US20160160077A1 - Three-dimensional objects produced from materials having multiple mechanisms of hardening - Google Patents

Three-dimensional objects produced from materials having multiple mechanisms of hardening Download PDF

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Publication number
US20160160077A1
US20160160077A1 US14/977,938 US201514977938A US2016160077A1 US 20160160077 A1 US20160160077 A1 US 20160160077A1 US 201514977938 A US201514977938 A US 201514977938A US 2016160077 A1 US2016160077 A1 US 2016160077A1
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United States
Prior art keywords
component
build
dimensional
light
polymerization
Prior art date
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Abandoned
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US14/977,938
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English (en)
Inventor
Jason P. Rolland
Kai Chen
Justin Poelma
James Goodrich
Robert Pinschmidt
Joseph M. DeSimone
Lloyd M. Robeson
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Carbon Inc
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Carbon3D Inc
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First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=54938697&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20160160077(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Carbon3D Inc filed Critical Carbon3D Inc
Priority to US14/977,938 priority Critical patent/US20160160077A1/en
Assigned to CARBON3D, INC. reassignment CARBON3D, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DESIMONE, JOSEPH M., GOODRICH, JAMES, PINSCHMIDT, Robert, ROBESON, LLOYD M., ROLLAND, JASON P., CHEN, KAI, POELMA, Justin
Publication of US20160160077A1 publication Critical patent/US20160160077A1/en
Assigned to CARBON, INC. reassignment CARBON, INC. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: CARBON3D, INC.
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
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Definitions

  • the present invention concerns materials, methods and apparatus for the fabrication of solid three-dimensional objects from liquid materials, and objects so produced.
  • construction of a three-dimensional object is performed in a step-wise or layer-by-layer manner.
  • layer formation is performed through solidification of photo curable resin under the action of visible or UV light irradiation.
  • Two techniques are known: one in which new layers are formed at the top surface of the growing object; the other in which new layers are formed at the bottom surface of the growing object.
  • an elastic separation layer is used to achieve “non-destructive” separation of solidified material at the bottom construction plane.
  • Other approaches such as the B9CreatorTM 3-dimensional printer marketed by B9Creations of Deadwood, S. Dak., USA, employ a sliding build plate. See, e.g., M. Joyce, US Patent App. 2013/0292862 and Y. Chen et al., US Patent App. 2013/0295212 (both Nov. 7, 2013); see also Y. Pan et al., J. Manufacturing Sci. and Eng. 134, 051011-1 (October 2012). Such approaches introduce a mechanical step that may complicate the apparatus, slow the method, and/or potentially distort the end product.
  • Described herein are methods, systems and apparatus (including associated control methods, systems and apparatus), for the production of a three-dimensional object by additive manufacturing.
  • the method is carried out continuously.
  • the three-dimensional object is produced from a liquid interface.
  • continuous liquid interface production continuous liquid interphase printing
  • CLIP continuous liquid interphase printing
  • the present invention provides a method of forming a three-dimensional object, comprising: (a) (i) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween, or (ii) providing a carrier in a polymerizable liquid reservoir, the reservoir having a fill level, the carrier and the fill level 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 (or second reactive) component different from the first component; (c) irradiating the build region with light (through the optically transparent member when present) to form a solid polymer scaffold from the first component and advancing (e.g., advancing concurrently—that is, simultaneously, or sequentially in an alternating fashion with irradiating steps) the carrier away from the build surface to form a three-dimensional intermediate having the
  • a wash step may be included between formation of the three-dimensional intermediate and the subsequent solidifying and/or curing step (d) which by which the three-dimensional object is formed.
  • Any suitable wash liquid may be employed (e.g., BIO-SOLVTM solvent replacement; PURPLE POWERTM degreaser/cleaner; SIMPLE GREEN® all purpose cleaner; a 50:50 volume:volume mixture of water and isopropanol, etc. See also, U.S. Pat. No. 5,248,456).
  • the second component comprises: (i) a polymerizable liquid solubilized in or suspended in the first component; (ii) a polymerizable solid solubilized in the first component; or (iii) a polymer solubilized in the first component. In other embodiments, the second component comprises: (i) a polymerizable solid suspended in the first component; or (ii) solid thermoplastic or thermoset polymer particles suspended in the first component.
  • the first component comprises a blocked or reactive blocked prepolymer and (optionally but in some embodiments preferably) a reactive diluent
  • the second component comprises a chain extender.
  • the first components react together to form a blocked polymer scaffold during the irradiating step, which is unblocked by heating or microwave irradiating during the second step to in turn react with the chain extender.
  • the reactive blocked component comprises a reactive blocked diisocyanate and/or chain extender, alone or in combination with a reactive blocked prepolymer, and other unblocked constituents (e.g., polyisocyanate oligomer, diisocyanate, reactive diluents, and/or chain extender).
  • reactive blocked prepolymers, diisocyanates, and/or chain extenders are blocked by reaction of (i.e., are the reaction product of a reaction between) a polyisocyanate oligomer, a diisocyanate, and/or a chain extender with an amine(meth)acrylate, alcohol(meth)acrylate, maleimide, or n-vinylformamide monomer blocking agent.
  • the three-dimensional intermediate is collapsible or compressible (e.g., elastic).
  • the scaffold is continuous; in other embodiments, the scaffold is discontinuous (e.g., an open or closed cell foam, which foam may be regular (e.g., geometric, such as a lattice) or irregular).
  • the scaffold is discontinuous (e.g., an open or closed cell foam, which foam may be regular (e.g., geometric, such as a lattice) or irregular).
  • the three-dimensional object comprises a polymer blend (e.g., an interpenetrating polymer network, a semi-interpenetrating polymer network, a sequential interpenetrating polymer network) formed from the first component and the second component.
  • a polymer blend e.g., an interpenetrating polymer network, a semi-interpenetrating polymer network, a sequential interpenetrating polymer network
  • the polymerizable liquid comprises from 1, 2 or 5 percent by weight to 20, 30, 40, 90 or 99 percent by weight of the first component; and from 1, 10, 60, 70 or 80 percent by weight to 95, 98 or 99 percent by weight of the second component (optionally including one or more additional components). In other embodiments, the polymerizable liquid comprises from 1, 2 or 5 percent by weight to 20, 30, 40, 90 or 99 percent by weight of the second component; and from 1, 10, 60, 70 or 80 percent by weight to 95, 98 or 99 percent by weight of the first component (optionally including one or more additional components).
  • the solidifying and/or curing step (d) is carried out concurrently with the irradiating step (c) and: (i) the solidifying and/or curing step is carried out by precipitation; (ii) the irradiating step generates heat from the polymerization of the first component in an amount sufficient to thermally solidify or polymerize the second component (e.g., to a temperature of 50 or 80 to 100° C., for polymerizing polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)); and (iii) the second component (e.g., a light or ultraviolet light curable epoxy resin) is solidified by the same light as is the first component in the irradiating step.
  • the second component e.g., a light or ultraviolet light curable epoxy resin
  • the solidifying and/or curing step (d) is carried out subsequent to the irradiating step (c) and is carried out by: (i) heating or microwave irradiating the second solidifiable component; (ii) irradiating the second solidifiable component with light at a wavelength different from that of the light in the irradiating step (c); (iii) contacting the second polymerizable component to water; or (iv) contacting the second polymerizable component to a catalyst.
  • the second component comprises precursors to a polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), a silicone resin, or natural rubber, and the solidifying and/or curing step is carried out by heating or microwave irradiating.
  • a polyurethane, polyurea, or copolymer thereof e.g., poly(urethane-urea)
  • silicone resin e.g., silicone resin, or natural rubber
  • the second component comprises a cationically cured resin (e.g., an epoxy resin or a vinyl ether) and the solidifying and/or curing step is carried out by irradiating the second solidifiable component with light at a wavelength different from that of the light in the irradiating step (c).
  • a cationically cured resin e.g., an epoxy resin or a vinyl ether
  • the second component comprises a precursor to a polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), and the solidifying and/or curing step is carried out by contacting the second component to water (e.g., in liquid, gas, or aerosol form).
  • a precursor to a polyurethane, polyurea, or copolymer thereof e.g., poly(urethane-urea)
  • water e.g., in liquid, gas, or aerosol form
  • Suitable examples of such precursors include, but are not limited to, those described in B. Baumbach, Silane Terminated Polyurethanes (Bayer MaterialScience 2013).
  • the second component comprises a precursor to a polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), a silicone resin, a ring-opening metathesis polymerization resin, or a click chemistry resin (alkyne monomers in combination with compound plus an azide monomers), and the solidifying and/or curing step is carried out by contacting the second component to a polymerization catalyst (e.g., a metal catalyst such as a tin catalyst, and/or an amine catalyst, for polyurethane/polyurea resins; platinum or tin catalysts for silicone resins; ruthenium catalysts for ring-opening metathesis polymerization resins; copper catalyst for click chemistry resins; etc., which catalyst is contacted to the article as a liquid aerosol, by immersion, etc.), or an aminoplast containing resin, such as one containing N-(alkoxymethyl)acrylamide, hydroxyl groups, and a blocked acid
  • the irradiating step and/or advancing step is carried out while also concurrently:
  • the first component comprises a free radical polymerizable liquid and the inhibitor comprises oxygen; or the first component comprises an acid-catalyzed or cationically polymerizable liquid, and the inhibitor comprises a base.
  • the gradient of polymerization zone and the dead zone together have a thickness of from 1 to 1000 microns.
  • the gradient of polymerization zone is maintained for a time of at least 5, 10, 20 or 30 seconds, or at least 1 or 2 minutes.
  • the advancing is carried out at a cumulative rate of at least 0.1, 1, 10, 100 or 1000 microns per second.
  • the build surface is substantially fixed or stationary in the lateral and/or vertical dimensions.
  • the method further comprises vertically reciprocating the carrier with respect to the build surface to enhance or speed the refilling of the build region with the polymerizable liquid.
  • a further aspect of the invention is a polymerizable liquid substantially as described herein above and below, and/or for use in carrying out a method as described herein.
  • the polymerizable liquid (or “dual cure resin”) has a viscosity of 100, 200, 500 or 1,000 centipoise or more at room temperature and/or under the operating conditions of the method, up to a viscosity of 10,000, 20,000, or 50,000 centipoise or more, at room temperature and/or under the operating conditions of the method.
  • One particular embodiment of the inventions disclosed herein is a method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof, the method comprising: (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 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; (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 chain extender; and then (d) heating or microwave irradiating
  • the solidifiable or polymerizable liquid is changed at least once during the method with a subsequent solidifiable or polymerizable liquid; optionally where the subsequent solidifiable or polymerizable liquid is cross-reactive with each previous solidifiable or polymerizable liquid during the subsequent curing, to form an object having a plurality of structural segments covalently coupled to one another, each structural segment having different structural (e.g., tensile) properties.
  • a further aspect of the inventions disclosed herein is a polymerizable liquid useful for the production of a three-dimensional object comprised of polyurethane, polyurea, or a copolymer thereof by additive manufacturing, the polymerizable liquid comprising a mixture of:
  • polymerizable liquids used in the present invention include a non-reactive pigment or dye.
  • a non-reactive pigment or dye examples include, but are not limited to, (i) titanium dioxide (e.g., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g. in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight).
  • a Lewis acid or an oxidizable tin salt is included in the polymerizable liquid (e.g., in an amount of from 0.01 or 0.1 to 1 or 2 percent by weight, or more) in an amount effective to accelerate the formation of the three-dimensional intermediate object during the production thereof.
  • a further aspect of the inventions disclosed herein is a three dimensional object comprised of: (a) a light polymerized first component; and (b) a second solidified component (e.g., a further reacted, polymerized or chain extended component) different from the first component; optionally but in some embodiments preferably subject to the proviso that: (i) the second component does not contain a cationic polymerization photoinitiator, and/or (ii) the three dimensional object is produced by the process of continuous liquid interface production.
  • a second solidified component e.g., a further reacted, polymerized or chain extended component
  • the object further comprises: (c) a third solidified (or further reacted, polymerized, or chain extended) component different from the first and second component, with the object having at least a first structural segment and a second structural segment covalently coupled to one another, the first structural segment comprised of the second solidified component, the second structural segment comprised of the third solidified component; and both the first and second structural segments comprised of the same or different light polymerized first component.
  • a third solidified (or further reacted, polymerized, or chain extended) component different from the first and second component with the object having at least a first structural segment and a second structural segment covalently coupled to one another, the first structural segment comprised of the second solidified component, the second structural segment comprised of the third solidified component; and both the first and second structural segments comprised of the same or different light polymerized first component.
  • the object comprises a polymer blend formed from the first component and the second component.
  • the object may be one that has a shape that cannot be formed by injection molding or casting.
  • FIG. 1 is a schematic illustration of one embodiment of a method of the present invention.
  • FIG. 2 is a perspective view of one embodiment of an apparatus of the present invention.
  • FIG. 3 is a first flow chart illustrating control systems and methods for carrying out the present invention.
  • FIG. 4 is a second flow chart illustrating control systems and methods for carrying out the present invention.
  • FIG. 5 is a third flow chart illustrating control systems and methods for carrying out the present invention.
  • FIG. 6 is a top view of a 3 inch by 16 inch “high aspect” rectangular build plate (or “window”) assembly of the present invention, where the film dimensions are 3.5 inch by 17 inch.
  • FIG. 7 is an exploded view of the build plate of FIG. 6 , showing the tension ring and tension ring spring plate.
  • FIG. 8 is a side sectional view of the build plates of FIGS. 6-9 , showing how the tension member tensions and rigidifies the polymer film.
  • FIG. 9 is a top view of a 2.88 inch diameter round build plate of the invention, where the film dimension may be 4 inches in diameter.
  • FIG. 10 is an exploded view of the build plate of FIG. 8 .
  • FIG. 11 shows various alternate embodiments of the build plates of FIGS. 7-10 .
  • FIG. 12 is a front perspective view of an apparatus according to an exemplary embodiment of the invention.
  • FIG. 13 is a side view of the apparatus of FIG. 12 .
  • FIG. 14 is a rear perspective view of the apparatus of FIG. 12 .
  • FIG. 15 is a perspective view of a light engine assembly used with the apparatus of FIG. 12 .
  • FIG. 16 is a front perspective view of an apparatus according to another exemplary embodiment of the invention.
  • FIG. 17A is a schematic diagram illustrating tiled images.
  • FIG. 17B is a second schematic diagram illustrating tiled images.
  • FIG. 17C is a third schematic diagram illustrating tiled images.
  • FIG. 18 is a front perspective view of an apparatus according to another exemplary embodiment of the invention.
  • FIG. 19 is a side view of the apparatus of FIG. 18 .
  • FIG. 20 is a perspective view of a light engine assembly used with the apparatus of FIG. 18 .
  • FIG. 21 is a graphic illustration of a process of the invention indicating the position of the carrier in relation to the build surface or plate, where both advancing of the carrier and irradiation of the build region is carried out continuously. Advancing of the carrier is illustrated on the vertical axis, and time is illustrated on the horizontal axis.
  • FIG. 22 is a graphic illustration of another process of the invention indicating the position of the carrier in relation to the build surface or plate, where both advancing of the carrier and irradiation of the build region is carried out stepwise, yet the dead zone and gradient of polymerization are maintained. Advancing of the carrier is again illustrated on the vertical axis, and time is illustrated on the horizontal axis.
  • FIG. 23 is a graphic illustration of still another process of the invention indicating the position of the carrier in relation to the build surface or plate, where both advancing of the carrier and irradiation of the build region is carried out stepwise, the dead zone and gradient of polymerization are maintained, and a reciprocating step is introduced between irradiation steps to enhance the flow of polymerizable liquid into the build region.
  • Advancing of the carrier is again illustrated on the vertical axis, and time is illustrated on the horizontal axis.
  • FIG. 24 is a detailed illustration of an reciprocation step of FIG. 23 , showing a period of acceleration occurring during the upstroke (i.e., a gradual start of the upstroke) and a period of deceleration occurring during the downstroke (i.e., a gradual end to the downstroke).
  • FIG. 25A depicts a dual cure system employing a thermally cleavable end group.
  • I Crosslinked blocked diisocyanate prepolymer containing unreacted chain extender.
  • II Polymer blend of: i) linear ethylenically unsaturated blocking monomer copolymerized with reactive diluent and ii) linear thermoplastic polyurethane.
  • FIG. 25B depicts a method of the present invention carried out with (meth)acrylate blocked diisocyanates (ABDIs).
  • ABSIs (meth)acrylate blocked diisocyanates
  • I Crosslinked blocked diisocyanate containing unreacted soft segment and chain extender.
  • II Polymer blend of: i) linear ethylenically unsaturated blocking monomer copolymerized with reactive diluent and ii) linear thermoplastic polyurethane.
  • FIG. 25C depicts a method of the present invention carried out with (meth)acrylate blocked chain extenders (ABCEs).
  • ABCEs (meth)acrylate blocked chain extenders
  • I Crosslinked blocked diisocyanate containing chain extender containing unreacted soft segment and chain extender.
  • spatially relative terms such as “under,” “below,” “lower,” “over,” “upper” and the like, may be used herein for ease of description to describe an element's or feature's relationship to another element(s) or feature(s) as illustrated in the figures. It will be understood that the spatially relative terms are intended to encompass different orientations of the device in use or operation in addition to the orientation depicted in the figures. For example, if the device in the figures is inverted, elements described as “under” or “beneath” other elements or features would then be oriented “over” the other elements or features. Thus the exemplary term “under” can encompass both an orientation of over and under.
  • the device may otherwise be oriented (rotated 90 degrees or at other orientations) and the spatially relative descriptors used herein interpreted accordingly.
  • the terms “upwardly,” “downwardly,” “vertical,” “horizontal” and the like are used herein for the purpose of explanation only, unless specifically indicated otherwise.
  • first, second, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. Rather, these terms are only used to distinguish one element, component, region, layer and/or section, from another element, component, region, layer and/or section. Thus, a first element, component, region, layer or section discussed herein could be termed a second element, component, region, layer or section without departing from the teachings of the present invention.
  • the sequence of operations (or steps) is not limited to the order presented in the claims or figures unless specifically indicated otherwise.
  • Shape to be imparted to refers to the case where the shape of the intermediate object slightly changes between formation thereof and forming the subsequent three-dimensional product, typically by shrinkage (e.g., up to 1, 2 or 4 percent by volume), expansion (e.g., up to 1, 2 or 4 percent by volume), removal of support structures, or by intervening forming steps (e.g., intentional bending, stretching, drilling, grinding, cutting, polishing, or other intentional forming after formation of the intermediate product, but before formation of the subsequent three-dimensional product).
  • the three dimensional intermediate may also be washed, if desired, before further curing, and/or before, during, or after any intervening forming steps.
  • Hydrocarbyl refers to a bifunctional hydrocarbon group, which hydrocarbon may be aliphatic, aromatic, or mixed aliphatic and aromatic, and optionally containing one or more (e.g. 1, 2, 3, or 4) heteroatoms (typically selected from N, O, and S). Such hydrocarbyl groups may be optionally substituted and may contain from 1, 2, or 3 carbon atoms, up to 6, 8 or 10 carbon atoms or more, and up to 40, 80, or 100 carbon atoms or more.
  • Heating may be active heating (e.g., in an oven, such as an electric, gas, or solar oven), or passive heating (e.g., at ambient temperature). Active heating will generally be more rapid than passive heating and in some embodiments is preferred, but passive heating—such as simply maintaining the intermediate at ambient temperature for a sufficient time to effect further cure—is in some embodiments preferred.
  • Diaisocyanate and “polyisocyanate” are used interchangeably herein and refer to aliphatic, cycloaliphatic, and aromatic isocyanates that have at least 2, or in some embodiments more than 2, isocyanate (NCO) groups per molecule, on average. In some embodiments, the isocyanates have, on average, 3 to 6, 8 or 10 or more isocyanate groups per molecule. In some embodiments, the isocyanates may be a hyperbranched or dendrimeric isocyanate (e.g., containing more than 10 isocyanate groups per molecule, on average).
  • isocyanates include, but are not limited to, methylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI)), para-phenyl diisocyanate (PPDI), 4,4′-dicyclohexylmethane-diisocyanate (HMDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), triphenylmethane-4,4′4′′-triisocyanate, toluene-2,4,6-triyl triisocyanate, 1,3,5-triazine-2,4,6-triisocyanate, ethyl ester L-lysine triisocyanate, etc., including combinations thereof.
  • MDI methylene diphenyl diisocyanate
  • TDI toluene diisocyanate
  • PPDI para-phenyl diisocyanate
  • HMDI 4,4′-dicyclohe
  • Oxidizable tin salts useful for carrying out the present invention include, but are not limited to, stannous butanoate, stannous octoate, stannous hexanoate, stannous heptanoate, stannous linoleate, stannous phenyl butanoate, stannous phenyl stearate, stannous phenyl oleate, stannous nonanoate, stannous decanoate, stannous undecanoate, stannous dodecanoate, stannous stearate, stannous oleate stannous undecenoate, stannous 2 -ethylhexoate, dibutyl tin dilaurate, dibutyl tin dioleate, dibutyl tin distearate, dipropyl tin dilaurate, dipropyl tin dioleate, dipropyl tin distearate
  • fillers may be solid or liquid, organic or inorganic, and may include reactive and non-reactive rubbers: siloxanes, acrylonitrile-butadiene rubbers; reactive and non-reactive thermoplastics (including but not limited to: poly(ether imides), maleimide-styrene terpolymers, polyarylates, polysulfones and polyethersulfones, etc.) inorganic fillers such as silicates (such as talc, clays, silica, mica), glass, carbon nanotubes, graphene, cellulose nanocrystals, etc., including combinations of all of the foregoing.
  • Suitable fillers include tougheners, such as core-shell rubbers, as discussed below.
  • One or more polymeric and/or inorganic tougheners can be used as a filler in the present invention. See generally US Patent Application Publication No. 20150215430.
  • the toughener may be uniformly distributed in the form of particles in the cured product. The particles could be less than 5 microns (um) in diameter.
  • Such tougheners include, but are not limited to, those formed from elastomers, branched polymers, hyperbranched polymers, dendrimers, rubbery polymers, rubbery copolymers, block copolymers, core-shell particles, oxides or inorganic materials such as clay, polyhedral oligomeric silsesquioxanes (POSS), carbonaceous materials (e.g., carbon black, carbon nanotubes, carbon nanofibers, fullerenes), ceramics and silicon carbides, with or without surface modification or functionalization.
  • PES polyhedral oligomeric silsesquioxanes
  • block copolymers include the copolymers whose composition is described in U.S. Pat. No.
  • core-shell particles examples include the core-shell (dendrimer) particles whose compositions are described in US20100280151A1 (Nguyen et al., Toray Industries, Inc., 2010) for an amine branched polymer as a shell grafted to a core polymer polymerized from polymerizable monomers containing unsaturated carbon-carbon bonds, core-shell rubber particles whose compositions are described in EP 1632533A1 and EP 2123711A1 by Kaneka Corporation, and the “KaneAce MX” product line of such particle/epoxy blends whose particles have a polymeric core polymerized from polymerizable monomers such as butadiene, styrene, other unsaturated carbon-carbon bond monomer, or their combinations, and a polymeric shell compatible with the epoxy, typically polymethylmethacrylate, polyglycidylmethacrylate, polyacrylonitrile or similar polymers, as discussed further below.
  • core-shell (dendrimer) particles
  • block copolymers in the present invention are the “JSR SX” series of carboxylated polystyrene/polydivinylbenzenes produced by JSR Corporation; “Kureha Paraloid” EXL-2655 (produced by Kureha Chemical Industry Co., Ltd.), which is a butadiene alkyl methacrylate styrene copolymer; “Stafiloid” AC-3355 and TR-2122 (both produced by Takeda Chemical Industries, Ltd.), each of which are acrylate methacrylate copolymers; and “PARALOID” EXL-2611 and EXL-3387 (both produced by Rohm & Haas), each of which are butyl acrylate methyl methacrylate copolymers.
  • suitable oxide particles include NANOPDX®TM produced by nanoresins AG. This is a master blend of functionalized nanosilica particles and an epoxy.
  • Core-shell rubbers are particulate materials (particles) having a rubbery core. Such materials are known and described in, for example, US Patent Application Publication No. 20150184039, as well as US Patent Application Publication No. 20150240113, and U.S. Pat. Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere.
  • the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)).
  • the average particle size of the core-shell rubber nanoparticles is less than 500 nm, e.g., less than 300 nm, less than 200 nm, less than 100 nm, or even less than 50 nm.
  • such particles are spherical, so the particle size is the diameter; however, if the particles are not spherical, the particle size is defined as the longest dimension of the particle.
  • the rubbery core can have a Tg of less than ⁇ 25° C., more preferably less than ⁇ 50° C., and even more preferably less than ⁇ 70° C.
  • the Tg of the rubbery core may be well below ⁇ 100° C.
  • the core-shell rubber also has at least one shell portion that preferably has a Tg of at least 50° C.
  • core it is meant an internal portion of the core-shell rubber.
  • the core may form the center of the core-shell particle, or an internal shell or domain of the core-shell rubber.
  • a shell is a portion of the core-shell rubber that is exterior to the rubbery core.
  • the shell portion (or portions) typically forms the outermost portion of the core-shell rubber particle.
  • the shell material can be grafted onto the core or is cross-linked.
  • the rubbery core may constitute from 50 to 95%, or from 60 to 90%, of the weight of the core-shell rubber particle.
  • the core of the core-shell rubber may be a polymer or copolymer of a conjugated diene such as butadiene, or a lower alkyl acrylate such as n-butyl-, ethyl-, isobutyl- or 2-ethylhexylacrylate.
  • the core polymer may in addition contain up to 20% by weight of other copolymerized mono-unsaturated monomers such as styrene, vinyl acetate, vinyl chloride, methyl methacrylate, and the like.
  • the core polymer is optionally cross-linked.
  • the core polymer optionally contains up to 5% of a copolymerized graft-linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
  • a copolymerized graft-linking monomer having two or more sites of unsaturation of unequal reactivity, such as diallyl maleate, monoallyl fumarate, allyl methacrylate, and the like, at least one of the reactive sites being non-conjugated.
  • the core polymer may also be a silicone rubber. These materials often have glass transition temperatures below ⁇ 100° C.
  • Core-shell rubbers having a silicone rubber core include those commercially available from Wacker Chemie, Kunststoff, Germany, under the trade name Genioperl.
  • the shell polymer which is optionally chemically grafted or cross-linked to the rubber core, can be polymerized from at least one lower alkyl methacrylate such as methyl methacrylate, ethyl methacrylate or t-butyl methacrylate. Homopolymers of such methacrylate monomers can be used. Further, up to 40% by weight of the shell polymer can be formed from other monovinylidene monomers such as styrene, vinyl acetate, vinyl chloride, methyl acrylate, ethyl acrylate, butyl acrylate, and the like. The molecular weight of the grafted shell polymer can be between 20,000 and 500,000.
  • One suitable type of core-shell rubber has reactive groups in the shell polymer which can react with an epoxy resin or an epoxy resin hardener.
  • Glycidyl groups are suitable. These can be provided by monomers such as glycidyl methacrylate.
  • Core-shell rubber particles as described therein include a cross-linked rubber core, in most cases being a cross-linked copolymer of butadiene, and a shell which is preferably a copolymer of styrene, methyl methacrylate, glycidyl methacrylate and optionally acrylonitrile.
  • the core-shell rubber is preferably dispersed in a polymer or an epoxy resin, also as described in the document.
  • Suitable core-shell rubbers include, but are not limited to, those sold by Kaneka Corporation under the designation Kaneka Kane Ace, including the Kaneka Kane Ace 15 and 120 series of products, including Kanaka Kance Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, and Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
  • Kaneka Kane Ace including the Kaneka Kane Ace 15 and 120 series of products, including Kanaka Kance Ace MX 120, Kaneka Kane Ace MX 153, Kaneka Kane Ace MX 154, Kaneka Kane Ace MX 156, Kaneka Kane Ace MX170, and Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
  • Dual cure systems as described herein may include a first curable system (sometimes referred to as “Part A” or herein) that is curable by actinic radiation, typically light, and in some embodiments ultraviolet (UV) light).
  • a first curable system (sometimes referred to as “Part A” or herein) that is curable by actinic radiation, typically light, and in some embodiments ultraviolet (UV) light).
  • Any suitable polymerizable liquid can be used as the first component.
  • the liquid (sometimes also referred to as “liquid resin” “ink,” or simply “resin” herein) can include a monomer, particularly photopolymerizable and/or free radical polymerizable monomers, and a suitable initiator such as a free radical initiator, and combinations thereof.
  • Examples include, but are not limited to, acrylics, methacrylics, acrylamides, styrenics, olefins, halogenated olefins, cyclic alkenes, maleic anhydride, alkenes, alkynes, carbon monoxide, functionalized oligomers, multifunctional cute site monomers, functionalized PEGs, etc., including combinations thereof.
  • liquid resins, monomers and initiators include but are not limited to those set forth in U.S. Pat. Nos. 8,232,043; 8,119,214; 7,935,476; 7,767,728; 7,649,029; WO 2012129968 A1; CN 102715751 A; JP 2012210408 A.
  • the polymerizable liquid comprises a free radical polymerizable liquid (in which case an inhibitor may be oxygen as described below), in other embodiments the polymerizable liquid comprises an acid catalyzed, or cationically polymerized, polymerizable liquid. In such embodiments the polymerizable liquid comprises monomers contain groups suitable for acid catalysis, such as epoxide groups, vinyl ether groups, etc.
  • suitable monomers include olefins such as methoxyethene, 4-methoxystyrene, styrene, 2-methylprop-1-ene, 1,3-butadiene, etc.; heterocyclic monomers (including lactones, lactams, and cyclic amines) such as oxirane, thietane, tetrahydrofuran, oxazoline, 1,3, dioxepane, oxetan-2-one, etc., and combinations thereof.
  • olefins such as methoxyethene, 4-methoxystyrene, styrene, 2-methylprop-1-ene, 1,3-butadiene, etc.
  • heterocyclic monomers including lactones, lactams, and cyclic amines
  • a suitable (generally ionic or non-ionic) photoacid generator (PAG) is included in the acid catalyzed polymerizable liquid, examples of which include, but are not limited to onium salts, sulfonium and iodonium salts, etc., such as diphenyl iodide hexafluorophosphate, diphenyl iodide hexafluoroarsenate, diphenyl iodide hexafluoroantimonate, diphenyl p-methoxyphenyl triflate, diphenyl p-toluenyl triflate, diphenyl p-isobutylphenyl triflate, diphenyl p-tert-butylphenyl triflate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium
  • suitable resins includes photocurable hydrogels like poly(ethylene glycols) (PEG) and gelatins.
  • PEG hydrogels have been used to deliver a variety of biologicals, including Growth factors; however, a great challenge facing PEG hydrogels crosslinked by chain growth polymerizations is the potential for irreversible protein damage.
  • Conditions to maximize release of the biologicals from photopolymerized PEG diacrylate hydrogels can be enhanced by inclusion of affinity binding peptide sequences in the monomer resin solutions, prior to photopolymerization allowing sustained delivery.
  • Gelatin is a biopolymer frequently used in food, cosmetic, pharmaceutical and photographic industries. It is obtained by thermal denaturation or chemical and physical degradation of collagen. There are three kinds of gelatin, including those found in animals, fish and humans. Gelatin from the skin of cold water fish is considered safe to use in pharmaceutical applications. UV or visible light can be used to crosslink appropriately modified gelatin. Methods for crosslinking gelatin include cure derivatives from dyes such as Rose Bengal.
  • a suitable resin includes photocurable silicones.
  • UV cure silicone rubber such as SilioprenTM UV Cure Silicone Rubber can be used as can LOCTITETM Cure Silicone adhesives sealants.
  • Applications include optical instruments, medical and surgical equipment, exterior lighting and enclosures, electrical connectors/sensors, fiber optics, gaskets, and molds.
  • Biodegradable resins are particularly important for implantable devices to deliver drugs or for temporary performance applications, like biodegradable screws and stents (U.S. Pat. Nos. 7,919,162; 6,932,930).
  • Biodegradable copolymers of lactic acid and glycolic acid (PLGA) can be dissolved in PEG di(meth)acrylate to yield a transparent resin suitable for use.
  • Polycaprolactone and PLGA oligomers can be functionalized with acrylic or methacrylic groups to allow them to be effective resins for use.
  • a particularly useful resin is photocurable polyurethanes (including, polyureas, and copolymers of polyurethanes and polyureas (e.g., poly(urethane-urea)).
  • a photopolymerizable polyurethane/polyurea composition comprising (1) a polyurethane based on an aliphatic diisocyanate, poly(hexamethylene isophthalate glycol) and, optionally, 1,4-butanediol; (2) a polyfunctional acrylic ester; (3) a photoinitiator; and (4) an anti-oxidant, can be formulated so that it provides a hard, abrasion-resistant, and stain-resistant material (U.S. Pat. No. 4,337,130).
  • Photocurable thermoplastic polyurethane elastomers incorporate photoreactive diacetylene diols as chain extenders.
  • high performance resins are used. Such high performance resins may sometimes require the use of heating to melt and/or reduce the viscosity thereof, as noted above and discussed further below.
  • examples of such resins include, but are not limited to, resins for those materials sometimes referred to as liquid crystalline polymers of esters, ester-imide, and ester-amide oligomers, as described in U.S. Pat. Nos. 7,507,784; 6,939,940.
  • thermoset resins are sometimes employed as high-temperature thermoset resins, in the present invention they further comprise a suitable photoinitiator such as benzophenone, anthraquinone, and fluorenone initiators (including derivatives thereof), to initiate cross-linking on irradiation, as discussed further below.
  • a suitable photoinitiator such as benzophenone, anthraquinone, and fluorenone initiators (including derivatives thereof), to initiate cross-linking on irradiation, as discussed further below.
  • Particularly useful resins for dental applications include EnvisionTEC's Clear Guide, EnvisionTEC's E-Denstone Material.
  • Particularly useful resins for hearing aid industries include EnvisionTEC's e-Shell 300 Series of resins.
  • Particularly useful resins include EnvisionTEC's HTM140IV High Temperature Mold Material for use directly with vulcanized rubber in molding/casting applications.
  • a particularly useful material for making tough and stiff parts includes EnvisionTEC's RC31 resin.
  • Particularly useful resin for investment casting applications include EnvisionTEC's Easy Cast EC500 resin and MadeSolid FireCast resin.
  • the liquid resin or polymerizable material can have solid particles suspended or dispersed therein. Any suitable solid particle can be used, depending upon the end product being fabricated.
  • the particles can be metallic, organic/polymeric, inorganic, or composites or mixtures thereof.
  • the particles can be nonconductive, semi-conductive, or conductive (including metallic and non-metallic or polymer conductors); and the particles can be magnetic, ferromagnetic, paramagnetic, or nonmagnetic.
  • the particles can be of any suitable shape, including spherical, elliptical, cylindrical, etc.
