# US 11,440,266 B2 · Methods of producing epoxy three-dimensional objects from materials having multiple mechanisms of hardening

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- Number: US 11,440,266 B2
- Document ID: US11440266B2
- Status: Granted
- Kind: B2
- Application number: 16/204,141
- Filed: 2018-11-29
- Published: 2019-04-18
- Granted: 2022-09-13
- 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/US11440266B2

## 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 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 including 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 polymer scaffold from the first component and also 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, and containing the second solidifiable component carried in the scaffold in unsolidified and/or uncured form; and (d) concurrently with or subsequent to the irradiating step, solidifying and/or curing the second solidifiable component in the three-dimensional intermediate to form the three-dimensional object.

## Claims

### Claim 1

A method of forming a three-dimensional object comprising epoxy, 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, said second component comprising epoxy precursors;
(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 the same shape as, or a shape to be imparted to, said three-dimensional object and containing said second solidifiable component carried in said 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 three-dimensional object comprising epoxy.

### Claim 2 (depends on 1)

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

### Claim 3 (depends on 1)

The method of claim 1, wherein said second 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.

### Claim 4 (depends on 1)

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

### Claim 5 (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 component.

### Claim 6 (depends on 1)

The method of claim 1, wherein said polymerizable liquid comprises:
from 1 or 10 percent by weight to 40, 90 or 99 percent by weight of said first component; and
from 1, 10 or 60 percent by weight to 90 or 99 percent by weight of said second component.

### Claim 7 (depends on 1)

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

### Claim 8 (depends on 1)

The method of claim 1, wherein: step (d) is carried out under conditions in which said solid polymer scaffold degrades and forms a constituent necessary for the polymerization of said second component.

### Claim 9 (depends on 1)

The method of claim 1, wherein said irradiating and/or said advancing steps are carried out while also concurrently:
(i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and
(ii) continuously maintaining a gradient of polymerization zone between said dead zone and said solid polymer scaffold and in contact with each thereof, said gradient of polymerization zone comprising said first component in partially cured form.

### Claim 10 (depends on 9)

The method of claim 9, further comprising vertically reciprocating said carrier with respect to the build surface to enhance or speed the refilling of the build region with the polymerizable liquid.

### Claim 11 (depends on 1)

The method of claim 1, said first component comprising monomers and/or prepolymers comprising reactive end groups selected from the group consisting of acrylates, methacrylates, α-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.

### Claim 12 (depends on 1)

The method of claim 1, said epoxy precursors comprising reactive end groups selected from the group consisting of: epoxy/amine, epoxy/hydroxyl, and mixtures thereof.

### Claim 13 (depends on 1)

The method of claim 1, wherein said three-dimensional object comprises an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network.

### Claim 14 (depends on 1)

The method of claim 1, wherein said object has a shape that cannot be formed by injection molding or casting.

### Claim 15 (depends on 1)

The method of claim 1, wherein said three-dimensional object comprises:
(i) enclosed cavities, partially open cavities, repeating unit cells, open cell foams, closed cell foams, or combinations thereof;
(ii) a waveguide, prism, lens, or combination thereof; and/or
(iii) a wall, strut, beam, tie, or combination thereof.

### Claim 16 (depends on 1)

The method of claim 1, said first component comprising monomers and/or prepolymers comprising reactive end groups selected from the group consisting of acrylates, methacrylates, and mixtures thereof.

### Claim 17 (depends on 1)

The method of claim 1, wherein said polymerizable liquid further comprises thermoplastic particles or thermoset particles.

### Claim 18 (depends on 1)

The method of claim 1, wherein said three-dimensional object comprises an epoxy network cured by the reaction of a diepoxide with a diamine.

### Claim 19 (depends on 1)

The method of claim 1, wherein said polymerizable liquid further comprises a UV-curable reactive diluent that is miscible with the epoxy precursors prior to said step (d).

### Claim 20 (depends on 18)

The method of claim 18, wherein said polymerizable liquid further comprises a UV-curable reactive diluent that is miscible with the epoxy precursors prior to said step (d).

### Claim 21 (depends on 20)

The method of claim 20, wherein said three-dimensional object comprises an interpenetrating polymer network, a semi-interpenetrating polymer network, or a sequential interpenetrating polymer network.