# US 11,299,579 B2 · Water cure methods for producing three-dimensional objects from materials having multiple mechanisms of hardening

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- Number: US 11,299,579 B2
- Document ID: US11299579B2
- Status: Granted
- Kind: B2
- Application number: 16/803,350
- Filed: 2020-02-27
- Published: 2020-06-18
- Granted: 2022-04-12
- Earliest claimed: 2014-06-23
- Assignees: Carbon, Inc.
- Applicants: Carbon, Inc.
- Inventors: Jason P. Rolland; Kai Chen; Justin Poelma; James Goodrich; Robert Pinschmidt; Joseph M. DeSimone; Lloyd M. Robeson
- Web page: https://patentgrep.com/patent/US11299579B2

## CPC

- B29C 64/40: Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
- B29C 35/0805: {using electromagnetic radiation}
- B29C 64/106: using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C 64/124: using layers of liquid which are selectively solidified
- B29C 64/129: characterised by the energy source therefor, e.g. by global irradiation combined with a mask
- B29C 64/135: the energy source being concentrated, e.g. scanning lasers or focused light sources
- 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
- B29C 64/255: Enclosures for the building material, e.g. powder containers
- B29C 64/286: Optical filters, e.g. masks
- B29C 64/386: Data acquisition or data processing for additive manufacturing
- 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)}
- B29D 11/00009: {Production of simple or compound lenses}
- B29D 11/00663: {Production of light guides}
- B33Y 10/00: Processes of additive manufacturing
- B33Y 30/00: Apparatus for additive manufacturing; Details thereof or accessories therefor
- B33Y 50/02: for controlling or regulating additive manufacturing processes
- B33Y 70/00: Materials specially adapted for additive manufacturing
- B33Y 80/00: Products made by additive manufacturing
- C08F 220/34: Esters containing nitrogen {, e.g. N,N-dimethylaminoethyl (meth)acrylate}
- C08F 283/006: {on to polymers provided for in C08G18/00 (C08F283/004 takes precedence)}
- C08F 290/067: {Polyurethanes; Polyureas}
- C08G 18/10: Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G 18/244: {tin salts of carboxylic acids}
- C08G 18/40: High-molecular-weight compounds {(C08G18/2805 takes precedence)}
- C08G 18/42: Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G 18/4825: {Polyethers containing two hydroxy groups (C08G18/4833 - C08G18/5096 take precedence)}
- C08G 18/4854: {Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group}
- C08G 18/69: Polymers of conjugated dienes {(hydrogenated polymers of conjugated dienes C08G18/6208)}
- C08G 18/73: acyclic
- 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}
- C08G 18/758: {containing two or more cycloaliphatic rings}
- C08G 18/7671: {containing only one alkylene bisphenyl group}
- C08G 18/81: Unsaturated isocyanates or isothiocyanates
- C08G 18/8175: {with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen}
- C08J 5/00: Manufacture of articles or shaped materials containing macromolecular substances (manufacture of semi-permeable membranes B01D67/00 - B01D71/00)
- C08K 3/01: characterized by their specific function
- C08K 3/013: Fillers, pigments or reinforcing additives
- C08K 5/0008: {Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59}
- C08K 5/0041: {Optical brightening agents, organic pigments}
- C08L 75/04: Polyurethanes
- C08L 75/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- C09D 135/02: Homopolymers or copolymers of esters (C09D135/06, C09D135/08 take precedence)
- C09D 175/04: Polyurethanes
- C09D 175/08: from polyethers
- 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, H10P76/00, H05K)
- G03F 7/0037: {Production of three-dimensional images}
- G03F 7/027: Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds (G03F7/075 takes precedence)
- 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)
- G03F 7/0757: {Macromolecular compounds containing Si-O, Si-C or Si-N bonds (G03F7/0752 takes precedence)}
- G03F 7/38: Treatment before imagewise removal, e.g. prebaking {(G03F7/265 takes precedence)}
- B29C 71/02: Thermal after-treatment {(B29C71/0063 and B29C71/0072 take precedence)}
- B29C 2033/0005: {with transparent parts, e.g. permitting visual inspection of the interior of the cavity}
- B29C 2035/0827: {using UV radiation}
- B29C 2035/0855: {using microwave}
- B29K 2075/00: Use of {PU, i.e.} polyureas or polyurethanes {or derivatives thereof}, as moulding material
- B29K 2075/02: {Polyureas}
- B29K 2105/0002: {monomers or prepolymers}
- B29K 2105/0058: {Liquid or visquous}
- B29K 2105/0073: {Solution}
- B29K 2105/0091: {IPN, i.e. interpenetrating polymer networks}
- B29K 2105/043: {Skinned foam}
- B29K 2105/16: Fillers
- B29K 2105/251: {Particles, powder or granules (expandable particles B29K2105/046)}
- B29K 2509/00: Use of inorganic materials not provided for in groups {B29K2503/00 - B29K2507/00,} as filler
- B29K 2995/0026: Transparent
- B29L 2011/00: Optical elements, e.g. lenses, prisms
- B29L 2011/0016: {Lenses}
- B29L 2011/0075: {Light guides, optical cables}
- B29L 2031/001: {Profiled members, e.g. beams, sections}
- B29L 2031/10: Building elements, e.g. bricks, blocks, tiles, panels, posts, beams {(frameless domes B29L2025/00, doors B29L2031/724)}
- C08J 2375/14: Polyurethanes having carbon-to-carbon unsaturated bonds
- 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)
- B29D: PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE (making granules B29B9/00; making preforms B29B11/00)
- 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
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)
- 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)
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- 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

A method of forming a three-dimensional object (e.g. comprised of polyurethane, polyurea, or copolymer thereof) is carried out by: (a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween; (b) filling the build region with a polymerizable liquid, the polymerizable liquid comprising a mixture of: (i) a light polymerizable liquid first component, and (ii) a second solidifiable component that is different from the first component; (c) irradiating the build region with light through the optically transparent member to form a solid blocked polymer scaffold and advancing the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object, with the intermediate containing the second solidifiable component; and then (d) contacting the three-dimensional intermediate to water to form the three-dimensional object.

