Non-isocyanate polyurethane inks for 3D printing

Abstract

The Company provides inks for use with 3D printers. In some embodiments, the inks described herein include a cyclic carbonate monomer and an amine monomer. Additionally, in some examples, the inks described herein also include an ethylenically unsaturated monomer, such as a (meth)acrylate. Furthermore, in some examples, the inks described herein further include a colorant, such as a molecular dye, a particulate inorganic pigment, or a particulate organic colorant. The inks described herein may also include one or more additives selected from the group consisting of inhibitors, stabilizers, photoinitiators, and photosensitizers.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority to U.S. Provisional Patent Application No. 62 / 305,051, filed March 8, 2016, which is incorporated by reference in its entirety. [Technical field]

[0002] This application relates to inks, and more particularly, to inks for use in three-dimensional (3D) printing systems. [Background technology]

[0003] Some commercially available 3D printers, such as the Project™ 3D printer from 3D Systems, Inc. of Rock Hill, South Carolina, use ink (also known as build material) that is jetted as a liquid through a printhead to form various 3D objects, articles, or parts. Other 3D printing systems also use ink that is jetted through a printhead or dispensed onto a substrate. In some examples, the ink is a solid at ambient temperature and changes to a liquid at an elevated jetting temperature. In other examples, the ink is a liquid at ambient temperature. Additionally, in some examples, the ink can be cured after it is dispensed and / or deposited on a substrate.

[0004] Other 3D printers form 3D articles from reservoirs, vats, or containers of fluid or powdered ink or build material. In some cases, a binder material or a laser, digital light processing (DLP), or other energy source is used to selectively solidify or consolidate layers of the ink or build material in a stepwise or layer-by-layer manner to provide the 3D article.

[0005] Inks for 3D printing systems can be used to form a variety of articles for a variety of applications, such as in the manner described above. However, some inks for 3D printing systems include (meth)acrylates as the primary curable material. Such inks can provide high print resolution, but the printed 3D articles can have limited toughness. Other inks can provide both high resolution and high toughness, but can suffer from the presence of one or more toxic or non-biocompatible materials. Thus, there is a need for improved 3D printing inks, including inks that can provide a combination of desired properties, such as, for example, high print resolution, high toughness, reduced toxicity, and reduced skin sensitization or irritation of the printed 3D articles. Summary of the Invention [Means for solving the problem]

[0006] In one aspect, inks for use with 3D printers are described herein, which in some embodiments may provide one or more advantages over conventional inks. In some embodiments, for example, the inks described herein can provide printed 3D articles with high print resolution, high toughness, reduced toxicity, and reduced skin sensitization or irritation. Reduced toxicity and reduced skin sensitization or irritation can be achieved, at least in part, by elimination of isocyanates and / or isocyanate decomposition or reaction products.

[0007] In some embodiments, an ink for use in the 3D printing systems described herein comprises a cyclic carbonate monomer and an amine monomer. Such an ink may be particularly useful for 3D printing systems, such as contact stereolithography (cSLA) printing systems or other stereolithography (SLA) printing systems, where the cyclic carbonate and amine monomers are mixed under conditions (e.g., time and temperature conditions) that are insufficient for substantial reaction between the cyclic carbonate and amine monomers to occur prior to printing.

[0008] Alternatively, 3D printing may be performed using multiple inks, where a first ink includes a cyclic carbonate monomer and a second ink includes an amine monomer, as described further below. Such dual ink systems may be particularly useful for 3D printing systems, such as multi-jet modeling (MJM) systems, where it is desirable not to mix the cyclic carbonate monomer with the amine monomer prior to printing.

[0009] Additionally, in some embodiments, the cyclic carbonate monomers of the inks described herein further comprise one or more additional curable moieties other than the cyclic carbonate moiety of the monomer. For example, in some examples, the cyclic carbonate monomers comprise one or more ethylenically unsaturated moieties, such as one or more (meth)acrylate moieties. Some such monomers may comprise novel chemical species. Thus, in another aspect, novel dual-functional polymerizable species are described herein. In yet another aspect, the use of such species for adhesive and / or coating applications is also described herein.

[0010] Furthermore, in some examples, the inks described herein further include one or more curable materials or monomers other than the cyclic carbonate monomers and the amine monomers. For example, in some embodiments, the inks further include an ethylenically unsaturated monomer, such as a (meth)acrylate monomer. In some examples, the ethylenically unsaturated monomers described herein may be polymerized separately from the cyclic carbonate and amine monomers of the ink. For example, the cyclic carbonate and amine monomers of the ink may react with each other to form a first polymer network, and the (meth)acrylate monomers (or other additional curable materials) of the ink may react with each other to form a second polymer network. In such cases, the first and second polymer networks may be separate or different polymer networks. Furthermore, in some embodiments, the first and second polymer networks may together form an interpenetrating polymer network. Furthermore, the first and second polymer networks may be formed by different polymerization processes.

[0011] As mentioned above, 3D printing may be performed according to the present disclosure using a single ink capable of forming a polymer or oligomer from a cyclic carbonate and an amine, or using a combination of different inks that, when combined, can form a polymer or oligomer from a cyclic carbonate and an amine. Thus, in another aspect, a kit for use in a 3D printing system is described herein. In some embodiments, such a kit includes a first ink comprising a cyclic carbonate monomer and a second ink comprising an amine monomer. Moreover, in some such examples, the first ink further comprises an ethylenically unsaturated monomer, such as a (meth)acrylate.

[0012] It should be understood that the inks described herein, whether "stand-alone" inks or inks as part of a kit, may further comprise one or more additional components in addition to the curable materials described above. For example, in some embodiments, the inks described herein further comprise one or more additives selected from the group consisting of colorants, inhibitors, stabilizers, photoinitiators, and photosensitizers.

[0013] In another aspect, the present specification describes the use of a 3D printing composition, which comprises the ink or kit described above. For example, in some examples, the present specification describes the use of a 3D printing composition that comprises an ink containing a cyclic carbonate monomer and an amine monomer.

[0014] In yet another aspect, a 3D printing system is described herein. Such a 3D printing system may include a 3D printing composition as described above, such as a composition including an ink or kit as described above. In some embodiments, the 3D printing system described herein includes a 3D printer with at least one ink dispenser or ink reservoir and a composition as described herein disposed within the ink dispenser or ink reservoir. The composition may include any ink as described herein for use in 3D printing. For example, in some examples, the 3D printing system described herein includes a 3D printer with at least one of an ink dispenser and an ink reservoir and an ink disposed within the ink dispenser, the ink reservoir, or both, the ink including a cyclic carbonate monomer. Furthermore, in some examples, such a 3D printer further includes a second ink dispenser or reservoir and a second ink disposed within the second ink dispenser or reservoir, the second ink including an amine monomer.

[0015] In another aspect, described herein is a method of printing a 3D article, the method being carried out using one or more inks described herein. In some examples, such methods include selectively jetting or depositing a layer of ink in a fluid state onto a substrate, the ink comprising a cyclic carbonate monomer and an amine monomer. Furthermore, in some examples, the ink layer is deposited in a layer-by-layer manner according to a computer-readable image of the 3D article. Furthermore, in some embodiments, the methods described herein further include thermally curing the cyclic carbonate monomer and the amine monomer. Such curing may be performed in a layer-by-layer manner during the printing process or in a "post-processing" step, such as a curing step performed after printing of all layers of the article is completed. Furthermore, regardless of when curing is performed during the process, such curing may include reacting the cyclic carbonate monomer with the amine monomer to form a polyurethane. Furthermore, in some examples, the ink used in the methods described herein comprises one or more (meth)acrylates, the methods further include curing the (meth)acrylates with electromagnetic radiation, such as ultraviolet (UV) light or visible light. Such a curing step may include polymerizing the ethylenically unsaturated portion of the (meth)acrylate to form a poly(meth)acrylate. Furthermore, in some instances, the poly(meth)acrylate and the polyurethane may together form an interpenetrating polymer network, as further described herein.

[0016] As mentioned above, the method of printing a 3D article described herein may be performed with multiple inks rather than one ink described herein. Such a method may, in some examples, include selectively depositing a layer of a first ink in a fluid state on a substrate and selectively depositing a layer of a second ink in a fluid state on a substrate, the first ink and the second ink comprising the first ink and the second ink, respectively, of a kit described herein. In particular, the first ink may comprise a cyclic carbonate monomer and the second ink may comprise an amine monomer. Furthermore, in some embodiments, the first ink comprises one or more (meth)acrylates, and the method further comprises photocuring the one or more (meth)acrylates, e.g., with UV light. Such curing may include polymerizing the ethylenically unsaturated moieties of the (meth)acrylates to form a poly(meth)acrylate. The method described herein may further comprise curing the cyclic carbonate monomers of the first ink and the amine monomers of the second ink, e.g., by thermally curing the monomers. Curing in this manner may include reacting a cyclic carbonate monomer with an amine monomer to form a polyurethane. As further described herein, the poly(meth)acrylate and polyurethane together may form an interpenetrating polymer network.

[0017] Further, in other embodiments, the method of printing a 3D article described herein does not necessarily include jetting or depositing an ink described herein on a substrate according to digital data representing the 3D article. Instead, in some examples, the method of printing a 3D article described herein includes holding ink in a fluid state in a container, and selectively applying energy to the ink in the container to solidify at least a portion of a first fluid layer of ink, thereby forming a first solidified layer that defines a first cross-section of the article. The ink may include any ink described above. Furthermore, such a method may further include raising or lowering the first solidified layer to provide a second fluid layer of ink on a surface of the fluid ink in the container, and selectively applying energy to the ink in the container to solidify at least a portion of the second fluid layer of ink, thereby forming a second solidified layer that defines a second cross-section of the article. The first cross-section and the second cross-section are bound to each other in the z-direction.

[0018] In another aspect, printed 3D articles are described herein. Such articles can be formed from one or more inks and / or using one or more methods described herein.

[0019] These and other embodiments are described in more detail in the detailed description that follows. [Brief description of the drawings]

[0020] [Figure 1] Reaction scheme for forming cyclic carbonate monomers suitable for use in inks according to some embodiments described herein. [Diagram 2] Reaction scheme for forming cyclic carbonate monomers suitable for use in inks according to some embodiments described herein. [Diagram 3] Reaction scheme for forming cyclic carbonate monomers suitable for use in inks according to some embodiments described herein. [Figure 4]Reaction scheme for forming cyclic carbonate monomers suitable for use in inks according to some embodiments described herein. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] The embodiments described herein can be more readily understood by reference to the following detailed description, examples, and drawings. However, the elements, devices, and methods described herein are not limited to the specific embodiments shown in the detailed description, examples, and drawings. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

[0022] Moreover, all ranges disclosed herein are to be understood to encompass all subranges subsumed therein, for example, the stated range "1.0 to 10.0" is to be interpreted to include any and all subranges beginning with a minimum value equal to or greater than 1.0 and ending with a maximum value equal to or less than 10.0, such as 1.0 to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.

[0023] Additionally, all ranges disclosed herein should be considered to include the endpoints of the range unless otherwise specified. For example, a range "between 5 and 10" or "5 to 10" should generally be considered to include the endpoints of 5 and 10.

[0024] Additionally, when the phrase "up to" is used in connection with an amount or quantity, the amount should be understood to be at least a detectable amount or quantity. For example, a material present in an amount "up to" a particular amount may be present in an amount from a detectable amount up to and including the particular amount.

[0025] The terms "three-dimensional printing system," "three-dimensional printer," "printing," and the like, broadly describe various solid freeform manufacturing techniques for creating three-dimensional articles or objects by stereolithography, selective deposition, jetting, fused deposition modeling, multi-jet modeling, as well as other additive manufacturing techniques now known or that will become known in the art that use build materials or inks to produce three-dimensional objects.

[0026] I. 3D printing inks and kits In one aspect, inks for use with 3D printers are described herein. In some embodiments, the inks described herein include cyclic carbonate monomers and amine monomers. Additionally, in some examples, the inks described herein also include ethylenically unsaturated monomers, such as (meth)acrylates. Additionally, the inks described herein, in some examples, further include a colorant, such as a molecular dye, a particulate inorganic pigment, or a particulate organic colorant. The inks described herein may also further include one or more additives selected from the group consisting of inhibitors, stabilizers, photoinitiators, and photosensitizers.

[0027] Turning now to a detailed discussion of the specific components of the ink, the inks described herein include a cyclic carbonate monomer. For purposes of reference herein, a "monomer" is understood to be a chemical species having one or more functional groups or moieties that can react with one another to form one or more covalent bonds, particularly as part of a polymerization reaction. Any cyclic carbonate monomer not inconsistent with the objectives of the present disclosure can be used. For example, the cyclic carbonate monomer may include multiple cyclic carbonate moieties, such as two, three, or four cyclic carbonate moieties. In some examples, the cyclic carbonate monomer has a structure of Formula (A1), Formula (A2), Formula (A3), or Formula (A4): [ka] [ka] [ka] [ka] wherein R1, R2, R3, and R4 are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety. For example, in some examples, in the structure of formula (A2), R1 is (CH2)4, and R2 and R3 are each CH2.

