Light-cured resin material, 3D printing method, application of light-cured resin material and dental prosthesis

Abstract

The invention relates to the technical field of dental materials, and provides a light-cured resin material, a 3D printing method, application of the light-cured resin material and a dental prosthesis. The light-cured resin material comprises the following raw materials in parts by mass: 25-40 parts of a first light-cured resin monomer; 25 to 40 parts of a second light-cured resin monomer; 0.01 to 1 part of a photoinitiator; 10 to 40 parts of a filling agent; and 1 to 10 parts of a plasticizer, the first light-cured resin monomer comprises a light-cured resin monomer containing at least one polyacrylate functional group, and the second light-cured resin comprises a light-cured resin monomer with dilutability. The light-cured resin material disclosed by the invention is good in mechanical property, biocompatibility and resin affinity.

Description

Technical Field

[0001] The present application relates to the technical field of dental materials, and in particular to a photocurable resin material, a 3D printing method and application thereof, and a dental restoration. Background Art

[0002] Dental 3D printing resins are 3D printing materials specifically used in the dental field. They usually have good biocompatibility, precise dimensional accuracy, and mechanical properties suitable for dental applications. These resins can be used in multiple dental fields, including orthodontics, restorations, and surgical guide production. However, the mechanical properties, biocompatibility, and resin affinity of 3D printing resin materials are poor. Summary of the invention

[0003] Based on this, an embodiment of the present application provides a photocurable resin material with good mechanical properties, biocompatibility and resin affinity, a 3D printing method and its application, and a dental restoration.

[0004] In a first aspect, the present application provides a photocurable resin material, wherein the raw materials of the photocurable resin material include, by weight:

[0005] 25 to 40 parts of the first photocurable resin monomer;

[0006] 25 to 40 parts of the second photocurable resin monomer;

[0007] Photoinitiator 0.01~1 part;

[0008] 10 to 40 parts of filler; and

[0009] Plasticizer 1 to 10 parts.

[0010] The first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin includes a photocurable resin monomer having dilutability.

[0011] In some embodiments, the first photocurable resin monomer includes at least one of bisphenol A propylene glycol dimethacrylate, triethylene glycol dimethacrylate, methyl methacrylate, hydroxyethyl methacrylate, dimethacrylate urethane, bisphenol A glycidyl dimethacrylate, polyethylene glycol dimethacrylate and ethylene glycol dimethacrylate.

[0012] In some embodiments, the second photocurable resin monomer includes at least one of hydroxyethyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, acryloyl morpholine, tripropylene glycol diacrylate, and tetrahydrofuran acrylate.

[0013] In some embodiments, the photoinitiator includes at least one of a free radical photoinitiator and a cationic photoinitiator.

[0014] In some embodiments, the plasticizer includes at least one of di(2-ethylhexyl) phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebacate, and 1,6-hexanediol dimethacrylate.

[0015] In some embodiments, the mass proportion of spherical particles in the filler is ≥50%.

[0016] In some embodiments, the filler includes a first filler and a second filler.

[0017] Optionally, the mass ratio of the first filler to the second filler is (1-10):1.

[0018] Optionally, the volume average particle size Dv50 of the first filler is 1 μm to 10 μm.

[0019] Optionally, the volume average particle size Dv50 of the second filler is 1 nm to 100 nm.

[0020] Optionally, the first filler includes at least one of quartz powder, silicon powder, glass powder and ytterbium fluoride powder.

[0021] Optionally, the second filler includes white carbon black.

[0022] In a second aspect, the present application provides a 3D printing method, the 3D printing method comprising:

[0023] forming a resin base mold;

[0024] The photocurable resin material described in the first aspect is 3D printed onto the surface of the resin base mold, and photocured to form an appearance layer of the object to be printed.

[0025] In some embodiments, the method of forming the resin base mold includes:

[0026] A mixed liquid containing the first resin is used for 3D printing to form a resin base mold having the shape of the object to be printed.

[0027] In some embodiments, the first resin includes a hot melt resin.

[0028] Optionally, the first resin comprises polycaprolactone.

[0029] In some embodiments, the mixed liquid further includes a binder.

[0030] Optionally, the binder comprises polyethylene glycol acrylate.

