Materials for photoinitiated cationic ring-opening polymerization and their uses

Abstract

The present disclosure relates to materials for photoinitiated cationic ring-opening polymerization (ROP). The present disclosure also relates to the use of such materials, for example, in 3D printing.

Description

[Technical Field]

[0001] Related Applications This application claims the benefit of U.S. Provisional Patent Application No. 63 / 037,226, filed June 10, 2020, the entire contents of which are incorporated by reference. [Background technology]

[0002] Additive manufacturing, also known as 3D printing, generally refers to a relatively broad class of techniques for producing parts by computer-controlled methods that conform to desired 3D specifications, e.g., solid models. Many different types of materials have been used in such 3D printing, and different materials offer corresponding advantages and / or disadvantages for different manufacturing techniques. For example, a materials review can be found in Ligon et al. (Chemical Reviews 117(15):10212-10290(2017)).

[0003] In one type of manufacturing technique, inkjet printing technology is used to jet the material to be deposited onto a partially fabricated object. The jetted material is typically UV-cured immediately after deposition to form a thin layer of hardened material. To achieve precision manufacturing, some techniques use mechanical methods to maintain a precise interlayer structure, for example, using mechanical rollers or "planarizers" to control the surface shape, thereby controlling the accuracy of the fabricated object. Therefore, rapid curing is an important feature to enable planarization and obtain a precisely fabricated object. However, the material properties obtained with such inks may not be sufficient.

[0004] There is a need for new materials that can be used as inks in 3D printing. The present disclosure addresses this need. Summary of the Invention

[0005] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; and (ii) a polyol.

[0006] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; (ii) a polyol; and (iii) a cure catalyst (e.g., a photoinitiator).

[0007] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; (ii) a polyol; (iii) a cure catalyst (e.g., a photoinitiator); and (iv) a sensitizer.

[0008] In some aspects, the present disclosure provides materials of construction comprising the combinations disclosed herein.

[0009] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; and (ii) a polyol.

[0010] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; (ii) a polyol; and (iii) a cure catalyst (e.g., a photoinitiator).

[0011] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; (ii) a polyol; (iii) a cure catalyst (e.g., a photoinitiator); and (iv) a sensitizer.

[0012] In some aspects, the present disclosure provides kits comprising the combinations disclosed herein.

[0013] In some embodiments, the present disclosure provides a kit comprising: (i) a first building material comprising a ring-containing agent and / or polyol; (ii) a cure catalyst; and (iii) a second building material comprising a ring-containing agent and / or polyol; and (iv) a sensitizer.

[0014] In some embodiments, the present disclosure provides kits comprising a build material comprising (i) a ring-containing agent and / or a polyol, and (ii) a cure catalyst, and a support material.

[0015] In some embodiments, the present disclosure provides kits comprising a build material comprising (i) a ring-containing agent and / or polyol, (ii) a cure catalyst, and (iii) a sensitizer, and a support material.

[0016] In some embodiments, the present disclosure provides a kit comprising: a first building material comprising (i) a ring-containing agent and / or polyol, and (ii) a cure catalyst; a second building material comprising (iii) a ring-containing agent and / or polyol, and (iv) a sensitizer; and a support material.

[0017] In some aspects, the present disclosure provides a method of preparing a hardened material comprising subjecting a combination, build material, or kit disclosed herein to hardening conditions.

[0018] In some aspects, the present disclosure provides a combination, building material, or kit as disclosed herein for the preparation of a hardened material, said preparation comprising subjecting said combination, building material, or kit to hardening conditions.

[0019] In some aspects, the present disclosure provides the use of a combination, building material, or kit described herein in the manufacture of a hardened material, said manufacture comprising subjecting said combination, building material, or kit to curing conditions.

[0020] In some aspects, the present disclosure provides a cured material prepared by the methods described herein.

[0021] In some aspects, the present disclosure provides methods of printing objects using the combinations, build materials, or kits disclosed herein.

[0022] In some aspects, the present disclosure provides a combination, build material, or kit as disclosed herein for printing an object.

[0023] In some embodiments, the present disclosure provides a system for 3D printing comprising: (i) a printer (e.g., an inkjet printer); and (ii) an ink comprising the combination disclosed herein.

[0024] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. As used herein, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, suitable methods and materials are described below. All publications, patent applications, patents, and other references mentioned herein are incorporated by reference. No reference cited herein is admitted to be prior art to the claimed invention. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and not intended to be limiting. In the event of a conflict between the chemical structure and the name of a compound disclosed herein, the chemical structure shall control.

[0025] Other features and advantages of the present disclosure will become apparent from the following detailed description and claims. [Brief explanation of the drawings]

[0026] [Figure 1] FIG. 1 is a schematic diagram of an exemplary 3D printer.

[0027] [Figure 2] FIG. 2 is a schematic diagram of an alternative exemplary 3D printer. DETAILED DESCRIPTION OF THE INVENTION

[0028] Without wishing to be bound by theory, the present disclosure relates to the discovery of new materials for photoinitiated cationic ring-opening polymerization (ROP). Such materials may be suitable for use as inks for 3D printing. In some embodiments, such materials can enable 3D printing processes that do not require contact to control the surface shape of the printed object, for example, 3D printing processes that use a non-contact (e.g., optical) feedback approach.

[0029] Suitable applications and systems for the materials of the present disclosure are described, for example, in U.S. Provisional Application No. 62 / 777,422 and International Application No. PCT / US2019 / 065436, which are incorporated by reference. Combinations, Materials, and Kits of the Present Disclosure

[0030] In some embodiments, the present disclosure provides combinations, materials, or kits for photoinitiated cationic ring-opening polymerization (ROP).

[0031] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; and (ii) a polyol.

[0032] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; (ii) a polyol; and (iii) a cure catalyst (e.g., a photoinitiator).

[0033] In some embodiments, the present disclosure provides a combination comprising: (i) a ring-containing agent; (ii) a polyol; (iii) a cure catalyst (e.g., a photoinitiator); and (iv) a sensitizer.

[0034] In some aspects, the present disclosure provides materials of construction comprising the combinations disclosed herein.

[0035] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; and (ii) a polyol.

[0036] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; (ii) a polyol; and (iii) a cure catalyst (e.g., a photoinitiator).

[0037] In some embodiments, the present disclosure provides a build material comprising: (i) a ring-containing agent; (ii) a polyol; (iii) a cure catalyst (e.g., a photoinitiator); and (iv) a sensitizer.

[0038] In some aspects, the present disclosure provides kits comprising the combinations disclosed herein.

[0039] In some embodiments, the present disclosure provides a kit comprising: (i) a first building material comprising a ring-containing agent and / or polyol; (ii) a cure catalyst; and (iii) a second building material comprising a ring-containing agent and / or polyol; and (iv) a sensitizer.

[0040] In some embodiments, the present disclosure provides kits comprising a build material comprising (i) a ring-containing agent and / or a polyol, and (ii) a cure catalyst, and a support material.

[0041] In some embodiments, the present disclosure provides kits comprising a build material comprising (i) a ring-containing agent and / or polyol, (ii) a cure catalyst, and (iii) a sensitizer, and a support material.

[0042] In some embodiments, the present disclosure provides a kit comprising: a first building material comprising (i) a ring-containing agent and / or polyol, and (ii) a cure catalyst; a second building material comprising (iii) a ring-containing agent and / or polyol, and (iv) a sensitizer; and a support material.

[0043] In some embodiments, the combination, construction material, or kit further comprises a strengthening agent.

[0044] In some embodiments, the combination, construction material, or kit further comprises a stabilizer.

[0045] In some embodiments, the combination, construction material, or kit further comprises a surfactant.

[0046] In some embodiments, the combination, construction material, or kit further comprises a colorant.

[0047] For the materials described herein, the ring-containing agent, polyol, cure catalyst, sensitizer, and toughening agent can each, where applicable, be selected from the groups described herein, and it is understood that any group described herein for any of the ring-containing agent, polyol, cure catalyst, sensitizer, and toughening agent can be combined with any group described herein for one or more of the remaining ring-containing agents, polyols, cure catalysts, sensitizers, and toughening agents, where applicable. Ring-containing agents

[0048] In some embodiments, the ring-containing agent comprises an oxirane agent, an oxetane agent, or a combination thereof.

[0049] In some embodiments, the ring-containing agent comprises an oxirane agent.

[0050] In some embodiments, the ring-containing agent comprises an oxetane agent.

[0051] In some embodiments, the ring-containing agents comprise oxirane agents and oxetane agents.

[0052] In some embodiments, the ring-containing agent (eg, an oxirane agent, an oxetane agent, or a combination thereof) is also a surfactant.

[0053] In some embodiments, the oxirane agent is a monomer.

[0054] In some embodiments, the oxirane agent is a polymer.

[0055] In some embodiments, the ring-containing agent is [ka] wherein: [ka] each independently represents a direct or indirect bond to the remainder of the ring-containing agent.

[0056] In some embodiments, [ka] each independently represents a substitution.

[0057] In some embodiments, the ring-containing agent comprises a cycloaliphatic moiety, a resorcinol moiety, a phenol formaldehyde moiety, a bisphenol moiety, or any combination thereof.

[0058] In some embodiments, the ring-containing agent is selected from the group consisting of limonene dioxide, (3,4-epoxycyclohexane)methyl 3'-4'-epoxycyclohexyl-carboxylate, bis((3,4-epoxycyclohexyl)-methyl)adipate, 7-oxabicyclo[4.1.0]heptan-3-ylmethyl (e.g., UviCure S105 or UviCure S105E)), bis((3,4-epoxycyclohexyl)methyl)adipate (UviCure S128), 3-ethyloxetane-3-methanol (e.g., UviCure S130), 3-ethyl-3-[(phenylmethoxy)methyl]-oxetane (e.g., UviCure S140), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (e.g., UviCure S150), S150), 4,4-bis(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl (e.g., UviCure S160), 3-ethyl-3-(methacryloyloxy)methyloxetane (e.g., UviCureS170), EPALLOY® 5000, EPALLOY® 5001LC, EPALLOY® 5200, EPALLOY® 7200, EPALLOY® 9000, ERISYS® RDGE, ERISYS® RDGE-H, EPALLOY® 8220, EPALLOY® 8230, EPALLOY® 8240, EPALLOY® 8250, EPALLOY® 8280, EPALLOY® 7192, ERISYS® RF-50, ERISYS® RN-25, ERISYS® RN- 3650, EPALLOY® 9237-70, EPALLOY® 7138, EPALLOY® 7170, ERISYS® GE-60, ERISYS® GE-61, ERISYS® EGDGE, ERISYS® GE-20, ERISYS® GE21, ERISYS® GE-22, ERISYS® GE-24, ERISYS® GE-25, ERISYS® GE-29, ERISYS® GE-30, ERISYS® GE-31, ERISYS® GE-35, ERISYS® GE-35 H, ERISYS®GE-36, ERISYS® GE-38, ERISYS® GE-40, ERISYS® GA-240, ERISYS® GS-110, ERISYS® GS-120, ERISYS® GE-5, ERISYS® GE-6, ERISYS® GE-7, ERISYS® GE-8, ERISYS® GE-10, ERISYS® GE-11, ERISYS® GE-13, sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of brominated neopentyl glycol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether, castor oil glycidyl ether, propoxylated glycerin triglycidyl ether, polyglycerin-3-polyglycidyl ether, epoxidized pentaerythritol, epoxidized cyclohexanedimethanol, epoxidized metaxylylenediamine, glycidyl esters of neodecanoic acid, glycidyl esters of dimer acid, n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C8-C 10 Aliphatic glycidyl ether, C 12 -C 14 Comprising an aliphatic glycidyl ether, o-cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, Silmer® EPC C50, Silmer® EPC F418-F, Silmer® EP D208, Silmer® EPC Di-50, or any combination thereof.

[0059] In some embodiments, the ring-containing agent comprises limonene dioxide, (3,4-epoxycyclohexane)methyl 3',4'-epoxycyclohexyl-carboxylate, bis((3,4-epoxycyclohexyl)-methyl)adipate, or any combination thereof.

[0060] In some embodiments, the ring-containing agent comprises 7-oxabicyclo[4.1.0]heptan-3-ylmethyl (e.g., UviCure S105 or UviCure S105E), bis((3,4-epoxycyclohexyl)methyl)adipate (UviCure S128), 3-ethyloxetane-3-methanol (e.g., UviCure S130), 3-ethyl-3-[(phenylmethoxy)methyl]oxetane (e.g., UviCure S140), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene (e.g., UviCure S150), 4,4-bis(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl (e.g., UviCure S160), 3-ethyl-3-(methacryloyloxy)methyloxetane (e.g., UviCure S170), or any combination thereof.

[0061] In some embodiments, the ring-containing agent comprises 7-oxabicyclo[4.1.0]heptan-3-ylmethyl (eg, UviCure S105 or UviCure S105E).

[0062] In some embodiments, the ring-containing agent comprises UviCure S105.

[0063] In some embodiments, UviCure S105 is present at a concentration of about 50±30% w / w, about 50±20% w / w, about 50±10% w / w, about 50±5% w / w, about 50±4% w / w, about 50±3% w / w, about 50±2% w / w, or about 50±1% w / w (e.g., about 50% w / w).

[0064] In some embodiments, UviCure S105 is present at a concentration of about 50±30% w / w, about 40±20% w / w, about 40±10% w / w, about 40±5% w / w, about 40±4% w / w, about 40±3% w / w, about 40±2% w / w, or about 40±1% w / w (e.g., about 40% w / w).

[0065] In some embodiments, UviCure S105 is present at a concentration of about 20±10% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w).

[0066] In some embodiments, UviCure S105 is present at a concentration of about 5±3% w / w, about 5±2% w / w, about 5±1% w / w, about 5±0.9% w / w, about 5±0.8% w / w, about 5±0.7% w / w, about 5±0.6% w / w, about 5±0.5% w / w, about 5±0.4% w / w, about 5±0.3% w / w, about 5±0.2% w / w, or about 5±0.1% w / w (e.g., about 5% w / w).

[0067] In some embodiments, the ring-containing agent comprises a commercially available composition branded EPALLOY®.

[0068] In some embodiments, the ring-containing agent comprises EPALLOY® 5000, EPALLOY® 5001LC, EPALLOY® 5200, or any combination thereof.

[0069] In some embodiments, the ring-containing agent comprises EPALLOY® 7200, EPALLOY® 9000, or a combination thereof.

[0070] In some embodiments, the ring-containing agent comprises a commercially available composition under the trademark ERISYS®.

[0071] In some embodiments, the ring-containing agent comprises ERISYS® RDGE, ERISYS® RDGE-H, or a combination thereof.

[0072] In some embodiments, the ring-containing agent comprises EPALLOY® 8220, EPALLOY® 8230, EPALLOY® 8240, EPALLOY® 8250, EPALLOY® 8280, or a combination thereof.

[0073] In some embodiments, the ring-containing agent comprises EPALLOY® 7192.

[0074] In some embodiments, the ring-containing agent comprises EPALLOY® 8220.

[0075] In some embodiments, EPALLOY® 8220 is present at a concentration of about 20±10% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w).

[0076] In some embodiments, EPALLOY® 8215 is present at a concentration of about 15±10% w / w, about 15±5% w / w, about 15±4% w / w, about 15±3% w / w, about 15±2% w / w, or about 15±1% w / w (e.g., about 15% w / w).

[0077] In some embodiments, the ring-containing agent comprises ERISYS® RF-50, ERISYS® RN-25, ERISYS® RN-3650, or any combination thereof.

