WO2017040883A1 - Cyanate ester dual cure resins for additive manufacturing - Google Patents

Cyanate ester dual cure resins for additive manufacturing Download PDF

Info

Publication number
WO2017040883A1
WO2017040883A1 PCT/US2016/050035 US2016050035W WO2017040883A1 WO 2017040883 A1 WO2017040883 A1 WO 2017040883A1 US 2016050035 W US2016050035 W US 2016050035W WO 2017040883 A1 WO2017040883 A1 WO 2017040883A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
percent
phenyl
weight
cyanatophenyl
Prior art date
Application number
PCT/US2016/050035
Other languages
French (fr)
Inventor
Matthew S. MENYO
Jason P. Rolland
Original Assignee
Carbon, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Carbon, Inc. filed Critical Carbon, Inc.
Priority to JP2018511267A priority Critical patent/JP7069006B2/en
Priority to CN201680051002.0A priority patent/CN108350145B/en
Priority to EP16766748.4A priority patent/EP3344676B1/en
Priority to US15/754,086 priority patent/US10471655B2/en
Publication of WO2017040883A1 publication Critical patent/WO2017040883A1/en
Priority to US16/576,844 priority patent/US11040483B2/en
Priority to US16/576,862 priority patent/US11090859B2/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10Processes of additive manufacturing
    • B29C64/106Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065Preparatory processes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/20Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B29C64/264Arrangements for irradiation
    • B29C64/277Arrangements for irradiation using multiple radiation means, e.g. micromirrors or multiple light-emitting diodes [LED]
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02Thermal after-treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00Processes of additive manufacturing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065Preparatory processes
    • C08G73/0655Preparatory processes from polycyanurates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/065Preparatory processes
    • C08G73/0655Preparatory processes from polycyanurates
    • C08G73/0661Preparatory processes from polycyanurates characterised by the catalyst used
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14Modified phenol-aldehyde condensates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0833Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using actinic light
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • B29C2035/0855Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation using microwave
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/02Thermal after-treatment
    • B29C2071/022Annealing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0805Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using electromagnetic radiation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2039/00Use of polymers with unsaturated aliphatic radicals and with a nitrogen or a heterocyclic ring containing nitrogen in a side chain or derivatives thereof as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2079/00Use of polymers having nitrogen, with or without oxygen or carbon only, in the main chain, not provided for in groups B29K2061/00 - B29K2077/00, as moulding material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B33ADDITIVE MANUFACTURING TECHNOLOGY
    • B33YADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00Materials specially adapted for additive manufacturing
    • B33Y70/10Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials

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.
  • Hull US Patent No. 5,236,637.
  • Other approaches are shown in US Patent No. 7,438,846, US Patent No. 7,892,474; M. Joyce, US Patent App. 2013/0292862; Y. Chen et al., US Patent App. 2013/0295212 (both Nov. 7, 2013); Y.
  • Cyanate esters are an important class of high-temperature thermosets used in aerospace, computing, and other industries. These materials have extremely high glass transition temperatures (up to 400°C), high tensile strength, high modulus, and low dielectric constant, dielectric loss and moisture uptake. The materials are low-viscosity liquids, semisolids, and solids that are thermally cured at elevated temperatures and have heretofore been considered therefore incompatible with traditional 3D printing (or so called additive manufacturing methods on their own).
  • cyanate esters with UV- curable oligomers and reactive diluents.
  • a curable resin incorporating a radiation- cured network and a heat-cured thermoset consisting of a cyanate ester is described.
  • This resin allows the creation of 3D printed parts. These parts exhibit desirable mechanical properties (ultimate tensile strength, modulus), desirable thermal properties (heat deflection temperature, glass transition temperature, degradation temperature, low thermal shrinkage), and/or desirable dielectric properties (low dielectric constant, low dielectric loss).
  • the method generally comprises:
  • said cyanate ester dual cure resin comprises:
  • At least one cyanate ester compound, and/or a prepolymer thereof e.g., a homoprepolymer and/or heteroprepolymer thereof, each said cyanate ester compound independently having a structure of Formula 1: wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic (e.g., C5 to C12 cycloaliphatic) group;
  • a filler e.g., silica, a toughener such as a core-shell rubber, etc., including combinations thereof;
  • a co-monomer and/or a co-prepolymer e.g., co-polymerizable with the aforesaid cyanate ester compound and/or prepolymer thereof.
  • Resins useful for carrying out such methods, and products produced from such methods, are also described.
  • a Lewis acid or an oxidizable tin salt is included in the polymerizable liquid or resin (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.
  • 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.
  • polymerizable liquids used in the present invention include 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 prcent 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 (Hi) an organic ultraviolet light absorber such as a hydroxybenzophcnonc, 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).
  • Non-limiting example dual cure of UV-curable network and cyanate ester network.
  • 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).
  • 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 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.
  • compositions useful for additive manufacturing comprise, consist of, or consist essentially of:
  • a photoinitiator e.g., a free-radical polymerization photoinitiator, including combinations thereof, particularly Ultraviolet light (UV) photoinitiators
  • a photoinitiator e.g., a free-radical polymerization photoinitiator, including combinations thereof, particularly Ultraviolet light (UV) photoinitiators
  • At least one cyanate ester compound, and/or a prepolymer thereof e.g., a homoprepolymer and/or heteroprepolymer thereof, each said cyanate ester compound independently having a structure of Formula I : wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic (e.g., C5 to C12 cycloaliphatic) group;
  • a filler e.g., silica
  • a co-monomer and/or a co-prepolymer e.g., co-po 1 ym erizabl c with the aforesaid cyanate ester compound and/or prepolymer thereof.
  • R is a phenyl, naphthyl. anthryl, phenanthryl. or pyrenyl group (usubstituted, or optionally substituted). (See, e.g., US Patent No. 3,448,079).
  • R is a phenyl, biphenyl, naphthyl, bisfphenyl (methane. bis(phenyl)ethane, bis(phenyl)propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis(phenyl)sulfone, bis(phcnyi) phosphine oxide. bis(phenyl)silane, bis( phenyl jhexafluoropropane, bi s(pheny 1 )tri fl uoroethane.
  • the cyanate ester compound is selected from the group consisting of: 1,3-, or 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene; 1,3,6-tricyanatoaphthalene; 2,2' or 4,4'-dicyanatobiphenyl; bis(4-cyanathophenyl) methane; 2,2-bis(4-cyanatophenyl) propane; 2,2-bis(3,5-dichloro-4- cyanatophenyl (propane.
  • said metal catalyst is a chelate or oxide of a metal selected from the group consisting of divalent copper, zinc, manganese, tin, lead, cobalt and nickel, trivalent iron, cobalt, manganese and aluminum, and tetravalent titanium (See, e.g., US Patent Nos. 4,785,075; 4,604,452; and 4,847,233).
  • the said metal catalyst is a metal salt of an organic acid of at least one metal selected from the group consisting of copper, zinc. lead, nickel, iron, tin and cobalt.
  • the metal catalyst is present in the range of 10 or 30 to 600, 1,00, or 10,000 microequivalents of said metal catalyst as compared to the total weight of said at least one cyanate ester or prepolymer thereof.
  • the nucleophilic co-catalyst is an alkylphenol or imidazole present in the amount of 2 or 5 to 60 or 100 milliequivalents of active hydrogen per equivalent of cyanate ester group.
  • the nucleophilic co-catalyst is selected from the group consisting of nonylphenol, dodecylphenol, o-cresol, 2-sec.butylphenol and 2,6 dinonylphenol, 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, l-benzyl-2-methylimidazole, l-propyl-2-methylimidazole, 1-cyanoethyl- 2-methylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 1 -eyanoethyl-2- undecylimidazole, l-cyanoethyl-2-phenylimidazole, or 1 -guanaminoethyl-2- methylimidazole, or water (including adventitious water absorption).
  • water including adventitious water
  • the nucleophilic co-catalyst is a component of the monomers and/or prepolymers, present in the amount of about 10 or 40 to about 400 or 800 milliequivalents of active hydrogen per equivalent of cyanate group.
  • the nucleophilic co-catalyst is absent (as a separate chemical entity) and wherein said monomers and/or prepolymers contain urethane, urea, and/or phenolic groups (and hence serves as an intrinsic nucleophilic co-catalyst).
  • the monomers and/or prepolymers polymerizable by exposure to actinic radiation or light comprising reactive end groups selected from the group consisting of acrylates, methacrylates, a -olefins, N-vinyls, acrylamides, methacryl amides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
  • reactive end groups selected from the group consisting of acrylates, methacrylates, a -olefins, N-vinyls, acrylamides, methacryl amides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
  • Any suitable co-monomer and/or prepolymer thereof that is polymerizable with the cyanate ester (or prepolymer thereof) may optionally be used in the present invention, including but not limited to amine, epoxy, phenol, bismaleimide, and benzoxazine co- monomers, and/or co-prepolymers thereof. See, e.g., J. Bauer and M. Bauer, Cyanate ester based resin systems for snap-cure applications, Microsystem Technologies 8, 58-62 (2002). Examines of suitable benzoxazine co-monomers and/or co-prepolymers include, but are not limited to.
  • benzoxazines derived from the reaction of formaldehyde and either aniline or methylamine with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4- hydroxyphenyl)methane (bisphenol F), 4.4 * thiodiphenol. See also US Patent Nos. 6,207,786, 5,543,516 and 6,620,905. Such benzoxazines may be incorporated into the composition in any suitable amount, such as from 0.1 or 5 percent by weight to 30 or 49 percent by weight.
  • 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.
  • reactive and non-reactive rubbers 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
  • the light absorbing pigment or dye is:
  • titanium dioxide e.g., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight
  • carbon black e.g., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight
  • an organic ultraviolet light absorber e.g., a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotri azoic ultraviolet light absorber
  • an organic ultraviolet light absorber e.g., a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotri azoic ultraviolet light absorber
  • the diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
  • the resin/polymerizable liquid comprises:
  • Cyanate ester prepolymers may be included in the composition in the form of prepolymers thereof.
  • the inclusion of such prepolymers can improve the properties of the three-dimensional object being produced, such as by reducing thermal shrinkage, reducing sweating, and/or reducing cracking during the second curing step, without substantially adversely affecting the properties of the final product.
  • Examples of such prepolymers include, but are not limited to, those based on 2,2-bis(4-hydroxyphenyl)propane dicyanate (bisphenol A dicyanate), 2,2-bis(4-hydroxyphenyl)ethane dicyanate (bisphenol E dicyanate), and cyanated novolacs.
  • All of the cyanate ester content of the composition may be provided in the form of prepolymers, or some of the cyanate ester content of the composition may be provided in the form of prepolymers ⁇ e.g., in a weight ratio of cyanate ester monomer(s) to cyanate prepolymer(s) of from 1 : 100 or 1 : 10 to 100: 1 or 10: 1 ).
  • these prepolymers comprise, consist of, or consist essentially of the reaction product of cyanate ester monomers reacted to degrees of conversion of the cyanate groups of from 1 or 5 percent to 20 or 40 percent (of initial cyanate functionality, group or substituents), leading to prepolymers with molecular weights of from 200 or 400 g/mol to 4,000 or 8,000 g/mol.
  • 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.
  • 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, di butyl tin dilaurate, dibutyl tin dioleate, dibutyl tin distearate, dipropyl tin dilaurate, dipropyl tin dioleate, dipropyl tin distearate, di
  • 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.
  • Tougheners 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, fuUerenes), 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 US2010028015 l Al (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 1632533 Al and EP 212371 1 Al 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 "J SR. 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 TPv-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 NANOPOXSTM 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 US Patent 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 aerylonitrile.
  • 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 MX 170. and Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
  • the shelf life of the resin, and/or the pot life of the resin during production of an object may be extended by including a stabilizer in the resin, typically in an amount of from about 0.001 or 0.01 percent by weight, up to 0.1, 0.5, or 1 percent by weight.
  • Suitable stabilizers include, but are not limited to, acids having a pKa below 2, such as p-toluene sulfonic acid, polyphosphoric acid esters, etc. See, e.g., US Patent No. 4,839,442.
  • the three dimensional intermediate is preferably formed from resins as described above by additive manufacturing, typically bottom-up or top-down additive manufacturing.
  • additive manufacturing typically bottom-up or top-down additive manufacturing.
  • Such methods are known and described in, for example, U.S. Patent No. 5,236,637 to Hull, US Patent Nos. 5,391.072 and 5.529.473 to Lawton.
  • U.S. Patent No. 8,110,135 to El-Siblani U.S. Patent Application Publication Nos. 2013/0292862 to Joyce and 2013/0295212 to Chen et al, and PCT Application Publicaiton No. WO 2015/164234 to Robeson et al.
  • the disclosures of these patents and applications are incorporated by reference herein in their entirety.
  • top-down three-dimensional fabrication is carried out by:
  • 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:
  • 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 thee 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).
  • CLIP is known and described in, for example, PCT Applications Nos. PCT US2014/015486 (published as US Patent No. 9,211,678 on December 15, 2015); PCT/US2014/015506 (also published as US Patent No. 9,205,601 on December 8, 2015), PCT/US2014/015497 (also published as US 2015/0097316, and to publish as US Patent No 9,216,546 on Dec. 22, 2015), and in J. Tumbleston, D. Shirvanyants, N. Ermoshkin et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (published online 16 March 2015).
  • CLIP employs features of a bottom-up three dimensional fabrication as described above, but the the irradiating and/or said advancing steps are carried out while also concurrently maintaining a stable or persistent liquid interface between the growing object and the build surface or window, such as by: (i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and (ii) continuously maintaining a gradient of polymerization zone (such as an active surface) between the dead zone and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the first component in partially cured form.
  • the optically transparent member comprises a semipermeable member (e.g., a fiuoropolymer). and the continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through the optically transparent member, thereby creating a gradient of inhibitor in the dead zone and optionally in at least a portion of the gradient of polymerization zone.
  • the stable liquid interface may be achieved by other techniques, such as by providing an immiscible liquid as the build surface between the polymerizable liquid and the optically transparent member, by feeding a lubricant to the build surface (e.g., through an optically transparent member which is semipermeable thereto, and/or serves as a reservoir thereof), etc.
  • 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.
  • 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 may be employed.
  • gas inhibitors which are dissolved in liquids e.g. oils or lubricants may be employed.
  • oxygen dissolved in a fluorinated fluid may be employed. 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.
  • 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).
  • CLIP may be carried out in different operating modes operating modes (that is, different manners of advancing the carrier and build surface away from one another), including continuous, intermittent, reciprocal, and combinations thereof.
  • the advancing step is carried out continuously, at a uniform or variable rate, with either constant or intermittent illumination or exposure of the build area to the light source.
  • 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.
  • 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 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 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 soli dill able or polymerizable liquid is changed at least once during the method with a subsequent solidifiable or polymerizable liquid (e.g., by switching a "window " or "build surface " and associated reservoir of polymerizable liquid in the apparatus): 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 e.g., a rigid funnel or liquid connector segment, covalently coupled to a flexible pipe or tube segment).
  • the three-dimensional intermediate may be removed from the carrier, optionally washed, any supports optionally removed, any other modifications optionally made (cutting, welding, adhesively bonding, joining, grinding, drilling, etc. ), and then heated and/or microwave irradiated sufficiently to further cure the resin and form the three dimensional object.
  • additional modifications may also be made following the heating and/or microwave irradiating step.
  • Washing may be carried out with any suitable organic or aqueous wash liquid, or combination thereof, including solutions, suspensions, emulsions, microemulsions, etc.
  • suitable wash liquids include, but are not limited to water, alcohols (e.g., methanol, ethanol. isopropanol. etc. ). benzene, toluene, etc.
  • wash solutions may optionally contain additional constituents such as surfactants, etc.
  • a currently preferred wash liquid is a 50:50 (volume: olume) solution of water and isopropanol. Wash methods such as those described in US Patent No. 5,248,456 may be employed and are included therein.
  • 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.
  • the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300 °C (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature).
  • the intermediate may be heated in a stepwise manner at a first temperature of about 70°C to about 150°C, and then at a second temperature of about 150°C to 200 or 250 °C, with the duration of each heating depending on the size, shape, and/or thickness of the intermediate.
  • the intermediate may be cured by a ramped heating schedule, with the temperature ramped from ambient temperature through a temperature of 70 to 150 °C, and up to a final (oven) temperature of 250 or 300 °C, at a change in heating rate of 0.5°C per minute, to 5 °C per minute. (See, e.g., US Patent No. 4,785,075).
  • the resins and methods described above are particularly useful for making three- dimensional objects that are strong and stiff, and/or tolerate high temperatures.
  • Examples of products that may be produced by the methods and resins described herein include, but are not limited to, heat shields or housings in automobiles, aircraft, and boats (e.g., "under-the- hood” heat shields or housings), as micro-meteor deflectors for satellites and spacecraft, as pump housings, impellers, injection molds, injection mold cores, healthcare applications where parts must survive high temperature for sterilization, electronics packaging, etc.
  • the methods and resins described herein are used to make surgical instruments (for example, retractors, dilators, dissectors and probes, graspers such as forceps, clamps and occluders for blood vessels and other organs, distracters, suction tips, housings for powered devices such as surgical drills and dermatomes, scopes and probes, measurement instruments such as rulers and calipers, handles for cutting instruments such as scalpels and scissors, cataract removal instruments, surgical jigs and guides such as for orthopedic surgery, etc.).
  • Intraoral devices including, but not limited to, surgical guides for dental applications, retainers for corrective orthodontic applications, palatal expanders, tongue thrust instruments, trays for delivery of drugs and bleaching agents, etc.).
  • the instruments may be computer-generated custom instruments, or patient-specific instruments.
  • patient-specific instruments that may be made with the materials and compositions described herein include, but are not limited to, custom jigs for removal of bone tumors; custom jigs and guides for orthopedic surgery, etc. See. e.g., US Patent Nos.
  • the formed material was washed and cured for 30 minutes at 140°C, 30 minutes at 160°C, 2 hours at 180°C, 1 hour at 220°C, and 1 hour at 240°C to yield the desired product.
  • the mechanical properties of dual cured products were evaluated by producing dual cured three dimensional mechanical test samples (e.g., "dog bone” samples) in the foregoing manner. Material properties are given in Table 1 below. Table 1. Materials properties of product
  • This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 5 mW/cm 2 at a speed of 100 mm/hour.
  • CLIP continuous liquid interface production
  • the formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, 60 minutes at 220°C, and 60 minutes at 240°C to yield the desired product.
  • the mechanical properties of products produced from such resins resins were evaluated by producing dual cured mechanical test samples in this manner, and are given in Table 3 below. Table 3. Materials properties of product.
  • This resin was formed into an intermediate product using continuous liquid interface production (CLIP) in continuous print mode, using a 385 nm LED projector with a light intensity of 5 mW/cm at a print speed of 100 mm/hour.
  • CLIP continuous liquid interface production
  • the formed material was washed and pre-cured for 90 minutes at 95 °C.
  • the final product part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product.
  • the mechanical properties of products so produced were evaluated by producing mechanical test samples from the dual cure resins.
  • This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 5 mW/cm at a print speed of 100 mm/hour.
  • CLIP continuous liquid interface production
  • the formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product.
  • the mechanical properties of parts so produced were evaluated by directly producing mechanical test samples, and are given in Table 4 below.
  • This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm at a speed of 133 mm/hour.
  • CLIP continuous liquid interface production
  • the formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product.
  • the mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 6 below.
  • This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm 2 at a speed of 133 mm/hour.
  • CLIP continuous liquid interface production
  • the part was cured for 60 minutes at 95 °C. 120 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product.
  • the mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 7 below. In addition to the decrease in thermal shrinkage, the amount of resin bleed and part cracking during thermal cure decreased dramatically from 0-27% prepolymer conversion.
  • This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm 2 at a speed of 133 mm/hour.
  • CLIP continuous liquid interface production
  • the part was cured for 60 minutes at 95°C, 120 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product.
  • the mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 8 below. Table 8. Materials properties of product