[0031] Optionally, the mass of the binder is 1% to 5% of the mass of the first resin.

[0032] In a third aspect, the present application provides a use of the photocurable resin material as described in the first aspect or a dental restoration prepared by the 3D printing method as described in the second aspect in the preparation of dental products.

[0033] In a fourth aspect, the present application provides a dental restoration, wherein the dental restoration is prepared by the 3D printing method described in the second aspect, and the dental restoration comprises:

[0034] Resin base mold;

[0035] An appearance layer is arranged on the surface of the resin base mold, and the outer surface of the appearance layer has the appearance shape of the dental restoration.

[0036] Compared with the traditional technology, this application has at least the following beneficial effects:

[0037] The present application uses a first photocurable resin, a second photocurable resin, a photoinitiator, a filler and a plasticizer for coordinated coordination, and can be matched with a resin base mold to improve 3D printing efficiency.

[0038] The first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin monomer includes a diluent photocurable resin monomer, which effectively improves the mechanical strength and biocompatibility of the photocurable resin material, and improves the affinity of the photocurable resin material with other resin materials, so that the photocurable resin material can be stably attached to the surface of other resin materials, thereby improving the applicability of the photocurable resin and the strength of the printed model. Therefore, the photocurable resin material of the present application can be printed on the resin matrix to form an appearance layer, effectively improving the efficiency and accuracy of 3D printing. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a graph showing the accuracy test results of the dental restoration prepared in Example 1 of the present application.

[0040] Figure 2 This is a graph showing the accuracy test results of the dental restoration prepared in Example 2 of the present application.

[0041] Figure 3 This is a graph showing the accuracy test results of the dental restoration prepared in Comparative Example 1 of the present application.

[0042] Figure 4 This is a graph showing the accuracy test results of the dental restoration prepared in Comparative Example 2 of the present application. DETAILED DESCRIPTION

[0043] Below in conjunction with the embodiments and examples, the present application is further described in detail. These embodiments and examples are only used to illustrate the present application and are not used to limit the scope of the present application. The purpose of providing these embodiments and examples is to make the understanding of the disclosure of the present application more thorough and comprehensive. It should also be understood that the present application can be implemented in many different forms, and is not limited to the embodiments and examples described herein. Those skilled in the art can make various changes or modifications without violating the connotation of the present application, and the equivalent form obtained also falls within the protection scope of the present application. In addition, in the description below, a large number of specific details are given in order to provide a more comprehensive understanding of the present application. It should be understood that the present application can be implemented without one or more of these details.

[0044] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0045] In this application, "optionally", "optional", and "optional" mean optional or dispensable, that is, any one of the two parallel schemes of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0046] In this application, the terms "first", "second", etc. in "the first aspect", "the second aspect", etc. are used only for descriptive purposes and cannot be understood as indicating or implying relative importance or quantity, nor can they be understood as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first", "second", etc. only serve the purpose of non-exhaustive enumeration and description, and it should be understood that they do not constitute a closed limitation on quantity.

[0047] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0048] In the present application, when it comes to a numerical interval (i.e., a numerical range), unless otherwise specified, the distribution of the optional numerical values ​​in the numerical interval is considered to be continuous, and includes the two numerical endpoints (i.e., the minimum and maximum values) of the numerical interval, and each numerical value between the two numerical endpoints. Unless otherwise specified, when the numerical interval only refers to an integer in the numerical interval, it includes the two endpoint integers of the numerical range, and each integer between the two endpoints, which is equivalent to directly listing each integer. When multiple numerical ranges are provided to describe features or characteristics, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical range disclosed in the present application should be understood to include any and all sub-ranges included therein. The "numerical value" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. "Numerical interval" allows for a broad range of quantitative intervals such as percentage intervals, ratio intervals, and ratio intervals.

[0049] All documents mentioned in this application are cited as references in this application, just as each document is cited as reference separately. Unless they conflict with the application purpose and / or technical solution of this application, the cited documents involved in this application are cited with all contents and all purposes. When the cited documents are involved in this application, the definitions of relevant technical features, terms, nouns, phrases, etc. in the cited documents are also cited. When the cited documents are involved in this application, the examples and preferred methods of the cited relevant technical features can also be incorporated into this application as references, but are limited to the implementation of this application. It should be understood that when the cited content conflicts with the description in this application, the present application shall prevail or be modified adaptively according to the description of this application.

