3D printing resin material and method for 3D-printing dental hard occlusal splint by using 3D printing resin material

Abstract

The present application relates to the technical field of 3D printing materials, and discloses a 3D printing resin material and a method for 3D-printing a dental hard occlusal splint by using the 3D printing resin material. The 3D printing resin material comprises the following raw materials in parts by weight: 5-50 parts of multi-curable blocked polyurethane acrylate, 5-50 parts of an acrylate resin, 15-55 parts of an acrylamide monomer and / or an acrylate monomer containing hydroxyl or carboxyl, 1-4 parts of an initiator, 0.01-2 parts of an absorbent, and 0.5-3 parts of nanosilicon dioxide. The dental hard occlusal splint 3D-printed by using the 3D printing resin material of the present application has excellent biocompatibility, high strength, high modulus, excellent tear resistance, excellent abrasion resistance, low water absorption value, and low dissolution value.

Description

Methods for 3D Printing Dental Rigid Jaw Pads Based on 3D Printing Resin Materials and Their Applications Cross-reference to related applications

[0001] This application claims priority to Chinese Patent Application No. 202411947790.4, filed on December 26, 2024, entitled “3D Printing Resin Material and Application Thereto: Method for 3D Printing of Dental Rigid Cavity Pads”, the entire contents of which are incorporated herein by reference. Technical Field

[0002] This application relates to the field of 3D printing materials technology, and more particularly to a 3D printing resin material and a method for 3D printing dental rigid jaw pads. Background Technology

[0003] In recent years, with the popularization of 3D printing digital light processing (DLP) technology, its application areas have been continuously expanding. Simultaneously, with the expansion of the types and scope of national centralized procurement of medical devices, 3D printing technology has received considerable attention in the medical device field, especially in dental treatment. The personalized, differentiated, and high-precision needs of dentistry perfectly match the demands of 3D printing technology. Currently, the main applications of 3D printing technology in dentistry include surgical guides, dental restorative working models, temporary crowns and bridges, and denture bases. Furthermore, more requirements have been placed on the types and properties of materials. Among these, the 3D printing of rigid dental occlusal pads has also seen some development, primarily for retainers to consolidate teeth and jaw deformities after orthodontic treatment, and occlusal pads for treating temporomandibular joint disorders.

[0004] However, the current mainstream method for 3D printing rigid jaw pads involves clinics acquiring patients' dental data using dental scanners, transmitting the data to dental labs, which then print corresponding tooth models. These models are then thermoformed onto the 3D-printed mold using a PETG / TPU film of a specific thickness. This process is an indirect production method utilizing 3D printing technology, resulting in significant material waste, a complex manufacturing process, and a long production cycle.

[0005] Using 3D printing technology to directly print dental jaw pads can significantly improve manufacturing efficiency, further simplify the production process, and reduce material waste, thereby reducing production costs. Simultaneously, directly printed jaw pads allow for customized thickness designs in specific areas using design software, resulting in a better patient experience. However, rigid jaw pads require high strength, high modulus, excellent tear resistance, excellent abrasion resistance, low water absorption, low solubility, and excellent biocompatibility, presenting significant material challenges. Currently, there are no products in China that can be directly 3D printed as rigid jaw pads.

[0006] In addition, existing 3D printing material systems suffer from problems such as low molding accuracy, poor wear resistance, inability to balance strength and toughness, and poor tear resistance, which cannot meet the application requirements of dental rigid jaw pads. Summary of the Invention

[0007] The purpose of this application is to develop a 3D-printable rigid dental occlusal pad with the following advantages: excellent biocompatibility (cell viability greater than 90%), high strength (yield stress greater than 40 MPa), yield strain greater than 4%, high modulus (tensile elastic modulus greater than 1600 MPa), excellent tear resistance (right-angle tear strength greater than 100 kN / m), excellent abrasion resistance (abrasion mass loss less than 0.25 g / 1000 r), low water absorption (water absorption rate less than 32 μg / mm3), and low solubility (solubility less than 1.6 μg / mm3).