Abstract

A method of forming a three-dimensional object is carried out by: (a) providing a cyanate ester dual cure resin; (b) forming a three-dimensional intermediate from said resin, where said intermediate has the shape of, or a shape to be imparted to, said three-dimensional object, and where said resin is solidified by exposure to light; (c) optionally washing the three-dimensional intermediate, and then (d) heating and/or microwave irradiating said three-dimensional intermediate sufficiently to further cure said resin and form said three-dimensional object. Compositions useful for carrying out the method, and products made from the method, are also described.

Description

CYANATE ESTER DUAL CURE RESINS
FOR ADDITIV E MANUFACTURING
Matthew S. Menyo and Jason P. Rolland
Related Applications
This application claims the benefit of United States Provisional Patent Application Serial No. 62/214,601, filed September 4, 2015, and of United States Provisional Patent Application Serial No. 62/270,635, filed December 22, 2015, the disclosures of which are incorporated by reference herein in their entirety.
Field of the Invention
The present invention concerns materials, methods and apparatus for the fabrication of solid three-dimensional objects from liquid materials, and objects so produced.
Background of the Invention
In conventional additive or three-dimensional fabrication techniques, construction of a three-dimensional object is performed in a step-wise or layer-by-layer manner. In particular, 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 early example is Hull, US Patent No. 5,236,637. Other approaches are shown in US Patent No. 7,438,846, US Patent No. 7,892,474; M. Joyce, US Patent App. 2013/0292862; Y. Chen et al., US Patent App. 2013/0295212 (both Nov. 7, 2013); Y. Pan et al., ./. Manufacturing Sci. and Eng. 134, 05101 1 -1 (Oct. 2012), and numerous other references. Materials for use in such apparatus are generally limited, and there is a need for new resins which will provide diverse material properties for different product families if three-dimensional fabrication is to achieve its full potential.
Southwell, Xu et al., US Patent Application Publication No. 2012/0251841 , describe liquid radiation curable resins for additive fabrication, but these comprise a cationic photoinitiator (and hence are limited in the materials which may be used) and are suggested only for layer by layer fabrication. See also US Patent No. 8,980,971 to Ueda (DSM). Velankar, Pazos, and Cooper, Journal of Applied Polymer Science 162, 1361 (1996), describe UV-curable urethane acrylates formed by a deblocking chemistry, but they are not suggested for additive manufacturing, and no suggestion is made on how those materials may be adapted to additive manufacturing.
Cyanate esters are an important class of high-temperature thermosets used in aerospace, computing, and other industries. These materials have extremely high glass transition temperatures (up to 400°C), high tensile strength, high modulus, and low dielectric constant, dielectric loss and moisture uptake. The materials are low-viscosity liquids, semisolids, and solids that are thermally cured at elevated temperatures and have heretofore been considered therefore incompatible with traditional 3D printing (or so called additive manufacturing methods on their own).
Summary of the Invention
We address the aforesaid issues by, in general, blending cyanate esters with UV- curable oligomers and reactive diluents. Herein, a curable resin incorporating a radiation- cured network and a heat-cured thermoset consisting of a cyanate ester is described. This resin allows the creation of 3D printed parts. These parts exhibit desirable mechanical properties (ultimate tensile strength, modulus), desirable thermal properties (heat deflection temperature, glass transition temperature, degradation temperature, low thermal shrinkage), and/or desirable dielectric properties (low dielectric constant, low dielectric loss).
Accordingly, described herein is a method of forming a three-dimensional object is described herein. The method generally comprises:
(a) providing a cyanate ester dual cure resin (also referred to herein as a "polymerizable liquid");
(b) forming a three-dimensional intermediate from said resin, where said intermediate has the shape of, or a shape to be imparted to, said three-dimensional object, and where said resin is solidified by exposure to light;
(c) optionally, but in some embodiments preferably, washing the three dimensional intermediate, and then
(d) heating and/or microwave irradiating said three-dimensional intermediate sufficiently to further cure said resin and form said three-dimensional object;
wherein said cyanate ester dual cure resin comprises:
(i) a photoinitiator; (ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light:
(iii) optionally, a light absorbing pigment or dye;
(iv) optionally, a metal catalyst;
(v) optionally, a nucleophilic co-catalyst;
(vi) at least one cyanate ester compound, and/or a prepolymer thereof (e.g., a homoprepolymer and/or heteroprepolymer thereof), each said cyanate ester compound independently having a structure of Formula 1:
Figure imgf000004_0001
wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic (e.g., C5 to C12 cycloaliphatic) group;
(vii) optionally a diluent (including reactive diluents);
(viii) optionally a filler (e.g., silica, a toughener such as a core-shell rubber, etc., including combinations thereof); and
(ix) optionally, a co-monomer and/or a co-prepolymer (e.g., co-polymerizable with the aforesaid cyanate ester compound and/or prepolymer thereof).
Resins useful for carrying out such methods, and products produced from such methods, are also described.
In some embodiments, a Lewis acid or an oxidizable tin salt is included in the polymerizable liquid or resin (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.
In some embodiments of the methods and compositions described above and below, 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.
The resins and methods described herein are particularly useful for forming three- dimensional objects that must be strong and stiff, and/or heat tolerant. In some embodiments, polymerizable liquids used in the present invention include 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 prcent 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 (Hi) an organic ultraviolet light absorber such as a hydroxybenzophcnonc, 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).
Non-limiting examples and specific embodiments of the present invention are explained in greater detail in the specification set forth below. The disclosures of all United States Patent references cited herein are to be incorporated herein by reference in their entirety.
Brief Description of the Drawings
Figure 1. Non-limiting example of cyanate ester trimerization.
Figure 2. Non-limiting example dual cure of UV-curable network and cyanate ester network.
Figure 3. Impeller produced from a dual cure cyanate ester resin.
Detailed Description of Illustrative Embodiments
The present invention is now described more fully hereinafter with reference to the accompanying drawings, in which embodiments of the invention are shown. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein; rather these embodiments are provided so that this disclosure will be thorough and complete and will fully convey the scope of the invention to those skilled in the art.
As used herein, the term "and/or" includes any and all possible combinations or one or more of the associated listed items, as well as the lack of combinations when interpreted in the alternative ("or").
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the specification and claims and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein. Well- known functions or constructions may not be described in detail for brevity and/or clarity.
"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).
1. Resins.
As noted above, the present invention includes cyanate ester dual cure resin compositions useful for additive manufacturing. Such compositions comprise, consist of, or consist essentially of:
(i) a photoinitiator (e.g., a free-radical polymerization photoinitiator, including combinations thereof, particularly Ultraviolet light (UV) photoinitiators);
(ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light (when in combination with said photoinitiator);
(iii) optionally, a light absorbing pigment or dye;
(iv) optionally, a metal catalyst;
(v) optionally, a nucleophilic co-catalyst;
(vi) at least one cyanate ester compound, and/or a prepolymer thereof (e.g., a homoprepolymer and/or heteroprepolymer thereof), each said cyanate ester compound independently having a structure of Formula I :
Figure imgf000006_0001
wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic (e.g., C5 to C12 cycloaliphatic) group;
(vii) optionally a diluent (including reactive diluents);
(viii) optionally a filler (e.g., silica); and (ix) optionally, a co-monomer and/or a co-prepolymer (e.g., co-po 1 ym erizabl c with the aforesaid cyanate ester compound and/or prepolymer thereof).
In some embodiments of the foregoing, R is a phenyl, naphthyl. anthryl, phenanthryl. or pyrenyl group (usubstituted, or optionally substituted). (See, e.g., US Patent No. 3,448,079).
In some embodiments of the foregoing, R is a phenyl, biphenyl, naphthyl, bisfphenyl (methane. bis(phenyl)ethane, bis(phenyl)propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis(phenyl)sulfone, bis(phcnyi) phosphine oxide. bis(phenyl)silane, bis( phenyl jhexafluoropropane, bi s(pheny 1 )tri fl uoroethane. or bis(phenyl)dicyclopentadiene group, or a phenol formaldehyde resin, (optionally substituted from 1 or 2 to 4 or 6 times with, for example, C1-C4 alkyl, C1-C4 alkoxy, halo, etc. (See, e.g., US Patent Application Publication No. 20140335341).
In some embodiments, the cyanate ester compound is selected from the group consisting of: 1,3-, or 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene; 1,3,6-tricyanatoaphthalene; 2,2' or 4,4'-dicyanatobiphenyl; bis(4-cyanathophenyl) methane; 2,2-bis(4-cyanatophenyl) propane; 2,2-bis(3,5-dichloro-4- cyanatophenyl (propane. 2,2-bis(3-dibromo-4-dicyanatophenyl)propane; bis(4- cyanatophenyl)ether; bis(4-cyanatophenyl)thioether; bis(4-cyanatophenyl)sulfone; tris(4- cy anatopheny 1 (pho sph i te ; tris(4-cyanatophenyl (phosphate; bis(3-chloro-4- cyanatopheny I (methane: 4-cyanatobiphenyl; 4-cum y 1 cyan ato benzene ; 2-tert-butyl- 1,4- dicyanatobenzene; 2,4-dimethyl- 1 ,3-dicyanatobenzene; 2,5-di-tert-butyl-l ,4 dicyanatobenzene; tetramethyl- 1,4-dicyanatobenzene; 4-chloro- 1 ,3-dicyanatobenzene; 3 ,3 ' ,5 ,5 ' -tetramethyl -4,4' dicyanatodiphenyl bi s( 3 -chloro-4-cyanatophenyl (methane: 1,1,1- tris(4-cyanatophenyl)ethane; 1 , 1 -bis(4-cyanatophenyl (ethane; 2,2-bis(3 ,5-dichloro-4- cyanatophenyl )propane; 2,2-bis(3,5 dibromo-4-cyanatophenyl (propane; bis(p- cyanophenoxyphenoxy (benzene;
Figure imgf000007_0001
cyanated novolacs produced by reacting a novolac with cyanogen halide; cyanated bisphenol polycarbonate oligomers produced by reacting a bisphenol polycarbonate oligomer with cyanogen halide; and mixtures thereof, (see, e.g.. OS Patent No. 4,371.689).
In some embodiments of the foregoing, said metal catalyst is a chelate or oxide of a metal selected from the group consisting of divalent copper, zinc, manganese, tin, lead, cobalt and nickel, trivalent iron, cobalt, manganese and aluminum, and tetravalent titanium (See, e.g., US Patent Nos. 4,785,075; 4,604,452; and 4,847,233). In some embodiments, the said metal catalyst is a metal salt of an organic acid of at least one metal selected from the group consisting of copper, zinc. lead, nickel, iron, tin and cobalt.
In some embodiments, the metal catalyst is present in the range of 10 or 30 to 600, 1,00, or 10,000 microequivalents of said metal catalyst as compared to the total weight of said at least one cyanate ester or prepolymer thereof.
In some embodiments, the nucleophilic co-catalyst is an alkylphenol or imidazole present in the amount of 2 or 5 to 60 or 100 milliequivalents of active hydrogen per equivalent of cyanate ester group.
In some embodiments, the nucleophilic co-catalyst is selected from the group consisting of nonylphenol, dodecylphenol, o-cresol, 2-sec.butylphenol and 2,6 dinonylphenol, 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2-phenylimidazole, 2-ethyl 4-methylimidazole, l-benzyl-2-methylimidazole, l-propyl-2-methylimidazole, 1-cyanoethyl- 2-methylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 1 -eyanoethyl-2- undecylimidazole, l-cyanoethyl-2-phenylimidazole, or 1 -guanaminoethyl-2- methylimidazole, or water (including adventitious water absorption). (See, e.g., US Patent No. 4,371,689)
In some embodiments, the nucleophilic co-catalyst is a component of the monomers and/or prepolymers, present in the amount of about 10 or 40 to about 400 or 800 milliequivalents of active hydrogen per equivalent of cyanate group.
In some embodiments, the nucleophilic co-catalyst is absent (as a separate chemical entity) and wherein said monomers and/or prepolymers contain urethane, urea, and/or phenolic groups (and hence serves as an intrinsic nucleophilic co-catalyst).
In some embodiments, the monomers and/or prepolymers polymerizable by exposure to actinic radiation or light comprising reactive end groups selected from the group consisting of acrylates, methacrylates, a -olefins, N-vinyls, acrylamides, methacryl amides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers. (See, e.g., US Patent Application Publication No. 2015/0072293 to DeSimone et al).
Any suitable co-monomer and/or prepolymer thereof that is polymerizable with the cyanate ester (or prepolymer thereof) may optionally be used in the present invention, including but not limited to amine, epoxy, phenol, bismaleimide, and benzoxazine co- monomers, and/or co-prepolymers thereof. See, e.g., J. Bauer and M. Bauer, Cyanate ester based resin systems for snap-cure applications, Microsystem Technologies 8, 58-62 (2002). Examines of suitable benzoxazine co-monomers and/or co-prepolymers include, but are not limited to. benzoxazines derived from the reaction of formaldehyde and either aniline or methylamine with 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4- hydroxyphenyl)methane (bisphenol F), 4.4* thiodiphenol. See also US Patent Nos. 6,207,786, 5,543,516 and 6,620,905. Such benzoxazines may be incorporated into the composition in any suitable amount, such as from 0.1 or 5 percent by weight to 30 or 49 percent by weight.