[0078] In some embodiments, the ring-containing agent comprises EPALLOY® 9237-70, EPALLOY® 7138, EPALLOY® 7170, or any combination thereof.

[0079] In some embodiments, the ring-containing agent is ERISYS® GE-60, ERISYS® GE-61, ERISYS® EGDGE, ERISYS® GE-20, ERISYS® GE-21, ERISYS® GE-22, ERISYS® GE-24, ERISYS® GE-25, ERISYS® GE-29, ERISYS® GE-30, ERISYS® GE-31, ERISYS® GE-35, ERISYS® GE-36, ERISYS® GE-37, ERISYS® GE-38, ERISYS® GE-39, ERISYS® GE-40, ERISYS® GE-41, ERISYS® GE-42, ERISYS® GE-43, ERISYS® GE-44, ERISYS® GE-45, ERISYS® GE-46, ERISYS® GE-47, ERISYS® GE-48, ERISYS® GE-49, ERISYS® GE-50, ERISYS® GE-51, ERISYS® GE-52, ERISYS® GE-53, ERISYS® GE-54, ERISYS® GE-55, ERISYS® GE-56, ERISYS® GE-57, ERISYS® GE-58, ERISYS® GE-59, ERISYS® GE-60, ERISYS® GE-61, ERISYS® EGDGE, ERISYS® GE-20, ERISYS® GE-21, ERISYS® GE-22, ERISYS® GE-24, ERISYS® GE-25, ERISYS® GE-29, ERISYS® GE-30, ERISYS® GE-31, ERISYS® GE-35, ERISYS® GE-59 H, ERISYS® GE-36, ERISYS® GE-38, ERISYS® GE-40, ERISYS® GA-240, ERISYS® GS-110, ERISYS® GS-120, ERISYS® GE-5, ERISYS® GE-6, ERISYS® GE-7, ERISYS® GE-8, ERISYS® GE-10, ERISYS® GE-11, ERISYS® GE-13 or any combination thereof.

[0080] In some embodiments, the ring-containing agent comprises ERISYS® GE-13.

[0081] In some embodiments, ERISYS® GE-13 is present at a concentration of about 10±5% w / w, about 10±4% w / w, about 10±3% w / w, about 10±2% w / w, about 10±1% w / w, about 10±0.9% w / w, about 10±0.8% w / w, about 10±0.7% w / w, about 10±0.6% w / w, about 10±0.5% w / w, about 10±0.4% w / w, about 10±0.3% w / w, about 10±0.2% w / w, or about 10±0.1% w / w (e.g., about 10% w / w).

[0082] In some embodiments, the ring-containing agent comprises sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of brominated neopentyl glycol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether, castor oil glycidyl ether, propoxylated glycerin triglycidyl ether, polyglycerin-3-polyglycidyl ether, epoxidized pentaerythritol, epoxidized cyclohexanedimethanol, or any combination thereof.

[0083] In some embodiments, the ring-containing agent comprises an epoxidized metaxylylenediamine.

[0084] In some embodiments, the ring-containing agent comprises a glycidyl ester of neodecanoic acid, a glycidyl ester of dimer acid, or a combination thereof.

[0085] In some embodiments, the ring-containing agent is n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C8-C 10 Aliphatic glycidyl ether, C 12 -C 14 aliphatic glycidyl ethers or any combination thereof.

[0086] In some embodiments, the ring-containing agent comprises o-cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, or any combination thereof.

[0087] In some embodiments, the ring-containing agent comprises a commercially available composition under the trademark Silmer®.

[0088] In some embodiments, the ring-containing agent comprises Silmer® EPC C50, Silmer® EPC F418-F, Silmer® EP D208, Silmer® EPC Di-50, or any combination thereof.

[0089] In some embodiments, the ring-containing agent comprises Silmer® EPC F418-F.

[0090] In some embodiments, the oxirane agent is present at a concentration of about 99% w / w or less, about 98% w / w or less, about 97% w / w or less, about 96% w / w or less, about 95% w / w or less, about 90% w / w or less, about 85% w / w or less, about 80% w / w or less, about 75% w / w or less, about 70% w / w or less, about 65% w / w or less, or about 60% w / w or less.

[0091] In some embodiments, the oxirane agent is present at a concentration of about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, about 4% w / w or more, about 5% w / w or more, about 10% w / w or more, about 15% w / w or more, about 20% w / w or more, about 25% w / w or more, about 30% w / w or more, about 35% w / w or more, about 40% w / w or more, about 45% w / w or more, or about 50% w / w or more.

[0092] In some embodiments, the oxirane agent is present at a concentration of about 45±20% w / w, about 45±15% w / w, about 45±10% w / w, about 45±8% w / w, about 45±6% w / w, about 45±5% w / w, about 45±4% w / w, about 45% w / w, about 45±2% w / w, or about 45±1% w / w (e.g., about 45% w / w).

[0093] In some embodiments, the oxirane agent is present at a concentration of about 55±20% w / w, about 55±15% w / w, about 55±10% w / w, about 55±8% w / w, about 55±6% w / w, about 55±5% w / w, about 55±4% w / w, about 55% w / w, about 55±2% w / w, or about 55±1% w / w (e.g., about 55% w / w).

[0094] In some embodiments, the oxirane agent is present at a concentration of about 65±20% w / w, about 65±15% w / w, about 65±10% w / w, about 65±8% w / w, about 65±6% w / w, about 65±5% w / w, about 65±4% w / w, about 65% w / w, about 65±2% w / w, or about 65±1% w / w (e.g., about 65% w / w).

[0095] In some embodiments, the oxetane agent is a monomer.

[0096] In some embodiments, the oxetane agent is a polymer.

[0097] In some embodiments, the oxetane agent is [ka] where: [ka] each independently represents a direct or indirect bond to the remainder of the oxetane agent.

[0098] In some embodiments, [ka] each independently represents a substitution.

[0099] In some embodiments, the oxetane agent comprises 3-ethyl-3-[(phenylmethoxy)methyl]-oxetane, 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, 3-ethyloxetane-3-methanol, 4,4-bis(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 3-ethyl-3-(methacryloyloxy)methyloxetane, or any combination thereof.

[0100] In some embodiments, the oxetane agent comprises 3-ethyl-3-[(phenylmethoxy)methyl]-oxetane.

[0101] In some embodiments, the oxetane agent comprises 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene.

[0102] In some embodiments, the oxetane agent comprises 3-ethyloxetane-3-methanol.

[0103] In some embodiments, the oxetane agent comprises 4,4-bis(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl.

[0104] In some embodiments, the oxetane agent comprises 3-ethyl-3-(methacryloyloxy)methyloxetane.

[0105] In some embodiments, the oxetane agent is present at a concentration of about 60% w / w or less, about 55% w / w or less, about 50% w / w or less, about 45% w / w or less, about 40% w / w or less, about 35% w / w or less, about 30% w / w or less, about 25% w / w or less, or about 20% w / w or less.

[0106] In some embodiments, the oxetane agent is present at a concentration of about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, about 4% w / w or more, about 5% w / w or more, about 10% w / w or more, or about 15% w / w or more.

[0107] In some embodiments, the oxetane agent is present at a concentration of about 15±10% w / w, about 15±8% w / w, about 15±6% w / w, about 15±5% w / w, about 15±4% w / w, about 15±2% w / w, or about 15±1% w / w (e.g., about 15% w / w).

[0108] In some embodiments, the oxetane agent is present at a concentration of about 20±15% w / w, about 20±10% w / w, about 20±8% w / w, about 20±6% w / w, about 20±5% w / w, about 20±4% w / w, about 20% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w).

[0109] In some embodiments, the oxetane agent is present at a concentration of about 25±15% w / w, about 25±10% w / w, about 25±8% w / w, about 25±6% w / w, about 25±5% w / w, about 25±4% w / w, about 25% w / w, about 25±2% w / w, or about 25±1% w / w (e.g., about 25% w / w). polyol

[0110] In some embodiments, the polyol comprises a diol, a triol, a tetrol, a dendritic polyol, or any combination thereof.

[0111] In some embodiments, the polyol comprises a diol.

[0112] In some embodiments, the polyol comprises a triol.

[0113] In some embodiments, the polyol comprises a tetrol.

[0114] In some embodiments, the polyol comprises a polyol.

[0115] In some embodiments, the polyol comprises polycaprolactone, polypropylene, polyethylene, or polytetrahydrofuran.

[0116] In some embodiments, the polyol comprises a polycaprolactone diol, a polypropylene diol, a polyethylene diol, or any combination thereof.

[0117] In some embodiments, the polyol comprises polycaprolactone triol, polypropylene triol, polyethylene triol, or any combination thereof.

[0118] In some embodiments, the polyol comprises polycaprolactone triol, polypropylene triol, polyethylene triol, or any combination thereof.

[0119] In some embodiments, the polyol comprises a polycaprolactone diol, a polycaprolactone triol, a polycaprolactone tetrol, or any combination thereof.

[0120] In some embodiments, the polyol (e.g., polycaprolactone diol, polycaprolactone triol, or polycaprolactone tetrol) has a molecular weight of about 8000 or less, about 7500 or less, about 7000 or less, about 6500 or less, about 6000 or less, about 5500 or less, about 5000 or less, about 4500 or less, about 4000 or less, about 3500 or less, about 3400 or less, about 3300 or less, about 3200 or less, about 3100 or less, about 3000 or less, about 2900 or less, about 2800 or less, about 2700 or less, about 2600 or less, about 2500 or less, about 2400 or less, about 2300 or less, about 2200 or less, about 2100 or less, or about 2000 or less.

[0121] In some embodiments, the polyol (e.g., polycaprolactone diol, polycaprolactone triol, or polycaprolactone tetrol) has a molecular weight of about 200 or greater, about 300 or greater, about 400 or greater, about 500 or greater, about 600 or greater, about 700 or greater, about 800 or greater, about 900 or greater, about 1000 or greater, about 1100 or greater, about 1200 or greater, about 1300 or greater, about 1400 or greater, or about 1500 or greater.

[0122] In some embodiments, the polyol comprises a polycaprolactone diol.

[0123] In some embodiments, the polyol (e.g., polycaprolactone diol) has a molecular weight of about 2000±1500, about 2000±1400, about 2000±1300, about 2000±1200, about 2000±1100, about 2000±1000, about 2000±900, about 2000±800, about 2000±700, about 2000±600, about 2000±500, about 2000±400, about 2000±300, about 2000±200, about 2000±100, about 2000±50, about 2000±40, about 2000±30, about 2000±20, or about 2000±10 (e.g., about 2000).

[0124] In some embodiments, the polyol (e.g., polycaprolactone diol) has a molecular weight of about 530±300, about 530±200, about 530±100, about 530±50, about 530±40, about 530±30, about 530±20, or about 530±10 (e.g., about 530).

[0125] In some embodiments, the polyol is a polycaprolactone diol having a molecular weight of about 530.

[0126] In some embodiments, the polycaprolactone diol (e.g., having a molecular weight of about 530) is present at a concentration of about 20±10% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w).

[0127] In some embodiments, the polyol comprises a polycaprolactone triol.

[0128] In some embodiments, the polyol (e.g., polycaprolactone triol) has a molecular weight of about 900±600, about 900±500, about 900±400, about 900±300, about 900±200, about 900±100, about 900±50, about 900±40, about 900±30, about 900±20, or about 900±10 (e.g., about 900).

[0129] In some embodiments, the polyol (e.g., polycaprolactone triol) has a molecular weight of about 300±100, about 300±50, about 300±40, about 300±30, about 300±20, or about 300±10 (e.g., about 300).

[0130] In some embodiments, the polyol comprises a commercially available composition branded Capa®.

[0131] In some embodiments, the polyol comprises Capa® 2043, Capa® 2047A, Capa® 2054J, Capa® 20610AJ, Capa® 2065, Capa® 3050J, Capa® 3031, Capa® 3091, Capa® 3050J, Capa® 3022, Capa® 4101, Capa® 8015D, or any combination thereof.

[0132] In some embodiments, the polyol comprises Capa® 2043, Capa® 3031, or a combination thereof.

[0133] In some embodiments, Capa® 2043 is present at a concentration of 12.5±5% w / w, 12.5±4% w / w, 12.5±3% w / w, 12.5±2% w / w, or 12.5±1% w / w (e.g., 12.5% ​​w / w).

[0134] In some embodiments, Capa® 2043 is present at a concentration of 10±5% w / w, 10±4% w / w, 10±3% w / w, 10±2% w / w, or 10±1% w / w (e.g., 10% w / w).

[0135] In some embodiments, Capa® 3031 is present at a concentration of 20±10% w / w, 20±5% w / w, 20±4% w / w, 20±3% w / w, 20±2% w / w, or 20±1% w / w (e.g., 20% w / w).

[0136] In some embodiments, Capa® 3031 is present at a concentration of 15±10% w / w, 15±5% w / w, 15±4% w / w, 15±3% w / w, 15±2% w / w, or 15±1% w / w (e.g., 15% w / w).

[0137] In some embodiments, Capa® 3031 is present at a concentration of 10±5% w / w, 10±4% w / w, 10±3% w / w, 10±2% w / w, or 10±1% w / w (e.g., 10% w / w).

[0138] In some embodiments, the polyol comprises Capromer™ PD4-05, Capromer™ PT1-05, Capromer™ PD1-10, Capromer™ PD1-20A, Capromer™ PD1-20, or any combination thereof.

[0139] In some embodiments, the polyol comprises Capromer™ PD4-05.

[0140] In some embodiments, Capromer™ PD4-05 is present at a concentration of 16±10% w / w, 16±5% w / w, 16±4% w / w, 16±3% w / w, 16±2% w / w, or 16±1% w / w (e.g., 16% w / w).

[0141] In some embodiments, the polyol comprises a polypropylene diol, a polypropylene triol, or a polypropylene tetrol.

[0142] In some embodiments, the polyol comprises polypropylene glycol.

[0143] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 300 or more, about 400 or more, about 500 or more, about 600 or more, about 700 or more, about 800 or more, about 900 or more, about 1000 or more, about 1100 or more, about 1200 or more, about 1300 or more, about 1400 or more, about 1500 or more, about 2000 or more, about 2500 or more, about 3000 or more, about 3500 or more, about 4000 or more, about 4500 or more, or about 5000 or more.

[0144] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 8000 or less, about 7000 or less, about 6000 or less, about 5000 or less, about 4000 or less, about 3000 or less, about 2000 or less, about 1000 or less, about 900 or less, about 800 or less, about 700 or less, about 600 or less, about 500 or less, about 400 or less, or about 300 or less.

[0145] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 2700±1500, about 2700±1400, about 2700±1300, about 2700±1200, about 2700±1100, about 2700±1000, about 2700±900, about 2700±800, about 2700±700, about 2700±600, about 2700±500, about 2700±400, about 2700±300, about 2700±200, about 2700±100, about 2700±50, about 2700±40, about 2700±30, about 2700±20, or about 2700±10 (e.g., about 2700).

[0146] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 2000±1500, about 2000±1400, about 2000±1300, about 2000±1200, about 2000±1100, about 2000±1000, about 2000±900, about 2000±800, about 2000±700, about 2000±600, about 2000±500, about 2000±400, about 2000±300, about 2000±200, about 2000±100, about 2000±50, about 2000±40, about 2000±30, about 2000±20, or about 2000±10 (e.g., about 2000).

