Methods for producing a dental mold, dental implant or dental aligner from materials having multiple mechanisms of hardening

• US 10,647,879 B2
• Filed: 04/26/2018
• Issued: 05/12/2020
• Est. Priority Date: 06/23/2014
• Status: Active Grant

• Current Assignee: Carbon, Inc.
• Original Assignee: Carbon, Inc.
• Inventors: Rolland, Jason P., Chen, Kai, Poelma, Justin, Goodrich, James, Pinschmidt, Robert, DeSimone, Joseph M., Robeson, Lloyd M.
• Primary Examiner(s): Whiteley, Jessica
• Application Number:
  US15/963,550
• Publication Number:
  US 20180265738A1
• Time in Patent Office: 747 Days
• Field of Search: 522 81, 522 71, 522 1, 522189, 522184, 522 6, 520 1
• CPC Class Codes: B29C 2033/0005 with transparent parts, e.g. permitting visual inspection of the interior of the cavity
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 2035/0855 using microwave
• CPC Class Codes: B29C 35/0805 using electromagnetic radiation
• CPC Class Codes: B29C 64/106 using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
• CPC Class Codes: B29C 64/124 using layers of liquid which are selectively solidified
• CPC Class Codes: B29C 64/129 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
• CPC Class Codes: B29C 64/135 the energy source being concentrated, e.g. scanning lasers or focused light sources
• CPC Class Codes: B29C 64/165 using a combination of solid and fluid materials, e.g. a powder selectively bound by a liquid binder, catalyst, inhibitor or energy absorber
• CPC Class Codes: B29C 64/255 Enclosures for the building material, e.g. powder containers
• CPC Class Codes: B29C 64/286 Optical filters, e.g. masks
• CPC Class Codes: B29C 64/386 Data acquisition or data processing for additive manufacturing
• CPC Class Codes: B29C 64/40 Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
• CPC Class Codes: B29C 71/0009 using liquids, e.g. solvents, swelling agents spectacle cases, e.g. for cleaning contact lenses A45C11/04; disinfecting or sterilising contact lenses A61L12/00, using liquid substances A61L2/20; cleaning involving the use of liquid in general B08B3/00; for hydrating contact lenses B29D11/00067
• CPC Class Codes: B29C 71/02 Thermal after-treatment B29C71/0063 and B29C71/0072 take precedence
• CPC Class Codes: B29D 11/00009 Production of simple or compound lenses
• CPC Class Codes: B29D 11/00663 Production of light guides
• CPC Class Codes: B29K 2075/00 Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
• CPC Class Codes: B29K 2075/02 Polyureas
• CPC Class Codes: B29K 2105/0002 monomers or prepolymers
• CPC Class Codes: B29K 2105/0058 : Liquid or visquous
• CPC Class Codes: B29K 2105/0073 : Solution
• CPC Class Codes: B29K 2105/0091 : IPN, i.e. interpenetrating polymer networks
• CPC Class Codes: B29K 2105/043 : Skinned foam
• CPC Class Codes: B29K 2105/16 : Fillers
• CPC Class Codes: B29K 2105/251 : Particles, powder or granules expandable particles B29K2105/046
• CPC Class Codes: B29K 2509/00 : Use of inorganic materials not provided for in groups B29K2503/00 - B29K2507/00, as filler
• CPC Class Codes: B29K 2995/0026 : Transparent
• CPC Class Codes: B29L 2011/00 : Optical elements, e.g. lenses, prisms
• CPC Class Codes: B29L 2011/0016 : Lenses
• CPC Class Codes: B29L 2011/0075 : Light guides, optical cables
• CPC Class Codes: B29L 2031/001 : Profiled members, e.g. beams, sections
• CPC Class Codes: B29L 2031/10 : Building elements, e.g. bricks, blocks, tiles, panels, posts, beams frameless domes B29L2025/00, doors B29L2031/724
• CPC Class Codes: B33Y 10/00 : Processes of additive manufacturing
• CPC Class Codes: B33Y 30/00 : Apparatus for additive manufacturing; Details thereof or accessories therefor
• CPC Class Codes: B33Y 50/02 : for controlling or regulating additive manufacturing processes
• CPC Class Codes: B33Y 70/00 : Materials specially adapted for additive manufacturing
• CPC Class Codes: B33Y 80/00 : Products made by additive manufacturing
• CPC Class Codes: C08F 220/1808 : C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
• CPC Class Codes: C08F 220/1811 : C10or C11-(Meth)acrylate, e.g. isodecyl (meth)acrylate, isobornyl (meth)acrylate or 2-naphthyl (meth)acrylate
• CPC Class Codes: C08F 220/34 : Esters containing nitrogen , e.g. N,N-dimethylaminoethyl (meth)acrylate
• CPC Class Codes: C08F 222/102 : of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
• CPC Class Codes: C08F 222/1063 : of alcohol terminated polyethers
• CPC Class Codes: C08F 283/006 : on to polymers provided for in C08G18/00 C08F283/004 takes precedence
• CPC Class Codes: C08F 290/067 : Polyurethanes; Polyureas
• CPC Class Codes: C08G 18/10 : Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• CPC Class Codes: C08G 18/244 : tin salts of carboxylic acids
• CPC Class Codes: C08G 18/40 : High-molecular-weight compounds C08G18/2805 takes precedence
• CPC Class Codes: C08G 18/42 : Polycondensates having carboxylic or carbonic ester groups in the main chain
• CPC Class Codes: C08G 18/48 : Polyethers
• CPC Class Codes: C08G 18/4825 : Polyethers containing two hydroxy groups C08G18/4833 - C08G18/5096 take precedence
• CPC Class Codes: C08G 18/4854 : Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
• CPC Class Codes: C08G 18/672 : Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08G 18/69 : Polymers of conjugated dienes hydrogenated polymers of conjugated dienes C08G18/6208
• CPC Class Codes: C08G 18/73 : acyclic
• CPC Class Codes: C08G 18/755 : and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• CPC Class Codes: C08G 18/758 : containing two or more cycloaliphatic rings
• CPC Class Codes: C08G 18/7671 : containing only one alkylene bisphenyl group
• CPC Class Codes: C08G 18/81 : Unsaturated isocyanates or isothiocyanates
• CPC Class Codes: C08G 18/8175 : with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• CPC Class Codes: C08J 2375/14 : Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C08J 5/00 : Manufacture of articles or shaped materials containing macromolecular substances manufacture of semi-permeable membranes B01D67/00 - B01D71/00
• CPC Class Codes: C08K 3/01 : characterized by their specific function
• CPC Class Codes: C08K 3/013 : Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 5/0008 : Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• CPC Class Codes: C08K 5/0041 : Optical brightening agents, organic pigments
• CPC Class Codes: C08L 75/04 : Polyurethanes
• CPC Class Codes: C08L 75/14 : Polyurethanes having carbon-to-carbon unsaturated bonds
• CPC Class Codes: C09D 135/02 : Homopolymers or copolymers of esters C09D135/06, C09D135/08 take precedence
• CPC Class Codes: C09D 175/04 : Polyurethanes
• CPC Class Codes: C09D 175/08 : from polyethers
• CPC Class Codes: G03F 7/00 : Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor using photoresist structures for special production processes, see the relevant places, e.g. B44C, H01L, e.g. H01L21/00, H05K
• CPC Class Codes: G03F 7/0037 : Production of three-dimensional images
• CPC Class Codes: G03F 7/027 : Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds G03F7/075 takes precedence
• CPC Class Codes: G03F 7/038 : Macromolecular compounds which are rendered insoluble or differentially wettable G03F7/075 takes precedence; macromolecular azides G03F7/012; macromolecular diazonium compounds G03F7/021
• CPC Class Codes: G03F 7/0757 : Macromolecular compounds containing Si-O, Si-C or Si-N bonds G03F7/0752 takes precedence
• CPC Class Codes: G03F 7/38 : Treatment before imagewise removal, e.g. prebaking G03F7/265 takes precedence