[0008] To achieve the above objectives, this application introduces a multi-curing, closed-cell polyurethane acrylate into the material used for 3D printing of dental rigid jaw pads. This resin contains both photocurable and thermocurable groups, further enhancing the degree of reaction. Simultaneously, the closed-cell polyurethane acrylate improves the resin's stability. Furthermore, the application incorporates acrylate monomers containing hydroxyl or carboxyl groups and / or acrylamide monomers, as well as acrylate resins with high toughness and high Tg, using nano-silica as a filler to further improve the wear resistance of the 3D printed material while maintaining high transparency (light transmittance greater than 85%).

[0009] Specifically, the objective of this application is achieved through the following technical solution: providing a 3D printing resin material, comprising the following raw material components by weight:

[0010] 5-50 parts of multi-curing blocked polyurethane acrylate, preferably 30 parts;

[0011] 5-50 parts of acrylate resin, preferably 20 parts;

[0012] 15-55 parts of acrylamide monomer and / or acrylate monomer containing hydroxyl or carboxyl groups, preferably 40 parts;

[0013] Initiator 1-4 parts, preferably 2 parts;

[0014] The absorbent is 0.01-2 parts, preferably 0.1 parts;

[0015] 0.5-3 parts of nano-silica, preferably 1.5 parts;

[0016] The multi-cured blocked polyurethane acrylate is prepared by mixing and reacting diol and isocyanate under a catalyst at 60-90℃, followed by the addition of ethyl 2-(tert-butylamino)methacrylate for further mixing and reaction to achieve end-capping; the catalyst is selected from one or more of organozinc and organobismuth catalysts.

[0017] Preferably, the multi-curing blocked polyurethane acrylate is prepared from the following raw material components:

[0018] Preferably, the diol is selected from one or more of polyethylene glycol (PEG), polypropylene glycol (PPG), dimethyl hydroxy silicone oil, hydroxyl-terminated polybutadiene, and hydroxyl-terminated polybutylene adipate.

[0019] Preferably, the isocyanate is selected from one or more of hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), and hydrogenated MDI (HMDI).

[0020] In some specific embodiments, the catalyst is one or more of environmentally friendly organozinc and organobismuth catalysts, such as BCAT-E16, BCAT-E20, BCAT-E25A, BCAT-E28A, BCAT-T100R, BCAT-E20CX, ZCAT-EY18, ZCAT-EZ22, ZCAT-T50, BX-EM14, and BX-EM23 from Guangzhou Yourun Synthetic Materials Co., Ltd.

[0021] Preferably, the multi-curing blocked polyurethane acrylate is prepared by mixing a diol and an isocyanate, adding a catalyst, mixing for 3-7 hours at a temperature of 60-90℃ and a shear rate of 10-25 m / s, and then adding ethyl 2-(tert-butylamino)methacrylate and mixing for 2-4 hours for end-capping.

[0022] In one specific embodiment, the raw materials and preparation of the multi-curing blocked polyurethane acrylate are as follows.

[0023] raw material:

[0024] Preparation: After mixing PEG-800 and diphenylmethane diisocyanate, BX-EM23 was added. The mixture was stirred at 80℃ and a shear rate of 15 m / s for 4 h. Then, ethyl 2-(tert-butylamino)methacrylate was added and the mixture was stirred for another 3 h to obtain a multi-cured blocked polyurethane acrylate.

[0025] Preferably, the acrylate resin is selected from (meth)acrylate resins with high toughness (elongation at break > 10%) and high Tg (Tg > 50℃), specifically from Sartoma's CN1963NS, CN1964NS, CN1993CG, CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, and CN9021N. S, CN9062, CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN991NS, and one or more of Dymax's BR-930D, BR-941D, BR-952, BR-970BT, BR-970H, BR-990, BR-372, BR-571, BR-741, BR-744BT, BR-744SD, BR-742MS, BR-345, BR-374, BR-541S, BR-571, BR-582I10, BR-202, BR-541MB, and BR-571MB.

