Curable composition for use in a high temperature lithography-based photopolymerization process and method of producing crosslinked polymers therefrom

Patent metadata

Field	Value
Publication number	US-12042353-B2
Application number	US-202217883390-A
Country	US
Kind code	B2
Filing date	Aug 8, 2022
Priority date	May 4, 2018
Publication date	Jul 23, 2024
Grant date	Jul 23, 2024

Abstract

Provided herein are curable compositions for use in a high temperature lithography-based photopolymerization process, a method of producing crosslinked polymers using said curable compositions, crosslinked polymers thus produced, and orthodontic appliances comprising the crosslinked polymers.

First claim

What is claimed is:

1. An orthodontic appliance comprising a crosslinked polymer, the crosslinked polymer comprising:
a first repeating unit having a number average molecular weight of greater than 5 kDa, wherein the first repeating unit is derived from a (poly)carbonate-(poly)urethane dimethacrylate oligomer;
a second repeating unit having a number average molecular weight of 0.4 to 5 kDa, wherein the second repeating unit is derived from a (poly)urethane dimethacrylate oligomer; and
a third repeating unit derived from a monomer of the following formula:

wherein:
R 8 represents optionally substituted C 3 -C 10 cycloalkyl, optionally substituted 3- to 10-membered heterocycloalkyl, or optionally substituted C 6 -C 10 aryl;
R 9 represents H or C 1 -C 6 alkyl;
each R 10 independently represents halo, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, Si(R 11 ) 3 , P(O)(OR 12 ) 12 , or N(R 13 ) 2 ;
each R 11 independently represents C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
each R 12 independently represents C 1 -C 6 alkyl or C 6 -C 10 aryl;
each R 13 independently represents H or C 1 -C 6 alkyl;
X is absent, C 1 -C 3 alkylene, 1- to 3-membered heteroalkylene, or (CH 2 CH 2 O) r ;
Y is absent or C 1 -C 6 alkylene;
q is an integer from 0 to 4; and
r is an integer from 1 to 4, and

wherein each dashed line represents a bond to a carbon atom, and
wherein the crosslinked polymer has an elongation at break greater than or equal to 5% when measured according to ISO 527-2 5B.

2. The orthodontic appliance of claim 1 , wherein the crosslinked polymer further has one or more of the following properties:
a tensile modulus greater than or equal to 100 MPa;
a tensile strength at yield greater than or equal to 5 MPa;
an elongation at yield greater than or equal to 4%;
a stress relaxation of greater than or equal to 5% of the initial load; and
a glass transition temperature of greater than or equal to 90° C.

3. The orthodontic appliance of claim 2 , wherein the crosslinked polymer exhibits an elongation at break from 5% to 250%, a tensile modulus from 100 MPa to 2000 MPa, a tensile strength at yield from 5 MPa to 85 MPa, an elongation at yield from 4% to 10%, a stress relaxation from 5% to 45% of the initial load and a glass transition temperature of 90° C. to 150° C.

4. An orthodontic appliance comprising a crosslinked polymer prepared from a curable composition, the curable composition comprising:
a crosslinker;
a toughness modifier, wherein the toughness modifier is a polymerizable oligomer having a number average molecular weight of greater than 5 kDa and wherein a content of the toughness modifier is such that the crosslinked polymer has an elongation at break greater than or equal to 5% when measured according to ISO 527-2 5B; and
a reactive diluent, wherein the reactive diluent is a polymerizable compound having a molecular weight of 0.1 to 1.0 kDa and wherein a content of the reactive diluent is such that a viscosity of curable the composition is 1 to 70 Pa·s at 110° C.

5. The orthodontic appliance of claim 4 , wherein the crosslinker is operative to crosslink the toughness modifier and the reactive diluent to form the crosslinked polymer upon exposure to actinic radiation and/or heat, the crosslinker having a higher glass transition temperature than the toughness modifier and a number average molecular weight of 0.4 to 5 kDa.

