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EP-4378970-B1 - PHOTOTHERMAL-CURING RESIN COMPOSITION, AND PREPARATION METHOD THEREFOR AND USE THEREOF

EP4378970B1EP 4378970 B1EP4378970 B1EP 4378970B1EP-4378970-B1

Inventors

  • ZHANG, JIAXIN
  • LI, HONGWEN
  • DUAN, Guangyuan
  • XING, LINLIN

Dates

Publication Date
20260506
Application Date
20220708

Claims (13)

  1. A photothermal-curing resin composition, wherein the resin composition comprises following components by weight parts: a prepolymer 30 weight parts; a monomer 5~50 weight parts; a photoinitiator 0.01~5 weight parts; a thermal initiator 0.01~5 weight parts; a fumed silica 0.01~40 weight parts; and a glass powder 0.01~40 weight parts, wherein the prepolymer comprises any one or a combination of at least two of polyurethane acrylate, urethane dimethacrylate, bisphenol A-dimethacrylate glycidyl ester, ethoxybisphenol A dimethacrylate, or bisphenol A glycerol dimethacrylate, the monomer comprises any one or a combination of at least two of triethylene glycol dimethacrylate, hydroxyethyl methacrylate, or hydroxypropyl methacrylate, and the glass powder comprises glass powder with a particle size of 0.6~0.8 µm and glass powder with a particle size of 0.3~0.5 µm.
  2. The resin composition according to claim 1, wherein the thermal initiator comprises any one or a combination of at least two of dibenzoyl peroxide, azodiisobutyronitrile, or di-tert-butyl peroxide.
  3. The resin composition according to claim 1, wherein the photoinitiator comprises any one or a combination of at least two of 2,4,6-trimethylbenzoyl-ethoxy-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide.
  4. The resin composition according to claim 1, wherein the fumed silica is fumed silica after lipophilic treatment.
  5. The resin composition according to claim 1 or 6, wherein a particle size of the fumed silica is 10~30 nm.
  6. The resin composition according to claim 1, wherein the glass powder is glass powder containing barium.
  7. The resin composition according to claim 1 or 6, wherein a mass ratio between the glass powder with the particle size of 0.6~0.8 µm and the glass powder with the particle size of 0.3~0.5 µm is (1~3): 1.
  8. The resin composition according to claim 1, wherein the resin composition further comprises any one or a combination of at least two of a catalyst, a dispersant, an antifoaming agent, a colorant, and an inhibitor, preferably, a content of the catalyst in the resin composition is 0.05~0.2 weight parts; preferably, the catalyst comprises dimethylaminoethyl methacrylate; preferably, a content of the dispersant in the resin composition is 0.01 ~ 5 weight parts; preferably, the dispersant comprises any one or a combination of at least two of zinc stearate, sodium stearate, and stearic acid; preferably, a content of the antifoaming agent in the resin composition is 0.01~5 weight parts; preferably, the antifoaming agent comprises any one or a combination of at least two of a polymer antifoaming agent, organosilicon antifoaming agent, or organosilicon/polymer composite antifoaming agent; preferably, a content of the colorant in the resin composition is 0 ~ 5 weight parts and not equal to 0; preferably, the colorant comprises any one or a combination of at least two of titanium oxide, iron oxide red, iron oxide yellow, iron oxide black, or carbon black; preferably, a content of the inhibitor in the resin composition is 0.005 ~ 0.1 weight parts; and preferably, the inhibitor comprises any one or a combination of at least two of 2,6-di-tert-butyl-p-cresol, tert-butyl-catechol, or p-phenol monobutyl ether.
  9. A preparation method of the resin composition according to any one of claims 1~8, wherein the preparation method comprises following steps: (1) mixing the monomer, the photoinitiator, the thermal initiator, an optional dispersant, an optional antifoaming agent, an optional catalyst, and an optional colorant, so as to obtain a mixed monomer; (2) mixing the mixed monomer obtained in step (1) and the prepolymer, so as to obtain a mixed resin; and (3) mixing the mixed resin obtained in step (2), the fumed silica, and the glass powder, so as to obtain the resin composition.
  10. A temporary crown and bridge of 3D printing, wherein preparation raw materials of the temporary crown and bridge of 3D printing comprises the resin composition according to any one of claims 1~8 or the resin composition prepared by the preparation method according to claim 11.
  11. A preparation method of the temporary crown and bridge of 3D printing according to claim 10, wherein the preparation method comprises: 3D printing and post-curing the resin composition according to any one of claims 1~8 or the resin composition prepared by the preparation method according to claim 11, so as to obtain the temporary crown and bridge of 3D printing.
  12. The preparation method according to claim 11, wherein the post-curing comprises a combination of photo curing and thermal curing, preferably, a wavelength of the photo curing is 355~410 nm; and preferably, a temperature of the thermal curing is 30~100°C.
  13. Use of the temporary crown and bridge of 3D printing according to claim 10 or the temporary crown and bridge of 3D printing prepared by the preparation method according to claim 11 or 12 as an oral restorative material or an oral implant material.