[0028] Further, in some examples, the cyclic carbonate monomer has a structure of formula (A5): [ka] where n is an integer from 1 to 36. The cyclic carbonate monomer of the inks described herein may have a structure of formula (A6): [ka]

[0029] In yet another embodiment, the cyclic carbonate monomer has a structure of Formula (A7), Formula (A8), or Formula (A9): [ka] [ka] [ka] wherein m is an integer from 1 to 36, and R5 is a straight or branched C2 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety. In some embodiments, for example, R5 is (CH2)6.

[0030] In some examples, the cyclic carbonate monomer has a structure of Formula (A10), Formula (A11), Formula (A12), or Formula (A13): [ka] [ka] [ka] [ka] wherein R1, R2, and R3 are each independently a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R5 is a linear or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety. In some embodiments, for example, R1 is (CH2) 1~10 (e.g., (CH2)8), R2 is (CH2) or (CH2)2, R3 is (CH2) or (CH2)2, and R5 is (CH2)6 or (C6H4)-C(Me)2-(C6H4).

[0031] Cyclic carbonate monomers such as those mentioned above may be commercially available (e.g., from SPECIFIC POLYMERS, as in the case of monomers having the structure of formula (A2) or (A6)) or may be obtained by reacting a first species containing a hydroxyl moiety and a cyclic carbonate moiety with a second species containing one or more isocyanate moieties. In this manner, one or more cyclic carbonate moieties of the first species may be attached to the second species through the formation of one or more urethane bonds, such as those of the structures of formula (A7), (A8), and (A9) above. Cyclic carbonate monomers such as those having the structures of (A10), (A11), and (A12) may also be formed as described in U.S. Pat. No. 3,072,613. For example, a cyclic carbonate monomer having the structure of formula (A10), where R2 and R3 are both CH2, may be formed by the reaction of diglycerol with diethyl carbonate, including the use of a basic catalyst. Similarly, a cyclic carbonate monomer having the structure of formula (A2), for example where R2 and R3 are both CH2 and R1 is a bisphenol alkane residue (e.g., (C6H4)-C(Me)2-(C6H4)), can be formed by the addition reaction of carbon dioxide to a diglycidyl compound.

[0032] Furthermore, in some embodiments described herein, the cyclic carbonate monomer may contain one or more other curable or polymerizable moieties in addition to the cyclic carbonate moiety of the monomer. For example, in some examples, the cyclic carbonate monomer contains one or more ethylenically unsaturated moieties, such as one or more (meth)acrylate moieties. Some such monomers may be novel chemical species. Thus, in another aspect, novel dual-functional polymerizable species are described herein.

[0033] In some examples, the cyclic carbonate monomer has the structure of formula (A14): [ka] wherein R1 and R2 are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3. In some embodiments, for example, R1 is CH2CH2, R2 is CH2, and R6 is CH3. Monomers having the structure of formula (A14) can be prepared according to the scheme shown in FIG. 1 or as described in Ochiai et al., J. Polym. Sci., Part A: Polym. Chem., 2007, 45, 5781-5789.

[0034] In other examples, the cyclic carbonate monomer has a structure of formula (A15) or a structure of formula (A16): [ka] [ka] wherein R1 is a linear or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R5 is a linear or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3. For example, in some examples, R1 is CH2CH2, R5 is (CH2)6, and R6 is CH3. Monomers having the structure of formula (A15) can be prepared according to the scheme shown in Figure 2. Monomers having the structure of formula (A16) can also be prepared according to the scheme in Figure 2, except that the specific cyclohexane-based diisocyanate starting material shown in Figure 2 can be replaced with other C2-C36 diisocyanates (such as 1,6-hexane diisocyanate).

[0035] In yet another embodiment, the cyclic carbonate monomer of the inks described herein has a structure of formula (A17) or a structure of formula (A18): [ka] [ka] where m is an integer from 1 to 36; R1 is a linear or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3. For example, in some instances, m is 6, R1 is CH2CH2, and R6 is CH3. Monomers having the structure of formula (A17) can be prepared according to the scheme shown in Figure 3. As shown in Figure 3, the stoichiometric representation n has a value of 2 (as indicated by the statistical product). However, n can generally have any value between 0.5 and 2. When n is 0.5, a monomer having the structure of formula (A18) is provided.

[0036] Further, in some instances, the cyclic carbonate monomer has the structure of formula (A19): [ka] wherein R2 is a straight or branched C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3. For example, in some embodiments, R2 is CH2 and R6 is CH3. Such species are commercially available from SPECIFIC POLYMERS (France) and can be prepared as described in U.S. Pat. No. 7,414,127.

[0037] In another example, the cyclic carbonate monomer has the structure of formula (A20): [ka] wherein R2 is a straight or branched chain C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R6 is H or CH3; R7 is a straight or branched chain C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH2CH(R8)O) n R8 is H or CH3; and n is an integer from 1 to 100. For example, in some embodiments, R2 is CH2, R6 is CH3, and R7 is CH2CH2. Monomers having the structure of formula (A20) can be prepared as described in U.S. Pat. No. 2,979,514.

[0038] Further, in some examples, the cyclic carbonate monomer has the structure of formula (A21): [ka] wherein R2 and R9 are each independently a straight or branched chain C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R6 is H or CH3; R7 is a straight or branched chain C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH2CH(R8)O) n R8 is H or CH3; and n is an integer from 1 to 100. For example, in some embodiments, R2 is CH2, R6 is CH3, R7 is CH2CH2, and R9 is CH2CH2. Monomers having the structure of formula (A21) can be prepared according to the scheme shown in FIG.

[0039] Other cyclic carbonate monomers may also be used in the inks described herein. Furthermore, it should be understood that the cyclic carbonate monomer component of the inks described herein may include only one chemical species or may include multiple different chemical species. For example, in some instances, the cyclic carbonate monomer of the inks described herein includes multiple different cyclic carbonate species.

[0040] Further, the cyclic carbonate monomer components may be present in the ink in any amount in total not inconsistent with the objectives of the present disclosure. For example, in some examples, the inks described herein include up to 70%, up to 60%, up to 50%, up to 40%, or up to 30% by weight of cyclic carbonate monomer, based on the total weight of the ink. In some examples, the inks include 10-70%, 10-60%, 10-50%, 10-40%, 10-30%, 20-60%, 20-50%, 30-70%, 30-60%, 30-50%, 40-70%, or 40-60% by weight of cyclic carbonate monomer, based on the total weight of the ink.

[0041] The inks described herein also include an amine monomer. Any amine monomer not inconsistent with the objectives of the present disclosure may be used. For example, in some examples, the amine monomer includes multiple amine moieties, such as two amine moieties or more than two (three or more) amine moieties. In some examples, the amine monomer is an α,ω-diamine, such as an amine monomer having the structure of formula (B1): H2N-R 10 -NH2(B1) In the formula, R 10 is a straight or branched C1 to C36 alkyl or alkylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

[0042] The amine monomers described herein may include at least one secondary or tertiary amine moiety. Other amine monomers may also be used in the inks described herein. It is further understood that the amine monomer component of the inks described herein may include only one chemical species or may include multiple different chemical species. For example, in some instances, the amine monomers of the inks described herein include multiple different amine species.

[0043] Further, the amine monomer components may be present in the ink in any amount in total not inconsistent with the objectives of the present disclosure. For example, in some examples, the inks described herein include up to 70%, up to 60%, up to 50%, up to 40%, or up to 30% by weight of the amine monomer, based on the total weight of the ink. In some examples, the inks include 10-70%, 10-60%, 10-50%, 10-40%, 10-30%, 20-60%, 20-50%, 30-70%, 30-60%, 30-50%, 40-70%, or 40-60% by weight of the amine monomer, based on the total weight of the ink.

[0044] The inks described herein may, in some examples, further comprise additional curable materials or monomers in addition to the monomers described above. In particular, such monomers may be different or additional to the amine monomers and cyclic carbonate monomers. Furthermore, in some examples, the additional curable monomers may be polymerized separately from the cyclic carbonate and amine monomers of the ink. For example, in some examples, the cyclic carbonate and amine monomers of the ink may react with each other to form a first polymer network, and the additional curable monomers of the ink may react with each other to form a second polymer network. In such cases, the first and second polymer networks may be separate or different polymer networks. Furthermore, in some embodiments, the first and second polymer networks may together form an interpenetrating polymer network. Furthermore, the first and second polymer networks may be formed by different polymerization processes.

[0045] For purposes of reference herein, an additional "curable material" includes a chemical species having one or more curable or polymerizable moieties. For purposes of reference herein, a "polymerizable component" includes a moiety that can be polymerized or cured to provide a 3D printed article or object. Such polymerization or curing can be performed in any manner not inconsistent with the objectives of the present disclosure. In some embodiments, for example, polymerization or curing includes irradiating the polymerizable or curable material with electromagnetic radiation having sufficient energy to initiate a polymerization or crosslinking reaction. For example, in some examples, UV radiation can be utilized. Thus, in some examples, the polymerizable moiety includes a photopolymerizable or photocurable moiety, such as a UV polymerizable moiety. In some embodiments, the curable materials described herein are photopolymerizable or photocurable at wavelengths ranging from about 300 nm to about 400 nm, or from about 320 nm to about 380 nm. Alternatively, in other examples, the curable material is photopolymerizable in visible wavelengths of the electromagnetic spectrum, such as wavelengths ranging from 450 nm to 650 nm.

[0046] Additionally, the polymerization reaction may, in some instances, include a free radical polymerization reaction, such as between points of unsaturation, including ethylenically unsaturated points. Other polymerization reactions may also be used. As will be appreciated by those skilled in the art, the polymerization reaction used to polymerize or cure the curable materials described herein may include the reaction of multiple "monomers" or species having one or more functional groups or moieties that can react with each other to form one or more covalent bonds.

[0047] One non-limiting example of the curable or polymerizable moiety of the additional curable material or monomer described herein is an ethylenically unsaturated moiety such as a vinyl moiety, an allyl moiety, or a (meth)acrylate moiety, where the term "(meth)acrylate" includes an acrylate or a methacrylate, or a mixture or combination thereof. Thus, in some embodiments, the additional curable monomer of the ink described herein comprises a (meth)acrylate.

[0048] Further, the additional curable materials described herein may be monofunctional, difunctional, trifunctional, tetrafunctional, pentafunctional, or higher functional curable materials. For purposes of reference herein, a "monofunctional" curable material includes species that include one curable or polymerizable moiety. Similarly, a "difunctional" curable material includes species that include two curable or polymerizable moieties; a "trifunctional" curable material includes species that include three curable or polymerizable moieties; a "tetrafunctional" curable material includes species that include four curable or polymerizable moieties; and a "pentafunctional" curable material includes species that include five curable or polymerizable moieties. Thus, in some embodiments, the additional monofunctional curable material of the inks described herein comprises a mono(meth)acrylate, the difunctional curable material of the inks described herein comprises a di(meth)acrylate, the trifunctional curable material of the inks described herein comprises a tri(meth)acrylate, the tetrafunctional curable material of the inks described herein comprises a tetra(meth)acrylate, and the pentafunctional curable material of the inks described herein comprises a penta(meth)acrylate. Other monofunctional, difunctional, trifunctional, tetrafunctional, and pentafunctional curable materials can also be used.

[0049] Additionally, mono-, di-, tri-, tetra-, and penta-functional curable materials may, in some instances, include relatively low molecular weight species or relatively high molecular weight species. For example, the curable materials may include or be either "monomer" or molecular species (i.e., species that are not themselves polymeric or oligomeric, relatively low molecular weight species, or relatively low viscosity species) or "oligomeric" species (i.e., species that are themselves polymeric or oligomeric, relatively high molecular weight species, or relatively high viscosity species) that can undergo further polymerization, such as, for example, via one or more unsaturation points as described herein. Thus, in some instances, a population of "monomers" or molecular species in a curable material may have a consistent or well-defined molecular structure and / or formula throughout the population (e.g., as may be illustrated by a specified mass of ethoxylated (4) bisphenol A diacrylate). On the other hand, a population of "oligomeric" species in a curable material may have molecular structures and / or formulas that vary throughout the population (e.g., as may be illustrated by a particular cluster of urethane acrylates having a non-uniform molecular weight distribution, or by a particular cluster of ethoxylated polyethylene glycols having a distribution of ethylene glycol units and / or a distribution of ethoxy units within the population). Furthermore, the weight average molecular weight of "oligomeric" curable materials may generally be in the range of about 400-10,000, about 600-10,000, or about 500-7,000. On the other hand, the molecular weight of "monomeric" curable materials may generally be less than 600, less than 500, less than 400, less than 300, less than 200, or less than 100. Furthermore, in some embodiments, a "monomeric" curable material has a viscosity of 500 centipoise (cP) or less at 25° C., as measured in accordance with ASTM standard D2983, while an "oligomeric" curable material has a viscosity of 1000 cP or more at 25° C., as measured in accordance with ASTM standard D2983.

