Photosensitive resin composition and 3D printing dental orthodontic appliance

Abstract

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

Description

Technical Field

[0001] The invention relates to a photosensitive resin composition and a 3D printed dental orthodontic appliance. Background Art

[0002] In recent years, with the rapid development of 3D printing digital light processing (DLP), the application fields are also constantly expanding, such as education, industry, jewelry, medical and other industries. Among them, the application of 3D printing technology in the dental market has attracted particular attention. The personalized, differentiated and high-precision dental needs are perfectly matched with 3D printing technology. At present, the application of 3D printing technology in the dental market is becoming more and more extensive, such as 3D printing surgical guides, dental restoration models, temporary crowns, bridges, veneers, etc. With the development of 3D printing and polymer material technology, 3D printing for orthodontic appliances has also achieved certain development.

[0003] However, the current mainstream method of making orthodontic appliances with 3D printing is that the clinic obtains the patient's tooth data through a dental scanner, and then transmits the data to the dental processing factory. The processing factory uses design software to design the tooth models of each stage of the correction process, and then prints the tooth models of each stage of the correction process through 3D printing technology as mold models, and then uses a certain thickness of PETG film material to heat and blister the 3D printed mold model. This process is an indirect production process using 3D printing technology. Due to the characteristics of thermoplastic molding, the thickness uniformity of the produced appliance is poor, the precision is low, the production process is complex, the cycle is long, and 3D printing and consumption of a large number of thermoplastic molding mold models are required.

[0004] Using 3D printing technology to directly print dental appliances can greatly improve the production efficiency of appliances, further simplify the production process, reduce material loss during the production process, and thus further reduce production costs. At the same time, directly printing appliances can directly design appliances with customized thickness in local areas through design software, which has better correction effects and diagnosis and treatment experience. Summary of the invention

[0005] To this end, an 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 for dental orthodontic appliances using 3D printing technology.

[0006] The photosensitive resin composition of the present invention comprises the following components in parts by weight: 1-30 parts of multifunctional polyurethane (meth) acrylate, wherein 3≤multifunctionality<9; Aliphatic polyurethane (meth) acrylate 10-60 parts; 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers having hydroxyl and / or carboxyl groups; 0.5-10 parts of silicon dioxide nanopowder; Curing agent 0.5-5 parts; 1-5 parts of initiator; and Absorbent 0.01-2 parts.

[0007] In some embodiments, the (meth)acrylate monomer with a hydroxyl group and / or a carboxyl group is selected from any one or more of cyclotrimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, (6) ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.

[0008] In some embodiments, the curing agent is any one or more of hexamethylene diisocyanate (HDI), toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), and dicyclohexylmethane-4,4'-diisocyanate (HMDI).

[0009] In some embodiments, the initiator is any one or more of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

[0010] 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-xylyl)-1,3,5-triazine-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2)-5-n-hexaneoxy, and UV1990.

[0011] In some embodiments, the acrylamide monomer is any one or more of 4-acryloylmorpholine, dimethylaminopropylacrylamide, diethylacrylamide, N-hydroxyethylacrylamide, and N,N-dimethylacrylamide.

[0012] In some embodiments, the silica nanopowder has a particle size of 5-500 nm.

[0013] 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 multifunctional polyurethane (meth) acrylate, wherein 3≤multifunctionality<9; 10-60 parts of aliphatic polyurethane (meth) acrylate; 5-40 parts of at least one of a (meth) acrylate monomer with hydroxyl and / or carboxyl group and acrylamide monomer; 0.5-10 parts of silicon dioxide nanopowder; 0.5-5 parts of curing agent; 1-5 parts of initiator; and 0.01-2 parts of absorbent to obtain the photosensitive resin composition.

[0014] In some embodiments, the mixing is performed in a dispersion tank.

[0015] Another object of the present invention is to provide a dental orthodontic appliance, which is 3D printed using the photosensitive resin composition.

[0016] The photosensitive resin composition of the present invention can be used to directly print a dental appliance through 3D printing technology. The dental appliance has high printing accuracy, clamping force, good tensile attenuation performance, and good toughness. DETAILED DESCRIPTION

[0017] In order to better illustrate the purpose, complete technical route and advantages of the present invention, the present invention will be further described in detail below in conjunction with specific embodiments. However, the embodiments described below are only part of the embodiments of the present invention and do not include all embodiments. Based on the embodiments of the present invention, other embodiments that can be obtained by those skilled in the art without paying creative work all belong to the protection scope of the present invention.