  • the particles can be of any suitable size (for example, ranging from 1 nm to 20 um average diameter).
  • the particles can comprise an active agent or detectable compound as described below, though these may also be provided dissolved solubilized in the liquid resin as also discussed below.
  • magnetic or paramagnetic particles or nanoparticles can be employed.
  • the liquid resin can have additional ingredients solubilized therein, including pigments, dyes, active compounds or pharmaceutical compounds, detectable compounds (e.g., fluorescent, phosphorescent, radioactive), etc., again depending upon the particular purpose of the product being fabricated.
  • additional ingredients include, but are not limited to, proteins, peptides, nucleic acids (DNA, RNA) such as siRNA, sugars, small organic compounds (drugs and drug-like compounds), etc., including combinations thereof.
  • Non-Reactive Light Absorbers are non-Reactive Light Absorbers.
  • polymerizable liquids for carrying out the present invention include a non-reactive pigment or dye that absorbs light, particularly UV light.
  • Suitable examples of such light absorbers include, but are not limited to: (i) titanium dioxide (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), (ii) carbon black (e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (iii) an organic ultraviolet light absorber such as a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotriazole ultraviolet light absorber (e.g., Mayzo BLS1326) (e.g., included in an amount of 0.001 or 0.005 to 1, 2 or 4 percent by weight).
  • titanium dioxide e.g., included in an amount of from 0.05 or 0.1 to 1 or 5 percent
  • organic ultraviolet light absorbers include, but are not limited to, those described in U.S. Pat. Nos. 3,213,058; 6,916,867; 7,157,586; and 7,695, 643, the disclosures of which are incorporated herein by reference.
  • Inhibitors or polymerization inhibitors for use in the present invention may be in the form of a liquid or a gas.
  • gas inhibitors are preferred.
  • liquid inhibitors such as oils or lubricants (e.g., fluorinated oils such as perfluoropolyethers) may be employed, as inhibitors (or as release layers that maintain a liquid interface)).
  • the specific inhibitor will depend upon the monomer being polymerized and the polymerization reaction.
  • the inhibitor can conveniently be oxygen, which can be provided in the form of a gas such as air, a gas enriched in oxygen (optionally but in some embodiments preferably containing additional inert gases to reduce combustibility thereof), or in some embodiments pure oxygen gas.
  • the inhibitor can be a base such as ammonia, trace amines (e.g. methyl amine, ethyl amine, di and trialkyl amines such as dimethyl amine, diethyl amine, trimethyl amine, triethyl amine, etc.), or carbon dioxide, including mixtures or combinations thereof.
  • trace amines e.g. methyl amine, ethyl amine, di and trialkyl amines such as dimethyl amine, diethyl amine, trimethyl amine, triethyl amine, etc.
  • carbon dioxide including mixtures or combinations thereof.
  • the polymerizable liquid may carry live cells as “particles” therein.
  • Such polymerizable liquids are generally aqueous, and may be oxygenated, and may be considered as “emulsions” where the live cells are the discrete phase.
  • Suitable live cells may be plant cells (e.g., monocot, dicot), animal cells (e.g., mammalian, avian, amphibian, reptile cells), microbial cells (e.g., prokaryote, eukaryote, protozoal, etc.), etc.
  • the cells may be of differentiated cells from or corresponding to any type of tissue (e.g., blood, cartilage, bone, muscle, endocrine gland, exocrine gland, epithelial, endothelial, etc.), or may be undifferentiated cells such as stem cells or progenitor cells.
  • the polymerizable liquid can be one that forms a hydrogel, including but not limited to those described in U.S. Pat. Nos. 7,651,683; 7,651,682; 7,556,490; 6,602,975; 5,836,313; etc.
  • FIG. 2 A non-limiting embodiment of an apparatus of the invention is shown in FIG. 2 . It comprises a radiation source 11 such as a digital light processor (DLP) providing electromagnetic radiation 12 which though reflective mirror 13 illuminates a build chamber defined by wall 14 and a rigid or flexible build plate 15 forming the bottom of the build chamber, which build chamber is filled with liquid resin 16 .
  • the bottom of the chamber 15 is constructed of a build plate comprising a rigid or flexible semipermeable member as discussed further below.
  • the top of the object under construction 17 is attached to a carrier 18 .
  • the carrier is driven in the vertical direction by linear stage 19 , although alternate structures can be used as discussed below.
  • a liquid resin reservoir, tubing, pumps liquid level sensors and/or valves can be included to replenish the pool of liquid resin in the build chamber (not shown for clarity) though in some embodiments a simple gravity feed may be employed.
  • Drives/actuators for the carrier or linear stage, along with associated wiring, can be included in accordance with known techniques (again not shown for clarity).
  • the drives/actuators, radiation source, and in some embodiments pumps and liquid level sensors can all be operatively associated with a suitable controller, again in accordance with known techniques.
  • Build plates 15 used to carry out the present invention generally comprise or consist of a (typically rigid or solid, stationary, and/or fixed, although in some embodiments flexible) semipermeable (or gas permeable) member, alone or in combination with one or more additional supporting substrates (e.g., clamps and tensioning members to tension and stabilize an otherwise flexible semipermeable material).
  • the semipermeable member can be made of any suitable material that is optically transparent at the relevant wavelengths (or otherwise transparent to the radiation source, whether or not it is visually transparent as perceived by the human eye—i.e., an optically transparent window may in some embodiments be visually opaque), including but not limited to porous or microporous glass, and the rigid gas permeable polymers used for the manufacture of rigid gas permeable contact lenses.
  • the semipermeable member is formed of a material that does not swell when contacted to the liquid resin or material to be polymerized (i.e., is “non-swellable”).
  • Suitable materials for the semipermeable member include amorphous fluoropolymers, such as those described in U.S. Pat. Nos. 5,308,685 and 5,051,115.
  • fluoropolymers are particularly useful over silicones that would potentially swell when used in conjunction with organic liquid resin inks to be polymerized.
  • silicone based window materials maybe suitable.
  • the solubility or permeability of organic liquid resin inks can be dramatically decreased by a number of known parameters including increasing the crosslink density of the window material or increasing the molecular weight of the liquid resin ink.
  • the build plate may be formed from a thin film or sheet of material which is flexible when separated from the apparatus of the invention, but which is clamped and tensioned when installed in the apparatus (e.g., with a tensioning ring) so that it is tensioned and stabilized in the apparatus.
  • a tensioning ring e.g., TEFLON AF® fluoropolymers, commercially available from DuPont.
  • Additional materials include perfluoropolyether polymers such as described in U.S. Pat. Nos. 8,268,446; 8,263,129; 8,158,728; and 7,435,495.
  • the terms “stationary” or “fixed” with respect to the build plate is intended to mean that no mechanical interruption of the process occurs, or no mechanism or structure for mechanical interruption of the process (as in a layer-by-layer method or apparatus) is provided, even if a mechanism for incremental adjustment of the build plate (for example, adjustment that does not lead to or cause collapse of the gradient of polymerization zone) is provided).
  • the semipermeable member typically comprises a top surface portion, a bottom surface portion, and an edge surface portion.
  • the build surface is on the top surface portion; and the feed surface may be on one, two, or all three of the top surface portion, the bottom surface portion, and/or the edge surface portion.
  • the feed surface is on the bottom surface portion, but alternate configurations where the feed surface is provided on an edge, and/or on the top surface portion (close to but separate or spaced away from the build surface) can be implemented with routine skill.
  • the semipermeable member has, in some embodiments, a thickness of from 0.01, 0.1 or 1 millimeters to 10 or 100 millimeters, or more (depending upon the size of the item being fabricated, whether or not it is laminated to or in contact with an additional supporting plate such as glass, etc., as discussed further below.
  • the permeability of the semipermeable member to the polymerization inhibitor will depend upon conditions such as the pressure of the atmosphere and/or inhibitor, the choice of inhibitor, the rate or speed of fabrication, etc.
  • the permeability of the semipermeable member to oxygen may be from 10 or 20 Barrers, up to 1000 or 2000 Barrers, or more.
  • a semipermeable member with a permeability of 10 Barrers used with a pure oxygen, or highly enriched oxygen, atmosphere under a pressure of 150 PSI may perform substantially the same as a semipermeable member with a permeability of 500 Barrers when the oxygen is supplied from the ambient atmosphere under atmospheric conditions.
  • the semipermeable member may comprise a flexible polymer film (having any suitable thickness, e.g., from 0.001, 0.01, 0.05, 0.1 or 1 millimeters to 1, 5, 10, or 100 millimeters, or more), and the build plate may further comprise a tensioning member (e.g., a peripheral clamp and an operatively associated strain member or stretching member, as in a “drum head”; a plurality of peripheral clamps, etc., including combinations thereof) connected to the polymer film and to fix and tension, stabilize or rigidify the film (e.g., at least sufficiently so that the film does not stick to the object as the object is advanced and resiliently or elastically rebound therefrom).
  • a tensioning member e.g., a peripheral clamp and an operatively associated strain member or stretching member, as in a “drum head”; a plurality of peripheral clamps, etc., including combinations thereof
  • the film has a top surface and a bottom surface, with the build surface on the top surface and the feed surface preferably on the bottom surface.
  • the semipermeable member comprises: (i) a polymer film layer (having any suitable thickness, e.g., from 0.001, 0.01, 0.1 or 1 millimeters to 5, 10 or 100 millimeters, or more), having a top surface positioned for contacting the polymerizable liquid and a bottom surface, and (ii) a gas permeable, optically transparent supporting member (having any suitable thickness, e.g., from 0.01, 0.1 or 1 millimeters to 10, 100, or 200 millimeters, or more), contacting the film layer bottom surface.
  • the supporting member has a top surface contacting the film layer bottom surface, and the supporting member has a bottom surface which may serve as the feed surface for the polymerization inhibitor.
  • Any suitable materials that are semipermeable that is, permeable to the polymerization inhibitor may be used.
  • the polymer film or polymer film layer may, for example, be a fluoropolymer film, such as an amorphous thermoplastic fluoropolymer like TEFLON AF 1600TM or TEFLON AF 2400TM fluoropolymer films, or perfluoropolyether (PFPE), particularly a crosslinked PFPE film, or a crosslinked silicone polymer film.
  • PFPE perfluoropolyether
  • the supporting member comprises a silicone or crosslinked silicone polymer member such as a polydimethylsiloxane polydmiethylxiloxane member, a gas permeable polymer member, or a porous or microporous glass member.
  • Films can be laminated or clamped directly to the rigid supporting member without adhesive (e.g., using PFPE and PDMS materials), or silane coupling agents that react with the upper surface of a PDMS layer can be utilized to adhere to the first polymer film layer.
  • UV-curable, acrylate-functional silicones can also be used as a tie layer between UV-curable PFPEs and rigid PDMS supporting layers.
  • the carrier When configured for placement in the apparatus, the carrier defines a “build region” on the build surface, within the total area of the build surface. Because lateral “throw” (e.g., in the X and/or Y directions) is not required in the present invention to break adhesion between successive layers, as in the Joyce and Chen devices noted previously, the area of the build region within the build surface may be maximized (or conversely, the area of the build surface not devoted to the build region may be minimized). Hence in some embodiments, the total surface area of the build region can occupy at least fifty, sixty, seventy, eighty, or ninety percent of the total surface area of the build surface.
  • the various components are mounted on a support or frame assembly 20 .
  • the support or frame assembly is comprised of a base 21 to which the radiation source 11 is securely or rigidly attached, a vertical member 22 to which the linear stage is operatively associated, and a horizontal table 23 to which wall 14 is removably or securely attached (or on which the wall is placed), and with the build plate fixed, either permanently or removably, to form the build chamber as described above.
  • the build plate can consist of a single unitary and integral piece of a semipermeable member, or can comprise additional materials.
  • a porous or microporous glass can be laminated or fixed to a semipermeable material.
  • a semipermeable member as an upper portion can be fixed to a transparent lower member having purging channels formed therein for feeding gas carrying the polymerization inhibitor to the semipermeable member (through which it passes to the build surface to facilitate the formation of a release layer of unpolymerized liquid material, as noted above and below).
  • purge channels may extend fully or partially through the base plate:
  • the purge channels may extend partially into the base plate, but then end in the region directly underlying the build surface to avoid introduction of distortion. Specific geometries will depend upon whether the feed surface for the inhibitor into the semipermeable member is located on the same side or opposite side as the build surface, on an edge portion thereof, or a combination of several thereof.
  • any suitable radiation source can be used, depending upon the particular resin employed, including electron beam and ionizing radiation sources.
  • the radiation source is an actinic radiation source, such as one or more light sources, and in particular one or more ultraviolet light sources.
  • Any suitable light source can be used, such as incandescent lights, fluorescent lights, phosphorescent or luminescent lights, a laser, light-emitting diode, etc., including arrays thereof.
  • the light source preferably includes a pattern-forming element operatively associated with a controller, as noted above.
  • the light source or pattern forming element comprises a digital (or deformable) micromirror device (DMD) with digital light processing (DLP), a spatial modulator (SLM), or a microelectromechanical system (MEMS) mirror array, a liquid crystal display (LCD) panel, a mask (aka a reticle), a silhouette, or a combination thereof.
  • DMD digital (or deformable) micromirror device
  • DLP digital light processing
  • SLM spatial modulator
  • MEMS microelectromechanical system
  • LCD liquid crystal display
  • mask aka a reticle
  • silhouette or a combination thereof. See, U.S. Pat. No. 7,902,526.
  • the light source comprises a spatial light modulation array such as a liquid crystal light valve array or micromirror array or DMD (e.g., with an operatively associated digital light processor, typically in turn under the control of a suitable controller), configured to carry out exposure or irradiation of the polymerizable liquid without a mask, e.g., by maskless photolithography.
  • a spatial light modulation array such as a liquid crystal light valve array or micromirror array or DMD (e.g., with an operatively associated digital light processor, typically in turn under the control of a suitable controller), configured to carry out exposure or irradiation of the polymerizable liquid without a mask, e.g., by maskless photolithography.
  • such movement may be carried out for purposes such as reducing “burn in” or fouling in a particular zone of the build surface.
  • lateral movement (including movement in the X and/or Y direction or combination thereof) of the carrier and object (if such lateral movement is present) is preferably not more than, or less than, 80, 70, 60, 50, 40, 30, 20, or even 10 percent of the width (in the direction of that lateral movement) of the build region.
  • the carrier is mounted on an elevator to advance up and away from a stationary build plate
  • the converse arrangement may be used: That is, the carrier may be fixed and the build plate lowered to thereby advance the carrier away therefrom.
  • Numerous different mechanical configurations will be apparent to those skilled in the art to achieve the same result.
  • adhesion of the article to the carrier may sometimes be insufficient to retain the article on the carrier through to completion of the finished article or “build.”
  • an aluminum carrier may have lower adhesion than a poly(vinyl chloride) (or “PVC”) carrier.
  • PVC poly(vinyl chloride)
  • any of a variety of techniques can be used to further secure the article to a less adhesive carrier, including but not limited to the application of adhesive tape such as “Greener Masking Tape for Basic Painting #2025 High adhesion” to further secure the article to the carrier during fabrication.
  • the methods and apparatus of the invention can include process steps and apparatus features to implement process control, including feedback and feed-forward control, to, for example, enhance the speed and/or reliability of the method.
  • a controller for use in carrying out the present invention may be implemented as hardware circuitry, software, or a combination thereof.
  • the controller is a general purpose computer that runs software, operatively associated with monitors, drives, pumps, and other components through suitable interface hardware and/or software.
  • Suitable software for the control of a three-dimensional printing or fabrication method and apparatus as described herein includes, but is not limited to, the ReplicatorG open source 3d printing program, 3DPrintTM controller software from 3D systems, Slic3r, Skeinforge, KISSlicer, Repetier-Host, PrintRun, Cura, etc., including combinations thereof.
  • Process parameters to directly or indirectly monitor, continuously or intermittently, during the process include, but are not limited to, irradiation intensity, temperature of carrier, polymerizable liquid in the build zone, temperature of growing product, temperature of build plate, pressure, speed of advance, pressure, force (e.g., exerted on the build plate through the carrier and product being fabricated), strain (e.g., exerted on the carrier by the growing product being fabricated), thickness of release layer, etc.
  • Known parameters that may be used in feedback and/or feed-forward control systems include, but are not limited to, expected consumption of polymerizable liquid (e.g., from the known geometry or volume of the article being fabricated), degradation temperature of the polymer being formed from the polymerizable liquid, etc.
  • Process conditions to directly or indirectly control, continuously or step-wise, in response to a monitored parameter, and/or known parameters include, but are not limited to, rate of supply of polymerizable liquid, temperature, pressure, rate or speed of advance of carrier, intensity of irradiation, duration of irradiation (e.g. for each “slice”), etc.
  • the temperature of the polymerizable liquid in the build zone, or the temperature of the build plate can be monitored, directly or indirectly with an appropriate thermocouple, non-contact temperature sensor (e.g., an infrared temperature sensor), or other suitable temperature sensor, to determine whether the temperature exceeds the degradation temperature of the polymerized product. If so, a process parameter may be adjusted through a controller to reduce the temperature in the build zone and/or of the build plate. Suitable process parameters for such adjustment may include: decreasing temperature with a cooler, decreasing the rate of advance of the carrier, decreasing intensity of the irradiation, decreasing duration of radiation exposure, etc.
  • the intensity of the irradiation source e.g., an ultraviolet light source such as a mercury lamp
  • a photodetector to detect a decrease of intensity from the irradiation source (e.g., through routine degradation thereof during use). If detected, a process parameter may be adjusted through a controller to accommodate the loss of intensity. Suitable process parameters for such adjustment may include: increasing temperature with a heater, decreasing the rate of advance of the carrier, increasing power to the light source, etc.
  • control of temperature and/or pressure to enhance fabrication time may be achieved with heaters and coolers (individually, or in combination with one another and separately responsive to a controller), and/or with a pressure supply (e.g., pump, pressure vessel, valves and combinations thereof) and/or a pressure release mechanism such as a controllable valve (individually, or in combination with one another and separately responsive to a controller).
  • a pressure supply e.g., pump, pressure vessel, valves and combinations thereof
  • a pressure release mechanism such as a controllable valve
  • the controller is configured to maintain the gradient of polymerization zone described herein (see, e.g., FIG. 1 ) throughout the fabrication of some or all of the final product.
  • the specific configuration e.g., times, rate or speed of advancing, radiation intensity, temperature, etc.
  • Configuration to maintain the gradient of polymerization zone may be carried out empirically, by entering a set of process parameters or instructions previously determined, or determined through a series of test runs or “trial and error”; configuration may be provided through pre-determined instructions; configuration may be achieved by suitable monitoring and feedback (as discussed above), combinations thereof, or in any other suitable manner.
  • a method and apparatus as described above may be controlled by a software program running in a general purpose computer with suitable interface hardware between that computer and the apparatus described above.
  • a software program running in a general purpose computer with suitable interface hardware between that computer and the apparatus described above.
  • Numerous alternatives are commercially available. Non-limiting examples of one combination of components is shown in FIGS. 3 to 5 , where “Microcontroller” is Parallax Propeller, the Stepper Motor Driver is Sparkfun EasyDriver, the LED Driver is a Luxeon Single LED Driver, the USB to Serial is a Parallax USB to Serial converter, and the DLP System is a Texas Instruments LightCrafter system.
  • the three dimensional intermediate is preferably formed from resins as described above by additive manufacturing, typically bottom-up or top-down additive manufacturing.
  • top-down three-dimensional fabrication is carried out by:
  • a polymerizable liquid i.e., the resin
  • said polymerizable liquid comprising a mixture of (i) a light (typically ultraviolet light) polymerizable liquid first component, and (ii) a second solidifiable component of the dual cure system;
  • a wiper blade, doctor blade, or optically transparent (rigid or flexible) window may optionally be provided at the fill level to facilitate leveling of the polymerizable liquid, in accordance with known techniques.
  • the window provides a build surface against which the three dimensional intermediate is formed, analogous to the build surface in bottom-up three dimensional fabrication as discussed below.
  • bottom-up three dimensional fabrication is carried out by:
  • a polymerizable liquid i.e., the resin
  • said polymerizable liquid comprising a mixture of (i) a light (typically ultraviolet light) polymerizable liquid first component, and (ii) a second solidifiable component of the dual cure system;
  • the build surface is stationary during the formation of the three dimensional intermediate; in other embodiments of bottom-up three dimensional fabrication as implemented in the context of the present invention, the build surface is tilted, slid, flexed and/or peeled, and/or otherwise translocated or released from the growing three dimensional intermediate, usually repeatedly, during formation of the three dimensional intermediate.
  • the polymerizable liquid is maintained in liquid contact with both the growing three dimensional intermediate and the build surface during both the filling and irradiating steps, during fabrication of some of, a major portion of, or all of the three dimensional intermediate.
  • the growing three dimensional intermediate is fabricated in a layerless manner (e.g., through multiple exposures or “slices” of patterned actinic radiation or light) during at least a portion of the formation of the three dimensional intermediate.
  • the growing three dimensional intermediate is fabricated in a layer-by-layer manner (e.g., through multiple exposures or “slices” of patterned actinic radiation or light), during at least a portion of the formation of the three dimensional intermediate.
  • a lubricant or immiscible liquid may be provided between the window and the polymerizable liquid (e.g., a fluorinated fluid or oil such as a perfluoropolyether oil).
  • the growing three dimensional intermediate is fabricated in a layerless manner during the formation of at least one portion thereof, and that same growing three dimensional intermediate is fabricated in a layer-by-layer manner during the formation of at least one other portion thereof.
  • operating mode may be changed once, or on multiple occasions, between layerless fabrication and layer-by-layer fabrication, as desired by operating conditions such as part geometry.
  • the intermediate is formed by continuous liquid interface production (CLIP), as discussed further below.
  • CLIP continuous liquid interface production
  • the present invention provides (in some embodiments) a method of forming a three-dimensional object, comprising the steps of: (a) providing a carrier and a build plate, the build plate comprising a semipermeable member, the semipermeable member comprising a build surface and a feed surface separate from the build surface, with the build surface and the carrier defining a build region therebetween, and with the feed surface in fluid contact with a polymerization inhibitor; then (concurrently and/or sequentially) (b) filing the build region with a polymerizable liquid, the polymerizable liquid contacting the build segment, (c) irradiating the build region through the build plate to produce a solid polymerized region in the build region, with a liquid film release layer comprised of the polymerizable liquid formed between the solid polymerized region and the build surface, the polymerization of which liquid film is inhibited by the polymerization inhibitor; and (d) advancing the carrier with the polymerized region adhered thereto away from the build surface on the
  • the method includes (e) continuing and/or repeating steps (b) through (d) 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 object.
  • the method can be carried out in a continuous fashion, though it will be appreciated that the individual steps noted above may be carried out sequentially, concurrently, or a combination thereof. Indeed, the rate of steps can be varied over time depending upon factors such as the density and/or complexity of the region under fabrication.
  • the present invention in some embodiments permits elimination of this “back-up” step and allows the carrier to be advanced unidirectionally, or in a single direction, without intervening movement of the window for re-coating, or “snapping” of a pre-formed elastic release-layer.
  • reciprocation is utilized not for the purpose of obtaining release, but for the purpose of more rapidly filling or pumping polymerizable liquid into the build region.
  • the thickness of the gradient of polymerization zone is in some embodiments at least as great as the thickness of the dead zone.
  • the dead zone has a thickness of from 0.01, 0.1, 1, 2, or 10 microns up to 100, 200 or 400 microns, or more, and/or the gradient of polymerization zone and the dead zone together have a thickness of from 1 or 2 microns up to 400, 600, or 1000 microns, or more.
  • the gradient of polymerization zone may be thick or thin depending on the particular process conditions at that time.
  • the gradient of polymerization zone is thin, it may also be described as an active surface on the bottom of the growing three-dimensional object, with which monomers can react and continue to form growing polymer chains therewith.
  • the gradient of polymerization zone, or active surface is maintained (while polymerizing steps continue) for a time of at least 5, 10, 15, 20 or 30 seconds, up to 5, 10, 15 or 20 minutes or more, or until completion of the three-dimensional product.
  • the method may further comprise the step of disrupting the gradient of polymerization zone for a time sufficient to form a cleavage line in the three-dimensional object (e.g., at a predetermined desired location for intentional cleavage, or at a location in the object where prevention of cleavage or reduction of cleavage is non-critical), and then reinstating the gradient of polymerization zone (e.g. by pausing, and resuming, the advancing step, increasing, then decreasing, the intensity of irradiation, and combinations thereof).
  • the advancing step is carried out sequentially in uniform increments (e.g., of from 0.1 or 1 microns, up to 10 or 100 microns, or more) for each step or increment. In some embodiments, the advancing step is carried out sequentially in variable increments (e.g., each increment ranging from 0.1 or 1 microns, up to 10 or 100 microns, or more) for each step or increment.
  • the size of the increment, along with the rate of advancing, will depend in part upon factors such as temperature, pressure, structure of the article being produced (e.g., size, density, complexity, configuration, etc.)
  • the advancing step is carried out continuously, at a uniform or variable rate.
  • the rate of advance (whether carried out sequentially or continuously) is from about 0.1 1, or 10 microns per second, up to about to 100, 1,000, or 10,000 microns per second, again depending again depending on factors such as temperature, pressure, structure of the article being produced, intensity of radiation, etc
  • the filling step is carried out by forcing the polymerizable liquid into the build region under pressure.
  • the advancing step or steps may be carried out at a rate or cumulative or average rate of at least 0.1, 1, 10, 50, 100, 500 or 1000 microns per second, or more.
  • the pressure may be whatever is sufficient to increase the rate of the advancing step(s) at least 2, 4, 6, 8 or 10 times as compared to the maximum rate of repetition of the advancing steps in the absence of the pressure.
  • a pressure of 10, 20, 30 or 40 pounds per square inch (PSI) up to, 200, 300, 400 or 500 PSI or more may be used.
  • PSI pounds per square inch
  • both the feed surface and the polymerizable liquid can be are in fluid contact with the same compressed gas (e.g., one comprising from 20 to 95 percent by volume of oxygen, the oxygen serving as the polymerization inhibitor.
  • the size of the pressure vessel can be kept smaller relative to the size of the product being fabricated and higher pressures can (if desired) be more readily utilized.
  • the irradiating step is in some embodiments carried out with patterned irradiation.
  • the patterned irradiation may be a fixed pattern or may be a variable pattern created by a pattern generator (e.g., a DLP) as discussed above, depending upon the particular item being fabricated.
  • a pattern generator e.g., a DLP
  • each irradiating step may be any suitable time or duration depending on factors such as the intensity of the irradiation, the presence or absence of dyes in the polymerizable material, the rate of growth, etc.
  • each irradiating step can be from 0.001, 0.01, 0.1, 1 or 10 microseconds, up to 1, 10, or 100 minutes, or more, in duration.
  • the interval between each irradiating step is in some embodiments preferably as brief as possible, e.g., from 0.001, 0.01, 0.1, or 1 microseconds up to 0.1, 1, or 10 seconds.
  • the pattern may vary hundreds, thousands or millions of times to impart shape changes on the three-dimensional object being formed.
  • the pattern generator may have high resolution with millions of pixel elements that can be varied to change the shape that is imparted.
  • the pattern generator may be a DLP with more than 1,000 or 2,000 or 3,000 or more rows and/or more than 1,000 or 2,000 or 3,000 or more columns of micromirrors, or pixels in a liquid crystal display panel, that can be used to vary the shape.
  • the three-dimensional object may be formed through the gradient of polymerization allowing the shape changes to be imparted while continuously printing.
  • this allows complex three-dimensional objects to be formed at high speed with a substantially continuous surface without cleavage lines or seams.
  • thousands or millions of shape variations may be imparted on the three-dimensional object being formed without cleavage lines or seams across a length of the object being formed of more than 1 mm, 1 cm, 10 cm or more or across the entire length of the formed object.
  • the object may be continuously formed through the gradient of polymerization at a rate of more than 1, 10, 100, 1000, 10000 or more microns per second.
  • the build surface is flat; in other the build surface is irregular such as convexly or concavely curved, or has walls or trenches formed therein. In either case the build surface may be smooth or textured.
  • Curved and/or irregular build plates or build surfaces can be used in fiber or rod formation, to provide different materials to a single object being fabricated (that is, different polymerizable liquids to the same build surface through channels or trenches formed in the build surface, each associated with a separate liquid supply, etc.
  • the carrier include one or more feed channels therein.
  • the carrier feed channels are in fluid communication with the polymerizable liquid supply, for example a reservoir and associated pump.
  • Different carrier feed channels may be in fluid communication with the same supply and operate simultaneously with one another, or different carrier feed channels may be separately controllable from one another (for example, through the provision of a pump and/or valve for each).
  • Separately controllable feed channels may be in fluid communication with a reservoir containing the same polymerizable liquid, or may be in fluid communication with a reservoir containing different polymerizable liquids.
  • valve assemblies different polymerizable liquids may in some embodiments be alternately fed through the same feed channel, if desired.
  • the carrier is vertically reciprocated with respect to the build surface to enhance or speed the refilling of the build region with the polymerizable liquid.
  • the vertically reciprocating step which comprises an upstroke and a downstroke, is carried out with the distance of travel of the upstroke being greater than the distance of travel of the downstroke, to thereby concurrently carry out the advancing step (that is, driving the carrier away from the build plate in the Z dimension) in part or in whole.
  • the speed of the upstroke gradually accelerates (that is, there is provided a gradual start and/or gradual acceleration of the upstroke, over a period of at least 20, 30, 40, or 50 percent of the total time of the upstroke, until the conclusion of the upstroke, or the change of direction which represents the beginning of the downstroke. Stated differently, the upstroke begins, or starts, gently or gradually.
  • the speed of the downstroke gradually decelerates (that is, there is provided a gradual termination and/or gradual deceleration of the downstroke, over a period of at least 20, 30, 40, or 50 percent of the total time of the downstroke. Stated differently, the downstroke concludes, or ends, gently or gradually.
  • the vertically reciprocating step is carried out over a total time of from 0.01 or 0.1 seconds up to 1 or 10 seconds (e.g., per cycle of an upstroke and a downstroke).
  • the upstroke distance of travel is from 0.02 or 0.2 millimeters (or 20 or 200 microns) to 1 or 10 millimeters (or 1000 to 10,000 microns).
  • the distance of travel of the downstroke may be the same as, or less than, the distance of travel of the upstroke, where a lesser distance of travel for the downstroke serves to achieve the advancing of the carrier away from the build surface as the three-dimensional object is gradually formed.
  • the vertically reciprocating step does not cause the formation of gas bubbles or a gas pocket in the build region, but instead the build region remains filled with the polymerizable liquid throughout the reciprocation steps, and the gradient of polymerization zone or region remains in contact with the “dead zone” and with the growing object being fabricated throughout the reciprocation steps.
  • a purpose of the reciprocation is to speed or enhance the refilling of the build region, particularly where larger build regions are to be refilled with polymerizable liquid, as compared to the speed at which the build region could be refilled without the reciprocation step.
  • the advancing step is carried out intermittently at a rate of 1, 2, 5 or 10 individual advances per minute up to 300, 600, or 1000 individual advances per minute, each followed by a pause during which an irradiating step is carried out.
  • one or more reciprocation steps e.g., upstroke plus downstroke
  • the reciprocating steps may be nested within the advancing steps.
  • the individual advances are carried out over an average distance of travel for each advance of from 10 or 50 microns to 100 or 200 microns (optionally including the total distance of travel for each vertically reciprocating step, e.g., the sum of the upstroke distance minus the downstroke distance).
  • Apparatus for carrying out the invention in which the reciprocation steps described herein are implemented substantially as described above, with the drive associated with the carrier, and/or with an additional drive operatively associated with the transparent member, and with the controller operatively associated with either or both thereof and configured to reciprocate the carrier and transparent member with respect to one another as described above.
  • the light is concentrated or “focused” at the build region to increase the speed of fabrication. This may be accomplished using an optical device such as an objective lens.
  • the speed of fabrication may be generally proportional to the light intensity.
  • the build speed in millimeters per hour may be calculated by multiplying the light intensity in milliWatts per square centimeter and a multiplier.
  • the multiplier may depend on a variety of factors, including those discussed below.
  • a range of multipliers, from low to high, may be employed. On the low end of the range, the multiplier may be about 10, 15, 20 or 30. On the high end of the multiplier range, the multiplier may be about 150, 300, 400 or more.
  • a band pass filter may be used with a mercury bulb light source to provide 365 ⁇ 10 nm light measured at Full Width Half Maximum (FWHM).
  • a band pass filter may be used with an LED light source to provide 375 ⁇ 15 nm light measured at FWHM.
  • polymerizable liquids used in such processes are, in general, free radical polymerizable liquids with oxygen as the inhibitor, or acid-catalyzed or cationically polymerizable liquids with a base as the inhibitor.
  • Some specific polymerizable liquids will of course cure more rapidly or efficiently than others and hence be more amenable to higher speeds, though this may be offset at least in part by further increasing light intensity.
  • the “dead zone” may become thinner as inhibitor is consumed. If the dead zone is lost then the process will be disrupted.
  • the supply of inhibitor may be enhanced by any suitable means, including providing an enriched and/or pressurized atmosphere of inhibitor, a more porous semipermeable member, a stronger or more powerful inhibitor (particularly where a base is employed), etc.
  • lower viscosity polymerizable liquids are more amenable to higher speeds, particularly for fabrication of articles with a large and/or dense cross section (although this can be offset at least in part by increasing light intensity).
  • the viscosity of the polymerizable liquid can advantageously be reduced by heating the polymerizable liquid, as described above.
  • speed of fabrication can be enhanced by introducing reciprocation to “pump” the polymerizable liquid, as described above, and/or the use of feeding the polymerizable liquid through the carrier, as also described above, and/or heating and/or pressurizing the polymerizable liquid, as also described above.
  • Each light engine may be configured to project an image (e.g., an array of pixels) into the build region such that a plurality of “tiled” images are projected into the build region.
  • the term “light engine” can mean an assembly including a light source, a DLP device such as a digital micromirror or LCD device and an optical device such as an objective lens.
  • the “light engine” may also include electronics such as a controller that is operatively associated with one or more of the other components.
  • FIGS. 17A-17C This is shown schematically in FIGS. 17A-17C .
  • the light engine assemblies 130 A, 130 B produce adjacent or “tiled” images 140 A, 140 B.
  • the images are slightly misaligned; that is, there is a gap between them.
  • the images are aligned; there is no gap and no overlap between them.
  • FIG. 17C there is a slight overlap of the images 140 A and 140 B.
  • the configuration with the overlapped images shown in FIG. 17C is employed with some form of “blending” or “smoothing” of the overlapped regions as generally discussed in, for example, U.S. Pat. Nos. 7,292,207, 8,102,332, 8,427,391, 8,446,431 and U.S. Patent Application Publication Nos. 2013/0269882, 2013/0278840 and 2013/0321475, the disclosures of which are incorporated herein in their entireties.