Any suitable filler may be used in connection with the present invention, depending on the properties desired in the part or object to be made. Thus, 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.
In some embodiments, the light absorbing pigment or dye is:
(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., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or
(Hi) an organic ultraviolet light absorber (e.g., a hydroxybenzophenone, hydroxyphenylbenzotriazole, oxanilide, benzophenone, thioxanthone, hydroxyphenyltriazine, and/or benzotri azoic ultraviolet light absorber) (e.g., in an amount of 0.001 or 0.005 to 1 or 2 percent by weight).
In some embodiments, the diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
In some embodiments, the resin/polymerizable liquid comprises:
(i) from 0.1 to 4 percent by weight of said photoinitiator,
(ii) from 10 to 90 percent by weight of said monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light,
(iii) from 0.1 to 2 percent by weight of said light absorbing pigment or dye when present, (iv) from 0.001 to 0.1 percent by weight of said metal catalyst when present;
(v) from 0.1 to 10 percent by weight of said nucleophilic co-catalyst when present;
(vi) from 10 to 90 percent by weight of said cyanate ester compound and/or prepolymer thereof;
(vii) from 1 to 40 percent by weight of said reactive diluents when present;
(viii) from 1 to 50 percent by weight of said filler when present; and
(ix) from 0.1, 1 or 5 to 20, 40 or 50 percent by weight of a co-monomer and/or a co- prepolymer when present.
Cyanate ester prepolymers. In some embodiments, some or all of the cyanate ester compound(s) may be included in the composition in the form of prepolymers thereof. In some embodiments, the inclusion of such prepolymers can improve the properties of the three-dimensional object being produced, such as by reducing thermal shrinkage, reducing sweating, and/or reducing cracking during the second curing step, without substantially adversely affecting the properties of the final product. Examples of such prepolymers include, but are not limited to, those based on 2,2-bis(4-hydroxyphenyl)propane dicyanate (bisphenol A dicyanate), 2,2-bis(4-hydroxyphenyl)ethane dicyanate (bisphenol E dicyanate), and cyanated novolacs. All of the cyanate ester content of the composition may be provided in the form of prepolymers, or some of the cyanate ester content of the composition may be provided in the form of prepolymers {e.g., in a weight ratio of cyanate ester monomer(s) to cyanate prepolymer(s) of from 1 : 100 or 1 : 10 to 100: 1 or 10: 1 ).
In some embodiments, these prepolymers comprise, consist of, or consist essentially of the reaction product of cyanate ester monomers reacted to degrees of conversion of the cyanate groups of from 1 or 5 percent to 20 or 40 percent (of initial cyanate functionality, group or substituents), leading to prepolymers with molecular weights of from 200 or 400 g/mol to 4,000 or 8,000 g/mol.
In some embodiments, 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. 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, di butyl tin dilaurate, dibutyl tin dioleate, dibutyl tin distearate, dipropyl tin dilaurate, dipropyl tin dioleate, dipropyl tin distearate, dibutyl tin dihexanoate, and combinations thereof. See also US Patent Nos. 5,298,532; 4,421,822; and 4,389,514, the disclosures of which are incorporated herein by reference. In addition to the foregoing oxidizable tin salts, Lewis acids such as those described in Chu et al. in Macromolecular Symposia, Volume 95, Issue 1, pages 233-242, June 1995 are known to enhance the polymerization rates of free-radical polymerizations and are included herein by reference.
Any suitable filler may be used in connection with the present invention, depending on the properties desired in the part or object to be made. Thus, 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.
Tougheners. 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, fuUerenes), ceramics and silicon carbides, with or without surface modification or functionalization. Examples of block copolymers include the copolymers whose composition is described in U.S. Pat. No. 6,894,113 (Court et al., Atofina, 2005) and include "NANOSTRENTH®™" SBM (polystyrene-polybutadiene- polymethacrylate), and AMA (polymethacrylate-polybutylacrylate-polymethacrylate), both produced by Arkema. Other suitable block copolymers include FORTEGRA®™ and the amphiphilic block copolymers described in U.S. Pat. No. 7,820,760B2, assigned to Dow Chemical. Examples of known core-shell particles include the core-shell (dendrimer) particles whose compositions are described in US2010028015 l Al (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 1632533 Al and EP 212371 1 Al 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. Also suitable as block copolymers in the present invention are the "J SR. 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 TPv-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. Examples of suitable oxide particles include NANOPOXS™ produced by nanoresins AG. This is a master blend of functionalized nanosilica particles and an epoxy.
Core-shell rubbers. 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 US Patent Nos. 6,861,475, 7,625,977, 7,642,316, 8,088,245, and elsewhere.
In some embodiments, the core-shell rubber particles are nanoparticles (i.e., having an average particle size of less than 1000 nanometers (nm)). Generally, 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. Typically, 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.
In some embodiments, 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. By "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.
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, Munich, 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.
One example of a suitable core-shell rubber is of the type described in US Patent
Application Publication No. 2007/0027233 (EP 1 632 533 Al). 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 aerylonitrile. 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 MX 170. and Kaneka Kane Ace MX 257 and Kaneka Kane Ace MX 120 core-shell rubber dispersions, and mixtures thereof.
Stabilizers. In some embodiments, the shelf life of the resin, and/or the pot life of the resin during production of an object, may be extended by including a stabilizer in the resin, typically in an amount of from about 0.001 or 0.01 percent by weight, up to 0.1, 0.5, or 1 percent by weight. Suitable stabilizers include, but are not limited to, acids having a pKa below 2, such as p-toluene sulfonic acid, polyphosphoric acid esters, etc. See, e.g., US Patent No. 4,839,442.
2. Methods.
The three dimensional intermediate is preferably formed from resins as described above by additive manufacturing, typically bottom-up or top-down additive manufacturing. Such methods are known and described in, for example, U.S. Patent No. 5,236,637 to Hull, US Patent Nos. 5,391.072 and 5.529.473 to Lawton. U.S. Patent No. 7.438.846 to John. US Patent No. 7,892,474 to Shkolnik. U.S. Patent No. 8,110,135 to El-Siblani, U.S. Patent Application Publication Nos. 2013/0292862 to Joyce and 2013/0295212 to Chen et al, and PCT Application Publicaiton No. WO 2015/164234 to Robeson et al. The disclosures of these patents and applications are incorporated by reference herein in their entirety.
In general, top-down three-dimensional fabrication is carried out by:
(a) providing a polymerizable liquid reservoir having a polymerizable liquid fill level and a carrier positioned in the reservoir, the carrier and the fill level defining a build region therebetween;
(b) filling the build region with 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; and then (c) irradiating the build region with light to form a solid polymer scaffold from the first component and also advancing (typically lowering) the carrier away from the build surface to form a three-dimensional intermediate having the same shape as. or a shape to be imparted to, the three-dimensional object and containing said second solidifiable component (e.g.. a second reactive component ) carried in the scaffold in unsolidiiied and/or uncured form.
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. In the case of an optically transparent window, 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.
In general, bottom-up three dimensional fabrication is carried out by:
(a) providing a carrier and an optically transparent member having a build surface, the carrier and the build surface defining a build region therebetween:
(b) filling the build region with a polymerizable liquid {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; and then
(c) irradiating the build region with light through said optically transparent member to form a solid polymer scaffold from the first component and also advancing (typically raising) the carrier away from the build surface to form a three-dimensional intermediate having the same shape as, or a shape to be imparted to, the three-dimensional object and containing said second solidifiable component (e.g.. a second reactive component) carried in the scaffold in unsolidified and/or uncured form.
In some embodiments of bottom up or top down three dimensional fabrication as implemented in the context of the present invention, 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.
In some embodiments of bottom up or top down three dimensional fabrication as carried out in the context of the present invention, the polymerizable liquid (or resin) is maintained in liquid contact with both the growing thee 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.
In some embodiments of bottom-up or top down three dimensional fabrication as carried out in the context of the present invention, 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.
In some embodiments of bottom up or top down three dimensional fabrication as carried out in the context of the present invention, 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.
In some embodiments of bottom up or top down three dimensional fabrication employing a rigid or flexible optically transparent window, 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).
From the foregoing it will be appreciated that, in some embodiments of bottom-up or top down three dimensional fabrication as carried out in the context of the present invention, 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. Thus, 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.
In preferred embodiments, the intermediate is formed by continuous liquid interface production (CLIP). CLIP is known and described in, for example, PCT Applications Nos. PCT US2014/015486 (published as US Patent No. 9,211,678 on December 15, 2015); PCT/US2014/015506 (also published as US Patent No. 9,205,601 on December 8, 2015), PCT/US2014/015497 (also published as US 2015/0097316, and to publish as US Patent No 9,216,546 on Dec. 22, 2015), and in J. Tumbleston, D. Shirvanyants, N. Ermoshkin et al., Continuous liquid interface production of 3D Objects, Science 347, 1349-1352 (published online 16 March 2015). In some embodiments, CLIP employs features of a bottom-up three dimensional fabrication as described above, but the the irradiating and/or said advancing steps are carried out while also concurrently maintaining a stable or persistent liquid interface between the growing object and the build surface or window, such as by: (i) continuously maintaining a dead zone of polymerizable liquid in contact with said build surface, and (ii) continuously maintaining a gradient of polymerization zone (such as an active surface) between the dead zone and the solid polymer and in contact with each thereof, the gradient of polymerization zone comprising the first component in partially cured form. In some embodiments of CLIP, the optically transparent member comprises a semipermeable member (e.g., a fiuoropolymer). and the continuously maintaining a dead zone is carried out by feeding an inhibitor of polymerization through the optically transparent member, thereby creating a gradient of inhibitor in the dead zone and optionally in at least a portion of the gradient of polymerization zone.
In some embodiments, the stable liquid interface may be achieved by other techniques, such as by providing an immiscible liquid as the build surface between the polymerizable liquid and the optically transparent member, by feeding a lubricant to the build surface (e.g., through an optically transparent member which is semipermeable thereto, and/or serves as a reservoir thereof), etc.
While the dead zone and the gradient of polymerization zone do not have a strict boundary therebetween (in those locations where the two meet), the thickness of the gradient of polymerization zone is in some embodiments at least as great as the thickness of the dead zone. Thus, in some embodiments, 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. Thus the gradient of polymerization zone may be thick or thin depending on the particular process conditions at that time. Where 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. In some embodiments, 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.
Inhibitors, or polymerization inhibitors, for use in the present invention may be in the form of a liquid or a gas. In some embodiments, gas inhibitors are preferred. In some embodiments, liquid inhibitors such as oils or lubricants may be employed. In further embodiments, gas inhibitors which are dissolved in liquids (e.g. oils or lubricants) may be employed. For example, oxygen dissolved in a fluorinated fluid. The specific inhibitor will depend upon the monomer being polymerized and the polymerization reaction. For free radical polymerization monomers, 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. In alternate embodiments, such as where the monomer is polymerized by photoacid generator initiator, 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.
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).
CLIP may be carried out in different operating modes operating modes (that is, different manners of advancing the carrier and build surface away from one another), including continuous, intermittent, reciprocal, and combinations thereof.
Thus in some embodiments, the advancing step is carried out continuously, at a uniform or variable rate, with either constant or intermittent illumination or exposure of the build area to the light source.