[0026] Preferably, the acrylamide monomer and / or the acrylate monomer containing hydroxyl or carboxyl groups are selected from one or more of the following: cyclotrimethylolpropane methyl acetal acrylate, acrylic acid, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, dipropylene glycol diacrylate, dipropylene glycol diacrylate, (2) bisphenol A dimethacrylate oxyacetate, (4) bisphenol A dimethacrylate oxyacetate, (6) bisphenol A dimethacrylate oxyacetate, tricyclodecanediethanol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 4-acryloylmorpholine, dimethylaminopropylacrylamide, diethylacrylamide, N-hydroxyethylacrylamide, and N,N-dimethylacrylamide.

[0027] Preferably, the initiator is selected from one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone.

[0028] Preferably, the absorber is selected from at least one of triazine-based ultraviolet absorbers and benzophenone-based ultraviolet absorbers. In some specific embodiments, the triazine-based ultraviolet absorber may be selected from 2-[4,6-bis(2,4-dimethylyl)-1,3,5-triazin-2-yl]-5-(octoxy)phenol (UV-1164), 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexaneoxy (UV-1577), UV1990 (Eutec Chemical), etc., and their derivatives; the benzophenone-based ultraviolet absorber may be selected from any one or more of 2-hydroxy-4-n-octoxybenzophenone (UV-531), 2,4-dihydroxybenzophenone (UV-O), 2-hydroxy-4-methoxybenzophenone (UV-9), etc., and their derivatives.

[0029] Preferably, the nano-silica has a particle size of 3-100 nanometers and is selected from Evonik's... 200V 300 380 805 E812 Any one or more of E972.

[0030] In one specific embodiment, the 3D printing resin material comprises the following parts by weight of raw materials:

[0031] This application also provides a method for 3D printing rigid dental occlusal pads, including the following steps:

[0032] Mix the above-mentioned raw materials of 3D printing resin material evenly according to the weight parts;

[0033] A three-dimensional mechanical test model is printed using a 3D printer, cured for 5-30 minutes at a wavelength of 200-800nm, a radiation intensity of 20-100mw / cm2, and a temperature of 40-60℃, and then heat-treated at 80-130℃ for 1-3 hours.

[0034] In some specific embodiments, the method for 3D printing rigid dental occlusal pads includes the following steps:

[0035] The raw materials of the above-mentioned 3D printing resin material are added to the stirring and dispersing vessel in sequence, the rotation speed is adjusted to the range of 500-2000 r / min, that is, to provide a shear line speed of 10-25 m / s, the temperature is controlled in the range of 30-70℃ (preferably 50℃), and the stirring and dispersing is carried out for 2-6 hours (preferably 4 hours).

[0036] A three-dimensional mechanical test model is printed using a 3D printer, cleaned with 75% medical alcohol, dried with a compressed air gun, and cured in a curing chamber at a wavelength of 200-800nm ​​(preferably 405nm), 20-100mw / cm2 (preferably 50mw / cm2), and 40-60℃ (preferably 50℃) for 5-30 minutes (preferably 10 minutes). Then, it is heat-treated in an oven at 80-130℃ (preferably 110℃) for 1-3 hours (preferably 2 hours).

[0037] The 3D printing resin material of this application introduces a multi-curing closed polyurethane acrylate, which can improve the reactivity and stability of the resin. Combined with acrylate monomers containing hydroxyl or carboxyl groups and / or acrylamide monomers, as well as acrylate resins with high toughness and high Tg, and nano-silica filler, the printing speed is fast, which can further improve the wear resistance of the 3D printed material, while also ensuring high transparency.