[0147] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 1500±1000, about 1500±900, about 1500±800, about 1500±700, about 1500±600, about 1500±500, about 1500±400, about 1500±300, about 1500±200, about 1500±100, about 1500±50, about 1500±40, about 1500±30, about 1500±20, or about 1500±10 (e.g., about 1500).

[0148] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 1000±600, about 1000±500, about 1000±400, about 1000±300, about 1000±200, about 1000±100, about 1000±50, about 1000±40, about 1000±30, about 1000±20, or about 1000±10 (e.g., about 1000).

[0149] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 725±400, about 725±300, about 725±200, about 725±100, about 725±50, about 725±40, about 725±30, about 725±20, or about 725±10 (e.g., about 725).

[0150] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 450±200, about 450±100, about 450±50, about 450±40, about 450±30, about 450±20, or about 450±10 (e.g., about 450).

[0151] In some embodiments, the polyol (e.g., polypropylene glycol) has a molecular weight of about 425±200, about 425±100, about 425±50, about 425±40, about 425±30, about 425±20, or about 425±10 (e.g., about 425).

[0152] In some embodiments, the polyol comprises polypropylene glycol P400, polypropylene glycol P425, polypropylene glycol P1000, polypropylene glycol P1200, polypropylene glycol P2000, or any combination thereof.

[0153] In some embodiments, the polyol comprises a polyethylene diol, a polyethylene triol, or a polyethylene tetrol.

[0154] In some embodiments, the polyol comprises polyethylene glycol.

[0155] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 300 or greater, about 400 or greater, about 500 or greater, about 600 or greater, about 700 or greater, about 800 or greater, about 900 or greater, about 1000 or greater, about 1100 or greater, about 1200 or greater, about 1300 or greater, about 1400 or greater, about 1500 or greater, about 2000 or greater, or about 2500 or greater.

[0156] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 8000 or less, about 7000 or less, about 6000 or less, about 5000 or less, about 4000 or less, about 3500 or less, about 3000 or less, about 2000 or less, about 1000 or less, about 900 or less, about 800 or less, about 700 or less, about 600 or less, about 500 or less, about 400 or less, or about 300 or less.

[0157] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 2000±1100, about 2000±1000, about 2000±900, about 2000±800, about 2000±700, about 2000±600, about 2000±500, about 2000±400, about 2000±300, about 2000±200, about 2000±100, about 2000±50, about 2000±40, about 2000±30, about 2000±20, or about 2000±10 (e.g., about 2000).

[0158] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 1500±700, about 1500±600, about 1500±500, about 1500±400, about 1500±300, about 1500±200, about 1500±100, about 1500±50, about 1500±40, about 1500±30, about 1500±20, or about 1500±10 (e.g., about 1500).

[0159] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 1000±500, about 1000±400, about 1000±300, about 1000±200, about 1000±100, about 1000±50, about 1000±40, about 1000±30, about 1000±20, or about 1000±10 (e.g., about 1000).

[0160] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 600±300, about 600±200, about 600±100, about 600±50, about 600±40, about 600±30, about 600±20, or about 600±10 (e.g., about 600).

[0161] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 400±200, about 400±100, about 400±50, about 400±40, about 400±30, about 400±20, or about 400±10 (e.g., about 400).

[0162] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 300±200, about 300±100, about 300±50, about 300±40, about 300±30, about 300±20, or about 300±10 (e.g., about 300).

[0163] In some embodiments, the polyol (e.g., polyethylene glycol) has a molecular weight of about 200±100, about 200±50, about 200±40, about 200±30, about 200±20, or about 200±10 (e.g., about 200).

[0164] In some embodiments, the polyol comprises polytetrahydrofuran diol, polytetrahydrofuran triol, or polytetrahydrofuran tetrol.

[0165] In some embodiments, the polyol comprises polytetrahydrofuran diol.

[0166] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 300 or more, about 400 or more, about 500 or more, about 600 or more, about 700 or more, about 800 or more, about 900 or more, about 1000 or more, about 1100 or more, about 1200 or more, about 1300 or more, about 1400 or more, about 1500 or more, or about 2000 or more. n )).

[0167] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 8000 or less, about 7000 or less, about 6000 or less, about 5000 or less, about 4000 or less, about 3500 or less, about 3400 or less, about 3300 or less, about 3200 or less, about 3100 or less, about 3000 or less, about 2900 or less, about 2800 or less, about 2700 or less, about 2600 or less, about 2500 or less, about 2000 or less, about 1500 or less, about 1000 or less, about 900 or less, about 800 or less, about 700 or less, about 600 or less, about 500 or less, about 400 or less, about 300 or less, or about 200 or less. n )).

[0168] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 2000±1100, about 2000±1000, about 2000±900, about 2000±800, about 2000±700, about 2000±600, about 2000±500, about 2000±400, about 2000±300, about 2000±200, about 2000±100, about 2000±50, about 2000±40, about 2000±30, about 2000±20, or about 2000±10. n)) (e.g., about 2000).

[0169] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 1800±900, about 1800±800, about 1800±700, about 1800±600, about 1800±500, about 1800±400, about 1800±300, about 1800±200, about 1800±100, about 1800±50, about 1800±40, about 1800±30, about 1800±20, or about 1800±10. n )) (e.g., about 1800).

[0170] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 1400±700, about 1400±600, about 1400±500, about 1400±400, about 1400±300, about 1400±200, about 1400±100, about 1400±50, about 1400±40, about 1400±30, about 1400±20, or about 1400±10. n )) (e.g., about 1400).

[0171] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 1000±500, about 1000±400, about 1000±300, about 1000±200, about 1000±100, about 1000±50, about 1000±40, about 1000±30, about 1000±20, or about 1000±10. n )) (e.g., about 1000).

[0172] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 650±300, about 650±200, about 650±100, about 650±50, about 650±40, about 650±30, about 650±20, or about 650±10. n )) (e.g., about 650).

[0173] In some embodiments, the polyol (e.g., polytetrahydrofuran diol) has a molecular weight (e.g., number average molecular weight (M)) of about 250±100, about 250±50, about 250±40, about 250±30, about 250±20, or about 250±10. n )) (e.g., about 250).

[0174] In some embodiments, the polyol has a number average molecular weight (M n ) is a polytetrahydrofuran diol having the formula

[0175] In some embodiments, the number average molecular weight (M n ) is present in a concentration of about 15±10% w / w, 15±5% w / w, 15±4% w / w, 15±3% w / w, 15±2% w / w, or 15±1% w / w (e.g., 15% w / w).

[0176] In some embodiments, the polyol comprises a dendritic polyol.

[0177] In some embodiments, the polyol comprises a polyester dendritic polyol, a polyether dendritic polyol, a polythioether dendritic polyol, a polyamide dendritic polyol, a polyetherketone dendritic polyol, a polyalkyleneimine dendritic polyol, a polyamidoamine dendritic polyol, a polyetheramide dendritic polyol, a polyarylene dendritic polyol, a polyalkylene dendritic polyol, an aromatic polyalkylene dendritic polyol, a polyarylacetylene dendritic polyol, a phosphorus- or silicon-containing dendritic polyol, or any combination thereof.

[0178] In some embodiments, the polyol comprises a commercially available composition branded Boltorn™.

[0179] In some embodiments, the polyol comprises Boltorn™ H2004, Boltorn™ H311, Boltorn™ P1000, Boltorn™ P500, Boltorn™ P501, Boltorn™ U3000, Boltorn™ W3000, Boltorn™ H20, Boltorn™ H2003, Boltorn™ H2004, Boltorn™ H30, Boltorn™ H40, or any combination thereof.

[0180] In some embodiments, the polyol comprises a dendritic polyol as described in J. Polymer Science: Part A: Polymer Chemistry, 42:3110-3115 (2004).

[0181] In some embodiments, the polyol comprises a commercially available composition branded Hybrane™.

[0182] In some embodiments, the polyol comprises Hybrane™ P1000, Hybrane™ S1200, Hybrane™ H1500, Hybrane™ PS2550, or any combination thereof.

[0183] In some embodiments, the polyol (e.g., diol, triol, tetrol, or dendritic polyol) is present at a concentration of about 60% w / w or less, about 55% w / w or less, about 50% w / w or less, about 45% w / w or less, about 40% w / w or less, about 35% w / w or less, about 30% w / w or less, about 25% w / w or less, about 20% w / w or less, about 15% w / w or less, about 10% w / w or less, about 5% w / w or less, about 4% w / w or less, about 3% w / w or less, about 2% w / w or less, or about 1% w / w or less.

[0184] In some embodiments, the polyol (e.g., diol, triol, tetrol, or dendritic polyol) is present at a concentration of about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, about 4% w / w or more, about 5% w / w or more, about 6% w / w or more, about 7% w / w or more, about 8% w / w or more, about 9% w / w or more, about 10% w / w or more, about 15% w / w or more, or about 20% w / w or more.

[0185] In some embodiments, the polyol (e.g., diol, triol, tetrol, or dendritic polyol) is present in an amount of about 1% w / w, about 2% w / w, about 3% w / w, about 4% w / w, about 5% w / w, about 6% w / w, about 7% w / w, about 8% w / w, about 9% w / w, about 10% w / w, about 11% w / w, about 12% w / w, about 13% w / w, about 14% w / w, about 15% w / w, about 16% w / w, about 17% w / w, about 18% w / w, about 19% w / w, about 20% w / w, about 21% w / w, about 22% w / w, about 23% w / w, about 24% w / w, about 25% w / w, about 26% w / w, about 27% w / w, about 28% w / w, about 29% w / w, about 30% w / w, about 31% w / w, about 32% w / w, about 33% w / w, about 34% w / w, about 35% w / w, about 36% w / w, about 37% w / w, about 38% w / w, about 39% w / w, about 40% w / w, about 41% w / w, about 42% w / w, about 43% w / w, about 44% w / w, about 45% w / w, about 46% w / w, about 47% w / w, about 48% w / w, about 49% w / w, about 50% w / w, about 51% w / w, about 52% w / w, about 53% w / w, about 54% about 19% w / w, about 20% w / w, about 21% w / w, about 22% w / w, about 23% w / w, about 24% w / w, about 25% w / w, about 26% w / w, about 27% w / w, about 28% w / w, about 29% w / w, about 30% w / w, about 31% w / w, about 32% w / w, about 33% w / w, about 34% w / w, about 35% w / w, about 36% w / w, about 37% w / w, about 38% w / w, about 39% w / w or about 40% w / w.

[0186] In some embodiments, the polyol (e.g., diol, triol, tetrol, or dendritic polyol) is present at a concentration of about 20±15% w / w, about 20±10% w / w, about 20±9% w / w, about 20±8% w / w, about 20±7% w / w, about 20±6% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w). curing catalyst

[0187] In some embodiments, the cure catalyst is a latent catalyst.

[0188] In some embodiments, the latent catalyst is a photolatent catalyst or a chemically latent catalyst.

[0189] In some embodiments, the curing catalyst is activated by radiation.

[0190] In some embodiments, the curing catalyst is activated by ultraviolet light.

[0191] In some embodiments, the cure catalyst is activated by a sensitizer.

[0192] In some embodiments, the cure catalyst is a photoinitiator.

[0193] In some embodiments, the cure catalyst (eg, photoinitiator) comprises a cationic photoinitiator, an anionic photoinitiator, or a combination thereof.

[0194] In some embodiments, the cure catalyst (eg, photoinitiator) comprises a cationic photoinitiator.

[0195] In some embodiments, the cure catalyst (eg, photoinitiator) is a precursor to an acid (eg, a cation).

[0196] In some embodiments, the cure catalyst (eg, photoinitiator) is converted to or releases an acid (eg, a cation) upon activation.

[0197] In some embodiments, the cure catalyst (eg, photoinitiator) is an iodonium catalyst.

[0198] In some embodiments, the cure catalyst (eg, photoinitiator) is a sulfonium catalyst.

[0199] In some embodiments, the curing catalyst (eg, photoinitiator) comprises an organic photoinitiator, an inorganic photoinitiator, or a combination thereof.

[0200] In some embodiments, the curing catalyst (eg, photoinitiator) comprises an organic photoinitiator.

[0201] In some embodiments, the cure catalyst (eg, photoinitiator) comprises an organic cationic photoinitiator.

[0202] In some embodiments, the curing catalyst (e.g., photoinitiator) is selected from the group consisting of bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, bis(4-tert-butylphenyl)iodonium triflate, Boc-methoxyphenyldiphenylsulfonium triflate, (4-tert-butylphenyl)diphenylsulfonium triflate, diphenyliodonium hexafluorophosphate, diphenyliodonium nitrate, diphenyliodonium p-toluenesulfonate, diphenyliodonium triflate, (4-fluorophenyl)diphenylsulfonium triflate, n-hydroxynaphthalimide triflate, n-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butanesulfonate, (4-iodophenyl)diphenylsulfonium triflate, triarylsulfonium triflate, (4-methoxyphenyl)diphenylsulfonium triflate, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, (4-methylthiophenyl)methylphenylsulfonium triflate, 1-naphthyldiphenylsulfonium triflate, (4-phenoxyphenyl)diphenylsulfonium triflate, (4-phenylthiophenyl)diphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate, triarylsulfonium hexafluorophosphate, triphenylsulfonium perfluoro-1-butanthronate, triphenylsulfonium triflate, tris(4-tert-butylphenyl)sulfonium perfluoro-1-butanthronate, tris(4-tert-butylphenyl)sulfonium triflate, or any combination thereof.

[0203] In some embodiments, the curing catalyst (e.g., photoinitiator) comprises bis-(4-t-butylphenyl)iodonium hexafluorophosphate, 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, bis(4-dodecylphenyl)iodonium hexafluoroantimonate, (sulfanediyldibenzene-4,1-diyl)bis(diphenylsulfonium)bis(hexafluoroantimonate), (4-{[4-(diphenylsulfanilium)phenyl]-sulfanyl}phenyl)diphenylsulfonium bishexafluorophosphate, 4,4′-dimethyldiphenyliodonium hexafluorophosphate, or any combination thereof.

[0204] In some embodiments, the curing catalyst (eg, photoinitiator) comprises a commercially available composition branded Irgacure®.

[0205] In some embodiments, the curing catalyst (eg, photoinitiator) comprises Irgacure® 290.

[0206] In some embodiments, the curing catalyst (e.g., photoinitiator) comprises Esacure 1187, Omnicat 250, Omnicat 270, Omnicat 320, Omnicat 432, Omnicat 440, Omnicat 445, Omnicat 550, Omnicat BL 550, or any combination thereof.

[0207] In some embodiments, the cure catalyst (e.g., photoinitiator) is selected from the group consisting of SpeedCure 937 (bis(4-dodecylphenyl)iodonium hexafluoroantimonate), SpeedCure 938 (bis-(4-t-butylphenyl)-iodonium hexafluorophosphate), SpeedCure 939 (4-isopropyl-4′-methyldiphenyliodonium tetrakis-(pentafluorophenyl)borate), SpeedCure 976 ((sulfanediyldibenzene-4,1-diyl)bis-(diphenylsulfonium)bis(hexafluoroantimonate) in propylene carbonate), SpeedCure 976D ((sulfanediyldibenzene-4,1-diyl)bis(diphenylsulfonium)bis(hexafluoroantimonate) in reactive solvent), SpeedCure 976s ((sulfanediyldibenzene-4,1-diyl)bis(diphenylsulfonium)bis(hexafluoroantimonate), SpeedCure 992 ((4-{[4-(diphenylsulfanilium)phenyl]sulfanyl}-phenyl)diphenylsulfonium bishexafluorophosphate) in propylene carbonate), or any combination thereof.

