Photosensitive resin composition and 3D printed orthodontic appliance

Abstract

The application discloses a photosensitive resin composition and a 3D printing dental orthodontic appliance, and the photosensitive resin composition comprises the following components in parts by weight: a multifunctional polyurethane (meth) acrylate 1-30 parts, wherein 3<= multifunctionality <9; an aliphatic polyurethane (meth) acrylate 10-60 parts; at least one of a (meth) acrylate monomer with a hydroxyl group and / or a carboxyl group and an acrylamide monomer 5-40 parts; a nano-silicon dioxide powder 0.5-10 parts; a curing agent 0.5-5 parts; an initiator 1-5 parts; and an absorbent 0.01-2 parts. The photosensitive resin composition can be applied to a dental appliance through a 3D printing technology.

Description

Technical Field

[0001] This invention relates to a photosensitive resin composition and a 3D-printed dental orthodontic appliance. Background Technology

[0002] In recent years, with the rapid development of 3D printing digital light processing (DLP) technology, its application areas have been continuously expanding, including education, industry, jewelry, and healthcare. Among these, the application of 3D printing technology in the dental market has received particular attention. The personalized, differentiated, and high-precision needs of dental patients perfectly align with 3D printing technology. Currently, the application of 3D printing technology in the dental market is becoming increasingly widespread, including 3D-printed surgical guides, dental restorative working models, temporary crowns, bridges, and veneers. With the development of 3D printing and polymer materials technology, the fabrication of orthodontic appliances using 3D printing has also seen some progress.

[0003] However, the current mainstream method for 3D printing orthodontic appliances involves clinics acquiring patients' dental data via dental scanners, transmitting the data to a dental lab, which then uses design software to create tooth models for each stage of treatment. These models are then 3D printed as molds, and finally, a PETG film of a certain thickness is heat-formed onto the 3D-printed molds. This process is an indirect production method utilizing 3D printing technology. Due to the limitations of thermoforming, the resulting appliances exhibit poor thickness uniformity, low precision, and a complex, time-consuming manufacturing process, requiring extensive 3D printing and thermoforming molds.

[0004] Using 3D printing technology to directly print dental appliances can significantly improve manufacturing efficiency, further simplify the manufacturing process, and reduce material waste, thereby further reducing production costs. Furthermore, directly printed appliances can be designed using design software to customize the thickness of specific areas, resulting in better orthodontic outcomes and a better patient experience. Summary of the Invention

[0005] Therefore, one object of the present invention is to provide a photosensitive resin composition. The photosensitive resin composition of the present invention can be used as a printing material in 3D printing technology for dental orthodontic appliances.

[0006] The photosensitive resin composition of the present invention comprises the following components in parts by weight:

[0007] 1-30 parts of multifunctional polyurethane (meth)acrylate, wherein 3 ≤ multifunctionality < 9;

[0008] 10-60 parts of aliphatic polyurethane (meth)acrylate;

[0009] 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers containing hydroxyl and / or carboxyl groups;

[0010] 0.5-10 parts of silica nanoparticles;

[0011] Hardener 0.5-5 parts;

[0012] 1-5 parts of initiator; and

[0013] Absorbent 0.01-2 parts.

[0014] In some embodiments, the hydroxyl and / or carboxyl (meth)acrylate monomer is selected from any one or more of the following: cyclotrimethylolpropane methyl acetal acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, dipropylene glycol diacrylate, ditripropylene glycol diacrylate, (2) bisphenol A dimethacrylate oxyacetyl acrylate, (4) bisphenol A dimethacrylate oxyacetyl acrylate, (6) bisphenol A dimethacrylate oxyacetyl acrylate, tricyclodecanediethanol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.

[0015] In some embodiments, the curing agent is any one or more of hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), phenylmethylene diisocyanate (XDI), isoflurone diisocyanate (IPDI), and dicyclohexylmethane-4,4'-diisocyanate (HMDI).

[0016] In some embodiments, the initiator is any one or more of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonate ethyl ester, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone.

[0017] In some embodiments, the absorbent is any one or more of 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-[4,6-bis(2,4-dimethylyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexaneoxy, and UV1990.

[0018] In some embodiments, the acrylamide monomer is any one or more of 4-acryloylmorpholine, dimethylaminopropylacrylamide, diethylacrylamide, N-hydroxyethylacrylamide, and N,N-dimethylacrylamide.

[0019] In some embodiments, the particle size of the silica nanoparticles is 5-500 nm.

[0020] Another object of the present invention is to provide a method for preparing a photosensitive resin composition, the method comprising mixing 1-30 parts of a multifunctional polyurethane (meth)acrylate, wherein 3 ≤ multifunctionality < 9; 10-60 parts of an aliphatic polyurethane (meth)acrylate; 5-40 parts of at least one of a (meth)acrylate monomer with hydroxyl and / or carboxyl groups and an acrylamide monomer; 0.5-10 parts of silica nanoparticles; 0.5-5 parts of a curing agent; 1-5 parts of an initiator; and 0.01-2 parts of an absorbent to obtain the photosensitive resin composition.