[0050] In traditional technology, 3D printing liquid resin formulas are usually composed of reactive monomers and / or oligomers containing (meth)acrylates and epoxides, which will rapidly photopolymerize when exposed to light stimulation in the presence of a photoinitiator to form a cross-linked polymer network. However, the mechanical strength and biocompatibility of traditional 3D printing resins are poor and cannot meet the requirements for the use of dental products.

[0051] In a first aspect, the present application provides a photocurable resin material. The raw materials of the photocurable resin material include, by weight:

[0052] 25 to 40 parts of the first photocurable resin monomer;

[0053] 25 to 40 parts of the second photocurable resin monomer;

[0054] Photoinitiator 0.01~1 part;

[0055] 10 to 40 parts of filler; and

[0056] Plasticizer 1 to 10 parts.

[0057] The first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin includes a photocurable resin monomer having dilutability.

[0058] The proportion of the first photocurable resin monomer may be, for example, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts. The proportion of the second photocurable resin monomer may be, for example, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, 34 parts, 36 parts, 38 parts or 40 parts. The proportion of the photoinitiator may be, for example, 0.01 parts, 0.03 parts, 0.05 parts, 0.1 parts, 0.5 parts, 1 parts, 2 parts, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts. The proportion of the filler may be 10 parts, 13 parts, 16 parts, 19 parts, 22 parts, 25 parts, 28 parts, 31 parts, 34 parts, 37 parts or 40 parts. The amount of plasticizer can be 1 part, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts or 10 parts.

[0059] The present application uses a first photocurable resin, a second photocurable resin, a photoinitiator, a filler and a plasticizer to cooperate with each other, and can be matched with a resin base mold to improve the efficiency of 3D printing. Among them, the first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin monomer includes a diluent photocurable resin monomer, which effectively improves the mechanical strength and biocompatibility of the photocurable resin material, and improves the affinity of the photocurable resin material with other resin materials, and can make the photocurable resin material stably adhere to the surface of other resin materials, improve the applicability of the photocurable resin and the strength of the printed model. Therefore, the photocurable resin material of the present application can be printed on the resin matrix to form an appearance layer, effectively improving the efficiency and accuracy of 3D printing.

[0060] In some embodiments, the first photocurable resin monomer includes at least one of bisphenol A propylene glycol dimethacrylate (BisGMA), triethylene glycol dimethacrylate (TEGDMA), methyl methacrylate (MMA), hydroxyethyl methacrylate (HEMA), dimethacrylate urethane (UDMA), bisphenol A dimethacrylate glycidyl ester (BisEMA), polyethylene glycol dimethacrylate (PEGDMA) and ethylene glycol dimethacrylate (EGDMA). Further, bisphenol A propylene glycol dimethacrylate (BisGMA), dimethacrylate urethane (UDMA) and triethylene glycol dimethacrylate (TEGDMA) may be selected.

[0061] Optionally, the first photocurable resin monomer includes UDMA and TEGDMA. The first photocurable resin monomer selected in the present application can improve the affinity with other resins while maintaining the photocurable resin material with high mechanical strength and biocompatibility. Specifically, UDMA and TEGDMA are used together with moderate viscosity, which is easy to prepare and use, and can make the material formed after curing have good toughness, high strength, good light transmittance and low dimensional shrinkage.

[0062] Further optionally, the mass fraction of UDMA can be 10 to 30 parts, for example, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30 parts. The mass fraction of TEGDMA can be 10 to 30 parts, for example, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30 parts.

[0063] In some embodiments, the second photocurable resin monomer includes at least one of hydroxyethyl acrylate (HEA), isobornyl acrylate (IBOA), tripropylene glycol diacrylate (TPGDA), acryloyl morpholine (ACMO), tripropylene glycol diacrylate (TPGDA), and tetrahydrofuran acrylate (THFA).

[0064] In some embodiments, the second photocurable resin monomer includes AMCO and THFA. The second photocurable resin monomer selected in the present application can make the photocurable resin material have mechanical strength, biocompatibility and resin affinity. Specifically, AMCO and THFA are used together to achieve high curing accuracy, and the viscosity of the photocurable resin material can be adjusted, so that the model cured after printing has high hardness and dimensional stability.