[0208] In some embodiments, the cure catalyst (eg, photoinitiator) comprises SpeedCure 992.

[0209] In some embodiments, SpeedCure 992 is present at a concentration of about 2±1.5% w / w, about 2±1.4% w / w, about 2±1.3% w / w, about 2±1.2% w / w, about 2±1.0% w / w, about 2±0.9% w / w, about 2±0.8% w / w, about 2±0.7% w / w, about 2±0.6% w / w, about 2±0.5% w / w, about 2±0.4% w / w, about 2±0.3% w / w, about 2±0.2% w / w, or about 2±0.1% w / w (e.g., about 2% w / w).

[0210] In some embodiments, the cure catalyst (eg, photoinitiator) comprises SpeedCure 976s.

[0211] In some embodiments, SpeedCure 976s is present at a concentration of about 2±1.7% w / w, about 2±1.6% w / w, about 2±1.5% w / w, about 2±1.4% w / w, about 2±1.3% w / w, about 2±1.2% w / w, about 2±1.0% w / w, about 2±0.9% w / w, about 2±0.8% w / w, about 2±0.7% w / w, about 2±0.6% w / w, about 2±0.5% w / w, about 2±0.4% w / w, about 2±0.3% w / w, about 2±0.2% w / w, or about 2±0.1% w / w.

[0212] In some embodiments, the curing catalyst (e.g., photoinitiator) is present at a concentration of about 15% w / w or less, about 10% w / w or less, about 9% w / w or less, about 8% w / w or less, about 7% w / w or less, about 5% w / w or less, about 6% w / w or less, about 4% w / w or less, about 3% w / w or less, about 2% w / w or less, about 1% w / w or less, about 0.9% w / w or less, about 0.8% w / w or less, about 0.7% w / w or less, about 0.6% w / w or less, about 0.5% w / w, about 0.4% w / w, about 0.3% w / w, about 0.2% w / w or less, or about 0.1% w / w or less.

[0213] In some embodiments, the photoinitiator is present at a concentration of about 0.01% w / w or more, about 0.02% w / w or more, about 0.03% w / w or more, about 0.04% w / w or more, about 0.05% w / w or more, about 0.06% w / w or more, about 0.07% w / w or more, about 0.08% w / w or more, about 0.09% w / w or more, about 0.1% w / w or more, about 0.2% w / w or more, about 0.3% w / w or more, about 0.4% w / w or more, about 0.5% w / w or more, about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, or about 4% w / w or more.

[0214] In some embodiments, the curing catalyst (e.g., photoinitiator) is present in an amount of about 0.01% w / w, about 0.02% w / w, about 0.03% w / w, about 0.04% w / w, about 0.05% w / w, about 0.06% w / w, about 0.07% w / w, about 0.08% w / w, about 0.09% w / w, about 0.1% w / w, about 0.15% w / w, about 0.2% w / w, about 0.25% w / w, about 0.3% w / w, about 0.35% w / w, or about It is present at a concentration of 0.4% w / w, about 0.45% w / w, about 0.5% w / w, about 0.6% w / w, about 0.7% w / w, about 0.8% w / w, about 0.9% w / w, about 1% w / w, about 1.5% w / w, about 2% w / w, about 2.5% w / w, about 3% w / w, about 3.5% w / w, about 4% w / w, about 4.5% w / w, about 5% w / w, about 6% w / w, about 7% w / w, about 8% w / w, about 9% w / w or about 10% w / w. sensitizer

[0215] In some embodiments, the sensitizer is selected from isopropylthioxanthone (ITX), anthracene, and derivatives thereof.

[0216] In some embodiments, the sensitizer comprises, for example, isopropylthioxanthone (ITX) to activate the iodonium catalyst.

[0217] In some embodiments, the sensitizer comprises anthracene, for example, to sensitize iodonium or sulfonium catalysts.

[0218] In some embodiments, the sensitizer comprises a derivative of anthracene.

[0219] In some embodiments, the sensitizer comprises 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, or a combination thereof.

[0220] In some embodiments, the sensitizer comprises 9,10-diethoxyanthracene.

[0221] In some embodiments, the sensitizer comprises 9,10-diethoxyanthracene.

[0222] In some embodiments, the sensitizer comprises a commercially available composition branded ANTRACURE®.

[0223] In some embodiments, the sensitizer comprises ANTHRACURE® UVS 1101, ANTHRACURE® UVS 1331, or a combination thereof.

[0224] In some embodiments, the sensitizer comprises ANTHRACURE® UVS 1101.

[0225] In some embodiments, ANTHRACURE® UVS 1101 is present at a concentration of about 0.27±0.2% w / w, about 0.27±0.15% w / w, about 0.27±0.1% w / w, about 0.27±0.09% w / w, about 0.27±0.08% w / w, about 0.27±0.07% w / w, about 0.27±0.06% w / w, about 0.27±0.05% w / w, about 0.27±0.04% w / w, about 0.27±0.03% w / w, about 0.27±0.02% w / w, or about 0.27±0.01% w / w (e.g., about 0.27% w / w).

[0226] In some embodiments, the sensitizer comprises SpeedCure 2-ITX (2-isopropylthioxanthone), SpeedCure 7010 (polymeric thioxanthone), SpeedCure 7010-L (a mixture of polymeric thioxanthone and trimethylolpropane ethoxylate triacrylate), SpeedCure CPTX (1-chloro-4-propoxythioxanthone), SpeedCure DETX (2,4-diethylthioxanthone), SpeedCure EAQ (2-ethylanthraquinone), SpeedCure ITX (a mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone), SpeedCure VLT (bis(η-cyclopentadienyl)-bis[2,6-difluoro-3-(pyrrol-1-yl)phenyl]titanium, or any combination thereof.

[0227] In some embodiments, the sensitizer is present at a concentration of about 5% w / w or less, about 4% w / w or less, about 3% w / w or less, about 2% w / w or less, about 1% w / w or less, about 0.9% w / w or less, about 0.8% w / w or less, about 0.7% w / w or less, about 0.6% w / w or less, about 0.5% w / w, about 0.4% w / w, about 0.3% w / w, about 0.2% w / w or less, or about 0.1% w / w or less.

[0228] In some embodiments, the sensitizer is present at a concentration of about 0.01% w / w or more, about 0.02% w / w or more, about 0.03% w / w or more, about 0.04% w / w or more, about 0.05% w / w or more, about 0.06% w / w or more, about 0.07% w / w or more, about 0.08% w / w or more, about 0.09% w / w or more, about 0.1% w / w or more, about 0.2% w / w or more, about 0.3% w / w or more, or about 0.4% w / w or more.

[0229] In some embodiments, the sensitizer is present at a concentration of about 0.01% w / w, about 0.02% w / w, about 0.03% w / w, about 0.04% w / w, about 0.05% w / w, about 0.06% w / w, about 0.07% w / w, about 0.08% w / w, about 0.09% w / w, about 0.1% w / w, about 0.15% w / w, about 0.2% w / w, about 0.25% w / w, about 0.3% w / w, about 0.35% w / w, about 0.4% w / w, about 0.45% w / w, or about 0.5% w / w. Strengthener

[0230] In some embodiments, the combination, material, or kit further comprises a fortifying agent.

[0231] In some embodiments, the toughening agent comprises a polymer.

[0232] In some embodiments, the toughening agent comprises a monomer.

[0233] In some embodiments, the toughening agent comprises a cross-linking agent.

[0234] In some embodiments, the toughening agent comprises a prepolymer.

[0235] In some embodiments, the toughening agent comprises a homopolymer, a copolymer, or a combination thereof.

[0236] In some embodiments, the toughening agent comprises a homopolymer.

[0237] In some embodiments, the toughening agent comprises a butadiene homopolymer.

[0238] In some embodiments, the toughening agent comprises a copolymer.

[0239] In some embodiments, the toughening agent comprises a butadiene acrylonitrile copolymer.

[0240] In some embodiments, the strengthening agent comprises a commercially available composition branded Hypro®.

[0241] In some embodiments, the fortifier is Hypro® 1300X68 ETBN, Hypro® 2000X174 ETB, Hypro® 1300X40 ETBN, Hypro® 1300X63 ETBN, Hypro® 1300X33LC VTBNX, Hypro® 1300X43LC VTBNX, Hypro® 2000X168LC VTB, Hypro® 1300X16 ATBN, Hypro® 1300X21 ATBN, Hypro® 1300X35 ATBN, Hypro® 1300X42 ATBN, Hypro® 1300X45 ATBN, Hypro® 1300X8 CTBN, Hypro® 1300X08F CTBN, Hypro® 1300X9 CTBNX, Hypro® 1300X13 CTBN, Hypro® 1300X13CL CTBN, Hypro® 1300X13F CTBN, Hypro® 1300X13NA CTBN, Hypro® 1300X18 CTBNX, Hypro® 1300X31 CTBN, Hypro® 1300X47 CTBN, Hypro® 2000X162 CTB, Hypro® 2000X172 CTB, or any combination thereof.

[0242] In some embodiments, the toughener comprises Hypro® 1300X68 ETBN, Hypro® 2000X174 ETB, Hypro® 1300X40 ETBN, Hypro® 1300X63 ETBN, or any combination thereof.

[0243] In some embodiments, the toughening agent comprises a commercially available composition branded B-Tough™.

[0244] In some embodiments, the toughening agent comprises B-Tough™ A1, B-Tough™ A2, B-Tough™ A3, B-Tough™ C2r, B-Tough™ C2x, or any combination thereof.

[0245] In some embodiments, the strengthening agent comprises a commercially available composition branded Trixene®.

[0246] In some embodiments, the strengthening agent comprises Trixene® BI 7770, Trixene® BI 7771, Trixene® BI 7772, Trixene® BI 7774, Trixene® BI 7779, or any combination thereof.

[0247] In some embodiments, the strengthening agent comprises a commercially available composition branded Curalite™.

[0248] In some embodiments, the strengthening agent comprises Curalite™ Ox, Curalite™ Ox Plus, Curalite™ Pro Ox C20, Curalite™ Pro Ox C50, or a combination thereof.

[0249] In some embodiments, the strengthening agent comprises Curalite™ Ox, Curalite™ OxPlus, or a combination thereof.

[0250] In some embodiments, the strengthening agent comprises Curalite™ Ox.

[0251] In some embodiments, the strengthening agent comprises Curalite™ OxPlus.

[0252] In some embodiments, Curalite™ Ox is present at about 20±10% w / w, about 20±9% w / w, about 20±8% w / w, about 20±7% w / w, about 20±6% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w.

[0253] In some embodiments, Curalite™ OxPlus is present at a concentration of about 7.5±4% w / w, about 7.5±3% w / w, about 7.5±2% w / w, about 7.5±1% w / w, about 7.5±0.9% w / w, about 7.5±0.8% w / w, about 7.5±0.7% w / w, about 7.5±0.6% w / w, about 7.5±0.7.5% w / w, about 7.5±0.4% w / w, about 7.5±0.3% w / w, about 7.5±0.2% w / w, or about 7.5±0.1% w / w (e.g., about 7.5% w / w).

[0254] In some embodiments, Curalite™ OxPlus is present at a concentration of about 5±4% w / w, about 5±3% w / w, about 5±2% w / w, about 5±1% w / w, about 5±0.9% w / w, about 5±0.8% w / w, about 5±0.7% w / w, about 5±0.6% w / w, about ±0.5% w / w, about 5±0.4% w / w, about 5±0.3% w / w, about 5±0.2% w / w, or about 5±0.1% w / w (e.g., about 5% w / w).

[0255] In some embodiments, the toughening agent comprises particles (eg, core-shell particles).

[0256] In some embodiments, the particles (eg, core-shell particles) comprise MZ-120, SX-005, or a combination thereof.

[0257] In some embodiments, the combination, material, or kit comprises a mixture of particles (eg, core-shell particles) and a polyol.

[0258] In some embodiments, the combination, material, or kit comprises Kane Ace® MX-710, Kane Ace® MX-714, or a combination thereof.

[0259] In some embodiments, the combination, material, or kit comprises a mixture of particles (eg, core-shell particles) and a ring-containing agent (eg, 7-oxabicyclo[4.1.0]heptan-3-ylmethyl).

[0260] In some embodiments, the combination, material, or kit comprises a mixture of particles (eg, core-shell particles) and 7-oxabicyclo[4.1.0]heptan-3-ylmethyl.

[0261] In some embodiments, the mixture comprises about 15% w / w, about 20% w / w, about 25% w / w, 30% w / w, about 31% w / w, about 32% w / w, about 33% w / w, about 34% w / w, about 35% w / w, about 40% w / w, about 45% w / w, or about 50% w / w of particles (e.g., core-shell particles).

[0262] In some embodiments, the mixture comprises 30% w / w particles (eg, core-shell particles).

[0263] In some embodiments, the combination, material, or kit comprises Kane Ace® MX-962, Kane Ace® MX-125, Kane Ace® MX-156, Kane Ace® MX-965, Kane Ace® MX-136, Kane Ace® MX-550, Kane Ace® MX-551, Kane Ace® MX-553, or any combination thereof.

[0264] In some embodiments, the combination, material, or kit comprises Kane Ace® MX-553.

[0265] In some embodiments, the combination, material, or kit comprises METABLEN™ S-2501, METABLEN™ SX005, METABLEN™ C-223S, METABLEN™ E-870A, METABLEN™ E875A, METABLEN™ W-300A, METABLEN™ W450A, METABLEN™ W-600A, or any combination thereof.

[0266] In some embodiments, Kane Ace® MX-553 is present at a concentration of about 70±35% w / w, about 70±30% w / w, about 70±25% w / w, about 70±20% w / w, about 70±15% w / w, about 70±10% w / w, about 70±9% w / w, about 70±8% w / w, about 70±7% w / w, about 70±6% w / w, about 70±5% w / w, about 70±4% w / w, about 70±3% w / w, about 70±2% w / w, or about 70±1% w / w (e.g., about 70% w / w).

[0267] In some embodiments, Kane Ace® MX-553 is present at a concentration of about 65±35% w / w, about 65±30% w / w, about 65±25% w / w, about 65±20% w / w, about 65±15% w / w, about 65±10% w / w, about 65±9% w / w, about 65±8% w / w, about 65±7% w / w, about 65±6% w / w, about 65±5% w / w, about 65±4% w / w, about 65±3% w / w, about 65±2% w / w, or about 65±1% w / w (e.g., about 65% w / w).

[0268] In some embodiments, Kane Ace® MX-553 is present at a concentration of 55±35% w / w, about 55±30% w / w, about 55±25% w / w, about 55±20% w / w, about 55±15% w / w, about 55±10% w / w, about 55±9% w / w, about 55±8% w / w, about 55±7% w / w, about 55±6% w / w, about 55±5% w / w, about 55±4% w / w, about 55±3% w / w, about 55±2% w / w, or about 55±1% w / w (e.g., about 55% w / w).

[0269] In some embodiments, the toughening agent (e.g., a monomer, crosslinker, prepolymer, homopolymer, or copolymer) is present at a concentration of about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, about 4% w / w or more, about 5% w / w or more, about 6% w / w or more, about 7% w / w or more, about 8% w / w or more, about 9% w / w or more, about 10% w / w or more, about 15% w / w or more, about 20% w / w or more, about 25% w / w or more, about 30% w / w or more, about 35% w / w or more, about 40% w / w or more, about 45% w / w or more, or about 50% w / w or more.