  • the tiled images can allow for larger build areas without sacrificing light intensity, and therefore can facilitate faster build speeds for larger objects. It will be understood that more than two light engine assemblies (and corresponding tiled images) may be employed. Various embodiments of the invention employ at least 4, 8, 16, 32, 64, 128 or more tiled images.
  • the polymerizable liquid comprises a first light polymerizable component (sometimes referred to as “Part A” herein) and a second component that solidifies by another mechanism, or in a different manner from, the first component (sometimes referred to as “Part B” herein), typically by further reacting, polymerizing, or chain extending. Numerous embodiments thereof may be carried out. In the following, note that, where particular acrylates such as methacrylates are described, other acrylates may also be used.
  • Part A comprises or consists of a mix of monomers and/or prepolymers that can be polymerized by exposure to actinic radiation or light.
  • This resin can have a functionality of 2 or higher (though a resin with a functionality of 1 can also be used when the polymer does not dissolve in its monomer).
  • a purpose of Part A is to “lock” the shape of the object being formed or create a scaffold for the one or more additional components (e.g., Part B).
  • Part A is present at or above the minimum quantity needed to maintain the shape of the object being formed after the initial solidification. In some embodiments, this amount corresponds to less than ten, twenty, or thirty percent by weight of the total resin (polymerizable liquid) composition.
  • Part A can react to form a cross-linked polymer network or a solid homopolymer.
  • Suitable reactive end groups suitable for Part A constituents, monomers, or prepolymers include, but are not limited to: acrylates, methacrylates, ⁇ -olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
  • Part A solidifies by solidification of Part A.
  • Part B a second reactive resin component
  • This secondary reaction preferably occurs without significantly distorting the original shape defined during the solidification of Part A.
  • Alternative approaches would lead to a distortion in the original shape in a desired manner.
  • the solidification of Part A is continuously inhibited during printing within a certain region, by oxygen or amines or other reactive species, to form a liquid interface between the solidified part and an inhibitor-permeable film or window (e.g., is carried out by continuous liquid interphase/interface printing).
  • Part B may comprise, consist of or consist essentially of a mix of monomers and/or prepolymers that possess reactive end groups that participate in a second solidification reaction after the Part A solidification reaction.
  • Part B could be added simultaneously to Part A so it is present during the exposure to actinide radiation, or Part B could be infused into the object made during the 3D printing process in a subsequent step.
  • Examples of methods used to solidify Part B include, but are not limited to, contacting the object or scaffold to heat, water or water vapor, light at a different wavelength than that at which Part A is cured, catalysts, (with or without additional heat), evaporation of a solvent from the polymerizable liquid (e.g., using heat, vacuum, or a combination thereof), microwave irradiation, etc., including combinations thereof.
  • Suitable reactive end group pairs suitable for Part B constituents, monomers or prepolymers include, but are not limited to: epoxy/amine, epoxy/hydroxyl, oxetane/amine, oxetane/alcohol, isocyanate*/hydroxyl, Isocyanate*/amine, isocyanate/carboxylic acid, anhydride/amine, amine/carboxylic acid, amine/ester, hydroxyl/carboxylic acid, hydroxyl/acid chloride, amine/acid chloride, vinyl/Si—H (hydrosilylation), Si—Cl/hydroxyl, Si—Cl/amine, hydroxyl/aldehyde, amine/aldehyde, hydroxymethyl or alkoxymethyl amide/alcohol, aminoplast, alkyne/Azide (also known as one embodiment of “Click Chemistry,” along with additional reactions including thiolene, Michael additions, Diels-Alder reactions, nucleophilic substitution reactions, etc.),
  • oximes diene/dienophiles for Diels-Alder reactions
  • olefin metathesis polymerization olefin polymerization using Ziegler-Natta catalysis
  • ring-opening polymerization including ring-opening olefin metathesis polymerization, lactams, lactones, Siloxanes, epoxides, cyclic ethers, imines, cyclic acetals, etc.
  • Part B components useful for the formation of polymers described in “Concise Polymeric Materials Encyclopedia” and the “Encyclopedia of Polymer Science and Technology” are hereby incorporated by reference.
  • an organic peroxide may be included in the polymerizable liquid or resin, for example to facilitate the reaction of potentially unreacted double bonds during heat and/or microwave irradiation curing.
  • Such organic peroxides may be included in the resin or polymerizable liquid in any suitable amount, such as from 0.001 or 0.01 or 0.1 percent by weight, up to 1, 2, or 3 percent by weight.
  • suitable organic peroxides include, but are not limited to, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane (e.g., LUPEROX 101TM), dilauroyl peroxide (e.g.
  • LUPEROX LPTM benzoyl peroxide (e.g., LUPEROX A98TM), and bis(tert-butyldioxyisopropyl)benzene (e.g., VulCUP RTM), etc., including combinations thereof.
  • organic peroxides are available from a variety of sources, including but not limited to Arkema (420 rue d'Estienne d'Orves, 92705 Colombes Cedex, France).
  • a particularly useful embodiment for implementing the invention is for the formation of elastomers.
  • Tough, high-elongation elastomers are difficult to achieve using only liquid UV-curable precursors.
  • thermally cured materials polyurethanes, silicones, natural rubber
  • These thermally curable elastomers on their own are generally incompatible with most 3D printing techniques.
  • a low-viscosity UV curable material (Part A) are blended with thermally-curable precursors to form (preferably tough) elastomers (e.g. polyurethanes, polyureas, or copolymers thereof (e.g., poly(urethane-urea)), and silicones) (Part B).
  • the UV curable component is used to solidify an object into the desired shape using 3D printing as described herein and a scaffold for the elastomer precursors in the polymerizable liquid.
  • the object can then be heated after printing, thereby activating the second component, resulting in an object comprising the elastomer.
  • a particularly useful example may be in the formation and adhesion of sneaker components.
  • Part B may simply consist of small particles of a pre-formed polymer. After the solidification of Part A, the object may be heated above the glass transition temperature of Part B in order to fuse the entrapped polymeric particles.
  • Part B may consist of a pre-formed polymer dissolved in a solvent. After the solidification of Part A into the desired object, the object is subjected to a process (e.g. heat+vacuum) that allows for evaporation of the solvent for Part B, thereby solidifying Part B.
  • a process e.g. heat+vacuum
  • the reactive chemistries in Part A can be thermally cleaved to generate a new reactive species after the solidification of Part A.
  • the newly formed reactive species can further react with Part B in a secondary solidification.
  • An exemplary system is described by Velankar, Pezos and Cooper, Journal of Applied Polymer Science, 62, 1361-1376 (1996).
  • the acrylate/methacrylate groups in the formed object are thermally cleaved to generated diisocyanate prepolymers that further react with blended chain-extender to give high molecular weight polyurethanes/polyureas within the original cured material or scaffold.
  • Such systems are, in general, dual-hardening systems that employ blocked or reactive blocked prepolymers, as discussed in greater detail below. It may be noted that later work indicates that the thermal cleavage above is actually a displacement reaction of the chain extender (usually a diamine) with the hindered urea, giving the final polyurethanes/polyureas without generating isocyanate intermediates.
  • the chain extender usually a diamine
  • the components may be mixed in a continuous manner prior to being introduced to the printer build plate. This may be done using multi-barrel syringes and mixing nozzles.
  • Part A may comprise or consist of a UV-curable di(meth)acrylate resin
  • Part B may comprise or consist of a diisocyanate prepolymer and a polyol mixture.
  • the polyol can be blended together in one barrel with Part A and remain unreacted.
  • a second syringe barrel would contain the diisocyanate of Part B.
  • the material can be stored without worry of “Part B” solidifying prematurely.
  • a constant time is defined between mixing of all components and solidification of Part A.
  • melt-processed acrylonitrile-butadiene-styrene resin may be formulated with a second UV-curable component that can be activated after the object is formed by FDM. New mechanical properties could be achieved in this manner.
  • melt-processed unvulcanized rubber is mixed with a vulcanizing agent such as sulfur or peroxide, and the shape set through FDM, then followed by a continuation of vulcanization.
  • the solidifying and/or curing step (d) is carried out subsequent to the irradiating step (e.g., by heating or microwave irradiating); the solidifying and/or curing step (d) is carried out under conditions in which the solid polymer scaffold degrades and forms a constituent necessary for the polymerization of the second component (e.g., a constituent such as (i) a prepolymer, (ii) a diisocyanate or polyisocyanate, and/or (iii) a polyol and/or diol, where the second component comprises precursors to a polyurethane/polyurea resin).
  • a constituent such as (i) a prepolymer, (ii) a diisocyanate or polyisocyanate, and/or (iii) a polyol and/or diol, where the second component comprises precursors to a polyurethane/polyurea resin.
  • Such methods may involve the use of reactive or non-reactive blocking groups on or coupled to a constituent of the first component, such that the constituent participates in the first hardening or solidifying event, and when de-protected (yielding free constituent and free blocking groups or blocking agents) generates a free constituent that can participate in the second solidifying and/or curing event.
  • de-protected yielding free constituent and free blocking groups or blocking agents
  • Some “dual cure” embodiments of the present invention are, in general, a method of forming a three-dimensional object, comprising:
  • the polymerizable liquid comprising a mixture of a blocked or reactive blocked prepolymer, optionally but in some embodiments preferably a reactive diluent, a chain extender, and a photoinitiator;
  • heating or microwave irradiating may cause the chain extender to react with the blocked or reactive blocked prepolymer or an unblocked product thereof).
  • the blocked or reactive blocked prepolymer comprises a polyisocyanate.
  • the blocked or reactive blocked prepolymer is 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:
  • R is a hydrocarbyl group
  • R′ is O or NH
  • Z is a blocking group, the blocking group optionally having a reactive terminal group (e.g., a polymerizable end group such as an epoxy, alkene, alkyne, or thiol end group, for example an ethylenically unsaturated end group such as a vinyl ether).
  • a reactive terminal group e.g., a polymerizable end group such as an epoxy, alkene, alkyne, or thiol end group, for example an ethylenically unsaturated end group such as a vinyl ether.
  • each A is an independently selected substituent of Formula (XI):
  • the blocked or reactive blocked prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one diisocyanate (e.g., a diisocyanate such as hexamethylene diisocyanate (HDI), bis-(4-isocyanatocyclohexyl)methane (HMDI), isophorone diisocyanate (IPDI), etc., a triisocyanate, etc.) with at least one polyol (e.g., a polyether or polyester or polybutadiene diol).
  • a diisocyanate such as hexamethylene diisocyanate (HDI), bis-(4-isocyanatocyclohexyl)methane (HMDI), isophorone diisocyanate (IPDI), etc., a triisocyanate, etc.
  • the reactive blocked prepolymer is blocked by reaction of a polyisocyanate with an amine(meth)acrylate monomer blocking agent (e.g., tertiary-butylaminoethyl methacrylate (TBAEMA), tertiary pentylaminoethyl methacrylate (TPAEMA), tertiary hexylaminoethyl methacrylate (THAEMA), tertiary-butylaminopropyl methacrylate (TBAPMA), acrylate analogs thereof, and mixtures thereof (see, e.g., US Patent Application Publication No. 20130202392). Note that all of these can be used as diluents as well.
  • TSAEMA tertiary-butylaminoethyl methacrylate
  • TPAEMA tertiary pentylaminoethyl methacrylate
  • TMAEMA tertiary hexylaminoethyl
  • blocking agents for isocyanate there are many blocking agents for isocyanate.
  • the blocking agent e.g., TBAEMA
  • cures e.g., from the actinic radiation or light
  • those skilled in the art can couple (meth)acrylate groups to known blocking agents to create additional blocking agents that can be used to carry out the present invention.
  • those skilled in the art can use maleimide, or substitute maleimide on other known blocking agents, for use in the present invention.
  • phenol type blocking agents e.g. phenol, cresol, xylenol, nitrophenol, chlorophenol, ethyl phenol, t-butylphenol, hydroxy benzoic acid, hydroxy benzoic acid esters, 2,
  • alcohol type blocking agents e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxyethanol, glycolic acid, glycolic acid esters, lactic acid, lactic acid ester, methylol urea, methylol melamine, diacetone alcohol, ethylene chlorohydrine, ethylene bromhydrine, 1,3-dichloro-2-propano
  • alcohol type blocking agents e.g. methanol, ethanol, n-propanol, isopropanol, n-butanol, isobut
  • acid amide type blocking agents e.g. acetoanilide, acetoanisidine amide, acrylamide, methacrylamide, acetic amide, stearic amide, benzamide, etc.
  • imide type blocking agents e.g. succinimide, phthalimi
  • N-phenyl carbamic acid phenyl ester, 2-oxazolidone, etc. imine type blocking agents (e.g. ethylene imine, etc.), oxime type blocking agents (e.g. formaldoxime, acetaldoximine, acetoxime, methylethyl ketoxime, diacetylomonoxime, benzophenoxime, cyclohexanonoxime, etc.) and sulfurous acid salt type blocking agents (e.g. sodium bisulfite, potassium bisulfite, etc.).
  • imine type blocking agents e.g. ethylene imine, etc.
  • oxime type blocking agents e.g. formaldoxime, acetaldoximine, acetoxime, methylethyl ketoxime, diacetylomonoxime, benzophenoxime, cyclohexanonoxime, etc.
  • sulfurous acid salt type blocking agents e.g. sodium bisulfite, potassium bisulfite, etc.
  • the diisocyanate or isocyanate-functional oligomer or prepolymer is blocked with an aldehyde blocking agent, such as a formyl blocking agent.
  • aldehyde blocking agent such as a formyl blocking agent.
  • examples include but are not limited to 2-formyloxyethyl(meth)acrylate (FEMA) (or other aldehyde-containing acrylate or methacrylate) with a diisocyanate or isocyanate functional oligomer or polymer.
  • FEMA 2-formyloxyethyl(meth)acrylate
  • reaction product of such an aldehyde blocking agent and an isocyanate can in some embodiments possess an advantage over TBAEMA blocked ABPUs by reducing hydrogen bonding due to urea formation, in turn (in some embodiments) resulting in lower viscosity blocked isocyanates.
  • a second advantage is eliminating free amines within the final product (a product of the deblocking of TBAEMA from the ABPU) which might oxidize and cause yellowness or lead to degradation.
  • the reactive diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester (including derivatives thereof), polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
  • polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing e.g., acrylonitrile, styrene, divinyl benzene, vinyl toluene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl(meth)acrylate, amine(meth)acrylates as described above, and mixtures of any two or more of these) (see, e.g., US Patent Application Publication No. 20140072806).
  • the chain extender comprises at least one diol, diamine or dithiol chain extender (e.g., ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, the corresponding diamine and dithiol analogs thereof, lysine ethyl ester, arginine ethyl ester, p-alanine-based diamine, and random or block copolymers made from at least one diis
  • the polymerizable liquid comprises:
  • photoinitiator from 0.1 or 0.2 percent by weight to 1, 2 or 4 percent by weight of the photoinitiator.
  • additional ingredients such as dyes, fillers (e.g., silica), surfactants, etc., may also be included, as discussed in greater detail above.
  • An advantage of some embodiments of the invention is that, because these polymerizable liquids do not rapidly polymerize upon mixing, they may be formulated in advance, and the filling step carried out by feeding or supplying the polymerizable liquid to the build region from a single source (e.g., a single reservoir containing the polymerizable liquid in pre-mixed form), thus obviating the need to modify the apparatus to provide separate reservoirs and mixing capability.
  • a single source e.g., a single reservoir containing the polymerizable liquid in pre-mixed form
  • Three dimensional objects made by the process are, in some embodiments, collapsible or compressible (that is, elastic (e.g., has a Young's modulus at room temperature of from about 0.001, 0.01 or 0.1 gigapascals to about 1, 2 or 4 gigapascals, and/or a tensile strength at maximum load at room temperature of about 0.01, 0.1, or 1 to about 50, 100, or 500 megapascals, and/or a percent elongation at break at room temperature of about 10, 20 50 or 100 percent to 1000, 2000, or 5000 percent, or more).
  • elastic e.g., has a Young's modulus at room temperature of from about 0.001, 0.01 or 0.1 gigapascals to about 1, 2 or 4 gigapascals, and/or a tensile strength at maximum load at room temperature of about 0.01, 0.1, or 1 to about 50, 100, or 500 megapascals, and/or a percent elongation at break at room temperature of about 10, 20
  • FIG. 25A A non-limiting example of a dual cure system employing a thermally cleavable end group is shown in the FIG. 25A and the Scheme below:
  • blocking agent is cleaved and diisocyanate prepolymer is re-formed and quickly reacts with chain extenders or additional soft segment to form thermoplastic or thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), as follows:
  • the dual cure resin is comprised of a UV-curable (meth)acrylate blocked polyurethane (ABPU), a reactive diluent, a photoinitiator, and a chain extender(s).
  • the reactive diluent (10-50 wt %) is an acrylate or methacrylate that helps to reduce the viscosity of ABPU and will be copolymerized with the ABPU under UV irradiation.
  • the photoinitiator (generally about 1 wt %) can be one of those commonly used UV initiators, examples of which include but are not limited to such as acetophenones (diethoxyacetophenone for example), phosphine oxides diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), Irgacure 369, etc.
  • acetophenones diethoxyacetophenone for example
  • phosphine oxides diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), Irgacure 369, etc.
  • the ABPU resin After UV curing to form a intermediate shaped product having blocked polyurethane oligomers as a scaffold, and carrying the chain extender, the ABPU resin is subjected to a thermal cure, during which a high molecular weight polyurethane/polyurea is formed by a spontaneous reaction between the polyurethane/polyurea oligomers and the chain extender(s).
  • the polyurethane/polyurea oligomer can react with proper chain extenders through substitution of TBAEMA, N-vinylformamide (NVF) or the like by proper chain extenders, either by deblocking or displacement.
  • the thermal cure time needed can vary depending on the temperature, size, shape, and density of the product, but is typically between 1 to 6 hours depending on the specific ABPU systems, chain extenders and temperature.
  • a tertiary amine-containing (meth)acrylate e.g., t-butylaminoethyl methacrylate, TBAEMA
  • TBAEMA t-butylaminoethyl methacrylate
  • acrylate or methacrylate containing hydroxyl groups to terminate polyurethane/polyurea oligomers with isocyanate ends is used in UV curing resins in the coating field.
  • the formed urethane bonds between the isocyanate and hydroxyl groups are generally stable even at high temperatures.
  • the urea bond formed between the tertiary amine of TBAEMA and isocyanate of the oligomer becomes labile when heated to suitable temperature (for example, about 100° C.), regenerating the isocyanate groups that will react with the chain extender(s) during thermal-cure to form high molecular weight polyurethane (PU).
  • suitable temperature for example, about 100° C.
  • PU high molecular weight polyurethane
  • suitable temperature for example, about 100° C.
  • other (meth)acrylate containing isocyanate blocking functionality as generally used (such as N-vinylformamide, ⁇ -caprolactam, 1,2,3-triazole, methyl ethyl ketoxime, diethyl malonate, etc.
  • TBAEMA that is commercially available.
  • the used chain extenders can be diols, diamines, triols, triamines or their combinations or others.
  • TBAEMA may be used to terminate the isocyanate end groups of the prepolymer, which is derived from isocyanate tipped polyols.
  • the polyols (preferably with hydroxyl functionality of 2) used can be polyethers [especially polytetramethylene oxide (PTMO), polypropylene glycol (PPG)], polyesters [polycaprolactone (PCL), polycarbonate, etc.], polybutadiene and block copolymers such as PCL and PTMO block copolymer (Capa 7201A of Perstop, Inc.).
  • the molecular weight of these polyols can be 500 to 6000 Da, and 500-2000 Da are preferred.
  • diisocyanate e.g., toluene diisocyanate (TDI), methylene diphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated MDI (HMDI), para-phenyl diisocyanate (PPDI) etc.
  • TDI toluene diisocyanate
  • MDI methylene diphenyl diisocyanate
  • HDI hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • HMDI hydrogenated MDI
  • PPDI para-phenyl diisocyanate
  • Radical inhibitors such as hydroquinone (100-500 ppm) can be used to inhibit polymerization of (meth)acrylate during the reaction.
  • a three-dimensional product of the foregoing methods comprises (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), (ii) a cross-linked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), or (iii) combinations thereof (optionally blended with de-blocked blocking group which is copolymerized with the reactive diluents(s), for example as an interpenetrating polymer network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network).).
  • the three-dimensional product may also include unreacted photoinitiator remaining in the three-dimensional formed object. For example, in some embodiments, from 0.1 or 0.2 percent by weight to 1, 2 or 4 percent by weight of the photoinitiator may remain in the three-dimensional formed object or the photoinitiator may be present in lower amounts or only a trace amount.
  • the three-dimensional product may also include reacted photoinitiator fragments. For example, in some embodiments, the reacted photoinitiator fragments may be remnants of the first cure forming the intermediate product.
  • a three-dimensional product may comprise, consist of or consist essentially of all or any combination of a linear thermoplastic polyurethane, a cross-linked thermoset polyurethane, unreacted photoinitiator and reacted photoinitiator materials.
  • chain extenders with more than two reactive groups may be used to three dimensional objects comprised of a crosslinked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)).
  • Another embodiment provides a method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), the method comprising:
  • a polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked diisocyanate, (ii) a polyol and/or polyamine, (iii) a chain extender, (iv) a photoinitiator, and (v) optionally but in some embodiments preferably a reactive diluent (vi) optionally but in some embodiments preferably a pigment or dye, (vii) optionally but in some embodiments preferably a filler (e.g. silica),
  • a polymerizable liquid comprising a mixture of (i) a blocked or reactive blocked diisocyanate, (ii) a polyol and/or polyamine, (iii) a chain extender, (iv) a photoinitiator, and (v) optionally but in some embodiments preferably a reactive diluent (vi) optionally but in some embodiments preferably a pigment or dye, (vii) optionally but in some embodiments preferably a filler (
  • the blocked or reactive blocked diisocyanate is 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′):
  • each A′ is an independently selected substituent of Formula (XI′):
  • a blocked diisocyanate is prepared as shown in the Scheme below. Such blocked diisocyanates may be used in methods as shown in FIG. 25B .
  • the blocking agent is cleaved and the chain extender reacts to form thermoplastic or thermoset polyurethane, polyurea, or a copolymer thereof (e.g., poly(urethane-urea)), for example as shown below:
  • the chain extender reacts with the blocked diisocyanate, eliminates the blocking agent, in the process forming thermoplastic or thermoset polyurethane, polyurea, or a copolymer thereof (e.g., poly(urethane-urea)).
  • a three-dimensional product of the foregoing methods comprises (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), a(ii) cross-linked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), or (iii) combinations thereof (optionally blended with de-blocked blocking group which is copolymerized with the reactive diluents(s), for example as an interpenetrating polymer network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network).
  • the three-dimensional product may also include unreacted photoinitiator remaining in the three-dimensional formed object. For example, in some embodiments, from 0.1 or 0.2 percent by weight to 1, 2 or 4 percent by weight of the photoinitiator may remain in the three-dimensional formed object or the photoinitiator may be present in lower amounts or only a trace amount.
  • the three-dimensional product may also include reacted photoinitiator fragments. For example, in some embodiments, the reacted photoinitiator fragments may be remnants of the first cure forming the intermediate product.
  • a three-dimensional product may comprise, consist of or consist essentially of all or any combination of a linear thermoplastic polyurethane, a cross-linked thermoset polyurethane, unreacted photoinitiator and reacted photoinitiator materials.
  • chain extenders with more than two reactive groups may be used to three dimensional objects comprised of a crosslinked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)).
  • Another embodiment provides a method of forming a three-dimensional object comprised of polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), the method comprising:
  • a polymerizable liquid comprising a mixture of (i) a polyol and/or polyamine, (ii) a blocked or reactive blocked diisocyanate chain extender, (iii) optionally one or more additional chain extenders, (iv) a photoinitiator, and (v) optionally but in some embodiments preferably a reactive diluent (vi) optionally but in some embodiments preferably a pigment or dye, (vii) optionally but in some embodiments preferably a filler (e.g. silica);
  • a polymerizable liquid comprising a mixture of (i) a polyol and/or polyamine, (ii) a blocked or reactive blocked diisocyanate chain extender, (iii) optionally one or more additional chain extenders, (iv) a photoinitiator, and (v) optionally but in some embodiments preferably a reactive diluent (vi) optionally but in some embodiments preferably a pigment or dye, (vii)
  • the blocked or reactive blocked diisocyanate chain extender is 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′′):
  • R is a hydrocarbyl group
  • R′ is O or NH
  • Z is a blocking group, the blocking group optionally having a reactive terminal group (e.g., a polymerizable end group such as an epoxy, alkene, alkyne, or thiol end group, for example an ethylenically unsaturated end group such as a vinyl ether).
  • a reactive terminal group e.g., a polymerizable end group such as an epoxy, alkene, alkyne, or thiol end group, for example an ethylenically unsaturated end group such as a vinyl ether.
  • each A′′ is an independently selected substituent of Formula (XI′′):
  • FIG. 25C An example of method of the present invention carried out with the materials above is given in the FIG. 25C .
  • the blocked isocyanate-capped chain extender reacts either directly with soft segment and/or chain extender amine or alcohol groups, displacing the blocking agent; or (b) the blocked isocyanate-capped chain extender is cleaved and diisocyanate-capped chain extender is re-formed and reacts with soft segments and additional chain extender if necessary to yield thermoplastic or thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), such as follows:
  • a three-dimensional product of the foregoing methods comprises (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), (ii) a cross-linked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), or (iii) combinations thereof (optionally blended with de-blocked blocking group which is copolymerized with the reactive diluents(s), for example as an interpenetrating polymer network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network).
  • a linear thermoplastic polyurethane, polyurea, or copolymer thereof e.g., poly(urethane-urea)
  • a cross-linked thermoset polyurethane polyurea, or copolymer thereof
  • combinations thereof optionally blended with de-blocked blocking group which is copolymerized with
  • the three-dimensional product may also include unreacted photoinitiator remaining in the three-dimensional formed object. For example, in some embodiments, from 0.1 or 0.2 percent by weight to 1, 2 or 4 percent by weight of the photoinitiator may remain in the three-dimensional formed object or the photoinitiator may be present in lower amounts or only a trace amount.
  • the three-dimensional product may also include reacted photoinitiator fragments. For example, in some embodiments, the reacted photoinitiator fragments may be remnants of the first cure forming the intermediate product.
  • a three-dimensional product may comprise, consist of or consist essentially of all or any combination of a linear thermoplastic polyurethane, a cross-linked thermoset polyurethane, unreacted photoinitiator and reacted photoinitiator materials.
  • chain extenders with more than two reactive groups may be used to form three dimensional objects comprised of a crosslinked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)).
  • IPNs Interpenetrating Polymer Networks
  • polymerizable liquids comprising dual hardening systems such as described above are useful in forming three-dimensional articles that in turn comprise interpenetrating polymer networks. This area has been noted by Sperling at Lehigh University and K. C. Frisch at the University of Detroit, and others.
  • the polymerizable liquid and method steps are selected so that the three-dimensional object comprises the following:
  • amine ammonia permeable window or semipermeable member.
  • tetraethyl orthosilicate (TEOS), epoxy (diglycidyl ether of Bisphenol A), and 4 -amino propyl triethoxysilane are be added to a free radical crosslinker and in the process the free radical crosslinker polymerizes and contain the noted reactants which are then reacted in another step or stage. Reaction requires the presence of water and acid.
  • Photoacid generators could optionally be added to the mixture described above to promote the reaction of the silica based network. Note that if only TEOS is included one will end up with a silica (glass) network.
  • Prior IPN research contained a number of examples for hydrophobic-hydrophilic networks for improved blood compatibility as well as tissue compatibility for biomedical parts.
  • Poly(hydroxyethyl(meth)acrylate) is a typical example of a hydrophilic component.
  • Another option is to added poly(ethylene oxide)polyols or polyamines with a diisocyanate to produce polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), incorporated in the reactive system.
  • Precursors to phenolic resins involve either phenolic resoles (formaldehyde terminal liquid oligomers) or phenolic novolacs (phenol terminal solid oligomers crosslinkable with hexamethyltetraamine).
  • phenolic resoles can be considered.
  • the viscosity thereof may be high but dilution with alcohols (methanol or ethanol) may be employed.
  • Combination of the phenolic resole with the crosslinkable monomer can then provide a product formed from an IPN.
  • Reaction of the phenolic resole to a phenolic resin can occur above 100° in a short time range.
  • One variation of this chemistry would be to carbonize the resultant structure to carbon or graphite.
  • Carbon or graphite foam is typically produced from phenolic foam and used for thermal insulation at high temperatures.
  • Polyimides based on dianhydrides and diamines are amenable to the present process.
  • the polyimide monomers incorporated into the reactive crosslinkable monomer are reacted to yield an IPN structure.
  • Most of the dianhydrides employed for polyimides may be crystalline at room temperature but modest amounts of a volatile solvent can allow a liquid phase. Reaction at modest temperatures (e.g., in the range of about 100° C.) is possible to permit polyimide formation after the network is polymerized.
  • aniline and ammonium persulfate are used to produce a conductive part.
  • a post treatment with acid such as HCl vapor
  • polymerization to polyaniline can then commence.
  • IPNs Numerous of natural product based IPNs are known based on triglyceride oils such as castor oil. These can be incorporated into the polymerizable liquid along with a diisocyanate. Upon completion of the part the triglycerides can then be reacted with the diisocyanate to form a crosslinked polyurethane. Glycerol can of course also be used.
  • the molded crosslinked network are swollen with a monomer and free radical catalyst (peroxide) and optionally crosslinker followed by polymerization.
  • the crosslinked triacylate system should imbide large amounts of styrene, acrylate and/or methacrylate monomers allowing a sequential IPN to be produced.
  • Polyolefin catalysts e.g. metallocenes
  • ethylene or propylene
  • a combination to produce EPR rubber
  • the part can then contain a moderate to substantial amount of the polyolefin.
  • Ethylene, propylene and alpha olefin monomers should easily diffuse into the part to react with the catalyst at this temperature and as polymerization proceeds more olefin will diffuse to the catalyst site.
  • a large number of parts can be post-polymerized at the same time.
  • Three-dimensional products produced by the methods and processes of the present invention may be final, finished or substantially finished products, or may be intermediate products subject to further manufacturing steps such as surface treatment, laser cutting, electric discharge machining, etc., is intended.
  • Intermediate products include products for which further additive manufacturing, in the same or a different apparatus, may be carried out).
  • a fault or cleavage line may be introduced deliberately into an ongoing “build” by disrupting, and then reinstating, the gradient of polymerization zone, to terminate one region of the finished product, or simply because a particular region of the finished product or “build” is less fragile than others.
  • Numerous different products can be made by the methods and apparatus of the present invention, including both large-scale models or prototypes, small custom products, miniature or microminiature products or devices, etc.
  • Examples include, but are not limited to, medical devices and implantable medical devices such as stents, drug delivery depots, functional structures, microneedle arrays, fibers and rods such as waveguides, micromechanical devices, microfluidic devices, etc.
  • the product can have a height of from 0.1 or 1 millimeters up to 10 or 100 millimeters, or more, and/or a maximum width of from 0.1 or 1 millimeters up to 10 or 100 millimeters, or more.
  • the product can have a height of from 10 or 100 nanometers up to 10 or 100 microns, or more, and/or a maximum width of from 10 or 100 nanometers up to 10 or 100 microns, or more.
  • the ratio of height to width of the product is at least 2:1, 10:1, 50:1, or 100:1, or more, or a width to height ratio of 1:1, 10:1, 50:1, or 100:1, or more.
  • the product has at least one, or a plurality of, pores or channels formed therein, as discussed further below.
  • the processes described herein can produce products with a variety of different properties.
  • the products are rigid; in other embodiments the products are flexible or resilient.
  • the products are a solid; in other embodiments, the products are a gel such as a hydrogel.
  • the products have a shape memory (that is, return substantially to a previous shape after being deformed, so long as they are not deformed to the point of structural failure).
  • the products are unitary (that is, formed of a single polymerizable liquid); in some embodiments, the products are composites (that is, formed of two or more different polymerizable liquids). Particular properties will be determined by factors such as the choice of polymerizable liquid(s) employed.
  • the product or article made has at least one overhanging feature (or “overhang”), such as a bridging element between two supporting bodies, or a cantilevered element projecting from one substantially vertical support body.
  • overhang such as a bridging element between two supporting bodies, or a cantilevered element projecting from one substantially vertical support body.
  • the three-dimensional (3D) object may be formed with thousands or millions of shape variations imparted on the three-dimensional object while being formed.
  • the pattern generator generates different patterns of light to activate photoinitiator in the region of the gradient of polymerization to impart different shapes as the object is extracted through the gradient of polymerization.
  • the pattern generator may have high resolution with millions of pixel elements that can be varied to change the shape that is imparted.
  • the pattern generator may be a DLP with more than 1,000 or 2,000 or 3,000 or more rows and/or more than 1,000 or 2,000 or 3,000 or more columns of micromirrors, or pixels in an LCD panel, that can be used to vary the shape.
  • the object may be continuously formed through the gradient of polymerization at a rate of more than 1, 10, 100, 1000, 10000 or more microns per second.
  • this allows complex three-dimensional (3D) objects to be formed.
  • the 3D formed objects have complex non-injection moldable shapes.
  • the shapes may not be capable of being readily formed using injection molding or casting.
  • the shapes may not be capable of being formed by discrete mold elements that are mated to form a cavity in which fill material is injected and cured, such as a conventional two-part mold.
  • the 3D formed objects may include enclosed cavities or partially open cavities, repeating unit cells, or open-cell or closed-cell foam structures that are not amenable to injection molding and may including hundreds, thousands or millions of these structures or interconnected networks of these structures.
  • these shapes may be 3D formed using the methods described in the present application with a wide range of properties, including a wide range of elastomeric properties, tensile strength and elongation at break through the use of dual cure materials and/or interpenetrating polymer networks to form these structures.
  • the 3D objects may be formed without cleavage lines, parting lines, seams, sprue, gate marks or ejector pin marks that may be present with injection molding or other conventional techniques.
  • the 3D formed objects may have continuous surface texture (whether smooth, patterned or rough) that is free from molding or other printing artifacts (such as cleavage lines, parting lines, seams, sprue, gate marks or ejector pin marks) across more than 1 mm, 1 cm, 10 cm or more or across the entire length of the formed object.
  • complex 3D objects may be formed with no discrete layers visible or readily detectable from the printing process in the finished 3D object across more than 1 mm, 1 cm, 10 cm or more or across the entire length of the formed object.
  • the varying shapes imparted during the course of printing by the pattern generator may not be visible or detectable as different layers in the finished 3D object since the printing occurs through the gradient of polymerization zone (from which the 3D object is extracted as it is exposed by varying patterns projected from the pattern generator). While the 3D objects resulting from this process may be referred to as 3D printed objects, the 3D objects may be formed through continuous liquid interphase printing without the discrete layers or cleavage lines associated with some 3D printing processes.