[0065] Optionally, the mass fraction of AMCO can be 5 to 30 parts, for example, 5, 6, 8, 10, 12, 14, 16, 18, 20, 22, 24, 26, 28 or 30 parts. The mass fraction of THFA can be 5 to 20 parts, for example, 5, 6, 8, 10, 12, 14, 16, 18 or 20 parts.

[0066] In some embodiments, the photoinitiator includes at least one of a free radical photoinitiator and a cationic photoinitiator.

[0067] Optionally, the free radical photoinitiator includes camphorquinone, benzoin and derivatives, benzil initiators, alkyl phenone initiators, acyl phosphorus oxides, benzophenone initiators and thioxanthone initiators. For example, benzoin and derivatives include at least one of benzoin, benzoin dimethyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin butyl ether. Benzil initiators include at least one of diphenyl acetophenone and α, α-dimethoxy-α-phenyl acetophenone. Alkyl phenone initiators include at least one of α, α-diethoxy acetophenone, α-hydroxyalkyl phenone and α-aminoalkyl phenone. Acyl phosphorus oxides include at least one of aromatic acyl phosphine oxide and dibenzoylphenyl phosphine oxide. Benzophenone initiators include at least one of benzophenone, 2,4-dihydroxybenzophenone and Michler's ketone. Thioxanthone initiators include at least one of thiopropoxythioxanthone and isopropylthioxanthone.

[0068] Optionally, the cationic photoinitiator includes at least one of diaryl iodonium salts, triaryl iodonium salts, alkyl iodonium salts and cumene ferrocenium hexafluorophosphate.

[0069] In some embodiments, the photoinitiator includes TPO and a cationic photoinitiator. Optionally, the mass fraction of the photoinitiator can be 0.01 parts to 0.3 parts.

[0070] In some embodiments, the plasticizer includes at least one of di(2-ethylhexyl) phthalate (DOP), di(2-ethylhexyl) adipate (DOA), di(2-ethylhexyl) sebacate (DOS) and 1,6-hexanediol dimethacrylate (HDDMA). 1,6-hexanediol dimethacrylate (HDDMA) may be selected. Further optionally, the mass fraction of the plasticizer may be 2 to 8 parts. The plasticizer selected in the present application as above can not only improve the mechanical strength of the photocurable resin material, but also improve the resin affinity and improve the bonding effect with the resin base mold. Among them, HDDMA contains an acrylic group and has good compatibility with photocurable resin monomers and other resin materials, so that the resin affinity can be better improved, so that the photocurable resin material can be better attached to the resin material, and HDDMA has good plasticity, which can improve the mechanical strength of the model after curing.

[0071] In some embodiments, the mass proportion of spherical particles in the filler is ≥50%, for example, it can be 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 100%. The filler of the present application adopts spherical particles, and the interface defects of the interface surface contact are less, which is conducive to combining with different interfaces, thereby increasing the interface compatibility of the filler and the resin monomer.

[0072] It can be understood that spherical particles may refer to particles with a sphericity of ≥ 90%.

[0073] In some embodiments, the filler includes a first filler and a second filler.

[0074] Optionally, the mass ratio of the first filler to the second filler is (1-10):1, for example, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.

[0075] Optionally, the volume average particle size Dv50 of the first filler is 1 μm to 10 μm, for example, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm or 10 μm.

[0076] Optionally, the volume average particle size Dv50 of the second filler is 1 nm to 100 nm, for example, 1 nm, 5 nm, 10 nm, 20 nm, 30 nm, 40 nm, 50 nm, 60 nm, 70 nm, 80 nm, 90 nm or 100 nm.

[0077] In this application, the filler is divided into two particle sizes, wherein the first filler is mainly used as a filler for the photocurable resin material, providing mechanical support for the cured model and ensuring accuracy, while the spherical filler has good interface affinity and good compatibility with the resin material, and the second filler has a relatively small particle size, which can adjust the fluidity and viscosity of the photocurable resin material, thereby ensuring that the photocurable resin material has good wettability with other resin materials, thereby improving the resin affinity and compatibility. This application uses two fillers to cooperate with each other, while taking into account the 3D printing accuracy and operational convenience, and improving the infiltration and combination of the photocurable resin material and other resin materials.