[0021] In some implementations, the mixing is carried out in a dispersion vessel.

[0022] Another object of the present invention is to provide a dental orthodontic appliance that is 3D printed using a photosensitive resin composition.

[0023] The photosensitive resin composition of the present invention can be used to directly print dental appliances using 3D printing technology. These dental appliances have high printing accuracy, clamping force, and good tensile strength attenuation, while also exhibiting good toughness. Detailed Implementation

[0024] To better illustrate the objectives, complete technical approach, and advantages of this invention, the following detailed description will be provided in conjunction with specific embodiments. However, the embodiments described below are only a part of the embodiments of this invention and do not include all embodiments. Other embodiments that can be obtained by those skilled in the art without creative effort based on the embodiments of this invention are all within the protection scope of this invention.

[0025] In the embodiments described below, unless otherwise specified, the conventional methods used are all technical means recognized or commonly used by those skilled in the art, and the instruments, reagents, consumables, etc. used in the embodiments of the present invention can be obtained through legitimate commercial channels.

[0026] Currently available commercially available orthodontic appliances, often described as being directly 3D printed, typically rely on a single photopolymerization process, resulting in mechanical properties that often fail to meet practical requirements. This invention introduces a second curing agent and corresponding active monomers into the photosensitive resin composition. Under heat treatment conditions, this extends the material's molecular chains, thereby further improving its mechanical properties.

[0027] The photosensitive resin composition of the present invention comprises the following components in parts by weight:

[0028] 1-30 parts of multifunctional polyurethane (meth)acrylate, wherein 3 ≤ multifunctionality < 9;

[0029] 10-60 parts of aliphatic polyurethane (meth)acrylate;

[0030] 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers;

[0031] 0.5-10 parts of silica nanoparticles;

[0032] 1-5 parts of initiator; and

[0033] Absorbent 0.01-2 parts.

[0034] Multifunctional polyurethane (meth)acrylates possess high crosslinking density and high Tg, which can improve clamping force and provide better tensile strength decay resistance. Aliphatic polyurethane (meth)acrylates differ from aliphatic urethane dimethacrylates. Aliphatic polyurethane (meth)acrylates are oligomers with non-uniform molecular weights, typically synthesized from polyols, isocyanates, and acrylic acid in specific proportions; aliphatic urethane dimethacrylates are monomers, with a typical example being urethane dimethacrylate (UDMA), chemically formulated as C1... 23 H 38 N2O8. Aliphatic polyurethane (meth)acrylates possess high toughness and high Tg, which can improve toughness while maintaining good strength. Meth)acrylate monomers with hydroxyl and / or carboxyl groups have low viscosity, high Tg, and good toughness. While the double bonds participate in photocuring, they can further react with the curing agent under heating, extending the molecular chain and improving mechanical properties. Silica nanopowder can provide high strength, high transparency, and good toughness.

[0035] In some embodiments, the multifunctional polyurethane (meth)acrylate may be selected from any one or more of Sartoma's CN8898NS, CN9245, CN929, CN989NS, CN8007NS, CN8000NS, CN8001NS, CN8011NS, CN9006NS, CN9010NS, CN9110NS, CN972, CN9165, CN975NS, and Dymax's BR-144B, BR-144H15, BR116.

[0036] In some embodiments, the aliphatic polyurethane (meth)acrylate may be selected from Sartoma's CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN90 62. Any one or more of CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN991NS, Dymax's 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.

[0037] Example 1

[0038] The photosensitive resin composition comprises the following components in parts by weight:

[0039] 5 parts of 6-functionality polyurethane (meth)acrylate (Sartoma CN8000NS);

[0040] Aliphatic polyurethane (meth)acrylate (Dymax BR-742MS) 40 parts;

[0041] 5 parts of isobornyl methacrylate, 5 parts of tricyclodecanediethanol diacrylate, 5 parts of hydroxyethyl acrylate, and 10 parts of cyclotrimethylolpropane methyl acetal acrylate.

[0042] Two portions of silica nanopowder;

[0043] Curing agent: 0.5 parts hexamethylene diisocyanate (HDI)

[0044] Initiator: 1.5 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide; and

[0045] Absorbent: 0.1 parts of 2-hydroxy-4-n-octyloxybenzophenone (UV-531).

[0046] The above materials were added to the mixing and dispersing vessel in sequence, the rotation speed was adjusted to 500 r / min, which provides a shear line velocity of 5 m / s, the temperature was controlled in the range of 40℃, and the mixture was stirred and dispersed for 4 hours.

