# US 12,760,134 B2 · Curable composition with polymerizable monomers and fillers for additive manufacturing

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- Number: US 12,760,134 B2
- Document ID: US12760134B2
- Status: Granted
- Kind: B2
- Application number: 18/348,289
- Filed: 2023-07-06
- Published: 2024-01-18
- Granted: 2026-10-13
- Earliest claimed: 2022-07-06
- Assignees: Align Technology, Inc.
- Applicants: Align Technology, Inc.
- Inventors: Matthew Durban; John Michael Riedesel; Peter Dorfinger; Yan Chen
- Web page: https://patentgrep.com/patent/US12760134B2

## CPC

- C08F 222/102: {of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate}
- A61C 7/08: Mouthpiece-type retainers {or positioners, e.g. for both the lower and upper arch (arch-shaped medicament applicators for teeth or gums A61C19/063; mouthguards for protecting the teeth of sportsmen A63B71/085)}
- A61C 13/08: Artificial teeth; Making same (kilns for artificial teeth F27B)
- B29C 64/129: characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08F 2/50: with sensitising agents
- C08F 222/1065: {of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates}
- C08K 3/36: Silica
- B29K 2035/00: Use of polymers of unsaturated polycarboxylic acids {or derivatives thereof} as moulding material
- B29L 2031/7536: {Artificial teeth}
- B33Y 10/00: Processes of additive manufacturing
- B33Y 80/00: Products made by additive manufacturing
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- A61C: DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE (non-driven toothbrushes A46B; {tongue scrapers A61B17/24;} preparations for dentistry A61K6/00; preparations for cleaning the teeth or mouth A61K8/00, A61Q11/00)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29L: INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES

## Abstract

Disclosed herein are curable compositions containing a plurality of polymerizable monomers comprising at least 80 wt % of a crosslinker for additive manufacturing. The curable compositions comprise high-crosslinker content, and yield tough, lightweight polymeric materials suitable for dental appliances, including but not limited to aligners, attachment placement devices, incremental palatal expanders, dentures, crowns, etc.

## Claims

### Claim 1

A curable composition for additive manufacturing, the curable composition comprising:
a plurality of polymerizable monomers, which polymerizable monomers comprise at least 80 wt % of a crosslinker; and
at least 10 wt % of a filler material,
wherein the crosslinker comprises:
a first crosslinker having the following structure (I):
Y1—X1-L1-A-L2-X2—Y2, (I)
wherein:
A is a cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylencalkylene heterocycloalkylene, arylene, heteroarylene, alkylenearylene or alkylenearylenealkylene group;
L1 and L2 are independently an amide, ether, ester, carbonate, urethane or urea linkage;
X1 and X2 are independently an alkylene or heteroalkene linker; and
Y1 and Y2 are independently a polymerizable functional group, and
a second crosslinker having the following structure (II):
Y3—X3-L3-B-L4-X4—Y3, (II)
wherein:
B is a linear or branched alkylene or heteroalkylene group;
L3 and L4 are independently an optional amide, ether, ester, carbonate, urethane or urea linkage;
X3 and X4 are independently an optional alkylene or heteroalkene linker; and
Y3 and Y4 are independently a polymerizable functional group.

### Claim 2

A curable composition comprising:
a plurality of polymerizable monomers, which polymerizable monomers comprise at least 80 wt % of a crosslinker; and
at least 0.5 wt % of a wetting agent,
wherein the crosslinker comprises:
a first crosslinker having the following structure (I):
Y1—X1-L1-A-L2-X2—Y2, (I)
wherein:
A is a cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylenealkylene heterocycloalkylene, arylene, heteroarylene, alkylenearylene or alkylenearylenealkylene group;
L1 and L2 are independently an amide, ether, ester, carbonate, urethane or urea linkage;
X1 and X2 are independently an alkylene or heteroalkene linker; and
Y1 and Y2 are independently a polymerizable functional group, and
a second crosslinker having the following structure (II):
Y3—X3-L3-B-L4-X4—Y3, (II)
wherein:
B is a linear or branched alkylene or heteroalkylene group;
L3 and L4 are independently an optional amide ether ester, carbonate, urethane or urea linkage;
X3 and X4 are independently an optional alkylene or heteroalkene linker; and
Y3 and Y4 are independently a polymerizable functional group.