In other embodiments, 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.).
In some embodiments, 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.
In still other embodiments, 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. In some embodiments, 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.
In some embodiments, the soli dill able or polymerizable liquid is changed at least once during the method with a subsequent solidifiable or polymerizable liquid (e.g., by switching a "window" or "build surface" and associated reservoir of polymerizable liquid in the apparatus): 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 (e.g., a rigid funnel or liquid connector segment, covalently coupled to a flexible pipe or tube segment).
Once the three-dimensional intermediate is formed, it may be removed from the carrier, optionally washed, any supports optionally removed, any other modifications optionally made (cutting, welding, adhesively bonding, joining, grinding, drilling, etc. ), and then heated and/or microwave irradiated sufficiently to further cure the resin and form the three dimensional object. Of course, additional modifications may also be made following the heating and/or microwave irradiating step.
Washing may be carried out with any suitable organic or aqueous wash liquid, or combination thereof, including solutions, suspensions, emulsions, microemulsions, etc. Examples of suitable wash liquids include, but are not limited to water, alcohols (e.g., methanol, ethanol. isopropanol. etc. ). benzene, toluene, etc. Such wash solutions may optionally contain additional constituents such as surfactants, etc. A currently preferred wash liquid is a 50:50 (volume: olume) solution of water and isopropanol. Wash methods such as those described in US Patent No. 5,248,456 may be employed and are included therein.
After the intermediate is formed, optionally washed, etc., as described above, it is then heated and/or microwave irradiated to further cure the same. 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.
In some embodiments, the heating step is carried out at at least a first (oven) temperature and a second (oven) temperature, with the first temperature greater than ambient temperature, the second temperature greater than the first temperature, and the second temperature less than 300 °C (e.g., with ramped or step-wise increases between ambient temperature and the first temperature, and/or between the first temperature and the second temperature).
For example, the intermediate may be heated in a stepwise manner at a first temperature of about 70°C to about 150°C, and then at a second temperature of about 150°C to 200 or 250 °C, with the duration of each heating depending on the size, shape, and/or thickness of the intermediate. In another embodiment, the intermediate may be cured by a ramped heating schedule, with the temperature ramped from ambient temperature through a temperature of 70 to 150 °C, and up to a final (oven) temperature of 250 or 300 °C, at a change in heating rate of 0.5°C per minute, to 5 °C per minute. (See, e.g., US Patent No. 4,785,075).
It will be clear to those skilled in the art that the materials described in the current invention will be useful in other additive manufacturing techniques, including ink-jet printer- based methods.
3. Products.
The resins and methods described above are particularly useful for making three- dimensional objects that are strong and stiff, and/or tolerate high temperatures. Examples of products that may be produced by the methods and resins described herein include, but are not limited to, heat shields or housings in automobiles, aircraft, and boats (e.g., "under-the- hood" heat shields or housings), as micro-meteor deflectors for satellites and spacecraft, as pump housings, impellers, injection molds, injection mold cores, healthcare applications where parts must survive high temperature for sterilization, electronics packaging, etc.
In some embodiments, the methods and resins described herein are used to make surgical instruments (for example, retractors, dilators, dissectors and probes, graspers such as forceps, clamps and occluders for blood vessels and other organs, distracters, suction tips, housings for powered devices such as surgical drills and dermatomes, scopes and probes, measurement instruments such as rulers and calipers, handles for cutting instruments such as scalpels and scissors, cataract removal instruments, surgical jigs and guides such as for orthopedic surgery, etc.). surgical instrument trays, mounts and frames for surgical instruments. Intraoral devices (including, but not limited to, surgical guides for dental applications, retainers for corrective orthodontic applications, palatal expanders, tongue thrust instruments, trays for delivery of drugs and bleaching agents, etc.).
In some embodiments of surgical instruments, such as for surgical jigs and guides, and/or imaging jigs and guides, the instruments may be computer-generated custom instruments, or patient-specific instruments. Examples of patient-specific instruments that may be made with the materials and compositions described herein include, but are not limited to, custom jigs for removal of bone tumors; custom jigs and guides for orthopedic surgery, etc. See. e.g., US Patent Nos. 9,060,788; 9,066,734; 9,066,727; 8,932,299; 8,632,547; 8,591,516; 8715,289; 8,092,465; US Patent Application Publication Nos 2014/0025348 and 2012/0239045; and 2011/0106093.
Embodiments of the present invention are explained in greater detail in the following non-limiting examples.
Example 1
Cvanate Ester Dual Cure Resia and Product
57 grams of l,l'-bis(4-cyanatophenyl)ethane, 1.9 grams of a metal catalyst solution
(3000 ppm zinc(II) acetylacetonate hydrate in isobornyl acrylate), 28.5 grams of a commercially available urethane diacrylate (Sartomer PR013259), 28.5 grams of trimethylolpropane triacrylate, and 1.14 grams of phenylbis(2,4,6- tri methy lbenzoy 1 )phosphi ne oxide was mixed in a planetary centrifugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 5 mW/cm2 at a print speed of 100 mm/hour. The formed material was washed and cured for 30 minutes at 140°C, 30 minutes at 160°C, 2 hours at 180°C, 1 hour at 220°C, and 1 hour at 240°C to yield the desired product. The mechanical properties of dual cured products were evaluated by producing dual cured three dimensional mechanical test samples (e.g., "dog bone" samples) in the foregoing manner. Material properties are given in Table 1 below. Table 1. Materials properties of product
Tensile modulus (MPa) 3200-3500
Ultimate tensile strength (MPa) 100-110
Elongation (%) 4-5
Flexural Modulus (MPa) 3800-4200
Flexural Strength (MPa) 150-180
Glass transition temperature (DMA, °C) 200-210
Unnotched Izod impact strength (J/m) 200-400
Heat deflection temperature (°C) 198
Without wishing to be bound to any particular theory of the invention, it is believed that the resins described in this example react as described in Figures 1-2 below in the course of forming the dual cured three-dimensional object (where Figure 2 shows both dual cure reactions, and Figure 2 is a detail view of the second dual cure reaction shown in Scheme 1).
An example product (an impeller) produced from a dual cured resin as described above by a process as described above is shown in Figure 3.
Example 2
CE 1.1 Formulation
48 grams of l,l'-bis(4-cyanatophenyl)ethane, 2.5 grams of a metal catalyst solution (1500 ppm zinc(II) acetylacetonate hydrate in isobornyl aerylate). 5.3 grams of a commercially available urethane diacrylate (Sartomer CN983), 34.8 grams of trimethylolpropane triacrylate. 8.73 grams of a commercially available diacrylate (Sartomer CN120Z), 1.0 grams of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, and 0.1 grams of 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 run LED projector with a light intensity of 5 mW/crn2 at a speed of 100 mm/hour. The formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 2 below. Table 2. Materials properties of product
Tensile modulus (MPa) 3600-4000
Ultimate tensile strength (MPa) 90-100
Elongation (%) 3-6
Flexural Modulus (MPa)
Flexural Strength (MPa)
Glass transition temperature (°C) 210
Izod impact strength (J/m)
Heat deflection temperature (°C)
Figure imgf000023_0001
Sartomer CN120Z trimethy!oipropane triacrylate
Example 3
Resin with AroCv XU371™, and Product
24 grams of l,l'-bis(4-cyanatophenyl)ethane, 24 grams of a commercial novolac- based cyanate ester (Huntsman XU371), 2.5 grams of a metal catalyst solution ( 1500 ppm zinc(II) acelylacetonate hydrate in isobornyl acrylate). 25 grams of a commercially available urethane diacrylate (Sartomer CN983), 25 grams of trimethylolpropane triacrylate, and 1.0 grams of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 5 mW/cm2 at a speed of 100 mm/hour. The formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, 60 minutes at 220°C, and 60 minutes at 240°C to yield the desired product. The mechanical properties of products produced from such resins resins were evaluated by producing dual cured mechanical test samples in this manner, and are given in Table 3 below. Table 3. Materials properties of product.
Tensile modulus (MPa) 3900-4100
Ultimate tensile strength (MPa) 85-95
Elongation (%) 2-3
Flexural Modulus (MPa)
Flexural Strength (MPa)
Glass transition temperature (°C) 240
Izod impact strength (J/m)
Heat deflection temperature (°C)
Figure imgf000024_0001
Example 4
Resin with Irgacure 369™ and ITX„ and Product
48 grams of l ,l '-bis(4-cyanatophenyl)ethane, 2.5 grams of a metal catalyst solution (1500 ppm zinc(II) acetylacetonate hydrate in isobornyl acrylate), 5.3 grams of a commercially available urethane diacrylate (Sartomer CN983), 34.8 grams of trimethylolpropane triacrylate, 8.73 grams of a commercially available diacrylate (Sartomer CN120Z), 0.9 grams of 2-benzyl-2-dimethylamino-l-(4-morpholinophenyl)-butanone-l, and 0.1 grams of 2-isopropylthioxanthone was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into an intermediate product using continuous liquid interface production (CLIP) in continuous print mode, using a 385 nm LED projector with a light intensity of 5 mW/cm at a print speed of 100 mm/hour. The formed material was washed and pre-cured for 90 minutes at 95 °C. Following this pre-cure, the final product part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of products so produced were evaluated by producing mechanical test samples from the dual cure resins. Example 5
Resin without Urethane Acrylate and Product
50 grams of l ,l '-bis(4-cyanatophenyl)ethane, 2.5 grams of a metal catalyst solution (1500 ppm zinc(II) acetylacetonate hydrate in isobornyl acrylate), 6 grams of a commercially available diacrylate (Sartomer CN120Z), 14 grams of a commercially available diacrylate (Sartomer SR601), 20 grams of trimethylol propane triacrylate, 1 gram of 2-benzyl-2- dimethyIamino-1 -(4-morpholinophenyl)-butanone-l , and 0.1 grams of Wikoff black dispersion was mixed in a planetary centrigugal mixer to yield a homogeneous resin.
Figure imgf000025_0001
Sartomer CN601
This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 5 mW/cm at a print speed of 100 mm/hour. The formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of parts so produced were evaluated by directly producing mechanical test samples, and are given in Table 4 below.
Figure imgf000025_0002
Example 6
CE 1.2 Formulation
48 grams of l,l'-bis(4-cyanatophenyl)ethane, 0.004 grams zinc(II) acetylacetonate hydrate, 2.5 grams of isobornyl acrylate, 22.8 grams of trimethylolpropane trimethacrylate, 25.5 grams of a commercially available dimethacrylate (Sartomer C 154), and 1.75 grams of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm at a speed of 133 mm/hour. The formed material was washed and pre-cured for 90 minutes at 95°C. Following this pre-cure, the part was cured for 60 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 6 below.
Figure imgf000026_0001
Example 7
Cvanate Ester with Prepoiymer
l,r-bis(4-cyanatophenyl)ethane was heated at 120°C to promote partial polymerization before formulation. The degree of conversion was monitored by infrared spectroscopy and found to be 13% after 16 hours and 27% after 20 hours. Aliquots were removed at these times for formulation, printing, and characterization in the following manner:
48 grams of l,l'-bis(4-cyanatophenyl)ethane or prepoiymer thereof, 0.004 grams zinc(II) acetylacetonate hydrate, 2.5 grams of isobornyl acrylate, 22.8 grams of trimethylolpropane trimethacrylate, 25.5 grams of a commercially available dimethacrylate (Sartomer CN154), and 1.75 grams of phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm2 at a speed of 133 mm/hour. The part was cured for 60 minutes at 95 °C. 120 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 7 below. In addition to the decrease in thermal shrinkage, the amount of resin bleed and part cracking during thermal cure decreased dramatically from 0-27% prepolymer conversion.
Figure imgf000027_0002
Example 8
Cyanate Ester with Silica filler
24 grams of l ,l'-bis(4-cyanatophenyl)ethane, 24 grams of silicon dioxide (-99%, 0.5- 10 μηι (approx. 80% between 1-5 μκι), Sigma- Aldrich), 0.004 grams zinc(II) acetylacetonate hydrate, 2.5 grams of isobornyl acrylate, 22.8 grams of trimethylolpropane trimethacrylate, 25.5 grams of a commercially available dimethacrylate (Sartomer CN154), and 1.75 grams of
Figure imgf000027_0001
oxide was mixed in a planetary centrigugal mixer to yield a homogeneous resin. This resin was formed into a three dimensional intermediate using continuous liquid interface production (CLIP) in continuous exposure mode, using a 385 nm LED projector with a light intensity of 9 mW/cm2 at a speed of 133 mm/hour. The part was cured for 60 minutes at 95°C, 120 minutes at 120°C, 120 minutes at 180°C, and 60 minutes at 220°C to yield the desired product. The mechanical properties of dual cured products produced from such resins were evaluated by producing mechanical test samples in this manner, and are given in Table 8 below. Table 8. Materials properties of product
Modulus (before post-cure, MPa) 475
Tensile modulus (after post-cure, MPa) 5300-5700
Ultimate tensile strength (MPa) 80-90
Elongation (%) 1-3
Glass transition temperature (°C, tanD) 200
The foregoing is illustrative of the present invention, and is not to be construed as limiting thereof The invention is defined by the following claims, with equivalents of the claims to be included therein.