[0038] The dental rigid jaw pads 3D printed using the 3D printing resin material of this application have excellent biocompatibility (cell survival rate greater than 90%), high strength (yield stress greater than 40 MPa), yield strain greater than 4%, high modulus (tensile elastic modulus greater than 1600 MPa), excellent tear resistance (right-angle tear strength greater than 100 kN / m), abrasion resistance (abrasion mass loss less than 0.25 g / 1000 r), low water absorption (water absorption rate less than 32 μg / mm3), and low solubility (solubility less than 1.6 μg / mm3), while also maintaining high transparency (light transmittance greater than 85%). Detailed Implementation

[0039] The technical solutions of this application will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0040] It should be understood that, when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, integrals, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, integrals, steps, operations, elements, components and / or collections thereof.

[0041] The term “and / or” as used in the specification and appended claims means any combination of one or more of the associated listed items, as well as all possible combinations, and includes such combinations.

[0042] Example 1

[0043] Preparation of multi-cured blocked polyurethane acrylate: 63 parts by weight of PEG-800 and 40 parts by weight of diphenylmethane diisocyanate (MDI) were mixed, and 0.1 parts by weight of BX-EM23 were added. The mixture was stirred at 80°C and a shear rate of 15 m / s for 4 h. Then, 30 parts by weight of 2-(tert-butylamino)methacrylate were added for end-capping. After stirring for another 3 h, multi-cured blocked polyurethane acrylate was obtained.

[0044] Preparation of 3D printing resin material: By weight, 30 parts of multi-curing blocked polyurethane acrylate, 20 parts of BR-952, 20 parts of diethylacrylamide, 20 parts of hydroxyethyl methacrylate, 2 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of 2-(4,6-diphenyl-1,3,5-triazine-2)-5-n-hexaneoxy (UV-1577), and 1.5 parts of... 380 was added sequentially to the stirring and dispersing vessel, the rotation speed was adjusted to 1000 r / min, the temperature was controlled at 50℃, and the mixture was stirred and dispersed for 4 hours to obtain the 3D printing resin material.

[0045] 3D Printed Hard Dental Cavity Pad: A three-dimensional mechanical test model of a hard dental occlusal pad was printed using a 3D printer using 3D printing resin material. The model was cleaned with 75% medical alcohol, dried with a compressed air gun, and cured for 10 minutes in a curing chamber at 405nm wavelength, 50mw / cm2, and 50℃. Then, it was heat-treated at 110℃ in an oven for 2 hours to obtain the hard dental occlusal pad of Example 1.

[0046] Example 2

[0047] Preparation of multi-curing blocked polyurethane acrylate: 55 parts by weight of dimethyl hydroxy silicone oil and 35 parts by weight of hexamethylene diisocyanate (HDI) were mixed, and 0.05 parts by weight of BCAT-E20 were added. The mixture was stirred at 60°C and a shear rate of 10 m / s for 7 h. Then, 25 parts by weight of ethyl 2-(tert-butylamino)methacrylate were added for end-capping. After stirring for another 2 h, multi-curing blocked polyurethane acrylate was obtained.

[0048] Preparation of 3D printing resin material: By weight, 5 parts of multi-cured blocked polyurethane acrylate, 5 parts of CN1963NS, 5 parts of N-hydroxyethyl acrylamide, 10 parts of isobornyl acrylate, 1 part of (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, 0.01 parts of 2-hydroxy-4-n-octyloxybenzophenone (UV-531), and 0.5 parts of... E812 was added sequentially to a stirring and dispersing vessel, the rotation speed was adjusted to 500 r / min, the temperature was controlled at 30℃, and the mixture was stirred and dispersed for 6 hours to obtain 3D printing resin material.

[0049] 3D Printed Hard Dental Cavity Pad: A three-dimensional mechanical test model of a hard dental occlusal pad was printed using a 3D printer using 3D printing resin material. The model was cleaned with 75% medical alcohol, dried with a compressed air gun, and cured for 5 minutes in a curing chamber at 200nm wavelength, 100mw / cm2, and 60℃. Then, it was heat-treated in an oven at 80℃ for 3 hours to obtain the hard dental occlusal pad of Example 2.