  • the 3D formed object may include one or more repeating structural elements to form the 3D objects, including, for example, structures that are (or substantially correspond to) enclosed cavities, partially-enclosed cavities, repeating unit cells or networks of unit cells, foam cell, Kelvin foam cell or other open-cell or closed-cell foam structures, crisscross structures, overhang structures, cantilevers, microneedles, fibers, paddles, protrusions, pins, dimples, rings, tunnels, tubes, shells, panels, beams (including I-beams, U-beams, W-beams and cylindrical beams), struts, ties, channels (whether open, closed or partially enclosed), waveguides, triangular structures, tetrahedron or other pyramid shape, cube, octahedron, octagon prism, icosidodecahedron, rhombic triacontahedron or other polyhedral shapes or modules (including Kelvin minimal surface tetrakaide
  • a 3D formed object may include combinations of any of these structures or interconnected networks of these structures.
  • all or a portion of the structure of the 3D formed object may correspond (or substantially correspond) to one or more Bravais lattice or unit cell structures, including cubic (including simple, body-centered or face-centered), tetragonal (including simple or body-centered), monoclinic (including simple or end-centered), orthorhombic (including simple, body-centered, face-centered or end-centered), rhombohedral, hexagonal and triclinic structures.
  • the 3D formed object may include shapes or surfaces that correspond (or substantially correspond) to a catenoid, helicoid, gyroid or lidinoid, other triply periodic minimal surface (TPMS), or other geometry from the associate family (or Bonnet family) or Schwarz P (“Primitive”) or Schwarz D (“Diamond”), Schwarz H (“Hexagonal”) or Schwarz CLP (“Crossed layers of parallels”) surfaces, argyle or diamond patterns, lattice or other pattern or structure.
  • TPMS triply periodic minimal surface
  • the pattern generator may be programmed to vary rapidly during printing to impart different shapes into the gradient of polymerization with high resolution.
  • any of the above structural elements may be formed with a wide range of dimensions and properties and may be repeated or combined with other structural elements to form the 3D object.
  • the 3D formed object may include a single three-dimensional structure or may include more than 1, 10, 100, 1000, 10000, 100000, 1000000 or more of these structural elements.
  • the structural elements may be repeated structural elements of similar shapes or combinations of different structural elements and can be any of those described above or other regular or irregular shapes.
  • each of these structural elements may have a dimension across the structure of at least 10 nanometers, 100 nanometers, 10 microns, 100 microns, 1 mm, 1 cm, 10 cm, 50 cm or more or may have a dimension across the structure of less than 50 cm, 10 cm, 1 cm, 1 mm, 100 microns, 10 microns, 100 nanometers or 10 nanometers or less.
  • a height, width or other dimension across the structure may be in the range of from about 10 nanometers to about 50 cm or more or any range subsumed therein.
  • any range subsumed therein means any range that is within the stated range.
  • each of the structural elements may form a volume of the 3D object in the range of from about 10 square nanometers to about 50 square cm or more or any range subsumed therein.
  • each of the structural elements may form a cavity or hollow region or gap between surfaces of the structural element having a dimension across the cavity or hollow region or gap in the range of from about 10 nanometers to about 50 cm or more or any range subsumed therein or may define a volume within the expanse of the 3D formed object in the range of from about 10 square nanometers to about 50 square cm or more or any range subsumed therein.
  • the structural elements may be about the same size or the size may vary throughout the volume of the 3D formed object.
  • the sizes may increase or decrease from one side of the 3D formed object to another side (gradually or step-wise) or elements of different shapes may be intermixed in regular or irregular patterns (for example, a 3D elastomeric foam with varying sizes of open-cell and/or closed-cell cavities intermixed throughout the foam).
  • the 3D formed objects may have irregular shapes with overhangs, bridging elements or asymmetries or may otherwise have an offset center of gravity in the direction being formed.
  • the 3D formed object may be asymmetric.
  • the 3D formed object may not have rotational symmetry around any axis or may have rotational symmetry only around a single axis.
  • the 3D formed object may not have reflectional symmetry around any plane through the 3D formed object or may have reflectional symmetry only around a single plane.
  • the 3D object may have an offset center of gravity.
  • the center of gravity of the 3D formed object may not be at the positional center of the object.
  • the center of gravity may not be located along any central axis of the object.
  • the 3D formed object may be a shoe sole or insert that generally follows the contour of a foot.
  • the shoe sole or insert may tilt to the right or left and have different widths for the heel and toes.
  • the 3D formed object in this example will not have reflectional symmetry from side to side or front to back.
  • it may have reflectional symmetry from bottom to top if it is a uniformly flat shoe sole or insert.
  • the shoe sole or insert may be flat on one side and be contoured to receive the arch of a foot on the other side and, as a result, will not have reflectional symmetry from bottom to top either.
  • 3D formed objects for wearable, prosthetic or anatomical shapes or devices may have similar asymmetries and/or offset center of gravity.
  • a 3D formed object for a dental mold or dental implant may substantially conform to the shape of a tooth and may not have reflectional symmetry about any plane.
  • a 3D formed component for a wearable device may substantially conform to the shape of a body party and have corresponding asymmetries, such as athletic wear such as a right or left contoured shin guard or foam padding or insert for use between a hard shin guard or a helmet or other wearable component and the human body.
  • athletic wear such as a right or left contoured shin guard or foam padding or insert for use between a hard shin guard or a helmet or other wearable component and the human body.
  • the UV curable material in the composition may be adjusted to form a more rigid scaffold to avoid deformation.
  • objects with asymmetric shapes and/or offset center of gravity may be formed in pairs (or in other combinations) with connectors that are later removed, particularly if the 3D formed objects or protruding elements are relatively long.
  • an elastomeric 3D object may be formed along a length, and have an asymmetry, center of gravity offset and/or protruding element transverse to the length that is more than 10%, 20%, 30%, 40%, 50% or more of the length.
  • the 3D formed object may have a length of about 1 cm to 50 cm or more or any range subsumed therein and may have a transverse or lateral asymmetry or protruding element of about 1 cm to 50 cm or more or any range subsumed therein.
  • two or more of these objects may be formed together in a way that provides support for the transverse or protruding elements until the elastomeric material is cured and the objects are separated.
  • two shoe soles may be formed (e.g., when formed in the direction of their length) as a pair (for example, with rotated and inverted shoe soles formed together with small removable connectors between them) such that the soles provide support to one another while being formed.
  • other support structures may be formed and removed after curing of the elastomeric material.
  • 3D formed objects may have any of the above shapes or structures and may comprise or consist of or consist essentially of: (i) a linear thermoplastic polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), (ii) a cross-linked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)), and/or (iii) combinations thereof (optionally blended with de-blocked blocking group which is copolymerized with the reactive diluents(s), for example as an interpenetrating polymer network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network), and/or (iv) photoinitiator, including unreacted photoinitiator and/or reacted photoinitiator fragments.
  • a linear thermoplastic polyurethane, polyurea, or copolymer thereof e.g., poly(urethan
  • a silicone rubber 3D object may be formed.
  • silicone or poly(dimethylsiloxane) (PDMS) may be used as soft segment in the formation of these materials.
  • a (meth)acrylate-functional ABPU could be formed by first reacting an oligomeric PDMS diol or diamine with two equivalents of diisocyanate to form a PDMS urethane prepolymer. This material can be further reacted with TBAEMA or other reactive blocking agents described herein to form a reactive blocked PDMS prepolymer which could be blended with chain extenders and reactive diluents as described in the examples above.
  • the material may comprise, consists of or consist essentially of a UV-curable PDMS oligomer that is blended with a two-part thermally curable PDMS oligomer system.
  • 3D formed objects may have any of the above shapes or structures and may comprise or consist of or consist essentially of:
  • Phenylbis(2 4 6-trimethylbenzoyl)phosphine oxide is dissolved in isobornyl acrylate (IBA) with a THINKYTM mixer.
  • Methacryloxypropyl terminated polydimethylsiloxane (DMS-R31; Gelest Inc.) is added to the solution, followed by addition of Sylgard Part A and Part B (Corning PDMS precursors), and then further mixed with a THINKYTM mixer to produce a homogeneous solution.
  • the solution is loaded into an apparatus as described above and a three-dimensional intermediate is produced by ultraviolet curing as described above. The three-dimensional intermediate is then thermally cured at 100° C. for 12 hours to produce the final silicone rubber product.
  • an epoxy 3D object may be formed.
  • 3D formed objects may have any of the above shapes or structures and may comprise or consist of or consist essentially of:
  • EpoxAcast 690 resin part A and 3.040 g part B is mixed on a THINKYTM mixer.
  • 3.484 g is then mixed with 3.013 g of RKP5-78-1, a 65/22/13 mix of Sartomer CN9782/N-vinylpyrrolidone/diethyleneglycol diacrylate to give a clear blend which is cured under a Dymax ultraviolet lamp to produce an elastic 3D object.
  • RKP11-10-1 containing 3.517 g of the above epoxy and 3.508 g of RKP5-90-3 and 65/33/2/0.25 blend of Sartomer CN2920/N-vinylcaprolactam/N-vinylpyrrolidone/PPO initiator is cured similarly to form a flexible 3D object.
  • the 3D formed object may include sol-gel compositions, hydrophobic or hydrophilic compositions, phenolic resoles, cyanate esters, polyimides, conductive polymers, natural product based IPNs, sequential IPNs and polyolefin as described above.
  • 3D formed objects may have any of the shapes or structures described above and may comprise or consist of or consist essentially of a plurality of different materials in different regions of the 3D formed object with different tensile strength or other varying properties.
  • the differing materials may be selected from any of those describe above.
  • the process of fabricating the product may be paused or interrupted one or more times, to change the polymerizable liquid.
  • 3D formed objects may include multiple materials (which may, for example, be a thermoplastic or thermoset polyurethane, polyurea, or copolymer thereof or silicone rubber or epoxy or combination of the foregoing) with different tensile strengths as described further below.
  • any of the materials described herein may be sequentially changed to form a product having multiple distinct segments with different tensile properties, while still being a unitary product with the different segments covalently coupled to one another.
  • the polyurethane, polyurea, or copolymer thereof e.g., poly(urethane-urea)
  • silicone rubber or epoxy or combination of the foregoing may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the polyurethane, polyurea, or copolymer thereof e.g., poly(urethane-urea)
  • silicone rubber or epoxy or combination of the foregoing may comprise or consist of or consist essentially of an interpenetrating network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network.
  • the polyurethane, polyurea, or copolymer thereof may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of linear thermoplastic or thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)).
  • the linear thermoplastic or cross-linked thermoset polyurethane, polyurea, or copolymer thereof may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of a polymer blend of (i) linear ethylenically unsaturated blocking monomer copolymerized with reactive diluent and (ii) linear thermoplastic or cross-linked thermoset polyurethane, polyurea, or copolymer thereof (e.g., poly(urethane-urea)).
  • the polymer blend may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the linear thermoplastic or cross-linked polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of linear poly(meth)acrylate.
  • the polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of an interpenetrating network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network of ethylenically unsaturated monomer and crosslinked or linear polyurethane.
  • the network of ethylenically unsaturated monomer and crosslinked polyurethane may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the linear thermoplastic or cross-linked thermoset polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of crosslinked poly(meth)acrylate.
  • the polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of an interpenetrating network, a semi-interpenetrating polymer network, or as a sequential interpenetrating polymer network of ethylenically unsaturated monomer and linear thermoplastic or cross-linked thermoset polyurethane.
  • the network of ethylenically unsaturated monomer and linear thermoplastic or crosslinked thermoset polyurethane may comprise a majority of the 3D formed object by weight and may comprise more than 50%, 60%, 70%, 80% or 90% of the 3D formed object by weight.
  • the linear thermoplastic or cross-linked thermoset polyurethane, polyurea, or copolymer thereof may comprise or consist of or consist essentially of linear poly(meth)acrylate.
  • the 3D formed object may include sol-gel compositions, hydrophobic or hydrophilic compositions, phenolic resoles, cyanate esters, polyimides, conductive polymers, natural product based IPNs, sequential IPNs and polyolefin as described above.
  • the 3D formed object may include unreacted photoinitiator remaining in the 3D formed object. For example, in some embodiments, from 0.1 or 0.2 percent by weight to 1, 2 or 4 percent by weight of the photoinitiator may remain in the three-dimensional formed object or the photoinitiator may be present in lower amounts or only a trace amount.
  • the three-dimensional product may also include reacted photoinitiator fragments. For example, in some embodiments, the reacted photoinitiator fragments may be remnants of the first cure forming the intermediate product.
  • reacted photoinitiator fragments may remain in the three-dimensional formed object or the reacted photoinitiator fragments may be present in lower amounts or only a trace amount.
  • the end products will contain residual photoinitiator molecules and photoiniator fragments.
  • a photopolymerization will undergo the transformation outlined below.
  • initiation UV light cleaves the initiator into active radical fragments. These active radical fragments will go on to react with monomer group “M.”
  • M monomer group “M.”
  • the active monomer will react with additional monomers that attach to the growing polymer chain.
  • termination can occur either by recombination or by disproportionation.
  • 3D formed objects generated by the processes outlined herein may contain the following chemical products after the object is created:
  • photoinitiators may include the following:
  • R is any number of other atoms, including H, O, C, N, S.
  • ⁇ represents a free radical. Either of these components may go on to initiate polymerization and will therefore be covalently bound to the polymer network.
  • R is any number of other atoms including H, 0 , C, N, S.
  • ⁇ represents a free radical. Either of these components may go on to initiate polymerization and will therefore be covalently bound to the polymer network.
  • R is any number of other atoms including H, O, C, N, S.
  • ⁇ represents a free radical. Either of these components may go on to initiate polymerization and will therefore be covalently bound to the polymer network.
  • photoinitiators may be used in combination with amines.
  • the photoinitiators in the excited state serve to abstract a hydrogen atom from the amine, thus generating an active radical.
  • This radical can go on to initiator polymerization and will therefore become incorporated into the formed polymer network. This process is outlined below:
  • photoinitiators that may be used to generate such materials and therefore will generate fragments which are covalently attached to the formed polymer network include: triazines, ketones, peroxides, diketones, azides, azo derivatives, disulfide derivatives, disilane derivatives, thiol derivatives, diselenide derivatives, diphenylditelluride derivatives, digermane derivatives, distannane derivatives, carob-germanium compounds, carbon-silicon derivatives, sulfur-carbon derivatives, sulfur-silicon derivatives, peresters, Barton's ester derivatives, hydroxamic and thiohydroxamic acids and esters, organoborates, organometallic compounds, titanocenes, chromium complexes, alumate complexes, carbon-sulfur or sulfur-sulfur iniferter compounds, oxyamines, aldehydes, acetals, silanes, phosphorous-containing compounds, borane
  • Detection of the unique chemical fingerprint of photoinitiator fragments in a cured polymer object can be accomplished by a number of spectroscopic techniques. Particular techniques useful alone or in combination include: UV-Vis spectroscopy, fluorescence spectroscopy, infrared spectroscopy, nuclear magnetic resonance spectroscopy, mass spectrometry, atomic absorption spectroscopy, raman spectroscopy, and X-Ray photoelectron spectroscopy.
  • the structural properties of the 3D formed object may be selected together with the properties of the materials from which the 3D object is formed to provide a wide range of properties for the 3D object.
  • Dual cure materials and methods described above in the present application may be used to form complex shapes with desired materials properties to form a wide range of 3D objects.
  • 3D formed objects may be rigid and have, for example, a Young's modulus (MPa) in the range of about 800 to 3500 or any range subsumed therein, a Tensile Strength (MPa) in the range of about 30 to 100 or any range subsumed therein, and/or a percent elongation at break in the range of about 1 to 100 or any range subsumed therein.
  • MPa Young's modulus
  • MPa Tensile Strength
  • Non-limiting examples of such rigid 3D formed objects may include fasteners; electronic device housings; gears, propellers, and impellers; wheels, mechanical device housings; tools and other rigid 3D objects.
  • 3D formed objects may be semi-rigid and have, for example, a Young's modulus (MPa) in the range of about 300-2500 or any range subsumed therein, a Tensile Strength (MPa) in the range of about 20-70 or any range subsumed therein, and/or a percent elongation at break in the range of about 40 to 300 or 600 or any range subsumed therein.
  • rigid 3D formed objects may include structural elements; hinges including living hinges; boat and watercraft hulls and decks; wheels; bottles, jars and other containers; pipes, liquid tubes and connectors and other semi-rigid 3D objects.
  • 3D formed objects may be elastomeric and have, for example, a Young's modulus (MPa) in the range of about 0.5-40 or any range subsumed therein, a Tensile Strength (MPa) in the range of about 0.5-30 or any range subsumed therein, and/or a percent elongation at break in the range of about 50-1000 or any range subsumed therein.
  • MPa Young's modulus
  • MPa Tensile Strength
  • Non-limiting examples of such rigid 3D formed objects may include foot-wear soles, heels, innersoles and midsoles; bushings and gaskets; cushions; electronic device housings and other elastomeric 3D objects.
  • examples 18-61 are given materials for the formation of polyurethane products having a variety of different tensile properties, ranging from elastomeric, to semi-rigid, to flexible, as described above.
  • the process of fabricating the product may be paused or interrupted one or more times, to change the polymerizable liquid.
  • 3D formed objects may include multiple materials (which may, for example, be a thermoplastic or thermoset polyurethane, polyurea, or copolymer thereof) with different tensile strengths. While a fault line or plane may be formed in the intermediate by the interruption, if the subsequent polymerizable liquid is, in its second cure material, reactive with that of the first, then the two distinct segments of the intermediate will cross-react and covalently couple to one another during the second cure (e.g., by heating or microwave irradiation).
  • any of the materials described herein may be sequentially changed to form a product having multiple distinct segments with different tensile properties, while still being a unitary product with the different segments covalently coupled to one another.
  • a 3D object may be formed with a plurality of regions with different materials and properties.
  • a 3D formed object could have one or more regions formed from a first material or first group of one or more materials having a Tensile Strength (MPa) in the range of about 30-100 or any range subsumed therein, and/or one or more regions formed from a second material or second group of one or more materials having a Tensile Strength (MPa) in the range of about 20-70 or any range subsumed therein and/or one or more regions formed from a third material or third group of one or more materials having a Tensile Strength (MPa) in the range of about 0.5-30 or any range subsumed therein or any combination of the foregoing.
  • MPa Tensile Strength
  • the 3D object could have from 1-10 or more different regions (or any range subsumed therein) with varying tensile strength selected from any of the materials and tensile strengths described above.
  • a hinge can be formed, with the hinge comprising a rigid segment, coupled to a second elastic segment, coupled to a third rigid segment, by sequentially changing polymerizable liquids (e.g., from among those described in examples 19-60 above) during the formation of the three-dimensional intermediate.
  • a shock absorber or vibration dampener can be formed in like manner, with the second segment being either elastic or semi-rigid.
  • a unitary rigid funnel and flexible hose assembly can be formed in like manner.
  • FIG. 6 is a top view and FIG. 7 is an exploded view of a 3 inch by 16 inch “high aspect” rectangular build plate (or “window”) assembly of the present invention, where the film dimensions are 3.5 inches by 17 inches.
  • the greater size of the film itself as compared to the internal diameter of vat ring and film base provides a peripheral or circumferential flange portion in the film that is clamped between the vat ring and the film base, as shown in side-sectional view in FIG. 8 .
  • One or more registration holes may be provided in the polymer film in the peripheral or circumferential flange portion to aid in aligning the polymer film between the vat ring and film base, which are fastened to one another with a plurality of screws (not shown) extending from one to the other (some or all passing through holes in the peripheral edge of the polymer film) in a manner that securely clamps the polymer film therebetween.
  • a tension ring is provided that abuts the polymer film and stretches the film to tension, stabilize or rigidify the film.
  • the tension ring may be provided as a pre-set member, or may be an adjustable member. Adjustment may be achieved by providing a spring plate facing the tension ring, with one or more compressible elements such as polymer cushions or springs (e.g., flat springs, coil springs, wave springs etc.) therebetween, and with adjustable fasteners such as screw fasteners or the like passing from the spring plate through (or around) the tension ring to the film base.
  • Polymer films are preferably fluoropolymer films, such as an amorphous thermoplastic fluoropolymer, in a thickness of 0.01 or 0.05 millimeters to 0.1 or 1 millimeters, or more.
  • fluoropolymer films such as an amorphous thermoplastic fluoropolymer, in a thickness of 0.01 or 0.05 millimeters to 0.1 or 1 millimeters, or more.
  • Biogeneral Teflon AF 2400 polymer film which is 0.0035 inches (0.09 millimeters) thick
  • Random Technologies Teflon AF 2400 polymer film which is 0.004 inches (0.1 millimeters) thick.
  • Tension on the film is preferably adjusted with the tension ring to about 10 to 100 pounds, depending on operating conditions such as fabrication speed.
  • the vat ring, film base, tension ring, and tension ring spring plate may be fabricated of any suitable, preferably rigid, material, including metals (e.g., stainless steel, aluminum and aluminum alloys), carbon fiber, polymers, and composites thereof.
  • metals e.g., stainless steel, aluminum and aluminum alloys
  • carbon fiber e.g., carbon fiber, polymers, and composites thereof.
  • Registration posts and corresponding sockets may be provided in any of the vat ring, film base, tension ring and/or spring plate, as desired.
  • FIG. 9 is a top view and FIG. 10 is an exploded view of a 2.88 inch diameter round build plate of the invention, where the film dimension may be 4 inches in diameter. Construction is in like manner to that given in Example 1 above, with a circumferential wave spring assembly shown in place. Tension on the film preferably adjusted to a like tension as given in Example 1 above (again depending on other operating conditions such as fabrication speed).
  • FIG. 10 is an exploded view of the build plate of FIG. 8 .
  • FIG. 11 shows various alternate embodiments of the build plates of FIGS. 7-10 . Materials and tensions may be in like manner as described above.
  • FIG. 12 is a front perspective view
  • FIG. 13 is a side view
  • FIG. 14 is a rear perspective view of an apparatus 100 according to an exemplary embodiment of the invention.
  • the apparatus 100 includes a frame 102 and an enclosure 104 . Much of the enclosure 104 is removed or shown transparent in FIGS. 12-14 .
  • the apparatus 100 includes several of the same or similar components and features as the apparatus described above in reference to FIG. 2 .
  • a build chamber 106 is provided on a base plate 108 that is connected to the frame 102 .
  • the build chamber 106 is defined by a wall or vat ring 110 and a build plate or “window” such as one of the windows described above in reference to FIGS. 2 and 6-11 .
  • a carrier 112 is driven in a vertical direction along a rail 114 by a motor 116 .
  • the motor may be any suitable type of motor, such as a servo motor.
  • An exemplary suitable motor is the NXM45A motor available from Oriental Motor of Tokyo, Japan.
  • a liquid reservoir 118 is in fluid communication with the build chamber 106 to replenish the build chamber 106 with liquid resin.
  • tubing may run from the liquid reservoir 118 to the build chamber 106 .
  • a valve 120 controls the flow of liquid resin from the liquid reservoir 118 to the build chamber 106 .
  • An exemplary suitable valve is a pinch-style aluminum solenoid valve for tubing available from McMaster-Carr of Atlanta, Ga.
  • the frame 102 includes rails 122 or other some other mounting feature on which a light engine assembly 130 ( FIG. 15 ) is held or mounted.
  • a light source 124 is coupled to the light engine assembly 130 using a light guide entrance cable 126 .
  • the light source 124 may be any suitable light source such as a BlueWave® 200 system available from Dymax Corporation of Torrington, Conn.
  • the light engine or light engine assembly 130 includes condenser lens assembly 132 and a digital light processing (DLP) system including a digital micromirror device (DMD) 134 and an optical or projection lens assembly 136 (which may include an objective lens).
  • DLP digital light processing
  • DMD digital micromirror device
  • a suitable DLP system is the DLP DiscoveryTM 4100 system available from Texas Instruments, Inc. of Dallas, Tex. Light from the DLP system is reflected off a mirror 138 and illuminates the build chamber 106 . Specifically, an “image” 140 is projected at the build surface or window.
  • an electronic component plate or breadboard 150 is connected to the frame 102 .
  • a plurality of electrical or electronic components are mounted on the breadboard 150 .
  • a controller or processor 152 is operatively associated with various components such as the motor 116 , the valve 120 , the light source 124 and the light engine assembly 130 described above.
  • a suitable controller is the Propeller Proto Board available from Parallax, Inc. of Rocklin, Calif.
  • controller 152 Other electrical or electronic components operatively associated with the controller 152 include a power supply 154 and a motor driver 158 for controlling the motor 116 .
  • a motor driver 158 for controlling the motor 116 .
  • an LED light source controlled by pulse width modulation (PWM) driver 156 is used instead of a mercury lamp (e.g., the Dymax light source described above).
  • PWM pulse width modulation
  • a suitable power supply is a 24 Volt, 2.5 A, 60 W, switching power supply (e.g., part number PS1-60W-24 (HF60W-SL-24) available from Marlin P. Jones & Assoc, Inc. of Lake Park, Fla.). If an LED light source is used, a suitable LED driver is a 24 Volt, 1.4 A LED driver (e.g., part number 788-1041-ND available from Digi-Key of Thief River Falls, Minn.).
  • a suitable motor driver is the NXD20-A motor driver available from Oriental Motor of Tokyo, Japan.
  • the apparatus of FIGS. 12-15 has been used to produce an “image size” of about 75 mm by 100 mm with light intensity of about 5 mW/cm 2 .
  • the apparatus of FIGS. 12-15 has been used to build objects at speeds of about 100 to 500 mm/hr. The build speed is dependent on light intensity and the geometry of the object.
  • FIG. 16 is a front perspective view of an apparatus 200 according to another exemplary embodiment of the invention.
  • the apparatus 200 includes the same components and features of the apparatus 100 with the following differences.
  • the apparatus 200 includes a frame 202 including rails 222 or other mounting feature at which two of the light engine assemblies 130 shown in FIG. 15 may be mounted in a side-by-side relationship.
  • the light engine assemblies 130 are configured to provide a pair of “tiled” images at the build station 206 .
  • the use of multiple light engines to provide tiled images is described in more detail above.
  • the apparatus of FIG. 16 has been used to provide a tiled “image size” of about 150 mm by 200 mm with light intensity of about 1 mW/cm 2 .
  • the apparatus of FIG. 16 has been used to build objects at speeds of about 50 to 100 mm/hr. The build speed is dependent on light intensity and the geometry of the object.
  • FIG. 18 is a front perspective view and FIG. 19 is a side view of an apparatus 300 according to another exemplary embodiment of the invention.
  • the apparatus 300 includes the same components and features of the apparatus 100 with the following differences.
  • the apparatus 300 includes a frame 302 including rails 322 or other mounting feature at which a light engine assembly 330 shown in FIG. 20 may be mounted in a different orientation than the light assembly 130 of the apparatus 100 .
  • the light engine assembly 330 includes a condenser lens assembly 332 and a digital light processing (DLP) system including a digital micromirror device (DMD) 334 and an optical or projection lens assembly 336 (which may include an objective lens).
  • DLP digital light processing
  • DMD digital micromirror device
  • a suitable DLP system is the DLP DiscoveryTM 4100 system available from Texas Instruments, Inc. of Dallas, Tex.
  • Light from the DLP system illuminates the build chamber 306 .
  • an “image” 340 is projected at the build surface or window.
  • a reflective mirror is not used with the apparatus 300 .
  • the apparatus of FIGS. 18-20 has been used to provide “image sizes” of about 10.5 mm by 14 mm and about 24 mm by 32 mm with light intensity of about 200 mW/cm 2 and 40 mW/cm 2
  • the apparatus of FIGS. 18-20 has been used to build objects at speeds of about 10,000 and 4,000 mm/hr. The build speed is dependent on light intensity and the geometry of the object.
  • This Example illustrates the control of a method and apparatus of the invention with an example program written utilizing Lua scripting.
  • Program code corresponding to such instructions, or variations thereof that will be apparent to those skilled in the art, is written in accordance with known techniques based upon the particular microcontroller used.
  • a part consists of slices of polymer which are formed continuously.
  • the shape of each slice is defined by the frame that is being displayed by the light engine.
  • the frame represents the final output for a slice.
  • the frame is what manifests as the physical geometry of the part.
  • the data in the frame is what is projected by the printer to cure the polymer.
  • Slices can consist of procedural geometry, Slices of a 3D model or any combination of the two.
  • the slice generating process allows the user to have direct control over the composition of any frame.
  • a slice is a special type of 2D geometry derived from a 3D model of a part. It represents the geometry that intersects a plane that is parallel to the window. Parts are usually constructed by taking 3D models and slicing them at very small intervals. Each slice is then interpreted in succession by the printer and used to cure the polymer at the proper height.
  • Procedurally generated geometry can also be added to a slice. This is accomplished by invoking shape generation functions, such as “addcircle”, “addrectangle”, and others. Each function allows projection of the corresponding shape onto the printing window. A produced part appears as a vertically extruded shape or combination of shapes.
  • the coordinate system that the stage uses is usually calibrated such that the origin is 1-20 microns above the window.
  • Coordinate system of the projected slice is such that origin is located at the center of the print window.
  • Printing a sliced model consists of 4 main parts: Loading the data, preparing the printer, printing, and shutdown.
  • Model modelFilePath “Chess King.svg”
  • numSlices loadslices(modelFilePath) Preparing the printer it is important to do two things before printing. You must first turn on the light engine with the relay function, and if applicable, the desired fluid height should be set.
  • the first step of the printing process is to calibrate the system and set the stage to its starting position by calling gotostart.
  • Next we begin a for loop in which we print each slice.
  • the first line of the for loop uses the infoline command to display the current slice index in the sidebar.
  • Next we determine the height at which the next slice should be cured. That value is stored to nextHeight. Following this we move the stage to the height at which the next slice needs to be cured. To ensure a clean print it can sometimes be necessary to wait for oxygen to diffuse into the resin. Therefore we call sleep for a half second (the exact time for preExposureTime is defined in the constants section as well).
  • the final step in the printing process is to shut down the printer. Call relay(false) to turn the light engine off. If you are using fluid control, call setlevels(0,0) to ensure the valve is shut off. Finally it is a good idea to move the stage up a bit after printing to allow for easy removal of the part.
  • gotostart The main purpose of gotostart is to calibrate the stage. This function resets the coordinate system to have the origin at the lowest point, where the limit switch is activated. Calling this command will move the stage down until the limit switch in the printer is activated; this should occur when the stage is at the absolute minimum height.
  • gotostart( ) moves stage to start at the maximum speed which varies from printer to printer. gotostart( )—moving to origin at default speed gotostart(number speed) moves stage to start at speed given in millimeters/hour. gotostart(15000)—moving stage to origin at 15000 mm/hr
  • moveto (number targetHeight, number speed) moveto(25, 15000)—moving to 25 mm at 15,000 mm/hr moveto(number targetHeight, number speed, number acceleration)
  • This version of the function allows an acceleration to be defined as well as speed. The stage starts moving at initial speed and then increases by acceleration.
  • moveby allows the user to change the height of the stage by a desired amount at a given speed. Safe upper and lower limits to speed and acceleration are ensured internally. moveby(number dHeight, number initalSpeed)
  • addcircle(number x, number y, number radius, number sliceIndex) addcircle draws a circle in the specified slice.
  • text(number x, number y, number scale, string text, number sliceIndex) addtext draws text on the specified slice starting at position ‘x, y’ with letters of size ‘scale’.
  • set of functions can be used with printer models that support fluid control. Before the script finishes executing, setlevels(0,0) should be called to ensure that the pump stops pumping fluid into the vat.
  • the math standard library contains several different functions that are useful in calculating geometry.
  • the string object is most useful in printing for manipulating info strings. For details contact LabLua at Departamento de Informatica, PUC-Rio, Rua Marquês de S ⁇ o Vicente, 225; 22451-900 Rio de Janeiro, RJ, Brazil
  • This example shows a Lua script program corresponding to Example 7 above for continuous three dimension printing.
  • This example shows a Lua script program for two fitted parts that use procedural geometry.
  • FIG. 21 A process of the present invention is illustrated in FIG. 21 , where the vertical axis illustrates the movement of the carrier away from the build surface.
  • the vertical movement or advancing step (which can be achieved by driving either the carrier or the build surface, preferably the carrier), is continuous and unidirectional, and the irradiating step is carried out continuously.
  • Polymerization of the article being fabricated occurs from a gradient of polymerization, and hence creation of “layer by layer” fault lines within the article is minimized.
  • FIG. 22 An alternate embodiment of the present invention is illustrated in FIG. 22 .
  • the advancing step is carried out in a step-by-step manner, with pauses introduced between active advancing of the carrier and build surface away from one another.
  • the irradiating step is carried out intermittently, in this case during the pauses in the advancing step.
  • Sufficient inhibitor can be supplied by any of a variety of techniques, including but not limited to: utilizing a transparent member that is sufficiently permeable to the inhibitor, enriching the inhibitor (e.g., feeding the inhibitor from an inhibitor-enriched and/or pressurized atmosphere), etc.
  • enriching the inhibitor e.g., feeding the inhibitor from an inhibitor-enriched and/or pressurized atmosphere
  • the more rapid the fabrication of the three-dimensional object that is, the more rapid the cumulative rate of advancing
  • the more inhibitor will be required to maintain the dead zone and the adjacent gradient of polymerization.
  • FIG. 23 A still further embodiment of the present invention is illustrated in FIG. 23 .
  • the advancing step is carried out in a step-by-step manner, with pauses introduced between active advancing of the carrier and build surface away from one another.
  • the irradiating step is carried out intermittently, again during the pauses in the advancing step.
  • the ability to maintain the dead zone and gradient of polymerization during the pauses in advancing and irradiating is taken advantage of by introducing a vertical reciprocation during the pauses in irradiation.
  • Reciprocation in the vertical or Z axis can be carried out at any suitable speed in both directions (and the speed need not be the same in both directions), although it is preferred that the speed when reciprocating away is insufficient to cause the formation of gas bubbles in the build region.
  • Example 10 As in Example 10 above, as long as the inhibitor of polymerization is supplied to the dead zone in an amount sufficient to maintain the dead zone and the adjacent gradient of polymerization during the reciprocation, the gradient of polymerization is maintained, the formation of layers within the article of manufacture is minimized or avoided, and the polymerization/fabrication remains continuous, even though the irradiating and advancing steps are not.
  • the resin was 3D formed using an apparatus as described herein.
  • a “honeycomb” object was formed at a speed of 160 mm/hr using a light intensity setting of 1.2 mV (when measured using a volt meter equipped with a optical sensor). Total printing time was approximately 10 minutes.
  • the part was removed from the print stage, rinsed with hexanes, and placed into an oven set at 110° C. for 12 hours.