Claims

We claim:
1. A method of forming a three-dimensional object, comprising:
(a) providing a cyanate ester dual cure resin;
(b) forming a three-dimensional intermediate from said resin, where said intermediate has the shape of, or a shape to be imparted to, said three-dimensional object, and where said resin is solidified by exposure to light;
(c) optionally washing the three-dimensional intermediate, and then
(d) heating and/or microwave irradiating said three-dimensional intermediate sufficiently to further cure said resin and form said three-dimensional object;
wherein said cyanate ester dual cure resin comprises:
(i) a photoinitiator;
(ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light;
(iii) optionally, a light absorbing pigment or dye;
(iv) optionally, a metal catalyst;
(v) optionally, a nucleophilic co-catalyst;
(vi) at least one cyanate ester compound, and/or a prepolymer thereof {e.g., a homoprepolymer and/or heteroprepolymer thereof), each said cyanate ester compound independently having a structure of Formula I:
Figure imgf000029_0001
wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic group;
(vii) optionally a diluent;
(viii) optionally a filler; and
(ix) optionally, a co-monomer and/or a co-prepolymer.
2. The method of claim 1, wherein R is a phenyl, naphthyl, anthryl. phenanthryl, or pyrenyl group.
3. The method of claim 1, wherein R is a phenyl, hiphenyl. naphthyl, bis( phenyl (methane. bis(phenyl)ethane, bis( phenyl (propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis(phenyl)sulfone, bis(phenyl) phosphine oxide, bisi phenyl (silane, bis(phenyl)hexafluoropropane. bis(phenyl)trifluoroethane, or bis(phenyl)dicyclopentadiene group, or a phenol formaldehyde resin.
4. The method of claim 1, wherein said cyanate ester compound is selected from the group consisting of: 1,3-, or 1 ,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2,6- or 2,7-dicyanatonaphthalene; 1,3,6-tricyanatoaphthalene; 2,2' or 4,4'- dicyanatobiphenyl; bis(4-cyanathophenyl) methane; 2,2-bis(4-cyanatophenyl) propane; 2,2- bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3-dibromo-4-dicyanatophenyl)propane; bi s(4-cy anat opheny 1 (ether: bis(4-cyanatophenyl)thioether; bis(4-cyanatophenyl)sulfone; tris(4-cyanatophenyl)phosphite; tris(4-cyanatophenyl)phosphate; bis(3-chloro-4- cy anatopheny 1 (methane; 4-cyanatobiphenyl; 4-cumylcyanatobenzene; 2-tert-butyl-l ,4- dicyanatobenzene; 2,4-dimethyl- 1.3-dieyanatobenzene; 2.5-di-tert-butyl-l .4 dicyanatobenzene; tetramethyl- 1 ,4-dicyanatobenzene; 4-chloro- 1 ,3 -dicyanatobenzene; 3,3',5,5'-tetramethyl-4,4' dicyanatodiphenylbis(3-chloro-4-cyanatophenyl)methane; 1,1,1- tris(4-cyanatophenyl)ethane; l,l-bis(4-cyanatophenyl)ethane; 2,2-bis(3,5-dichloro-4- cyanatophenyl )propane; 2,2-bis(3,5 dibromo-4-cyanatophenyl)propane; bis(p- cyanophenoxyphenoxy (benzene; di(4-cyanatophenyl)ketone; cyanated novolacs produced by reacting a novolac with cyanogen halide; cyanated bisphenol polycarbonate oligomers produced by reacting a bisphenol polycarbonate oligomer with cyanogen halide; and mixtures thereof..
5. The method of claim 1 to 4, wherein said metal catalyst is a chelate or oxide of a metal selected from the group consisting of divalent copper, zinc, manganese, tin, lead, cobalt and nickel, trivalent iron, cobalt, manganese and aluminum, and tetravalent titanium.
6. The method of claim 1 to 4, wherein said metal catalyst is a metal salt of an organic acid of at least one metal selected from the group consisting of copper, zinc, lead, nickel, iron, tin and cobalt.
7. The method of any preceding claim, wherein said metal catalyst is present in the range of 10 or 30 to 600, 1,00, or 10,000 microequivalents of said metal catalyst as compared to the total weight of said at least one cyanate ester or prepolymer thereof.
8. The method of claim 1 to 7, wherein said nucleophilic co-catalyst is an alkylphenol or imidazole present in the amount of 2 or 5 to 60 or 100 milliequivalents of active hydrogen per equivalent of cyanate ester group.
9. The method of claim 1 to 7, wherein said nucleophilic co-catalyst is selected from the group consisting of nonylphenol, dodecylphenol, o-cresol, 2-sec.butylphenol and 2,6 dinonylphenol, 2-methylimidazole, 2-undecylimidazole, 2-heptadecyl imidazole, 2- phenylimidazole, 2-ethyl 4-methylimidazole, l-benzyl-2-methylimidazole, l-propyl-2- methy] imidazole. 1 -cyanoethyl-2-methylimidazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, l -cyanoethyl-2-undecyl imidazole, l-cyanoethyl-2-phenylimidazole, or l-guanaminoethyl-2- methylimidazole, or water.
10. The method of claim 1 to 7, wherein said nucleophilic co-catalyst is a component of the monomers and/or prepolymers , present in the amount of about 10 or 40 to about 400 or 800 milliequivalents of active hydrogen per equivalent of cyanate group.
11. The method of claim 10, wherein said nucleophilic co-catalyst is absent and wherein said monomers and/or prepolymers contain urethane, urea, and/or phenolic groups.
12. The method of claim 1 to 1 1, said monomers and/or prepolymers polymerizable by exposure to actinic radiation or light comprising reactive end groups selected from the group consisting of acrylates, methacrylates, a-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
13. The method of claim 1 to 12, wherein said light absorbing pigment or dye is:
(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., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or
(in) an organic ultraviolet light absorber (e.g., 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 or 2 percent by weight).
14. The method of claim 1 to 13, wherein said diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
15. The method of claim 1 to 14, wherein said co-monomer and/or prepolymer thereof is selected from the group consisting of amine, epoxy, phenol, bismaleimide, and benzoxazine co-monomers, and/or co-prepolymers thereof.
16. The method of claim 1 to 15, wherein said resin comprises at least one cyanate ester prepolymer.
17. The method of claim 16, wherein said cyanate ester prepolymer comprises the reaction product of cyanate ester monomers, has a molecular weight of 200 grams/mole to 8,000 grams/mole, and a degree of conversion of cyanate groups of from 1 to 40 percent.
18. The method of claim 1 to 17, wherein said resin comprises:
(i) from 0.1 to 4 percent by weight of said photoinitiator,
(ii) from 10 to 90 percent by weight of said monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light,
(iii) from 0.1 to 2 percent by weight of said light absorbing pigment or dye when present,
(iv) from 0.001 to 0.1 percent by weight of said metal catalyst when present;
(v) from 0.1 to 10 percent by weight of said nucleophilic co-catalyst when present;
(vi) from 10 to 90 percent by weight of said cyanate ester compound and/or prepolymer thereof; (vii) from 1 to 40 percent by weight of said diluent when present;
(viii) from 1 to 50 percent by weight of said filler when present; and
(ix) from 0.1 to 49 percent by weight of said co-monomer and/or prepolymer thereof when present.
19. The method of claim 1 to 18. wherein said forming step is carried out by additive manufacturing (e.g., bottom-up or top-down three-dimensional fabrication).
20. The method of claim 18, wherein said forming step is carried out by:
(i) by either bottom-up three dimensional fabrication between a carrier and a build surface or top-down three dimensional fabrication between a carrier and a fill level, the fill level optionally defined by a build surface; and/or
(ii) , optionally with a stationary build surface; and/or
(Hi) optionally while maintaining the resin in liquid contact with both the intermediate object and the build surface, and/or
(iv) optionally with said forming step carried out in a layerless manner,
each during the formation of at least a portion of the three dimensional intermediate.
21 The method of claim 1 to 18, wherein said forming step is carried out by continuous liquid interlace production (CLIP).
22. The method of claim 20 or 21, wherein said forming step is carried out between a carrier and a build surface, said method further comprising vertically reciprocating said carrier with respect to the build surface to enhance or speed the refilling of the build region with the resin.
23. The method of claim 1 to 22, wherein said three-dimensional object comprises a polymer blend, interpenetrating polymer network, semi-interpenetrating polymer network, or sequential interpenetrating polymer network.
24. The method of any preceding claim, wherein said heating step is carried out at at least a first temperature and a second temperature, with said first temperature greater than ambient temperature, said second temperature greater than said first temperature, and said second temperature less than 300 °C (e.g., with ramped or step-wise increases between ambient temperature and said first temperature, and/or between said first temperature and said second temperature).
25. A cyanate ester dual cure resin composition useful for additive manufacturing. comprising:
(i) a photoinitiator;
(ii) monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light;
(iii) optionally, a light absorbing pigment or dye;
(iv) optionally, a metal catalyst;
(v) optionally, a nucleophilic co-catalyst;
(vi) at least one cyanate ester compound, and/or a prepolymer thereof (e.g., a homoprepolymer and/or heteroprepolymer thereof), each said cyanate ester compound independently having a structure of Formula I :
Figure imgf000034_0001
wherein m is 2, 3, 4, or 5, and R is an aromatic or aliphatic group;
(vii) optionally a diluent;
(viii) optionally a filler; and
(ix) optionally, a co-monomer and/or a co-prepolymer.
26. The composition of claim 25. wherein R is a phenyl, naphthyl. anthryl. phenanthryl, or pyrenyl group.
27. The composition of claim 25, wherein R is a phenyl, biphenyl, naphthyl, bis(phenyl)methane, bis(phenyl)ethane, bis(phenyl)propane, bis(phenyl)butane, bis(phenyl)ether, bis(phenyl)thioether, bis( phenyl )sulfone. bis(phenyl) phosphine oxide, bis(phenyl)silane, bis(phenyl)hexafluoropropane, bis(phenyl)trifluoroethane, or bis( phenyl )dicyclopentadiene group, or a phenol formaldehyde resin.
28. The composition of claim 25, wherein said cyanate ester compound is selected from the group consisting of: 1,3-, or 1,4-dicyanatobenzene; 1,3,5-tricyanatobenzene; 1,3-, 1,4-, 1,6-, 1,8-, 2.6- or 2,7-dicyanatonaphthalene; 1.3.6-tricyanatoaphthalene; 2,2' or 4.4'- dicyanatobiphenyl; bis(4-cyanathophenyl) methane; 2,2-bis(4-cyanatophenyl) propane; 2,2- bis(3,5-dichloro-4-cyanatophenyl)propane, 2,2-bis(3-dibromo-4-dicyanatophenyl)propane; bis(4-cyanatophenyl)ether; bis(4-cyanatophenyl)thioether; bis(4-cyanatophenyl)sulfone; tris(4-cyanatophenyl)phosphite; tris(4-cyanatophenyl)phosphate; bis(3-chloro-4- cyanatophenyl (methane; 4-cyanatobiphenyl; 4-cumylcyanatobenzene; 2-tcrt-butyl-l .4- dicyanatobenzene; 2.4-dimethyl- 1.3 -dicyanatobenzene; 2.5-di-tert-butyl-l .4 dicyanatobenzene; tetramethyl- 1 ,4-dicyanatobenzene; 4-chloro- 1 ,3 -dicyanatobenzene; 3 ,3 ' ,5,5 ' -tetramethyl -4,4' dicyanatodiphenylbis(3-chloro-4-cyanatophenyl)methane; 1,1,1- tris(4-cyanatophenyl)ethane; 1 , 1 -bis(4-cyanatophenyl)ethane; 2,2-bis(3,5-dichloro-4- cyanatophenyl )propane; 2,2-bis(3,5 dibromo-4-cyanatophenyl)propane; bis(p- cyanophenoxyphenoxy (benzene; di(4-cyanatophenyl)ketone; cyanated novolacs produced by reacting a novolac with cyanogen halide; cyanated bisphenol polycarbonate oligomers produced by reacting a bisphenol polycarbonate oligomer with cyanogen halide; and mixtures thereof.
29. The composition of claim 25 to 28, wherein said metal catalyst is a chelate or oxide of a metal selected from the group consisting of divalent copper, zinc, manganese, tin, lead, cobalt and nickel, trivalent iron, cobalt, manganese and aluminum, and tetravalent titanium.
30. The composition of claim 25 to 28, wherein said metal catalyst is a metal salt of an organic acid of at least one metal selected from the group consisting of copper, zinc, lead, nickel, iron, tin and cobalt.
31. The composition of claim 25 to 30, wherein said metal catalyst is present in the range of 10 or 30 to 600, 1,00, or 10,000 microequivalents of said metal catalyst as compared to the total weight of said at least one cyanate ester or prepolymer thereof.
32. The composition of claim 25 to 31 , wherein said nucleophilic co-catalyst is an alky] phenol or imidazole present in the amount of 2 or 5 to 60 or 100 milliequivalents of active hydrogen per equivalent of cyanate ester group.
33. The composition of claim 25 to 31 , wherein said nucleophilic co-catalyst is selected from the group consisting of nonylphenol. dodecylphenol. o-cresol, 2- sec.butylphenol and 2.6 dinonylphenol, 2-methylimidazole, 2-undecylimidazole, 2- heptadecyl imidazole, 2-phenylimidazole, 2 -ethyl 4-methylimidazole, l-benzyl-2- methylimidazole, l-propyl-2-methylimidazole, l-cyanoethyl-2-methylimidazole, 1 - cyanoethyl-2-ethyl -4-methylimidazole, l-cyanoethyl-2-undecylimidazole, 1 -cyanoethyl-2- phenylimidazole, or 1-guanaminoethyl -2-methylimidazole, or water (including adventitious water absorption).
34. The composition of claim 25 to 31, wherein said nucleophilic co-catalyst is a component of the monomers and/or prepolymers , present in the amount of about 10 or 40 to about 400 or 800 milliequivalents of active hydrogen per equivalent of cyanate group.
35. The composition of claim 34, wherein said nucleophilic co-catalyst is absent (as a separate chemical entity) and wherein said monomers and/or prepolymers contain urethane, urea, and/or phenolic groups (and hence serves as an intrinsic nucleophilic co-catalyst).
36. The composition of claim 25 to 35, said monomers and/or prepolymers polymerizable by exposure to actinic radiation or light comprising reactive end groups selected from the group consisting of acrylates, methacrylates, oc-olefins, N-vinyls, acrylamides, methacrylamides, styrenics, epoxides, thiols, 1,3-dienes, vinyl halides, acrylonitriles, vinyl esters, maleimides, and vinyl ethers.
37. The composition of claim 25 to 36, wherein said light absorbing pigment or dye is:
(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., in an amount of from 0.05 or 0.1 to 1 or 5 percent by weight), and/or (in) an organic ultraviolet light absorber (e.g., 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 or 2 percent by weight).
38. The composition of claim 25 to 37, wherein said diluent comprises an acrylate, a methacrylate, a styrene, an acrylic acid, a vinylamide, a vinyl ether, a vinyl ester, polymers containing any one or more of the foregoing, and combinations of two or more of the foregoing.
39. The composition of claim 25 to 38, wherein said co-monomer and/or prepolymer thereof is selected from the group consisting of amine, epoxy, phenol, bismaleimide, and benzoxazine co-monomers, and/or co-prepolymers thereof.
40. The composition of claim 25 to 39, wherein said resin comprises at least one cyanate ester prepolymer.
41. The composition of claim 40, wherein said cyanate ester prepolymer comprises the reaction product of cyanate ester monomers, has a molecular weight of 200 grams/mole to 8,000 grams/mole, and a degree of conversion of cyanate groups of from 1 to 40 percent.
42. The composition of claim 25 to 41, wherein said resin comprises:
(i) from 0.1 to 4 percent by weight of said photoinitiator,
(ii) from 10 to 90 percent by weight of said monomers and/or prepolymers that are polymerizable by exposure to actinic radiation or light,
(iii) from 0.1 to 2 percent by weight of said light absorbing pigment or dye when present,
(iv) from 0.001 to 0.1 percent by weight of said metal catalyst when present;
(v) from 0.1 to 10 percent by weight of said nucleophilic co-catalyst when present;
(vi) from 10 to 90 percent by weight of said cyanate ester compound and/or prepolymer thereof;
(vii) from 1 to 40 percent by weight of said diluent when present;
(viii) from 1 to 50 percent by weight of said filler when present; and (ix) from 0.1 to 49 percent by weight of said co-monomer and/or prepolymer thereof when present.
43. A method of composition of any preceding claim, said resin further comprising a stabilizer, such as an acid having a pKa of 2 or less (e.g., p-toluene sulfonic acid), included in said composition in an amount of from 0.001 or 0.01 percent by weight to 0.5 or 1 percent by weight.
44. A product produced by a method of claim 1 to 24 or 43.
45. An intermediate product produced by a method of claim 1 to 24 or 43. before carrying out said heating and/or microwave irradiating step (d).
PCT/US2016/050035 2015-09-04 2016-09-02 Cyanate ester dual cure resins for additive manufacturing WO2017040883A1 (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
JP2018511267A JP7069006B2 (en) 2015-09-04 2016-09-02 Cyanate ester double curable resin for laminated modeling
CN201680051002.0A CN108350145B (en) 2015-09-04 2016-09-02 Cyanate ester dual cure resin for additive manufacturing
EP16766748.4A EP3344676B1 (en) 2015-09-04 2016-09-02 Cyanate ester dual cure resins for additive manufacturing
US15/754,086 US10471655B2 (en) 2015-09-04 2016-09-02 Cyanate ester dual resins for additive manufacturing
US16/576,844 US11040483B2 (en) 2015-09-04 2019-09-20 Cyanate ester dual cure resins for additive manufacturing
US16/576,862 US11090859B2 (en) 2015-09-04 2019-09-20 Cyanate ester epoxy dual cure resins for additive manufacturing