6. The orthodontic appliance of claim 5 , wherein the crosslinker comprises TGM1, TGM2, TGM3, TGM4, H1188, a compound of formula (I), 1,10-decanediol dimethacrylate (D3MA), 1,12-dodecanediol dimethacrylate (D4MA), or mixtures thereof,
wherein:
TGM1 has the following structures:

TGM2 has the following structures:

TGM3 has the following structures:

TGM4 has the following structures:

H1188 the following structures:

 and
the compound of formula (I) has the following structure:

wherein:
each R 1 and each R 2 independently represent a divalent, linear, branched or cyclic C 5 -C 15 aliphatic radical, with the proviso that at least one of R 1 and R 2 is or comprises a C 5 -C 6 cycloaliphatic structure,
each R 3 independently represents a divalent, linear or branched C 2 -C 4 alkyl radical, and
n is an integer from 1 to 5.

7. The orthodontic appliance of claim 4 , wherein the curable composition comprises 5 to 50 wt %, based on the total weight of the composition, of the crosslinker.

8. The orthodontic appliance of claim 4 , wherein the content of the reactive diluent is such that the viscosity of the composition is less than 70 Pa·s at 90° C.

9. The orthodontic appliance of claim 4 , wherein a glass transition temperature (Tg) of the toughness modifier is less than 0° C.

10. The orthodontic appliance of claim 4 , wherein the curable composition comprises 20 to 50 wt %, based on the total weight of the composition, of the toughness modifier.

11. The orthodontic appliance of claim 4 , wherein the toughness modifier is a poly)carbonate-(poly)urethane dimethacrylate oligomer according to any one of the following chemical formulas (II), (III), (IV) or (V):

wherein:
each R 4 and each R 5 independently represent a divalent, linear, branched or cyclic C 5 -C 15 aliphatic radical;
each R 6 independently represents a divalent, linear or branched C 2 -C 4 alkyl radical;
each R 7 independently represents a divalent, linear, branched C 2 -C 6 alkyl radical, or is absent;
each n is independently an integer from 1 to 10;
each m is independently an integer from 1 to 20;
each o is independently an integer from 5 to 50 or is absent; and
p is an integer from 1 to 40 or is absent.

12. The orthodontic appliance of claim 4 , wherein the reactive diluent is operative to reduce the viscosity of the curable composition by at least 10%.

13. The orthodontic appliance of claim 4 , wherein the reactive diluent comprises at least one mono- or multifunctional-methacrylate based compound.

14. The orthodontic appliance of claim 13 , wherein the reactive diluent comprises a compound according to the following chemical formula (VII):

wherein:
R 8 represents optionally substituted C 3 -C 10 cycloalkyl, optionally substituted 3- to 10-membered heterocycloalkyl, or optionally substituted C 6 -C 10 aryl;
R 9 represents H or C 1 -C 6 alkyl;
each R 10 independently represents halo, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, P(O)(OR 12 ) 2 , or N(R 13 ) 2 ;
each R 11 independently represents C 1 -C 6 alkyl or C 1 -C 6 alkoxy;
each R 12 indep

Assignees

• Align Technology Inc

Inventors

• Liska Robert
• Gorsche Christian
• Harakaly Gyorgy
• Kury Markus
• Stampfl Jurgen
• Dorfinger Peter
• Chen Yan
• Li Chunhua
• Kaza Srinivas

Classifications

• B22F10/60

  Treatment of workpieces or articles after build-up · CPC title

• B22F10/38

  to achieve specific product aspects, e.g. surface smoothness, density, porosity or hollow structures · CPC title

• B22F10/20

  Direct sintering or melting · CPC title

• B22F10/12

  by photopolymerisation, e.g. stereolithography [SLA] or digital light processing [DLP] · CPC title

• C08G18/44

  Polycarbonates · CPC title