# US 12,006,401 B2 · Resin suitable for three-dimensional printing

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- Number: US 12,006,401 B2
- Document ID: US12006401B2
- Status: Granted
- Kind: B2
- Application number: 17/709,606
- Filed: 2022-03-31
- Published: 2022-10-13
- Granted: 2024-06-11
- Earliest claimed: 2021-04-05
- Assignees: James R. Glidewell Dental Ceramics, Inc.
- Applicants: James R. Glidewell Dental Ceramics, Inc.
- Inventors: Derek A. Lublin
- Web page: https://patentgrep.com/patent/US12006401B2

## CPC

- C08G 81/00: Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers (involving only carbon-to-carbon unsaturated bond reactions C08F299/00 {; polyester-amides C08G69/44; polyester-imides C08G73/16; polyamides-imides C08G73/14; block- or graft polymers containing polysiloxane sequences C08G77/42})
- B33Y 70/00: Materials specially adapted for additive manufacturing
- C08F 290/067: {Polyurethanes; Polyureas}
- C08G 18/44: Polycarbonates
- C08K 5/132: Phenols containing keto groups {, e.g. benzophenones}
- C08L 75/16: having terminal carbon-to-carbon unsaturated bonds
- C09D 187/005: {Block or graft polymers not provided for in groups C09D101/00 - C09D185/04}
- C08K 5/005: {Stabilisers against oxidation, heat, light, ozone}
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C08L: COMPOSITIONS OF MACROMOLECULAR COMPOUNDS (compositions based on polymerisable monomers C08F, C08G; artificial filaments or fibres D01F; textile treating compositions D06)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

A polymeric resin that includes a photocured reaction product of at least one urethane (meth)acrylate polymer that includes at least one polycarbonate unit; at least one monofunctional monomer; and at least one crosslinking agent.

## Claims

### Claim 1

A polymeric resin comprising a photocured reaction product of a composition of components consisting of:
at least one urethane (meth)acrylate polymer that includes at least one polycarbonate unit;
at least one monofunctional monomer;
at least one crosslinking agent comprising a multifunctional monomer having at least three (meth)acrylate functional groups that undergo crosslinking, wherein the crosslinking agent comprises 1 to 5 wt % based on the total weight of the polymeric resin;
at least one photoinitiator; and
a UV blocker.

### Claim 2 (depends on 1)

The resin of claim 1, wherein the urethane (meth)acrylate polymer has a polymer backbone, wherein the polymer backbone includes the at least one polycarbonate unit.

### Claim 3 (depends on 1)

The resin of claim 1, wherein the urethane (meth)acrylate polymer includes at least one of a co-polymeric polycarbonate unit and a co-reacted urethane acrylate unit.

### Claim 4 (depends on 1)

The resin of claim 1, wherein the urethane (meth)acrylate polymer has the formula (III):
(Acr)y(A)(Q)(PC)[(Q)(PC)]x(Q)(A)(Acr)y
wherein
(Acr)y(A) is the residue of hydroxyalkyl acrylate or hydroxyalkyl methacrylate having an alkyl moiety, A, and where said alkyl, A, has 2 to 5 carbon atoms and wherein Acr is an acrylate or methacrylate moiety; y is the number of acrylate or methacrylate groups linked to moiety A;
Q is the residue of one or more organic diisocyanates, which are connected with A via a urethane linkage;
PC is the residue of an alkylene diol polycarbonate of the formula (IV):
HO(ROCOO)nROH
wherein
R is one or more (C2 to C10) alkylene or one or more (C6 to C12) aromatic group;
y is an integer from 1 to 5;
x is from 1 to 20;
n is an integer from 1 to 10,000; and
PC and Q are connected via a urethane group.

### Claim 5 (depends on 1)

The resin of claim 1, wherein the monofunctional monomer has a glass transition temperature (Tg) of greater than 50° C.

### Claim 6 (depends on 1)

The resin of claim 1, wherein the monofunctional monomer has a viscosity of less than 100 cP at 25° C.

### Claim 7 (depends on 1)

The resin of claim 1, wherein the monofunctional monomer is hydrophobic.

### Claim 8 (depends on 1)

The resin of claim 1, wherein the monofunctional monomer has a single (meth)acrylate group.

### Claim 9 (depends on 1)

The resin of claim 1, wherein the monofunctional monomer is isobornyl acrylate (IBOA), isobornyl methacrylate (IBOMA), dihydrodicyclopentadienyl acrylate (DCPA), tort-butyl methacrylate (TBMA), cyclohexyl methacrylate (CHMA), benzyl methacrylate (BzMA), or a mixture thereof.

### Claim 10 (depends on 1)

The resin of claim 1, wherein the crosslinking agent has a viscosity of less than 1000 cP at 25° C.

### Claim 11 (depends on 1)

The resin of claim 1, wherein the crosslinking agent is hydrophobic.

### Claim 12 (depends on 1)

The resin of claim 1, wherein the crosslinking agent is trimethylolpropane trimethacrylate (TMPTMA), trimethylolpropane triacrylate (TMPTA), trimethylolpropane ethoxy triacrylate (TMPEOTA), pentaerythritol triacrylate (PETA), or a mixture thereof.

### Claim 13 (depends on 1)

The resin of claim 1, wherein the resin is three-dimensional-printed.

### Claim 14 (depends on 1)

The resin of claim 1, wherein the resin has a degree of polymerization conversion of at least 90%, as measured by ATR-FTIR.

### Claim 15 (depends on 1)

The resin of claim 1, wherein the resin has a tensile strength of 20 to 50 MPa, as measured via ASTM D638-14.

### Claim 16 (depends on 1)

The resin of claim 1, wherein the resin has an elongation to break of 50 to 200%, as measured via ASTM D638-14.

### Claim 17 (depends on 1)

The resin of claim 1, wherein the resin has a flexural strength of 20 to 70 MPa as measured via ASTM D790-17.

### Claim 18 (depends on 1)

The resin of claim 1, wherein the resin has a flexural modulus of 1000 to 2000 MPa, as measured via ASTM D790-17.

### Claim 19 (depends on 1)

The resin of claim 1, wherein the resin has an impact strength of 15 to 75 J/m, as measured via ASTM D256-10 (Notched Izod).