  • the part After heating, the part maintained its original shape generated during the initial printing, and it had transformed into a tough, durable, elastomer having an elongation at break around 200%
  • the resin was 3D formed using an apparatus as described herein.
  • the cylindrical object was formed at a speed of 50 mm/hr using a light intensity setting of 1.2 mV (when measured using a volt meter equipped with an optical sensor). Total printing time was approximately 15 minutes.
  • the part was removed from the print stage, rinsed with hexanes, and placed into an oven set at 110° C. for 12 hours.
  • the part After heating, the part maintained its original shape generated during the initial printing, and it had transformed into a tough, durable, elastomer having an elongation at break around 400%
  • the PTMO can be replaced by polypropylene glycol (PPG, such as 1000 Da PPG (PPG1k)) or other polyesters or polybuadiene diols.
  • PPG polypropylene glycol
  • IPDI or HDI can be replaced by other diisocyanates.
  • the molar stoichiometry of the polyol:diisocyanate:TBAEMA is preferably 1:2:2.
  • ABPU resins can be formed (optionally but preferably by continuous liquid interphase/interface printing) at up to 100 mm/hr using the formulations in Table 1 to generate elastomers with low hysteresis after thermally cured at 100° C. for 2 to 6 hours, depending on the diisocyanates used in ABPU and the chain extender(s).
  • Dog-bone-shaped specimens were formed by continuous liquid interface printing with different ABPUs (varying the diisocyanate and polyol used for the synthesis) and reactive diluents.
  • Table 2 shows the mechanical properties of some of the thermally cured dog-bone samples at room temperature.
  • DEGMA means di(ethylene glycol)methyl ether methacrylate
  • IBMA means isoboronyl methacrylate
  • POM means 4,4′-Diaminodicyclohexyl methane
  • BDO means 1,4-butanediol
  • PPO means Phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide
  • MDEA means 4,4′-methylene-bis-(2,6-diethylaniline
  • 2-EHMA means 2-ethylhexyl methacrylate
  • tensile specimens (sometimes referred to as “dog-bone samples” in reference to their shape), were loaded onto an Instron 5964 testing apparatus with Instron BLUEHILL3 measurement software (Instron, 825 University Ave, Norwood, Mass., 02062-2643, USA). The samples are oriented vertically and parallel to the direction of testing. Cast and flood cured samples were fully cured using a DNMAX 5000 EC-Series enclosed UV flood lamp (225 mW/cm 2 ) for from thirty to ninety seconds of exposure. Table 3 below summarizes the types of tensile specimens tested, general material property (rigid or non-rigid), and the associated strain rate.
  • the samples were tested at a rate such that the sample ruptures at a time between 30 seconds to 5 minutes to ensure that sample strain rate is slow enough to capture plastic deformation in the samples.
  • Persuant to ASTM D-638 measure the Young's modulus (modulus of elasticity) (slope of the stress-strain plot between 5-10% elongation), tensile strength at break, tensile strength at yield, percent elongation at break, percent elongation at yield.
  • a strain rate is chosen such that the part with the lowest strain-at-break (%) will fail within 5 minutes. This often means that a slower strain rate will be necessary for rigid samples.
  • Cured elastomer specimens were prepared in the same manner as in Example 19 but using the formulation in Table 5. The cured specimens were tested following ASTM standard on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 5.
  • Cured elastomer specimens were prepared in the same manner as in Example 19 but using the formulation in Table 6. The cured specimens were tested following ASTM standard on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 6.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 12.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 12.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 13.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 13.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 14 by mixing all the components together.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 14.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 16.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 16.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 17.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 17.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 18.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 18.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 19.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 19.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 20.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 20.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 21.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 21.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 22.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 22.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 23.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 23.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 24.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 24.
  • Cured elastomer specimens were prepared in the same manner as in Example 22 but using the formulation in Table 25.
  • the elastomer specimens were tested following ASTM standard D638-10 on an Instron apparatus for mechanical properties as described above, which properties are summarized in Table 25.
  • Cured elastomer specimens are prepared in the same manner as in Example 20 but using the formulation in Table 31 below.
  • the cure specimens give elastomeric properties similar to those disclosed above.
  • Polymerizable materials as described in the examples, or detailed description, above (or variations thereof that will be apparent to those skilled in the art) provide products with a range of different elastic properties. Examples of those ranges of properties, from rigid, through semi-rigid (rigid and flexible), to elastomeric. Particular types of products that can be made from such materials include but are not limited to those given in Table 32 below.
  • the products may contain reacted photoinitiator fragments (remnants of the first cure forming the intermediate product) when produced by some embodiments of methods as described above. It will be appreciated that the properties may be further adjusted by inclusion of additional materials such as fillers and/or dyes, as discussed above.
  • “Fastener” includes, but is not limited to, nuts, bolts, screws, expansion fasteners, clips, buckles, etc
  • “Electronic device housing” includes, but is not limited to, partial and complete cell phone housings, tablet computer housings, personal computer housings, electronic recorder and storage media housings, video monitor housings, keyboard housings, etc.
  • “Mechanical device housing” includes, but is not limited to, partial and complete gear housings, pump housings, motor housings, etc.
  • “Structural elements” as used herein includes, but is not limited to, shells, panels, rods, beams (e.g., I-beams, U-beams, W-beams, cylindrical beams, channels, etc), struts, ties, etc., for applications including architectural and building, civil engineering, automotive and other transportation (e.g., automotive body panel, hood, chassis, frame, roof, bumper, etc.), etc.
  • “Tools” includes, but is not limited to, impact tools such as hammers, drive tools such as screwdrivers, grasping tools such as pliers, etc., including component parts thereof (e.g., drive heads, jaws, and impact heads).
  • examples 18-61 are given materials for the formation of polyurethane products having a variety of different tensile properties, ranging from elastomeric, to semi-rigid, to flexible, as described in Example 62 above.
  • the process of fabricating the product may be paused or interrupted one or more times, to change the polymerizable liquid. While a fault line or plane may be formed in the intermediate by the interruption, if the subsequent polymerizable liquid is, in its second cure material, reactive with that of the first, then the two distinct structural segments of the intermediate will cross-react and covalently couple to one another during the second cure (e.g., by heating or microwave irradiation).
  • any of the materials described in examples 19-60 above may be sequentially changed to form a product having multiple distinct structural segments with different tensile properties, while still being a unitary product with the different segments covalently coupled to one another.
  • a hinge can be formed, with the hinge comprising a rigid segment, coupled to a second elastic segment, coupled to a third rigid segment, by sequentially changing polymerizable liquids (e.g., from among those described in examples 19-60 above) during the formation of the three-dimensional intermediate.
  • a shock absorber or vibration dampener can be formed in like manner, with the second segment being either elastic or semi-rigid.
  • a unitary rigid funnel and flexible hose assembly can be formed in like manner.
  • Sequential changing of the polymerizable liquid can be carried out with a multi-port, feed-through carrier, system, such as described in PCT Application Publication No. WO 2015/126834, or, where the polymerizable liquid is supplied in a reservoir positioned above the build surface, providing the reservoir and build surface as interchangeable cartridges that can be changed out or swapped during a pause in fabrication.
  • Phenylbis(2-(6-trimethylbenzoyl)phosphine oxide (PPO) is dissolved in isobornyl acrylate (IBA) with a THINKYTM mixer.
  • Methacryloxypropyl terminated polydimethylsiloxane (DMS-R31; Gelest Inc.) is added to the solution, followed by addition of Sylgard Part A and Part B (Corning PDMS precursors), and then further mixed with a THINKYTM mixer to produce a homogeneous solution.
  • the solution is loaded into an apparatus as described above and a three-dimensional intermediate is produced by ultraviolet curing as described above. The three-dimensional intermediate is then thermally cured at 100° C. for 12 hours to produce the final silicone rubber product. Parts by weight and tensile properties are given in Table 33 below.
  • EpoxAcast 690 resin part A and 3.040 g part B were mixed on a THINKYTM mixer. 3.484 g was then mixed with 3.013 g of RKP5-78-1, a 65/22/13 mix of Sartomer CN9782/N-vinylpyrrolidone/diethyleneglycol diacrylate to give a clear blend which was cured in a “dog bone” shaped sample mold (for tensile strength testing) for 2 minutes under a Dymax ultraviolet lamp to give a very elastic but weak dog bone sample.
  • RKP11-10-1 contained 3.517 g of the above epoxy and 3.508 g of RKP5-90-3 and 65/33/2/0.25 blend of Sartomer CN2920/N-vinylcaprolactam/N-vinylpyrrolidone/PPO initiator cured similarly to give a very flexible dog bone.
  • RKP1-17-2D a 66/33/1 mix of CN2920/NVC/DPO initiator was blended with EpoxAcure 690 in a 1:1 ratio and 2:1 ratio
  • the 1:1 epoxy/acrylate dual cure formulation previously prepared failed to print in a CLIP apparatus as described above, at 100 or 60 mm/hr, but a 1:2 ratio gave a decent argyle pattern at 60 mm/hr.
  • the Smooth-On EpoxAcure 690/CN2920/NVC argyle was post-cured at room temperature to a clear, flexible, if tacky, sample. Dog bones were also prepared.

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US15/428,708 Active 2035-08-31 US10240066B2 (en) 2014-06-23 2017-02-09 Methods of producing polyurea three-dimensional objects from materials having multiple mechanisms of hardening
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US16/803,350 Active US11299579B2 (en) 2014-06-23 2020-02-27 Water cure methods for producing three-dimensional objects from materials having multiple mechanisms of hardening
US17/068,962 Active US11312084B2 (en) 2014-06-23 2020-10-13 Methods for producing helmet inserts with materials having multiple mechanisms of hardening
US17/655,275 Active US11850803B2 (en) 2014-06-23 2022-03-17 Methods for producing three-dimensional objects with apparatus having feed channels
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US15/428,708 Active 2035-08-31 US10240066B2 (en) 2014-06-23 2017-02-09 Methods of producing polyurea three-dimensional objects from materials having multiple mechanisms of hardening
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US16/556,404 Active 2035-10-03 US11358342B2 (en) 2014-06-23 2019-08-30 Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening
US16/803,047 Active US10899868B2 (en) 2014-06-23 2020-02-27 Methods for producing footwear with materials having multiple mechanisms of hardening
US16/803,350 Active US11299579B2 (en) 2014-06-23 2020-02-27 Water cure methods for producing three-dimensional objects from materials having multiple mechanisms of hardening
US17/068,962 Active US11312084B2 (en) 2014-06-23 2020-10-13 Methods for producing helmet inserts with materials having multiple mechanisms of hardening
US17/655,275 Active US11850803B2 (en) 2014-06-23 2022-03-17 Methods for producing three-dimensional objects with apparatus having feed channels
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Cited By (60)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017222602A1 (en) * 2016-06-20 2017-12-28 B9Creations, LLC System and method for reducing three-dimensional additive manufacturing production time
US20180056607A1 (en) * 2016-08-30 2018-03-01 Microsoft Technology Licensing, Llc Printing three dimensional objects using perforated brims
WO2018057330A1 (en) * 2016-09-12 2018-03-29 University Of Washington Vat photopolymerization additive manufacturing of multi-material parts
WO2018085758A1 (en) * 2016-11-07 2018-05-11 Dscales, Llc System for printing three dimensional objects using a liquid-matrix support
WO2018118832A1 (en) 2016-12-23 2018-06-28 Carbon, Inc. Adhesive sheet for securing 3d object to carrier platform and method of using same
WO2018129023A1 (en) 2017-01-05 2018-07-12 Carbon, Inc. Dual cure stereolithography resins containing diels-alder adducts
WO2018165090A1 (en) 2017-03-09 2018-09-13 Carbon, Inc. Tough, high temperature polymers produced by stereolithography
WO2018182974A1 (en) 2017-03-27 2018-10-04 Carbon, Inc. Method of making three-dimensional objects by additive manufacturing
US10150280B2 (en) 2013-05-14 2018-12-11 Holo, Inc. Apparatus for fabrication of three dimensional objects
WO2018226943A1 (en) 2017-06-08 2018-12-13 Carbon, Inc. Blocking groups for light polymerizable resins useful in additive manufacturing
US10155345B2 (en) 2015-02-05 2018-12-18 Carbon, Inc. Method of additive manufacturing by fabrication through multiple zones
US10166725B2 (en) 2014-09-08 2019-01-01 Holo, Inc. Three dimensional printing adhesion reduction using photoinhibition
US10245785B2 (en) 2017-06-16 2019-04-02 Holo, Inc. Methods for stereolithography three-dimensional printing
US10316213B1 (en) 2017-05-01 2019-06-11 Formlabs, Inc. Dual-cure resins and related methods
US10335997B2 (en) 2017-10-02 2019-07-02 Global Filtration Systems Method of stabilizing a photohardening inhibitor-permeable film in the manufacture of three-dimensional objects
US10350823B2 (en) 2015-12-22 2019-07-16 Carbon, Inc. Dual precursor resin systems for additive manufacturing with dual cure resins
US10421233B2 (en) 2017-05-15 2019-09-24 Holo, Inc. Viscous film three-dimensional printing systems and methods
US10471655B2 (en) 2015-09-04 2019-11-12 Carbon, Inc. Cyanate ester dual resins for additive manufacturing
US10470520B2 (en) 2013-03-14 2019-11-12 Under Armour, Inc. Shoe with lattice structure
US10575588B2 (en) 2017-03-27 2020-03-03 Adidas Ag Footwear midsole with warped lattice structure and method of making the same
USD879434S1 (en) 2018-02-15 2020-03-31 Adidas Ag Sole
USD879428S1 (en) 2018-02-15 2020-03-31 Adidas Ag Sole
WO2020068720A1 (en) 2018-09-25 2020-04-02 Carbon, Inc. Dual cure resins for additive manufacturing
USD880131S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
USD880120S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
USD880122S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
USD882227S1 (en) 2018-02-15 2020-04-28 Adidas Ag Sole
US10647873B2 (en) 2015-10-30 2020-05-12 Carbon, Inc. Dual cure article of manufacture with portions of differing solubility
US10702012B2 (en) 2015-05-08 2020-07-07 Under Armour, Inc. Footwear midsole with lattice structure formed between platforms
USD890485S1 (en) 2018-11-12 2020-07-21 Adidas Ag Shoe
US10750820B2 (en) 2015-05-08 2020-08-25 Under Armour, Inc. Midsole lattice with hollow tubes for footwear
US20210017381A1 (en) * 2018-03-30 2021-01-21 Arkema France Curable compositions for use as adhesives having properties capable of being altered based on external stimuli and methods of making and using the same
US10935891B2 (en) 2017-03-13 2021-03-02 Holo, Inc. Multi wavelength stereolithography hardware configurations
US10932521B2 (en) 2017-03-27 2021-03-02 Adidas Ag Footwear midsole with warped lattice structure and method of making the same
US10968307B2 (en) 2014-06-23 2021-04-06 Carbon, Inc. Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening
US10975193B2 (en) 2015-09-09 2021-04-13 Carbon, Inc. Epoxy dual cure resins for additive manufacturing
US11076656B2 (en) 2015-06-29 2021-08-03 Adidas Ag Soles for sport shoes
US11135765B2 (en) * 2017-08-11 2021-10-05 Carbon, Inc. Serially curable resins useful in additive manufacturing
US11135766B2 (en) 2017-06-29 2021-10-05 Carbon, Inc. Products containing nylon 6 produced by stereolithography and methods of making the same
US11141919B2 (en) 2015-12-09 2021-10-12 Holo, Inc. Multi-material stereolithographic three dimensional printing
US11167375B2 (en) 2018-08-10 2021-11-09 The Research Foundation For The State University Of New York Additive manufacturing processes and additively manufactured products
US11220054B2 (en) 2017-10-02 2022-01-11 Global Filtration Systems Method of stabilizing a photohardening inhibitor-permeable film in the manufacture of three-dimensional objects
DE102020124546A1 (de) 2020-09-21 2022-03-24 Audi Aktiengesellschaft 3D-Druckverfahren zur Herstellung eines 3D-Bauteils
US11351735B2 (en) 2018-12-26 2022-06-07 Holo, Inc. Sensors for three-dimensional printing systems and methods
US11376786B2 (en) 2017-04-21 2022-07-05 Carbon, Inc. Methods and apparatus for additive manufacturing
US11400644B2 (en) * 2017-10-27 2022-08-02 Carbon, Inc. Reduction of polymerization inhibitor irregularity on additive manufacturing windows
EP4049841A1 (de) 2021-02-26 2022-08-31 Cubicure GmbH Hybridharzzusammensetzung
US11440256B2 (en) 2018-06-15 2022-09-13 Howmedica Osteonics Corp. Stackable build plates for additive manufacturing powder handling
US11458673B2 (en) 2017-06-21 2022-10-04 Carbon, Inc. Resin dispenser for additive manufacturing
US11548215B2 (en) 2017-06-30 2023-01-10 Nikon Corporation Method of producing an optical device and a corresponding system
US11589647B2 (en) 2020-10-13 2023-02-28 Adidas Ag Footwear midsole with anisotropic mesh and methods of making the same
USD980595S1 (en) 2020-10-13 2023-03-14 Adidas Ag Shoe
USD980594S1 (en) 2020-10-13 2023-03-14 Adidas Ag Shoe
US11685117B2 (en) 2016-07-01 2023-06-27 Carbon, Inc. Three-dimensional printing methods for reducing bubbles by de-gassing through build plate
US11786008B2 (en) 2020-10-07 2023-10-17 Adidas Ag Footwear with 3-D printed midsole
US11832683B2 (en) 2019-12-27 2023-12-05 Asics Corporation Shock absorber, shoe sole and shoe
USD1022425S1 (en) 2020-10-07 2024-04-16 Adidas Ag Shoe
EP4369098A1 (de) 2022-11-14 2024-05-15 Cubicure GmbH Harzzusammensetzung
US11992084B2 (en) 2020-10-13 2024-05-28 Adidas Ag Footwear midsole with 3-D printed mesh having an anisotropic structure and methods of making the same
KR102672870B1 (ko) 2018-03-30 2024-06-05 아르끄마 프랑스 외부 자극을 기반으로 변형될 수 있는 특성을 가진 접착제로서 이용하기 위한 경화성 조성물 및 이의 제조 방법 및 이용 방법

Families Citing this family (395)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10159296B2 (en) 2013-01-18 2018-12-25 Riddell, Inc. System and method for custom forming a protective helmet for a customer's head
US9925440B2 (en) 2014-05-13 2018-03-27 Bauer Hockey, Llc Sporting goods including microlattice structures
US9975295B2 (en) 2014-08-12 2018-05-22 Carbon, Inc. Acceleration of stereolithography
JP6439338B2 (ja) * 2014-09-16 2018-12-19 コニカミノルタ株式会社 三次元造形方法および三次元造形装置
WO2016085914A1 (en) 2014-11-24 2016-06-02 Ppg Industries Ohio, Inc. Coreactive materials and methods for three-dimensional printing
GB201501089D0 (en) * 2015-01-22 2015-03-11 Univ Greenwich Stent
KR20170115070A (ko) 2015-02-05 2017-10-16 카본, 인크. 비연속 노광에 의한 적층체 제조방법
WO2016140886A1 (en) 2015-03-05 2016-09-09 Carbon3D, Inc. Fabrication of three dimensional objects with multiple operating modes
WO2016140891A1 (en) 2015-03-05 2016-09-09 Carbon3D, Inc. Continuous liquid interface production with sequential patterned exposure
US10792857B2 (en) * 2015-03-13 2020-10-06 The University Of North Carolina At Chapel Hill Polymeric microneedles and rapid additive manufacturing of the same
WO2016149151A1 (en) 2015-03-13 2016-09-22 Carbon3D, Inc. Three-dimensional printing with concurrent delivery of different polymerizable liquids
WO2016149104A1 (en) 2015-03-13 2016-09-22 Carbon3D, Inc. Three-dimensional printing with flexible build plates
US20160263837A1 (en) 2015-03-13 2016-09-15 Carbon3D, Inc. Methods, systems, and computer program products for determining fabrication parameters used in three-dimensional (3d) continuous liquid interface printing (clip) systems, and related printers
WO2016149097A1 (en) 2015-03-13 2016-09-22 Carbon3D, Inc. Three-dimensional printing with reduced pressure build plate unit
WO2016172788A1 (en) * 2015-04-30 2016-11-03 Fortier, Raymond Improved stereolithography system
US10492888B2 (en) 2015-07-07 2019-12-03 Align Technology, Inc. Dental materials using thermoset polymers
WO2017040156A1 (en) * 2015-09-01 2017-03-09 The Board Trustees Of The Leland Stanford Junior University Systems and methods for additive manufacturing of hybrid multi-material constructs and constructs made therefrom
US10792868B2 (en) 2015-09-09 2020-10-06 Carbon, Inc. Method and apparatus for three-dimensional fabrication
JP2017052177A (ja) * 2015-09-09 2017-03-16 富士ゼロックス株式会社 三次元造形物の製造方法、三次元造形用支持材、三次元造形用支持材カートリッジ、及び三次元造形用組成物セット
ITUB20154169A1 (it) 2015-10-02 2017-04-02 Thelyn S R L Metodo e apparato di foto-indurimento a substrato auto-lubrificante per la formazione di oggetti tridimensionali.
IL287642B (en) 2015-10-30 2022-07-01 Seurat Tech Inc Add-on and device creation system
US11891485B2 (en) * 2015-11-05 2024-02-06 Carbon, Inc. Silicone dual cure resins for additive manufacturing
US20170144373A1 (en) * 2015-11-23 2017-05-25 Battelle Memorial Institute Method and system for three-dimensional printing of conductive materials
US10647054B2 (en) 2015-12-22 2020-05-12 Carbon, Inc. Accelerants for additive manufacturing with dual cure resins
US10343331B2 (en) 2015-12-22 2019-07-09 Carbon, Inc. Wash liquids for use in additive manufacturing with dual cure resins
WO2017112751A1 (en) 2015-12-22 2017-06-29 Carbon, Inc. Blocked silicone dual cure resins for additive manufacturing
US10501572B2 (en) * 2015-12-22 2019-12-10 Carbon, Inc. Cyclic ester dual cure resins for additive manufacturing
WO2017112682A1 (en) 2015-12-22 2017-06-29 Carbon, Inc. Fabrication of compound products from multiple intermediates by additive manufacturing with dual cure resins
WO2017112571A1 (en) * 2015-12-22 2017-06-29 Carbon, Inc. Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products
CN109071981B (zh) 2016-03-08 2022-10-11 3D系统公司 用于3d印刷的非异氰酸酯聚氨酯油墨
US10933609B2 (en) * 2016-03-31 2021-03-02 The Regents Of The University Of California Composite foam
CN105799168B (zh) * 2016-04-06 2018-10-30 南京增材制造研究院发展有限公司 一种防粘减阻纳米结构槽底连续快速曝光光固化打印机
CN116285487A (zh) 2016-04-07 2023-06-23 3D系统公司 用于3d印刷的硫醇-烯油墨
US10239238B2 (en) * 2016-04-15 2019-03-26 Zhejiang University Method for fast building three-dimension polymer structures based on digital light patterning
US20190168221A1 (en) * 2016-04-15 2019-06-06 Vortex Biosciences, Inc. Microfluidic Chips and Cartridges and Systems Utilizing Microfluidic Chips and Cartridges
EP3426465B1 (de) * 2016-05-12 2020-03-18 Hewlett-Packard Development Company, L.P. Temperaturkontrolle vor dem schmelzen
CN106015307A (zh) * 2016-05-13 2016-10-12 北京斯帝欧科技有限公司 合页和用于制造该合页的方法
EP3455264A4 (de) * 2016-05-13 2020-05-20 MSI Coatings Inc. System und verfahren zur verwendung einer durch led-uv mit niedrigem strahlungsfluss härtbaren zusammensetzung ohne flüchtige organische verbindungen
PL3464402T3 (pl) * 2016-05-23 2021-08-02 Dow Global Technologies Llc Sposób ulepszenia wykończenia powierzchni wyrobów wytwarzanych przyrostowo
KR102377461B1 (ko) * 2016-05-31 2022-03-23 노오쓰웨스턴 유니버시티 3차원 물체의 제조 방법 및 그의 장치
US10500786B2 (en) 2016-06-22 2019-12-10 Carbon, Inc. Dual cure resins containing microwave absorbing materials and methods of using the same
JP7153570B2 (ja) 2016-06-30 2022-10-14 スリーエム イノベイティブ プロパティズ カンパニー 高粘度成分を含むプリント可能な組成物及びそれから３ｄ物品を生成する方法
KR102261399B1 (ko) * 2016-06-30 2021-06-07 신에쓰 가가꾸 고교 가부시끼가이샤 자외선 경화성 실리콘 조성물 및 그의 경화물
EP3484692A4 (de) * 2016-07-14 2020-04-15 University of Southern California Schiebefenstersieb für verkürzte harznachfüllzeit in der stereolithografie
US11033796B2 (en) 2016-07-20 2021-06-15 Riddell, Inc. System and methods for designing and manufacturing a bespoke protective sports helmet
US11565472B2 (en) 2016-07-21 2023-01-31 Hewlett-Packard Development Company, L.P. Additively formed 3D object with conductive channel
WO2018022785A1 (en) * 2016-07-26 2018-02-01 Ppg Industries Ohio, Inc. Three-dimensional printing processes using 1,1-di-activated vinyl compounds
US10241401B2 (en) * 2016-08-01 2019-03-26 Macdermid Graphics Solutions Llc Method of making a flexographic printing plate
US11021558B2 (en) * 2016-08-05 2021-06-01 Johnson & Johnson Vision Care, Inc. Polymer compositions containing grafted polymeric networks and processes for their preparation and use
EP3500231A1 (de) 2016-08-19 2019-06-26 The Procter and Gamble Company Polymermaterialien und daraus hergestellte artikel
JP2019529972A (ja) 2016-08-26 2019-10-17 モレキュラー インプリンツ， インコーポレイテッドＭｏｌｅｃｕｌａｒ Ｉｍｐｒｉｎｔｓ，Ｉｎｃ． モノリシック高屈折率フォトニックデバイス
JP7065351B2 (ja) * 2016-09-02 2022-05-12 パナソニックＩｐマネジメント株式会社 三次元形状造形物の製造方法
EP3520707A4 (de) * 2016-09-27 2019-09-11 FUJIFILM Corporation Objekt zum einsetzen, photoakustische messvorrichtung mit einem objekt zum einsetzen und verfahren zur herstellung eines objekts zum einsetzen
US10625470B2 (en) * 2016-09-28 2020-04-21 Ada Foundation 3D printing of composition-controlled copolymers
WO2018080501A1 (en) * 2016-10-27 2018-05-03 Hewlett-Packard Development Company, Lp Generating additive manufacturing instructions
WO2018080537A1 (en) 2016-10-31 2018-05-03 Hewlett-Packard Development Company, L.P. 3d printer with a uv light absorbing agent
CN110023056B (zh) 2016-11-21 2021-08-24 卡本有限公司 通过递送反应性组分用于后续固化来制造三维物体的方法
US20190315062A1 (en) * 2016-11-22 2019-10-17 Covestro Deutschland Ag Method and system for producing an article by layer-by-layer buildup in a stamping process
US11535568B2 (en) * 2016-11-30 2022-12-27 Hrl Laboratories, Llc Monomer formulations and methods for 3D printing of preceramic polymers
PL3548522T3 (pl) * 2016-12-05 2023-01-16 Covestro Deutschland Ag Sposób wytwarzania obiektu z prekursora i zastosowanie żywicy sieciowalnej rodnikowo w sposobie wytwarzania addytywnego
JP7109438B2 (ja) 2016-12-05 2022-07-29 アーケマ・インコーポレイテッド 重合開始剤ブレンド物、およびそのような重合開始剤ブレンド物を含む３ｄプリンティングに有用な光硬化性組成物
US11643479B2 (en) 2016-12-05 2023-05-09 Covestro Deutschland Ag Method for producing an article by layer-by-layer buildup with separately patterned resin and initiator wherein the resin has a storage modulus greater than loss modulus at 20 C
US11738511B2 (en) * 2016-12-08 2023-08-29 Igneous IP Holdings, LLC Additive manufacturing using foaming radiation-curable resin
US20200009769A1 (en) * 2016-12-14 2020-01-09 Covestro Deutschland Ag Method for producing a 3d printed, foam-filed object
WO2018111548A1 (en) 2016-12-14 2018-06-21 Carbon, Inc. Methods and apparatus for washing objects produced by stereolithography
US10933580B2 (en) 2016-12-14 2021-03-02 Carbon, Inc. Continuous liquid interface production with force monitoring and feedback
CN108215173A (zh) * 2016-12-15 2018-06-29 上海普利生机电科技有限公司 能够自动连续打印的光固化型三维打印设备、方法及系统
US11179926B2 (en) 2016-12-15 2021-11-23 General Electric Company Hybridized light sources
WO2018112770A1 (zh) * 2016-12-21 2018-06-28 北京工业大学 多轴机械系统与视觉监视相结合的3d打印方法与装置
EP3559744A1 (de) 2016-12-23 2019-10-30 3M Innovative Properties Company Bedruckbare zusammensetzungen mit polymeren und polymerisierbaren komponenten, artikel und verfahren zur herstellung von artikeln daraus
US20180207863A1 (en) * 2017-01-20 2018-07-26 Southern Methodist University Methods and apparatus for additive manufacturing using extrusion and curing and spatially-modulated multiple materials
KR101966333B1 (ko) * 2017-01-24 2019-04-08 주식회사 캐리마 복수개의 화면으로 분할되는 대형화면 노광시스템을 구비한 3d프린터
WO2018143954A1 (en) 2017-01-31 2018-08-09 Hewlett-Packard Development Company, L.P. Build material particle fusing in a chamber containing vapor
US11148357B2 (en) * 2017-02-13 2021-10-19 Carbon, Inc. Method of making composite objects by additive manufacturing
US11214649B2 (en) * 2017-02-17 2022-01-04 Basf Se Reactive thermoplastic polyurethane based on blocked isocyanates
US11857023B2 (en) 2017-02-27 2024-01-02 Kornit Digital Technologies Ltd. Digital molding and associated articles and methods
US20190039309A1 (en) * 2017-02-27 2019-02-07 VoxeI8,Inc. Methods of 3d printing articles with particles
US20190039311A1 (en) 2017-02-27 2019-02-07 Voxel8, Inc. Systems and methods for 3d printing articles of footwear with property gradients
US11904614B2 (en) 2017-02-27 2024-02-20 Kornit Digital Technologies Ltd. Multi-input print heads for three-dimensionally printing and associated systems and methods
US11470908B2 (en) 2017-02-27 2022-10-18 Kornit Digital Technologies Ltd. Articles of footwear and apparel having a three-dimensionally printed feature
US11701813B2 (en) 2017-02-27 2023-07-18 Kornit Digital Technologies Ltd. Methods for three-dimensionally printing and associated multi-input print heads and systems
WO2018159493A1 (ja) * 2017-03-03 2018-09-07 キヤノン株式会社 立体造形用の光硬化性組成物、それを用いた立体物の製造方法、および樹脂
JP6946095B2 (ja) * 2017-03-03 2021-10-06 キヤノン株式会社 立体造形用の光硬化性組成物、それを用いた立体物の製造方法、および樹脂
US10933579B2 (en) * 2017-03-10 2021-03-02 Prellis Biologics, Inc. Methods and systems for printing biological material
US11085018B2 (en) 2017-03-10 2021-08-10 Prellis Biologics, Inc. Three-dimensional printed organs, devices, and matrices
US10384394B2 (en) 2017-03-15 2019-08-20 Carbon, Inc. Constant force compression lattice
WO2018169821A1 (en) 2017-03-15 2018-09-20 Carbon, Inc. Integrated additive manufacturing systems
CN110520298A (zh) 2017-03-23 2019-11-29 卡本有限公司 可用于通过增材制造来制造物体的唇缘支撑物
EP3381959A1 (de) 2017-03-27 2018-10-03 Covestro Deutschland AG Dual cure-verfahren unter verwendung von thermisch latenten zinnkatalysatoren
US10574014B2 (en) * 2017-03-27 2020-02-25 Aptiv Technologies Limited Method for sealing electric terminal assembly
WO2018183440A1 (en) * 2017-03-28 2018-10-04 Ford Global Technologies, Llc Bio-based polyurethane resin for additive manufacturing
DE112018001072T5 (de) 2017-03-28 2019-11-21 Ford Global Technologies, Llc Stabilisierte additive herstellungsartikel
US10239255B2 (en) 2017-04-11 2019-03-26 Molecule Corp Fabrication of solid materials or films from a polymerizable liquid
EP3609942A1 (de) * 2017-04-12 2020-02-19 Basf Se Thermoplastisches polyurethan und verbundartikel
US10369557B2 (en) * 2017-04-12 2019-08-06 International Business Machines Corporation Three-dimensional printed objects for chemical reaction control
CN110312608B (zh) * 2017-04-17 2022-04-19 惠普发展公司，有限责任合伙企业 增材制造包含第二材料的3d物体
US20180304541A1 (en) * 2017-04-19 2018-10-25 Carbon, Inc. 3d lattice supports for additive manufacturing
WO2018194805A1 (en) 2017-04-21 2018-10-25 Carbon, Inc. Dental model and die assembly and method of making the same
IT201700051624A1 (it) * 2017-05-12 2018-11-12 U Invest S R L Scarpa di sicurezza defaticante.