## Claims

### Claim 1

A method of forming a three-dimensional object, 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 the first component;
(c) irradiating said build region with light through said optically transparent member to form a solid polymer scaffold from the first component and advancing said carrier away from said build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, said three-dimensional object, with said intermediate containing said second solidifiable component carried in the scaffold in unsolidified or uncured form; and then
(d) subsequent to the irradiating step, curing the second solidifiable component by contacting said three-dimensional intermediate to water, to form from said three-dimensional intermediate said three-dimensional object.

### Claim 2 (depends on 1)

The method of claim 1, wherein said water is in liquid, gas, or aerosol form.

### Claim 3 (depends on 1)

The method of claim 1, wherein said curing step (d) further comprises heating or microwave irradiating said three-dimensional intermediate concurrent with and/or subsequent to the contacting of said three-dimensional intermediate to water.

### Claim 4 (depends on 1)

The method of claim 1, wherein said three-dimensional object is comprised of polyurethane, polyurea, or a copolymer thereof, and the second solidifiable component comprises precursors to a polyurethane, polyurea, or a copolymer thereof.

### Claim 5 (depends on 4)

The method of claim 4, wherein the second solidifiable component comprises a blocked or reactive blocked diisocyanate.

### Claim 6 (depends on 4)

The method of claim 4, wherein the second solidifiable component comprises a diisocyanate that is not blocked with a blocking agent.

### Claim 7 (depends on 1)

The method of claim 1, wherein said three-dimensional object comprises (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof, (ii) a cross-linked thermoset polyurethane, polyurea, or copolymer thereof, or (iii) a combination thereof.

### Claim 8 (depends on 1)

The method of claim 1, wherein the second solidifiable component comprises precursors to a water-curable silicone resin.

### Claim 9 (depends on 1)

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

### Claim 10 (depends on 1)

The method of claim 1, wherein the second solidifiable component comprises a polymerizable solid suspended in said first component, or solid thermoplastic or thermoset polymer particles suspended in said first component.

### Claim 11 (depends on 1)

The method of claim 1, wherein said three-dimensional intermediate is collapsible or compressible.

### Claim 12 (depends on 1)

The method of claim 1, wherein the solid polymer scaffold is discontinuous.

### Claim 13 (depends on 1)

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.

### Claim 14 (depends on 1)

The method of claim 1, said polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked prepolymer, (ii) a chain extender, (iii) a photoinitiator, (iv) optionally a polyol and/or a polyamine, (v) optionally a reactive diluent, (vi) optionally a pigment or dye, and (vii) optionally a filler.

### Claim 15 (depends on 14)

The method of claim 14, wherein the blocked or reactive blocked prepolymer comprises a compound of the formula A-X-A, where X is a hydrocarbyl group and each A is an independently selected substituent of Formula (X):
where R is a hydrocarbyl group, R′ is O or NH, and Z is a blocking group, said blocking group optionally having a reactive terminal group.

### Claim 16 (depends on 14)

The method of claim 14, wherein the blocked or reactive blocked prepolymer comprises a blocked or reactive blocked diisocyanate.

### Claim 17 (depends on 14)

The method of claim 14, wherein the blocked or reactive blocked prepolymer comprises a reactive blocked diisocyanate blocked by reaction of a polyisocyanate oligomer with an amine (meth)acrylate, alcohol (meth)acrylate, maleimide, or n-vinylformamaide monomer blocking agent.

### Claim 18 (depends on 14)

The method of claim 14, wherein the blocked or reactive blocked prepolymer comprises a reactive blocked diisocyanate blocked by reaction of a polyisocyanate with a tertiary-butylaminoethyl methacrylate (TBAEMA), a tertiary pentylaminoethyl methacrylate (TPAEMA), a tertiary hexylaminoethyl methacrylate (THAEMA), a tertiary-butylaminopropyl methacrylate (TBAPMA), an acrylate analog thereof, or a mixture of two or more thereof.

### Claim 19 (depends on 18)

The method of claim 18, wherein the reactive diluent is present and copolymerizes with the reactive blocked diisocyanate during the irradiating step.

### Claim 20 (depends on 19)

The method of claim 19, wherein said reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, or a combination of two or more of the foregoing.

### Claim 21 (depends on 14)

The method of claim 14, wherein the chain extender comprises a polyamine.

### Claim 22 (depends on 14)

The method of claim 14, wherein the chain extender comprises a polyol.

### Claim 23 (depends on 1)

The method of claim 1, wherein the method comprises repeating steps (b) and (c) to produce a subsequent polymerized region adhered to a previous polymerized region until the continued or repeated deposition of polymerized regions adhered to one another forms the three-dimensional intermediate.