[0078] Optionally, the first filler includes at least one of quartz powder, silicon powder, glass powder and ytterbium fluoride powder.

[0079] Optionally, the second filler includes white carbon black.

[0080] A second aspect of the present application provides a 3D printing method, the 3D printing method comprising:

[0081] forming a resin base mold;

[0082] The photocurable resin material described in the first aspect is 3D printed onto the surface of the resin base mold, and photocured to form an appearance layer of the object to be printed.

[0083] In traditional technology, the method of 3D printing is layer-by-layer printing, that is, the built model is sliced, and then printed layer by layer and then bonded, and most of the time, one material is used for printing. However, for dental products, the printing efficiency is low and the cost is high, and it is difficult to meet the mechanical properties and biocompatibility of the material at the same time. However, the present application first uses a resin to form a resin base mold as the frame of the product to achieve mechanical support, and further forms the appearance layer of the product with the surface of the photocurable resin printing paper resin base mold of the present application, which has mechanical strength, biocompatibility and resin affinity. Among them, since the resin base mold is located inside the product, it does not need to have a high surface accuracy, and can be provided in advance or formed by 3D printing. Furthermore, the resin base mold uses easy-to-form materials, which can quickly form the skeleton, greatly saving printing time. The printing of the appearance layer uses the photocurable resin material of the present application. Since it only prints the appearance of the product, the amount used is small, and the photocurable resin material has high printing accuracy and good affinity with the resin base mold. During the printing process of the photocurable resin material of the present application, the photocurable resin material can stably adhere to the surface of the resin base mold, effectively improving the printing efficiency and printing accuracy, and the formed product meets the requirements of mechanical strength and biocompatibility.

[0084] In some embodiments, the method of forming the resin base mold includes:

[0085] A mixed liquid containing the first resin is used for 3D printing to form a resin base mold having the shape of the object to be printed.

[0086] The present application adopts 3D printing to form a resin base mold, and a material with fast printing speed and low precision can be used as a support frame for the product.

[0087] In some embodiments, the first resin includes a hot-melt resin. The present application uses a hot-melt resin as the material of the resin base mold. The hot-melt resin has a fast printing speed. Although the surface precision of the resin base mold formed by it is poor, it does not need to be subjected to surface treatment and can be directly used to print the appearance layer. The rough surface of the product after printing with the hot-melt resin can be used to increase the attachment area of ​​the photocurable resin material, and further improve the bonding force between the appearance layer and the resin base mold.

[0088] Optionally, the first resin includes polycaprolactone. The present application uses polycaprolactone as the material of the resin base mold, which has good affinity with the photocurable resin material of the present application.

[0089] In some embodiments, the mixed liquid further includes a binder.

[0090] Optionally, the binder includes polyethylene glycol acrylate (PEGDMA). In the present application, PEGDMA is also mixed in the first resin, so that the resin base mold material has an acrylic group, which can not only improve the bonding strength between the resin base mold and the photocurable resin material of the present application, but also improve the toughness of the resin base mold.

[0091] Optionally, the mass of the binder is 1% to 5% of the mass of the first resin, for example, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5% or 5.0%.

[0092] A third aspect of the present application provides an application of the photocurable resin material as described in the first aspect or a dental restoration prepared by the 3D printing method as described in the second aspect in the preparation of a dental product.

[0093] It is understandable that the photocurable resin material of the present application has mechanical strength, biocompatibility and resin affinity. Therefore, it meets the requirements of dental products and can be used for dental products such as dental restorations and dental trays. Moreover, the 3D printing method of the present application is highly efficient and accurate, and is suitable for the manufacture of dental products.

[0094] A fourth aspect of the present application provides a dental restoration, wherein the dental restoration is prepared by the 3D printing method described in the second aspect, and the dental restoration comprises:

[0095] Resin base mold;

[0096] An appearance layer is arranged on the surface of the resin base mold, and the outer surface of the appearance layer has the appearance shape of the dental restoration.

[0097] In some embodiments, the thickness of the appearance layer is 10 μm to 500 μm, for example, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm or 500 μm. The thickness of the appearance layer is selected as above in the present application to effectively ensure the appearance accuracy and the mechanical strength of the model after curing.