[0270] In some embodiments, the toughening agent (e.g., monomer, crosslinker, prepolymer, homopolymer, or copolymer) is present at a concentration of about 80% w / w or less, about 70% w / w or less, about 60% w / w or less, about 50% w / w or less, about 45% w / w or less, about 40% w / w or less, about 35% w / w or less, about 30% w / w or less, about 25% w / w or less, about 20% w / w or less, about 15% w / w or less, about 10% w / w or less, about 9% w / w or less, about 8% w / w or less, about 7% w / w or less, about 6% w / w or less, or about 5% w / w or less.

[0271] In some embodiments, the toughening agent (e.g., a monomer, crosslinker, prepolymer, homopolymer, or copolymer) is present at a concentration of about 20±10% w / w, about 20±9% w / w, about 20±8% w / w, about 20±7% w / w, about 20±6% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w (e.g., about 20% w / w).

[0272] In some embodiments, the toughening agent (e.g., a monomer, crosslinker, prepolymer, homopolymer, or copolymer) is present at a concentration of about 15±10% w / w, about 15±9% w / w, about 15±8% w / w, about 15±7% w / w, about 15±6% w / w, about 15±5% w / w, about 15±4% w / w, about 15±3% w / w, about 15±2% w / w, or about 15±1% w / w (e.g., about 15% w / w).

[0273] In some embodiments, the toughening agent (e.g., a monomer, crosslinker, prepolymer, homopolymer, or copolymer) is present at a concentration of about 10±5% w / w, about 10±4% w / w, about 10±3% w / w, about 10±2% w / w, or about 10±1% w / w (e.g., about 10% w / w).

[0274] In some embodiments, the toughening agent comprises a block copolymer.

[0275] In some embodiments, the toughening agent comprises a diblock copolymer, a triblock copolymer, or a combination thereof.

[0276] In some embodiments, the toughening agent comprises a diblock copolymer.

[0277] In some embodiments, the toughening agent comprises a triblock copolymer.

[0278] In some embodiments, the toughening agent (e.g., a block copolymer) is present at a concentration of about 25% w / w or less, about 20% w / w or less, about 15% w / w or less, about 10% w / w or less, about 9% w / w or less, about 8% w / w or less, about 7% w / w or less, about 6% w / w or less, or about 5% w / w or less.

[0279] In some embodiments, the toughening agent (e.g., a block copolymer) is present at a concentration of about 1% w / w or more, about 2% w / w or more, about 3% w / w or more, about 4% w / w or more, about 5% w / w or more, about 6% w / w or more, about 7% w / w or more, about 8% w / w or more, about 9% w / w or more, about 10% w / w or more, about 15% w / w or more, or about 20% w / w or more.

[0280] In some embodiments, the toughening agent (e.g., a block copolymer) is present at a concentration of about 10±5% w / w, about 10±4% w / w, about 10±3% w / w, about 10±2% w / w, or about 10±1% w / w (e.g., about 10% w / w).

[0281] In some embodiments, the toughening agent (e.g., a block copolymer) is present at a concentration of about 5±4% w / w, about 5±3% w / w, about 5±2% w / w, about 5±1% w / w, about 5±0.9% w / w, about 5±0.8% w / w, about 5±0.7% w / w, about 5±0.6% w / w, about 5±0.5% w / w, about 5±0.4% w / w, about 5±0.3% w / w, about 5±0.2% w / w, or about 5±0.1% w / w (e.g., about 5% w / w). stabilizers

[0282] In some embodiments, the compound, material, or kit further comprises a stabilizer.

[0283] In some embodiments, the stabilizer comprises a tertiary amine compound.

[0284] In some embodiments, the tertiary amine compound is methyldiethanolamine, ethyldiethanolamine, propyldiethanolamine, butyldiethanolamine, methyldipropanolamine, ethyldipropanolamine, propyldipropanolamine, butyldipropanolamine, or any combination thereof.

[0285] In some embodiments, the tertiary amine compound is methyldiethanolamine.

[0286] In some embodiments, the tertiary amine compound is ethyldiethanolamine.

[0287] In some embodiments, the tertiary amine compound is propyldiethanolamine.

[0288] In some embodiments, the tertiary amine compound is butyldiethanolamine.

[0289] In some embodiments, the tertiary amine compound is methyldipropanolamine.

[0290] In some embodiments, the tertiary amine compound is ethyldipropanolamine.

[0291] In some embodiments, the tertiary amine compound is propyldipropanolamine.

[0292] In some embodiments, the tertiary amine compound is butyldipropanolamine.

[0293] In some embodiments, the stabilizer comprises a sulfide compound.

[0294] In some embodiments, the sulfide compound is a dialkyl sulfide, diaryl sulfide, or alkylaryl sulfide.

[0295] In some embodiments, the sulfide is dodecyl sulfide or diphenyl sulfide.

[0296] Other suitable stabilizers are described, for example, in US Pat. No. 7,845,785 (incorporated by reference).

[0297] In some embodiments, the stabilizer is present at a concentration of about 5% w / w or less, about 4% w / w or less, about 3% w / w or less, about 2% w / w or less, about 1% w / w or less, about 0.9% w / w or less, about 0.8% w / w or less, about 0.7% w / w or less, about 0.6% w / w or less, about 0.5% w / w or less, about 0.4% w / w or less, about 0.3% w / w or less, about 0.2% w / w or less, or 0.1% w / w or less.

[0298] In some embodiments, the stabilizer is present at a concentration of about 0.01% w / w or more, about 0.02% w / w or more, about 0.03% w / w or more, about 0.04% w / w or more, about 0.05% w / w or more, about 0.06% w / w or more, about 0.07% w / w or more, about 0.08% w / w or more, about 0.09% w / w or more, about 0.1% w / w or more, about 0.2% w / w or more, about 0.3% w / w or more, or about 0.4% w / w or more.

[0299] In some embodiments, the sensitizer is present at a concentration of about 0.01% w / w, about 0.02% w / w, about 0.03% w / w, about 0.04% w / w, about 0.05% w / w, about 0.06% w / w, about 0.07% w / w, about 0.08% w / w, about 0.09% w / w, about 0.1% w / w, about 0.15% w / w, about 0.2% w / w, about 0.25% w / w, about 0.3% w / w, about 0.35% w / w, about 0.4% w / w, about 0.45% w / w, or about 0.5% w / w. surfactants

[0300] In some embodiments, the combination, material, or kit further comprises a surfactant.

[0301] In some embodiments, the surfactant is also a ring-containing agent.

[0302] In some embodiments, the surfactant comprises sorbitol polyglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, polypropylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, diglycidyl ether of brominated neopentyl glycol, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, castor oil triglycidyl ether, castor oil glycidyl ether, propoxylated glycerin triglycidyl ether, polyglycerin-3-polyglycidyl ether, epoxidized pentaerythritol, epoxidized cyclohexanedimethanol, or any combination thereof.

[0303] In some embodiments, the surfactant comprises an epoxidized metaxylylenediamine.

[0304] In some embodiments, the surfactant comprises a glycidyl ester of neodecanoic acid, a glycidyl ester of dimer acid, or a combination thereof.

[0305] In some embodiments, the surfactant is n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C8-C 10 Aliphatic glycidyl ether, C 12 -C 14 aliphatic glycidyl ethers or any combination thereof.

[0306] In some embodiments, the surfactant comprises o-cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, phenyl glycidyl ether, or any combination thereof.

[0307] In some embodiments, the surfactant comprises a commercially available composition under the trademark Silmer®.

[0308] In some embodiments, the surfactant comprises Silmer® EPC C50, Silmer® EPC F418-F, Silmer® EP D208, Silmer® EPC Di-50, or any combination thereof.

[0309] In some embodiments, the surfactant comprises Silmer® EPC F418-F.

[0310] In some embodiments, Silmer® EPC F418-F is present at a concentration of about 0.05±0.03% w / w, about 0.05±0.02% w / w, about 0.05±0.01% w / w, about 0.05±0.005% w / w, about 0.05±0.004% w / w, about 0.05±0.003% w / w, about 0.05±0.002% w / w, or about 0.05±0.001% w / w (e.g., 0.05% w / w). coloring agent

[0311] In some embodiments, the combination, material, or kit comprises a colorant.

[0312] In some embodiments, the colorant comprises a pigment, a dye, or a combination thereof.

[0313] In some embodiments, the colorant comprises a pigment.

[0314] In some embodiments, the pigment is an organic pigment, an inorganic pigment, or a combination thereof.

[0315] In some embodiments, the colorant comprises a dye.

[0316] In some embodiments, the dye is an organic dye, an inorganic dye, or a combination thereof.

[0317] Without wishing to be bound by theory, the pigment or dye may enable optical sensing (e.g., scanning) of the deposited material during printing. In some embodiments, the combination or build material including the pigment or dye is colored, thereby enabling optical sensing (e.g., scanning) of the deposited material by its color. In some embodiments, the combination or build material including the pigment or dye is colorless but fluorescent, thereby enabling optical sensing (e.g., scanning) of the deposited material by its fluorescence. Exemplary Embodiments of Materials

[0318] In some embodiments, the ring-containing agent comprises ERISYS® GE-13, UviCure S105, EPALLOY® 8220, or any combination thereof; the polyol comprises polycaprolactone diol, Capa® 2043, Capa® 3031, Capromer™ PD4-05, polytetrahydrofuran diol, or any combination thereof; the toughening agent comprises Curalite™ Ox, Curalite™ OxPlus, Kane Ace® MX-553, or any combination thereof; the surfactant comprises Silmer® EPC F418-F; the cure catalyst comprises SpeedCure 992; and the sensitizer comprises ANTHRACURE® UVS 1101.

[0319] In some embodiments, the ring-containing agent comprises UviCure S105 and EPALLOY® 8220, the polyol comprises polytetrahydrofuran diol, the toughening agent comprises Curalite™ Ox, the surfactant comprises Silmer® EPC F418-F, the cure catalyst comprises SpeedCure 992, and the sensitizer comprises ANTHRACURE® UVS 1101.

[0320] In some embodiments, the ring-containing agent is present in a concentration of about 50±30% w / w, about 50±20% w / w, about 50±10% w / w, about 50±5% w / w, about 50±4% w / w, about 50±3% w / w, about 50±2% w / w, or about 50±1% w / w. S105 and EPALLOY® 8220 present in a concentration of about 15±10% w / w, about 15±5% w / w, about 15±4% w / w, about 15±3% w / w, about 15±2% w / w, or about 15±1% w / w, wherein the polyol comprises polytetrahydrofuran diol present in a concentration of about 15±10% w / w, about 15±5% w / w, about 15±4% w / w, about 15±3% w / w, about 15±2% w / w, or about 15±1% w / w, and the toughening agent is present in a concentration of about 20±10% w / w, about 20±9% w / w, about 20±8% w / w, about 20±7% w / w, about Curalite™ Ox present in a concentration of about 20±6% w / w, about 20±5% w / w, about 20±4% w / w, about 20±3% w / w, about 20±2% w / w, or about 20±1% w / w, and the surfactant is Silmer® EPC present in a concentration of about 0.05±0.03% w / w, about 0.05±0.02% w / w, about 0.05±0.01% w / w, about 0.05±0.005% w / w, about 0.05±0.004% w / w, about 0.05±0.003% w / w, about 0.05±0.002% w / w, or about 0.05±0.001% w / w. F418-F, wherein the cure catalyst is present at a concentration of about 2±1.5% w / w, about 2±1.4% w / w, about 2±1.3% w / w, about 2±1.2% w / w, about 2±1.0% w / w, about 2±0.9% w / w, about 2±0.8% w / w, about 2±0.7% w / w, about 2±0.6% w / w, about 2±0.5% w / w, about 2±0.4% w / w, about 2±0.3% w / w, about 2±0.2% w / w, or about 2±0.1% w / w. 992, and the sensitizer is about 0.27±0.2% w / w, about 0.27±0.15% w / w, about 0.27±0.1% w / w, about 0.27±0.09% w / w, about 0.27±0.08% w / w, about 0.27±0.07% w / w, about 0.27±0.06% w / w, about 0.27±0.05% w / w, about 0.27±0.04% w / w, about 0.27±0.03% w / w, about 0.27±0.02% w / w or about 0.27±0.ANTHRACURE® UVS 1101 present at a concentration of 0.1% w / w. Material properties

[0321] In some embodiments, the material has a viscosity of about 5 cp or more, about 6 cp or more, about 7 cp or more, when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C. cp or more, about 8 cp or more, about 9 cp or more, about 10 cp or more, about 11 cp or more, about 12 cp or more, about 13 cp or more, about 14 cp or more, about 15 cp or more, about 20 cp or more, about 25 cp or more, about 30 cp or more, about 35 cp or more, about 40 cp or more, about 45 cp or more, about 50 cp or more, about 60 cp or more, about 70 cp or more, about 80 cp or more, or about 90 cp or more.

[0322] In some embodiments, the material has a viscosity of about 150 cp or less, about 140 cp or less, about 130 cp or less, about 120 cp or less, about 110 cp or less, about 100 cp or less, about 90 cp or less, about 80 cp or less, about 70 cp or less, about 60 cp or less, about 50 cp or less, about 40 cp or less, about 30 cp or less, about 20 cp or less, or about 15 cp or less when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0323] In some embodiments, the material has a viscosity of about 120 cp or less, about 110 cp or less, about 100 cp or less, about 90 cp or less, about 80 cp or less, about 70 cp or less, about 60 cp or less, about 50 cp or less, about 40 cp or less, about 30 cp or less, about 20 cp or less, or about 15 cp or less when measured at a temperature of about 70°C.

[0324] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0325] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 20°C.

[0326] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 25°C.

[0327] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 30°C.

[0328] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 35°C.

[0329] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 40°C.

[0330] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 45°C.

[0331] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 50°C.

[0332] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 55°C.

[0333] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 60°C.

[0334] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 65°C.

[0335] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 70°C.

[0336] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 75°C.

[0337] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 80°C.

[0338] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 85°C.

[0339] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 90°C.

[0340] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 95°C.

[0341] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 100°C.

[0342] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 110°C.

[0343] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 120°C.

[0344] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 130°C.

[0345] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 140°C.

[0346] In some embodiments, the material has a viscosity of about 10 cp to about 15 cp when measured at a temperature of about 150°C.

[0347] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0348] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 20°C.

[0349] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 25°C.

[0350] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 30°C.

[0351] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 35°C.

[0352] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 40°C.

[0353] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 45°C.

[0354] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 50°C.

[0355] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 55°C.

[0356] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 60°C.

[0357] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 65°C.

[0358] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 70°C.

[0359] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 75°C.

[0360] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 80°C.

[0361] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 85°C.

[0362] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 90°C.

[0363] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 95°C.

[0364] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 100°C.

[0365] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 110°C.

[0366] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 120°C.

[0367] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 130°C.

[0368] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 140°C.

[0369] In some embodiments, the material has a viscosity of about 100 cp or less when measured at a temperature of about 150°C.

[0370] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0371] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 20°C.

[0372] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 25°C.

[0373] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 30°C.

[0374] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 35°C.

[0375] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 40°C.

[0376] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 45°C.

[0377] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 50°C.

[0378] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 55°C.

[0379] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 60°C.

[0380] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 65°C.

[0381] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 70°C.

[0382] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 75°C.

[0383] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 80°C.

[0384] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 85°C.

[0385] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 90°C.

[0386] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 95°C.

[0387] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 100°C.

[0388] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 110°C.

[0389] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 120°C.

[0390] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 130°C.

[0391] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 140°C.