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US201562214601P 2015-09-04 2015-09-04
US62/214,601 2015-09-04
US201562270635P 2015-12-22 2015-12-22
US62/270,635 2015-12-22

Related Child Applications (3)

Application Number Title Priority Date Filing Date
US15/754,086 A-371-Of-International US10471655B2 (en) 2015-09-04 2016-09-02 Cyanate ester dual resins for additive manufacturing
US16/576,862 Continuation US11090859B2 (en) 2015-09-04 2019-09-20 Cyanate ester epoxy dual cure resins for additive manufacturing
US16/576,844 Continuation US11040483B2 (en) 2015-09-04 2019-09-20 Cyanate ester dual cure resins for additive manufacturing

Publications (1)

Publication Number Publication Date
WO2017040883A1 true WO2017040883A1 (en) 2017-03-09

Family

ID=56940401

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2016/050035 WO2017040883A1 (en) 2015-09-04 2016-09-02 Cyanate ester dual cure resins for additive manufacturing

Country Status (5)

Country Link
US (3) US10471655B2 (en)
EP (1) EP3344676B1 (en)
JP (1) JP7069006B2 (en)
CN (1) CN108350145B (en)
WO (1) WO2017040883A1 (en)

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106947205A (en) * 2017-04-19 2017-07-14 塑成科技(北京)有限责任公司 A kind of epoxy phenolic resin of Stereo Lithography Apparatus Rapid Prototyping and preparation method thereof
CN108559263A (en) * 2018-05-25 2018-09-21 黑龙江省科学院石油化学研究院 A kind of high temperature resistant bismaleimide resin composite material skin covering of the surface and preparation method thereof
CN108976788A (en) * 2018-06-05 2018-12-11 宁波市石生科技有限公司 A kind of resisting three-dimensional manufacture material and the method using material manufacture three-dimensional article
CN109275983A (en) * 2018-09-30 2019-01-29 嘉兴学院 A kind of high flexibility insole and preparation method thereof
WO2019167895A1 (en) * 2018-03-01 2019-09-06 コニカミノルタ株式会社 Resin composition and production method for three dimensional shaped object using same, and three dimensional shaped object
WO2019193961A1 (en) * 2018-04-02 2019-10-10 コニカミノルタ株式会社 Resin composition, method for manufacturing three-dimensionally shaped article using same, and three-dimensionally shaped article
CN110520276A (en) * 2017-03-27 2019-11-29 卡本有限公司 The method for manufacturing three-dimension object by increasing material manufacturing
WO2020055682A1 (en) 2018-09-10 2020-03-19 Carbon, Inc. Dual cure additive manufacturing resins for production of flame retardant objects
WO2020065655A1 (en) 2018-09-28 2020-04-02 Stratasys Ltd. Three-dimensional inkjet printing of a thermally stable object
EP3632941A1 (en) 2018-10-01 2020-04-08 Cubicure GmbH Resin composition
US11352514B1 (en) 2021-06-09 2022-06-07 Altana New Technologies Gmbh Dual-curable inkjet composition
US20220195236A1 (en) * 2020-12-23 2022-06-23 Formlabs, Inc. Multi-component composition for additive manufacturing
US11376799B2 (en) 2018-09-28 2022-07-05 Stratasys Ltd. Method for additive manufacturing with partial curing
US11401353B2 (en) 2019-05-30 2022-08-02 Rogers Corporation Photocurable compositions for stereolithography, method of forming the compositions, stereolithography methods using the compositions, polymer components formed by the stereolithography methods, and a device including the polymer components
US11407169B2 (en) 2018-10-18 2022-08-09 Rogers Corporation Method for the manufacture of a spatially varying dielectric material, articles made by the method, and uses thereof
US11482790B2 (en) 2020-04-08 2022-10-25 Rogers Corporation Dielectric lens and electromagnetic device with same
US11552390B2 (en) 2018-09-11 2023-01-10 Rogers Corporation Dielectric resonator antenna system
US11559946B2 (en) 2019-08-14 2023-01-24 Mighty Buildings, Inc. 3D printing of a composite material via sequential dual-curing polymerization
US11616302B2 (en) 2018-01-15 2023-03-28 Rogers Corporation Dielectric resonator antenna having first and second dielectric portions
US11619039B2 (en) 2020-03-05 2023-04-04 Mighty Buildings, Inc. Three-dimensional printed building components and structures
US11637377B2 (en) 2018-12-04 2023-04-25 Rogers Corporation Dielectric electromagnetic structure and method of making the same
CN116323826A (en) * 2021-06-09 2023-06-23 阿尔塔纳新技术有限公司 Dual cure cyanate ester ink jet compositions
WO2023247374A1 (en) 2022-06-23 2023-12-28 Technische Universität Wien Cyanate esters as monomers in polymerisable compositions

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018165090A1 (en) 2017-03-09 2018-09-13 Carbon, Inc. Tough, high temperature polymers produced by stereolithography
CN109280361B (en) * 2018-09-30 2021-02-26 嘉兴学院 Thermoplastic elastomer material and preparation method thereof
WO2020117407A1 (en) 2018-12-07 2020-06-11 Carbon, Inc. Methods of surface finishing objects produced by additive manufacturing
CN112480324B (en) * 2019-09-11 2022-07-19 中国科学院福建物质结构研究所 Raw material composition for preparing light-cured resin, light-cured resin prepared from raw material composition and application of light-cured resin
CN112280370B (en) * 2020-11-19 2022-05-17 中国科学院兰州化学物理研究所 Cyanate ester ink for 3D printing and preparation method and application thereof
CN113087852B (en) * 2021-04-26 2022-06-28 中国科学院兰州化学物理研究所 Cyanate ester shape memory polymer material capable of being printed in 4D mode and preparation method thereof, cyanate ester shape memory polymer device and application thereof
WO2023139578A1 (en) 2022-01-18 2023-07-27 Noga 3D Innovations Ltd Dual-cure epoxy resins for 3d printing of high-performance materials
WO2023220523A1 (en) 2022-05-09 2023-11-16 Carbon, Inc. Method for direct coloration of resins for additive manufacturing
CN116589883B (en) * 2023-06-20 2024-01-30 中国科学院兰州化学物理研究所 Cyanate ester ink, preparation method thereof, cyanate ester shape memory material and application