[0098] The embodiments of the present application will be described in detail below in conjunction with examples. It should be understood that these examples are only used to illustrate the present application and are not intended to limit the scope of the present application. The experimental methods for which specific conditions are not specified in the following examples are preferably referred to the guidance provided in the present application, and can also be based on the experimental manual or normal conditions in this area, can also be based on the conditions recommended by the manufacturer, or refer to experimental methods known in the art.

[0099] Example 1

[0100] Weigh the following raw materials according to mass fraction, including:

[0101] UDMA 25 parts;

[0102] TEGDMA 10 parts;

[0103] AMCO 14.93;

[0104] THFA 15 parts;

[0105] 10 parts of white carbon black;

[0106] 20 parts of spherical silicon dioxide;

[0107] HDDMA 5 parts;

[0108] TPO 0.06 parts; and,

[0109] DPIHFP 0.01 parts.

[0110] The volume average particle size Dv50 of white carbon black is 50 nm, the volume average particle size Dv50 of spherical silica is 5 μm, and DPIHFP is diphenyliodonium hexafluorophosphate.

[0111] The above raw materials are mixed to obtain a photocurable resin material.

[0112] The present application also provides a 3D printing method for a dental restoration, comprising the following steps:

[0113] S1, mixing PCL and PEGDMA to obtain a mixture, wherein the mass of PEGDMA is 3% of the mass of PCL;

[0114] S2, 3D printing the mixture in S1 to form a resin base mold;

[0115] S3. Form an appearance layer with a thickness of 300 μm on the surface of the 3D printing paper resin base mold using the above-mentioned photocurable resin material to obtain a dental restoration.

[0116] Example 2

[0117] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0118] UDMA 25 parts;

[0119] TEGDMA 10 parts;

[0120] AMCO 25;

[0121] THFA 15 parts;

[0122] 5 parts of white carbon black;

[0123] 15 parts of spherical silicon dioxide;

[0124] HDDMA 4.96 copies;

[0125] 0.03 parts of camphorquinone; and

[0126] DPIHFP 0.01 parts.

[0127] Example 3

[0128] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0129] UDMA 25 parts;

[0130] TEGDMA 10 parts;

[0131] AMCO 9.93;

[0132] THFA 20 parts;

[0133] 10 parts of white carbon black;

[0134] 20 parts of spherical silicon dioxide;

[0135] HDDMA 5 parts;

[0136] TPO 0.06 parts; and,

[0137] DPIHFP 0.01 parts.

[0138] Example 4

[0139] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0140] UDMA 20 parts;

[0141] TEGDMA 5 parts;

[0142] AMCO 25;

[0143] THFA 9.96 parts;

[0144] 5 parts of white carbon black;

[0145] 30 parts of spherical silicon dioxide;

[0146] HDDMA 5 parts;

[0147] 0.03 parts of camphorquinone; and

[0148] DPIHFP 0.01 parts.

[0149] Example 5

[0150] A photocurable resin material and a dental restoration were prepared according to the method of Example 1, except that white carbon black was replaced with an equal mass fraction of spherical silica.

[0151] Example 6

[0152] A photocurable resin material and a dental restoration were prepared according to the method of Example 1, except that the spherical silica was replaced with an equal mass fraction of white carbon black.

[0153] Example 7

[0154] A photocurable resin material and a dental restoration were prepared according to the method of Example 1, except that the volume average particle size Dv50 of the spherical silica was 20 μm.

[0155] Example 8

[0156] A photocurable resin material and a dental restoration were prepared according to the method of Example 1, except that the volume average particle size Dv50 of the spherical silica was 0.5 μm.

[0157] Example 9

[0158] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that in step S1 of the 3D printing method of the dental restoration, PEGDMA was not added to the mixture.

[0159] Comparative Example 1

[0160] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0161] UDMA 25 parts;

[0162] TEGDMA 25 parts;

[0163] AMCO 9.97 copies;

[0164] THFA 5 parts;

[0165] 10 parts of white carbon black;

[0166] 20 parts of angular silicon dioxide;

[0167] 5 parts of HDDMA; and,

[0168] TPO 0.03 parts.