[0392] In some embodiments, the material has a viscosity of about 60 cp to about 100 cp when measured at a temperature of about 150°C.

[0393] In some embodiments, the material has a surface tension of about 5 mN / m or more, about 6 mN / m or more, about 7 mN / m or more, about 8 mN / m or more, about 9 mN / m or more, about 10 mN / m or more, about 12 mN / m or more, about 14 mN / m or more, about 16 mN / m or more, about 18 mN / m or more, about 20 mN / m or more, or about 25 mN / m or more when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0394] In some embodiments, the material is measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C. In this case, the surface tension is about 50 mN / m or less, about 45 mN / m or less, about 40 mN / m or less, about 39 mN / m or less, about 38 mN / m or less, about 37 mN / m or less, about 36 mN / m or less, about 35 mN / m or less, about 34 mN / m or less, about 33 mN / m or less, about 32 mN / m or less, about 31 mN / m or less, or about 30 mN / m or less.

[0395] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 20°C, about 25°C, about 30°C, about 35°C, about 40°C, about 45°C, about 50°C, about 55°C, about 60°C, about 65°C, about 70°C, about 75°C, about 80°C, about 85°C, about 90°C, about 95°C, about 100°C, about 110°C, about 120°C, about 130°C, about 140°C, or about 150°C.

[0396] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 20°C.

[0397] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 25°C.

[0398] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 30°C.

[0399] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 35°C.

[0400] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 40°C.

[0401] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 45°C.

[0402] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 50°C.

[0403] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 55°C.

[0404] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 60°C.

[0405] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 65°C.

[0406] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 70°C.

[0407] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 75°C.

[0408] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 80°C.

[0409] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 85°C.

[0410] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 90°C.

[0411] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 95°C.

[0412] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 100°C.

[0413] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 110°C.

[0414] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 120°C.

[0415] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 130°C.

[0416] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 140°C.

[0417] In some embodiments, the material has a surface tension of about 20 mN / m to about 35 mN / m when measured at a temperature of about 150°C. Hardening of build materials

[0418] In some embodiments, the build material is deposited (eg, jetted) under build deposition conditions (eg, build jetting conditions).

[0419] In some embodiments, the build material is cured under build curing conditions.

[0420] In some embodiments, the build material is liquid under build deposition conditions (eg, build jetting conditions).

[0421] In some embodiments, the build material is a wax.

[0422] In some embodiments, the build material has a melting point that is at or below the temperature of the build deposition conditions.

[0423] In some embodiments, the build material is transformed into a solid (eg, via a phase change) upon deposition.

[0424] In some embodiments, the build material, upon deposition, is converted to a solid by curing.

[0425] In some embodiments, the build material, upon deposition, is converted to a solid by curing.

[0426] In some embodiments, the build material is UV curable.

[0427] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) relative to the support material.

[0428] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) under supported curing conditions.

[0429] In some embodiments, the build material is substantially stable (eg, chemically and / or physically) relative to the hardened support material.

[0430] In some embodiments, the curing catalyst, upon activation, cures the build material but not the support material.

[0431] In some embodiments, the build cure conditions include irradiation.

[0432] In some embodiments, the radiation is light.

[0433] In some embodiments, the radiation is ultraviolet or visible light.

[0434] In some embodiments, the radiation is ultraviolet radiation.

[0435] In some embodiments, the radiation is visible light.

[0436] In some embodiments, the curing conditions further include elevated temperatures.

[0437] In some embodiments, the elevated temperature is about 30°C or higher, about 35°C or higher, about 40°C or higher, about 45°C or higher, about 50°C or higher, about 55°C or higher, about 60°C or higher, about 65°C or higher, about 70°C or higher, about 75°C or higher, about 80°C or higher, about 85°C or higher, about 90°C or higher, about 95°C or higher, about 100°C or higher, about 110°C or higher, about 120°C or higher, about 130°C or higher, about 140°C or higher, about 150°C or higher, about 160°C or higher, about 170°C or higher, about 180°C or higher, about 190°C or higher, about 200°C or higher, about 250°C or higher, about 300°C or higher, about 350°C or higher, about 400°C or higher, about 450°C or higher, or about 500°C or higher.

[0438] In some embodiments, the elevated temperature is about 500°C or less, about 450°C or less, about 400°C or less, about 350°C or less, about 300°C or less, about 250°C or less, about 200°C or less, about 190°C or less, about 180°C or less, about 170°C or less, about 160°C or less, about 150°C or less, about 140°C or less, about 130°C or less, about 120°C or less, about 110°C or less, about 100°C or less, about 90°C or less, about 80°C or less, about 70°C or less, about 60°C or less, or about 50°C or less.

[0439] In some embodiments, build cure conditions include a substantial absence of air (eg, oxygen).

[0440] In some embodiments, the build cure conditions include being substantially free of water.

[0441] In some embodiments, the hardened build material is substantially stable (eg, chemically and / or physically) relative to the hardened support material.

[0442] In some embodiments, the hardened build material is substantially stable (eg, chemically and / or physically) under support removal conditions.

[0443] In some embodiments, the build material comprises a polymer.

[0444] In some embodiments, the polymer is formed by ring-opening polymerization. Hardened material

[0445] In some aspects, the present disclosure provides a cured material as described herein.

[0446] In some aspects, the present disclosure provides a cured material prepared by the methods described herein.

[0447] In some embodiments, the cured material has a viscosity of about 2.0 kJ / m 2 Above, about 2.5kJ / m 2 Above, approximately 3.0kJ / m 2 Above, approximately 3.5kJ / m 2 Above, approximately 4.0kJ / m 2 Above, approximately 4.5kJ / m 2 More than 5.0kJ / m 2 Above, approximately 5.5kJ / m 2 Above, approximately 6.0kJ / m 2 Above, approximately 6.5kJ / m 2 Above, approximately 7.0kJ / m 2 Above, approximately 7.5kJ / m 2 or approximately 8.0 kJ / m 2 It has a notched Izod impact strength of at least 1000 kJ / cm2.

[0448] In some embodiments, the cured material has a viscosity of about 15 kJ / m 2 Below, approximately 14kJ / m 2 Below, approximately 13kJ / m 2 Below, approximately 12kJ / m 2 Below, approximately 11kJ / m 2 Below, approximately 10kJ / m 2Below, approximately 9kJ / m 2 Below, approximately 8kJ / m 2 Below, approximately 7kJ / m 2 Below, approximately 6kJ / m 2 , about 5kJ / m 2 , about 4kJ / m 2 or about 3 kJ / m 2 It has the following notched Izod impact strength:

[0449] In some embodiments, the cured material has a heat distortion temperature (e.g., at 0.45 MPa) of about 60°C or greater, about 65°C or greater, about 70°C or greater, about 75°C or greater, about 80°C or greater, about 85°C or greater, about 90°C or greater, about 95°C or greater, about 100°C or greater, about 110°C or greater, about 120°C or greater, about 130°C or greater, about 140°C or greater, or about 150°C or greater.

[0450] In some embodiments, the cured material has a tensile strength of about 20 MPa or greater, about 25 MPa or greater, about 30 MPa or greater, about 35 MPa or greater, about 40 MPa or greater, about 45 MPa or greater, about 50 MPa or greater, about 55 MPa or greater, about 60 MPa or greater, 65 MPa or greater, or about 70 MPa or greater.

[0451] In some embodiments, the cured material has a tensile strength of about 150 MPa or less, about 140 MPa or less, about 130 MPa or less, about 120 MPa or less, about 110 MPa or less, about 100 MPa or less, about 90 MPa or less, about 85 MPa or less, about 80 MPa or less, about 75 MPa or less, or about 70 MPa or less.

[0452] In some embodiments, the cured material has a tensile strength of about 90±50 MPa, about 90±45 MPa, about 90±40 MPa, about 90±35 MPa, about 90±30 MPa, about 90±25 MPa, about 90±20 MPa, about 90±15 MPa, about 90±10 MPa, about 90±9 MPa, about 90±8 MPa, about 90±7 MPa, about 90±6 MPa, about 90±5 MPa, about 90±4 MPa, about 90±3 MPa, about 90±2 MPa, or about 90±1 MPa (e.g., about 90 MPa).

[0453] In some embodiments, the cured material has a tensile strength of about 70±50 MPa, about 70±45 MPa, about 70±40 MPa, about 70±35 MPa, about 70±30 MPa, about 70±25 MPa, about 70±20 MPa, about 70±15 MPa, about 70±10 MPa, about 70±9 MPa, about 70±8 MPa, about 70±7 MPa, about 70±6 MPa, about 70±5 MPa, about 70±4 MPa, about 70±3 MPa, about 70±2 MPa, or about 70±1 MPa (e.g., about 70 MPa).

[0454] In some embodiments, the cured material has a tensile strength of about 45±30 MPa, about 45±25 MPa, about 45±20 MPa, about 45±15 MPa, about 45±10 MPa, about 45±9 MPa, about 45±8 MPa, about 45±7 MPa, about 45±6 MPa, about 45±5 MPa, about 45±4 MPa, about 45±3 MPa, about 45±2 MPa, or about 45±1 MPa (e.g., about 45 MPa).

[0455] In some embodiments, the cured material has an elongation at break of about 0.1% or more, about 0.2% or more, about 0.3% or more, about 0.4% or more, about 0.5% or more, about 0.6% or more, about 0.7% or more, about 0.8% or more, about 0.9% or more, about 1% or more, about 1.5% or more, about 2% or more, about 2.5% or more, about 3% or more, about 3.5% or more, about 4% or more, about 4.5% or more, about 5% or more, about 6% or more, about 7% or more, or about 8% or more.

[0456] In some embodiments, the cured material has an elongation at break of about 50% or less, about 45% or less, about 40% or less, about 35% or less, about 30% or less, about 25% or less, about 20% or less, about 15% or less, about 14% or less, about 13% or less, about 12% or less, about 11% or less, about 10% or less, about 9% or less, about 8% or less, about 7% or less, about 6% or less, or about 5% or less.

[0457] In some embodiments, the cured material has an elongation at break of about 10±5%, about 10±4%, about 10±3%, about 10±2%, about 10±1%, about 10±0.9%, about 10±0.8%, about 10±0.7%, about 10±0.6%, about 10±0.5%, about 10±0.4%, about 10±0.3%, about 10±0.2%, or about 10±0.1% (e.g., about 10%).

[0458] In some embodiments, the cured material has an elongation at break of about 7±5%, about 7±4%, about 7±3%, about 7±2%, about 7±1%, about 7±0.9%, about 7±0.8%, about 7±0.7%, about 7±0.6%, about 7±0.5%, about 7±0.4%, about 7±0.3%, about 7±0.2%, or about 7±0.1% (e.g., about 7%).

[0459] In some embodiments, the cured material has an elongation at break of about 5±3%, about 5±2%, about 5±1%, about 5±0.9%, about 5±0.8%, about 5±0.7%, about 5±0.6%, about 5±0.5%, about 5±0.4%, about 5±0.3%, about 5±0.2%, or about 5±0.1% (e.g., about 5%).

[0460] In some embodiments, the cured material has an elongation at break of about 3±2%, about 3±1%, about 3±0.9%, about 3±0.8%, about 3±0.7%, about 3±0.6%, about 3±0.5%, about 3±0.4%, about 3±0.3%, about 3±0.2%, or about 3±0.1% (e.g., about 3%).

[0461] In some embodiments, the cured material has an elongation at break of about 1±0.6%, about 1±0.5%, about 1±0.4%, about 1±0.3%, about 1±0.2%, or about 1±0.1% (e.g., about 1%).

[0462] In some embodiments, the cured material has a Young's modulus of about 0.1 MPa or greater, about 0.2 MPa or greater, about 0.3 MPa or greater, about 0.4 MPa or greater, about 0.5 MPa or greater, about 0.6 MPa or greater, about 0.7 MPa or greater, about 0.8 MPa or greater, about 0.9 MPa or greater, about 1.0 MPa or greater, about 1.1 MPa or greater, about 1.2 MPa or greater, about 1.3 MPa or greater, about 1.4 MPa or greater, about 1.5 MPa or greater, about 1.6 MPa or greater, about 1.7 MPa or greater, about 1.8 MPa or greater, about 1.9 MPa or greater, about 2.0 MPa or greater, about 2.1 MPa or greater, about 2.2 MPa or greater, about 2.3 MPa or greater, about 2.4 MPa or greater, about 2.5 MPa or greater, about 2.6 MPa or greater, about 2.7 MPa or greater, about 2.8 MPa or greater, about 2.9 MPa or greater, or about 3.0 MPa or greater.

[0463] In some embodiments, the cured material has a Young's modulus of about 10 MPa or less, about 9 MPa or less, about 8 MPa or less, about 7 MPa or less, about 6 MPa or less, about 5 MPa or less, about 4.5 MPa or less, about 4 MPa or less, about 3.9 MPa or less, about 3.8 MPa or less, about 3.7 MPa or less, about 3.6 MPa or less, about 3.5 MPa or less, about 3.4 MPa or less, about 3.3 MPa or less, about 3.2 MPa or less, about 3.1 MPa or less, about 3.0 MPa or less, about 2.9 MPa or less, about 2.8 MPa or less, about 2.7 MPa or less, about 2.6 MPa or less, about 2.5 MPa or less, about 2.4 MPa or less, about 2.3 MPa or less, about 2.2 MPa or less, about 2.1 MPa or less, or about 2.0 MPa or less.

[0464] In some embodiments, the cured material has a Young's modulus of about 3.2±2.0 MPa, about 3.2±1.9 MPa, about 3.2±1.8 MPa, about 3.2±1.7 MPa, about 3.2±1.6 MPa, about 3.2±1.5 MPa, about 3.2±1.4 MPa, about 3.2±1.3 MPa, about 3.2±1.2 MPa, about 3.2±1.1 MPa, about 3.2±1.0 MPa, about 3.2±0.9 MPa, about 3.2±0.8 MPa, about 3.2±0.7 MPa, about 3.2±0.6 MPa, about 3.2±0.5 MPa, about 3.2±0.4 MPa, about 3.2±0.3 MPa, about 3.2±0.2 MPa, or about 3.2±0.1 MPa (e.g., about 3.2 MPa).

[0465] In some embodiments, the cured material has a Young's modulus of about 2.5±2.0 MPa, about 2.5±1.9 MPa, about 2.5±1.8 MPa, about 2.5±1.7 MPa, about 2.5±1.6 MPa, about 2.5±1.5 MPa, about 2.5±1.4 MPa, about 2.5±1.3 MPa, about 2.5±1.2 MPa, about 2.5±1.1 MPa, about 2.5±1.0 MPa, about 2.5±0.9 MPa, about 2.5±0.8 MPa, about 2.5±0.7 MPa, about 2.5±0.6 MPa, about 2.5±0.5 MPa, about 2.5±0.4 MPa, about 2.5±0.3 MPa, about 2.5±0.2 MPa, or about 2.5±0.1 MPa (e.g., about 2.5 MPa).

[0466] In some embodiments, the cured material has a Young's modulus of about 1.8±1.5 MPa, about 1.8±1.4 MPa, about 1.8±1.3 MPa, about 1.8±1.2 MPa, about 1.8±1.1 MPa, about 1.8±1.0 MPa, about 1.8±0.9 MPa, about 1.8±0.8 MPa, about 1.8±0.7 MPa, about 1.8±0.6 MPa, about 1.8±0.5 MPa, about 1.8±0.4 MPa, about 1.8±0.3 MPa, about 1.8±0.2 MPa, or about 1.8±0.1 MPa (e.g., about 1.8 MPa).