### Claim 3

A curable composition comprising:
a plurality of polymerizable monomers, which polymerizable monomers comprise at least 80 wt % of a crosslinker;
wherein the curable composition is configured to develop a color defined by an L* value between 70 and 95, an a* value of between −11 and 1, and a b* value of between 2 and 22 upon curing, and
wherein the crosslinker comprises:
a first crosslinker having the following structure (I):
Y1—X1-L1-A-L2-X2—Y2, (I)
wherein:
A is a cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylenealkylene heterocycloalkylene, arylene, heteroarylene, alkylenearylene or alkylenearylenealkylene group;
L1 and L2 are independently an amide, ether, ester, carbonate, urethane or urea linkage;
X1 and X2 are independently an alkylene or heteroalkene linker; and
Y1 and Y2 are independently a polymerizable functional group, and
a second crosslinker having the following structure (II):
Y3—X3-L3-B-L4-X4—Y3, (II)
wherein:
B is a linear or branched alkylene or heteroalkylene group;
L3 and L4 are independently an optional amide, ether, ester, carbonate, urethane or urea linkage;
X3 and X4 are independently an optional alkylene or heteroalkene linker; and
Y3 and Y4 are independently a polymerizable functional group.

### Claim 4 (depends on 1)

The curable composition of claim 1, wherein the crosslinker is at least 90 wt % of the polymerizable monomers.

### Claim 5 (depends on 1)

The curable composition of claim 1, wherein the crosslinker is at least 95 wt % of the polymerizable monomers.

### Claim 6 (depends on 1)

The curable composition of claim 1, wherein the crosslinker comprises a plurality of crosslinkers with different molecular weights.

### Claim 7 (depends on 1)

The curable composition of claim 1, wherein between 50 and 100 wt % of the crosslinker comprise two polymerizable functional groups.

### Claim 8 (depends on 1)

The curable composition of claim 1, wherein between 50 and 100 wt % of the crosslinker comprise at least 14 atoms between polymerizable functional groups.

### Claim 9 (depends on 1)

The curable composition of claim 1, wherein the curable composition is photocurable, chemically curable, thermocurable, or any combination thereof.

### Claim 10 (depends on 1)

The curable composition of claim 1, wherein the curable composition is photocurable.

### Claim 11 (depends on 1)

The curable composition of claim 1, wherein between 50 and 100 mol percent of functional groups of the plurality of polymerizable monomers are ethylenically unsaturated functional groups.

### Claim 12 (depends on 1)

The curable composition of claim 1, wherein between 50 and 100 mol percent of functional groups of the plurality of polymerizable monomers are acrylate, methacrylate, or a combination thereof.

### Claim 13 (depends on 1)

The curable composition of claim 1, wherein between 50 and 100 wt % of the polymerizable monomers comprise a molecular weight of at least 250 Da.

### Claim 14 (depends on 1)

The curable composition of claim 1, wherein the filler material comprises a silica, a glass, a radiopaque material, a ceramic, a metal, a metal oxide, a crystal, a pre-polymerized species or any combination thereof.

### Claim 15 (depends on 1)

The curable composition of claim 1, wherein the curable composition comprises between 10 and 60 wt % of the filler material.

### Claim 16 (depends on 1)

The curable composition of claim 1, wherein the curable composition comprises between 10 and 20 wt % of the filler material.

### Claim 17 (depends on 1)

The curable composition of claim 1, wherein the curable composition comprises between about 60 wt % and about 90 wt % of the polymerizable monomers.

### Claim 18 (depends on 1)

The curable composition of claim 1, further comprising a wetting agent.

### Claim 19 (depends on 1)

The curable composition of claim 1, wherein the wetting agent comprises a siloxane.

### Claim 20 (depends on 1)

The curable composition of claim 1, further comprising a pigment.

### Claim 21 (depends on 20)

The curable composition of claim 20, wherein the pigment is inorganic or organometallic.

### Claim 22 (depends on 1)

The curable composition of claim 1, further comprising a photoinitiator.

### Claim 23 (depends on 22)

The curable composition of claim 22, wherein the photoinitiator comprises an oligomer or a polymer.

### Claim 24 (depends on 1)

The curable composition of claim 1, wherein the curable composition is configured to develop a color defined by an L* value between 70 and 95, an a* value of between −11 and 1, and a b* value of between 2 and 22 upon curing.

### Claim 25 (depends on 1)

The curable composition of claim 1, wherein the curable composition is configured to develop a color defined by an L* value between 78 and 87, an a* value of between −7 and −3, and a b* value of between 8 and 16 upon curing.

### Claim 26 (depends on 1)

The curable composition of claim 1, wherein:
1) A has one of the following structures:
2) B has one of the following structures:
wherein m is an integer from 1 to 20.