[0050] Example 3

[0051] Preparation of multi-cured blocked polyurethane acrylate: 65 parts by weight of hydroxyl-terminated polybutylene adipate and 45 parts of phthalimide diisocyanate (XDI) were mixed, and 0.3 parts of ZCAT-EY18 were added. The mixture was stirred at 90°C and a shear rate of 25 m / s for 3 h. Then, 35 parts of 2-(tert-butylamino)methacrylate were added for end-capping. After stirring for another 4 h, multi-cured blocked polyurethane acrylate was obtained.

[0052] Preparation of 3D printing resin materials: By weight, 50 parts of multi-cured blocked polyurethane acrylate, 50 parts of CN9021NS, 30 parts of N,N-dimethylacrylamide, 25 parts of (2) bisphenol A dimethacrylate, 4 parts of 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2 parts of 2-hydroxy-4-methoxybenzophenone (UV-9), 3 parts of E812 was added sequentially to the stirring and dispersing vessel, the rotation speed was adjusted to 2000 r / min, the temperature was controlled at 70℃, and the mixture was stirred and dispersed for 2 hours to obtain the 3D printing resin material.

[0053] 3D Printed Hard Dental Cavity Pad: A three-dimensional mechanical test model of a hard dental occlusal pad was printed using a 3D printer from 3D printing resin material. The model was cleaned with 75% medical alcohol, dried with a compressed air gun, and cured for 30 minutes in a curing chamber at 800nm ​​wavelength, 20mw / cm2, and 40℃. Then, it was heat-treated in an oven at 130℃ for 1 hour to obtain the hard dental occlusal pad of Example 3.

[0054] Example 4

[0055] Preparation of multi-cured blocked polyurethane acrylate: 60 parts by weight of polypropylene glycol, 20 parts by isoflurane diisocyanate (IPDI), and 20 parts by weight of toluene diisocyanate (TDI) were mixed, and 0.2 parts by weight of BCAT-E28A were added. The mixture was stirred at 70°C and a shear rate of 20 m / s for 5 h. Then, 32 parts by weight of 2-(tert-butylamino)methacrylate were added for end-capping. After stirring for another 3 h, multi-cured blocked polyurethane acrylate was obtained.

[0056] Preparation of 3D printing resin material: By weight, 20 parts of multi-curing blocked polyurethane acrylate, 45 parts of BR-952, 40 parts of isobornyl acrylate, 2 parts of phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, 0.05 parts of 2,4-dihydroxybenzophenone (UV-O), and 1.5 parts of... 380 was added sequentially to the stirring and dispersing vessel, the rotation speed was adjusted to 1000 r / min, the temperature was controlled at 50℃, and the mixture was stirred and dispersed for 4 hours to obtain the 3D printing resin material.

[0057] 3D Printed Hard Dental Cavity Pad: A three-dimensional mechanical test model of a hard dental occlusal pad was printed using a 3D printer from 3D printing resin material. The model was cleaned with 75% medical alcohol, dried with a compressed air gun, and cured for 10 minutes in a curing chamber at 405nm wavelength, 50mw / cm2, and 50℃. Then, it was heat-treated at 110℃ in an oven for 2 hours to obtain the hard dental occlusal pad of Example 4.

[0058] Example 5

[0059] Preparation of multi-curing blocked polyurethane acrylate: 58 parts by weight of methyl hydroxy silicone oil and 42 parts by weight of dimethyl diisocyanate (XDI) were mixed, and 0.1 parts by weight of BCAT-T100R were added. The mixture was stirred at 80°C and a shear rate of 20 m / s for 4 h. Then, 28 parts by weight of ethyl 2-(tert-butylamino)methacrylate were added for end-capping. After stirring for another 4 h, multi-curing blocked polyurethane acrylate was obtained.

