036] Fluoride ions are combined with crown ethers as carriers through chemical reactions in polar aprotic solvents to form stable host-guest complexes. The coordination ratio of fluoride ions to crown ethers is generally 1:1.

[0037] The mechanism of the coordination reaction is taken as an example of the crown ether of fluoride ion and 15-crown-5 ether, as follows:

[0038] The crown ether structure diagram of 15-crown-5 ether is drawn as follows

[0039] Each vertex in the ring represents a carbon atom, and each "O" in the ring represents an oxygen atom. The crown ether of 15-crown-5 ether has 5 oxygen atoms and a 15-membered ring.

[0040] In 15-crown-5 and fluoride anion (F - ) in the coordination process, all five oxygen atoms in the ring participate in the coordination. These oxygen atoms interact with F through their lone pair electrons. - Forming coordination bonds to stabilize F - .

[0041]

[0042] The coordination process is as follows:

[0043] 1. Oxygen atoms involved in coordination: All five oxygen atoms of 15-crown-5 participate in the coordination with the fluoride anion, forming coordination bonds with the fluoride anion through lone pairs of electrons, and wrapping the fluoride anion in the center of the ring;

[0044] 2. Changes in solvent environment: Tetrabutylammonium fluoride (TBAF) loses fluoride ions (F - ) to form tetrabutylammonium cation. Dimethyl sulfoxide (DMSO) or N,N-dimethylformamide, as a polar aprotic solvent, can dissolve many ionic compounds, but it does not directly react chemically with tetrabutylammonium cation. Tetrabutylammonium cation can exist stably as part of the solvent environment without changing its own structure.

[0045] 3. Changes in the structure of fluorine compounds: The original coordination relationship between oxygen atoms and carbon atoms remains unchanged, and 15-crown-5 maintains its ring structure. However, the fluoride anion is small in size and negatively charged, and can be well wrapped and stabilized by the crown ether ring structure, and the overall structure remains relatively stable. - )After the coordination is completed, the formed compound is generally a neutral compound.

[0046] Coordination reaction conditions:

[0047] Acidity and alkalinity: The reaction is carried out under neutral or weakly alkaline conditions to avoid protonation or neutralization of crown ethers or fluoride ions. The solvents DMSO or DMF are neutral themselves and can also provide a suitable environment.

[0048] Reaction temperature: usually below room temperature (10-25°C) or slightly higher temperature (25-50°C). High temperature can accelerate the coordination process, but excessive temperature should be avoided to prevent decomposition.

[0049] Anhydrous conditions: The reaction should be carried out under anhydrous conditions to avoid moisture affecting the activity and coordination process of fluoride ions.

[0050] The electrical properties of crown ethers mainly refer to their affinity for specific ions, which is related to the electronegativity of heteroatoms (such as oxygen) in the crown ether molecule. Fluoride ions, as highly electronegative anions, can form strong hydrogen bonds and electrostatic interactions with highly electronegative oxygen atoms. Therefore, crown ethers should contain multiple oxygen atoms to effectively bind to fluoride ions.

[0051] Reaction temperature: Too high a temperature may lead to overreaction of the solvent or reactants, especially in the presence of ozone, the reactivity of ozone may increase with increasing temperature. A reasonable temperature should be between 13°C and 15°C. Lower temperatures help control the reaction rate and avoid potential side reactions.

[0052] Reaction time: Avoid incomplete reaction or overreaction. A reasonable reaction time can be 15-18 hours.

[0053] Reaction concentration: The concentration of reactants depends on the solubility of the solvent and the desired product concentration. Higher concentrations may increase the reaction rate, but may also cause solubility problems or undesirable side reactions. Reasonable fluoride ion concentration ranges between 0.4M and 1.0M, which helps ensure sufficient reactant contact and reaction efficiency while avoiding solvent oversaturation.

[0054] Ozone environmental concentration: Ozone has a significant impact on reaction efficiency and product stability. Since ozone has high oxidizing properties and potential hazards (including damage to human health and materials), it is reasonable to control the ozone concentration in the closed chamber to 0.3ppm-1.0ppm (parts per million). Figure 2 As shown, the chemical reaction can be carried out in a closed environment of ozone to generate a host-guest complex, or it can be carried out in an ozone-free environment. The fluorine content during product storage in an ozone-free environment has a significant impact, so it is preferred to carry out the chemical reaction in a closed environment of ozone.

