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

Patent metadata

Field	Value
Publication number	US-11389276-B2
Application number	US-201816753871-A
Country	US
Kind code	B2
Filing date	Nov 9, 2018
Priority date	Nov 22, 2017
Publication date	Jul 19, 2022
Grant date	Jul 19, 2022

Abstract

The present disclosure provides a photopolymerizable composition. The photopolymerizable composition includes at least one urethane component, at least one monofunctional reactive diluent, an initiator, and optionally an inhibitor. The present disclosure also provides an article including the reaction product of the photopolymerizable composition. Further, the present disclosure provides a method of making an article. The method includes (i) providing a photopolymerizable composition and (ii) selectively curing the photopolymerizable composition to form an article. The method optionally also includes (iii) curing unpolymerized urethane component and/or reactive diluent remaining after step (ii). Further, methods are provided, including receiving, by a manufacturing device having one or more processors, a digital object comprising data specifying an article; and generating, with the manufacturing device by an additive manufacturing process, the article based on the digital object. A system is also provided, including 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 article.

First claim

The invention claimed is:

1. An article comprising a reaction product of a photopolymerizable composition, wherein the article is an orthodontic article, wherein the photopolymerizable composition comprises a blend of:
a. 30 to 70 wt. %, inclusive, of at least one urethane component;
b. 25 to 70 wt. %, inclusive, of at least one monofunctional reactive diluent, wherein the at least one monofunctional reactive diluent comprises at least one monofunctional reactive diluent having a T g of up to but not including 25 degrees Celsius and wherein i) the at least one monofunctional reactive diluent comprises phenoxy ethyl methacrylate in an amount of 20 to 80 wt. % of the total amount of the at least one monofunctional reactive diluent, or ii) the at least one monofunctional reactive diluent is present in the form a prepolymer, or both i) and ii), and wherein the at least one monofunctional reactive diluent further comprises at least one monofunctional reactive diluent having a T g of 25 degrees Celsius or greater;
c. optionally at least one multifunctional reactive diluent in an amount of 1 to 30 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition;
d. 0.1 to 5 wt. %, inclusive, of at least one initiator; and
e. an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition.

2. The article of claim 1 , wherein the at least one urethane component 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 article of claim 1 , wherein the at least one monofunctional reactive diluent comprises a compatibilizer present in an amount of at least 30 wt. % of the amount of the at least one urethane component.

4. The article of claim 1 , wherein the at least one monofunctional reactive diluent comprises a (meth)acrylate, an alkyl (meth)acrylate, a phenoxy (meth)acrylate, a hydroxy alkyl (meth)acrylate, or a combination thereof.

5. The article of claim 1 , wherein the at least one monofunctional reactive diluent comprises phenoxy ethyl methacrylate in an amount of 20 to 80 wt. % of the total amount of the at least one monofunctional reactive diluent.

6. The article of claim 1 , wherein the at least one multifunctional reactive diluent is present and comprises a polyester methacrylate.

7. The article of claim 1 , wherein the at least one monofunctional reactive diluent comprises a monofunctional reactive diluent exhibiting a hydrophilic-lipophilic balance (HLB) value of less than 10.

8. The article of claim 1 , wherein the at least one initiator comprises a photoinitiator, a thermal initiator, or a combination thereof.

9. The article of claim 1 , wherein the at least one monofunctional reactive diluent is present in the form a prepolymer.

10. The article of claim 1 , wherein the at least one urethane component comprises at least one pendant group comprising a photoinitiator.

11. The article of claim 1 , wherein the article comprises a plurality of layers.

12. The article of claim 1 , exhibiting an elongation at break of 40% or greater.

13. The article of claim 1 , exhibiting a tensile strength of 20 MegaPascals (MPa) or greater, as determined according to ASTM D638-10.

14. The article of claim 1 , exhibiting a modulus of 500 MPa or greater, as determined according to ASTM D638-10.

15. A non-transitory machine readable medium comprising data representing a three-dimensional model of an orthodontic article, when accessed by one or more processors interfacing with a 3D printer, causes the 3D printer to create an article comprising a reaction product of a photopolymerizable composition comprising a blend of:
a. 30 to 70 wt. %, inclusive, of at least one urethane component;
b. 25 to 70 wt. %, inclusive, of at least one monofunctional reactive diluent, wherein the at least one monofunctional reactive diluent comprises at least one monofunctional reactive diluent having a T g of up to but not including 25 degrees Celsius and wherein i) the at least one monofunctional reactive diluent comprises phenoxy ethyl methacrylate in an amount of 20 to 80 wt. % of the total amount of the at least one monofunctional reactive diluent, or ii) the at least one monofunctional reactive diluent is present in the form a prepolymer, or both i) and ii), and wherein the at least one monofunctional reactive diluent further comprises at least one monofunctional reactive diluent having a T g of 25 degrees Celsius or greater;
c. optionally at least one multifunctional reactive diluent in an amount of 1 to 30 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition;
d. 0.1 to 5 wt. %, inclusive, of at least one initiator; and
e. an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition.

16. A method comprising:
a. receiving, by a manufacturing device having one or more processors, a digital object comprising data specifying a plurality of layers of an orthodontic article; and
b. generating, with the manufacturing device by an additive manufacturing process, the article based on the digital object, the orthodontic article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising a blend of:
i. 30 to 70 wt. %, inclusive, of at least one urethane component;
ii. 25 to 70 wt. %, inclusive, of at least one monofunctional reactive diluent, wherein the at least one monofunctional reactive diluent comprises at least one monofunctional reactive diluent having a T g of up to but not including 25 degrees Celsius and wherein i) the at least one monofunctional reactive diluent comprises phenoxy ethyl methacrylate in an amount of 20 to 80 wt. % of the total amount of the at least one monofunctional reactive diluent, or ii) the at least one monofunctional reactive diluent is present in the form a prepolymer, or both i) and ii), and wherein the at least one monofunctional reactive diluent further comprises at least one monofunctional reactive diluent having a T g of 25 degrees Celsius or greater;
iii. optionally at least one multifunctional reactive diluent in an amount of 1 to 30 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition;
iv. 0.1 to 5 wt. %, inclusive, of at least one initiator; and
v. an optional inhibitor in an amount of 0.001 to 1 wt. %, inclusive, if present, based on the total weight of the photopolymerizable composition.

17. The article of claim 1 , further comprising at least one filler selected the group consisting of from silica, alumina, zirconia, and discontinuous fibers.

Assignees

• 3M Innovative Properties Co
• 3M Innovative Properties Comany

Inventors

• Parkar Zeba
• Janoski Jonathan E
• Thomas Carla S
• Devoe Robert J
• Abuelyaman Ahmed S
• Nelson Eric W
• Ross Richard B
• Riedesel John M

Classifications

• B33Y70/10

  Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials · CPC title

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• C08F220/1808

  C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate · CPC title

• C08F290/067

  Polyurethanes; Polyureas · CPC title

• B33Y80/00

  Products made by additive manufacturing · CPC title