Citations (52)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3448079A (en) 1965-05-26 1969-06-03 Bayer Ag Phenolic resins containing cyanic ester groups
US4371689A (en) 1979-08-08 1983-02-01 Mitsubishi Gas Chemical Company, Inc. Curable resin composition comprising cyanate ester and acrylic alkenyl ester
US4389514A (en) 1980-09-26 1983-06-21 Congoleum Corporation Accelerated polymerization of acrylic monomers initiated by dialkyl and diaralkyl peroxide free radical generators in the presence of tin accelerators
US4421822A (en) 1979-08-20 1983-12-20 Minnesota Mining And Manufacturing Co. Ultraviolet polymerization of acrylate monomers using oxidizable tin compounds
US4604452A (en) 1985-10-21 1986-08-05 Celanese Corporation Metal carboxylate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US4785075A (en) 1987-07-27 1988-11-15 Interez, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US4839442A (en) 1986-11-24 1989-06-13 Hi-Tek Polymers, Inc. Low viscosity noncrystalline dicyanate ester blends with prepolymers of dicyanate esters
US4847233A (en) 1987-07-27 1989-07-11 Hi-Tek Polymers, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US5236637A (en) 1984-08-08 1993-08-17 3D Systems, Inc. Method of and apparatus for production of three dimensional objects by stereolithography
US5248456A (en) 1989-06-12 1993-09-28 3D Systems, Inc. Method and apparatus for cleaning stereolithographically produced objects
US5298532A (en) 1989-12-21 1994-03-29 Minnesota Mining And Manufacturing Company Method of accelerating photoiniferter polymerization, polymer produced thereby, and product produced therewith
US5391072A (en) 1990-10-29 1995-02-21 E. I. Du Pont De Nemours And Company Solid imaging apparatus having a semi-permeable film
US5529473A (en) 1990-07-05 1996-06-25 E. I. Du Pont De Nemours And Company Solid imaging system using differential tension elastomerc film
US5543516A (en) 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems
EP0945744A2 (en) * 1998-03-26 1999-09-29 Hughes Electronics Corporation Front end preparation procedure for coupling of light into a multi-mode fiber
US6207786B1 (en) 1998-11-10 2001-03-27 Edison Polymer Innovation Corporation Ternary systems of benzoxazine, epoxy, and phenolic resins
US6620905B1 (en) 2002-02-23 2003-09-16 National Starch And Chemical Investment Holding Corporation Curable compositions containing benzoxazine
US6861475B2 (en) 2002-10-16 2005-03-01 Rohm And Haas Company Smooth, flexible powder coatings
US6894113B2 (en) 2000-05-31 2005-05-17 Atofina Thermoset materials with improved impact resistance
EP1632533A1 (en) 2003-06-09 2006-03-08 Kaneka Corporation Process for producing modified epoxy resin
US7438846B2 (en) 2001-04-23 2008-10-21 Envisiontec Gmbh Apparatus and method for the non-destructive separation of hardened material layers from a flat construction plane
EP2123711A1 (en) 2007-02-28 2009-11-25 Kaneka Corporation Thermosetting resin composition having rubbery polymer particle dispersed therein, and process for production thereof
US7625977B2 (en) 2007-06-20 2009-12-01 Dow Global Technologies Inc. Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener
US7642316B2 (en) 2004-10-14 2010-01-05 Dow Global Technologies, Inc. Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom
US7820760B2 (en) 2004-11-10 2010-10-26 Dow Global Technologies Inc. Amphiphilic block copolymer-modified epoxy resins and adhesives made therefrom
US20100280151A1 (en) 2009-05-04 2010-11-04 Toray Industries, Inc. Toughened fiber reinforced polymer composite with core-shell particles
US7892474B2 (en) 2006-11-15 2011-02-22 Envisiontec Gmbh Continuous generative process for producing a three-dimensional object
US20110106093A1 (en) 2009-10-29 2011-05-05 Zimmer, Inc. Patient-specific mill guide
US8088245B2 (en) 2007-04-11 2012-01-03 Dow Global Technologies Llc Structural epoxy resins containing core-shell rubbers
US8092465B2 (en) 2006-06-09 2012-01-10 Biomet Manufacturing Corp. Patient specific knee alignment guide and associated method
US8110135B2 (en) 2007-10-26 2012-02-07 Envisiontec Gmbh Process and freeform fabrication system for producing a three-dimensional object
US20120239045A1 (en) 2011-03-17 2012-09-20 Zimmer, Inc. Patient-specific instruments for total ankle arthroplasty
US20120251841A1 (en) 2009-12-17 2012-10-04 Dsm Ip Assets, B.V. Liquid radiation curable resins for additive fabrication comprising a triaryl sulfonium borate cationic photoinitiator
US20130295212A1 (en) 2012-04-27 2013-11-07 University Of Southern California Digital mask-image-projection-based additive manufacturing that applies shearing force to detach each added layer
US20130292862A1 (en) 2012-05-03 2013-11-07 B9Creations, LLC Solid Image Apparatus With Improved Part Separation From The Image Plate
US8591516B2 (en) 2006-02-27 2013-11-26 Biomet Manufacturing, Llc Patient-specific orthopedic instruments
US8632547B2 (en) 2010-02-26 2014-01-21 Biomet Sports Medicine, Llc Patient-specific osteotomy devices and methods
US20140025348A1 (en) 2012-07-23 2014-01-23 Zimmer, Inc. Patient-specific instrumentation for implant revision surgery
US8715289B2 (en) 2011-04-15 2014-05-06 Biomet Manufacturing, Llc Patient-specific numerically controlled instrument
US20140335341A1 (en) 2011-12-12 2014-11-13 Lg Chem, Ltd. Cyanate esters-based adhesive resin composition for fabrication of circuit board and flexible metal clad laminate comprising the same
US8932299B2 (en) 2010-06-18 2015-01-13 Howmedica Osteonics Corp. Patient-specific total hip arthroplasty
US20150072293A1 (en) 2013-08-14 2015-03-12 Eipi Systems, Inc. Continuous liquid interphase printing
US8980971B2 (en) 2007-03-20 2015-03-17 Dsm Ip Assets B.V. Stereolithography resin compositions and three-dimensional objects made therefrom
US20150097316A1 (en) 2013-02-12 2015-04-09 Carbon3D, Inc. Method and apparatus for three-dimensional fabrication with feed through carrier
US9060788B2 (en) 2012-12-11 2015-06-23 Biomet Manufacturing, Llc Patient-specific acetabular guide for anterior approach
US9066727B2 (en) 2010-03-04 2015-06-30 Materialise Nv Patient-specific computed tomography guides
US9066734B2 (en) 2011-08-31 2015-06-30 Biomet Manufacturing, Llc Patient-specific sacroiliac guides and associated methods
US20150184039A1 (en) 2012-08-27 2015-07-02 Dow Global Technologies Llc Accelerated and toughened two part epoxy adhesives
US20150215430A1 (en) 2014-01-30 2015-07-30 Thomson Licensing Per port ethernet packet processing mode by device type
US20150240113A1 (en) 2012-09-17 2015-08-27 3N Innovative Properties Company Powder coating epoxy compositions, methods, and articles
WO2015164234A1 (en) 2014-04-25 2015-10-29 Carbon3D, Inc. Continuous three dimensional fabrication from immiscible liquids
WO2016126779A1 (en) * 2015-02-05 2016-08-11 Carbon3D, Inc. Method of additive manufacturing by fabrication through multiple zones

Family Cites Families (53)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2628417C2 (en) 1976-06-24 1985-08-14 Bayer Ag, 5090 Leverkusen Curable Mixtures
JPS5626951A (en) 1979-08-08 1981-03-16 Mitsubishi Gas Chem Co Inc Curable resin composition
JPS5626911A (en) 1979-08-08 1981-03-16 Mitsubishi Gas Chem Co Inc Curable resin composition
JPS56110760A (en) 1980-02-06 1981-09-02 Mitsubishi Gas Chem Co Inc Curable resin composition
JPS56141321A (en) 1980-04-08 1981-11-05 Mitsubishi Gas Chem Co Inc Photosetting resin composition
US4740583A (en) 1984-05-11 1988-04-26 General Electric Company Method for converting cyclic polycarbonate oligomer mixtures to linear polycarbonate, and composition resulting therefrom
US4600760A (en) 1984-08-09 1986-07-15 The Dow Chemical Company Thermosettable resin composition containing alkenyl phenyl cyanate
US4775741A (en) 1986-07-21 1988-10-04 General Electric Company Preparation of resin composition from cyclic polycarbonate oligomers from spirobiindane bisphenol
US4757132A (en) 1986-10-20 1988-07-12 General Electric Company Cyclic polyester oligomer polymerization
JPH0757532B2 (en) 1988-10-19 1995-06-21 松下電工株式会社 Three-dimensional shape forming method
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.
US5143785A (en) 1990-08-20 1992-09-01 Minnesota Mining And Manufacturing Company Cyanate ester adhesives for electronic applications
US5466744A (en) 1990-11-05 1995-11-14 General Electric Company Polymerization of macrocyclic poly(alkylene dicarboxylate) oligomers
EP0525578A1 (en) 1991-08-02 1993-02-03 E.I. Du Pont De Nemours And Company Photopolymer composition for the production of three-dimensional objects
DE69315003T2 (en) 1992-07-17 1998-03-12 Ethicon Inc Radiation-curable urethane-acrylate prepolymers and cross-linked polymers
US5264061A (en) 1992-10-22 1993-11-23 Motorola, Inc. Method of forming a three-dimensional printed circuit assembly
US5679719A (en) 1993-03-24 1997-10-21 Loctite Corporation Method of preparing fiber/resin composites
US5744557A (en) 1993-06-16 1998-04-28 Minnesota Mining And Manufacturing Company Energy-curable cyanate/ethylenically unsaturated compositions
DE59407524D1 (en) 1993-08-26 1999-02-04 Ciba Geigy Ag Liquid radiation-curable composition, especially for stereolithography
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
US5494981A (en) 1995-03-03 1996-02-27 Minnesota Mining And Manufacturing Company Epoxy-cyanate ester compositions that form interpenetrating networks via a Bronsted acid
US5707780A (en) 1995-06-07 1998-01-13 E. I. Du Pont De Nemours And Company Photohardenable epoxy composition
US5498651A (en) 1995-06-19 1996-03-12 General Electric Company Method for polymerizing macrocyclic polyester oligomers
JP3498439B2 (en) * 1995-08-04 2004-02-16 住友電気工業株式会社 Curable resin composition, molded article using the same, and method for producing the same
EP0945755B1 (en) 1998-03-25 2002-06-05 Agfa-Gevaert A photosensitive image-forming element containing silver halide cristals internally modified with a metal-halogen-fluorine complex
KR100339183B1 (en) * 1998-07-13 2002-05-31 포만 제프리 엘 Die attachment with reduced adhesive bleed-out
US6632893B2 (en) 1999-05-28 2003-10-14 Henkel Loctite Corporation Composition of epoxy resin, cyanate ester, imidazole and polysulfide tougheners
US6658314B1 (en) 1999-10-06 2003-12-02 Objet Geometries Ltd. System and method for three dimensional model printing
DE19961926A1 (en) 1999-12-22 2001-07-05 Basf Coatings Ag Mixtures of substances curable thermally with actinic radiation and their use
ATE465434T1 (en) * 2000-02-08 2010-05-15 Huntsman Adv Mat Switzerland LIQUID, RADIATION-CURED COMPOSITION, PARTICULARLY FOR STEREOLITHOGRAPHY
US7300619B2 (en) 2000-03-13 2007-11-27 Objet Geometries Ltd. Compositions and methods for use in three dimensional model printing
US6309797B1 (en) 2000-04-26 2001-10-30 Spectra Group Limited, Inc. Selectively colorable polymerizable compositions
JP4382978B2 (en) 2000-12-04 2009-12-16 学校法人神奈川大学 Photo-curing / thermosetting resin composition
DE10115505B4 (en) 2001-03-29 2007-03-08 Basf Coatings Ag Thermal and actinic radiation curable aqueous dispersions, process for their preparation and their use
US6709738B2 (en) 2001-10-15 2004-03-23 3M Innovative Properties Company Coated substrate with energy curable cyanate resin
CA2557226A1 (en) 2004-03-22 2005-10-06 Huntsman Advanced Materials (Switzerland) Gmbh Photocurable compositions
JP2008516820A (en) 2004-10-19 2008-05-22 ロールス−ロイス・コーポレーション Method and apparatus associated with anisotropic shrinkage of sintered ceramic articles
US8334025B2 (en) * 2005-10-27 2012-12-18 3D Systems, Inc. Antimony-free photocurable resin composition and three dimensional article
WO2007056561A2 (en) 2005-11-09 2007-05-18 Liquidia Technologies, Inc. Medical device, materials, and methods
US20080103226A1 (en) 2006-10-31 2008-05-01 Dsm Ip Assets B.V. Photo-curable resin composition
US8128393B2 (en) 2006-12-04 2012-03-06 Liquidia Technologies, Inc. Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom
JP4863288B2 (en) * 2007-03-20 2012-01-25 Jsr株式会社 Photo-curable resin composition for optical three-dimensional modeling and three-dimensional modeling
CA2681201C (en) 2007-04-03 2016-06-14 Basf Se Photoactivable nitrogen bases
WO2012033483A1 (en) * 2010-09-07 2012-03-15 3M Innovative Properties Company Curable resin composition and multi-layer laminate manufactured using the same
US8801418B2 (en) 2011-01-31 2014-08-12 Global Filtration Systems Method and apparatus for making three-dimensional objects from multiple solidifiable materials
EP2757118A1 (en) 2013-01-17 2014-07-23 Allnex Belgium, S.A. Radiation curable aqueous compositions with reversible drying.
WO2014126830A2 (en) * 2013-02-12 2014-08-21 Eipi Systems, Inc. Method and apparatus for three-dimensional fabrication
CN103571211A (en) 2013-10-13 2014-02-12 甘春丽 Dual-curing composition
JP6433651B2 (en) 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 Adhesive, adhesive-attached member, and connection method between members
KR20170023977A (en) 2014-06-23 2017-03-06 카본, 인크. Polyurethane resins having multiple mechanisms of hardening for use in producing three-dimensional objects
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
US9708440B2 (en) 2015-06-18 2017-07-18 Novoset, Llc High temperature three dimensional printing compositions