[0055] S2, purifying the host-guest complex and verifying the purified host-guest complex.

[0056] After obtaining the host-guest complex, the unreacted starting materials, by-products and other impurities in the reaction mixture are removed through purification steps to ensure the high purity of the target compound. In many applications, the presence of impurities may interfere with the performance of the compound, and purification can obtain more reliable experimental results. Subsequently, the structure of the compound can also be verified by various analytical techniques to confirm and verify the success of the synthetic route and determine the exact structure of the compound.

[0057] Separation and purification can adopt existing purification processes, for example, the crown ether complex containing fluoride ions can be separated from the reaction mixture by appropriate separation techniques (such as distillation, chromatography or crystallization), and further purified. Taking centrifugal separation as an example, a medium speed (such as 5000 rpm) and a short time (such as 5-10 minutes) can be set.

[0058] Analytical technology characterization can use NMR (nuclear magnetic resonance), mass spectrometry (MS), X-ray crystallography and other techniques to characterize the structure of the obtained host-guest complex and confirm that the fluoride ions have been successfully blocked.

[0059] S3, mixing the verified host-guest complex with a 3D printing substrate to obtain a raw material for 3D printing.

[0060] The verified host-guest complex is mixed with the 3D printing substrate to obtain the raw material for 3D printing. During the mixing process, at least one of a diluent, a photoinitiator, a UV blocker, an inhibitor, and an antioxidant can be added as needed.

[0061] In one embodiment, the weight of the host-guest complex is 0.1% to 1% of the weight of the 3D printing substrate. Preferably, the weight of the host-guest complex is 0.1% to 0.2% of the weight of the 3D printing substrate.

[0062] S4, according to the design parameters, the raw materials are 3D printed to manufacture anti-caries dental appliances, and the viscosity range of the raw materials at a printing temperature of 20°C is 200-1000 mPa·s.

[0063] According to the design parameters, the raw materials are 3D printed to manufacture anti-caries dental appliances. The viscosity range of the raw materials at a printing temperature of 20°C is 200-1000mPa·s. The viscosity range of the raw materials at a printing temperature of 20°C is 200-1000mPa·s; the viscosity range of the raw materials at a printing temperature of 50°C is 50-800mPa·s.

[0064] The host-guest complex is stable during the manufacturing process and storage, and the phenomenon that the caries-preventing dental appliance prepared in a 37°C water bath environment (equivalent to the intraoral wearing environment) slowly releases fluoride ions can be explained by the basic principles of host-guest chemistry:

[0065] 1. Relatively stable during manufacturing and storage:

[0066] The formation of the host-guest complex is based on non-covalent interactions such as hydrogen bonding, hydrophobic interactions, van der Waals forces, and electrostatic interactions. These interactions are stable enough to maintain the structure of the complex without being destroyed during manufacturing (no water in the 3D printing substrate) and storage, thereby preventing the release of fluoride ions.

[0067] 2. Fluoride ions begin to be slowly released in the oral wearing environment:

[0068] First, the increase in temperature will increase the thermal motion of the molecules, resulting in a relative weakening of the host-guest interaction. In a 37°C water bath environment, the increase in temperature may lead to partial dissociation of non-covalent interactions, allowing fluoride ions to be slowly released from the complex. This temperature-dependent release mechanism is particularly common in drug delivery systems to achieve controlled release at body temperature.

[0069] Second, in a water bath environment, water molecules can penetrate into the host-guest complex as a solvent, forming hydrogen bonds or other types of interactions with fluoride ions and crown ethers. The effect of this solvent intervention may further weaken the interaction between crown ethers and fluoride ions, causing the fluoride ions to gradually dissociate. As a polar solvent, water is particularly good at destroying or weakening non-covalent bonds between hosts and guests.

[0070] In summary, under certain conditions, there is a dynamic equilibrium between the host-guest complex and free fluoride ions. Although the equilibrium may be biased towards the formation of the complex under manufacturing and storage conditions, under 37°C water bath conditions, the effects of temperature and solvent may shift the equilibrium towards the dissociation of the complex, thereby allowing the release of fluoride ions.

[0071] like Figure 2 As shown, whether the process preparation is carried out in an ozone-enclosed environment has a significant impact on the fluorine content during product storage, but does not prevent the presence of fluoride ions in the prepared anti-caries dental appliance. In order to extend the storage time of the anti-caries dental appliance, ozone control reaction can be added in step S1.