DE102017110984A1 (de) 2017-05-19 2018-11-22 Isotech Holding Corporation Llc Schuhschaft mit dreidimensionalen Ziermustern aus Polyurethan und Verfahren zur Herstellung desselben sowie Schuh mit dem derartigen Schuhschaft
DE202017103049U1 (de) 2017-05-19 2017-06-27 Isotech Holding Corporation Llc Schuhschaft mit dreidimensionalen Ziermustern aus Polyurethan sowie Schuh mit dem derartigen Schuhschaft
JP2020524483A (ja) 2017-05-25 2020-08-20 プレリス バイオロジクス，インク． 三次元印刷された器官、デバイス、およびマトリックス
CN108927993B (zh) * 2017-05-26 2020-12-15 三纬国际立体列印科技股份有限公司 多光源模块的光固化3d打印方法
KR102217758B1 (ko) 2017-05-29 2021-02-22 스트라타시스 엘티디. 박리가능한 희생 구조물의 적층 가공을 위한 방법 및 시스템
WO2018222968A1 (en) 2017-06-01 2018-12-06 Nike Innovate C.V. Methods of manufacturing articles utilizing foam particles
US10532554B2 (en) * 2017-06-02 2020-01-14 3D Systems, Inc. Three dimensional printing system with automation features
WO2018229095A1 (de) * 2017-06-14 2018-12-20 Covestro Deutschland Ag Additives fertigungsverfahren unter verwendung von aminen zur nachhärtung
DE102017210384B3 (de) 2017-06-21 2018-08-30 Sirona Dental Systems Gmbh Behälter zum Einsatz in Stereolithographie-Anlagen und Stereolithographie-Anlage
US20190001658A1 (en) * 2017-06-30 2019-01-03 General Electric Company Systems and method for advanced additive manufacturing
WO2019002540A1 (de) 2017-06-30 2019-01-03 Covestro Deutschland Ag Additives herstellungsverfahren mit einem thermoplastischen radikalisch vernetzbaren aufbaumaterial
KR102307951B1 (ko) 2017-07-10 2021-09-30 휴렛-팩커드 디벨롭먼트 컴퍼니, 엘.피. 가상 빌드 볼륨에서의 세그먼트
EP3625030B1 (de) 2017-07-14 2021-10-27 Hewlett-Packard Development Company, L.P. 3d-druck
CN110997744B (zh) 2017-07-25 2022-06-24 3M创新有限公司 包含氨基甲酸酯组分和反应性稀释剂的光致聚合型组合物、制品和方法
WO2019027417A1 (en) * 2017-07-31 2019-02-07 Hewlett-Packard Development Company, L.P. OBJECTS HAVING HEARTS COMPRISING BINDERS OF METAL NANOPARTICLES
WO2019032449A1 (en) * 2017-08-07 2019-02-14 The Penn State Research Foundation OBTAINING COMPOSITION OF FUNCTIONAL GRADIENT MATERIALS BY BICONTINUOUS MESOSTRUCTURAL GEOMETRY IN ADDITIVE MANUFACTURE
US10434704B2 (en) 2017-08-18 2019-10-08 Ppg Industries Ohio, Inc. Additive manufacturing using polyurea materials
CN107603201B (zh) * 2017-09-07 2021-02-26 金华造物新材料有限公司 一种饰品和牙科精密铸造用3d打印光敏树脂
JP7398364B2 (ja) 2017-09-11 2023-12-14 スリーエム イノベイティブ プロパティズ カンパニー 放射線硬化性組成物及び積層造形プロセスを使用して作製された複合材物品
US10688737B2 (en) 2017-09-14 2020-06-23 General Electric Company Method for forming fiber-reinforced polymer components
EP3684826B1 (de) 2017-09-22 2022-04-20 Carbon, Inc. Herstellung lichtdurchlässiger gegenstände durch generative fertigung
US10590066B2 (en) 2017-09-29 2020-03-17 3D-Biomaterials, Llc Biocompositions for 3D printing
TW201915592A (zh) * 2017-09-29 2019-04-16 揚明光學股份有限公司 三維列印系統及其製造方法
WO2019074790A1 (en) 2017-10-09 2019-04-18 Carbon, Inc. PERFORMANCE OPTIMIZATION IN ADDITIVE MANUFACTURING
AT520499B1 (de) * 2017-10-12 2021-10-15 Swarovski Optik Kg Verfahren zur Herstellung einer fernoptischen Vorrichtung
WO2019083833A1 (en) 2017-10-23 2019-05-02 Carbon, Inc. CORRECTION OF WINDOW VARIABILITY IN ADDITIVE MANUFACTURE
WO2019083876A1 (en) 2017-10-26 2019-05-02 Carbon, Inc. REDUCTION OF WITHDRAWAL OR LOWERING IN OBJECTS PRODUCED BY ADDITIVE MANUFACTURING
WO2019089252A1 (en) 2017-10-31 2019-05-09 Carbon, Inc. Mass customization in additive manufacturing
US11602899B2 (en) 2017-10-31 2023-03-14 Carbon, Inc. Efficient surface texturing of objects produced by additive manufacturing
US11254052B2 (en) 2017-11-02 2022-02-22 General Electric Company Vatless additive manufacturing apparatus and method
AU2018357941A1 (en) 2017-11-02 2020-06-11 Magic Leap, Inc. Preparing and dispensing polymer materials and producing polymer articles therefrom
US20190129308A1 (en) 2017-11-02 2019-05-02 Taiwan Green Point Enterprises Co., Ltd. Digital masking system, pattern imaging apparatus and digital masking method
US11590691B2 (en) 2017-11-02 2023-02-28 General Electric Company Plate-based additive manufacturing apparatus and method
WO2019099347A1 (en) 2017-11-20 2019-05-23 Carbon, Inc. Light-curable siloxane resins for additive manufacturing
US11904031B2 (en) 2017-11-22 2024-02-20 3M Innovative Properties Company Orthodontic articles comprising polymerized composition comprising at least two free-radical initiators
WO2019104079A1 (en) * 2017-11-22 2019-05-31 3M Innovative Properties Company Orthodontic articles comprising polymerized composition comprising at least two free-radical initiators
CN111372959B (zh) 2017-11-22 2022-09-02 3M创新有限公司 包含氨基甲酸酯组分和单官能反应性稀释剂的光致聚合型组合物、制品和方法
JP7066384B2 (ja) * 2017-11-27 2022-05-13 キヤノン株式会社 ブロックイソシアネート、光硬化性組成物、樹脂、および立体物の製造方法
US11065864B2 (en) * 2017-11-27 2021-07-20 City University Of Hong Kong Hybrid polymeric structure, a method for fabricating a hybrid polymeric structure and a method for connecting two polymeric layers with the hybrid polymeric structure
CN111356738B (zh) * 2017-11-30 2022-07-26 惠普发展公司，有限责任合伙企业 用于三维打印的抗聚结剂
US11479628B2 (en) 2017-12-08 2022-10-25 Carbon, Inc. Shelf stable, low tin concentration, dual cure additive manufacturing resins
DE102017130124B4 (de) 2017-12-15 2023-08-03 Technische Hochschule Wildau (Fh) Additives Fertigungsverfahren auf Basis von Polyisocyanaten
JP7195325B2 (ja) * 2017-12-28 2022-12-23 ストラタシス リミテッド 剥離可能な犠牲構造の付加製造のための方法及びシステム
US11370185B2 (en) * 2018-01-11 2022-06-28 E-Vision Smart Optics, Inc. Three-dimensional (3D) printing of electro-active lenses
US10821668B2 (en) 2018-01-26 2020-11-03 General Electric Company Method for producing a component layer-by- layer
US10821669B2 (en) 2018-01-26 2020-11-03 General Electric Company Method for producing a component layer-by-layer
US11034789B2 (en) 2018-01-30 2021-06-15 Johnson & Johnson Vision Care, Inc. Ophthalmic devices containing localized grafted networks and processes for their preparation and use
US10961341B2 (en) 2018-01-30 2021-03-30 Johnson & Johnson Vision Care, Inc. Ophthalmic devices derived from grafted polymeric networks and processes for their preparation and use
CN108274582B (zh) * 2018-02-08 2024-04-05 广东工业大学 一种基于光固化成型的增材制造平台
WO2019158599A1 (de) * 2018-02-16 2019-08-22 Covestro Deutschland Ag Verfahren zum applizieren eines ein schmelzbares polymer enthaltenden materials, insbesondere eines schmelzklebstoffes oberhalb seiner zersetzungstemperatur
WO2019165052A1 (en) 2018-02-21 2019-08-29 Carbon, Inc. Methods of reducing distortion of additively manufactured objects
CN111801216B (zh) 2018-02-21 2021-11-16 卡本有限公司 在增材制造期间增强物体与载体的粘合
US10779817B2 (en) 2018-02-21 2020-09-22 Ethicon Llc Three dimensional adjuncts
USD882782S1 (en) 2018-02-21 2020-04-28 Ethicon Llc Three dimensional adjunct
US10980533B2 (en) 2018-02-21 2021-04-20 Ethicon Llc Three dimensional adjuncts
PL234153B1 (pl) * 2018-02-26 2020-01-31 Chuptys Janusz Contissi Drukarka do druku przestrzennego
WO2019168807A1 (en) 2018-03-02 2019-09-06 Carbon, Inc. Sustainable additive manufacturing resins and methods of recycling
WO2019169211A1 (en) * 2018-03-02 2019-09-06 Formlabs, Inc. Latent cure resins and related methods
WO2019190902A1 (en) 2018-03-27 2019-10-03 Carbon, Inc. Functional surface coating methods foradditively manufactured products
WO2019195417A1 (en) 2018-04-03 2019-10-10 Massachusetts Institute Of Technology Programmable soft materials containing ferromagnetic domains and methods of making
CN112166039B (zh) * 2018-04-06 2023-09-05 聚合-医药有限公司 用于光致聚合增材制造的方法和组合物
US20190309163A1 (en) * 2018-04-10 2019-10-10 The Procter & Gamble Company Polymeric Materials and Articles Manufactured There From
US11723875B2 (en) 2018-04-10 2023-08-15 The Procter & Gamble Company Polymeric materials and articles manufactured there from
WO2019204258A1 (en) 2018-04-17 2019-10-24 Carbon, Inc. Temperature regulated stereolithography apparatus with infrared heating
WO2019204095A1 (en) 2018-04-20 2019-10-24 Carbon, Inc. Bonded surface coating methods for additively manufactured products
JP6997341B2 (ja) 2018-04-23 2022-01-17 カーボン，インコーポレイテッド 付加製造のための樹脂抽出機
KR20210003915A (ko) 2018-05-04 2021-01-12 얼라인 테크널러지, 인크. 고온 석판인쇄-기반 광중합 공정에서 사용하기 위한 경화형 조성물 및 이로부터 가교 중합체를 제조하는 방법
WO2019217641A1 (en) 2018-05-11 2019-11-14 Carbon, Inc. Sustainable chemistry systems for recyclable dental models and other additively manufactured products
WO2019222094A1 (en) 2018-05-14 2019-11-21 Carbon, Inc. Stereolithography apparatus with individually addressable light source arrays
AT521316A1 (de) * 2018-06-07 2019-12-15 All Bones Gmbh Polymermischung sowie deren Verwendung im 3D-Druck
WO2019245892A1 (en) 2018-06-20 2019-12-26 Carbon, Inc. Method of treating additive manufacturing objects with a compound of interest
WO2020005706A1 (en) * 2018-06-27 2020-01-02 Carbon, Inc. Additive manufacturing method including thermal modeling and control
CN108859114B (zh) * 2018-06-28 2020-06-19 西安交通大学 一种用于连续面成型3d打印的透光透气舱及操作方法
EP3813763A1 (de) 2018-06-29 2021-05-05 3M Innovative Properties Company Kieferorthopädische artikel mit einer gehärteten, freiradikalisch polymerisierbaren zusammensetzung mit verbesserter festigkeit in wässriger umgebung
EP3814117A4 (de) 2018-06-29 2022-09-21 Intrepid Automation Druckprozessanpassung mit geschlossenem regelkreis basierend auf echtzeitrückkopplung
TWI818046B (zh) * 2018-07-16 2023-10-11 德商科思創德意志股份有限公司 施加含有游離ｎｃｏ基團的可熔性聚合物材料的方法
DE102018117631A1 (de) * 2018-07-20 2020-01-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Innovatives Materialsystem und Verfahren zur Fertigung von patientenindividuellen Komfort-Ohrpassstücken für die Hörakustik-, Audio und Gehörschutzbranche
US11884976B2 (en) * 2018-07-20 2024-01-30 Illumina, Inc. Resin composition and flow cells incorporating the same
US10525315B1 (en) 2018-07-20 2020-01-07 Harry Matthew Wells Grip assembly for sports equipment
WO2020023823A1 (en) 2018-07-27 2020-01-30 Carbon, Inc. Branched reactive blocked prepolymers for additive manufacturing
US10780640B2 (en) 2018-07-30 2020-09-22 Intrepid Automation Multiple image projection system for additive manufacturing
WO2020028498A1 (en) 2018-08-01 2020-02-06 Carbon, Inc. Method for rapid encapsulation of microelectronic devices
US11292186B2 (en) 2018-08-01 2022-04-05 Carbon, Inc. Production of low density products by additive manufacturing
US20210242097A1 (en) 2018-08-02 2021-08-05 Carbon, Inc. Method of Packaging an Integrated Circuit
US11399589B2 (en) 2018-08-16 2022-08-02 Riddell, Inc. System and method for designing and manufacturing a protective helmet tailored to a selected group of helmet wearers
US11203156B2 (en) 2018-08-20 2021-12-21 NEXA3D Inc. Methods and systems for photo-curing photo-sensitive material for printing and other applications
US11192305B2 (en) 2018-08-24 2021-12-07 Carbon, Inc. Window cassettes for reduced polymerization inhibitor irregularity during additive manufacturing
CN108929410A (zh) * 2018-08-27 2018-12-04 宁波市石生科技有限公司 一种用于光固化三维制造的材料以及用该材料应用
US11504903B2 (en) 2018-08-28 2022-11-22 Carbon, Inc. 1K alcohol dual cure resins for additive manufacturing
US11407183B2 (en) 2018-08-31 2022-08-09 Carbon, Inc. Additively manufactured objects with pre-formed bonding features and methods of making the same
US11376792B2 (en) 2018-09-05 2022-07-05 Carbon, Inc. Robotic additive manufacturing system
CN109228303A (zh) * 2018-09-10 2019-01-18 宁波市石生科技有限公司 一种利用多波长光进行3d打印的方法
CN115943062A (zh) 2018-09-10 2023-04-07 卡本有限公司 用于生产阻燃物体的双固化增材制造树脂
US11135744B2 (en) 2018-09-13 2021-10-05 Carbon, Inc. Reversible thermosets for additive manufacturing
EP3623287B1 (de) * 2018-09-17 2021-03-24 Safran Landing Systems UK Limited Flugzeugfahrwerkskomponente
KR102610546B1 (ko) * 2018-09-20 2023-12-05 피피지 인더스트리즈 오하이오 인코포레이티드 티올-함유 조성물
US20210354203A1 (en) * 2018-09-21 2021-11-18 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN112639034A (zh) 2018-09-24 2021-04-09 巴斯夫欧洲公司 用于3d打印的可uv固化组合物
WO2020069152A1 (en) 2018-09-26 2020-04-02 Carbon, Inc. Spin cleaning method and apparatus for additive manufacturing
CN112867597A (zh) * 2018-09-26 2021-05-28 阿肯色州立大学托管会 用于3d打印的树脂挤出打印头
WO2020065653A1 (en) 2018-09-27 2020-04-02 Stratasys Ltd. Method and system for additive manufacturing with a sacrificial structure for easy removal
IL281855B (en) * 2018-09-28 2022-07-01 Stratasys Ltd Additive manufacturing process with partial fusion
WO2020069167A1 (en) 2018-09-28 2020-04-02 Carbon, Inc. Removable build platform for an additive manufacturing apparatus
WO2020069060A1 (en) 2018-09-28 2020-04-02 Carbon, Inc. Thermally regulated window cassette for additive manufacturing apparatus
JP7491910B2 (ja) * 2018-09-28 2024-05-28 ストラタシス リミテッド 熱的に安定な物体の三次元インクジェット印刷
CN217435033U (zh) 2018-09-28 2022-09-16 卡本有限公司 用于增材制造设备的可移除窗盒
US11565774B2 (en) 2018-10-03 2023-01-31 Adam Jon Noah Additive manufactured water resistant closed-cell lattice structure for marine hull cavities
WO2020072075A1 (en) * 2018-10-05 2020-04-09 Hewlett-Packard Development Company, L.P. Three-dimensional printing
US11472975B2 (en) * 2018-10-08 2022-10-18 Vista Applied Materials, Inc. Formulation composition for 3D additive manufacturing and processing method of the same
TWI691529B (zh) * 2018-10-08 2020-04-21 致達應材股份有限公司 ３ｄ積層製造用之混合式配方組合物與其製程方法
US11304471B2 (en) 2018-10-12 2022-04-19 Carbon, Inc. Moisture controlling lattice liners for helmets and other wearable articles
US20210341031A1 (en) 2018-10-22 2021-11-04 Carbon, Inc. Shock absorbing lattice structure produced by additive manufacturing
WO2020086372A1 (en) 2018-10-22 2020-04-30 Carbon, Inc. Lattice transitioning structures in additively manufactured products
EP3643479B1 (de) 2018-10-24 2021-01-06 Ivoclar Vivadent AG Verfahren und vorrichtung zum aufbau eines formkörpers durch stereolithographisches aushärten von baumaterial durch photopolymerisation
WO2020092485A1 (en) 2018-10-31 2020-05-07 Carbon, Inc. Apparatuses for additively manufacturing three-dimensional objects
US11052875B2 (en) 2018-11-07 2021-07-06 Ford Global Technologies, Llc Defroster system for a motor vehicle
AU2019377511B2 (en) 2018-11-09 2024-02-01 NEXA3D Inc. Three-dimensional printing system
FR3088610B1 (fr) * 2018-11-15 2021-01-22 Renault Sas Corps de planche de bord a structure lacunaire et conduits de circulation de fluide integres
WO2020107005A1 (en) 2018-11-21 2020-05-28 Riddell, Inc. Protective recreational sports helmet with components additively manufactured to manage impact forces
KR102115367B1 (ko) * 2018-11-23 2020-05-26 주식회사 그래피 환자 맞춤형 깁스의 제조를 위한 3d 프린터용 광경화형 조성물
US11498274B2 (en) 2018-12-03 2022-11-15 Carbon, Inc. Window thermal profile calibration in additive manufacturing
EP3984401B1 (de) 2018-12-06 2023-06-07 Nike Innovate C.V. Verfahren zur herstellung von artikeln unter verwendung von schaumpartikeln
KR102196036B1 (ko) * 2018-12-06 2020-12-29 주식회사 덴티스 3차원 적층체의 상태에 따라 자외선 출력 가변이 가능한 자외선 광 경화장치
WO2020117407A1 (en) 2018-12-07 2020-06-11 Carbon, Inc. Methods of surface finishing objects produced by additive manufacturing
WO2020123873A1 (en) * 2018-12-12 2020-06-18 Riddell, Inc. Systems and methods for providing training opportunities based on physiological parameter of persons engaged in physical activity
WO2020131675A1 (en) 2018-12-21 2020-06-25 Carbon, Inc. Energy absorbing dual cure polyurethane elastomers for additive manufacturing
CN113166355B (zh) 2018-12-21 2023-12-22 Sika技术股份公司 双组分聚氨酯组合物的3d打印方法
CN109605737A (zh) * 2018-12-28 2019-04-12 源秩科技（上海）有限公司 一种光固化3d打印系统和打印方法
CN117209694A (zh) 2018-12-31 2023-12-12 浙江迅实科技有限公司 用于制造3d聚合结构的双固化方法和系统
US11110649B2 (en) 2019-01-04 2021-09-07 Carbon, Inc. Additively manufactured products having a matte surface finish
EP3877156B1 (de) 2019-01-07 2023-01-04 Carbon, Inc. Systeme und verfahren zur harzrückgewinnung in der generativen fertigung
WO2020146092A1 (en) 2019-01-09 2020-07-16 Carbon, Inc. Systems and apparatuses for additive manufacturing with process update and lock down
EP3680274A1 (de) 2019-01-14 2020-07-15 Basf Se Hydroxyurethan-(meth)acrylatpräpolymere zur verwendung im 3d-druck
EP3680263A1 (de) 2019-01-14 2020-07-15 Basf Se Limonenbasierte (meth)acrylate zur verwendung im 3d-druck
US11642843B2 (en) 2019-01-18 2023-05-09 Hewlett-Packard Development Company, L.P. Three-dimensional printing
US11859027B2 (en) 2019-01-18 2024-01-02 Carbon, Inc. Apparatus for determining the photosensitivity of a stereolithography resin
KR20210122823A (ko) 2019-02-01 2021-10-12 바스프 에스이 폴리우레탄 및 이를 포함하는 uv-수분 이중 경화 pu 반응성 핫멜트
US11794412B2 (en) 2019-02-20 2023-10-24 General Electric Company Method and apparatus for layer thickness control in additive manufacturing
US11498283B2 (en) 2019-02-20 2022-11-15 General Electric Company Method and apparatus for build thickness control in additive manufacturing
US11679555B2 (en) 2019-02-21 2023-06-20 Sprintray, Inc. Reservoir with substrate assembly for reducing separation forces in three-dimensional printing
US10766194B1 (en) 2019-02-21 2020-09-08 Sprintray Inc. Apparatus, system, and method for use in three-dimensional printing
US11801642B2 (en) 2019-02-26 2023-10-31 Carbon, Inc. Resin level detection in additive manufacturing
US11992878B2 (en) 2019-02-27 2024-05-28 Hewlett-Packard Development Company, L.P. Cure time for 3D printing green parts
US11478986B2 (en) 2019-03-04 2022-10-25 Mighty Buildings, Inc. Reactor for prepolymerization of a photopolymerizable material
US11179891B2 (en) 2019-03-15 2021-11-23 General Electric Company Method and apparatus for additive manufacturing with shared components
US11167473B2 (en) 2019-03-18 2021-11-09 NEXA3D Inc. System for additive manufacture
DE102019107161A1 (de) * 2019-03-20 2020-09-24 Herding Gmbh Filtertechnik Filterelement und Verfahren zur Herstellung eines Filterelements
EP3921103A4 (de) * 2019-03-22 2022-11-02 Hewlett-Packard Development Company, L.P. Dreidimensionales drucken mit blockierten polyisocyanaten
JP2022524222A (ja) 2019-03-29 2022-04-28 アズール・３ディー・インコーポレイテッド マルチプロジェクタ３次元印刷のためのデバイス、システム、および方法
US11555095B2 (en) 2019-03-29 2023-01-17 Carbon, Inc. Dual cure resin for the production of moisture-resistant articles by additive manufacturing
US10967573B2 (en) 2019-04-02 2021-04-06 NEXA3D Inc. Tank assembly and components thereof for a 3D printing system
US11235533B2 (en) 2019-04-26 2022-02-01 Carbon, Inc. Resin viscosity detection in additive manufacturing
US20220143917A1 (en) 2019-04-30 2022-05-12 Carbon, Inc. Mass customization in additive manufacturing
WO2020223058A1 (en) 2019-04-30 2020-11-05 Carbon, Inc. Low viscosity dual cure additive manufacturing resins
GB201906987D0 (en) * 2019-05-17 2019-07-03 Univ Birmingham tunable materials
EP3972812A4 (de) * 2019-05-20 2023-07-12 Global Filtration Systems, A DBA of Gulf Filtration Systems Inc. Verfahren zur stabilisierung eines photohärtenden inhibitorpermeablen films bei der herstellung von dreidimensionalen objekten
CA3157206A1 (en) 2019-05-21 2020-11-26 Bauer Hockey Ltd. Helmets comprising additively-manufactured components
US20200367477A1 (en) * 2019-05-24 2020-11-26 Alexander SCHOFIELD Artificial coral articles and preparation methods thereof
WO2020251541A1 (en) * 2019-06-10 2020-12-17 Hewlett-Packard Development Company, L.P. Three-dimensional printing with triethylene glycol fusing agents
US11713395B2 (en) 2019-06-13 2023-08-01 Luxcreo (Beijing) Inc. Resin materials for making three-dimensional objects and methods of using the same
EP3962980A4 (de) * 2019-06-13 2022-07-06 Luxcreo (Beijing) Inc. Harzmaterialien zur herstellung von dreidimensionalen objekten und verfahren zu ihrer verwendung
US11376787B2 (en) 2019-06-18 2022-07-05 Carbon, Inc. Additive manufacturing method and apparatus for the production of dental crowns and other objects
US20220297382A1 (en) 2019-06-24 2022-09-22 Carbon, Inc. Preemptive apparatus failure detection in additive manufacturing
WO2020263480A1 (en) 2019-06-28 2020-12-30 Carbon, Inc. Dual cure additive manufacturing resins for the production of objects with mixed tensile properties
WO2021001479A1 (en) 2019-07-02 2021-01-07 Sika Technology Ag Two-component polyurethane composition for the production of large scale models and tools by 3d printing
CN112265262B (zh) * 2019-07-08 2023-08-15 上海普利生机电科技有限公司 一种光固化型3d打印装置
CN114007847A (zh) * 2019-07-09 2022-02-01 清锋（北京）科技有限公司 用于打印三维物体的多官能团预聚物及其使用方法
US20220129039A1 (en) * 2019-07-11 2022-04-28 Hewlett-Packard Development Company, L.P. Electronic device housings with shock absorbers
JP2022541473A (ja) 2019-07-17 2022-09-26 アルケマ フランス （メタ）アクリレート官能化オリゴマー並びにそのようなオリゴマーを調製及び使用する方法
US11890809B2 (en) 2019-07-17 2024-02-06 Hewlett-Packard Development Company, L.P. Three-dimensional printing
EP4003709A4 (de) * 2019-07-23 2023-08-16 Adaptive 3D Technologies, LLC Thiol-acrylat-elastomere für den 3d-druck
EP3771471A1 (de) 2019-07-31 2021-02-03 Freie Universität Berlin Lichthärtbare zusammensetzungen
US20220266514A1 (en) 2019-08-06 2022-08-25 Carbon, Inc. Additive manufacturing apparatus with purged light engine
US11840023B2 (en) * 2019-08-30 2023-12-12 Carbon, Inc. Mutliphysics model for inverse warping of data file in preparation for additive manufacturing
US11518098B2 (en) 2019-08-30 2022-12-06 Carbon, Inc. Divided resin cassettes for enhanced work flow in additive manufacturing of dental products and the like
WO2021046376A1 (en) 2019-09-06 2021-03-11 Carbon, Inc. Cushions containing shock absorbing triply periodic lattice and related methods
EP3791807B1 (de) 2019-09-16 2023-10-04 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791808A1 (de) 2019-09-16 2021-03-17 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791809A1 (de) 2019-09-16 2021-03-17 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791800A1 (de) 2019-09-16 2021-03-17 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791806A1 (de) 2019-09-16 2021-03-17 Ethicon LLC Komprimierbare nichtfaserige zusätze
US11672537B2 (en) 2019-09-16 2023-06-13 Cilag Gmbh International Compressible non-fibrous adjuncts
EP4052656A1 (de) 2019-09-16 2022-09-07 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791810B1 (de) 2019-09-16 2023-12-20 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791799A1 (de) 2019-09-16 2021-03-17 Ethicon LLC Komprimierbare nichtfaserige zusätze
EP3791804B1 (de) 2019-09-16 2023-11-29 Ethicon LLC Komprimierbare nichtfaserige zusätze
US11490890B2 (en) 2019-09-16 2022-11-08 Cilag Gmbh International Compressible non-fibrous adjuncts
CN114641241A (zh) 2019-09-16 2022-06-17 卡本有限公司 用于增材制造的生物可吸收性树脂
EP3986626A1 (de) 2019-09-20 2022-04-27 Carbon, Inc. Reinigung von generativ gefertigten gegenständen durch vakuumzyklusnukleierung
US20220371277A1 (en) 2019-09-25 2022-11-24 Carbon, Inc. Particle coating methods for additively manufactured products
WO2021072118A1 (en) * 2019-10-09 2021-04-15 Poly-Med, Inc. Curable polymeric compositions
US20210115249A1 (en) * 2019-10-22 2021-04-22 Covestro Llc Annealed thermoplastic materials
EP4048199A1 (de) 2019-10-25 2022-08-31 Carbon, Inc. Mechanisch anisotrope 3d-gedruckte flexible polymerhülle
EP4055071A1 (de) 2019-11-07 2022-09-14 Basf Se Wasserspülbare zusammensetzungen zur verwendung beim 3d-drucken
US11787105B2 (en) * 2019-11-14 2023-10-17 Rolls-Royce Corporation Fused filament fabrication of components including predetermined yield points based on composition functions
WO2021101801A1 (en) 2019-11-18 2021-05-27 Carbon, Inc. Partial dentures and methods of making the same
EP4070939A1 (de) * 2019-11-19 2022-10-12 NIKE Innovate C.V. Verfahren zum herstellen von artikeln, die schaumpartikel aufweisen
TWI820340B (zh) * 2019-12-02 2023-11-01 大陸商清鋒（北京）科技有限公司 用於製備三維物體的樹脂材料及其使用方法
CN113025172A (zh) * 2019-12-09 2021-06-25 广东三和化工科技有限公司 一种气雾型底盘涂料及其制备方法
EP3834894A1 (de) 2019-12-09 2021-06-16 Harry Matthew Wells Griffanordnung für sportausrüstung
WO2021118699A1 (en) 2019-12-13 2021-06-17 Carbon, Inc. Additive manufacturing from a velocity induced dead zone
EP3838592A1 (de) 2019-12-17 2021-06-23 Evonik Operations GmbH Zusammensetzung enthaltend polyester für die generative fertigung
US11713367B2 (en) 2019-12-23 2023-08-01 Carbon, Inc. Inhibition of crystallization in polyurethane resins
JP7411410B2 (ja) * 2019-12-27 2024-01-11 株式会社アシックス 緩衝材、靴底および靴
JP7396892B2 (ja) * 2019-12-27 2023-12-12 株式会社アシックス 靴底および靴
US11981778B2 (en) 2020-01-17 2024-05-14 Carbon, Inc. Chemical recycling of additively manufactured objects
US20230063606A1 (en) * 2020-01-20 2023-03-02 Hewlett-Packard Development Company, L.P. Three-dimensional printing
CN114096612A (zh) * 2020-01-27 2022-02-25 日立能源瑞士股份公司 用于电气部件的光辐射可固化的环氧树脂
US11440259B2 (en) 2020-01-31 2022-09-13 Carbon, Inc. Resin reclamation centrifuge rotor for additively manufactured objects
EP3865281B1 (de) 2020-02-14 2023-01-18 Ivoclar Vivadent AG Stereolithographie-vorrichtung
TWI748350B (zh) * 2020-02-20 2021-12-01 所羅門股份有限公司 尺寸檢測方法及系統
JP2023519812A (ja) 2020-02-28 2023-05-15 カーボン，インコーポレイテッド 三次元物体を製造する方法
US20230095658A1 (en) 2020-02-28 2023-03-30 Carbon, Inc. One part moisture curable resins for additive manufacturing
WO2021183741A1 (en) 2020-03-12 2021-09-16 Carbon, Inc. Partially reversible thermosets useful for recycling
WO2021183263A1 (en) 2020-03-13 2021-09-16 Carbon, Inc. Additively manufactured products having a matte surface finish
WO2021202655A1 (en) 2020-04-03 2021-10-07 Carbon, Inc. Resins and methods for additive manufacturing of energy absorbing three-dimensional objects
JP2023530810A (ja) * 2020-04-13 2023-07-20 クロミス ファイバーオプティクス インコーポレイテッド 非晶質架橋フッ素コポリマーからなるガス分離物品ならびにその製造方法および使用方法
US20210317329A1 (en) * 2020-04-13 2021-10-14 Chromis Fiberoptics, Inc. Gas permeable windows composed of amorphous crosslinked fluorinated copolymers and methods of making and using thereof
US11655329B2 (en) 2020-04-24 2023-05-23 Carbon, Inc. Delayed action catalysts for dual cure additive manufacturing resins
WO2021222086A1 (en) 2020-04-28 2021-11-04 Carbon, Inc. Methods of making a three-dimensional object
CN111349197B (zh) * 2020-04-29 2020-08-11 苏州博理新材料科技有限公司 双重固化相分离型连续3d打印高精度光敏树脂组合物
WO2021221877A1 (en) 2020-04-30 2021-11-04 Carbon, Inc. Film applicator apparatus for additive manufacturing build platforms and related systems
WO2021221900A1 (en) 2020-04-30 2021-11-04 Carbon, Inc. Film remover apparatus for additive manufacturing build platforms and related methods
US11724443B2 (en) 2020-05-14 2023-08-15 Saudi Arabian Oil Company Additive manufacture-assisted method for making structural elements having controlled failure characteristics
US11548219B2 (en) 2020-05-15 2023-01-10 Carbon, Inc. Apparatus and methods for controlled validation of additive manufacturing systems
CN111732693A (zh) * 2020-06-29 2020-10-02 合肥小陀螺新材料科技有限公司 一种泥浆泵活塞用聚丙烯酸酯改性聚氨酯材料及制备方法
DE102020118671A1 (de) * 2020-07-15 2022-01-20 OSRAM Opto Semiconductors Gesellschaft mit beschränkter Haftung Verfahren zur herstellung eines bauelements und optoelektronisches bauelement
US11879023B2 (en) 2020-08-21 2024-01-23 United States Of America As Represented By The Secretary Of The Air Force Articles comprising crosslinked polymer network comprising thioether crosslinks and process of making and using same
CN111944119B (zh) * 2020-08-31 2022-09-06 上海奔佑新材料科技有限公司 一种用于3d打印手办的基于环保生物基的高韧性材料及其制备方法
USD1029255S1 (en) 2020-09-01 2024-05-28 Cilag Gmbh International Stapling cartridge assembly with a compressible adjunct
US11413819B2 (en) 2020-09-03 2022-08-16 NEXA3D Inc. Multi-material membrane for vat polymerization printer
WO2022060344A1 (en) * 2020-09-15 2022-03-24 Hewlett-Packard Development Company, L.P. Particulate build materials for three-dimensional printing
WO2022066565A1 (en) 2020-09-25 2022-03-31 Carbon, Inc. Epoxy dual cure resin for the production of moisture-resistant articles by additive manufacturing
CN112297669B (zh) * 2020-10-06 2022-06-07 杨帆 一种接触印相工艺的数码中间底的制作方法
WO2022076235A1 (en) 2020-10-09 2022-04-14 Carbon, Inc. Vapor spin cleaning of additively manufactured parts
CN112175224B (zh) * 2020-10-14 2022-10-14 泉州师范学院 一种提高fdm 3d打印tpu鞋材拉伸和耐折性能的方法
JP2023547826A (ja) 2020-10-19 2023-11-14 シーエムシー マテリアルズ リミティド ライアビリティ カンパニー 化学機械研磨パッドのために使用される紫外線硬化性樹脂
US11730224B2 (en) 2020-11-20 2023-08-22 LIFT Airborne Technologies LLC Latticed comfort liner
WO2022125881A1 (en) 2020-12-11 2022-06-16 Carbon, Inc. Force-regulated additive manufacturing
JP2022101228A (ja) 2020-12-24 2022-07-06 株式会社アシックス 靴底および靴
CN116323216A (zh) 2020-12-25 2023-06-23 株式会社藤仓 光造型装置、以及结构物的制造方法
CN112848304B (zh) * 2021-01-07 2023-01-24 青岛理工大学 一种电场辅助连续面曝光3d打印有序复合材料的制备方法
US11824510B2 (en) 2021-01-13 2023-11-21 Winchester Interconnect Corporation Balun
DE102021100620A1 (de) * 2021-01-14 2022-07-14 Bayerische Motoren Werke Aktiengesellschaft Verfahren zur additiven Herstellung eines dreidimensionalen Objekts
CN116724067A (zh) 2021-01-15 2023-09-08 赢创运营有限公司 硅酮氨基甲酸酯（甲基）丙烯酸酯以及它们在3d打印树脂和涂层组合物中的用途
KR102568142B1 (ko) * 2021-03-09 2023-08-22 (주)쓰리디머티리얼즈 우레아 반응 기반 3d 프린팅용 잉크 조성물 및 이를 이용한 3d 프린팅 방법
WO2022212475A1 (en) 2021-04-01 2022-10-06 Carbon, Inc. Hybrid surface lattices for additively manufactured products
WO2022212472A1 (en) 2021-04-01 2022-10-06 Carbon, Inc. Systems and methods for constructing lattice objects for additive manufacturing
WO2022225773A1 (en) 2021-04-22 2022-10-27 3D Systems, Inc. Stereolithography manufacturing system and method for high performance customized articles
US11950666B2 (en) * 2021-05-17 2024-04-09 EverWith Ltd. Method of manufacturing jewelry with artifacts such as cremation ashes embedded therein
EP4347679A1 (de) 2021-06-03 2024-04-10 Carbon, Inc. Verfahren zur schnellen herstellung von blockierten präpolymeren
WO2022266331A1 (en) 2021-06-16 2022-12-22 Carbon, Inc. Methods for surface coating additively manufactured objects
US11951679B2 (en) 2021-06-16 2024-04-09 General Electric Company Additive manufacturing system
US11731367B2 (en) 2021-06-23 2023-08-22 General Electric Company Drive system for additive manufacturing
US20220411634A1 (en) 2021-06-24 2022-12-29 Henkel Ag & Co. Kgaa Silicone formulation with high temperature stability and clarity
US11958249B2 (en) 2021-06-24 2024-04-16 General Electric Company Reclamation system for additive manufacturing
JP2023003758A (ja) 2021-06-24 2023-01-17 株式会社アシックス 靴底および靴
JP2023003757A (ja) 2021-06-24 2023-01-17 株式会社アシックス 緩衝材、靴底および靴
US11958250B2 (en) 2021-06-24 2024-04-16 General Electric Company Reclamation system for additive manufacturing
US20220411563A1 (en) 2021-06-28 2022-12-29 Covestro Llc Novel dual cure 3d printing resins
US11891469B2 (en) 2021-06-28 2024-02-06 Stratasys, Inc. Urethane acrylate composition
US11952457B2 (en) 2021-06-30 2024-04-09 Carbon, Inc. Bioabsorbable resin for additive manufacturing with non-cytotoxic photoinitiator
US11826950B2 (en) 2021-07-09 2023-11-28 General Electric Company Resin management system for additive manufacturing
KR20240039033A (ko) 2021-08-02 2024-03-26 바스프 에스이 우렛디온-함유 화합물을 포함하는 이중-경화 수지 조성물 및 이의 3d 프린팅에서의 용도
WO2023018757A1 (en) * 2021-08-10 2023-02-16 The Regents Of The University Of Colorado, A Body Corporate Systems and methods for three-dimensional printing
WO2023023188A1 (en) * 2021-08-19 2023-02-23 PolySpectra, Inc. Methods of making compositions from olefin metathesis photopolymers
WO2023028502A2 (en) 2021-08-24 2023-03-02 Carbon, Inc. Versatile lattice cell transitioning for additively manufactured products
US11884000B2 (en) 2021-08-27 2024-01-30 Carbon, Inc. One part, catalyst containing, moisture curable dual cure resins for additive manufacturing
WO2023031693A1 (en) * 2021-08-31 2023-03-09 3M Innovative Properties Company Infiltrated three-dimensional articles and methods of making same
US11813799B2 (en) 2021-09-01 2023-11-14 General Electric Company Control systems and methods for additive manufacturing
WO2023031140A1 (en) 2021-09-03 2023-03-09 Readily3D Sa Method for digital analytic correction of photoresponsive material reactivity in additive manufacturing
CA3231708A1 (en) * 2021-09-07 2023-03-16 University Of Maine System Board Of Trustees Selective particle entrapment and applications thereof
EP4155820A1 (de) * 2021-09-22 2023-03-29 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Echtzeitgesteuerte und -verifizierte mehrphotonenlithographie
US11912800B2 (en) 2021-09-29 2024-02-27 Johnson & Johnson Vision Care, Inc. Amide-functionalized polymerization initiators and their use in the manufacture of ophthalmic lenses
WO2023056425A1 (en) * 2021-10-01 2023-04-06 Bixby International Corporation Process for 3d printing of dental aligners
EP4166332A1 (de) * 2021-10-12 2023-04-19 Evonik Operations GmbH Additive zur verwendung in 3d-drucktechnologien
WO2023091331A1 (en) 2021-11-16 2023-05-25 Carbon, Inc. Method for additively manufacturing composite objects for securing to wearable articles and articles obtained thereby
WO2023091487A1 (en) * 2021-11-17 2023-05-25 The Johns Hopkins University Customized external cranioplasty and method of production
CN113929869B (zh) * 2021-11-29 2022-08-16 四川大学 双组份3d打印用聚脲材料以及3d打印聚脲制品的方法
JP2023104151A (ja) 2022-01-17 2023-07-28 株式会社アシックス 靴底および靴
JP2023152534A (ja) 2022-04-04 2023-10-17 株式会社アシックス 靴底および靴
WO2023220523A1 (en) 2022-05-09 2023-11-16 Carbon, Inc. Method for direct coloration of resins for additive manufacturing
WO2023225298A1 (en) * 2022-05-19 2023-11-23 Quadratic 3D, Inc. Volumetric three-dimensional (3d) printing system
WO2023230378A1 (en) * 2022-05-27 2023-11-30 3D Architech, Inc. Additive manufacturing and post-treatment of inorganic materials
WO2024002742A1 (en) 2022-06-29 2024-01-04 Evonik Operations Gmbh Silicone urethane (meth)acrylates and their use in coating compositions
WO2024011245A2 (en) * 2022-07-08 2024-01-11 Samtec, Inc. Additive manufactured waveguide
WO2024033289A1 (en) 2022-08-12 2024-02-15 Basf Se A photocurable oligomer containing uretdione groups, method of preparing the oligomer and dual-cure resin composition containing the oligomer thereof
WO2024059071A1 (en) * 2022-09-12 2024-03-21 Skyphos Industries, Inc. Additive manufacturing platform, resin, and improvements for microdevice fabrication
WO2024059259A1 (en) * 2022-09-15 2024-03-21 Rutgers, The State University Of New Jersey Composition and method for a root canal sealer
WO2024059936A1 (en) * 2022-09-20 2024-03-28 National Research Council Of Canada Three-dimensional surface patterning
WO2024069272A1 (en) * 2022-09-30 2024-04-04 National Research Council Of Canada Method of volumetric additive manufacturing
WO2024099798A1 (en) 2022-11-08 2024-05-16 Evonik Operations Gmbh Radiation curable compositions for additive manufacturing of high toughness articles
KR102639891B1 (ko) * 2022-11-10 2024-02-28 주식회사 월드바이오텍 실리콘 기반 형상 기억 고분자 및 이를 이용한 치아 교정 장치
US11890812B1 (en) * 2022-12-01 2024-02-06 Amplifi Tech (Xiamen) Limited 3D printing method and 3D printing formed body
CN116253985A (zh) * 2023-03-15 2023-06-13 山东基舜节能建材有限公司 一种玻璃纤维增强聚氨酯泡沫塑料及其制备方法
CN116120750B (zh) * 2023-04-04 2023-10-27 中国海洋大学 抗杀一体的复合弹性体、制备方法及防污应用

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120068A1 (en) * 1998-09-22 2002-08-29 Zms, Llc Near-net-shape polymerization process and materials suitable for use therewith
US20040126694A1 (en) * 2000-06-15 2004-07-01 Devoe Robert J. Microfabrication of organic optical elements
US20070205528A1 (en) * 2004-03-22 2007-09-06 Huntsman Advanced Materials Americans Inc. Photocurable Compositions
US20090107009A1 (en) * 2006-05-03 2009-04-30 Ashton Walter Bishop Footwear
US20120058314A1 (en) * 2009-05-15 2012-03-08 Kensuke Mikami Waterproof structure for electronic device
US20120077038A1 (en) * 2010-09-29 2012-03-29 Bayer Materialscience Llc A process for incorporating an interpenetrating network or blend into the surface layer of a polymeric article
US20130291404A1 (en) * 2012-05-03 2013-11-07 John William Follows Recovery shoe
US20140128132A1 (en) * 2012-10-12 2014-05-08 James L. Cox, III Case with interchangeable back plates
US8758860B1 (en) * 2012-11-07 2014-06-24 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior

Family Cites Families (311)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7695A (en) 1850-10-08 beaumont
US643A (en) 1838-03-17 John allen
US43955A (en) 1864-08-23 Improved
US3213058A (en) 1960-12-19 1965-10-19 American Cyanamid Co Polymers reacted with benzotriazole uv absorbers
USRE31406E (en) 1972-06-16 1983-10-04 Syntex (U.S.A.) Inc. Oxygen permeable contact lens composition, methods and article of manufacture
US3947426A (en) 1974-04-12 1976-03-30 Story Chemical Corporation Solid particle-form polymerizable polymeric material and compositions, structures and methods of employing and producing the same
NL7702518A (nl) 1977-03-09 1978-09-12 Akzo Nv Werkwijze voor het bekleden van een substraat met een stralingshardbare bekledingskompositie.
