IP Library › Granted Patent US 12,070,368
Granted Patent B2
US 12,070,368 · App. 17/274,208 · Granted Aug 27, 2024

3D-printed orthodontic splint made of crosslinked polymers

Inventors: Dirk Achten (Leverkusen, DE); Roland Wagner (Leverkusen, DE); Christoph Tomczyk (Leverkusen, DE); Thomas Buesgen (Leverkusen, DE)
Assignee: Stratasys Inc.
A61C7/08B33Y70/00B33Y80/00A61C2201/00B33Y10/00
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Quick Facts
Patent No.
US 12,070,368
App. No.
17/274,208
Granted
Aug 27, 2024
Kind
B2
Abstract

The present invention relates to an orthodontic splint made of a crosslinked polymer, wherein the crosslinked polymer has a glass transition temperature T g , determined by means of dynamic-mechanical analysis at a frequency of 1/s DMA as peak tan δ, of ≥25° C. and ≤60° C., a modulus of elasticity, determined by means of dynamic-mechanical analysis as the storage modulus E′ at a frequency of 1/s at 35° C., of ≥500 MPa and ≤4000 MPa, and a loss factor tan δ, determined by means of dynamic-mechanical analysis at a frequency of 1/s at 35° C., of ≥0.08. The invention further relates to a process for producing such splints.

Claims (33)

1. A method for producing an orthodontic aligner, comprising:

i) selecting a crosslinkable resin; and

ii) shaping the aligner by crosslinking the crosslinkable resin to form a crosslinked polymer,

wherein selecting the crosslinkable resin includes a criterion that a crosslinked polymer obtained after crosslinking of the crosslinkable resin has a glass transition temperature Tg, determined by dynamic mechanical analysis at a frequency of 1/s DMA as peak tan δ, of 25° C. and ≤60° C., an elasticity modulus, determined by dynamic mechanical analysis as storage modulus E′ at a frequency of 1/s at 35° C., of ≥500 MPa and ≤4000 MPa, and a loss factor tan δ, determined by dynamic mechanical analysis at a frequency of 1/s at 35° C., of ≥0.08,

wherein the crosslinkable resin comprises a first monomer and a second monomer, said first monomer being a (meth)acrylic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≤0° C., and said second monomer being a (meth)acrylic or styrenic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≥60° C., and where the first monomer is present in a fraction of ≥5 to ≤40 weight %, based on a total weight of the resin, and the second monomer is present in a fraction of ≥20 to ≤80 weight %, based on the total weight of the resin.

2. The method as claimed in claim 1 , wherein the aligner is shaped by crosslinking the crosslinkable resin in a casting mold corresponding to the aligner.

3. The method as claimed in claim 1 , wherein the aligner is shaped via an additive manufacturing method.

4. The method as claimed in claim 1 , wherein the crosslinkable resin has free isocyanate groups, measured by 13C NMR, in a concentration ≥1 wt %, based on a total weight of the crosslinkable resin.

5. The method as claimed in claim 1 , wherein the crosslinkable resin has free alcohol groups, measured by 13C NMR, in a concentration ≥0.5 wt %, based on a total weight of the crosslinkable resin.

6. An orthodontic aligner, comprising

a crosslinked polymer having a glass transition temperature Tg, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≥25° C. and ≤60° C., an elasticity modulus, determined by dynamic mechanical analysis as storage modulus E′ at a frequency of 1/s at 35° C., of ≥500 MPa and ≤4000 MPa, and a loss factor tan δ, determined by dynamic mechanical analysis at a frequency of 1/s at 35° C., of 0.08,

wherein the crosslinked polymer is a copolymer which comprises units based on a first monomer and a second monomer, said first monomer being a (meth)acrylic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≤0° C., and said second monomer being a (meth)acrylic or styrenic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≥60° C., and where units based on the first monomer are present in a fraction of ≥5 to ≤40 weight %, based on a total weight of the crosslinked polymer, and units based on the second monomer are present in a fraction of ≥20 to ≤80 weight %, based on the total weight of the crosslinked polymer, wherein the crosslinked polymer is obtained from a resin comprising:

15-20 weight % of a urethane (meth)acrylate containing isocyanurate groups,

1-5 weight % of alkanediol di(meth)acrylate,

20-30 weight % of monofunctional (meth)acrylate whose resultant homopolymer has a glass transition temperature of ≤0° C.;

50-60 weight % of monofunctional (meth)acrylate whose resultant homopolymer has a glass transition temperature of ≥60° C., each on the basis of the total weight of the resin.