[0169] This comparative example provides a 3D printing method for a dental restoration, comprising:

[0170] The photocurable resin material is directly used to print and form a dental restoration.

[0171] Comparative Example 2

[0172] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0173] UDMA 25 parts;

[0174] TEGDMA 25 parts;

[0175] AMCO 10;

[0176] THFA 5 parts;

[0177] 10.5 parts of white carbon black;

[0178] 19.39 parts of angular silicon dioxide;

[0179] HDDMA 5 parts;

[0180] EDMAB 0.08 parts; and,

[0181] TPO 0.03 parts.

[0182] Among them, EDMAB is N,N-dimethylbenzamide (Ethyl-4-dimethylamino benzoate).

[0183] This comparative example provides a 3D printing method for a dental restoration, comprising:

[0184] The photocurable resin material is directly used to print and form a dental restoration.

[0185] Comparative Example 3

[0186] The photocurable resin material and the dental restoration were prepared according to the method of Example 1, except that the raw materials included:

[0187] UDMA 25 parts;

[0188] TEGDMA 20 parts;

[0189] 4 servings of AMCO;

[0190] 11 parts of white carbon black;

[0191] 13.9 parts of spherical silicon dioxide;

[0192] Angular silicon dioxide 21 parts;

[0193] HDDMA 5 parts;

[0194] EDMAB 0.08 parts; and,

[0195] Camphorquinone 0.02 parts.

[0196] This comparative example provides a 3D printing method for a dental restoration, comprising:

[0197] The photocurable resin material is directly used to print and form a dental restoration.

[0198] The prepared dental restoration is subjected to a performance test, the method comprising:

[0199] Accuracy test: The printed dental restoration was compared with the standard dental model, and the Geomagic Wrap software was used to produce a comprehensive accuracy comparison. The test results are shown in Table 1, where the test results of Example 1 are shown in Table 1. Figure 1 As shown, the test results of Example 2 are as follows Figure 2 As shown, the test results of Comparative Example 1 are as follows Figure 3 As shown, the test results of Comparative Example 2 are as follows Figure 4 shown.

[0200] Hydrophilicity test: The hydrophilic contact angle of the dental restoration was tested. The test results are shown in Table 1.

[0201] Mechanical strength test:

[0202] Bending strength: According to the above embodiments and comparative examples, test specimens with a length of 80 mm, a width of 10 mm, and a thickness of 4 mm were prepared, and the bending strength test was carried out according to the determination standard of bending properties of plastics GB / T9341-2000. The test results are shown in Table 1.

[0203] Table 1

[0204]

[0205] From the above table we can see that:

[0206] (1) Compared with Examples 5-6, it can be seen that the filler of the present application adopts a combination of the first filler and the second filler, which not only has good affinity and good operability for the photocurable resin material, but also has good hydrophilicity, high mechanical strength and high printing accuracy after curing.

[0207] (2) Compared with Examples 7-8, it can be seen that the present application controls the particle size of the first filler to effectively ensure the fluidity and viscosity of the photocurable resin material, thereby improving the wettability of the photocurable resin material with the resin base mold, so that the cured model has the characteristics of high strength, high precision and good affinity. If the particle size is relatively small, although the printing accuracy is also relatively good, the hydrophilicity and mechanical strength of the cured model are not good. If the particle size is relatively large, it will significantly affect the mechanical strength and precision of the cured model.

[0208] (3) Compared with Example 9, it can be seen that the present application adds a binder to the resin base mold so that the resin base mold material has an acrylic group, which can not only improve the bonding strength between the resin base mold and the photocurable resin material of the present application, but also improve the toughness and strength of the resin base mold, thereby avoiding the occurrence of problems such as the appearance layer falling off due to external force.

[0209] (4) Compared with Example 1 to Comparative Examples 1-3, it can be seen that Comparative Examples 1-3 have poor affinity with the resin base mold and are difficult to stably adhere to the surface of the resin base mold. Therefore, the method of first printing the resin base mold and then printing the appearance layer cannot be used, and only the traditional printing method can be used. The printing time is slow. In addition, the printing accuracy of the photocurable resin material of the present application is high and the hydrophilicity is good.