Description

Technical Field The present disclosure belongs to the technical field of resin materials, and specifically relates to a photothermal-curing resin composition, and preparation method therefor and use thereof. Background Art A temporary crown and bridge is a type of temporary tooth crown or bridge body worn by a patient before finally wearing the tooth crown, which is used in a field of oral implantology and restoration. The conventional method to make the temporary crown and bridge is mainly to manually mix denture powder and denture water to mold. The molding is generally divided into intraoral molding or extraoral molding. The residual methacrylic acid resin has a very irritating and pungent odor, thus providing the patient with a pretty poor treatment experience. Currently, some processing plants use cutting technology to make PMMA temporary crown and bridge. The PMMA realizes digital processing, which increases the processing efficiency, but this technology has a very low material utilization rate, so that the material is wasted seriously. Additionally, the cutting process generates dust, which is less environmentally friendly. 3D printing is a type of additive manufacturing process, which can complete a processing of elaborate or hollow workpiece that is difficult to be made by cutting and is especially suitable for personalized data production, such as the temporary crown and bridge. The material utilization rate of the additive manufacturing is very high, which can save costs. Therefore, the use of 3D printing technology in the dental department is a key to realize a digitalization of the dental department. The 3D printing material used in the dental department is generally the photosensitive resin, which is cured and accumulated layer by layer via laser surface molding or spot molding on a 3D printing device with a certain emission wavelength, such that finally the desired printed workpiece is formed. In the method of 3D printing, it needs only two steps, namely, obtaining data and wearing the temporary crown, to make the temporary crown and bridge, where the operation is simple and therefore the operation time can be greatly reduced. With the rapid development of additive manufacturing technology, the temporary crown and bridge by 3D printing brings a new direction. However, the resin used for the 3D printing of the temporary crown and bridge not only needs a higher biocompatibility for the cured material, but also needs a better mechanical property. The performance of the temporary crown and bridge obtained by the 3D printing of the simple photo-curing system cannot satisfy the use of the temporary tooth crown. The completion of the photo-curing parts in the system after printed and molded is low and the overall performance is poor, and there will be the problem of stress shrinkage. The Chinese patent CN106947034A discloses a thermal post curing 3D printing photosensitive resin, a preparation method and application thereof. The photosensitive resin includes a prepolymer, diluent, photoinitiator, and thermal initiator, wherein a decomposition temperature of the thermal initiator at the half-life time of one hour is larger than or equal to 100° C. The weight parts of each of the components are as follows: 50~70 parts of the prepolymer, 30~50 parts of the diluent, 1~5 parts of the photoinitiator, and 0.5~5 parts of the thermal initiator. After molded by the photo-curing 3D printing, the post-curing method of the 3D printing photosensitive resin obtained by this invention can be selected from an oven or other stable constant-temperature heating equipment for thermal post curing. Therefore, the 3D printing photosensitive resin of thermal post curing is obtained, which extends the use in opaque samples, samples with complex shapes, ultra-thick samples, and the colored samples, etc., and also provides the samples with better mechanical property. However, the curing after printing and molding in the above prior art is only thermal curing, without further photo curing. The photo curing parts of this resin system has a low degree of completion and poor overall performance, and the resin compositions do not contain inorganic fillers, so that the resin composition ultimately obtained has stress shrinkage and low hardness. The Chinese patent CN110128773A discloses a photo/thermal double curing 3D printing method and product thereof, including the following steps: mixing raw materials for photo-curing 3D printing, and then carrying out the thermal curing to obtain the 3D printed product, wherein the raw materials include: polyurethane acrylate, diluent, initiator, epoxy resin, and thermal curing agent, wherein the polyurethane acrylate is obtained by end capping by acrylate with hydroxyl groups after isocyanate reacts with polyols. The polyols are polyester polyols or polyether glycols with a molecular weight not less than 1000. The method of this invention avoids a phenomenon that the thermal curing of the epox