[0050] Generally, any monomeric curable material not inconsistent with the objectives of the present disclosure may be used in the additional curable monomer of the ink. In some examples, the additional curable monomer comprises one or more (meth)acrylates, such as, for example, one or more monofunctional (meth)acrylates, difunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, and / or pentafunctional (meth)acrylates. In some embodiments, for example, the monomeric curable material comprises methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, or a combination thereof. acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2- or 3-ethoxypropyl (meth)acrylate, tetrahydrofurfuryl methacrylate, isobornyl (meth)acrylate, 2-(2-ethoxyethoxy)ethyl acrylate, cyclohexyl methacrylate, 2-phenoxyethyl acrylate, glycidyl acrylate, isodecyl acrylate, 2-phenoxyethyl (meth)acrylate, lauryl methacrylate, or combinations thereof. In some embodiments, the monomeric curable material comprises one or more of allyl acrylate, allyl methacrylate, triethylene glycol di(meth)acrylate, tricyclodecane dimethanol diacrylate, and cyclohexane dimethanol diacrylate.Further, in some examples, the monomeric curable material includes diacrylate and / or dimethacrylate esters of aliphatic, alicyclic, or aromatic diols, such as, for example, 1,3- or 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, tripropylene glycol, 1,4-dihydroxymethylcyclohexane, 2,2-bis(4-hydroxycyclohexyl)propane or bis(4-hydroxycyclohexyl)methane, hydroquinone, 4,4′-dihydroxybiphenyl, bisphenol A, bisphenol F, or bisphenol S. The curable materials described herein may also include 1,1-trimethylolpropane tri(meth)acrylate, pentaerythritol monohydroxytri(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, and / or bis(trimethylolpropane)tetra(meth)acrylate. Additionally, in some examples, the curable material may include ethoxylated or propoxylated species, such as ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol F, ethoxylated or propoxylated bisphenol S, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, or ethoxylated or propoxylated glycerol tri(meth)acrylate.

[0051] Additional non-limiting examples of commercially available monomer-curable materials that are useful in some embodiments described herein include: isobornyl acrylate (IBOA), available from SARTOMER under the trade name SR506; isobornyl methacrylate, available from SARTOMER under the trade name SR423A; triethylene glycol diacrylate, available from SARTOMER under the trade name SR272; triethylene glycol dimethacrylate, available from SARTOMER under the trade name SR205; Tricyclodecane dimethanol diacrylate, available under the trade name R833S; tris(2-hydroxyethyl)isocyanurate triacrylate, available under the trade name SR368 from SARTOMER; 2-phenoxyethyl acrylate, available under the trade name SR339 from SARTOMER; ethoxylated (3 mole) bisphenol A diacrylate, available under the trade name SR349 from SARTOMER; and dipentaerythritol pentaacrylate, available under the trade name SR399LV from SARTOMER. Other commercially available monomer curable materials may also be used.

[0052] Additionally, any oligomeric curable material not inconsistent with the objectives of the present disclosure may be used in the inks described herein. In some examples, for example, the additional curable material comprises a polyester (meth)acrylate oligomer, a urethane (meth)acrylate oligomer, or an epoxy (meth)acrylate oligomer. Furthermore, in some embodiments, the oligomeric curable material described herein comprises an aliphatic polyester urethane acrylate oligomer and / or an amine acrylate oligomer resin (e.g., EBECRYL7100, etc.). In some examples, the oligomeric curable material described herein comprises a polypropylene glycol mono(meth)acrylate or a polyethylene glycol mono(meth)acrylate. In some embodiments, the oligomeric curable material comprises a monofunctional aliphatic urethane (meth)acrylate. Additionally, in some examples, the oligomeric hardenable material comprises diacrylate and / or dimethacrylate esters of aliphatic, alicyclic, or aromatic diols, such as polyethylene glycol, ethoxylated or propoxylated neopentyl glycol, ethoxylated or propoxylated bisphenol A, ethoxylated or propoxylated bisphenol F, ethoxylated or propoxylated bisphenol S, ethoxylated or propoxylated 1,1,1-trimethylolpropane tri(meth)acrylate, or ethoxylated or propoxylated glycerol tri(meth)acrylate.

[0053] Some non-limiting examples of commercially available oligomeric curable materials that are useful in some embodiments described herein include: an alkoxylated tetrahydrofurfuryl acrylate available from SARTOMER under the trade name SR611; a monofunctional urethane acrylate available from RAHN USA under the trade name GENOMER1122; and an aliphatic urethane diacrylate available from ALLNEX under the trade name EBECRYL8402. Other commercially available oligomeric curable materials may also be used.

[0054] Urethane (meth)acrylates suitable for use in the inks described herein can be prepared by known methods, such as, in some examples, typically by reacting a hydroxyl-terminated urethane with acrylic or methacrylic acid to give the corresponding urethane (meth)acrylate, or by reacting an isocyanate-terminated prepolymer with a hydroxyalkyl acrylate or methacrylate to give the urethane (meth)acrylate. Suitable processes are disclosed, inter alia, in EP 114982 and EP 133908. The weight average molecular weight of such (meth)acrylate oligomers can be, in some examples, about 400 to 10,000, or about 500 to 7,000. Urethane (meth)acrylates are also commercially available from SARTOMER under the product names CN980, CN981, CN975 and CN2901, or from BOMAR Specialties under the product name BR-741. In some embodiments described herein, the urethane (meth)acrylate oligomer has a viscosity, measured in a manner consistent with ASTM D2983, in the range of about 140,000 centipoise (cP) to about 160,000 cP at about 50° C., or about 125,000 cP to about 175,000 cP at about 50° C. In some examples, the urethane (meth)acrylate oligomer has a viscosity, measured in a manner consistent with ASTM D2983, in the range of about 100,000 cP to about 200,000 cP at about 50° C., or about 10,000 cP to about 300,000 cP at about 50° C.

[0055] It should be understood that when both oligomeric and monomeric curable materials are included as additional monomers in the inks described herein, the ratio of oligomeric to monomeric curable material in the inks described herein can be selected to provide an ink with a viscosity suitable for use in a desired 3D printing system, such as a 3D printing system that uses a piezoelectric printhead to dispense the ink, or a stereolithography 3D printing system.

[0056] Moreover, the additional curable material may be present in the inks described herein in any amount consistent with the objectives of the present disclosure. In some examples, the additional curable material is present in an amount, in total, of up to about 80%, up to about 70%, up to about 60%, or up to about 50%, up to about 40%, up to about 30%, or up to about 20% by weight, based on the total weight of the ink. In some examples, the inks described herein comprise about 5-70% by weight of additional curable material, based on the total weight of the ink. In some embodiments, the inks comprise about 10-60%, 10-50%, 10-60%, 10-50%, 10-40%, 15-70%, 15-50%, 15-30%, 20-70%, 20-50%, 20-40%, or 30-60% by weight of additional curable material, based on the total weight of the ink.

[0057] As mentioned above, 3D printing can be performed according to the present disclosure with a single ink capable of forming a polymer or oligomer from a cyclic carbonate and an amine, or with a single ink capable of also forming additional polymers or oligomers from additional curable materials such as (meth)acrylate monomers. However, it is also possible to perform 3D printing with a combination of different inks that, when combined, can form a polymer or oligomer from a cyclic carbonate and an amine, and optionally also from additional curable materials such as (meth)acrylates. Thus, in another aspect, a kit for use in a 3D printing system is described herein. In some embodiments, such a kit comprises a first ink comprising a cyclic carbonate monomer and a second ink comprising an amine monomer. Furthermore, in some examples, the first ink and / or the second ink further comprises an additional curable material (other than the cyclic carbonate and the amine monomer), such as an ethylenically unsaturated monomer. In some examples, the ethylenically unsaturated monomer comprises a (meth)acrylate. Additionally, as described below, the first ink and / or the second ink may also include a photoinitiator.

[0058] It is understood that the cyclic carbonate monomers, amine monomers, ethylenically unsaturated monomers (or other additional curable materials), and photoinitiators of the kits described herein may include any of the cyclic carbonate monomers, amine monomers, ethylenically unsaturated monomers (or other additional curable materials), and photoinitiators described herein with respect to a "single" ink. Furthermore, it is also understood that the first or second inks of the kits described herein may include multiple cyclic carbonate species or mixtures thereof, multiple amine species or mixtures thereof, multiple ethylenically unsaturated species (or other additional curable materials) or mixtures thereof, and / or multiple photoinitiators or mixtures thereof. In general, any combination or mixture of different cyclic carbonate species, amine species, ethylenically unsaturated species (or other additional curable materials), and / or photoinitiators described herein may be used in the first ink and / or second ink of the kits described herein. However, in some examples, the inks described herein do not include both a primary or secondary amine species and an ethylenically unsaturated species such as a (meth)acrylate.

[0059] Furthermore, the multiple inks of the kit described herein may be used simultaneously or sequentially in a 3D printing process. Furthermore, when at least one ink of the kit includes an additional curable material such as a (meth)acrylate, the multiple inks of the kit together may provide different curable materials that form different polymer networks. In some such examples, the different curable materials and / or polymer networks of the different inks of the kit may be cured in a time-separated and / or spatially separated manner within the geometry of the 3D article. For example, in some embodiments, the curable material of the first (and / or second) ink may be cured during printing of the 3D article to provide a printed article having sufficient green strength to be handled and / or exhibit a desired feature resolution, and further, the different curable material of the second (and / or first) ink may be cured after printing, such as by placing the article in an oven for thermal curing of the second curable material. Similarly, in other examples, the curable material of a first ink is cured or polymerized in a first region of the printed 3D article, and the curable material of a second ink is cured or polymerized in a second region of the printed 3D article.

[0060] Furthermore, the two inks of the kits described herein may be used in separate ink dispensers or "channels" of a 3D printing system during 3D printing, or the two inks may be combined to form a single composition for forming a 3D article, as described below. Additionally, it should be understood that a "channel" of a 3D printing system may refer to a mechanism for depositing a single material from an ink dispenser, such as a print head. For example, a channel of a print head may refer to the ejection orifice of a particular material of the print head, alone or in combination with any material conduits, material storage compartments, and / or other hardware or software of the 3D printing system associated with the ejection orifices of that particular material. A channel may also refer to an entire print head dedicated to printing a single particular material, alone or in combination with any material conduits, material storage compartments, and / or other hardware or software of the 3D printing system associated with printing that single particular material from that channel.

[0061] Again, with regard to the specific components of the inks described herein, the inks described herein may further include one or more components in addition to the monomers and curable materials described above. For example, the inks described herein may further include a colorant, such as a molecular dye, a particulate inorganic pigment, or a particulate organic colorant. The inks described herein may also include one or more additives selected from the group consisting of inhibitors and stabilizers. Furthermore, the inks described herein may include one or more photoinitiators and / or one or more photosensitizers. Furthermore, it is understood that any ink described herein may include such additional components, regardless of whether the ink is part of a kit described herein or not.

[0062] The inks may include any colorant not inconsistent with the objectives of the present disclosure. The colorants of the inks described herein may be particulate colorants, such as particulate pigments, or molecular colorants, such as molecular dyes. Any such particulate or molecular colorants not inconsistent with the objectives of the present disclosure may be used. In some examples, for example, the colorants of the inks include inorganic pigments, such as TiO2 and / or ZnO. In some embodiments, the colorants of the inks include colorants for use in RGB, sRGB, CMY, CMYK, L*a*b*, or Pantone® colorization schemes. In some examples, one or more colorants of the inks described herein exhibit a white color. In other examples, the colorants exhibit a black color. Some non-limiting examples of colorants suitable for use in some embodiments described herein include SUN UVDJ107, SUN UVDJ150, SUN UVDJ322, SUN UVDJ350, SUN UVDJ354, RJA D3010-FX-Y150, RJA D3410-FX-Y150, RJA D3410-FX-K, PENN COLOR 9B898, and PENN COLOR 9B989. Furthermore, in some examples, the particulate colorants described herein have an average particle size of less than about 5 μm, or less than about 1 μm. In some examples, the particulate colorants described herein have an average particle size of less than about 500 nm, for example, less than about 400 nm, less than about 300 nm, less than about 250 nm, less than about 200 nm, or less than about 150 nm. In some examples, the particulate colorant has an average particle size of about 50 to 5000 nm, about 50 to 1000 nm, or about 50 to 500 nm.

[0063] The colorant may be present in the inks described herein in any amount not inconsistent with the objectives of the present disclosure. In some examples, the colorant is present in the ink in an amount up to about 2% by weight, alternatively about 0.005-2%, 0.01-2%, 0.01-1.5%, 0.01-1%, 0.01-0.5%, 0.1-2%, 0.1-1%, 0.1-0.5%, or 0.5-1.5% by weight, based on the total weight of the ink.