[0047] The photosensitive resin composition of Example 1 was printed into a physical object using a 3D printer based on the three-dimensional data of the mechanical component for mechanical performance testing. The object was cleaned with 75% medical alcohol, dried with a compressed air gun, and then tested at a wavelength of 405 nm and a pressure of 50 mw / cm². 3 The parts are then cured for 10 minutes in a curing oven at 60°C, and then heat-treated at 100°C in an oven for 60 minutes to obtain mechanical parts for mechanical property testing.

[0048] The mechanical components obtained in this embodiment were subjected to performance tests. The test methods and test results are shown in Table 1.

[0049] The mechanical component obtained in this embodiment has high clamping force and good tensile strength attenuation performance, while also maintaining good toughness.

[0050] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance using a 3D printer. After post-processing, the orthodontic appliance is obtained. The orthodontic appliance has high printing accuracy, clamping force and good tensile strength attenuation performance, while also taking into account good toughness.

[0051] Example 2

[0052] The photosensitive resin composition comprises the following components in parts by weight:

[0053] 1 part of 6-functional polyurethane (meth)acrylate (Sartoma CN9006 NS);

[0054] 60 parts of aliphatic polyurethane (meth)acrylate (Dymax BR-372);

[0055] 3 parts 4-acryloylmorpholine, 2 parts hydroxypropyl acrylate;

[0056] 0.5 parts of silica nanoparticles;

[0057] Curing agent: 0.5 parts toluene diisocyanate (TDI)

[0058] Initiator: 1.5 parts of ethyl 2,4,6-trimethylbenzoyl-phenylphosphonate; and

[0059] Absorbent: 0.1 parts of 2-hydroxy-4-methoxybenzophenone (UV-9).

[0060] The above materials were added to the stirring and dispersing vessel in sequence, the rotation speed was adjusted to 2000 r / min, which provides a shear line velocity of 21 m / s, the temperature was controlled at 40℃, and the mixture was stirred and dispersed for 6 hours.

[0061] The photosensitive resin composition of Example 2 was printed into a physical object using a 3D printer based on the three-dimensional data of the mechanical component for mechanical performance testing. After cleaning with 75% medical alcohol, it was dried with a compressed air gun at a wavelength of 405nm and a temperature of 50mw / cm². 3 The parts are then cured a second time in a curing oven at 60°C for 10 minutes. Finally, they are heat-treated in an oven at 120°C for 60 minutes to obtain mechanical parts for mechanical property testing.

[0062] The mechanical components obtained in this embodiment were subjected to performance tests. The test methods and test results are shown in Table 1.

[0063] The mechanical component obtained in this embodiment has high clamping force and good tensile strength attenuation performance, while also maintaining good toughness.

[0064] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance using a 3D printer. After post-processing, the orthodontic appliance is obtained. The orthodontic appliance has high printing accuracy, clamping force and good tensile strength attenuation performance, while also taking into account good toughness.

[0065] Example 3

[0066] The photosensitive resin composition comprises the following components in parts by weight:

[0067] 30 parts of 3-functional polyurethane (meth)acrylate (Sartoma CN989NS);

[0068] 10 parts of aliphatic polyurethane (meth)acrylate (Dymax BR-571);

[0069] 5 parts of dipropylene glycol diacrylate, 5 parts of hydroxypropyl methacrylate, 10 parts of isobornyl acrylate, (2) 10 parts of bisphenol A dimethacrylate and 10 parts of tricyclodecanediethanol diacrylate.

[0070] 10 parts of silica nanoparticles;

[0071] Curing agent: 0.5 parts of diphenylmethane diisocyanate (MDI)

[0072] Initiator: 1.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and

[0073] Absorbent: 0.1 parts of 2,4-dihydroxybenzophenone (UV-0).

[0074] The above materials were added to the stirring and dispersing vessel in sequence, the rotation speed was adjusted to 2000 r / min, which provides a shear line velocity of 21 m / s, the temperature was controlled at 40℃, and the mixture was stirred and dispersed for 2 hours.

[0075] The photosensitive resin composition of Example 3 was printed into a physical object using a 3D printer based on the three-dimensional data of the mechanical component for mechanical performance testing. After cleaning with 75% medical alcohol, it was dried with a compressed air gun at a wavelength of 405nm and a temperature of 50mw / cm². 3 The parts are then cured a second time in a curing oven at 60°C for 10 minutes. Finally, they are heat-treated in an oven at 110°C for 60 minutes to obtain mechanical parts for mechanical property testing.

[0076] The mechanical components obtained in this embodiment were subjected to performance tests. The test methods and test results are shown in Table 1.

[0077] The mechanical component obtained in this embodiment has high clamping force and good tensile strength attenuation performance, while also maintaining good toughness.