Patent Citations (56)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3448079A (en) 1965-05-26 1969-06-03 Bayer Ag Phenolic resins containing cyanic ester groups
US4371689A (en) 1979-08-08 1983-02-01 Mitsubishi Gas Chemical Company, Inc. Curable resin composition comprising cyanate ester and acrylic alkenyl ester
US4421822A (en) 1979-08-20 1983-12-20 Minnesota Mining And Manufacturing Co. Ultraviolet polymerization of acrylate monomers using oxidizable tin compounds
US4389514A (en) 1980-09-26 1983-06-21 Congoleum Corporation Accelerated polymerization of acrylic monomers initiated by dialkyl and diaralkyl peroxide free radical generators in the presence of tin accelerators
US5236637A (en) 1984-08-08 1993-08-17 3D Systems, Inc. Method of and apparatus for production of three dimensional objects by stereolithography
US4604452A (en) 1985-10-21 1986-08-05 Celanese Corporation Metal carboxylate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US4839442A (en) 1986-11-24 1989-06-13 Hi-Tek Polymers, Inc. Low viscosity noncrystalline dicyanate ester blends with prepolymers of dicyanate esters
US4847233A (en) 1987-07-27 1989-07-11 Hi-Tek Polymers, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US4785075A (en) 1987-07-27 1988-11-15 Interez, Inc. Metal acetylacetonate/alkylphenol curing catalyst for polycyanate esters of polyhydric phenols
US5248456A (en) 1989-06-12 1993-09-28 3D Systems, Inc. Method and apparatus for cleaning stereolithographically produced objects
US5298532A (en) 1989-12-21 1994-03-29 Minnesota Mining And Manufacturing Company Method of accelerating photoiniferter polymerization, polymer produced thereby, and product produced therewith
US5529473A (en) 1990-07-05 1996-06-25 E. I. Du Pont De Nemours And Company Solid imaging system using differential tension elastomerc film
US5391072A (en) 1990-10-29 1995-02-21 E. I. Du Pont De Nemours And Company Solid imaging apparatus having a semi-permeable film
US5543516A (en) 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems
EP0945744A2 (en) * 1998-03-26 1999-09-29 Hughes Electronics Corporation Front end preparation procedure for coupling of light into a multi-mode fiber
US6207786B1 (en) 1998-11-10 2001-03-27 Edison Polymer Innovation Corporation Ternary systems of benzoxazine, epoxy, and phenolic resins
US6894113B2 (en) 2000-05-31 2005-05-17 Atofina Thermoset materials with improved impact resistance
US7438846B2 (en) 2001-04-23 2008-10-21 Envisiontec Gmbh Apparatus and method for the non-destructive separation of hardened material layers from a flat construction plane
US6620905B1 (en) 2002-02-23 2003-09-16 National Starch And Chemical Investment Holding Corporation Curable compositions containing benzoxazine
US6861475B2 (en) 2002-10-16 2005-03-01 Rohm And Haas Company Smooth, flexible powder coatings
EP1632533A1 (en) 2003-06-09 2006-03-08 Kaneka Corporation Process for producing modified epoxy resin
US20070027233A1 (en) 2003-06-09 2007-02-01 Katsumi Yamaguchi Process for producing modified epoxy resin
US7642316B2 (en) 2004-10-14 2010-01-05 Dow Global Technologies, Inc. Rubber modified monovinylidene aromatic polymers and fabricated articles prepared therefrom
US7820760B2 (en) 2004-11-10 2010-10-26 Dow Global Technologies Inc. Amphiphilic block copolymer-modified epoxy resins and adhesives made therefrom
US8591516B2 (en) 2006-02-27 2013-11-26 Biomet Manufacturing, Llc Patient-specific orthopedic instruments
US8092465B2 (en) 2006-06-09 2012-01-10 Biomet Manufacturing Corp. Patient specific knee alignment guide and associated method
US7892474B2 (en) 2006-11-15 2011-02-22 Envisiontec Gmbh Continuous generative process for producing a three-dimensional object
EP2123711A1 (en) 2007-02-28 2009-11-25 Kaneka Corporation Thermosetting resin composition having rubbery polymer particle dispersed therein, and process for production thereof
US8980971B2 (en) 2007-03-20 2015-03-17 Dsm Ip Assets B.V. Stereolithography resin compositions and three-dimensional objects made therefrom
US8088245B2 (en) 2007-04-11 2012-01-03 Dow Global Technologies Llc Structural epoxy resins containing core-shell rubbers
US7625977B2 (en) 2007-06-20 2009-12-01 Dow Global Technologies Inc. Adhesive of epoxy resin, toughener and blocked isocyanate polytetrahydrofuran toughener
US8110135B2 (en) 2007-10-26 2012-02-07 Envisiontec Gmbh Process and freeform fabrication system for producing a three-dimensional object
US20100280151A1 (en) 2009-05-04 2010-11-04 Toray Industries, Inc. Toughened fiber reinforced polymer composite with core-shell particles
US20110106093A1 (en) 2009-10-29 2011-05-05 Zimmer, Inc. Patient-specific mill guide
US20120251841A1 (en) 2009-12-17 2012-10-04 Dsm Ip Assets, B.V. Liquid radiation curable resins for additive fabrication comprising a triaryl sulfonium borate cationic photoinitiator
US8632547B2 (en) 2010-02-26 2014-01-21 Biomet Sports Medicine, Llc Patient-specific osteotomy devices and methods
US9066727B2 (en) 2010-03-04 2015-06-30 Materialise Nv Patient-specific computed tomography guides
US8932299B2 (en) 2010-06-18 2015-01-13 Howmedica Osteonics Corp. Patient-specific total hip arthroplasty
US20120239045A1 (en) 2011-03-17 2012-09-20 Zimmer, Inc. Patient-specific instruments for total ankle arthroplasty
US8715289B2 (en) 2011-04-15 2014-05-06 Biomet Manufacturing, Llc Patient-specific numerically controlled instrument
US9066734B2 (en) 2011-08-31 2015-06-30 Biomet Manufacturing, Llc Patient-specific sacroiliac guides and associated methods
US20140335341A1 (en) 2011-12-12 2014-11-13 Lg Chem, Ltd. Cyanate esters-based adhesive resin composition for fabrication of circuit board and flexible metal clad laminate comprising the same
US20130295212A1 (en) 2012-04-27 2013-11-07 University Of Southern California Digital mask-image-projection-based additive manufacturing that applies shearing force to detach each added layer
US20130292862A1 (en) 2012-05-03 2013-11-07 B9Creations, LLC Solid Image Apparatus With Improved Part Separation From The Image Plate
US20140025348A1 (en) 2012-07-23 2014-01-23 Zimmer, Inc. Patient-specific instrumentation for implant revision surgery
US20150184039A1 (en) 2012-08-27 2015-07-02 Dow Global Technologies Llc Accelerated and toughened two part epoxy adhesives
US20150240113A1 (en) 2012-09-17 2015-08-27 3N Innovative Properties Company Powder coating epoxy compositions, methods, and articles
US9060788B2 (en) 2012-12-11 2015-06-23 Biomet Manufacturing, Llc Patient-specific acetabular guide for anterior approach
US20150097316A1 (en) 2013-02-12 2015-04-09 Carbon3D, Inc. Method and apparatus for three-dimensional fabrication with feed through carrier
US9205601B2 (en) 2013-02-12 2015-12-08 Carbon3D, Inc. Continuous liquid interphase printing
US9211678B2 (en) 2013-02-12 2015-12-15 Carbon3D, Inc. Method and apparatus for three-dimensional fabrication
US9216546B2 (en) 2013-02-12 2015-12-22 Carbon3D, Inc. Method and apparatus for three-dimensional fabrication with feed through carrier
US20150072293A1 (en) 2013-08-14 2015-03-12 Eipi Systems, Inc. Continuous liquid interphase printing
US20150215430A1 (en) 2014-01-30 2015-07-30 Thomson Licensing Per port ethernet packet processing mode by device type
WO2015164234A1 (en) 2014-04-25 2015-10-29 Carbon3D, Inc. Continuous three dimensional fabrication from immiscible liquids
WO2016126779A1 (en) * 2015-02-05 2016-08-11 Carbon3D, Inc. Method of additive manufacturing by fabrication through multiple zones

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
CHU ET AL., MACROMOLECULAR SYMPOSIA, vol. 95, no. 1, June 1995 (1995-06-01), pages 233 - 242
J. BAUER; M. BAUER: "Cyanate ester based resin systems for snap-cure applications", MICROSYSTEM TECHNOLOGIES, vol. 8, 2002, pages 58 - 62
J. TUMBLESTON; D. SHIRVANYANTS; N. ERMOSHKIN ET AL.: "Continuous liquid interface production of 3D Objects", SCIENCE, vol. 347, 16 March 2015 (2015-03-16), pages 1349 - 1352, XP055247221, DOI: doi:10.1126/science.aaa2397
VELANKAR; PAZOS; COOPER, JOURNAL OF APPLIED POLYMER SCIENCE, vol. 162, 1996, pages 1361
Y. PAN ET AL., J. MANUFACTURING SCI. AND ENG., vol. 13, October 2012 (2012-10-01), pages 051011-1

Cited By (35)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110520276A (en) * 2017-03-27 2019-11-29 卡本有限公司 The method for manufacturing three-dimension object by increasing material manufacturing
CN106947205A (en) * 2017-04-19 2017-07-14 塑成科技(北京)有限责任公司 A kind of epoxy phenolic resin of Stereo Lithography Apparatus Rapid Prototyping and preparation method thereof
US11616302B2 (en) 2018-01-15 2023-03-28 Rogers Corporation Dielectric resonator antenna having first and second dielectric portions
WO2019167895A1 (en) * 2018-03-01 2019-09-06 コニカミノルタ株式会社 Resin composition and production method for three dimensional shaped object using same, and three dimensional shaped object
JPWO2019167895A1 (en) * 2018-03-01 2021-02-25 コニカミノルタ株式会社 A resin composition, a method for manufacturing a three-dimensional model using the resin composition, and a three-dimensional model.
JP7180666B2 (en) 2018-03-01 2022-11-30 コニカミノルタ株式会社 RESIN COMPOSITION, METHOD FOR MANUFACTURING 3D PRODUCT USING THE SAME, AND 3D PRODUCT
WO2019193961A1 (en) * 2018-04-02 2019-10-10 コニカミノルタ株式会社 Resin composition, method for manufacturing three-dimensionally shaped article using same, and three-dimensionally shaped article
JPWO2019193961A1 (en) * 2018-04-02 2021-04-30 コニカミノルタ株式会社 A resin composition, a method for producing a three-dimensional model using the resin composition, and a three-dimensional model.
JP7163956B2 (en) 2018-04-02 2022-11-01 コニカミノルタ株式会社 RESIN COMPOSITION, METHOD FOR MANUFACTURING 3D PRODUCT USING THE SAME, AND 3D PRODUCT
CN108559263A (en) * 2018-05-25 2018-09-21 黑龙江省科学院石油化学研究院 A kind of high temperature resistant bismaleimide resin composite material skin covering of the surface and preparation method thereof
CN108559263B (en) * 2018-05-25 2020-11-10 黑龙江省科学院石油化学研究院 High-temperature-resistant bismaleimide resin composite material surface film and preparation method thereof
CN108976788A (en) * 2018-06-05 2018-12-11 宁波市石生科技有限公司 A kind of resisting three-dimensional manufacture material and the method using material manufacture three-dimensional article
US11407890B2 (en) 2018-09-10 2022-08-09 Carbon, Inc. Dual cure additive manufacturing resins for production of flame retardant objects
US11834574B2 (en) 2018-09-10 2023-12-05 Carbon, Inc. Dual cure additive manufacturing resins for production of flame retardant objects
WO2020055682A1 (en) 2018-09-10 2020-03-19 Carbon, Inc. Dual cure additive manufacturing resins for production of flame retardant objects
US11552390B2 (en) 2018-09-11 2023-01-10 Rogers Corporation Dielectric resonator antenna system
WO2020065655A1 (en) 2018-09-28 2020-04-02 Stratasys Ltd. Three-dimensional inkjet printing of a thermally stable object
US11376799B2 (en) 2018-09-28 2022-07-05 Stratasys Ltd. Method for additive manufacturing with partial curing
US11235511B2 (en) 2018-09-28 2022-02-01 Stratasys Ltd. Three-dimensional inkjet printing of a thermally stable object
US11613071B2 (en) 2018-09-28 2023-03-28 Stratasys Ltd. Cyanate ester kit for a thermally stable object
CN109275983A (en) * 2018-09-30 2019-01-29 嘉兴学院 A kind of high flexibility insole and preparation method thereof
WO2020070639A1 (en) 2018-10-01 2020-04-09 Cubicure Gmbh Resin composition
EP3632941A1 (en) 2018-10-01 2020-04-08 Cubicure GmbH Resin composition
US11407169B2 (en) 2018-10-18 2022-08-09 Rogers Corporation Method for the manufacture of a spatially varying dielectric material, articles made by the method, and uses thereof
US11637377B2 (en) 2018-12-04 2023-04-25 Rogers Corporation Dielectric electromagnetic structure and method of making the same
US11401353B2 (en) 2019-05-30 2022-08-02 Rogers Corporation Photocurable compositions for stereolithography, method of forming the compositions, stereolithography methods using the compositions, polymer components formed by the stereolithography methods, and a device including the polymer components
US11787878B2 (en) 2019-05-30 2023-10-17 Rogers Corporation Photocurable compositions for stereolithography, method of forming the compositions, stereolithography methods using the compositions, polymer components formed by the stereolithography methods, and a device including the polymer components
US11559946B2 (en) 2019-08-14 2023-01-24 Mighty Buildings, Inc. 3D printing of a composite material via sequential dual-curing polymerization
US11602896B2 (en) 2019-08-14 2023-03-14 Mighty Buildings, Inc. 3D printing of a composite material via sequential dual-curing polymerization
US11619039B2 (en) 2020-03-05 2023-04-04 Mighty Buildings, Inc. Three-dimensional printed building components and structures
US11482790B2 (en) 2020-04-08 2022-10-25 Rogers Corporation Dielectric lens and electromagnetic device with same
US20220195236A1 (en) * 2020-12-23 2022-06-23 Formlabs, Inc. Multi-component composition for additive manufacturing
US11352514B1 (en) 2021-06-09 2022-06-07 Altana New Technologies Gmbh Dual-curable inkjet composition
CN116323826A (en) * 2021-06-09 2023-06-23 阿尔塔纳新技术有限公司 Dual cure cyanate ester ink jet compositions
WO2023247374A1 (en) 2022-06-23 2023-12-28 Technische Universität Wien Cyanate esters as monomers in polymerisable compositions

Also Published As

Publication number Publication date
EP3344676A1 (en) 2018-07-11
US11040483B2 (en) 2021-06-22
US20200023576A1 (en) 2020-01-23
CN108350145A (en) 2018-07-31
JP2018527442A (en) 2018-09-20
US20190010343A1 (en) 2019-01-10
CN108350145B (en) 2021-06-22
JP7069006B2 (en) 2022-05-17
US20200039141A1 (en) 2020-02-06
US11090859B2 (en) 2021-08-17
US10471655B2 (en) 2019-11-12
EP3344676B1 (en) 2023-04-12

Similar Documents

Publication Publication Date Title
US11090859B2 (en) Cyanate ester epoxy dual cure resins for additive manufacturing
US20170173866A1 (en) Production of injection molds by additive manufacturing with dual cure resins
US11891485B2 (en) Silicone dual cure resins for additive manufacturing
US11814472B2 (en) Epoxy dual cure resins for additive manufacturing
Chen et al. Thermal stability, mechanical and optical properties of novel addition cured PDMS composites with nano-silica sol and MQ silicone resin
CN103831914B (en) Methods and materials for fabricating laminate nanomolds and nanoparticles therefrom
WO2017112751A1 (en) Blocked silicone dual cure resins for additive manufacturing
EP3849806B1 (en) Dual cure additive manufacturing resins for production of flame retardant objects
US20230129561A1 (en) Methods of making a three-dimensional object
JP2009079163A (en) Curable composition, cured silsesquioxane, and method for producing cured silsesquioxane
CN108250838A (en) A kind of composition for ink for direct write method 3D printing silicone structure
JP7163956B2 (en) RESIN COMPOSITION, METHOD FOR MANUFACTURING 3D PRODUCT USING THE SAME, AND 3D PRODUCT
JP5385832B2 (en) Curable resin composition and molded product obtained therefrom
KR101344873B1 (en) Copolymer compositions, heat-resistant resin obtained therefrom and manufacturing method thereof
US11905423B2 (en) Blocked silicone dual cure resins for additive manufacturing
CN114616087A (en) Additive manufacturing method for realizing three-dimensional part with excellent performance

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16766748

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2018511267

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2016766748

Country of ref document: EP