[0064] Additionally, the inks described herein further comprise, in some embodiments, one or more polymerization inhibitors and / or stabilizers. Polymerization inhibitors may be added to the inks to provide additional thermal stability to the composition. Any polymerization inhibitor not inconsistent with the objectives of the present disclosure may be used. Furthermore, the polymerization inhibitor may retard or slow the rate of polymerization and / or prevent polymerization from occurring for a period of time or "induction time" until the polymerization inhibitor is consumed. Furthermore, in some examples, the polymerization inhibitors described herein are "addition type" inhibitors. The inhibitors described herein may also be "chain transfer type" inhibitors. In some examples, a suitable polymerization inhibitor includes methoxyhydroquinone (MEHQ).

[0065] The stabilizer, in some embodiments, includes one or more antioxidants. The stabilizer may include any antioxidant not inconsistent with the objectives of the present invention. In some examples, suitable antioxidants include various aryl compounds, such as butylated hydroxytoluene (BHT), which may also be used as polymerization inhibitors in some embodiments described herein. More generally, a single species may act as both a stabilizer and a polymerization inhibitor. In some examples, multiple inhibitors and / or stabilizers may be used, where different inhibitors and / or stabilizers provide different effects and / or function synergistically.

[0066] The polymerization inhibitor and / or stabilizer may be present in the ink in any amount consistent with the objectives of the present disclosure. In some embodiments, the polymerization inhibitor is present in an amount ranging from about 0.01% to about 2% by weight, or from about 0.05% to about 1% by weight. Similarly, in some examples, the stabilizer is present in the ink in an amount ranging from about 0.1% to about 5% by weight, from about 0.5% to about 4% by weight, or from about 1% to about 3% by weight, based on the total weight of the ink.

[0067] The inks described herein may also include one or more photoinitiators. Any photoinitiator not inconsistent with the objectives of the present disclosure may be used. In some examples, the photoinitiator includes an α-cleavage type (unimolecular decomposition process) photoinitiator or a hydrogen abstraction type photosensitizer-tertiary amine synergist operable to absorb light between about 250 nm and about 400 nm, or between about 300 nm and about 385 nm to generate free radicals. Examples of α-cleavage type photoinitiators include Irgacure 184 (CAS 947-19-3), Irgacure 369 (CAS 119313-12-1), and Irgacure 819 (CAS 162881-26-7). An example of a photosensitizer-amine combination is Darocur BP (CAS 119-61-9) in combination with diethylaminoethyl methacrylate.

[0068] Additionally, in some examples, photoinitiators include benzoins, including benzoin ethers (e.g., benzoin methyl ether, benzoyl ethyl ether, and benzoyl isopropyl ether), benzoin phenyl ether, and benzoin acetate; acetophenones, including acetophenone, 2,2-dimethoxyacetophenone, and 1,1-dichloroacetophenone; benzil, benzil ketals (e.g., benzil dimethyl ketal and benzil diethyl ketal); anthraquinones, including 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, and 2-amylanthraquinone; triphenylphosphine, benzoylphosphine oxide (e.g., 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin benzophenone and 4,4'-bis(N,N'-dimethylamino)benzophenone; thioxanthone and xanthone; acridine derivatives; phenazine derivatives; quinoxaline derivatives or 1-phenyl-1,2-propanedione; 2-O-benzoyloxime; 1-aminophenyl ketone; or 1-hydroxyphenyl ketones such as 1-hydroxycyclohexyl phenyl ketone, phenyl 1-hydroxyisopropyl ketone, and 4-isopropyl phenyl 1-hydroxyisopropyl ketone.

[0069] The photoinitiator may also include photoinitiators operable for use with HeCd laser radiation sources, including acetophenone, 2,2-dialkoxybenzophenone, and 1-hydroxyphenyl ketones, such as 1-hydroxycyclohexyl phenyl ketone or 2-hydroxyisopropyl phenyl ketone (=2-hydroxy-2,2-dimethylacetophenone). Additionally, in some examples, the photoinitiator includes photoinitiators operable for use with Ar laser radiation sources, including benzil ketals, such as benzil dimethyl ketal. In some embodiments, the photoinitiator includes α-hydroxyphenyl ketone, benzil dimethyl ketal, or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, or mixtures thereof.

[0070] Another class of photoinitiators that can be included in the inks described herein include ionic dye-counterion compounds that can absorb actinic radiation to generate free radicals for polymerization initiation. Several ionic dye-counterion compounds and their modes of operation are disclosed in EP 0 223 587 A1, U.S. Pat. Nos. 4,751 ,102, 4,772,530 and 4,772,541.

[0071] The photoinitiator may be present in the inks described herein in any amount not inconsistent with the objectives of the present invention. In some embodiments, the photoinitiator is present in the ink in an amount up to about 5% by weight, based on the total weight of the ink. In some examples, the photoinitiator is present in an amount ranging from about 0.1% to about 5% by weight.

[0072] Additionally, in some embodiments, the inks described herein further comprise one or more photosensitizers. Generally, such sensitizers can be added to the ink to increase the effectiveness of one or more photoinitiators that may be present. In some embodiments, the sensitizer comprises isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX).

[0073] The sensitizer may be present in the ink in any amount consistent with the objectives of the present disclosure, in some embodiments, the sensitizer is present in an amount ranging from about 0.1% to about 2% by weight, or from about 0.5% to about 1% by weight, based on the total weight of the ink.

[0074] Moreover, in some examples, the inks described herein are further characterized by components that are not included or are included in small amounts in the ink. For example, in some embodiments, the inks described herein are free or substantially free of non-curing photoinitiators, including the non-curing photoinitiators described above. As used herein, an ink that is "substantially" free of non-curing photoinitiators or "substantially" excluded from non-curing photoinitiators may contain less than about 1% by weight, less than about 0.5% by weight, less than about 0.1% by weight, less than about 0.07% by weight, less than about 0.05% by weight, or less than about 0.01% by weight of non-curing photoinitiator based on the total weight of the ink. Thus, in some examples, the inks described herein contain 0-0.5% by weight, 0-0.1% by weight, 0-0.07% by weight, 0-0.05% by weight, or 0-0.01% by weight of non-curing photoinitiator based on the total weight of the ink. Additionally, as used herein, a "non-curing" photoinitiator can include any photoinitiator that does not contain a moiety that can be polymerized or cured with the curable material of the ink, such as an ethylenically unsaturated moiety, For example, in some examples, a non-curing photoinitiator does not contain a (meth)acrylate moiety.

[0075] The inks described herein may also exhibit various desirable properties. For example, the inks described herein may have any freezing point, melting point, and / or other phase transition temperature not inconsistent with the objectives of the present disclosure. In some examples, the inks have freezing and melting points consistent with temperatures used in some 3D printing systems, such as 3D printing systems designed for use with phase change inks. In some embodiments, the inks have a freezing point greater than about 40°C. In some examples, for example, the inks have a freezing point centered at a temperature range of about 45°C to about 55°C or about 50°C to about 80°C. In some examples, the inks have a freezing point less than about 40°C or less than about 30°C.

[0076] Moreover, in some embodiments described herein, the ink exhibits a sharp freezing point or other phase transition. In some cases, for example, the ink freezes in a narrow temperature range, such as in the range of about 1-10° C., about 1-8° C., or about 1-5° C. In some embodiments, an ink with a sharp freezing point freezes in a temperature range of X±2.5° C., where X is the temperature at which the freezing point is centered (e.g., X=65° C.).

[0077] Additionally, the inks described herein are, in some examples, fluid at jetting temperatures encountered in some 3D printing systems. Furthermore, in some embodiments, the ink solidifies once deposited on a surface during the creation of a three-dimensionally printed article or object. Alternatively, in other examples, the ink remains substantially fluid upon deposition on a surface. Solidification of the ink, in some embodiments, occurs through a phase change of the ink or components of the ink. The phase change may include a phase change from liquid to solid or from liquid to semi-solid. Furthermore, in some examples, solidification of the ink includes an increase in the viscosity of the ink, such as an increase in viscosity from a low viscosity state to a high viscosity state. Solidification of the ink may occur by curing of the ink.

[0078] Additionally, in some embodiments, the inks described herein, when uncured, have a viscosity profile that matches the requirements and parameters of one or more 3D printing systems, such as a multijet modeling or stereolithography system. In some examples, for example, the inks described herein have a dynamic viscosity in the range of about 8.0 cP to about 14.0 cP or about 9.0 cP to about 14.0 cP at a jetting temperature of the system, such as a temperature of about 80° C., as measured in accordance with ASTM standard D2983 (e.g., using a Brookfield Model DV-II+ viscometer). In some embodiments, the inks have a dynamic viscosity of about 9.5 to 12.5 cP or about 10.5 to 12.5 cP at a temperature of about 80° C. In some examples, the inks have a viscosity of about 8.0 to 10.0 cP at a temperature of about 85 to 87° C. In some embodiments, the inks described herein have a dynamic viscosity of about 8.0-19.0 cP, about 8.0-13.5 cP, about 11.0-14.0 cP, about 11.5-13.5 cP, or about 12.0-13.0 cP at a temperature of about 65° C., as measured according to ASTM standard D2983. In other examples, the inks described herein, when uncured, exhibit a dynamic viscosity of about 200-2000 cP, about 200-900 cP, about 300-900 cP, about 300-800 cP, about 400-1000 cP, about 400-900 cP, about 400-800 cP, about 400-600 cP, about 450-550 cP, about 500-700 cP, about 500-600 cP, or about 500-550 cP at 30° C. when measured according to ASTM D2983. In some examples, the inks described herein, when uncured, exhibit a dynamic viscosity of less than about 100 cP or greater than about 1000 cP when measured according to ASTM D2983.

[0079] Moreover, the inks described herein may, in some embodiments, exhibit one or more desirable combinations of characteristics. In some instances, for example, the ink in an uncured state has one or more of the following properties: 1. A freezing point of less than about 30° C., less than about 25° C., or less than about 15° C.; 2. A viscosity of about 9-14 cP at 70-95° C., or about 400-1000 cP at 25-35° C.; and 3. Thermal stability at room temperature (25℃) for at least 6 months As noted above, viscosity may be measured in accordance with ASTM D2983 (e.g., using a Brookfield Model DV-II+ viscometer). Additionally, for purposes of reference herein, a "thermally stable" material does not exhibit a viscosity change of more than about 35 percent over a specified period of time (e.g., 3 days) when measured at a specified temperature (e.g., room temperature) and at the beginning and end of the period. In some embodiments, the viscosity change is about 30 percent or less, or about 20 percent or less, based on the higher viscosity value. In some cases, the viscosity change is between about 10 percent and about 20 percent, or between about 25 percent and about 30 percent. Furthermore, in some embodiments, the viscosity change is an increase in viscosity.

[0080] The inks described herein may exhibit a variety of desirable properties in the cured or "green" state in addition to those described above. Ink in a "cured" state, as used herein, includes inks containing curable materials or polymerizable components that are at least partially polymerized and / or crosslinked, or that are substantially polymerized and / or crosslinked. For example, in some examples, the cured ink is at least about 51% polymerized or crosslinked, or at least about 60% polymerized or crosslinked. In some embodiments, the cured ink is at least about 70%, at least about 80%, at least about 90%, or at least about 95% polymerized or crosslinked. In some examples, the cured ink is about 50% to about 99% polymerized or crosslinked. The ink in its "raw" state is less than 50%, less than 40%, less than 30%, or less than 20% polymerized or crosslinked. In some examples, the ink in its raw state is 5-50%, 5-40%, 5-30%, 10-50%, 10-40%, 10-30%, 20-50%, 20-40%, 30-50%, or 30-40% polymerized or crosslinked. Furthermore, as will be appreciated by one of ordinary skill in the art, the "raw" state of the ink may be defined as the state of the ink during or after the layer-by-layer 3D printing process described herein, but before any post-processing curing steps are performed.

[0081] In some examples, the inks described herein, when cured or in the raw state, have an elongation at break of about 10-400%, 10-300%, 10-200%, 10-100%, 10-8%, 10-40%, 10-30%, 10-20%, 15-400%, 15-300%, 15-100%, 15-30%, 50-400%, 50-300%, 50-200%, 50-100%, 100-400%, 100-300%, 100-200%, 200-400, 200-300%, or 300-400%, as measured according to ASTM D638. Further, the cured or raw inks described herein may, in some examples, have a tensile strength of about 3500-7000 psi (about 24.1 MPa to about 48.3 MPa), or about 4000-6000 psi (about 27.6 MPa to about 41.4 MPa), as measured in accordance with ASTM D638. Additionally, the cured or raw inks described herein may, in some embodiments, have a tensile modulus of about 100-400 ksi (about 689 MPa to about 2758 MPa), or about 150-300 ksi (about 1034 MPa to about 2068 MPa), as measured in accordance with ASTM D638.