[0018] In the embodiments described below, unless otherwise specified, the conventional methods used are technical means generally 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 regular commercial channels.

[0019] The so-called direct 3D printed orthodontic appliances currently on the market are often a single light-curing method, and the mechanical properties are often difficult to meet actual requirements. The photosensitive resin composition of the present invention introduces a second curing agent and a corresponding active monomer, which expands the molecular chain of the material under heat treatment conditions, thereby further improving the mechanical properties of the material.

[0020] The photosensitive resin composition of the present invention comprises the following components in parts by weight: 1-30 parts of multifunctional polyurethane (meth) acrylate, wherein 3≤multifunctionality<9; Aliphatic polyurethane (meth) acrylate 10-60 parts; 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers; 0.5-10 parts of silicon dioxide nanopowder; 1-5 parts of initiator; and Absorbent 0.01-2 parts.

[0021] Among them, multifunctional polyurethane (meth) acrylate has high crosslinking density and high Tg, which can improve the clamping force and provide better tensile attenuation performance. Aliphatic polyurethane (meth) acrylate is different from aliphatic urethane dimethacrylate. Aliphatic polyurethane (meth) acrylate is an oligomer with uneven molecular weight. It is usually synthesized by polyol, isocyanate and acrylic acid in a certain proportion; aliphatic urethane dimethacrylate is a monomer. Typical substances such as dimethacrylate urethane (UDMA) have a chemical formula of C 23 H 38 N 2 O 8 Aliphatic polyurethane (meth) acrylate has high toughness and high Tg, which can improve toughness while taking into account good strength. (Meth) acrylate monomers with hydroxyl and / or carboxyl groups have low viscosity, high Tg, and good toughness. While the double bond participates in light curing, it can further react with the curing agent under heating to expand the molecular chain and improve the mechanical properties. Silica nanopowder can provide high strength and high transparency while having good toughness.

[0022] In some embodiments, the multifunctional polyurethane (meth) acrylate can be selected from any one or more of CN8898NS, CN9245, CN929, CN989NS, CN8007NS, CN8000NS, CN8001NS, CN8011NS, CN9006NS, CN9010NS, CN9110NS, CN972, CN9165, CN975NS of Sartomer, and BR-144B, BR-144H15, BR116 of Dymax.

[0023] In some embodiments, the aliphatic polyurethane (meth) acrylate can be selected from CN2920, CN2921, CN310NS, CN3211, CN8003NS, CN8010NS, CN8881NS, CN8883NS, CN8887NS, CN8889NS, CN8890NS, CN8891NS, CN8896NS, CN9001NS, CN9011, CN9014NS, CN9021NS, CN90 62. CN959, CN9290, CN959, CN964NS, CN969NS, CN983NS, CN991NS, any one or any combination of 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, BR-571MB.

[0024] Example 1 The photosensitive resin composition includes the following components in parts by weight: 6-functionality polyurethane (meth) acrylate (Sartomer CN8000NS) 5 parts; Aliphatic polyurethane (meth) acrylate (Dymax BR-742MS) 40 parts; 5 parts of isobornyl methacrylate, 5 parts of tricyclodecane dimethanol diacrylate, 5 parts of hydroxyethyl acrylate, 10 parts of cyclotrimethylolpropane formal acrylate; 2 parts of silicon dioxide nanopowder; Curing agent: Hexamethylene diisocyanate (HDI) 0.5 parts Initiator: 1.5 parts of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide; and Absorbent: 0.1 part of 2-hydroxy-4-n-octyloxybenzophenone (UV-531).

[0025] The above materials were added into the stirring and dispersing kettle in sequence, the rotation speed was adjusted to 500 r / min, i.e., a shear linear velocity of 5 m / s was provided, the temperature was controlled in the range of 40°C, and the stirring and dispersing was carried out for 4 hours.