Abstract

A polymerizable liquid, or resin, useful for the production by additive manufacturing of a three-dimensional object of polyurethane, polyurea, or a copolymer thereof, is described. The resin includes at least one of (i) a blocked or reactive blocked prepolymer, (ii) a blocked or reactive blocked diisocyanate, or (iii) a blocked or reactive blocked diisocyanate chain extender.

Claims

1. A method of forming a three-dimensional object, wherein said three-dimensional object is a dental mold, dental implant or dental aligner, comprising:

(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component;

(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said first component and also advancing said carrier away from said build surface to form a three-dimensional intermediate having a shape of said dental mold, dental implant or dental aligner, said three-dimensional intermediate containing said second solidifiable component carried in said solid polymer scaffold in unsolidified and/or uncured form; and

(d) subsequent to said irradiating step, heating, microwave irradiating, or both heating and microwave irradiating, said second solidifiable component in said three-dimensional intermediate to form said dental mold, dental implant or dental aligner,

wherein said forming comprises bottom-up stereolithography.

2. The method of claim 1, wherein said second solidifiable component comprises a polymerizable liquid solubilized in or suspended in said first component.

3. The method of claim 1, wherein said second solidifiable component comprises:

(i) a polymerizable solid suspended in said first component;

(ii) a polymerizable solid solubilized in said first component;

or

(iii) a polymer solubilized in said first component.

4. The method of claim 1, wherein said three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network formed from said first component and said second solidifiable component.

5. The method of claim 1, wherein step (d) is carried out by heating said second solidifiable component.

6. The method of claim 5, wherein:

said second solidifiable component comprises the precursors to a polyurethane, polyurea, or copolymer thereof, a silicone resin, an epoxy resin, a cyanate ester resin, or a natural rubber.

7. A dental mold, dental implant or dental aligner three-dimensional object produced by a method comprising:

(a) providing a carrier and an optically transparent member having a build surface, said carrier and said build surface defining a build region therebetween;

(b) filling said build region with a polymerizable liquid, said polymerizable liquid comprising a mixture of (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from said first component;

(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from said first component and also advancing said carrier away from said build surface to form a three-dimensional intermediate having a shape of said dental mold, dental implant or dental aligner, said three-dimensional intermediate containing said second solidifiable component carried in said solid polymer scaffold in unsolidified and/or uncured form; and

(d) subsequent to said irradiating step, heating, microwave irradiating, or both heating and microwave irradiating, said second solidifiable component in said three-dimensional intermediate to form said dental mold, dental implant or dental aligner,

wherein said forming comprises bottom-up stereolithography, and

wherein said first component comprises monomers and/or prepolymers polymerizable upon exposure to actinic radiation or light, and a reactive diluent.

8. The object of claim 7, wherein the object is a dental mold.

9. The object of claim 7, wherein the object is a dental implant.

10. The object of claim 7, wherein the object is a dental aligner.

11. The object of claim 7, wherein the object substantially conforms to the shape of a tooth.

12. The object of claim 7, wherein said object comprises a copolymer formed from the monomers and/or prepolymers polymerizable upon exposure to actinic radiation or light and the reactive diluent.

13. The object of claim 7, wherein said first component comprises a blocked or reactive blocked prepolymer.