US4133118A (en) 1977-05-06 1979-01-09 Khalsa Gurujot S Footwear construction
GB2030584B (en) 1978-10-03 1983-03-23 Lankro Chem Ltd Photopolymerisable solder resist compositions
US4337130A (en) 1980-06-25 1982-06-29 E. I. Du Pont De Nemours And Company Photocurable polyurethane film coatings
US4463143A (en) * 1981-12-28 1984-07-31 Ford Motor Company Diblocked diisocyanate urea urethane oligomers and coating compositions comprising same
US4528081A (en) 1983-10-03 1985-07-09 Loctite Corporation Dual curing silicone, method of preparing same and dielectric soft-gel compositions thereof
JPS60177029A (ja) 1984-02-21 1985-09-11 Toray Silicone Co Ltd オルガノポリシロキサン組成物の硬化方法
US5554336A (en) 1984-08-08 1996-09-10 3D Systems, Inc. Method and apparatus for production of three-dimensional objects by stereolithography
US5236637A (en) 1984-08-08 1993-08-17 3D Systems, Inc. Method of and apparatus for production of three dimensional objects by stereolithography
US4575330A (en) * 1984-08-08 1986-03-11 Uvp, Inc. Apparatus for production of three-dimensional objects by stereolithography
US4677179A (en) 1986-04-09 1987-06-30 W. R. Grace Storage stable, heat curable, coating composition
US4849320A (en) 1986-05-10 1989-07-18 Ciba-Geigy Corporation Method of forming images
DE3616681A1 (de) 1986-05-16 1987-11-19 Bayer Ag 1-aralkylpyrazole
US5051115A (en) 1986-05-21 1991-09-24 Linde Aktiengesellschaft Pressure swing adsorption process
ES2063737T3 (es) 1986-06-03 1995-01-16 Cubital Ltd Aparato y metodo para modelizacion tridimensional.
US5263130A (en) 1986-06-03 1993-11-16 Cubital Ltd. Three dimensional modelling apparatus
US4801477A (en) 1987-09-29 1989-01-31 Fudim Efrem V Method and apparatus for production of three-dimensional objects by photosolidification
US5141665A (en) 1987-03-31 1992-08-25 Sherman Laboratories, Inc. Cleaning, conditioning, storing and wetting system and method for rigid gas permeable contact lenses and other contact lenses
US4923906A (en) 1987-04-30 1990-05-08 Ciba-Geigy Corporation Rigid, gas-permeable polysiloxane contact lenses
US5070170A (en) 1988-02-26 1991-12-03 Ciba-Geigy Corporation Wettable, rigid gas permeable, substantially non-swellable contact lens containing block copolymer polysiloxane-polyoxyalkylene backbone units, and use thereof
JPH01233443A (ja) 1988-03-15 1989-09-19 Fujitsu Ltd パターン形成方法
US4996282A (en) 1988-03-24 1991-02-26 Desoto, Inc. Cationically curable polyurethane compositions having vinyl ether functionality
US5776409A (en) 1988-04-18 1998-07-07 3D Systems, Inc. Thermal stereolithograp using slice techniques
US5059359A (en) 1988-04-18 1991-10-22 3 D Systems, Inc. Methods and apparatus for production of three-dimensional objects by stereolithography
US5182056A (en) 1988-04-18 1993-01-26 3D Systems, Inc. Stereolithography method and apparatus employing various penetration depths
WO1989010254A1 (en) 1988-04-18 1989-11-02 3D Systems, Inc. Stereolithographic supports
US5711911A (en) 1988-04-18 1998-01-27 3D Systems, Inc. Method of and apparatus for making a three-dimensional object by stereolithography
US5256340A (en) 1988-04-18 1993-10-26 3D Systems, Inc. Method of making a three-dimensional object by stereolithography
US5772947A (en) 1988-04-18 1998-06-30 3D Systems Inc Stereolithographic curl reduction
US5523193A (en) 1988-05-31 1996-06-04 Texas Instruments Incorporated Method and apparatus for patterning and imaging member
US4972006A (en) 1988-09-08 1990-11-20 Desoto, Inc. Postcuring of unsaturated stereolithographic specimens using aqueous initiating baths
US5258146A (en) 1988-09-26 1993-11-02 3D Systems, Inc. Method of and apparatus for measuring and controlling fluid level in stereolithography
JPH0757532B2 (ja) 1988-10-19 1995-06-21 松下電工株式会社 三次元形状の形成方法
US5171490A (en) 1988-11-29 1992-12-15 Fudim Efrem V Method and apparatus for production of three-dimensional objects by irradiation of photopolymers
US5011635A (en) * 1989-05-18 1991-04-30 Desoto, Inc. Stereolithographic method and apparatus in which a membrane separates phases
US5143663A (en) 1989-06-12 1992-09-01 3D Systems, Inc. Stereolithography method and apparatus
JPH03244528A (ja) 1989-09-28 1991-10-31 Three D Syst Inc 実質的に平担な立体平版加工面の形成装置および方法
US5143817A (en) 1989-12-22 1992-09-01 E. I. Du Pont De Nemours And Company Solid imaging system
DE4004620C1 (en) * 1990-02-15 1991-09-05 Du Pont De Nemours (Deutschland) Gmbh, 6380 Bad Homburg, De Photo-structured layer of three=dimensional object prodn. - by using fusible plastisol or organosol contg. unsatd. monomer, photoinitiator and thermally reactive cpd.
GB9008577D0 (en) 1990-04-17 1990-06-13 Pilkington Diffractive Lenses Rigid gas permeable lenses
US5158858A (en) 1990-07-05 1992-10-27 E. I. Du Pont De Nemours And Company Solid imaging system using differential tension elastomeric film
US5192559A (en) 1990-09-27 1993-03-09 3D Systems, Inc. Apparatus for building three-dimensional objects with sheets
US5198159A (en) 1990-10-09 1993-03-30 Matsushita Electric Works, Ltd. Process of fabricating three-dimensional objects from a light curable resin liquid
US5122441A (en) * 1990-10-29 1992-06-16 E. I. Du Pont De Nemours And Company Method for fabricating an integral three-dimensional object from layers of a photoformable composition
US5597520A (en) 1990-10-30 1997-01-28 Smalley; Dennis R. Simultaneous multiple layer curing in stereolithography
US5271882A (en) 1990-11-09 1993-12-21 Tokai Kogyo Kabushiki Kaisha Blow molding process with sheet interposed between mold and product being molded
US5212048A (en) 1990-11-21 1993-05-18 Presstek, Inc. Silicone coating formulations and planographic printing plates made therewith
US5510226A (en) 1991-05-01 1996-04-23 Alliedsignal Inc. Stereolithography using vinyl ether-epoxide polymers
DE4125534A1 (de) 1991-08-01 1993-02-18 Eos Electro Optical Syst Verfahren und vorrichtung zum herstellen eines objekts mittels stereograhpie
EP0525578A1 (de) 1991-08-02 1993-02-03 E.I. Du Pont De Nemours And Company Photopolymerzusammensetzung zur Herstellung von dreidimensionalen Objekten
US5162469A (en) 1991-08-05 1992-11-10 Optical Research Inc. Composition for rigid gas permeable contact lenses
US5247180A (en) 1991-12-30 1993-09-21 Texas Instruments Incorporated Stereolithographic apparatus and method of use
US5296283A (en) 1992-01-13 1994-03-22 E. I. Du Pont De Nemours And Company Protective coating for machine-readable markings
EP0627911B1 (de) 1992-02-28 2000-10-25 Board Of Regents The University Of Texas System Photopolymerinierbare, biologisch abbaubare hydrogele als gewebekontaktmaterialien und trägerstoffe für kontrollierte freisetzung
CA2092131A1 (en) * 1992-03-27 1993-09-28 Victor Kadziela (Nmi) Low viscosity self-toughening acrylate composition
EP0579503B1 (de) 1992-07-17 1997-11-05 Ethicon Inc. Strahlenhärtbare Urethan-Acrylatprepolymere und vernetzte Polymere
US5310571A (en) 1992-09-01 1994-05-10 Allergan, Inc. Chemical treatment to improve oxygen permeability through and protein deposition on hydrophilic (soft) and rigid gas permeable (RGP) contact lenses
US5264061A (en) 1992-10-22 1993-11-23 Motorola, Inc. Method of forming a three-dimensional printed circuit assembly
TW269017B (de) 1992-12-21 1996-01-21 Ciba Geigy Ag
US5836313A (en) 1993-02-08 1998-11-17 Massachusetts Institute Of Technology Methods for making composite hydrogels for corneal prostheses
US5679719A (en) 1993-03-24 1997-10-21 Loctite Corporation Method of preparing fiber/resin composites
US5374500A (en) 1993-04-02 1994-12-20 International Business Machines Corporation Positive photoresist composition containing photoacid generator and use thereof
WO1995001355A1 (en) 1993-06-30 1995-01-12 Biocryst Pharmaceuticals, Inc. 9-deazahypoxanthines as pnp inhibitors
DE4326986C1 (de) * 1993-08-11 1994-12-22 Eos Electro Optical Syst Verfahren und Vorrichtung zum Herstellen von dreidimensionalen Objekten
EP0643329B2 (de) 1993-08-26 2002-02-06 Vantico AG Flüssige strahlungshärtbare Zusammensetzung, insbesondere für die Stereolithographie
US5418112A (en) 1993-11-10 1995-05-23 W. R. Grace & Co.-Conn. Photosensitive compositions useful in three-dimensional part-building and having improved photospeed
DE9319405U1 (de) 1993-12-17 1994-03-31 Forschungszentrum Informatik A Vorrichtung zur Herstellung eines dreidimensionalen Objekts (Modells) nach dem Prinzip der Photoverfestigung
EP0757621B1 (de) * 1994-04-25 2001-11-21 3D Systems, Inc. Fortschrittliche bautechniken in stereolithografie
US5705116A (en) 1994-06-27 1998-01-06 Sitzmann; Eugene Valentine Increasing the useful range of cationic photoinitiators in stereolithography
IL112140A (en) * 1994-12-25 1997-07-13 Cubital Ltd Method of forming three dimensional objects
JPH08192469A (ja) 1995-01-20 1996-07-30 Ushio Inc 光硬化性樹脂の硬化装置
TW350851B (en) 1995-01-31 1999-01-21 Ciba Sc Holding Ag Polymerizable composition and process for the preparation of network polymer
US5573721A (en) 1995-02-16 1996-11-12 Hercules Incorporated Use of a support liquid to manufacture three-dimensional objects
JP3246848B2 (ja) 1995-02-22 2002-01-15 アピックヤマダ株式会社 汎用ゲート位置樹脂モールド装置および樹脂モールド方法
JP2949121B2 (ja) 1995-03-13 1999-09-13 桐山 義行 紫外線硬化方法
JP3594263B2 (ja) 1995-03-25 2004-11-24 竹本油脂株式会社 光学的立体造形物の形成工程における光硬化性液状組成物層へのレベリング性付与方法
US5707780A (en) 1995-06-07 1998-01-13 E. I. Du Pont De Nemours And Company Photohardenable epoxy composition
KR0150766B1 (ko) 1995-08-19 1998-10-15 유현식 난연성을 갖는 열가소성 수지 조성물
JP3668310B2 (ja) * 1996-01-22 2005-07-06 三菱レイヨン株式会社 光学的立体造形用樹脂組成物
US5691541A (en) 1996-05-14 1997-11-25 The Regents Of The University Of California Maskless, reticle-free, lithography
JPH106346A (ja) 1996-06-19 1998-01-13 Takemoto Oil & Fat Co Ltd プラスチック成形型の製造方法及びプラスチック成形型
US6312134B1 (en) 1996-07-25 2001-11-06 Anvik Corporation Seamless, maskless lithography system using spatial light modulator
ES2144836T3 (es) 1996-07-29 2000-06-16 Ciba Sc Holding Ag Composicion liquida reticulable por radiacion, en especial para estereolitografia.
JP3724893B2 (ja) 1996-09-25 2005-12-07 ナブテスコ株式会社 光学的立体造形用樹脂組成物
US6054250A (en) 1997-02-18 2000-04-25 Alliedsignal Inc. High temperature performance polymers for stereolithography
JP2001527590A (ja) 1997-02-18 2001-12-25 アライド シグナル インコーポレイテッド ステレオリソグラフィのための耐熱性ポリマー
DE69800652T2 (de) 1997-02-25 2001-08-23 Du Pont Flexible, flammhemmende fotopolymerisierbare Zusammensetzung zur Beschichtung von Leiterplatten
US5945058A (en) 1997-05-13 1999-08-31 3D Systems, Inc. Method and apparatus for identifying surface features associated with selected lamina of a three-dimensional object being stereolithographically formed
CA2302685A1 (en) 1997-08-21 1999-02-25 Lester Bennington Dual curing silicone compositions
US6154596A (en) 1998-03-26 2000-11-28 Hughes Electronics Corporation Front end preparation procedure for efficient coupling and improved power handling of light into a multi-mode fiber
US6100007A (en) 1998-04-06 2000-08-08 Ciba Specialty Chemicals Corp. Liquid radiation-curable composition especially for producing cured articles by stereolithography having high heat deflection temperatures
JP2000007641A (ja) * 1998-06-17 2000-01-11 Takemoto Oil & Fat Co Ltd 光学的立体造形用樹脂及び光学的立体造形用樹脂組成物
EP1090061A4 (de) 1998-06-24 2002-01-30 Loctite Corp Auf zweierlei art härtbare siliconzusammensetzung
DE19860041A1 (de) 1998-12-23 2000-06-29 Basf Ag Durch Addition an Isocyanatgruppen als auch durch strahlungsinduzierte Addition an aktivierte C-C-Doppelbindungen härtbare Beschichtungsmittel
US6238852B1 (en) 1999-01-04 2001-05-29 Anvik Corporation Maskless lithography system and method with doubled throughput
US6391245B1 (en) 1999-04-13 2002-05-21 Eom Technologies, L.L.C. Method for creating three-dimensional objects by cross-sectional lithography
US6214276B1 (en) 1999-05-18 2001-04-10 Creo Srl Method of forming objects from thermosensitive composition
WO2000077085A1 (en) 1999-06-11 2000-12-21 Sydney Hyman Image making medium
US6248509B1 (en) 1999-07-27 2001-06-19 James E. Sanford Maskless photoresist exposure system using mems devices
US6658314B1 (en) * 1999-10-06 2003-12-02 Objet Geometries Ltd. System and method for three dimensional model printing
DE19961926A1 (de) 1999-12-22 2001-07-05 Basf Coatings Ag Thermisch mit aktinischer Strahlung härtbare Stoffgemische und ihre Verwendung
JP3971541B2 (ja) 1999-12-24 2007-09-05 富士通株式会社 半導体装置の製造方法及びこの方法に用いる分割金型
US6380285B1 (en) 2000-02-01 2002-04-30 Ciba Specialty Chemicals Corporation Bloom-resistant benzotriazole UV absorbers and compositions stabilized therewith
US6547552B1 (en) 2000-02-08 2003-04-15 Efrem V. Fudim Fabrication of three-dimensional objects by irradiation of radiation-curable materials
US7300619B2 (en) * 2000-03-13 2007-11-27 Objet Geometries Ltd. Compositions and methods for use in three dimensional model printing
DE10015408A1 (de) 2000-03-28 2001-10-11 Fraunhofer Ges Forschung Verfahren und Vorrichtung zur Herstellung von Bauteilen aus lichtaushärtbaren Werkstoffen
GB2361005B (en) 2000-04-04 2002-08-14 Ciba Sc Holding Ag Synergistic mixtures of uv-absorbers in polyolefins
EP1142912A1 (de) 2000-04-05 2001-10-10 Dsm N.V. Strahlungshärtbare Zusammensetzungen
DE10018987A1 (de) 2000-04-17 2001-10-31 Envision Technologies Gmbh Vorrichtung und Verfahren zum Herstellen von dreidimensionalen Objekten
US6309797B1 (en) 2000-04-26 2001-10-30 Spectra Group Limited, Inc. Selectively colorable polymerizable compositions
US7318718B2 (en) 2000-06-06 2008-01-15 Teijin Seiki Co., Ltd. Stereolithographic apparatus and method for manufacturing three-dimensional object
KR100583095B1 (ko) 2000-06-30 2006-05-24 주식회사 하이닉스반도체 광산 발생제와 함께 광 라디칼 발생제(ｐｒｇ)를 포함하는포토레지스트 조성물
US6500378B1 (en) 2000-07-13 2002-12-31 Eom Technologies, L.L.C. Method and apparatus for creating three-dimensional objects by cross-sectional lithography
US6649113B1 (en) * 2000-08-11 2003-11-18 Chris R. Manners Method to reduce differential shrinkage in three-dimensional stereolithographic objects
TW557298B (en) 2000-08-14 2003-10-11 Ciba Sc Holding Ag A compound, a photopolymerizible composition, a process for producing coatings and a method for causing a photoinitiator to accumulate at the surface of coatings
US6439869B1 (en) 2000-08-16 2002-08-27 Micron Technology, Inc. Apparatus for molding semiconductor components
DE10044670C1 (de) 2000-09-09 2002-06-13 Basf Coatings Ag Thermisch oder thermisch und mit aktinischer Strahlung härtbarer, nicht wäßriger Beschichtungsstoff, Verfahren zu seiner Herstellung und seine Verwendung
US6939940B2 (en) 2000-09-13 2005-09-06 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration Liquid crystalline thermosets from ester, ester-imide, and ester-amide oligomers
US6916855B2 (en) 2000-11-22 2005-07-12 Dsm Ip Assets B.V. Radiation curable compositions
JP4382978B2 (ja) 2000-12-04 2009-12-16 学校法人神奈川大学 光硬化性・熱硬化性樹脂組成物
JP4584478B2 (ja) * 2001-03-19 2010-11-24 コダック株式会社 画像形成方法
DE10115505B4 (de) * 2001-03-29 2007-03-08 Basf Coatings Ag Thermisch und mit aktinischer Strahlung härtbare wäßrige Dispersionen, Verfahren zu ihrer Herstellung und ihre Verwendung
DE20106887U1 (de) 2001-04-20 2001-09-06 Envision Technologies Gmbh Vorrichtung zum Herstellen eines dreidimensionalen Objekts
DE10119817A1 (de) 2001-04-23 2002-10-24 Envision Technologies Gmbh Vorrichtung und Verfahren für die zerstörungsfreie Trennung ausgehärteter Materialschichten von einer planen Bauebene
US7095484B1 (en) 2001-06-27 2006-08-22 University Of South Florida Method and apparatus for maskless photolithography
JP4312598B2 (ja) * 2001-07-26 2009-08-12 チバ ホールディング インコーポレーテッド 感光性樹脂組成物
US7023432B2 (en) 2001-09-24 2006-04-04 Geomagic, Inc. Methods, apparatus and computer program products that reconstruct surfaces from data point sets
US6841589B2 (en) 2001-10-03 2005-01-11 3D Systems, Inc. Ultra-violet light curable hot melt composition
US20030173713A1 (en) 2001-12-10 2003-09-18 Wen-Chiang Huang Maskless stereo lithography method and apparatus for freeform fabrication of 3-D objects
US20090047634A1 (en) * 2001-12-28 2009-02-19 Randall Rex Calvert Apparatus and method for root canal obturation
US7081291B2 (en) 2002-01-11 2006-07-25 Domco Tarkett Inc. Selectively embossed surface coverings and processes of manufacture
GB0212977D0 (en) 2002-06-06 2002-07-17 Vantico Ag Actinic radiation curable compositions and their use
JP2005534063A (ja) 2002-07-19 2005-11-10 ザ リージェンツ オブ ザ ユニバーシティ オブ コロラド， ア ボディー コーポレイト ３ｄ光重合デバイスの製造
US6833231B2 (en) 2002-07-31 2004-12-21 3D Systems, Inc. Toughened stereolithographic resin compositions
US7235195B2 (en) 2002-09-06 2007-06-26 Novartis Ag Method for making opthalmic devices
US7093756B2 (en) 2002-10-31 2006-08-22 Sap Aktiengesellschaft Distributed production control
US7750059B2 (en) 2002-12-04 2010-07-06 Hewlett-Packard Development Company, L.P. Polymer solution for nanoimprint lithography to reduce imprint temperature and pressure
US7211368B2 (en) 2003-01-07 2007-05-01 3 Birds, Inc. Stereolithography resins and methods
US20040170923A1 (en) 2003-02-27 2004-09-02 3D Systems, Inc. Colored stereolithographic resins
US6932930B2 (en) 2003-03-10 2005-08-23 Synecor, Llc Intraluminal prostheses having polymeric material with selectively modified crystallinity and methods of making same
US7105584B2 (en) 2003-04-18 2006-09-12 Nscg, Inc. Dual-cure silicone compounds exhibiting elastomeric properties
CN1997691B (zh) 2003-09-23 2011-07-20 北卡罗来纳大学查珀尔希尔分校 光固化的全氟聚醚用作微流体器件中的新材料
JP4044505B2 (ja) 2003-09-29 2008-02-06 独立行政法人科学技術振興機構 光酸発生剤
EP1682161A4 (de) 2003-10-29 2011-12-07 Gentis Inc Polymerisierbare emulsionen für die gewebeherstellung
US20050101684A1 (en) 2003-11-06 2005-05-12 Xiaorong You Curable compositions and rapid prototyping process using the same
WO2005101466A2 (en) 2003-12-19 2005-10-27 The University Of North Carolina At Chapel Hill Methods for fabricating isolated micro- and nano- structures using soft or imprint lithography
CA2554160A1 (en) 2004-01-23 2005-09-22 The University Of North Carolina At Chapel Hill Liquid materials for use in electrochemical cells
US8158728B2 (en) 2004-02-13 2012-04-17 The University Of North Carolina At Chapel Hill Methods and materials for fabricating microfluidic devices
DE102004012903A1 (de) 2004-03-17 2005-10-06 Bayer Materialscience Ag Niedrigviskose Allophanate mit aktinisch härtbaren Gruppen
JP5496457B2 (ja) 2004-03-24 2014-05-21 ポリィノボ バイオマテリアルズ ピーティワイ リミテッド 生分解性ポリウレタン及びポリウレタン尿素
DE102004022606A1 (de) 2004-05-07 2005-12-15 Envisiontec Gmbh Verfahren zur Herstellung eines dreidimensionalen Objekts mit verbesserter Trennung ausgehärteter Materialschichten von einer Bauebene
DE102004022961B4 (de) 2004-05-10 2008-11-20 Envisiontec Gmbh Verfahren zur Herstellung eines dreidimensionalen Objekts mit Auflösungsverbesserung mittels Pixel-Shift
EP1894705B1 (de) 2004-05-10 2010-08-25 Envisiontec GmbH Verfahren und Vorrichtung zur Herstellung eines dreidimensionalen Objekts mit Auflösungsverbesserung mittels Pixel-Shift
US7649029B2 (en) 2004-05-17 2010-01-19 3M Innovative Properties Company Dental compositions containing nanozirconia fillers
US7097302B2 (en) 2004-07-03 2006-08-29 Mcgregor Scott D Rigid gas permeable contact lens with 3-part curvature
US7556490B2 (en) 2004-07-30 2009-07-07 Board Of Regents, The University Of Texas System Multi-material stereolithography
US7292207B1 (en) 2004-08-27 2007-11-06 Sun Microsystems, Inc. Computing blending functions for the tiling of overlapped video projectors
EP1784302B1 (de) 2004-09-01 2016-07-06 Encapsys, Llc Verkapselte aushärtungssysteme
CA2584104C (en) 2004-10-19 2012-12-11 Rolls-Royce Corporation Method and apparatus associated with anisotropic shrink in sintered ceramic items
US7571556B2 (en) 2004-12-28 2009-08-11 Saucony, Inc. Heel grid system
US20060239986A1 (en) * 2005-01-26 2006-10-26 Perez-Luna Victor H Method for the formation of hydrogel multilayers through surface initiated photopolymerization
KR100637450B1 (ko) 2005-02-16 2006-10-23 한양대학교 산학협력단 플루오로알킬술폰늄염의 광산발생기가 치환된 화합물과 이를 중합한 공중합체
EP1705228A1 (de) 2005-03-22 2006-09-27 Nederlandse Organisatie voor toegepast-natuurwetenschappelijk Onderzoek TNO Härtbare Zusammensetzungen für Druckverfahren mit Hilfe eines kontinuierlichen Tintenstrahls und Methode dafür
US7358283B2 (en) 2005-04-01 2008-04-15 3D Systems, Inc. Radiation curable compositions useful in image projection systems
US7906061B2 (en) * 2005-05-03 2011-03-15 3D Systems, Inc. Bubble-free cross-sections for use in solid imaging
EP1720163A1 (de) * 2005-05-05 2006-11-08 Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. Filmformende lichtempfindliche Materialien für die von Licht eingeführte Erzeugung optischer Anisotropie
US7344731B2 (en) 2005-06-06 2008-03-18 Bausch & Lomb Incorporated Rigid gas permeable lens material
US7709544B2 (en) 2005-10-25 2010-05-04 Massachusetts Institute Of Technology Microstructure synthesis by flow lithography and polymerization
US8808815B2 (en) 2005-10-25 2014-08-19 Isp Investments Inc. Inkjet-receptive article
US20070178133A1 (en) * 2005-11-09 2007-08-02 Liquidia Technologies, Inc. Medical device, materials, and methods
DE602005013536D1 (de) 2005-11-18 2009-05-07 Agfa Graphics Nv Verfahren zur Herstellung einer Lithografiedruckform
US20070191506A1 (en) 2006-02-13 2007-08-16 3M Innovative Properties Company Curable compositions for optical articles
CN100340388C (zh) * 2006-03-03 2007-10-03 南京师范大学 制作三维物体和支撑的打印成型方法
WO2007124092A2 (en) 2006-04-21 2007-11-01 Cornell Research Foundation, Inc. Photoacid generator compounds and compositions
DE102006019963B4 (de) 2006-04-28 2023-12-07 Envisiontec Gmbh Vorrichtung und Verfahren zur Herstellung eines dreidimensionalen Objekts durch schichtweises Verfestigen eines unter Einwirkung von elektromagnetischer Strahlung verfestigbaren Materials mittels Maskenbelichtung
DE102006019964C5 (de) 2006-04-28 2021-08-26 Envisiontec Gmbh Vorrichtung und Verfahren zur Herstellung eines dreidimensionalen Objekts mittels Maskenbelichtung
CN101384959B (zh) 2006-05-01 2012-01-11 Dsmip财产有限公司 辐射固化树脂组合物及应用其的快速三维成像方法
US7636610B2 (en) 2006-07-19 2009-12-22 Envisiontec Gmbh Method and device for producing a three-dimensional object, and computer and data carrier useful therefor
US7524615B2 (en) 2006-08-14 2009-04-28 Gary Ganghui Teng Negative laser sensitive lithographic printing plate having specific photosensitive composition
US9415544B2 (en) 2006-08-29 2016-08-16 3D Systems, Inc. Wall smoothness, feature accuracy and resolution in projected images via exposure levels in solid imaging
EP2066721B1 (de) 2006-09-29 2017-12-27 Basf Se Fotolatente basen für systeme auf der basis von blockierten isocyanaten
EP2069866A2 (de) 2006-10-03 2009-06-17 Ciba Holding Inc. Lichthärtbare zusammensetzungen
US20080103226A1 (en) 2006-10-31 2008-05-01 Dsm Ip Assets B.V. Photo-curable resin composition
JP2010509090A (ja) 2006-11-10 2010-03-25 エンヴィジョンテック ゲーエムベーハー ３次元物体製造用連続生成法
US7892474B2 (en) 2006-11-15 2011-02-22 Envisiontec Gmbh Continuous generative process for producing a three-dimensional object
US8404173B2 (en) 2006-11-17 2013-03-26 Poof Technologies, Llc Polymer object optical fabrication process
US8128393B2 (en) 2006-12-04 2012-03-06 Liquidia Technologies, Inc. Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom
DE602006013855D1 (de) 2006-12-21 2010-06-02 Agfa Graphics Nv Tintenstrahldruckverfahren und Tintensätze
WO2008076184A1 (en) 2006-12-21 2008-06-26 Dow Corning Corporation Dual curing polymers and methods for their preparation and use
JP5073284B2 (ja) 2006-12-22 2012-11-14 ローランドディー．ジー．株式会社 三次元造形装置
US8003039B2 (en) 2007-01-17 2011-08-23 3D Systems, Inc. Method for tilting solid image build platform for reducing air entrainment and for build release
US8524816B2 (en) 2007-03-15 2013-09-03 Magni Industries, Inc. Coating resistant to bio-diesel fuels
ITVE20070020A1 (it) 2007-04-02 2008-10-03 Bifrangi S P A Pressa orizzontale perfezionata per forgiatura.