[0060] Preparation of 3D printing resin material: By weight, 25 parts of multi-cured blocked polyurethane acrylate, 25 parts of CN8890NS, 35 parts of diethylacrylamide, 2 parts of (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, 0.05 parts of 2-hydroxy-4-methoxybenzophenone (UV-9), and 1.5 parts of... E812 was added sequentially to the stirring and dispersing vessel, the rotation speed was adjusted to 1000 r / min, the temperature was controlled at 50℃, and the mixture was stirred and dispersed for 4 hours to obtain the 3D printing resin material.

[0061] 3D Printed Hard Dental Cavity Pad: A three-dimensional mechanical test model of a hard dental occlusal pad was printed using a 3D printer using 3D printing resin material. The model was cleaned with 75% medical alcohol, dried with a compressed air gun, and cured for 10 minutes in a curing chamber at 405nm wavelength, 50mw / cm2, and 50℃. Then, it was heat-treated at 110℃ in an oven for 2 hours to obtain the hard dental occlusal pad of Example 5.

[0062] In the course of this research, this application also explored jaw pads made in comparative proportions with different formulations and processing conditions, as detailed below.

[0063] Comparative Example 1

[0064] The difference between the preparation method of the jaw pad in Comparative Example 1 and Example 1 is that in the preparation of the multi-cured closed polyurethane acrylate, ethyl 2-(tert-butylamino)methacrylate is replaced with 2-hydroxyethyl methacrylate, and the other process steps are the same as in Example 1.

[0065] Comparative Example 2 (reaction temperature too low)

[0066] The preparation method of the jaw pad in Comparative Example 2 differs from that in Example 1 in that: in the preparation of the multi-cured closed polyurethane acrylate, after adding BX-EM23, it is stirred at 50°C, and the other process steps are the same as in Example 1.

[0067] Comparative Example 3 (Multi-curing blocked polyurethane with excessive acrylate content)

[0068] The difference between the preparation method of the jaw pad in Comparative Example 3 and Example 1 is that the amount of multi-cured closed polyurethane acrylate added in the preparation of the 3D printing resin material is 60 parts, and the other process steps are the same as in Example 1.

[0069] Comparative Example 4 (without added acrylate resins)

[0070] The preparation method of the jaw pad in Comparative Example 4 differs from that in Example 1 in that BR-952 is not added in the preparation of the 3D printing resin material, while the other process steps are the same as in Example 1.

[0071] Comparative Example 5 (Excessive content of acrylate resins)

[0072] The preparation method of the jaw pad in Comparative Example 5 differs from that in Example 1 in that the amount of BR-952 added in the preparation of the 3D printing resin material is 60 parts, and the other process steps are the same as in Example 1.

[0073] Comparative Example 6 (The content of acrylamide monomer and / or acrylate monomer containing hydroxyl or carboxyl groups is too low)

[0074] The preparation method of the jaw pad in Comparative Example 6 differs from that in Example 1 in that the amount of diethylacrylamide added in the preparation of the 3D printing resin material is 5 parts and the amount of hydroxyethyl methacrylate added is 5 parts, while the other process steps are the same as in Example 1.

[0075] Comparative Example 7 (excessive content of acrylamide monomer and / or acrylate monomers containing hydroxyl or carboxyl groups)

[0076] The difference between the preparation method of the jaw pad in Comparative Example 7 and Example 1 is that the amount of diethylacrylamide added in the preparation of the 3D printing resin material is 30 parts and the amount of hydroxyethyl methacrylate added is 30 parts, while the other process steps are the same as in Example 1.

[0077] Comparative Example 8 (without nano-silica)

[0078] The preparation method of the jaw pad in Comparative Example 8 differs from that in Example 1 in that no additives are used in the preparation of the 3D printing resin material. 380, the other process steps are the same as in Example 1.

[0079] Comparative Example 9 (excessive nano-silica content)

[0080] The difference between the preparation method of the jaw pad in Comparative Example 9 and Example 1 lies in the preparation of the 3D printing resin material. The amount of 380 added was 5 parts, and the other process steps were the same as in Example 1.