[0082] The inks described herein, including in the cured state, may also exhibit high biocompatibility and / or low cytotoxicity. For example, in some examples, the inks described herein, when cured, exhibit a cytotoxicity rating of less than 2, as measured according to ANSI / AAMI / ISO 10993-5:2009. In some embodiments, the inks described herein, when cured, exhibit a cytotoxicity rating of 0 or 1, as measured according to ANSI / AAMI / ISO 10993-5:2009.

[0083] Moreover, in some examples, the inks described herein, when cured, may exhibit more than one of the above properties. For example, in some embodiments, the inks, when cured, have a tensile strength of about 4000-6000 psi (about 27.6 MPa to about 41.4 MPa), when measured according to ASTM D638; a tensile modulus of about 150-300 ksi (about 1034 MPa to about 2068 MPa), when measured according to ASTM D638; an elongation at break of about 10-400%, when measured according to ASTM D638; and a cytotoxicity rating of 0 or 1, when measured according to ANSI / AAMI / ISO 10993-5:2009.

[0084] The inks described herein can be manufactured in any manner not inconsistent with the objectives of the present disclosure. In some embodiments, for example, the method of preparing the inks described herein includes mixing the components of the ink, melting the mixture, and filtering the molten mixture. The melting of the mixture is performed at a temperature of about 75° C., or in a range of about 75° C. to about 85° C., in some examples. In some embodiments, the inks described herein are manufactured by placing all the components of the ink in a reaction vessel and heating the resulting mixture to a temperature in a range of about 75° C. to about 85° C. while stirring. Heating and stirring are continued until the mixture reaches a substantially homogenized molten state. Typically, the molten mixture can be filtered while in a flowable state to remove any large, undesirable particles that may interfere with jetting or ejection or other printing processes. The filtered mixture can then be cooled to ambient temperature and stored until ready for use in a 3D printing system. In other examples, the components of the ink are mixed at ambient temperature (e.g., 20-25° C.) with no or minimal heating (e.g., to a temperature of 30-45° C.). Such methods may further comprise the step of filtering the resulting liquid mixture.

[0085] II. Use of 3D printing compositions In another aspect, the present specification describes the use of 3D printing compositions comprising the above-mentioned ink or kit.For example, in some examples, the present specification describes the use of 3D printing compositions comprising inks that contain cyclic carbonate monomers and amine monomers.However, any one or more of the inks described in section I above can be used for 3D printing.

[0086] III. 3D Printing System In yet another aspect, a 3D printing system is described herein. Such a 3D printing system may use or include the 3D printing compositions described above, such as compositions including one or more of the inks or kits described above. In some embodiments, the 3D printing system described herein includes a 3D printer with at least one of an ink dispenser and an ink reservoir, and an ink described herein disposed within the ink dispenser, the ink reservoir, or both. The ink comprises, consists of, or consists essentially of any ink described in Section I above. Furthermore, in some examples, the 3D printing system described herein includes a 3D printer with a first ink dispenser and a second ink dispenser, a first ink disposed within the first ink dispenser, and a second ink disposed within the second ink dispenser. The first ink and the second ink comprise, consist of, or consist essentially of the first ink and the second ink, respectively, described in Section I above.

[0087] Generally, any 3D printer not inconsistent with the objectives of this disclosure may contain or include the inks described herein, including ink dispensers and / or reservoirs. In some embodiments, for example, the 3D printer includes an inkjet or so-called multi-jet modeling (MJM) type 3D printer. In other examples, the 3D printer includes a stereolithography (SLA) type 3D printer, a digital light processing (DLP) type 3D printer, or a contacted SLA (cSLA) type printer. Other 3D printers may also be used.

[0088] IV. How to Print 3D Objects In another aspect, a method for printing a 3D article or object is described herein. The method for printing a 3D article or object described herein can include forming a 3D article from multiple layers of the ink described herein in a layer-by-layer manner. Any ink described in Section I above can be used. For example, in some examples, the ink includes a cyclic carbonate monomer and an amine monomer. Other inks described herein can also be used. Furthermore, in some examples, the method described herein includes selectively depositing a layer of the ink in a fluid state onto a substrate.

[0089] Additionally, the methods described herein may further include curing or polymerizing one or more curable materials of the ink, such as the cyclic carbonate monomers and amine monomers of the ink. Furthermore, when the ink includes multiple different curable materials, the different curable materials may be cured or polymerized in separate curing or polymerization steps that occur at different times and / or in different spatial regions of the layer of ink. Furthermore, the different curable materials may be cured in different manners.

[0090] For example, in some examples, the inks used in the methods described herein include a cyclic carbonate monomer, an amine monomer, and one or more additional (meth)acrylates. Furthermore, in some such examples, each of the cyclic carbonate monomers includes a (meth)acrylate moiety in addition to including one or more cyclic carbonate moieties. In such examples, the methods described herein include a step of curing or polymerizing the ethylenically unsaturated moieties of the one or more (meth)acrylates (and, if present, the (meth)acrylate moieties of the cyclic carbonate) to form a poly(meth)acrylate. For example, the (meth)acrylate can be cured or polymerized with UV light. Furthermore, in some embodiments, the method further includes a step of thermally curing or polymerizing the cyclic carbonate monomer and the amine monomer. Such a curing or polymerization step can include reacting the cyclic carbonate monomer with the amine monomer to form a polyurethane. Furthermore, in some examples, the polyurethane and the poly(meth)acrylate can form an interpenetrating polymer network together.

[0091] The step of curing one or more curable materials or monomers described herein can be carried out in any manner consistent with the objectives of the present disclosure. For example, in some examples, a layer of deposited ink may be cured (by at least one method or curing mechanism) prior to deposition of another or adjacent layer of ink. In some examples, the method of printing a 3D article described herein further comprises exposing the ink to electromagnetic radiation of a wavelength and intensity sufficient to cure at least one curable material of the ink, where curing may include polymerizing one or more polymerizable moieties or functional groups of one or more components of the at least one curable material. Furthermore, as described above, the step of curing one or more layers of deposited ink is carried out by exposing the one or more layers to electromagnetic radiation, such as UV light or visible light.

[0092] Curing may also be accomplished thermally. In some embodiments, thermal curing is accomplished using thermal energy or heat provided by a photocuring process described herein, such as thermal energy released by photoinitiated polymerization of one or more (meth)acrylates or other ethylenically unsaturated monomers. Thermal curing can also be accomplished by heating the ink (or an article formed from the ink) using a thermal energy source, such as an oven.

[0093] It should further be appreciated that the deposited ink (or components thereof) may be cured according to a second curing mechanism after curing the ink according to a first curing mechanism and / or after completing printing of the 3D article. For example, in some examples, one or more deposited inks may be cured by UV light in a layer-by-layer manner during layer-by-layer printing of the article, and then cured in another manner after completing the layer-by-layer printing. In some such embodiments, the step of later curing one or more deposited inks includes thermally curing one or more inks by heating the article. In some examples, the article is heated in a "post-processing" step, such as by placing the already formed article in an oven or other space at a high temperature. In some such examples, the article may be heated at a temperature and for a sufficient time to cure the uncured curable components of the ink from which the article is formed, as opposed to being heated at a lower temperature and / or for a shorter time that may be used to melt away or remove support material from a finished 3D article. However, in some cases, the support material, if present, may be dissolved away from the finished 3D article simultaneously with the thermal curing of the curable components of the ink. Furthermore, in some cases, the thermal curing step is performed during the layer-by-layer printing of such an article, rather than being performed as a post-processing step.

[0094] The method of printing a 3D article described herein may also include forming the 3D article from multiple layers of multiple inks described herein in a layer-by-layer manner. For example, in some embodiments, the method includes forming the 3D article from multiple layers of a first ink and multiple layers of a second ink. In some such examples, the method of printing a 3D article includes selectively depositing a layer of a first ink in a fluid state on a substrate, and selectively depositing a layer of a second ink in a fluid state on a substrate, the first ink and the second ink comprising the first ink and the second ink, respectively, described in Section I above. For example, the first ink may comprise a cyclic carbonate monomer and the second ink may comprise an amine monomer.

[0095] As with a "single" ink, methods described herein using multiple different inks may also include curing multiple curable materials of the inks, such as in separate curing steps performed at different times and / or in different spatial regions of one or more layers of ink. Furthermore, different curable materials may be cured in different manners, as described herein. For example, in some embodiments, a first ink includes one or more ethylenically unsaturated monomers in addition to a cyclic carbonate monomer, and the method includes curing the ethylenically unsaturated monomers of the first ink with UV light, and then thermally curing the cyclic carbonate and amine monomers.

[0096] The layers of ink can be deposited according to a computer-readable image of the 3D article. In some embodiments, the ink is deposited according to preselected computer-aided design (CAD) parameters. Furthermore, in some examples, one or more layers of the ink described herein have a thickness of about 10 μm to about 100 μm, about 10 μm to about 80 μm, about 10 μm to about 50 μm, about 20 μm to about 100 μm, about 20 μm to about 80 μm, or about 20 μm to about 40 μm. Other thicknesses are possible.

[0097] In addition, it should be understood that the methods of printing 3D articles described herein may include so-called multi-jet modeling or stereolithography 3D printing methods. For example, in some examples, the multi-jet method of printing 3D articles includes selectively depositing one or more layers of inks described herein in a fluid state onto a substrate, such as a build pad of a 3D printing system. Additionally, in some embodiments, the methods described herein further include supporting at least one of the one or more layers of inks with a support material. Any support material not inconsistent with the objectives of the present disclosure may be used.

[0098] Furthermore, in some embodiments, a preselected amount of the ink described herein is heated to an appropriate temperature and jetted through one or more print heads of a suitable inkjet printer to form a layer on a print pad in a print chamber. In some examples, each layer of ink is deposited according to preselected CAD parameters. A suitable print head for depositing the ink is, in some embodiments, a piezoelectric print head. Additional print heads suitable for depositing the ink and support material described herein are commercially available from various inkjet printing equipment manufacturers. For example, Xerox, Hewlett Packard, or Ricoh print heads may be used in some examples.

[0099] Additionally, in some embodiments, the inks described herein remain substantially fluid upon deposition. Alternatively, in other examples, the inks exhibit a phase change upon deposition and / or solidify upon deposition. Furthermore, in some examples, the temperature of the printing environment can be controlled such that the jetted droplets of ink solidify upon contact with the receiving surface. In other embodiments, the jetted droplets of ink do not solidify upon contact with the receiving surface and remain substantially fluid. Additionally, in some examples, after each layer is deposited, the deposited material is planarized and cured using electromagnetic (e.g., UV) radiation before deposition of the next layer. Optionally, several layers may be deposited before planarization and curing, or multiple layers may be deposited and cured, followed by deposition of one or more layers and then planarization without curing. Planarization compensates for the thickness of one or more layers before curing of the material by leveling the dispensed material to remove excess material and create a uniformly smooth exposed or flat upward surface on the printer's support platform. In some embodiments, the planarization is accomplished using a wiper device, such as a roller that may counter-rotate in one or more print directions, but not in one or more other print directions. In some examples, the wiper device comprises a roller and a wiper that removes excess material from the roller. Additionally, in some examples, the wiper device is heated. It is noted that the viscosity of the jetted ink described herein before curing is, in some embodiments, desirably sufficient to hold its shape and not be exposed to excessive viscous drag from the planarization device.

[0100] Moreover, the support material, if used, may be deposited in a manner consistent with that described above for the ink. The support material may be deposited according to preselected CAD parameters, for example, such that the support material is adjacent or contiguous with one or more layers of the ink. Jetted droplets of the support material, in some embodiments, solidify or solidify upon contact with the receiving surface. In some examples, the deposited support material also undergoes planarization.

[0101] The layer-by-layer deposition of the ink and support material may be repeated until the 3D article is formed. In some embodiments, the method of printing a 3D article further comprises removing the support material from the ink.

[0102] A stereolithography (SLA), contact SLA (cSLA), or digital light processing (DLP) 3D printer may also be used to form 3D articles from the inks described herein. For example, in some examples, a method of printing a 3D article includes holding one or more inks described herein in a fluid state in a container, and selectively applying energy to one or more inks in the container to solidify at least a portion of the fluid layer of ink, thereby forming a solidified layer that defines a cross-section of the 3D article. In addition, the method described herein may further include raising or lowering the solidified layer of ink to provide a new or second fluid layer of unsolidified ink on the surface of the fluid ink in the container, followed by selectively applying energy again to the ink in the container to solidify at least a portion of the new or second fluid layer of ink to form a second solidified layer that defines a second cross-section of the 3D article. Further, the first and second cross sections of the 3D article may be bonded or adhered to each other in the z-direction (or a build direction corresponding to the above-mentioned rising or lowering direction) by applying energy to solidify the ink. Further, selectively applying energy to the ink in the container may include applying electromagnetic radiation, such as UV radiation or visible radiation, having sufficient energy to cure the ink. In some examples, the UV light has an average wavelength of 320-380 nm, 340-370 nm, or 350-360 nm. In some examples, the curing radiation is provided by a computer-controlled laser beam, or a DLP light source or projector. Additionally, in some examples, raising or lowering the solidified layer of ink is performed using a lifting platform disposed within the container of fluid ink. The methods described herein may also include planarizing the new layer of fluid ink provided by raising or lowering the lifting platform. Such planarization may be performed by a wiper or roller in some examples.