[0210] Therefore, the present application adopts the coordinated cooperation of the first photocurable resin, the second photocurable resin, the photoinitiator, the filler and the plasticizer, and can be matched with the resin base mold to improve the 3D printing efficiency. Among them, the first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin monomer includes a resin monomer with diluency, which effectively improves the mechanical strength and biocompatibility of the photocurable resin material, and improves the affinity of the photocurable resin material with other resin materials, and can make the photocurable resin material stably adhere to the surface of other resin materials, improve the applicability of the photocurable resin and the strength of the printed model. Therefore, the photocurable resin material of the present application can be printed on the resin matrix to form an appearance layer, effectively improving the efficiency and accuracy of 3D printing.

[0211] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0212] The above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the application. It should be noted that, for a person of ordinary skill in the art, several modifications and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the present application shall be subject to the attached claims.

Claims

1. A photocurable resin material, characterized in that: The raw materials of the photocurable resin material include, by weight: 25 to 40 parts of the first photocurable resin monomer; 25 to 40 parts of the second photocurable resin monomer; Photoinitiator 0.01~1 part; 10 to 40 parts of filler; and 1 to 10 parts of plasticizer; The first photocurable resin monomer includes a photocurable resin monomer containing at least one polyacrylate functional group, and the second photocurable resin includes a photocurable resin monomer having dilutability.

2. The photocurable resin material according to claim 1, wherein: The photocurable resin material satisfies at least one of the following conditions: (1) the first photocurable resin monomer includes at least one of bisphenol A propylene glycol dimethacrylate, triethylene glycol dimethacrylate, methyl methacrylate, hydroxyethyl methacrylate, dimethacrylate urethane, bisphenol A glycidyl dimethacrylate, polyethylene glycol dimethacrylate and ethylene glycol dimethacrylate; (2) The second photocurable resin monomer includes at least one of hydroxyethyl acrylate, isobornyl acrylate, tripropylene glycol diacrylate, acryloyl morpholine, tripropylene glycol diacrylate and tetramethylene acrylate.

3. The photocurable resin material according to claim 1, wherein: The photocurable resin material satisfies at least one of the following conditions: (1) The photoinitiator includes at least one of a free radical photoinitiator and a cationic photoinitiator; (2) The plasticizer includes at least one of di(2-ethylhexyl) phthalate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) sebacate and 1,6-hexanediol dimethacrylate; (3) The mass proportion of spherical particles in the filler is ≥50%.

4. The photocurable resin material according to any one of claims 1 to 3, characterized in that: The filler includes a first filler and a second filler; Optionally, the mass ratio of the first filler to the second filler is (1-10):1; Optionally, the volume average particle size Dv50 of the first filler is 1 μm to 10 μm; Optionally, the volume average particle size Dv50 of the second filler is 1 nm to 100 nm; Optionally, the first filler includes at least one of quartz powder, silicon powder, glass powder and ytterbium fluoride powder; Optionally, the second filler includes white carbon black.

5. A 3D printing method, characterized in that: The 3D printing method comprises: forming a resin base mold; The photocurable resin material according to any one of claims 1 to 4 is 3D printed onto the surface of the resin base mold, and photocured to form an appearance layer of the object to be printed.

6. The 3D printing method according to claim 5, characterized in that: The method of forming the resin base mold comprises: A mixed liquid containing the first resin is used for 3D printing to form a resin base mold having the shape of the object to be printed.

7. The 3D printing method according to claim 6, characterized in that: The first resin includes a hot-melt resin; Optionally, the first resin comprises polycaprolactone.

8. The 3D printing method according to claim 6 or 7, characterized in that: The mixed liquid also includes a binder; Optionally, the binder comprises polyethylene glycol acrylate; Optionally, the mass of the binder is 1% to 5% of the mass of the first resin.

9. Use of the photocurable resin material according to any one of claims 1 to 4 or a dental restoration prepared by the 3D printing method according to any one of claims 5 to 8 in the preparation of dental products.

10. A dental restoration, characterized in that: The dental restoration is prepared by the 3D printing method according to any one of claims 5 to 8, and the dental restoration comprises: Resin base mold; An appearance layer is arranged on the surface of the resin base mold, and the outer surface of the appearance layer has the appearance shape of the dental restoration.

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