[0081] Comparative Example 10 (excessive content of ethyl 2-(tert-butylamino)methacrylate)

[0082] The preparation method of the jaw pad in Comparative Example 10 differs from that in Example 1 in that the amount of ethyl 2-(tert-butylamino)methacrylate added in the preparation of the multi-cured closed polyurethane acrylate is 45 parts, and the other process steps are the same as in Example 1.

[0083] Comparative Example 11 (2-(tert-butylamino)methacrylate ethyl ester content was too low)

[0084] The difference between the preparation method of the jaw pad in Comparative Example 11 and Example 1 is that in the preparation of the multi-cured closed polyurethane acrylate, the amount of ethyl 2-(tert-butylamino)methacrylate added is 15 parts, and the other process steps are the same as in Example 1.

[0085] Comparative Example 12 (MDI content too high)

[0086] The preparation method of the jaw pad in Comparative Example 12 differs from that in Example 1 in that the amount of MDI added in the preparation of the multi-cured closed polyurethane acrylate is 55 parts, and the other process steps are the same as in Example 1.

[0087] Comparative Example 13 (MDI content too low)

[0088] The preparation method of the jaw pad in Comparative Example 13 differs from that in Example 1 in that the amount of MDI added in the preparation of the multi-cured closed polyurethane acrylate is 25 parts, and the other process steps are the same as in Example 1.

[0089] The jaw pads obtained in Examples 1-13 were subjected to performance tests, and the test methods and results are shown in Table 1. Table 1: Performance Test Results of Jaw Pads in Examples 1-13

[0090] As can be seen from the test results in Table 1, the dental rigid occlusal pads of Examples 1-5 using the technical solution of this application all have yield stresses of over 40 MPa, yield strains of over 4%, tensile modulus of elasticity greater than 1600 MPa, right-angle tear strength greater than 100 kN / m, abrasion resistance mass loss less than 0.25 g / 1000 r, water absorption rate less than 32 μg / mm3, solubility less than 1.6 μg / mm3, in vitro cytotoxicity (cell survival rate %) greater than 90%, and high transparency (light transmittance greater than 85%). They possess excellent biocompatibility, high strength, high modulus, excellent tear resistance, excellent abrasion resistance, low water absorption, and low solubility, meeting the requirements and standards for dental rigid occlusal pads described in this application.

[0091] The performance test results of the occlusal pads in Comparative Examples 1-13 showed that the yield stress was less than 25 MPa, the yield strain was less than 4%, the tensile modulus of elasticity was less than 700 MPa, the right-angle tear strength was less than 100 kN / m, the abrasion resistance mass loss was greater than 0.25 g / 1000 r, the water absorption rate was greater than 32 μg / mm3, the solubility was greater than 1.6 μg / mm3, the light transmittance was less than 70%, and the in vitro cytotoxicity (cell survival rate%) was less than 70%, making them unsuitable for dental rigid occlusal pads.

[0092] The above description is merely a specific embodiment of this application, but the scope of protection of this application is not limited thereto. Any person skilled in the art can easily conceive of various equivalent modifications or substitutions within the technical scope disclosed in this application, and these modifications or substitutions should all be covered within the scope of protection of this application. Therefore, the scope of protection of this application should be determined by the scope of the claims. Industrial applicability

[0093] The dental rigid jaw pads 3D printed using the 3D printing resin material of this application have the following advantages: excellent biocompatibility (cell survival rate greater than 90%), high strength (yield stress greater than 40 MPa), yield strain greater than 4%, high modulus (tensile elastic modulus greater than 1600 MPa), excellent tear resistance (right-angle tear strength greater than 100 kN / m), excellent abrasion resistance (abrasion resistance mass loss less than 0.25 g / 1000 r), low water absorption (water absorption rate less than 32 μg / mm3), low solubility (solubility less than 1.6 μg / mm3), while also maintaining high transparency (light transmittance greater than 85%).