[0103] It should be understood that the above process may be repeated as many times as desired to provide a 3D article. For example, in some instances, the process may be repeated "n" times, where n may be up to about 100,000, up to about 50,000, up to about 10,000, up to about 5000, up to about 1000, or up to about 500. Thus, in some embodiments, a method of printing a 3D article as described herein may include selectively applying energy to the ink in the container to solidify at least a portion of the nth fluid layer of ink, thereby forming an nth solidified layer that defines an nth cross-section of the 3D article; raising or lowering the nth solidified layer of ink to provide an (n+1)th layer of unsolidified ink on a surface of the fluid ink in the container; selectively applying energy to the (n+1)th layer of ink in the container to solidify at least a portion of the (n+1)th layer of ink to form an (n+1)th solidified layer that defines the (n+1)th cross-section of the 3D article; raising or lowering the (n+1)th solidified layer of ink to provide an (n+2)th layer of unsolidified ink on a surface of the fluid ink in the container; and continuing to repeat the foregoing steps to form the 3D article. It should further be understood that one or more steps of the methods described herein, such as selectively applying energy to a layer of ink, may be performed according to an image of the 3D article in a computer readable format. The general method of 3D printing using stereolithography is further described in, among other places, U.S. Patent Nos. 5,904,889 and 6,558,606.

[0104] By carrying out the printing process described above, 3D articles printed from the inks described herein can be provided with high feature resolution. For purposes of reference herein, the "feature resolution" of an article can be the smallest dimension of a controllable physical feature of the article. The feature resolution of an article can be described in units of distance, such as micrometers (μm), or in units of dots per inch (dpi). As will be understood by those skilled in the art, higher feature resolution corresponds to higher dpi values ​​and also corresponds to shorter distances in μm. In some examples, an article formed by depositing or solidifying an ink described herein can have a feature resolution of about 500 μm or less, about 200 μm or less, about 100 μm or less, or about 50 μm or less, including resolution at high temperatures. In some embodiments, the article has a feature resolution between about 50 μm and about 500 μm, between about 50 μm and about 200 μm, between about 50 μm and about 100 μm, or between about 100 μm and about 200 μm. Correspondingly, in some examples, the feature resolution of the articles described herein is at least about 100 dpi, at least about 200 dpi, at least about 250 dpi, at least about 400 dpi, or at least about 500 dpi. In some examples, the feature resolution of the articles is between about 100 dpi and about 600 dpi, between about 100 dpi and about 250 dpi, or between about 200 dpi and about 600 dpi.

[0105] V. Printed 3D objects In another aspect, a printed 3D article is described herein. In some embodiments, the printed 3D article is formed from one or more inks described herein. Any ink described in Section I above herein may be used. For example, in some examples, the 3D article is formed from a single ink described herein, such as an ink that includes a cyclic carbonate monomer, an amine monomer, and one or more additional ethylenically unsaturated monomers, such as one or more additional (meth)acrylates. Furthermore, the cyclic carbonate monomer and the amine monomer may form a polyurethane together when cured. Similarly, the one or more (meth)acrylates may form a poly(meth)acrylate when cured. In some such examples, the polyurethane and the poly(meth)acrylate together form an interpenetrating polymer network.

[0106] The printed 3D articles described herein may be formed from a number of different inks. For example, in some embodiments, the printed 3D articles are formed from the first ink and the second ink described in Section I above. In some such examples, the first ink includes a cyclic carbonate monomer and the second ink includes an amine monomer. The first and / or second ink may also include a second curable material in addition to the cyclic carbonate and / or amine monomer. Such a second curable material of the first ink may, in some examples, include one or more (meth)acrylates or other ethylenically unsaturated monomers. Furthermore, as described above, such a second curable material of the first or second ink may form a polymer network (e.g., poly(meth)acrylate) that is different from the polymer network (e.g., polyurethane) formed from the cyclic carbonate and amine monomer.

[0107] VI. Adhesives and Coatings Described herein are inks, kits, systems, and methods for 3D printing. However, in alternative embodiments, compositions are also described herein for applications other than 3D printing. In particular, compositions are described herein for adhesive and / or coating applications.

[0108] In particular, in some embodiments, adhesives are described herein that include the above cyclic carbonate monomers, such as cyclic carbonates having one or more cyclic carbonate moieties and one or more ethylenically unsaturated moieties. In some examples, the one or more ethylenically unsaturated moieties include (meth)acrylate moieties. For example, in some examples, the cyclic carbonate has a structure of formula (A15), formula (A16), formula (A17), or formula (A18). Furthermore, the adhesives or adhesive compositions described herein, in some embodiments, include one or more components in addition to the cyclic carbonate species. In some examples, the adhesives or adhesive compositions further include a solvent, such as, for example, a polar or non-polar, hydrophobic or hydrophilic, aqueous or organic solvent.

[0109] In another aspect, coatings and coated substrates or devices are described herein. In some such embodiments, for example, a device comprises a substrate and a coating disposed on or over the substrate, the coating comprising the composition described above. In particular, in some examples, the coating comprises or is formed from a cyclic carbonate species described herein, such as a cyclic carbonate having one or more cyclic carbonate moieties and one or more ethylenically unsaturated moieties. In some embodiments, the one or more ethylenically unsaturated moieties comprise (meth)acrylate moieties. In some examples, the cyclic carbonate has a structure of formula (A15), formula (A16), formula (A17), or formula (A18). Moreover, the substrate of such coated devices can be formed from any material not inconsistent with the objectives of the present disclosure. In some examples, for example, the substrate comprises or is formed from an organic material, such as a thermoplastic material or another organic polymeric material. In other examples, the substrate comprises or is formed from an inorganic material, such as a metal, a metal oxide, or a glass. The coated substrates described herein may also include or be formed from composite materials, such as organic-inorganic composite materials, for example, fiberglass materials.

[0110] Some embodiments described herein are further illustrated in the following non-limiting examples. EXAMPLES

[0111] Example 1 Cyclic Carbonate Monomer A cyclic carbonate monomer having the structure of formula (A11) where R1 is (CH2)8 was prepared as follows: 12.0 g of sebacoyl chloride (SebCl), 10.4 g of triethylamine, and 80 g of methyltetrahydrofuran (mTHF) solvent were added to a 500 mL three-necked round bottom flask equipped with a large Teflon-coated football-shaped stirring magnet, constant pressure addition funnel, and condenser. The flask was placed in a Pyrex crystallizing dish (190x100, 2.5 L) filled with ice water and stirred / cooled for approximately 30 minutes. 11.8 g of glycerol carbonate and 20 g of mTHF were added to a 150 mL constant pressure addition funnel and then gently stirred until the solid glycerol carbonate was dissolved. The glycerol carbonate solution was added dropwise to the cooled sebacoyl chloride solution over a period of 30 minutes. Additional mTHF was added during the rest of the reaction to facilitate stirring. Stirring was continued for approximately 2 days. The final mixture was worked up by filtration using a vacuum flask and a Buchner funnel equipped with silica gel. The clear liquid was collected in the vacuum flask and subjected to rotary evaporation to obtain a clear viscous product.

[0112] Example 2 Cyclic Carbonate Monomer Cyclic carbonate monomers having the structure of formula (A14), where R1 is (CH2)2, R2 is CH2, and R6 is either CH3 or H, were prepared as follows: For the compound where R6=CH3, 620.6 g of isocyanatoethyl methacrylate (obtained from Synasia, Nantong, China) was added to a 2000 mL beaker equipped with a large Teflon-coated football-shaped stirring magnet. The solution was then stirred and heated in a 60°C silicone oil bath. A mixture of 476.7 g of glycerol carbonate (obtained from Huntsman Chemical) and 0.16 g of dibutyltin dilaurate (obtained from Sigmal Aldrich) was slowly added to the heated isocyanatoethyl methacrylate while maintaining the reaction temperature between 50°C and 80°C. After all of the mixture was added, 0.48 g of BHT (obtained from Sigma-Aldrich) was added and the resulting solution was stirred at 70-80°C for an additional 16 hours. The resulting product was a clear viscous liquid that showed no isocyanate peaks in FT-IR. For the compound with R6=H, a similar procedure was used, but the isocyanatoethyl methacrylate was replaced with a quantum equivalent amount of isocyanatoethyl acrylate (obtained from Synasia, Nantong, China).

[0113] Example 3 Cyclic Carbonate Monomer A cyclic carbonate monomer having the structure of formula (A15) was prepared as follows: To a 500 mL beaker equipped with a large Teflon-coated football-shaped stirring magnet was added 55.57 g of isophorone diisocyanate (obtained from Sima-Aldrich), isobornyl methacrylate (IBOMA, obtained from Evonik Industries), and 0.02 g of dibutyltin dilaurate (obtained from Sigma-Aldrich). The solution was stirred and heated in a silicone oil bath at 55-60°C. Next, 29.5 g of glycerol carbonate (obtained from Huntsman Chemical) was added gradually over a period of 30 minutes while maintaining the reaction temperature between 50°C and 80°C. After all the glycerol carbonate had been added, 0.04 g of BHT (obtained from Sigma-Aldrich) was added and the resulting solution was stirred at 60-70°C for an additional hour. Then, 32.53 g of hydroxyethyl methacrylate (obtained from Sigma-Aldrich) was slowly added over 0.2 h, and the resulting solution was stirred for an additional 16 h at 60-70° C. The product was a clear viscous liquid that did not show any isocyanate peaks in FT-IR.

[0114] Example 4 Cyclic Carbonate Monomer A cyclic carbonate monomer having the structure of formula (A13), where R2 and R3 are each (CH2)2, was prepared as follows: To a 1000 mL glass beaker was added a large Teflon-coated football-shaped stirring magnet, 47.2 g of glycerol carbonate (GC), 41.5 g of triethylamine, and 135 g of tetrahydrofuran (THF) solvent. The beaker was covered with a watch glass and placed in a Pyrex crystallizing dish (190x100, 2.5 L) filled with ice water to stir / cool for approximately 30 minutes. To a separate 250 mL beaker was added a Teflon-coated stirring magnet, 46.2 g of diethylene glycol bischloroformate (DEGBCF), and 70 g of ethyl alcohol solvent. The mixture was stirred until the DEGBC was dissolved. The DEGBCF solution was added dropwise to the cooled glycerol carbonate solution via a disposable pipette over a period of 45 minutes. After adding a few mL of the DEGBCF solution, a precipitate (the hydrochloride salt of triethylamine) was observed to form and continued to form throughout the addition. The precipitate became so thick in the beaker that it had to be kept stirred with a large stir bar during the latter DEGBCF additions. The mixture was left covered and set / stirred at room temperature for approximately 2 days. The product was isolated by filtration using a 600 mL coarse fritted Buchner funnel equipped with 300 g of silica gel and a 2 L vacuum flask. Fresh THF was added to wet the silica and the THF was allowed to elute by gravity through the silica-filled Buchner funnel into the attached 2 L vacuum flask. The final product mixture, including the salts formed, was then poured into the fritted funnel containing the THF-wetted silica while pulling a slight vacuum. Once the solvent had almost completely passed through the silica, the vacuum was removed and approximately 0.5 liters of fresh THF was added to the 1000 mL glass beaker, swirled, and slowly added to the fritted funnel and allowed to elute further through it. This washing process was repeated two times. The clear liquid collected in the 2 L vacuum flask was subjected to rotary evaporation or other evaporation techniques to remove the solvent, resulting in a clear viscous product.

[0115] Example 5 Cyclic Carbonate Monomer A cyclic carbonate monomer having the structure of formula (A12) where R5 is (CH2)6 was prepared as follows: To a 1000 mL glass beaker was added a large Teflon coated football-shaped stirring magnet, 47.2 g glycerol carbonate, 41.0 g triethylamine, and 180 g tetrahydrofuran (THF) solvent. The beaker was covered with a watch glass and placed in a Pyrex crystallizing dish (190x100, 2.5 L) filled with ice water to stir / cool for approximately 30 minutes. To a separate 250 mL beaker was added a Teflon coated stirring magnet, 47.2 g hexamethylene dichloroformate (HMDCF), and 50 g THF solvent. The mixture was stirred until the HMDCF was dissolved. The HMDCF solution was added dropwise to the cooled glycerol carbonate solution via a disposable pipette over a period of 45 minutes. After adding a few mL of HMDCF solution, a precipitate (the hydrochloride salt of triethylamine) was observed to form. The precipitate continued to form throughout the addition. The mixture was left covered and set / stirred at room temperature for approximately 2 days. Workup involved adding approximately 300 g of silica gel to a 600 mL coarse fritted Buchner funnel placed over a 2 L vacuum flask. Fresh THF was added to wet the silica and the THF was allowed to elute by gravity through the silica-filled Buchner funnel into the attached 2 L vacuum flask. The final product mixture, including the salts formed, was then poured into the fritted funnel containing the THF-wetted silica while pulling a slight vacuum. Once the solvent had almost completely passed through the silica, the vacuum was removed and approximately 0.5 liters of fresh THF was added to the 1000 mL glass beaker above, swirled, and slowly added to the fritted funnel and allowed to elute through it again. This washing process was repeated two times. The clear liquid collected in the 2 L vacuum flask was subjected to rotary evaporation or other evaporation techniques to remove the solvent, resulting in a clear viscous product.