[0026] The photosensitive resin composition of Example 1 was printed into a physical object based on the three-dimensional data of the mechanical parts for mechanical property testing by a 3D printer, cleaned with 75% medical alcohol, blown dry with a compressed air gun, and heated at a wavelength of 405 nm and 50 mW / cm 3, and perform secondary curing in a curing box at 60°C for 10 minutes, and then perform heat treatment in an oven at 100°C for 60 minutes to obtain a mechanical part for mechanical property testing.

[0027] The mechanical parts obtained in this embodiment were subjected to performance tests, and the test methods and test results are shown in Table 1.

[0028] The mechanical component obtained in this embodiment has high clamping force and good tensile force attenuation performance, while also having good toughness.

[0029] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance by a 3D printer, and the orthodontic appliance is obtained after post-processing. The orthodontic appliance has high printing accuracy, clamping force, and good tensile attenuation performance, while also having good toughness.

[0030] Example 2 The photosensitive resin composition includes the following components in parts by weight: 6-functionality polyurethane (meth) acrylate (Sartomer CN9006 NS) 1 part; Aliphatic polyurethane (meth) acrylate 60 parts (Dymax BR-372); 3 parts of 4-acryloylmorpholine, 2 parts of hydroxypropyl acrylate; 0.5 parts of silicon dioxide nanopowder; Curing agent: toluene diisocyanate (TDI) 0.5 parts Initiator: 1.5 parts of ethyl 2,4,6-trimethylbenzoyl-phenylphosphonate; and Absorbent: 0.1 part of 2-hydroxy-4-methoxybenzophenone (UV-9).

[0031] The above materials were added into the stirring and dispersing kettle in sequence, the rotation speed was adjusted to 2000 r / min, i.e., a shear linear velocity of 21 m / s was provided, the temperature was controlled at 40°C, and the stirring and dispersing was carried out for 6 hours.

[0032] The photosensitive resin composition of Example 2 was printed into a physical object based on the three-dimensional data of the mechanical parts for mechanical property testing by a 3D printer, cleaned with 75% medical alcohol, and dried with a compressed air gun. 3 The secondary curing was carried out in a curing box at 60°C for 10 minutes. Then, the heat treatment was carried out in an oven at 120°C for 60 minutes to obtain a mechanical part for mechanical property testing.

[0033] The mechanical parts obtained in this embodiment were subjected to performance tests, and the test methods and test results are shown in Table 1.

[0034] The mechanical component obtained in this embodiment has high clamping force and good tensile force attenuation performance, while also having good toughness.

[0035] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance by a 3D printer, and the orthodontic appliance is obtained after post-processing. The orthodontic appliance has high printing accuracy, clamping force, and good tensile attenuation performance, while also having good toughness.

[0036] Example 3 The photosensitive resin composition includes the following components in parts by weight: Trifunctional polyurethane (meth) acrylate (Sartomer CN989NS) 30 parts; Aliphatic polyurethane (meth) acrylate 10 parts (Dymax BR-571); 5 parts of dipropylene glycol diacrylate, 5 parts of hydroxypropyl methacrylate, 10 parts of isobornyl acrylate, (2) 10 parts of ethoxylated bisphenol A dimethacrylate, and 10 parts of tricyclodecane dimethanol diacrylate; 10 parts of silicon dioxide nanopowder; Curing agent: diphenylmethane diisocyanate (MDI) 0.5 parts Initiator: 1.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and Absorbent: 0.1 part of 2,4-dihydroxybenzophenone (UV-0).

[0037] The above materials were added into the stirring and dispersing kettle in sequence, the rotation speed was adjusted in the range of 2000 r / min, that is, a shear linear velocity of 21 m / s was provided, the temperature was controlled at 40°C, and the stirring and dispersing was carried out for 2 hours.

[0038] The photosensitive resin composition of Example 3 was printed into a physical object based on the three-dimensional data of the mechanical parts for mechanical property testing by a 3D printer, cleaned with 75% medical alcohol, and dried with a compressed air gun. 3 The secondary curing was carried out in a curing box at 60°C for 10 minutes. Then, the heat treatment was carried out in an oven at 110°C for 60 minutes to obtain a mechanical part for mechanical property testing.

[0039] The mechanical parts obtained in this embodiment were subjected to performance tests, and the test methods and test results are shown in Table 1.

[0040] The mechanical component obtained in this embodiment has high clamping force and good tensile force attenuation performance, while also having good toughness.

