Photopolymerizable compositions including a urethane component and a reactive diluent, articles, and methods

1. A photopolymerizable composition comprising:

(a) 50 to 90 wt. %, inclusive, of at least one urethane component; wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol;

(b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate;

(c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and

(d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition,

wherein the photopolymerizable composition has a viscosity at a temperature of 40 degrees Celsius of 10 Pa·s or less, as determined using a magnetic bearing rheometer using a 40 mm cone and plate measuring system at a shear rate of 0.1 l/s, wherein the photopolymerizable composition is free of monofunctional components, wherein a reaction product of the photopolymerizable composition exhibits an elongation at break of 25% or greater, and wherein an article comprising the reaction product is an orthodontic article comprising a plurality of layers.

2. The photopolymerizable composition of claim 1 , wherein the at least one urethane oligomer comprises a urethane (meth)acrylate, a urethane acrylamide, or combinations thereof, and wherein the at least one urethane component comprises a linking group selected from alkyl, polyalkylene, polyalkylene oxide, aryl, polycarbonate, polyester, polyamide, and combinations thereof.

3. The photopolymerizable composition of claim 1 , wherein the at least one reactive diluent comprises a molecular weight of 200 grams per mole to 400 grams per mole, inclusive.

4. The photopolymerizable composition of claim 1 , wherein the at least one reactive diluent comprises one or more of ethoxylated bisphenol A dimethacrylate, tetraethylene glycol dimethacrylate, triethyleneglycol dimethacrylate, 1,3-propanediol dimethacrylate, 1,2,4-butanetriol trimethacrylate, pentaerythritol tetramethacrylate, trishydroxyethyl-isocyanurate trimethacrylate, or a bis-methacrylate of a polyethylene glycol.

5. An orthodontic article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising:

(a) 50 to 90 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol;

(b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate;

(c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and

(d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components, wherein the article exhibits an elongation at break of 25% or greater, and wherein the article comprises a plurality of layers.

6. The orthodontic article of claim 5 , wherein the article comprises an orthodontic clear tray aligner.

7. The orthodontic article of claim 5 , comprising one or more channels, one or more undercuts, one or more perforations, or combinations thereof.

8. The orthodontic article of claim 5 , comprising an elongation at break of 30% or greater.

9. The orthodontic article of claim 5 , comprising a tensile strength of 20 MegaPascals (MPa) or greater, as determined according to ASTM D638-10.

10. The orthodontic article of claim 5 , comprising a modulus of 200 MPa or greater, as determined according to ASTM D638-10.

11. A method of making an article, the method comprising:

(i) providing a photopolymerizable composition comprising: (a) 50 to 90 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol; (b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate; (c) 0.1 to 5 wt. %, inclusive, of a photoinitiator;

and (d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components;

(ii) selectively curing the photopolymerizable composition to form an orthodontic article;

(iii) optionally curing unpolymerized urethane component and/or reactive diluent remaining after step (ii), wherein the article exhibits an elongation at break of 25% or greater; and

(iv) repeating steps (i) and (ii) to form multiple layers and create the article comprising a three dimensional structure prior to step (iii).

12. A non-transitory machine readable medium having data representing a three-dimensional model of an article, when accessed by one or more processors interfacing with a 3D printer, causes the 3D printer to create an orthodontic article, the article comprising:

a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: (a) 50 to 90 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol; (b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate; (c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and (d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components, and wherein the article exhibits an elongation at break of 25% or greater.

13. A method comprising:

retrieving, from a non-transitory machine readable medium, data representing a 3D model of an orthodontic article, the article comprising:

a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: (a) 50 to 90 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol; (b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate; (c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and (d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components;

executing, by one or more processors, a 3D printing application interfacing with a manufacturing device using the data; and

generating, by the manufacturing device, a physical object of the article, wherein the article exhibits an elongation at break of 25% or greater.

14. A method comprising:

receiving, by a manufacturing device having one or more processors, a digital object comprising data specifying a plurality of layers of an orthodontic article, the article comprising:

a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: (a) 50 to 90 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol; (b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate; (c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and (d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components; and

generating, with the manufacturing device by an additive manufacturing process, the article based on the digital object, wherein the article exhibits an elongation at break of 25% or greater.

15. A system comprising:

a display that displays a 3D model of an article; and

one or more processors that, in response to the 3D model selected by a user, cause a 3D printer to create a physical object of an orthodontic article, the article comprising:

a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: (a) 50 to 80 wt. %, inclusive, of at least one urethane component, wherein the at least one urethane component comprises a high Mn urethane component and a low Mn urethane component, wherein a ratio of the high Mn urethane component to the low Mn urethane component ranges from 95:5 high Mn urethane component to low Mn urethane component to 80:20 high Mn urethane component to low Mn urethane component, wherein the high Mn urethane component has a number average molecular weight of 1,000 grams per mole (g/mol) or greater, with the proviso that all branches off the backbone of the compound, if present, have a Mn of no more than 200 g/mol, and wherein the low Mn urethane component has either 1) a number average molecular weight of 100 g/mol or greater and up to but not including 1,000 g/mol, or 2) a number average molecular weight of 100 g/mol or greater and 2,000 g/mol or less, with the proviso that a number average molecular weight of any one or more linear portions between two reactive groups and/or branches is up to but not including 1,000 g/mol; (b) 5 to 50 wt. %, inclusive, of at least one reactive diluent, wherein the at least one reactive diluent has a molecular weight of 400 grams per mole or less, is free of any urethane functional groups, and comprises a methacrylate; (c) 0.1 to 5 wt. %, inclusive, of a photoinitiator; and (d) an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present; based on the total weight of the photopolymerizable composition, wherein the photopolymerizable composition is free of monofunctional components, and wherein the article exhibits an elongation at break of 25% or greater.