KR101514093B1 (ko) * 2007-04-03 2015-04-21 바스프 에스이 광활성화가능한 질소 염기
JP2010523776A (ja) * 2007-04-11 2010-07-15 バイエル・マテリアルサイエンス・アクチェンゲゼルシャフト 放射線硬化性および熱架橋性のポリ（ε−カプロラクトン）ポリエステルポリオールをベースとするＰＵ系
DE102007021245A1 (de) 2007-05-07 2008-11-13 Meiko Maschinenbau Gmbh & Co.Kg Desinfektionssteuerung durch Zielerregerauswahl
US7961157B2 (en) 2007-05-14 2011-06-14 Christie Digital Systems Usa, Inc. Configurable imaging system
DE102007024469B4 (de) * 2007-05-25 2009-04-23 Eos Gmbh Electro Optical Systems Verfahren zum schichtweisen Herstellen eines dreidimensionalen Objekts
WO2008151063A2 (en) * 2007-05-31 2008-12-11 Milton Meisner High definition versatile stereolithic method and material
JP2009013397A (ja) 2007-06-04 2009-01-22 Nitto Denko Corp 熱可塑性樹脂発泡体、およびその製造方法
US20090004579A1 (en) 2007-06-27 2009-01-01 Dsm Ip Assets B.V. Clear and colorless three-dimensional articles made via stereolithography and method of making said articles
EP2011631B1 (de) 2007-07-04 2012-04-18 Envisiontec GmbH Verfahren und Vorrichtung zum Herstellen eines dreidimensionalen Objekts
US20090035350A1 (en) 2007-08-03 2009-02-05 John Stankus Polymers for implantable devices exhibiting shape-memory effects
AT505533A1 (de) 2007-08-14 2009-02-15 Austria Tech & System Tech Verfahren zur herstellung von in einem auf einem träger aufgebrachten, insbesondere flexiblen polymermaterial ausgebildeten, optischen wellenleitern sowie leiterplatte und verwendung
DE102007040240A1 (de) 2007-08-25 2009-02-26 Bayer Materialscience Ag Verfahren zur Herstellung von niedrigviskosen Allophanaten mit aktinisch härtbaren Gruppen
EP2195361B1 (de) * 2007-10-03 2014-11-26 Polynovo Biomaterials Limited Hochmodulige polyurethan- und polyurethan/harnstoff-zusammensetzungen
EP2052693B2 (de) * 2007-10-26 2021-02-17 Envisiontec GmbH Verfahren und Formlosfabrikationssystem zur Herstellung eines dreidimensionalen Gegenstands
US7862176B2 (en) 2007-11-24 2011-01-04 Truform Optics Method of fitting rigid gas-permeable contact lenses from high resolution imaging
US8377623B2 (en) * 2007-11-27 2013-02-19 3D Systems, Inc. Photocurable resin composition for producing three dimensional articles having high clarity
US20090145314A1 (en) 2007-12-07 2009-06-11 Chemque, Inc. Intaglio Printing Methods, Apparatuses, and Printed or Coated Materials Made Therewith
US8286236B2 (en) 2007-12-21 2012-10-09 The Invention Science Fund I, Llc Manufacturing control system
EP2240405A4 (de) 2008-02-05 2011-06-15 John M Crain Beschichtungen mit funktionalisierten graphenschichten und damit beschichtete gegenstände
US7902526B2 (en) 2008-04-28 2011-03-08 Massachusetts Institute Of Technology 3D two-photon lithographic microfabrication system
DE102008028187A1 (de) 2008-06-12 2009-12-17 Giesecke & Devrient Gmbh Sicherheitselement mit optisch variablem Element.
TW201011531A (en) 2008-09-03 2010-03-16 Asustek Comp Inc Computer system and related method of logging BIOS update operation
US8666142B2 (en) 2008-11-18 2014-03-04 Global Filtration Systems System and method for manufacturing
US20100140850A1 (en) 2008-12-04 2010-06-10 Objet Geometries Ltd. Compositions for 3D printing
JP5492406B2 (ja) 2008-12-05 2014-05-14 株式会社ダイナ楽器 樹脂成形品のコーティング方法及び樹脂成形品
FR2940019B1 (fr) 2008-12-22 2011-03-25 Salomon Sas Chaussure a semelage ameliore
US8777602B2 (en) * 2008-12-22 2014-07-15 Nederlandse Organisatie Voor Tobgepast-Natuurwetenschappelijk Onderzoek TNO Method and apparatus for layerwise production of a 3D object
WO2010077097A2 (ko) 2008-12-30 2010-07-08 주식회사 캐리마 고속 적층식 광조형 장치
CN101776846B (zh) 2009-01-14 2012-07-18 北京光创物成材料科技有限公司 激光造型专用光固化组合物
JP2010248466A (ja) 2009-03-25 2010-11-04 Toyo Ink Mfg Co Ltd ラミネート用印刷インキ組成物
US8289346B2 (en) 2009-05-06 2012-10-16 Christie Digital Systems Usa, Inc. DLP edge blending artefact reduction
US20100323301A1 (en) 2009-06-23 2010-12-23 Huey-Ru Tang Lee Method and apparatus for making three-dimensional parts
US8446406B2 (en) 2009-07-03 2013-05-21 Lg Display Co., Ltd. Liquid crystal display
US9433256B2 (en) 2009-07-21 2016-09-06 Reebok International Limited Article of footwear and methods of making same
US8102332B2 (en) 2009-07-21 2012-01-24 Seiko Epson Corporation Intensity scaling for multi-projector displays
US8372330B2 (en) 2009-10-19 2013-02-12 Global Filtration Systems Resin solidification substrate and assembly
JP5503257B2 (ja) 2009-11-12 2014-05-28 株式会社トップ 組織回収袋
KR101995185B1 (ko) 2009-12-17 2019-07-01 디에스엠 아이피 어셋츠 비.브이. 트라이아릴 설포늄 보레이트 양이온 광개시제를 포함하는 적층식 제작을 위한 액체 방사선 경화성 수지
IT1397457B1 (it) 2010-01-12 2013-01-10 Dws Srl Piastra di modellazione per una macchina stereolitografica, macchina stereolitografica impiegante tale piastra di modellazione e utensile per la pulizia di tale piastra di modellazione.
JP2011143615A (ja) * 2010-01-14 2011-07-28 Asahi Kasei E-Materials Corp ３次元形状を有する構造体の製造方法及び３次元形状を有する構造体
KR101006414B1 (ko) 2010-03-10 2011-01-06 주식회사 캐리마 고속 적층식 광조형 장치
DE102010003884A1 (de) * 2010-04-12 2011-10-13 Voco Gmbh Dualhärtende, mehrkomponentige dentale Zusammensetzung
US8603612B2 (en) * 2010-04-22 2013-12-10 Xerox Corporation Curable compositions for three-dimensional printing
JP6027533B2 (ja) 2010-08-20 2016-11-16 ケース ウェスタン リザーブ ユニバーシティＣａｓｅ Ｗｅｓｔｅｒｎ Ｒｅｓｅｒｖｅ Ｕｎｉｖｅｒｓｉｔｙ インプラントの連続デジタル光処理による付加的製造
WO2012041519A2 (de) 2010-10-01 2012-04-05 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Photovernetzende elastomere für rapid prototyping
US20120080824A1 (en) 2010-10-01 2012-04-05 Acushnet Company Cast polyurethane and polyurea covers for golf balls
EP2436510A1 (de) 2010-10-04 2012-04-04 3D Systems, Inc. System und Harz zur schnellen Prototypisierung
CN102020911A (zh) * 2010-10-12 2011-04-20 广州贝特新材料有限公司 一种低挥发光凝浸渍绝缘漆
US8466250B2 (en) 2010-10-18 2013-06-18 Basf Se High-functionality polyetherols and preparation and use thereof
EP2632696B1 (de) * 2010-10-27 2020-07-29 Rize Inc. Verfahren und vorrichtung für die herstellung von dreidimensionalen gegenständen
KR20130141604A (ko) * 2010-11-19 2013-12-26 헨켈 코포레이션 접착제 조성물 및 이의 용도
US9309341B2 (en) 2010-12-20 2016-04-12 Agfa Graphics Nv Curable jettable fluid for making a flexographic printing master
WO2012106256A1 (en) * 2011-01-31 2012-08-09 Global Filtration Systems Method and apparatus for making three-dimensional objects from multiple solidifiable materials
DE102011015223A1 (de) 2011-03-25 2012-09-27 Heraeus Kulzer Gmbh Dualhärtbare Zusammensetzung, Verfahren zu ihrer Herstellung und die Verwendung zur Herstellung von Beschichtungen
CN102715751A (zh) 2011-03-30 2012-10-10 朱雪兵 凝胶垫及其紫外固化生产方法
CN102746785B (zh) 2011-04-19 2014-12-17 比亚迪股份有限公司 一种双重固化涂料组合物及其固化方法
CN106939078B (zh) 2011-05-09 2020-12-11 沙特阿美技术公司 聚合物组合物及方法
DE102011075544A1 (de) * 2011-05-10 2012-11-15 Evonik Röhm Gmbh Mehrfarbiger Fused Deposition Modeling Druck
EP2720852B1 (de) * 2011-06-15 2017-11-29 DSM IP Assets B.V. Verfahren und vorrichtung zur herstellung eines substratbasierten zusatzes
EP2537675B1 (de) 2011-06-21 2013-12-11 Agfa Graphics N.V. Härtbare, strahlbare Flüssigkeit zur Herstellung einer flexographischen Druckvorlage
JP5674041B2 (ja) 2011-08-11 2015-02-18 株式会社ダイフク 物品搬送設備
WO2013142830A1 (en) 2012-03-22 2013-09-26 The Regents Of The University Of Colorado, A Body Corporate Liquid deposition photolithography
US8869866B2 (en) 2012-04-15 2014-10-28 Christie Digital Systems Usa, Inc. Tiled display rotational assembly
US8786788B2 (en) 2012-04-20 2014-07-22 Mersive Technologies, Inc. System and method for image aspect preservation in multiple projector alignment
US9120270B2 (en) 2012-04-27 2015-09-01 University Of Southern California Digital mask-image-projection-based additive manufacturing that applies shearing force to detach each added layer
US9636873B2 (en) * 2012-05-03 2017-05-02 B9Creations, LLC Solid image apparatus with improved part separation from the image plate
US8860640B2 (en) 2012-05-30 2014-10-14 Christie Digital Systems Usa, Inc. Zonal illumination for high dynamic range projection
ITVI20120188A1 (it) 2012-07-30 2014-01-31 Dws Srl Confezione di resina stereolitografica e metodo di mescolamento di una resina stereolitografica contenuta in tale confezione
US20140055544A1 (en) 2012-08-27 2014-02-27 Camtek Ltd. Curable ink and a method for printing and curing the curable ink
JP5988775B2 (ja) 2012-08-29 2016-09-07 日立オートモティブシステムズ株式会社 ウォータポンプ
US20140085620A1 (en) 2012-09-24 2014-03-27 Maxim Lobovsky 3d printer with self-leveling platform
CN105142450B (zh) 2012-12-19 2018-06-12 新平衡运动公司 定制鞋类以及用于设计且制造其的方法
EP2935289B1 (de) * 2012-12-19 2019-06-26 IGM Group B.V. Derivate von bisacylphosphinsäure, ihre herstellung und verwendung als photoinitiatoren
CN203254661U (zh) 2012-12-31 2013-10-30 刘彦君 一种光固化快速成型装置
CN103029301B (zh) 2012-12-31 2016-02-10 刘彦君 一种光固化快速成型装置及其方法
EP2757118A1 (de) 2013-01-17 2014-07-23 Allnex Belgium, S.A. Strahlungshärtbare wässrige Zusammensetzungen mit umkehrbarer Trocknung
EP2956821B8 (de) 2013-02-12 2018-06-27 Carbon, Inc. Verfahren und vorrichtung für dreidimensionale herstellung
ES2588485T5 (es) 2013-02-12 2020-02-27 Carbon Inc Impresión de interfaz líquida continua
US9498920B2 (en) 2013-02-12 2016-11-22 Carbon3D, Inc. Method and apparatus for three-dimensional fabrication
WO2014165265A1 (en) 2013-03-12 2014-10-09 Dudley Kurt 3d printing using spiral buildup
US9573321B2 (en) 2013-03-14 2017-02-21 Stratasys Ltd. System and method for three-dimensional printing
WO2014159191A1 (en) 2013-03-14 2014-10-02 The Cleveland Clinic Foundation A method of producing a patient-specific three dimensional model having hard tissue and soft tissue portions
US20140265934A1 (en) 2013-03-15 2014-09-18 Federal-Mogul Corporation Vehicle interior lighting
CN112147844A (zh) 2013-07-04 2020-12-29 味之素株式会社 感光性树脂组合物
US10150258B2 (en) 2013-07-29 2018-12-11 Carnegie Mellon University Additive manufacturing of embedded materials
DE202013103446U1 (de) 2013-07-31 2013-08-26 Tangible Engineering Gmbh Kompakte Vorrichtung zur Herstellung eines dreidimensionalen Objekts durch Verfestigen eines fotohärtenden Materials
KR101956281B1 (ko) 2013-08-13 2019-03-08 삼성전기주식회사 수지 조성물, 이를 이용한 인쇄회로기판 및 그 제조방법
US9360757B2 (en) 2013-08-14 2016-06-07 Carbon3D, Inc. Continuous liquid interphase printing
US9456507B2 (en) 2013-10-07 2016-09-27 The Boeing Company Ecological method for constructing circuit boards
CN103571211A (zh) 2013-10-13 2014-02-12 甘春丽 双重固化组合物
JP6433651B2 (ja) 2013-11-21 2018-12-05 スリーエム イノベイティブ プロパティズ カンパニー 接着剤、接着剤付部材及び部材間の接続方法
CN103756236B (zh) 2014-01-06 2017-01-11 朱叶周 用于制备三维打印快速成型的软性打印材料的热塑性弹性体组合物
WO2015126834A1 (en) 2014-02-18 2015-08-27 Axletech International Ip Holdings, Llc Systems and methods for improved differential locks
CN103895231A (zh) 2014-04-09 2014-07-02 刘彦君 一种光固化快速成型装置及方法
WO2015164234A1 (en) 2014-04-25 2015-10-29 Carbon3D, Inc. Continuous three dimensional fabrication from immiscible liquids
CN105313332B (zh) 2014-06-09 2020-05-05 联合工艺公司 由两部分组成的热固性树脂增材制造系统
EP2955044B1 (de) 2014-06-14 2017-02-15 EFS-Gesellschaft für Hebe- und Handhabungstechnik mbh Montagevorrichtung zum Befestigen einer Dichtung
WO2015195924A1 (en) 2014-06-20 2015-12-23 Carbon3D, Inc. Three-dimensional printing with reciprocal feeding of polymerizable liquid
US10569465B2 (en) 2014-06-20 2020-02-25 Carbon, Inc. Three-dimensional printing using tiled light engines
WO2015195920A1 (en) 2014-06-20 2015-12-23 Carbon3D, Inc. Three-dimensional printing method using increased light intensity and apparatus therefore
EP4074485A1 (de) 2014-06-23 2022-10-19 Carbon, Inc. Verfahren zur herstellung von dreidimensionalen objekten aus materialien mit mehreren härtungsmechanismen
US9574039B1 (en) 2014-07-22 2017-02-21 Full Spectrum Laser Additive use in photopolymer resin for 3D printing to enhance the appearance of printed parts
EP3253558B1 (de) * 2015-02-05 2020-04-08 Carbon, Inc. Verfahren zur generativen fertigung durch herstellung durch mehrere zonen
KR20170115070A (ko) * 2015-02-05 2017-10-16 카본, 인크. 비연속 노광에 의한 적층체 제조방법
WO2016145050A1 (en) 2015-03-10 2016-09-15 Carbon3D, Inc. Microfluidic devices having flexible features and methods of making the same
EP3297950B1 (de) 2015-05-19 2020-11-04 Lawrence Carlson Stabiles basisches elektrolytmaterial und lösungsmittelmaterial damit
US9708440B2 (en) 2015-06-18 2017-07-18 Novoset, Llc High temperature three dimensional printing compositions
US10343331B2 (en) 2015-12-22 2019-07-09 Carbon, Inc. Wash liquids for use in additive manufacturing with dual cure resins
WO2017112571A1 (en) 2015-12-22 2017-06-29 Carbon, Inc. Dual cure additive manufacturing of rigid intermediates that generate semi-rigid, flexible, or elastic final products
US10647054B2 (en) 2015-12-22 2020-05-12 Carbon, Inc. Accelerants for additive manufacturing with dual cure resins
WO2017112653A1 (en) 2015-12-22 2017-06-29 Carbon, Inc. Dual precursor resin systems for additive manufacturing with dual cure resins
US10500786B2 (en) 2016-06-22 2019-12-10 Carbon, Inc. Dual cure resins containing microwave absorbing materials and methods of using the same

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020120068A1 (en) * 1998-09-22 2002-08-29 Zms, Llc Near-net-shape polymerization process and materials suitable for use therewith
US20040126694A1 (en) * 2000-06-15 2004-07-01 Devoe Robert J. Microfabrication of organic optical elements
US20070205528A1 (en) * 2004-03-22 2007-09-06 Huntsman Advanced Materials Americans Inc. Photocurable Compositions
US20090107009A1 (en) * 2006-05-03 2009-04-30 Ashton Walter Bishop Footwear
US20120058314A1 (en) * 2009-05-15 2012-03-08 Kensuke Mikami Waterproof structure for electronic device
US20120077038A1 (en) * 2010-09-29 2012-03-29 Bayer Materialscience Llc A process for incorporating an interpenetrating network or blend into the surface layer of a polymeric article
US20130291404A1 (en) * 2012-05-03 2013-11-07 John William Follows Recovery shoe
US20140128132A1 (en) * 2012-10-12 2014-05-08 James L. Cox, III Case with interchangeable back plates
US8758860B1 (en) * 2012-11-07 2014-06-24 Bayer Materialscience Llc Process for incorporating an ion-conducting polymer into a polymeric article to achieve anti-static behavior

Cited By (108)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10575586B2 (en) 2013-03-14 2020-03-03 Under Armour, Inc. Shoe with lattice structure
US11425963B2 (en) 2013-03-14 2022-08-30 Under Armour, Inc. Shoe with lattice structure
US10470520B2 (en) 2013-03-14 2019-11-12 Under Armour, Inc. Shoe with lattice structure
US10150280B2 (en) 2013-05-14 2018-12-11 Holo, Inc. Apparatus for fabrication of three dimensional objects
US11707893B2 (en) 2014-06-23 2023-07-25 Carbon, Inc. Methods for producing three-dimensional objects with apparatus having feed channels
US11440266B2 (en) 2014-06-23 2022-09-13 Carbon, Inc. Methods of producing epoxy three-dimensional objects from materials having multiple mechanisms of hardening
US10968307B2 (en) 2014-06-23 2021-04-06 Carbon, Inc. Methods of producing three-dimensional objects from materials having multiple mechanisms of hardening
US11850803B2 (en) 2014-06-23 2023-12-26 Carbon, Inc. Methods for producing three-dimensional objects with apparatus having feed channels
US10166725B2 (en) 2014-09-08 2019-01-01 Holo, Inc. Three dimensional printing adhesion reduction using photoinhibition
US10213956B2 (en) 2014-09-08 2019-02-26 Holo, Inc. Three dimensional printing adhesion reduction using photoinhibition
US10737438B2 (en) 2015-02-05 2020-08-11 Carbon, Inc. Method of additive manufacturing by fabrication through multiple zones
US10155345B2 (en) 2015-02-05 2018-12-18 Carbon, Inc. Method of additive manufacturing by fabrication through multiple zones
US10750820B2 (en) 2015-05-08 2020-08-25 Under Armour, Inc. Midsole lattice with hollow tubes for footwear
US10702012B2 (en) 2015-05-08 2020-07-07 Under Armour, Inc. Footwear midsole with lattice structure formed between platforms
US11076656B2 (en) 2015-06-29 2021-08-03 Adidas Ag Soles for sport shoes
US11090859B2 (en) 2015-09-04 2021-08-17 Carbon, Inc. Cyanate ester epoxy dual cure resins for additive manufacturing
US11040483B2 (en) 2015-09-04 2021-06-22 Carbon, Inc. Cyanate ester dual cure resins for additive manufacturing
US10471655B2 (en) 2015-09-04 2019-11-12 Carbon, Inc. Cyanate ester dual resins for additive manufacturing
US11814472B2 (en) 2015-09-09 2023-11-14 Carbon, Inc. Epoxy dual cure resins for additive manufacturing
US10975193B2 (en) 2015-09-09 2021-04-13 Carbon, Inc. Epoxy dual cure resins for additive manufacturing
US10647873B2 (en) 2015-10-30 2020-05-12 Carbon, Inc. Dual cure article of manufacture with portions of differing solubility
US11141919B2 (en) 2015-12-09 2021-10-12 Holo, Inc. Multi-material stereolithographic three dimensional printing
US11845225B2 (en) 2015-12-09 2023-12-19 Holo, Inc. Multi-material stereolithographic three dimensional printing
US10350823B2 (en) 2015-12-22 2019-07-16 Carbon, Inc. Dual precursor resin systems for additive manufacturing with dual cure resins
US11833744B2 (en) 2015-12-22 2023-12-05 Carbon, Inc. Dual precursor resin systems for additive manufacturing with dual cure resins
US11440244B2 (en) 2015-12-22 2022-09-13 Carbon, Inc. Dual precursor resin systems for additive manufacturing with dual cure resins
CN109311225A (zh) * 2016-06-20 2019-02-05 B9创造有限责任公司 一种用于减少三维增材制造生产时间的系统和方法
US11097451B2 (en) 2016-06-20 2021-08-24 B9Creations, LLC System and method for reducing three-dimensional additive manufacturing production time
JP7169270B2 (ja) 2016-06-20 2022-11-10 ビー９クリエーションズ エルエルシー 三次元付加製造生産時間を削減するためのシステムおよび方法
WO2017222602A1 (en) * 2016-06-20 2017-12-28 B9Creations, LLC System and method for reducing three-dimensional additive manufacturing production time
US10150257B1 (en) 2016-06-20 2018-12-11 B9Creations, LLC System and method for reducing three-dimensional additive manufacturing production time
JP2019518638A (ja) * 2016-06-20 2019-07-04 ビー９クリエーションズ エルエルシー 三次元付加製造生産時間を削減するためのシステムおよび方法
US10384374B2 (en) 2016-06-20 2019-08-20 B9Creations, LLC System and method for reducing three-dimensional additive manufacturing production time
US11685117B2 (en) 2016-07-01 2023-06-27 Carbon, Inc. Three-dimensional printing methods for reducing bubbles by de-gassing through build plate
US20180056607A1 (en) * 2016-08-30 2018-03-01 Microsoft Technology Licensing, Llc Printing three dimensional objects using perforated brims
US11518087B2 (en) * 2016-09-12 2022-12-06 University Of Washington Vat photopolymerization additive manufacturing of multi-material parts
WO2018057330A1 (en) * 2016-09-12 2018-03-29 University Of Washington Vat photopolymerization additive manufacturing of multi-material parts
WO2018085758A1 (en) * 2016-11-07 2018-05-11 Dscales, Llc System for printing three dimensional objects using a liquid-matrix support
US10232552B2 (en) 2016-11-07 2019-03-19 Dscales, Llc Method for three dimensional printing
US20190039306A1 (en) * 2016-11-07 2019-02-07 Dscales. Llc System for printing three dimensional objects using a liquid-matrix support
CN110177673A (zh) * 2016-11-07 2019-08-27 迪斯卡尔斯有限责任公司 用于使用液体基质支撑物打印三维物体的系统
WO2018118832A1 (en) 2016-12-23 2018-06-28 Carbon, Inc. Adhesive sheet for securing 3d object to carrier platform and method of using same
US11629202B2 (en) 2017-01-05 2023-04-18 Carbon, Inc. Dual cure stereolithography resins containing thermoplastic particles
WO2018129023A1 (en) 2017-01-05 2018-07-12 Carbon, Inc. Dual cure stereolithography resins containing diels-alder adducts
WO2018129020A1 (en) 2017-01-05 2018-07-12 Carbon, Inc. Dual cure stereolithography resins containing thermoplastic particles
US11208517B2 (en) 2017-01-05 2021-12-28 Carbon, Inc. Dual cure stereolithography resins containing diels-alder adducts
WO2018165090A1 (en) 2017-03-09 2018-09-13 Carbon, Inc. Tough, high temperature polymers produced by stereolithography
US10935891B2 (en) 2017-03-13 2021-03-02 Holo, Inc. Multi wavelength stereolithography hardware configurations
US11659889B2 (en) 2017-03-27 2023-05-30 Adidas Ag Footwear midsole with warped lattice structure and method of making the same
US10932521B2 (en) 2017-03-27 2021-03-02 Adidas Ag Footwear midsole with warped lattice structure and method of making the same
US10575588B2 (en) 2017-03-27 2020-03-03 Adidas Ag Footwear midsole with warped lattice structure and method of making the same
US11312066B2 (en) 2017-03-27 2022-04-26 Carbon, Inc. Method of making three-dimensional objects by additive manufacturing
WO2018182974A1 (en) 2017-03-27 2018-10-04 Carbon, Inc. Method of making three-dimensional objects by additive manufacturing
USD907904S1 (en) 2017-03-27 2021-01-19 Adidas Ag Shoe
US11376786B2 (en) 2017-04-21 2022-07-05 Carbon, Inc. Methods and apparatus for additive manufacturing
US10316213B1 (en) 2017-05-01 2019-06-11 Formlabs, Inc. Dual-cure resins and related methods
US10793745B2 (en) 2017-05-01 2020-10-06 Formlabs, Inc. Dual-cure resins and related methods
US11161301B2 (en) 2017-05-15 2021-11-02 Holo, Inc. Viscous film three-dimensional printing systems and methods
US10882251B2 (en) 2017-05-15 2021-01-05 Holo, Inc. Viscous film three-dimensional printing systems and methods
US10421233B2 (en) 2017-05-15 2019-09-24 Holo, Inc. Viscous film three-dimensional printing systems and methods
US10464259B2 (en) 2017-05-15 2019-11-05 Holo, Inc. Viscous film three-dimensional printing systems and methods
WO2018226943A1 (en) 2017-06-08 2018-12-13 Carbon, Inc. Blocking groups for light polymerizable resins useful in additive manufacturing
US11226559B2 (en) 2017-06-08 2022-01-18 Carbon, Inc. Blocking groups for light polymerizable resins useful in additive manufacturing
US10245785B2 (en) 2017-06-16 2019-04-02 Holo, Inc. Methods for stereolithography three-dimensional printing
US11400650B2 (en) 2017-06-16 2022-08-02 Holo, Inc. Methods and systems for stereolithography three-dimensional printing
US11724445B2 (en) 2017-06-21 2023-08-15 Carbon, Inc. Resin dispenser for additive manufacturing
US11458673B2 (en) 2017-06-21 2022-10-04 Carbon, Inc. Resin dispenser for additive manufacturing
US11135766B2 (en) 2017-06-29 2021-10-05 Carbon, Inc. Products containing nylon 6 produced by stereolithography and methods of making the same
US11548215B2 (en) 2017-06-30 2023-01-10 Nikon Corporation Method of producing an optical device and a corresponding system
US11654620B2 (en) * 2017-08-11 2023-05-23 Carbon, Inc. Serially curable resins useful in additive manufacturing
US20210394435A1 (en) * 2017-08-11 2021-12-23 Carbon, Inc. Serially curable resins useful in additive manufacturing
US11135765B2 (en) * 2017-08-11 2021-10-05 Carbon, Inc. Serially curable resins useful in additive manufacturing
US10414090B2 (en) 2017-10-02 2019-09-17 Global Filtration Systems Method of stabilizing a photohardening inhibitor-permeable film in the manufacture of three-dimensional objects
US10335997B2 (en) 2017-10-02 2019-07-02 Global Filtration Systems Method of stabilizing a photohardening inhibitor-permeable film in the manufacture of three-dimensional objects
US11220054B2 (en) 2017-10-02 2022-01-11 Global Filtration Systems Method of stabilizing a photohardening inhibitor-permeable film in the manufacture of three-dimensional objects
US11685110B2 (en) 2017-10-27 2023-06-27 Carbon, Inc. Reduction of polymerization inhibitor irregularity on additive manufacturing windows
US11400644B2 (en) * 2017-10-27 2022-08-02 Carbon, Inc. Reduction of polymerization inhibitor irregularity on additive manufacturing windows
USD879434S1 (en) 2018-02-15 2020-03-31 Adidas Ag Sole
USD879428S1 (en) 2018-02-15 2020-03-31 Adidas Ag Sole
USD880120S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
USD880131S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
USD882227S1 (en) 2018-02-15 2020-04-28 Adidas Ag Sole
USD880122S1 (en) 2018-02-15 2020-04-07 Adidas Ag Sole
US20210017381A1 (en) * 2018-03-30 2021-01-21 Arkema France Curable compositions for use as adhesives having properties capable of being altered based on external stimuli and methods of making and using the same
KR102672870B1 (ko) 2018-03-30 2024-06-05 아르끄마 프랑스 외부 자극을 기반으로 변형될 수 있는 특성을 가진 접착제로서 이용하기 위한 경화성 조성물 및 이의 제조 방법 및 이용 방법
US11993712B2 (en) * 2018-03-30 2024-05-28 Arkema France Curable compositions for use as adhesives having properties capable of being altered based on external stimuli and methods of making and using the same
US11440256B2 (en) 2018-06-15 2022-09-13 Howmedica Osteonics Corp. Stackable build plates for additive manufacturing powder handling
US11426818B2 (en) 2018-08-10 2022-08-30 The Research Foundation for the State University Additive manufacturing processes and additively manufactured products
US11167375B2 (en) 2018-08-10 2021-11-09 The Research Foundation For The State University Of New York Additive manufacturing processes and additively manufactured products
WO2020068720A1 (en) 2018-09-25 2020-04-02 Carbon, Inc. Dual cure resins for additive manufacturing
US11241822B2 (en) 2018-09-25 2022-02-08 Carbon, Inc. Dual cure resins for additive manufacturing
US11820072B2 (en) 2018-09-25 2023-11-21 Carbon, Inc. Dual cure resins for additive manufacturing
USD890485S1 (en) 2018-11-12 2020-07-21 Adidas Ag Shoe
US11351735B2 (en) 2018-12-26 2022-06-07 Holo, Inc. Sensors for three-dimensional printing systems and methods
US11832683B2 (en) 2019-12-27 2023-12-05 Asics Corporation Shock absorber, shoe sole and shoe
US11849799B2 (en) 2019-12-27 2023-12-26 Asics Corporation Shock absorber, shoe sole and shoe
DE102020124546B4 (de) 2020-09-21 2024-03-28 Audi Aktiengesellschaft 3D-Druckverfahren und Vorrichtung zur Herstellung eines 3D-Bauteils
DE102020124546A1 (de) 2020-09-21 2022-03-24 Audi Aktiengesellschaft 3D-Druckverfahren zur Herstellung eines 3D-Bauteils
US11786008B2 (en) 2020-10-07 2023-10-17 Adidas Ag Footwear with 3-D printed midsole
USD1022425S1 (en) 2020-10-07 2024-04-16 Adidas Ag Shoe
USD980595S1 (en) 2020-10-13 2023-03-14 Adidas Ag Shoe
US11589647B2 (en) 2020-10-13 2023-02-28 Adidas Ag Footwear midsole with anisotropic mesh and methods of making the same
US11992084B2 (en) 2020-10-13 2024-05-28 Adidas Ag Footwear midsole with 3-D printed mesh having an anisotropic structure and methods of making the same
USD980594S1 (en) 2020-10-13 2023-03-14 Adidas Ag Shoe
EP4049841A1 (de) 2021-02-26 2022-08-31 Cubicure GmbH Hybridharzzusammensetzung
WO2022180566A1 (en) 2021-02-26 2022-09-01 Cubicure Gmbh Hybrid resin composition for the 3d-printing of objects
EP4369098A1 (de) 2022-11-14 2024-05-15 Cubicure GmbH Harzzusammensetzung
WO2024105509A1 (en) 2022-11-14 2024-05-23 Cubicure Gmbh Resin composition

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