[0078] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance using a 3D printer. After post-processing, the orthodontic appliance is obtained. The orthodontic appliance has high printing accuracy, clamping force and good tensile strength attenuation performance, while also taking into account good toughness.

[0079] Comparative Example 1

[0080] The photosensitive resin composition comprises the following components in parts by weight:

[0081] 40 parts of 9-functionality polyurethane (meth)acrylate (CN9013 NS);

[0082] 20 parts of aliphatic polyurethane (meth)acrylate (Dymax BR-371MS);

[0083] 5 parts of isobornyl methacrylate, 5 parts of tricyclodecanediethanol diacrylate, 5 parts of tripropylene glycol diacrylate, and 10 parts of cyclotrimethylolpropane methyl acetal acrylate.

[0084] Two portions of silica nanopowder;

[0085] Initiator: 1.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and

[0086] Absorbent: 0.1 parts of 2,4-dihydroxybenzophenone (UV-0).

[0087] The above materials were added to the mixing and dispersing vessel in sequence, the rotation speed was adjusted to 2000 r / min, which provides a shear line velocity of 21 m / s, the temperature was controlled at 70℃, and the mixture was stirred and dispersed for 2 hours.

[0088] The photosensitive resin composition of Comparative Example 1 was printed into a physical object using a 3D printer based on the three-dimensional data of the mechanical component used for mechanical performance testing. After cleaning with 75% medical alcohol, it was dried with a compressed air gun and tested at a wavelength of 405nm and a pressure of 50mw / cm². 3 The parts are then cured for 10 minutes in a curing oven at 60°C to obtain mechanical parts for mechanical performance testing.

[0089] The obtained mechanical components underwent performance testing. The test methods and results are shown in Table 1.

[0090] The mechanical components obtained in the comparative model have lower elongation at break, lower right-angle tear strength, and relatively poor toughness.

[0091] Table 1

[0092]

[0093] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the embodiments described. Those skilled in the art can make various equivalent modifications or substitutions without departing from the spirit of the present invention, and these equivalent modifications or substitutions are all included within the scope defined by the claims of this application.

Claims

1. A photosensitive resin composition comprising the following components in parts by weight: 1-30 parts of multifunctional polyurethane (meth)acrylate, wherein 3 ≤ multifunctionality < 9; 10-60 parts of aliphatic polyurethane (meth)acrylate; 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers containing hydroxyl and / or carboxyl groups; 0.5-10 parts of silica nanoparticles; Hardener 0.5-5 parts; Initiator 1-5 parts; and Absorbent 0.01-2 parts.

2. The photosensitive resin composition according to claim 1, characterized in that, The (meth)acrylate monomers with hydroxyl and / or carboxyl groups are selected from any one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate.

3. The photosensitive resin composition according to claim 2, characterized in that, The photosensitive resin composition further includes: The following are listed: (1) cyclotrimethylolpropane methyl acetal acrylate, (2) isobornyl methacrylate, (3) isobornyl acrylate, (4) bisphenol A ethoxylate, (5) tricyclodecanedimethylol diacrylate, (6) ethoxylated bisphenol A dimethacrylate, tricyclodecanedimethylol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.

4. The photosensitive resin composition according to claim 1 or 2, characterized in that, The initiator is any one or more of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonate ethyl ester, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone.

5. The photosensitive resin composition according to claim 4, characterized in that, The absorbent is any one or more of 2-hydroxy-4-n-octyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-[4,6-bis(2,4-dimethylyl)-1,3,5-triazin-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2)-5-n-hexaneoxy, and UV1990.

6. The photosensitive resin composition according to claim 1, characterized in that, The acrylamide monomer is any one or more of dimethylaminopropylacrylamide and N-hydroxyethylacrylamide.

7. The photosensitive resin composition according to claim 6, characterized in that, The photosensitive resin composition further includes any one or more of 4-acryloylmorpholine, diethylacrylamide, and N,N-dimethylacrylamide.

8. The photosensitive resin composition according to claim 1, characterized in that, The particle size of the silica nanoparticles is 5-500 nm.

9. A dental orthodontic appliance, characterized in that, The dental orthodontic appliance is 3D printed using the photosensitive resin composition according to any one of claims 1-8.

10. A method for preparing a photosensitive resin composition, comprising: 1-30 parts of multifunctional polyurethane (meth)acrylate, wherein 3 ≤ multifunctionality < 9; 10-60 parts aliphatic polyurethane (meth)acrylate; The photosensitive resin composition is obtained by mixing 5-40 parts of at least one of (meth)acrylate monomers with hydroxyl and / or carboxyl groups and acrylamide monomers; 0.5-10 parts of silica nanoparticles; 0.5-5 parts of curing agent; 1-5 parts of initiator; and 0.01-2 parts of absorbent.

11. The method according to claim 10, characterized in that, The mixing is carried out in a dispersion vessel.

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