7. The orthodontic aligner as claimed in claim 6 , wherein the crosslinked polymer has an isocyanurate fraction, ascertained via 13C NMR, of ≥3%.

8. The orthodontic aligner as claimed in claim 6 , wherein the crosslinked polymer has a refractive index, measured with an Abbe refractometer, of ≥1.48 RI and ≤1.58 RI.

9. The orthodontic aligner as claimed in claim 6 , wherein the crosslinked polymer has a mean network arc length according to Flory and Huggins of ≥300 g/mol and ≤5000 g/mol.

10. The orthodontic aligner as claimed in claim 6 , wherein the crosslinked polymer is a transparent polymer having a light transmittance, measured in a UV-VIS spectrometer on a sample with a thickness of 1 mm in a wavelength range of 400-800 nm, of ≥50%.

11. The orthodontic aligner as claimed in claim 6 , wherein the crosslinked polymer is a transparent polymer comprising polyurethanes and/or polysilicones and has an Abbe number of ≥20.

12. An orthodontic aligner, comprising

a crosslinked polymer having a glass transition temperature Tg, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≥25° C. and ≤60° C., an elasticity modulus, determined by dynamic mechanical analysis as storage modulus E′ at a frequency of 1/s at 35° C., of ≥500 MPa and ≤4000 MPa, and a loss factor tan δ, determined by dynamic mechanical analysis at a frequency of 1/s at 35° C., of 0.08,

wherein the crosslinked polymer is a copolymer which comprises units based on a first monomer and a second monomer, said first monomer being a (meth)acrylic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≤0° C., and said second monomer being a (meth)acrylic or styrenic monomer whose homopolymer has a glass transition temperature, determined by dynamic mechanical analysis at a frequency of 1/s as peak tan δ, of ≥60° C., and where units based on the first monomer are present in a fraction of ≥5 to ≤40 weight %, based on a total weight of the crosslinked polymer, and units based on the second monomer are present in a fraction of ≥20 to ≤80 weight %, based on the total weight of the crosslinked polymer, wherein the crosslinked polymer is obtained from a resin comprising:

10-15 weight % of a urethane (meth)acrylate containing isocyanurate groups,

5-10 weight % of monofunctional methacrylate of a terpene alcohol,

20-35 weight % of monofunctional (meth)acrylate whose resultant homopolymer has a glass transition temperature of ≤0° C.;

55-60 weight % of monofunctional (meth)acrylate whose resultant homopolymer has a glass transition temperature of ≥60° C., each on the basis of the total weight of the resin.

13. The orthodontic aligner as claimed in claim 12 , wherein the crosslinked polymer has an isocyanurate fraction, ascertained via 13C NMR, of ≥3%.

14. The orthodontic aligner as claimed in claim 12 , wherein the crosslinked polymer has a refractive index, measured with an Abbe refractometer, of ≥1.48 RI and ≤1.58 RI.

15. The orthodontic aligner as claimed in claim 12 , wherein the crosslinked polymer has a mean network arc length according to Flory and Huggins of ≥300 g/mol and ≤5000 g/mol.

16. The orthodontic aligner as claimed in claim 12 , wherein the crosslinked polymer is a transparent polymer having a light transmittance, measured in a UV-VIS spectrometer on a sample with a thickness of 1 mm in a wavelength range of 400-800 nm, of ≥50%.

17. The orthodontic aligner as claimed in claim 12 , wherein the crosslinked polymer is a transparent polymer comprising polyurethanes and/or polysilicones and has an Abbe number of ≥20.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded May 23, 2023
From: COVESTRO INTELLECTUAL PROPERTY GMBH & CO. KG
To: STRATASYS INC.
Reel/Frame 063732/0249 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 9, 2021
From: ACHTEN, DIRK; WAGNER, ROLAND; TOMCZYK, CHRISTOPH; BUESGEN, THOMAS
To: COVESTRO INTELLECTUAL PROPERTY GMBH & CO. KG
Reel/Frame 055535/0861 →
Priority Claims (1)
EP 18195715 · Sep 20, 2018 · regional
Continuity (1)
Related Publication 20210315668A1 · Oct 14, 2021