[0467] In some embodiments, the hardened material has a Shore hardness of about 5D or greater, about 6D or greater, about 7D or greater, about 8D or greater, about 9D or greater, about 10D or greater, about 12D or greater, about 14D or greater, about 16D or greater, about 18D or greater, about 20D or greater, about 25D or greater, about 30D or greater, about 35D or greater, about 40D or greater, about 45D or greater, about 50D or greater, about 55D or greater, about 60D or greater, about 65D or greater, or about 70D or greater.

[0468] In some embodiments, the hardened material has a Shore hardness of about 150D or less, about 140D or less, about 130D or less, about 120D or less, about 110D or less, about 100D or less, about 90D or less, about 85D or less, about 80D or less, about 75D or less, or about 70D or less.

[0469] In some embodiments, the hardened material has a Shore hardness of about 90±50D, about 90±45D, about 90±40D, about 90±35D, about 90±30D, about 90±25D, about 90±20D, about 90±15D, about 90±10D, about 90±9D, about 90±8D, about 90±7D, about 90±6D, about 90±5D, about 90±4D, about 90±3D, about 90±2D, or about 90±1D (e.g., about 90D).

[0470] In some embodiments, the hardened material has a Shore hardness of about 55±30D, about 55±25D, about 55±20D, about 55±15D, about 55±10D, about 55±9D, about 55±8D, about 55±7D, about 55±6D, about 55±5D, about 55±4D, about 55±3D, about 55±2D, or about 55±1D (e.g., about 55D).

[0471] In some embodiments, the hardened material has a Shore hardness of about 20±15D, about 20±10D, about 20±9D, about 20±8D, about 20±7D, about 20±6D, about 20±5D, about 20±4D, about 20±3D, about 20±2D, or about 20±1D (e.g., about 20D). supporting material

[0472] In some embodiments, the support material is deposited (eg, jetted) under supported deposition conditions (eg, supported jetting conditions).

[0473] In some embodiments, the support material is cured under support curing conditions.

[0474] In some embodiments, the support material or hardened support material is removed under support removal conditions.

[0475] In some embodiments, the support material is liquid under supported deposition conditions (eg, supported jetting conditions).

[0476] In some embodiments, the support material is a wax.

[0477] In some embodiments, the support material has a melting point that is at or below the temperature of the support deposition conditions.

[0478] In some embodiments, the support material is transformed into a solid (eg, via a phase change) upon deposition.

[0479] In some embodiments, the support material, upon deposition, is converted to a solid by cooling.

[0480] In some embodiments, the support material is converted to a solid upon deposition by curing.

[0481] In some embodiments, the support material is UV curable.

[0482] In some embodiments, the support material is thermosetting.

[0483] In some embodiments, the supported curing conditions include irradiation (eg, visible or ultraviolet light).

[0484] In some embodiments, the supported curing conditions include elevated temperatures.

[0485] In some embodiments, the supported curing conditions include a substantial absence of air (eg, oxygen).

[0486] In some embodiments, the supported curing conditions include being substantially free of water.

[0487] In some embodiments, the hardened support material is substantially stable (eg, chemically and / or physically) relative to the build material.

[0488] In some embodiments, the hardened support material is substantially stable (eg, chemically and / or physically) under build cure conditions.

[0489] In some embodiments, the hardened support material comprises a polymer.

[0490] In some embodiments, the support removal conditions include adding a solvent to dissolve the hardened support material.

[0491] In some embodiments, the support removal conditions include mechanically removing the hardened support material.

[0492] In some embodiments, the support removal conditions include converting the support material from a solid to a liquid (eg, via a phase change).

[0493] Without wishing to be bound by theory, it is understood that the combinations, materials, or kits of the present disclosure may be useful as inks for 3D printing (e.g., jet-based 3D printing).

[0494] In some aspects, the present disclosure provides a method of preparing a hardened material comprising subjecting a combination, build material, or kit disclosed herein to hardening conditions.

[0495] In some aspects, the present disclosure provides a combination, building material, or kit as disclosed herein for the preparation of a hardened material, said preparation comprising subjecting said combination, building material, or kit to hardening conditions.

[0496] In some aspects, the present disclosure provides the use of a combination, building material, or kit described herein in the manufacture of a hardened material, said manufacture comprising subjecting said combination, building material, or kit to curing conditions.

[0497] In some embodiments, the build cure conditions include irradiation (eg, visible or ultraviolet light).

[0498] In some embodiments, the build cure conditions further include elevated temperatures.

[0499] In some embodiments, the build cure conditions further include chemical activation (eg, adding water).

[0500] In some aspects, the present disclosure provides a cured material prepared by the methods described herein.

[0501] In some aspects, the present disclosure provides methods of printing objects using the combinations, build materials, or kits disclosed herein.

[0502] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a build material described herein onto a support material; (ii) subjecting the deposited build material to curing conditions; Equipped with.

[0503] In some embodiments, the printing comprises: (i) depositing (e.g., spraying) a first building material described herein and a second building material described herein onto a support material; (ii) subjecting the deposited first build material and the deposited second build material to curing conditions; Equipped with.

[0504] In some embodiments, printing further comprises repeating the step of depositing material one or more times.

[0505] In some embodiments, printing further comprises optically sensing the deposited material and controlling one or more repeated depositions of the material in response to the sensing.

[0506] In some embodiments, optical sensing of the deposited material occurs when the material is at least partially cured.

[0507] In some embodiments, repeated deposition of material occurs when the previously deposited layer of material has at least partially cured.

[0508] In some embodiments, printing further comprises depositing an agent that enhances one or more of the mechanical, thermal and / or optical properties of the material.

[0509] In some embodiments, optically sensing the deposited material comprises capturing the surface of the object to be printed.

[0510] In some embodiments, optically sensing the deposited material comprises obtaining volumetric and / or tomographic data of the printed object.

[0511] In some embodiments, controlling the one or more iterations of deposition of material comprises modifying the one or more iterations of deposition of material in response to data produced by sensing using an active feedback loop.

[0512] In some embodiments, controlling one or more iterations of material deposition is based on measurements of the surface of the object to be printed.

[0513] In some embodiments, controlling one or more iterations of material deposition is based on volumetric and / or tomographic data of the object to be printed.

[0514] In some embodiments, printing further comprises heating the material to promote hardening of the material. Systems for using combinations, materials and kits

[0515] In some embodiments, the present disclosure provides a system for 3D printing, the system for 3D printing comprising: (i) a printer (e.g., an inkjet printer) (ii) an ink comprising the combination disclosed herein; Equipped with.

[0516] In some embodiments, a printer (e.g., an inkjet printer) includes one or more printer jets, an optical feedback scanner, and a controller that controls the ejection of ink from the one or more printer jets in response to optical feedback of the ejected ink.

[0517] In some embodiments, the printer (eg, an inkjet printer) further comprises an on-board printhead (eg, a printhead loaded with ink).

[0518] In some embodiments, the system further comprises a light source (e.g., an ultraviolet lamp or a visible light lamp) for curing the deposited layer of ink.

[0519] In some embodiments, the system further comprises software including instructions stored on a non-transitory machine-readable medium, the software executing the instructions to control one or more of the printing processes described herein.

[0520] The following description relates to an exemplary system for additive manufacturing, using, for example, a jet-based 3D printer 100 as shown in FIG. 1 . The printer 100 uses jets 120 (inkjets) to emit material for deposition onto layers of a partially fabricated object. In the printer shown in FIG. 1 , the object is fabricated on a build platform that is controlled to move relative to the jets in a raster-like pattern to form successive layers, in this example controlled to move relative to the jets to maintain a desired separation between the jets and the surface of the partially fabricated object. As shown, there are multiple jets 122, 124, with one jet 122 used to emit support material to form the object's support structure 142 and the other jet 124 used to emit build material to form the object 144 itself. For materials whose curing is initiated by an excitation signal, such as ultraviolet radiation, a curing signal generator 170 (e.g., an ultraviolet lamp) initiates curing of the material immediately after the material is jetted onto the object. In other embodiments, for example, multiple different materials may be used, with separate jets used for each material. In still other implementations, an excitation signal (e.g., optical, RF, etc.) need not necessarily be used, but rather, curing is induced chemically, for example, by mixing multiple components prior to jetting, by jetting separate components that are mixed together and induce curing on the object, etc. Note that in some examples, after additive deposition is complete, the object may be further cured (e.g., to complete the curing), for example, by exposing the object to further ultraviolet radiation.

[0521] The sensor 160 is used to determine physical characteristics of the partially fabricated object, including one or more of surface topography (e.g., a depth map characterizing the thickness / depth of the partially fabricated object) and subsurface (e.g., near-surface features including, e.g., tens or hundreds of deposited layers) features. Characteristics that can be sensed can include one or more of material density, material identity, and cure state. Various types of sensing can be used, including optical coherence tomography (OCT), laser profilometry, and / or multispectral optical sensing, which can be used to distinguish between different materials. In the illustrated printer, the sensor outputs a signal that can result in emission (e.g., fluorescence) and / or reflection, scattering, or absorption from or within the object. The sensor output signal can be provided from the top of the object (i.e., the most recently deposited portion), while in some embodiments, the sensor output signal can be obtained from below the material or from another direction.

[0522] Precision additive manufacturing using inkjet technology has introduced the use of optical scanning-based feedback to tailor material deposition to achieve precise object structures without the need for previously used mechanical approaches. For example, such optical feedback techniques are described in U.S. Pat. Nos. 10,252,466 and 10,456,984 (incorporated by reference). However, optical feedback-based printers have not become a widespread commercial approach to 3D printing, likely due to approaches that cannot achieve the precision obtainable with optical feedback or the relative simplicity of approaches that use mechanical approaches combined with fast-setting inks. Furthermore, many manufacturing materials suitable for jet-based additive manufacturing are not directly suitable for optical scanning because inadequate optical signal strength may propagate from the material during scanning. For example, materials may be inherently substantially transparent and not reflect adequate incident light to capture for accurate characterization of the manufactured object. However, the ability to scan deposited materials can be enhanced by appropriately incorporating optical-enhancing components into the manufacturing material. Further details regarding suitable optical enhancing components are provided in International Application No. PCT / US2019 / 59300, which is incorporated by reference.

[0523] By not requiring contact to control the surface topography of the fabricated object, this approach can tolerate the relatively slow curing of the composition (e.g., compared to acrylate compositions typically used in inkjet 3D printing), while maintaining the benefits of controlling the deposition process according to feedback during the fabrication process. This approach provides a method for fabricating precision objects, offering the benefits of the fabricated object's material properties, including, for example, isotropy, which may be at least in part the result of slow curing, and flexible structures that may not be obtainable with conventional jetted acrylates. Furthermore, where continued curing after scanning may alter the part's shape, for example, due to shrinkage, predictive techniques (e.g., using machine learning approaches, as described in International Application No. PCT / US2019 / 59567 (incorporated by reference)) may be used in the control process to predict such changes, making the cationic composition more amenable to precision jet fabrication approaches.

[0524] Controller 110 uses a model 190 of the object to be produced to control the movement of build platform 130 using motion actuators 150 (e.g., providing 3 degrees of motion) and controls the emission of material from jets 120 according to non-contact feedback of object properties determined via sensors 160. The feedback arrangement can be used to produce precise objects by compensating for the inherent unpredictable aspects of jetting (e.g., clogging of jet orifices) and unpredictable material changes after deposition, including, for example, flow, mixing, absorption, and hardening of the jetted material.

[0525] It is understood that the printer shown in Figure 1 is exemplary only and is not limiting in any way. Other printer configurations that may be used are described, for example, in U.S. Patent No. 10,252,466, U.S. Patent No. 10,456,984, U.S. Patent Application No. 2018 / 0056582, and Sitthi-Amorn et al. (ACM Transactions on Graphics 34(4): 129 (2015)).

[0526] In an alternative manufacturing process, an additive manufacturing step and a subsequent or overlapping part curing step impart two different mechanisms to the build material for the object parts: a phase change mechanism and a polymerization mechanism.

[0527] This phase change mechanism occurs during additive manufacturing and causes a phase change of the build material from liquid to non-liquid (e.g., at least partially solid, semi-solid, and / or quasi-solid), although the phase change is generally not due to polymerization. In this non-liquid state, the build material is sufficiently solidified for subsequent incremental deposition of material onto it (e.g., the non-liquid build material can support the weight of incrementally added material and / or the force of the material as it is jetted, e.g., preventing intermixing of the build material with the support material).

[0528] The polymerization mechanism occurs after the additive manufacturing of the object in a curing stage, or at least partially occurs after the additive manufacturing of the object in a curing stage. This mechanism hardens the build material through a polymerization process. In some instances, the polymerization mechanism is initiated after the additive manufacturing of the object is complete. In other instances, the polymerization mechanism is initiated before the additive manufacturing is complete, for example, during the phase change mechanism (e.g., both mechanisms are initiated simultaneously, or the polymerization mechanism is initiated during the phase change mechanism).

[0529] After the build material has sufficiently hardened (e.g., polymerized) during the curing stage to allow removal of the mold, the manufacturing process enters a part removal stage to remove the mold. Removal of the mold yields the manufactured part.

[0530] Referring to Figure 2, this alternative manufacturing process uses an injection-based three-dimensional printer 200, as shown in Figure 2. In the most general case, the manufacturing process includes three temporal phases: an additive manufacturing phase, a part curing phase, and a part removal phase. As described in more detail below, in some instances, the part curing phase occurs entirely after the additive manufacturing phase. In other instances, the additive manufacturing phase and the part curing phase overlap.

[0531] In the additive manufacturing stage, additive manufacturing is used to produce object 204 including a solid (e.g., hardened) mold structure 211 that forms a cavity (e.g., a closed structure or an open container) that defines the shape of part 212, and the cavity is filled with a semi-solid, unhardened, or partially hardened material in the shape of part 212. Solid mold structure 211 and / or semi-solid material are added layer by layer to form object 204.

[0532] In a part curing stage, which occurs at least in part upon completion of the additive manufacturing stage, the object 204 including the filled mold structure 211 is subjected to a curing process to polymerize the material within the cavity.

[0533] During the additive manufacturing and part curing stages, the material used to form part 212 (sometimes referred to as the "build material") undergoes two different mechanisms: a phase change mechanism and a polymerization mechanism.

[0534] This phase change mechanism occurs during additive manufacturing and causes a phase change of the build material from liquid to non-liquid (e.g., at least partially solid, semi-solid, and / or quasi-solid, where these three terms may be used interchangeably herein) In this non-liquid form, the build material is sufficiently solidified for subsequent incremental deposition of material thereon (e.g., the non-liquid build material can support the weight or force of incrementally applied material).

[0535] The polymerization mechanism occurs after the additive manufacturing of the object 204 during a curing stage, or occurs at least in part after the additive manufacturing of the object during a curing stage. This mechanism hardens the build material through a polymerization process. In some instances, the polymerization mechanism is initiated after the additive manufacturing of the object is complete. In other instances, the polymerization mechanism is initiated before the additive manufacturing is complete, for example, during the phase change mechanism (e.g., both mechanisms are initiated simultaneously, or the polymerization mechanism is initiated after or during the phase change mechanism).

