# US 11,999,861 B2 · Thermosetting compositions and forming three-dimensionalobjects therefrom > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 11,999,861 B2 - Document ID: US11999861B2 - Status: Granted - Kind: B2 - Application number: 17/881,097 - Filed: 2022-08-04 - Published: 2023-02-23 - Granted: 2024-06-04 - Earliest claimed: 2016-10-28 - Assignees: Stratasys, Inc. - Applicants: Stratasys Inc. - Inventors: Paulus Antonius Maria Steeman; Marco Marcus Matheus Driessen - Web page: https://patentgrep.com/patent/US11999861B2 ## CPC - C09D 11/101: Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing - B29C 64/124: using layers of liquid which are selectively solidified - B33Y 10/00: Processes of additive manufacturing - B33Y 70/00: Materials specially adapted for additive manufacturing - C08F 290/061: {Polyesters; Polycarbonates} - C08F 290/064: {Polymers containing more than one epoxy group per molecule} - C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds - C09D 11/104: Polyesters - C09D 11/107: from unsaturated acids or derivatives thereof - C09D 11/30: Inkjet printing inks - B29C 64/153: using layers of powder being selectively joined, e.g. by selective laser sintering or melting - B33Y 70/10: Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials - G03F 7/0388: {with ethylenic or acetylenic bands in the side chains of the photopolymer} - C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D) - B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00) - B33Y: ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS - G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G) ## Abstract Thermoset compositions and methods for forming three-dimensional articles via an additive fabrication process, and articles made therefrom are disclosed herein. In an embodiment, a composition comprises a first network-forming component comprising a TPA-based polyester comprising a backbone and having at least 2 polymerizable groups, one or more first network monomers, and a first network initiator. The backbone of the TPA-based polyester comprises the reaction product of a terephthalic acid and a polyol. The composition may further comprise a second network-forming component. ## Claims ### Claim 1 A composition for forming a three-dimensional object via an additive fabrication process comprising: a. from 30 to 100 wt %, based on the total weight of the composition, of a first network-forming component comprising: i. from 19.95 to 80 wt %, based on the total weight of the first network-forming component, of a TPA-based polyester comprising a backbone and having a number average of at least 2 polymerizable groups, wherein the backbone comprises the reaction product of one or more polyacids including a terephthalic acid and a polyol, wherein the polymerizable groups comprise acrylate, methacrylate, epoxy, oxetane, hydroxyl, itaconate, vinyl ether, allyl ether, maleate, or fumarate, and wherein the TPA-based polyester has a number average molecular weight of from 800 to 10000 g/mol and a Tg of at least 25° C.; ii. from 19.95 to 80 wt %, based on the total weight of the network-forming component, of one or more first network monomers having a number average of 0.95 to 1.1 polymerizable groups that are able to (co)polymerize with the polymerizable groups of the TPA-based polyester, wherein a linear polymer formed from the one or more first network monomers has a Tg of at least 25° C.; and iii. from 0.05 to 5 wt %, based on the total weight of the first network-forming component, of one or more first network initiators capable of initiating the polymerization of the TPA-based polyester and the first network monomer; and b. a second network-forming component comprising one or more second network compounds comprising polymerizable groups that do not (co)polymerize with the polymerizable groups of the TPA-based polyester, and a second network initiator for initiating the polymerization of the one or more second network compounds. ### Claim 2 (depends on 1) The composition of claim 1, wherein the first network initiator comprises a photo-initiator. ### Claim 3 (depends on 1) The composition of claim 1, wherein a film formed by polymerizing 90% or more of total the polymerizable groups in the composition has a tensile modulus measured at 150° C. of from 3 and 50 MPa and a Tg of 40° C. or higher. ### Claim 4 (depends on 1) The composition according to claim 1, wherein the polymerizable groups comprise endgroups. ### Claim 5 (depends on 4) The composition according to claim 4, wherein the polymerizable groups consist of endgroups. ### Claim 6 (depends on 4) The composition of claim 4, wherein the TPA-based polyester has a number average of from 2 to 3 endgroups, and wherein the amount, number average molecular weight, and number average of endgroups of the TPA-based polyester in the composition satisfies the following equation: XMPa ≤ 3 * R * T * [ ( 3 - f ) * ( ρ * w polyester M polyester ) + ( f - 2 ) * 3 * ( ρ * w polyester M polyester ) ] ≤ YMPa wherein R is the gas constant 8.314 cm3 MPa K−1 mol−1, T is 423.15 K, f is the number average of endgroups of the TPA-based polyester, p is the density of the TPA-based polyester in g/cm3, Mpolyester is the number average molecular weight of the TPA-based polyester in g/mol, wpolyester is the weight fraction of the TPA-based polyester in the first network-forming component, X is 3, and Y is 50. ### Claim 7 (depends on 1) The composition of claim 1, wherein at least 50 mol % of the one or more polyacids consists of the terephthalic acid. ### Claim 8 (depends on 1) The composition of claim 1, wherein at least 75 mol % of the one or more polyacids consists of the terephthalic acid. ### Claim 9 (depends on 1) The composition of claim 1, wherein the TPA-based polyester has a number average of from 2 to 3 endgroups. ### Claim 10 (depends on 1) The composition of claim 1, wherein the TPA-based polyester has a number average molecular weight of from 800 to 8000 g/mol. ### Claim 11 (depends on 4) The composition of claim 4, wherein a linear polymer formed from the one or more first network monomers has a Tg of 60° C. or more. ### Claim 12 (depends on 1) The composition of claim 1, wherein the one or more first network monomers have a molecular weight of 300 g/mol or less. ### Claim 13 (depends on 1) The composition of claim 1, wherein the one or more first network monomers comprises methyl (meth)acrylate, hydroxy ethyl (meth)acrylate, hydroxy propyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, or isobutyl (meth)acrylate. ### Claim 14 (depends on 1) The composition of claim 1, wherein the one or more first network monomers comprises cyclohexene oxide, tert-butyl glycidyl ether, 4-chlorophenyl glycidyl ether, cyclopentene oxide, exo-2,3-Epoxynorbornane, 1,2-Epoxy-3-phenoxypropane, (2,3-Epoxypropyl)benzene, N-(2,3-Epoxypropyl)phthalimide, exo-3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride, 3,4-Epoxytetrahydrothiophene-1,1-dioxide, Furfuryl glycidyl ether, glycidyl 4-methoxyphenyl ether, glycidyl 2-methylphenyl ether, isophorone oxide, a-Pinene oxide, cis-stilbene oxide, styrene oxide, Methyl,Methyl 7-oxabicyclo[4.1.0]heptane-3-carboxylate, 22-Ethylhexyl 7-oxabicyclo(4.1.0)heptane-3-carboxylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(3-hydroxypropyl)oxymethyloxetane, or 3-ethyl-3-(4-hydroxybutyl)oxymethyloxetane. ### Claim 15 (depends on 1) A method of forming a three-dimensional object comprising: a. forming a layer of the composition according to claim 1, b. curing the layer with electromagnetic radiation in order to form a desired shape, and c. repeating the steps of forming and curing a plurality of times to obtain a three-dimensional object.