[0116] Example 6 3D Printing Inks Inks according to some embodiments described herein were prepared as follows. Specifically, in this example, inks were prepared for use in "one-component" ink printing processes, such as SLA, cSLA, or DLP 3D printing. In general, one or more photoinitiators were first dissolved in the low viscosity UV-curable monomers (such as IBOMA, SR272, and / or SR205) by stirring. In some cases, heating was also performed while stirring. Next, the urethane acrylate oligomer (such as BR-371 or BR-571 MB) and the cyclic carbonate monomer were added and mixed using a mixer (obtained from Thinky Corporation). Then, one or more amine components were added and mixed using a mixer to obtain a "one-component" ink for casting or 3D printing processes, such as SLA, cSLA, or DLP.

[0117] Example 7 3D Printing Inks Inks according to some embodiments described herein were prepared as follows. Specifically, in this example, a first ink and a second ink were prepared. The first ink and the second ink may be used in the kits described herein. Alternatively, the first ink and the second ink may be combined with each other to form a single ink that may be used in a 3D printing system or method, with or without the use of one or more other inks, as described below.

[0118] Generally, the first ink (also referred to as "Part A") included a cyclic carbonate monomer having multiple cyclic carbonate moieties, as described in Section I above. The first ink also included a second curable material consisting of an additional (meth)acrylate monomer. Additionally, the first ink included a photoinitiator. The second ink (also referred to as "Part B") included an amine monomer having multiple primary or secondary amine moieties. Specific components of the first and second inks are described below.

[0119] The first ink ("Part A") contained 7.24 g of TMP tricarbonate (CAS No. 147876-32-2, available from SPECIFIC POLYMERS) (cyclic carbonate monomer); 27.93 g of triethylene glycol diacrylate (SR272, available from SARTOMER) (additional curable material); and 0.84 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO) (photoinitiator).

[0120] The second ink ("Part B") contained 7.14 g of Jeffamine T-403 (a triamine, available from HUNTSMAN CHEMICAL) (an amine monomer).

[0121] To prepare each ink, the individual components of each ink were combined and mixed. The mixture was heated with stirring to a temperature of about 20-25° C. Heating and stirring was continued until the mixture reached a substantially homogeneous liquid state. The liquid mixture was then filtered.

[0122] For use in MJM 3D printing, part A and part B are fed into two separate channels / ink dispensers, and then the two inks are mixed by jetting them into adjacent or nearby locations on the substrate, or into adjacent or nearby voxels. Such a method of mixing inks may also be referred to as "digital mixing." The jetted materials are then exposed to UV radiation for UV curing. In particular, the UV curing process cures the (meth)acrylate monomers of part A. During this process, some of the reaction between the cyclic carbonate monomers of part A and the amine monomers of part B may also occur. However, the extent of the reaction may be limited. A 3D article printed in this manner (without substantial reaction between the cyclic carbonate and the amine monomers) may have sufficient green strength to allow the article to be handled without causing damage to the article or loss of print resolution of the article. To complete the reaction between the cyclic carbonate and the amine monomers, the printed article may be placed in an oven to cure the cyclic carbonate and the amine monomers. Additionally, if a support material is used (such as a wax support material), this second or "post" curing step can also melt and remove the wax support material from the printed article. Post curing in an oven can occur at a temperature of 80-100° C. for a period of 2-4 hours. In some examples, the article is first heated in an oven at 80° C. for 2 hours, and then heated in an oven at 100° C. for an additional 2 hours.

[0123] For use in SLA, cSLA, or DLP 3D printing, parts A and B are mixed prior to use. The mixture is then delivered to a vat, reservoir, or ink cartridge for 3D printing. The photocuring that occurs during the SLA, cSLA, or DLP process polymerizes the (meth)acrylate monomers of part A, again providing the article with sufficient green strength to allow it to be handled after the printing process without damage or loss of print resolution. After printing, the article is removed from the vat or reservoir, optionally washed, and then may be placed in an oven to complete the reaction between the cyclic carbonate and the amine monomers as described above.

[0124] Example 8 3D Printing Inks Inks according to some embodiments described herein were prepared as follows. Specifically, in this example, a first ink and a second ink were prepared. The first ink and the second ink may be used in the kits described herein. Alternatively, the first ink and the second ink may be combined with each other to form a single ink that may be used in a 3D printing system or method, with or without the use of one or more other inks, as described below.

[0125] The first ink (also referred to as "Part A") included a cyclic carbonate monomer having a cyclic carbonate moiety and a (meth)acrylate moiety. Specifically, the first curable material had the structure of formula (A9) above, where R1 is CH2CH2, R2 is CH2, and R5 is CH3. The first ink also included an additional curable material consisting of an additional (meth)acrylate monomer. Additionally, the first ink included a photoinitiator. The second ink (also referred to as "Part B") included an amine monomer having multiple primary or secondary amine moieties. Specific components of the first and second inks are described below.

[0126] The first ink ("Part A") contained 20.5 g of Formula (A9) (cyclic carbonate moiety); 31.2 g of triethylene glycol dimethacrylate (SR205, available from SARTOMER) (additional curable material); and 0.94 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO) (photoinitiator).

[0127] The second ink ("Part B") contained 10.7 g of Jeffamine XTJ566 (triamine, available from HUNTSMAN CHEMICAL) (amine monomer). The amount of monomer was selected based on the desired molar ratio of cyclic carbonate moiety (in Part A) to amine moiety (in Part B). Typically, the ratio can range from 0.5:1 (cyclic carbonate:amine) to 2:1, or from 0.8:1 to 1.7:1. Furthermore, the weight ratio of the sum of the carbonate and amine monomer to the amount of additional (meth)acrylate diluent can range from 1:5 to 1:0 (carbonate + amine monomer:(meth)acrylate diluent).

[0128] To prepare each ink, the individual components of each ink were combined and mixed. The mixture was heated with stirring to a temperature of about 20-25° C. Heating and stirring was continued until the mixture reached a substantially homogeneous liquid state. The liquid mixture was then filtered.

[0129] For use in MJM 3D printing, part A and part B are fed into two separate channels / ink dispensers, and then the two inks are mixed by jetting them into adjacent or nearby locations on the substrate, or into adjacent or nearby voxels (digital mixing). The jetted materials are then exposed to UV radiation for UV curing. In particular, the UV curing process cures the (meth)acrylate monomers of part A, and the (meth)acrylate moieties of the cyclic carbonate monomers. During this process, some reaction between the cyclic carbonate moieties of the cyclic carbonate monomers of part A and the amine moieties of the amine monomers of part B may also occur. However, the extent of reaction may be limited. 3D articles printed in this manner (without substantial reaction between the cyclic carbonate moieties and the amine moieties) may have sufficient green strength to allow the article to be handled without causing damage to the article or loss of print resolution of the article. To complete the reaction between the cyclic carbonate and the amine monomers, the printed article may be placed in an oven to cure the cyclic carbonate and amine monomers. Additionally, if a support material is used (such as a wax support material), this second or "post" curing step can also melt and remove the wax support material from the printed article. Post curing in an oven can occur at a temperature of 80-100° C. for a period of 2-4 hours. In some examples, the article is first heated in an oven at 80° C. for 2 hours, and then heated in an oven at 100° C. for an additional 2 hours.

[0130] For use in SLA, cSLA, or DLP 3D printing, parts A and B are mixed prior to use. The mixture is then delivered to a vat, reservoir, or ink cartridge for 3D printing. The photocuring that occurs during the SLA, cSLA, or DLP process polymerizes the (meth)acrylate monomers of part A and the (meth)acrylate moieties of formula (A9), again providing the article with sufficient green strength to allow it to be handled after the printing process without damage or loss of print resolution. After printing, the article is removed from the vat or reservoir, optionally washed, and then may be placed in an oven to complete the reaction between the cyclic carbonate and the amine monomer as described above.

[0131] Example 9 3D Printing Inks Inks according to some embodiments described herein were prepared as follows. Specifically, in this example, a first ink and a second ink were prepared. The first ink and the second ink may be used in the kits described herein. Alternatively, the first ink and the second ink may be combined with each other to form a single ink that may be used in a 3D printing system or method, with or without the use of one or more other inks, as described below.

[0132] The first ink (also referred to as "Part A") included a cyclic carbonate monomer having a cyclic carbonate moiety and a (meth)acrylate moiety. The first ink also included an additional curable material consisting of an additional (meth)acrylate monomer. Additionally, the first ink included a photoinitiator. The second ink (also referred to as "Part B") included an amine monomer having multiple primary or secondary amine moieties. Specific components of the first and second inks are described below.

[0133] The first ink ("Part A") contained 20 g of carbonated glycerol methacrylate (cyclic carbonate monomer); 35 g of triethylene glycol dimethacrylate (SR205, available from SARTOMER) (additional curable material); and 1.0 g of 2,4,6-trimethylbenzoyldiphenylphosphine oxide (Lucirin TPO) (photoinitiator).

[0134] The second ink ("Part B") contained 15 g of Jeffamine XTJ566 (triamine, available from HUNTSMAN CHEMICAL) (amine monomer). The amounts of the various monomers and curable materials were selected based on the desired molar ratio of cyclic carbonate moieties (in Part A) to amine moieties (in Part B). Typically, the ratio can range from 0.5:1 (cyclic carbonate:amine) to 2:1, or from 0.8:1 to 1.7:1. Furthermore, the weight ratio of the sum of carbonate and amine monomer to the total amount of additional (meth)acrylate diluent can range from 1:5 to 1:0 (carbonate + amine monomer:(meth)acrylate diluent).

[0135] To prepare each ink, the individual components of each ink were combined and mixed. The mixture was heated with stirring to a temperature of about 75-85° C. Heating and stirring was continued until the mixture reached a substantially homogeneous liquid state. The molten mixture was then filtered.

[0136] For use in MJM 3D printing, part A and part B are fed into two separate channels / ink dispensers, and then the two inks are mixed by jetting them into adjacent or nearby locations on the substrate, or into adjacent or nearby voxels (digital mixing). The jetted materials are then exposed to UV radiation for UV curing. In particular, the UV curing process cures the (meth)acrylate monomers of part A, and the (meth)acrylate moieties of the cyclic carbonate monomers. During this process, some reaction between the cyclic carbonate moieties of the cyclic carbonate monomers of part A and the amine moieties of the amine monomers of part B may also occur. However, the extent of reaction may be limited. 3D articles printed in this manner (without substantial reaction between the cyclic carbonate moieties and the amine moieties) may have sufficient green strength to allow the article to be handled without causing damage to the article or loss of print resolution of the article. To complete the reaction between the cyclic carbonate moieties and the amine moieties, the printed article may be placed in an oven to cure the cyclic carbonate and amine monomers. Additionally, if a support material is used (such as a wax support material), this second or "post" curing step can also melt and remove the wax support material from the printed article. Post curing in an oven can occur at a temperature of 80-100° C. for a period of 2-4 hours. In some examples, the article is first heated in an oven at 80° C. for 2 hours, and then heated in an oven at 100° C. for an additional 2 hours.

[0137] For use in SLA, cSLA, or DLP 3D printing, parts A and B are mixed prior to use. The mixture is then delivered to a vat, reservoir, or ink cartridge for 3D printing. The photocuring that occurs during the SLA, cSLA, or DLP process polymerizes the (meth)acrylate monomers (additional curable materials) of part A and the (meth)acrylate moieties of the cyclic carbonate monomers, again providing the article with sufficient green strength to allow it to be handled after the printing process without damage or loss of print resolution. After printing, the article is removed from the vat or reservoir, optionally washed, and then may be placed in an oven to complete the reaction between the cyclic carbonate and amine monomers as described above.

[0138] All patents mentioned in this specification are incorporated herein by reference in their entirety. Various embodiments of the present invention have been described to achieve various objectives of the present invention. It is to be understood that these embodiments are merely illustrative of the principles of the present invention. Many modifications and adaptations will be readily apparent to those skilled in the art without departing from the spirit and scope of the present invention.

[0139] Other embodiments 1. An ink for use in a three-dimensional printing system, comprising: Cyclic carbonate monomers; and Amine Monomers Including, ink.