[0536] In the part removal step, the solid mold structure 211 is removed, resulting in the part 212. In some instances, the part removal step occurs after the part curing step, but in other instances, the part removal step may overlap with the part curing step (e.g., the part 212 is still curing, but has cured sufficiently to be removed from the solid mold structure 211). printer

[0537] During additive manufacturing, a printer 200 uses jets 202 (inkjets) to eject material for layer deposition to form an object 204 (shown in FIG. 2 as partially fabricated). In the printer shown in FIG. 2, the object 204 is fabricated on a build platform 206 that is controlled to move relative to the jets in a raster-like pattern (i.e., along the xy plane) to form successive layers, and in this example, relative to the jets (i.e., along the z-axis) to maintain a desired separation between the jets and the surface of the partially fabricated object 204.

[0538] As shown, there are multiple jets 208, 210, for example, a first jet 208 used to emit mold material 213 to form a solid (e.g., cured or semi-cured) mold structure 211 of the object 204, and a second jet 210 used to emit build material 214 to form an uncured or partially cured or semi-solid (e.g., gel or wax) portion 212 of the object 204. Further details of the properties of the mold material 213 and the build material 214 are described below.

[0539] A sensor 216 (sometimes referred to as a scanner) is positioned relative to (e.g., above) the object under fabrication 204 and is used to determine physical characteristics of the partially fabricated object. For example, the sensor 216 measures one or more of the surface topography (e.g., a depth map characterizing the thickness / depth of the partially fabricated object) and the subsurface (e.g., near the surface, which may contain tens or hundreds of deposition layers). Characteristics that can be sensed can include one or more of material density, material identity, and cure state. In the very general case, measurements from the sensor 216 are associated with a three-dimensional (i.e., x, y, z) coordinate system, where the x and y axes are treated as spatial axes in the plane of the build surface and the z axis is the height axis (i.e., the object grows as it is fabricated).

[0540] In some examples, in the context of a digital feedback loop for additive manufacturing, an additive manufacturing system builds an object by printing layers. The sensor 216 acquires 3D scanning information after the printer 200 prints one or more layers. For example, the sensor 216 scans a partial object (or an empty build platform), and then the printer prints a layer (or layers) of material (or materials). The sensor 216 then scans the (partially built) object again. The newly sensed depth by the sensor 216 should be the old depth minus the layer thickness (this assumes the sensor 216 is placed on top of the object being built, the object is built from the bottom layer to the top layer, and the distance between the sensor 216 and the build platform remains unchanged). Various types of sensing, such as optical coherence tomography (OCT) and laser profilometry, can be used to determine depth and volumetric information associated with the object being manufactured.

[0541] A controller 218 uses a model 220 of the object to be manufactured to control the movement of the build platform 206 using a motion actuator 222 (e.g., providing 3 degrees of movement) and controls the ejection of material from the jet 202 according to non-contact feedback of object properties determined via sensors 216. definition

[0542] When a combination, material, or kit is described as "comprising X" or "comprising at least one," such phrase is intended to refer to the combination, material, or kit including at least one X, but it is understood that this phrase is not intended to limit the combination, material, or kit to only comprising one X. That is, in the present disclosure, the terms "comprising X" and "comprising at least one X" are interchangeable.

[0543] As used herein, "ring-opening polymerization" or "ROP" refers to a form of chain extension polymerization in which the ends of polymer chains react repeatedly with cyclic monomers to form longer polymers. In some embodiments, the reactive centers (e.g., the ends of the polymer chains) are anionic or cationic.

[0544] As used herein, "cationic ring-opening polymerization" or "cationic ROP" refers to a ring-opening polymerization in which the reactive center (e.g., the end of a polymer chain) is a cation.

[0545] As used herein, "photoinitiated ring-opening polymerization" or "photoinitiated ROP" refers to ring-opening polymerization initiated by irradiation. In some embodiments, the irradiation is ultraviolet light ("UV-initiated"). In some embodiments, the irradiation is visible light ("visible-light-initiated").

[0546] As used herein, "photoinitiated cationic ring-opening polymerization" or "photoinitiated cationic ROP" refers to a ring-opening polymerization initiated by irradiation (e.g., ultraviolet or visible light) in which the reactive center (e.g., the end of a polymer chain) is cationic.

[0547] As used herein, "polyol" refers to an organic compound (e.g., a small molecule or polymer) that contains multiple hydroxyl groups. In some embodiments, the polyol is a diol, triol, or dendritic polyol.

[0548] As used herein, "photoinitiator" means an agent that generates a reactive species (e.g., a cation or anion) when exposed to radiation (e.g., ultraviolet or visible light) or when exposed to an activating sensitizer.

[0549] As used herein, "cationic photoinitiator" means a photoinitiator that generates cations when exposed to radiation (e.g., ultraviolet or visible light).

[0550] As used herein, "sensitizer" refers to an agent (e.g., a compound) that produces a chemical change (e.g., radial, cationic, or anionic) in another agent (e.g., a photoinitiator) in a photochemical process.

[0551] As used herein, "toughening agent" refers to an agent that enhances the ability of a material (e.g., a polymeric material) to absorb energy and undergo plastic deformation without fracture. In some embodiments, when certain conditions (e.g., curing conditions) are met, the toughening agent enhances the ability of a material (e.g., a cured material) to absorb energy and undergo plastic deformation without fracture.

[0552] As used herein, "pigment" refers to a colored, black, white, or fluorescent particulate organic or inorganic solid. In some embodiments, the pigment is insoluble in the vehicle or substrate in which it is incorporated and is essentially physically and chemically unaffected by the vehicle or substrate. In some embodiments, the pigment changes appearance by selectively absorbing and / or scattering light. In some embodiments, the pigment is dispersed in a vehicle or substrate for application, such as in the manufacture of inks or other polymeric materials. In some embodiments, the pigment retains its crystalline or particle structure during the coloring process.

[0553] As used herein, "dye" refers to a strongly colored or fluorescent organic substance that imparts color to a substrate by selective absorption of light. In some embodiments, the dye is soluble and / or undergoes an application process that disrupts, at least temporarily, any crystalline structure by absorption, dissolution, and mechanical retention, or ionic or covalent chemical bonding.

[0554] As used herein, "viscosity" refers to the ability of a composition (e.g., a material of the present disclosure) to resist deformation at a given rate.

[0555] As used herein, "surface tension" refers to the tendency of a surface of a composition (e.g., a material of the present disclosure) to contract to the smallest possible surface area. In some embodiments, surface tension is measured as the amount of force per unit length or the amount of energy per unit area.

[0556] As used herein, "curing" refers to the process of transforming a material by forming polymers and / or linking existing polymers within the material, thereby producing a hardened material. In some embodiments, this transformation is initiated by irradiation (e.g., ultraviolet or visible light).

[0557] As used herein, "notched Izod impact strength" refers to a mechanical property that measures the impact resistance of a solid material. In some embodiments, the impact resistance of a solid material is measured by a method in which a rotating arm is raised to a specific height (a certain potential energy) and then released. The arm is swung down to strike a notched sample, causing the sample to break. The height to which the arm is swung down after striking the sample determines the energy absorbed by the sample. Typically, notched samples are used to determine impact energy and notch sensitivity. Notched Izod impact strength is measured as the energy lost per unit cross-sectional area at the notch (e.g., kJ / m 2 In some embodiments, notched Izod impact strength is measured by ASTM D256.

[0558] As used herein, "heat deflection temperature" refers to the temperature at which a material will deform under a given load. In some embodiments, heat deflection temperature is measured by ASTM D648.

[0559] As used herein, "tensile strength" refers to the maximum stress a material can withstand while being stretched or pulled before breaking. In some embodiments, tensile strength is measured by ASTM D412, ASTM D624, or ASTM D638.

[0560] As used herein, "elongation at break" refers to the ratio of the increased length of a test specimen after break to its initial length at controlled temperature. In some embodiments, elongation at break is measured by ASTM D412, ASTM D624, or ASTM D638.

[0561] As used herein, "Young's modulus" refers to a mechanical property that measures the stiffness of a solid material. Young's modulus relates to the relationship between stress (force per unit area) and strain (proportional deformation) in a material in the linear elastic region of uniaxial deformation. In some embodiments, Young's modulus is measured by ASTM D412, ASTM D624, or ASTM D638.

[0562] As used herein, "Shore hardness" refers to the hardness of a material as measured by a Shore durometer. In some embodiments, the Shore hardness is measured by a Shore durometer type A, B, C, D, DO, E, M, O, OO, OOO-S, or R.

[0563] As used herein, "about" refers to a range that covers all normal variations recognized by one of ordinary skill in the relevant art. In some embodiments, "about" refers to a range of values ​​of 25%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, 11%, 10%, 9%, 8%, 7%, 6%, 4%, 2%, 1% or less in either direction (greater or lesser) of the stated reference value (except where that number exceeds 100% of possible values), unless otherwise specified or clear from the context.

[0564] As used herein, a "derivative" refers to a compound that, when compared to a reference compound, shares a common core structure and / or one or more properties with the reference compound. In some embodiments, when compared to the reference compound, a derivative is substituted with various groups as described herein.

[0565] As used herein, "substituted" means that any one or more hydrogen atoms on the designated atom are replaced with one selected from the described groups, provided that the normal valence of the designated atom is not exceeded and that the substitution results in a stable compound. When a substituent is oxo or keto (i.e., =0), two hydrogen atoms on the atom are replaced. Keto substituents are not present in aromatic moieties. As used herein, a cyclic double bond is a double bond formed between two adjacent ring atoms (e.g., C=C, C=N, or N=N). "Stable compound" and "stable structure" refer to a compound that is sufficiently robust that it can survive isolation to a useful degree of purity from a reaction mixture or materials to be an effective therapeutic agent. Such substituents may be, for example, alkyl, alkenyl, alkynyl, halogen, hydroxyl, alkylcarbonyloxy, arylcarbonyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, carboxylate, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aminocarbonyl, alkylaminocarbonyl, dialkylaminocarbonyl, alkylthiocarbonyl, alkoxyl, phosphate, phosphonate, phosphinate, amino (including alkylamino, dialkylamino, arylamino, diarylamino, and alkylarylamino), acylamino (including alkylcarbonylamino, arylcarbonylamino, carbamoyl, and ureido), amidino, imino, sulfhydryl, alkylthio, arylthio, thiocarboxylate, sulfate, alkylsulfinyl, sulfonate, sulfamoyl, sulfonamido, nitro, trifluoromethyl, cyano, azido, heterocyclyl, alkylaryl, or an aromatic or heteroaromatic moiety.

[0566] As used herein, expressions such as "one or more of A, B, or C," "one or more of A, B, or C," "one or more of A, B, and C," "one or more of A, B, and C," "selected from the group consisting of A, B, and C," "selected from A, B, and C," and the like are used interchangeably unless otherwise specified and mean all selected from the group consisting of A, B, and / or C, i.e., one or more A, one or more B, one or more C, or any combination thereof.

[0567] In this specification, all percentages and ratios are by weight unless otherwise specified. Other features and advantages of the present disclosure will become apparent from several different examples. The examples provided are illustrative of different components and methodologies useful in implementing the present disclosure. These examples do not limit the disclosure as set forth in the claims. Based on this disclosure, one skilled in the art will be able to identify and employ other components and methodologies useful in implementing the present disclosure.

[0568] All publications and patent documents cited herein are herein incorporated by reference to the same extent as if each individual publication or document was specifically and individually indicated to be incorporated by reference. The citation of publications and patent documents is not intended as an admission that any is pertinent prior art, nor does it constitute any admission as to the contents or date thereof. Having thus described the invention in writing, those skilled in the art will recognize that the invention can be practiced in various embodiments, and that the foregoing description and the following examples are intended to be illustrative and not limiting. Example Example 1. Preparation of exemplary materials

[0569] Four exemplary materials were prepared to evaluate the effects of various ingredients in the materials. For each exemplary material, a base composition was prepared, and then one or more ingredients were added to obtain the material. Details of the four exemplary materials are summarized in Tables 1A-1D below (* indicates that the amount is calculated assuming the base composition is 100%). It is understood that the values ​​in the tables are approximate and subject to experimental and instrumental variations. [Table 1A] [Table 1B] [Table 1C] [Table 1D] Example 2. Preparation of additional exemplary materials

[0570] To evaluate the effect of various components of the material, several exemplary materials were prepared and characterized. Details of the exemplary materials are summarized in Table 2. It is understood that the values ​​in the table are approximate and subject to experimental and instrumental variations. [Table 2] equivalent

[0571] The details of one or more embodiments of the present disclosure are described in the detailed description above. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present disclosure, the preferred methods and materials are described herein. Other features, objects, and advantages of the present disclosure will be apparent from the detailed description and claims. In this specification and the appended claims, the singular forms "a," "an," and "the" include the plural unless the context clearly dictates otherwise. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. All patents and publications cited herein are incorporated by reference.

[0572] The foregoing detailed description has been presented for illustrative purposes only and is not intended to limit the disclosure to the precise form set forth herein.

Claims

1. (i) ring-containing agents, including oxirane and oxetane agents; (ii) a polyol comprising polytetrahydrofuran diol; (iii) a curing catalyst, wherein the curing catalyst is a photoinitiator, and the photoinitiator is a sulfonium catalyst; and (iv) a stabilizer comprising a sulfide compound; and (v) a sensitizer comprising 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, or a combination thereof, wherein the sensitizer is present in a concentration of 0.5% w / w or less; (vi) a toughening agent comprising core-shell particles; A combination that includes.

2. The combination of claim 1, further comprising a surfactant, a colorant, or any combination thereof.

3. A combination described in claim 1 or 2, wherein the number average molecular weight (Mn) of the polyol is 250±100.

4. The combination of claim 1, wherein the curing catalyst comprises (sulfanediyldibenzene-4,1-diyl)bis(diphenylsulfonium)bis(hexafluoroantimonate), (4-{[4-(diphenylsulfanilium)phenyl]-sulfanyl}phenyl)diphenylsulfonium bishexafluorophosphate, or any combination thereof.

5. The combination of claim 1, wherein the oxetane agent comprises 3-ethyloxetane-3-methanol.

6. The combination of claim 1, wherein the oxirane agent comprises (3,4-epoxycyclohexane)methyl 3'-4'-epoxycyclohexyl-carboxylate.

7. A combination described in any one of claims 1 to 6, wherein the sulfide compound is a dialkyl sulfide.

8. A combination according to any one of claims 1 to 7, wherein the number average molecular weight (Mn) of the polyol is 250±50.

9. A combination described in any one of claims 1 to 8, wherein the concentration of the polyol is 15% w / w or less.

10. A ring-containing agent comprising: (3,4-epoxycyclohexane)methyl 3'-4'-epoxycyclohexyl-carboxylate at a concentration of 45±15% w / w; 3-ethyloxetane-3-methanol at a concentration of 15±5% w / w; an oxirane agent containing a bisphenol moiety or an oxetane agent containing a bisphenol moiety; a ring-containing agent comprising: Dialkyl sulfide at a concentration of 0.2±0.05% w / w; Polytetrahydrofuran diol at a concentration of 20±10% w / w; 9,10-diethoxyanthracene at a concentration of 0.2±0.05% w / w or less; and (sulfanediyldibenzene-4,1-diyl)bis(diphenylsulfonium)bis(hexafluoroantimonate) at a concentration of 2±0.2% w / w; Including combinations.

11. A method for producing a cured material, comprising the step of subjecting a combination according to any one of claims 1 to 10 to curing conditions.

12. A method for printing an object using a combination according to any one of claims 1 to 10, comprising: The printing (i) depositing the combination onto a support material; and (ii) subjecting the laminated combination to curing conditions; A method comprising:

13. (i) a printer; (ii) an ink comprising the combination according to any one of claims 1 to 10; A 3D printing system comprising:

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