[0072] like Figure 3 As shown, the release curve of fluoride ions of the prepared anti-caries dental appliance in the air at 25°C is relatively flat, and reaches equilibrium in about 10 days, which also proves that the anti-caries dental appliance has extremely high stability in a room temperature environment; and when the anti-caries dental appliance is worn in the mouth (37°C water bath), the anti-caries dental appliance can slowly release fluoride ions and the release period can also meet the wearing time of at least 2 weeks, which can provide users with continuous and stable oral protection effects.

[0073] The above method and anti-caries dental appliance utilize supramolecular chemistry principles and host-guest interaction screening to determine the specific interaction between crown ethers and fluoride ions, thereby successfully blocking fluoride ions in polar aprotic solvents. The generated host-guest complex has extremely high stability during the manufacturing and storage processes, and can slowly release fluoride ions in the intraoral wearing environment (37°C water bath), providing a continuous and stable oral protection effect, thereby achieving the blocking and controlled release of fluoride ions in the orthodontic appliance material.

[0074] In one embodiment, the fluoride is tetrabutylammonium fluoride. Tetrabutylammonium fluoride (TBAF) is used in a non-aqueous solvent system. TBAF has good solubility in organic solvents, and due to its larger organic cation and its unique structure, it helps to enhance the interaction between fluoride ions and crown ethers.

[0075] In one embodiment, the crown ether is any one of the crown ethers of 15-crown-5 ether, 12-crown-4 ether, and 18-crown-6 ether. The cavity diameter of these crown ethers is about Can be well matched with a diameter of about of fluoride ions.

[0076] 15-Crown-5: The inner diameter of the ring is approx. The molecular weight is about 248g / mol, and the CO bond length is about CC bond length is about The OCO bond angle is about 112 degrees, and the spatial configuration is a five-membered ring, which has a certain flexibility and can adapt to different ion sizes.

[0077] 18-Crown-6: The inner diameter of the ring is approx. The molecular weight is about 264g / mol, and the CO bond length is about CC bond length is about The OCO bond angle is about 112 degrees. The spatial configuration is a six-membered ring, which is highly flexible and suitable for encapsulating larger ions.

[0078] 12-crown-4: inner diameter approx. The molecular weight is about 176g / mol, and the CO bond length is about CC bond length is about The OCO bond angle is about 112 degrees, and the spatial configuration is also a three-dimensional ring structure, which is flexible and can adapt to the coordination of smaller ions.

[0079] In one embodiment, fluoride ions and crown ethers are mixed and reacted in a closed environment of ozone to form a host-guest complex, the reaction temperature is 13°C to 15°C; the reaction time is 15 to 18 hours, the fluoride ion concentration ranges from 0.5M to 0.8M, and the ozone concentration in the closed cavity is 0.5ppm-0.8ppm (parts per million).

[0080] For example, the 3D printing substrate may be a polyurethane matrix (PUA), in which case the determined fluoride ion may be tetrabutylammonium fluoride (TBAF); the crown ether may be the crown ether of 15-crown-5-ether; and the solvent may be dimethyl sulfoxide (DMSO) or N,N-dimethylformamide (DMF).

[0081] More specifically, in one embodiment, the 3D printing substrate comprises a polyurethane matrix, a methacrylate monomer having one or more single functional groups, a diluent, and a photoinitiator.

[0082] The polyurethane matrix (PUA) is prepolymerized polyurethane, accounting for 20% to 50% by weight of the total formula. The PUA is selected to have a moderate molecular weight (ranging from 1000 to 10000), good biocompatibility and appropriate mechanical strength.

[0083] The (meth)acrylate monomers having one or more single functional groups may be at least one of methyl methacrylate (MMA), 1,6-hexanediol diacrylate (HDDA), trimethylolpropane triacrylate (TMPTA), and the like.

[0084] The diluent can be 5% ethyl acetate. The diluent is used to adjust the viscosity of the substrate to ensure good printing fluidity.

[0085] The photoinitiator can be 2-hydroxy-2-methylpropionate (HMPP), accounting for 5% of the total formulation. The photoinitiator is used to ensure an effective photocuring reaction.

[0086] In one embodiment, the 3D printing substrate may include 55-75 weight percent of urethane (meth) acrylate, 15-25 weight percent of vinyl ester, 5-15 weight percent of di(meth)acrylate, and less than 5 weight percent of photoinitiator.