[0140] 2. The ink of embodiment 1, wherein the cyclic carbonate monomer comprises two cyclic carbonate moieties.

[0141] 3. The ink of embodiment 1 or 2, wherein the cyclic carbonate monomer contains three or four cyclic carbonate moieties.

[0142] 4. The ink of embodiment 1 or 2, wherein the cyclic carbonate monomer has a structure of Formula (A1), Formula (A2), Formula (A3), or Formula (A4): [ka] [ka] [ka] [ka] wherein R1, R2, R3, and R4 are each independently a straight or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

[0143] 5. The ink of any of the above embodiments, wherein the cyclic carbonate monomer has a structure of formula (A5): [ka] In the formula, n is an integer from 1 to 36.

[0144] 6. An ink according to any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A6). [ka]

[0145] 7. The ink of any of the above embodiments, wherein the cyclic carbonate monomer has a structure of formula (A8): [ka] wherein R5 is a straight or branched C2 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

[0146] 8. The ink of any of the above embodiments, wherein the cyclic carbonate monomer has a structure of formula (A9): [ka] In the formula, m is an integer of 1 to 36.

[0147] 9. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of Formula (A10), Formula (A11), Formula (A12), or Formula (A13): [ka] [ka] [ka] [ka] wherein R1, R2, and R3 are each independently a straight or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R5 is a straight or branched C2 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

[0148] 10. An ink according to any of the previous embodiments, wherein the cyclic carbonate monomer contains one or more ethylenically unsaturated moieties.

[0149] 11. The ink of embodiment 10, wherein the cyclic carbonate monomer comprises one or more (meth)acrylate moieties.

[0150] 12. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A14): [ka] During the ceremony, R1 and R2 are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0151] 13. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A15) or formula (A16): [ka] [ka] During the ceremony, R1 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R5 is a straight or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0152] 14. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A17) or formula (A18): [ka] [ka] During the ceremony, m is an integer from 1 to 36; R1 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0153] 15. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A19): [ka] During the ceremony, R2 is a straight or branched C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0154] 16. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A20): [ka] During the ceremony, R2 is a straight or branched C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R6 is H or CH3; R7 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH2CH(R8)O) n and; R8 is H or CH3; and n is an integer from 1 to 100.

[0155] 17. The ink of any of the previous embodiments, wherein the cyclic carbonate monomer has a structure of formula (A21): [ka] During the ceremony, R2 and R9 are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R6 is H or CH3; R7 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH2CH(R8)O) n and; R8 is H or CH3; and n is an integer from 1 to 100.

[0156] 18. An ink according to any of the previous embodiments, wherein the amine monomer comprises two amine moieties.

[0157] 19. An ink according to any of the previous embodiments, wherein the amine monomer contains more than two amine moieties.

[0158] 20. The ink of any of the previous embodiments, wherein the amine monomer has a structure of formula (B1): H2N-R 10 -NH2(B1) In the formula, R 10 is a straight or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

[0159] 21. An ink according to any of the above embodiments, wherein the amine monomer comprises at least one secondary or tertiary amine moiety.

[0160] 22. An ink according to any of the above embodiments, further comprising an ethylenically unsaturated monomer.

[0161] twenty three. 23. The ink of embodiment 22, wherein the ethylenically unsaturated monomer comprises a (meth)acrylate.

[0162] 24. A kit for use in a three-dimensional printing system, comprising: a first ink comprising a cyclic carbonate monomer; and A second ink containing an amine monomer Including the kit.

[0163] 25. The kit of embodiment 24, wherein the first ink further comprises an ethylenically unsaturated monomer.

[0164] 26. The kit of embodiment 25, wherein the ethylenically unsaturated monomer comprises a (meth)acrylate.

[0165] 27. The kit of embodiment 25 or 26, wherein the first ink and / or the second ink further comprises a photoinitiator.

[0166] 28. A three-dimensional printing system comprising: a three dimensional printer having at least one of an ink dispenser and an ink reservoir; and ink disposed within the ink dispenser, ink reservoir, or both; and A three-dimensional printing system, wherein the ink comprises a cyclic carbonate monomer.

[0167] 29. The system of embodiment 28, wherein the ink further comprises an amine monomer.

[0168] 30. The system of embodiment 29, wherein the ink further comprises an ethylenically unsaturated monomer.

[0169] 31. The system of embodiment 28, further comprising a second ink dispenser and a second ink disposed in the second ink dispenser, the second ink comprising an amine monomer.

[0170] 32. A method for printing a three-dimensional object, comprising: selectively depositing a layer of ink in a fluid state onto a substrate; 24. A method wherein the ink comprises the ink of any one of embodiments 1 to 23.

[0171] 33. The method of embodiment 32, wherein the layers of ink are deposited according to an image in computer-readable form of a three-dimensional article.

[0172] 34. The method of embodiment 32, wherein the ink comprises one or more (meth)acrylates, and the method further comprises curing the (meth)acrylates with UV light.

[0173] 35. The method of embodiment 34, further comprising thermally curing the cyclic carbonate monomer and the amine monomer.

[0174] 36. A method for printing a three-dimensional object, comprising: Selectively depositing a layer of a first ink in a fluid state onto a substrate; and selectively depositing a layer of the second ink in a fluid state onto a substrate; Including, 28. The method, wherein the first ink and the second ink comprise the first ink and the second ink, respectively, of any one of embodiments 24 to 27.

[0175] 37. The method of embodiment 36, wherein the first ink comprises one or more (meth)acrylates, and the method further comprises curing the (meth)acrylates with UV light.

[0176] 38. The method of embodiment 37, further comprising thermally curing the cyclic carbonate monomers of the first ink and the amine monomers of the second ink.

[0177] 39. A method for printing a three-dimensional object, comprising: maintaining the ink in a fluid state within a container; selectively applying energy to the ink in the reservoir to solidify at least a portion of a first fluid layer of the ink, thereby forming a first solidified layer defining a first cross-section of the article; raising or lowering the first solidified layer to provide a second fluid layer of ink on the surface of the fluid ink in the container; and selectively applying energy to the ink in the reservoir to solidify at least a portion of the second fluid layer of ink, thereby forming a second solidified layer defining a second cross-section of the article, the first cross-section and the second cross-section being bonded to one another in the z-direction; Including, 24. A method wherein the ink comprises the ink of any one of embodiments 1 to 23.

[0178] 40. The method of embodiment 39, comprising repeating the raising or lowering step and the subsequent selective application of energy step n times to form a three-dimensional article, where n is an integer up to 100,000.

[0179] 41. The method of embodiment 40, further comprising the step of heat curing the formed three-dimensional article after printing.

[0180] 42. The method of embodiment 41, wherein the step of heat curing the formed three-dimensional article comprises reacting a cyclic carbonate monomer with an amine monomer.

[0181] 43. The method of embodiment 42, wherein the ink further comprises one or more (meth)acrylates, and selectively applying energy to the ink in the container comprises selectively exposing the ink to UV radiation.

[0182] 44. The method of embodiment 43, wherein the (meth)acrylate of the ink is at least partially cured by exposing the ink to UV radiation.

[0183] 45. A printed three-dimensional article formed from an ink according to any one of embodiments 1-23.

[0184] 46. ​​Cyclic carbonate monomers and amine monomers, when cured, together form polyurethanes; the ink comprises one or more (meth)acrylates; the one or more (meth)acrylates, when cured, form a poly(meth)acrylate; and 46. ​​The article of embodiment 45, wherein the polyurethane and poly(meth)acrylate together form an interpenetrating polymer network.

[0185] 47. A printed three-dimensional article formed from the first ink and the second ink of any of embodiments 24-27.

[0186] 48. Cyclic carbonate monomers and amine monomers, when cured, together form polyurethanes; the first ink further comprises one or more (meth)acrylates; the one or more (meth)acrylates, when cured, form a poly(meth)acrylate; and 48. The article of embodiment 47, wherein the polyurethane and poly(meth)acrylate together form an interpenetrating polymer network.

[0187] 49. A composition comprising a cyclic carbonate having a structure of formula (A15): [ka] During the ceremony, R1 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0188] 50. A composition comprising a cyclic carbonate having a structure of formula (A16): [ka] During the ceremony, R1 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R5 is a straight or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0189] 51. A composition comprising a cyclic carbonate having a structure of formula (A17) or formula (A18): [ka] [ka] During the ceremony, m is an integer from 1 to 36; R1 is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and R6 is H or CH3.

[0190] 52. An adhesive comprising the composition according to any one of embodiments 49 to 51.

[0191] 53. Substrate; and A coating disposed on the substrate. An apparatus comprising: 52. A device, wherein the coating comprises the composition of any one of embodiments 49 to 51.

Claims

1. 1. A kit for use in a three dimensional printing system, comprising: a first ink comprising a cyclic carbonate monomer; and A second ink comprising an amine monomer containing two or more amine moieties. Including the kit.

2. The kit of claim 1 , wherein the first ink further comprises an ethylenically unsaturated monomer.

3. The kit of claim 2 , wherein the ethylenically unsaturated monomer comprises a (meth)acrylate.

4. The kit of any one of claims 1 to 3, wherein the cyclic carbonate monomer comprises a plurality of cyclic carbonate moieties.

5. The kit of any one of claims 1 to 3, wherein the cyclic carbonate monomer comprises two, three, or four cyclic carbonate moieties.

6. The kit according to any one of claims 1 to 3, wherein the cyclic carbonate monomer has a structure of formula (A1), formula (A2), formula (A3), formula (A4), or formula (A5): 【Chemistry 1】 【Chemistry 2】 【Chemistry 3】 【Chemistry 4】 【Chemistry 5】 [In the formula, R １ , R ２ , R ３ , and R ４ are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and n is an integer from 1 to 36.

7. The kit according to any one of claims 1 to 3, wherein the cyclic carbonate monomer has a structure of formula (A6), formula (A8), or formula (A9): 【Chemistry 6】 【Chemistry 7】 【Chemistry 8】 [In the formula, R ５ is a straight or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; and m is an integer from 1 to 36.

8. The kit according to any one of claims 1 to 3, wherein the cyclic carbonate monomer has a structure of formula (A10), formula (A11), formula (A12), or formula (A13): 【Chemistry 9】 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 [In the formula, R １ , R ２ , and R ３ are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ５ is a straight or branched C2 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

9. The kit of any one of claims 1 to 3, wherein the cyclic carbonate monomer comprises one or more ethylenically unsaturated moieties.

10. The kit of claim 9 , wherein the cyclic carbonate monomer comprises one or more (meth)acrylate moieties.

11. The kit of claim 9 , wherein the cyclic carbonate monomer has a structure of formula (A14), (A15), or (A16): 【Chemistry 13】 【Chemistry 14】 【Chemistry 15】 [In the formula, R １ and R ２ are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ５ is a straight or branched C2-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ６ is H or CH ３ is.]

12. The kit of claim 9, wherein the cyclic carbonate monomer has a structure of formula (A17) or formula (A18): 【Chemistry 16】 【Chemistry 17】 [In the formula, m is an integer from 1 to 36; R １ is a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ６ is H or CH ３ is.]

13. The kit of claim 9 , wherein the cyclic carbonate monomer has a structure of formula (A19), formula (A20), or formula (A21): 【Chemistry 18】 【Chemistry 19】 【Chemistry 20】 [In the formula, R ２ is a straight or branched C1-C20 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ２ ' and R ９ are each independently a straight or branched C1-C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety; R ６ is H or CH ３ and R ７ is a straight or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety, or (CH ２ CH(R ８ ) O) ｎ and R ８ is H or CH ３ and and n is an integer from 1 to 100.

14. The kit of any one of claims 1 to 13, wherein the amine monomer comprises two amine moieties.

15. The kit of any one of claims 1 to 13, wherein the amine monomer has a structure of formula (B1): H ２ N-R １０ -NH ２ (B1) [In the formula, R １０ is a straight or branched C1 to C36 alkyl or alkylene, alkenyl or alkenylene, aryl or arylene, or heteroaryl or heteroarylene moiety.

16. The kit of any one of claims 1 to 15, wherein the amine monomer comprises at least one secondary or tertiary amine moiety.

17. The kit of any one of claims 1 to 16, wherein the first ink and / or the second ink further comprises a photoinitiator.

18. The kit of any one of claims 1 to 17, wherein the second ink is free of ethylenically unsaturated species.

19. The kit of claim 18 , wherein the second ink is free of (meth)acrylates.

20. 1. A method for printing a three-dimensional object, comprising: Selectively depositing a layer of a first ink in a fluid state onto a substrate; and selectively depositing a layer of a second ink in a fluid state onto a substrate; Including, A method, wherein the first ink and the second ink comprise the first ink and the second ink, respectively, of any of claims 1 to 19.

21. 21. The method of claim 20, wherein the first ink comprises one or more (meth)acrylates, the method further comprising curing the (meth)acrylates with UV light.

22. 22. The method of claim 21, further comprising thermally curing the cyclic carbonate monomers of the first ink and the amine monomers of the second ink.

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