Claims

1. A 3D printing resin material, comprising the following raw materials in parts by weight: 5-50 parts of multi-cured blocked polyurethane acrylate; 5-50 parts of acrylate resin; 15-55 parts of acrylamide monomer and / or acrylate monomer containing hydroxyl or carboxyl groups; 1-4 parts of initiator; 0.01-2 parts of absorbent; 0.5-3 parts of nano silica; The multi-cured blocked polyurethane acrylate is prepared by mixing and reacting diol and isocyanate under a catalyst and at 60-90°C, followed by adding ethyl 2-(tert-butylamino)methacrylate for further mixing and reaction to achieve end-capping; the catalyst is selected from one or more of organozinc and organobismuth catalysts.

2. The 3D printing resin material according to claim 1, wherein, The aforementioned multi-curing blocked polyurethane acrylate is prepared from the following raw material components: 55-65 parts of diol, 35-45 parts isocyanate Catalyst 0.05-0.3 parts, 25-35 parts of 2-(tert-butylamino)methacrylate.

3. The 3D printing resin material according to claim 1 or 2, wherein, The diol is selected from one or more of polyethylene glycol, polypropylene glycol, dimethyl hydroxy silicone oil, hydroxyl-terminated polybutadiene, and hydroxyl-terminated polybutylene adipate.

4. The 3D printing resin material according to any one of claims 1-3, wherein, The isocyanate is selected from one or more of hexamethylene diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, phenylmethylene diisocyanate, isoflurone diisocyanate, and dicyclohexylmethane-4,4'-diisocyanate.

5. The 3D printing resin material according to any one of claims 1-4, wherein, The aforementioned multi-cured blocked polyurethane acrylate is prepared by mixing a diol and isocyanate, adding a catalyst, mixing for 3-7 hours at a temperature of 60-90℃ and a shear rate of 10-25 m / s, and then adding ethyl 2-(tert-butylamino)methacrylate and mixing for 2-4 hours for end-capping.

6. The 3D printing resin material according to any one of claims 1-5, wherein, The acrylate resins mentioned are selected from Sartoma's CN1963NS, CN1964NS, CN1993CG, CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN9062, CN959, CN9290, and C. N959, CN964NS, CN969NS, CN983NS, CN991NS, and one or more of Dymax's BR-930D, BR-941D, BR-952, BR-970BT, BR-970H, BR-990, BR-372, BR-571, BR-741, BR-744BT, BR-744SD, BR-742MS, BR-345, BR-374, BR-541S, BR-571, BR-582I10, BR-202, BR-541MB, and BR-571MB.

7. The 3D printing resin material according to any one of claims 1-6, wherein, The acrylamide monomer and / or acrylate monomer containing hydroxyl or carboxyl groups are selected from one or more of the following: cyclotrimethylolpropane methyl acetal acrylate, acrylic acid, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, dipropylene glycol diacrylate, dipropylene glycol diacrylate, (2) bisphenol A dimethacrylate oxyacetyl acrylate, (4) bisphenol A dimethacrylate oxyacetyl acrylate, (6) bisphenol A dimethacrylate oxyacetyl acrylate, tricyclodecanediethanol diacrylate, trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, 4-acryloylmorpholine, dimethylaminopropylacrylamide, diethylacrylamide, N-hydroxyethylacrylamide, and N,N-dimethylacrylamide.

8. The 3D printing resin material according to any one of claims 1-7, wherein, The initiator is selected from one or more of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone.

9. The 3D printing resin material according to any one of claims 1-8, wherein, The absorber is selected from at least one of triazine ultraviolet absorbers and benzophenone ultraviolet absorbers.

10. A method for 3D printing a rigid dental occlusal pad, comprising the following steps: By weight, the raw materials of the 3D printing resin material according to any one of claims 1-9 are mixed evenly; A three-dimensional mechanical test model is printed using a 3D printer, cured for 5-30 minutes at a wavelength of 200-800nm, a radiation intensity of 20-100mw / cm2, and a temperature of 40-60℃, and then heat-treated at 80-130℃ for 1-3 hours.

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