[0087] In one embodiment, the 3D printing substrate may contain 20 to 80 weight percent of methacrylate, 10 to 35 weight percent of reactive ethylenically unsaturated groups, and less than 5 weight percent of a photoinitiator.

[0088] Select the corresponding crown ether according to the ratio of the following monomers in the 3D printing substrate: methacrylate; vinyl ester.

[0089] The monomer and oligomer components in the PUA (polyurethane acrylate) system will affect the selection of crown ethers.

[0090] For example, the methacrylate monomer in the PUA system has high polarity and reactivity, which may react with the oxygen atom of the crown ether and interfere with the coordination of the crown ether with the fluoride ion. When its ratio is higher than 70%, a crown ether with higher coordination ability, such as 18-crown-6, can be selected.

[0091] For example, the vinyl ester in the PUA system is chemically inert and has better compatibility with crown ethers and fluoride ions, which can inhibit the side reactions between the oxygen atoms of the crown ether and the monomers. When its proportion is higher than 20%, common crown ethers such as 15-crown-5 can be selected, which have better sealing effects and enable the product to achieve better fluorine slow-release effects.

[0092] In one embodiment, the solvent is at least one of dimethyl sulfoxide and N,N-dimethylformamide.

[0093] In one of the embodiments, the method further includes S5, post-processing the anti-caries dental appliance, wherein the post-processing includes at least one of light curing and heat treatment.

[0094] Post-processing includes at least one step such as light curing and heat treatment to further stabilize the product structure and ensure stable encapsulation of fluoride and slow release in the oral environment.

[0095] In one embodiment, S4 3D prints the raw material to produce an anti-caries dental appliance, and the printing technology applied may be any one of stereolithography (SLA), digital light processing (DLP), etc. Key printing parameters may include:

[0096] Lighting time: 2s-15s;

[0097] Light intensity: 5-30mW / cm2;

[0098] Light wavelength: peak of spectral distribution 250-520nm;

[0099] Reaction temperature: 10℃-55℃;

[0100] The spot diameter is 0.05mm-0.15mm.

[0101] The above is only a specific implementation of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily conceived by any technician familiar with the technical field within the technical scope disclosed in the present application should be included in the protection scope of the present application.

Claims

1. A method for 3D printing an anti-caries dental appliance, characterized in that: include: S1, combining fluoride anions in fluoride with crown ether as a carrier by chemical reaction in a polar aprotic solvent to form a stable host-guest complex; the solubility of the fluoride and the crown ether in the solvent is greater than 10 g / L; S2, purifying the host-guest complex and verifying the purified host-guest complex; S3, mixing the verified host-guest complex with a 3D printing substrate to obtain a raw material for 3D printing; S4, according to the design parameters, 3D printing the raw material to manufacture an anti-caries dental appliance, wherein the viscosity range of the raw material at a printing temperature of 20° C. is 200-1000 mPa·s.

2. The method according to claim 1, characterized in that The fluoride is tetrabutylammonium fluoride.

3. The method according to claim 1, characterized in that: The crown ether is any one of the crown ether of 15-crown-5 ether, the crown ether of 12-crown-4 ether and the crown ether of 18-crown-6 ether.

4. The method according to claim 1, characterized in that The weight of the host-guest complex is 0.1% to 1% of the weight of the 3D printing substrate.

5. The method according to claim 1, characterized in that The fluoride ions and the crown ether are mixed and reacted in a closed environment of ozone to generate a host-guest complex, the reaction temperature is 13° C. to 15° C., and the reaction time is 15 to 18 hours.

6. The method according to claim 1, characterized in that The solvent is at least one of dimethyl sulfoxide and N,N-dimethylformamide.

7. The method according to claim 1, characterized in that The 3D printing substrate comprises 55-75 weight percent of urethane (meth) acrylate, 15-25 weight percent of vinyl ester, 5-15 weight percent of di(meth)acrylate, and less than 5 weight percent of photoinitiator.

8. The method according to claim 1, characterized in that The 3D printing substrate comprises 20 to 80 weight percent of methacrylate, 10 to 35 weight percent of reactive vinyl unsaturated groups, and less than 5 weight percent of a photoinitiator.

9. The method according to claim 1, characterized in that: The method further comprises S5, performing post-processing on the anti-caries dental appliance, wherein the post-processing comprises at least one step of light curing and heat treatment.

10. A 3D printed anti-caries dental appliance, characterized in that: The 3D printed caries-preventing dental appliance is printed by the method described in any one of claims 1 to 9.

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