[0041] The photosensitive resin composition of this embodiment is printed into a physical object based on the three-dimensional data of the orthodontic appliance by a 3D printer, and the orthodontic appliance is obtained after post-processing. The orthodontic appliance has high printing accuracy, clamping force, and good tensile attenuation performance, while also having good toughness.

[0042] Comparative Example 1 The photosensitive resin composition includes the following components in parts by weight: 9-functionality polyurethane (meth) acrylate (CN9013 NS) 40 parts; Aliphatic polyurethane (meth) acrylate 20 parts (Dymax BR-371MS); 5 parts of isobornyl methacrylate, 5 parts of tricyclodecane dimethanol diacrylate, 5 parts of tripropylene glycol diacrylate, and 10 parts of cyclotrimethylolpropane formal acrylate; 2 parts of silicon dioxide nanopowder; Initiator: 1.5 parts of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide; and Absorbent: 0.1 part of 2,4-dihydroxybenzophenone (UV-0).

[0043] The above materials were added into the stirring and dispersing kettle in sequence, the rotation speed was adjusted in the range of 2000 r / min, that is, a shear linear velocity of 21 m / s was provided, the temperature was controlled at 70°C, and the stirring and dispersing was carried out for 2 hours.

[0044] The photosensitive resin composition of comparative example 1 was printed into a physical object based on the three-dimensional data of the mechanical parts for mechanical property testing by a 3D printer, cleaned with 75% medical alcohol, and dried with a compressed air gun. 3 , and secondary curing was carried out in a curing box at 60°C for 10 minutes to obtain mechanical parts for mechanical property testing.

[0045] The obtained mechanical parts were subjected to performance tests. The test methods and test results are shown in Table 1.

[0046] The mechanical parts obtained in the comparative example have lower elongation at break and right-angle tear strength, and relatively poor toughness.

[0047] Table 1

[0048] The preferred embodiments of the present invention have been specifically described above, but the present invention is not limited to the embodiments. Those skilled in the art may make various equivalent modifications or substitutions without violating the spirit of the present invention. These equivalent modifications or substitutions are all included in 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; Aliphatic polyurethane (meth) acrylate 10-60 parts; 5-40 parts of at least one of (meth)acrylate monomers and acrylamide monomers having hydroxyl and / or carboxyl groups; 0.5-10 parts of silicon dioxide nanopowder; Curing agent 0.5-5 parts; 1-5 parts of initiator; and Absorbent 0.01-2 parts.

2. The photosensitive resin composition according to claim 1, It is characterized in that The (meth)acrylate monomer with hydroxyl and / or carboxyl groups is selected from any one or more of cyclotrimethylolpropane formal acrylate, isobornyl methacrylate, isobornyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, (2) ethoxylated bisphenol A dimethacrylate, (4) ethoxylated bisphenol A dimethacrylate, (6) ethoxylated bisphenol A dimethacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate, and ethoxylated trimethylolpropane triacrylate.

3. The photosensitive resin composition according to claim 1 or 2, It is characterized in that The initiator is any one or more of (2,4,6-trimethylbenzoyl)-diphenylphosphine oxide, (2,4,6-trimethylbenzoyl)-phenylphosphonic acid ethyl ester, phenyl bis(2,4,6-trimethylbenzoyl)phosphine oxide, camphorquinone, and 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone.

4. The photosensitive resin composition according to claim 3, It is 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-xylyl)-1,3,5-triazine-2-yl]-5-(octyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2)-5-n-hexaneoxy, and UV1990.

5. The photosensitive resin composition according to claim 1, It is characterized in that The acrylamide monomer is any one or any combination of 4-acryloylmorpholine, dimethylaminopropylacrylamide, diethylacrylamide, N-hydroxyethylacrylamide and N,N-dimethylacrylamide.

6. The photosensitive resin composition according to claim 1, It is characterized in that The particle size of the silicon dioxide nanopowder is 5-500nm.

7. A dental orthodontic appliance, It is characterized in that The dental orthodontic appliance is formed by 3D printing using the photosensitive resin composition described in any one of claims 1 to 6.

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

9. The method according to claim 8, It is characterized in that The mixing is carried out in a dispersion kettle.

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