Additives useful in 3D printing technologies

Abstract

To provide amine curing agent compositions useful in formulation additives, compositions comprising systems, resin formulations, and the use of these compositions in methods of manufacturing objects by additive manufacturing using 3D printing methodologies.SOLUTION: One or two carbon atoms vicinal to the carbon atom with a primary amine group in an amine curing agent have alkyl groups that increase size and bulkiness.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to amine curing agent compositions useful as compounding additives, systems containing these compositions, resin formulations, and the use of these compositions in methods for manufacturing objects by additive manufacturing using 3D printing methodologies. [Background technology]

[0002] "Additive manufacturing" is a general term applied to manufacturing methodologies that involve producing objects by adding materials that are joined together in an automated and controlled manner within a 3D frame or work envelope. The term additive manufacturing refers to this style of object production and is distinguished from "removal manufacturing," which refers to a process in which a 3D object is constructed by sequentially cutting and removing material from a solid block, as in CNC (computer numerical control) manufacturing. In typical removal manufacturing, a computer converts a design provided by computer-aided design (CAD) software into numbers representing the coordinates of the graphic design of the object, and these numerical controls allow the computer to guide the CNC machine through the 3D cutting process to produce the object.

[0003] In a 3D printing process, an object is formed by sequentially adding material layer by layer from a computer-aided design (CAD) model. The term "3D printing" covers a wide variety of processes in which materials are joined together by various means using computer control that guides the printing process according to the shape of the object. Typically, the three-dimensional shape of the object to be manufactured is translated into the coordinates of the object, which guide the printing device for the formation of the object.

[0004] There are various processes for manufacturing three-dimensional objects using additive manufacturing. Different processes may require different types of equipment and materials depending on the physical transformations involved in the 3D printing process. These processes can be classified into the following categories: a) material extrusion; b) powder bed fusion; c) lamination; d) binder injection; e) directed energy deposition; f) liquid additive manufacturing; g) stereolithography; h) computed axial lithography.

[0005] A typical methodology used in material extrusion is called fused deposition modeling (FDM) or fused deposition modeling, which involves extruding a fluid flow or bed of material, allowing it to solidify and harden to form layers. The material used is typically a thermoplastic, which passes through a heated extrusion nozzle head or printer extruder, where it is heated to its melting point and extruded onto the surface being formed. In this technique or process, the nozzle head heats the material and adjusts the amount of energy as needed. The extrusion head is moved through three axes of motion guided by a series of motors from a microcontroller linked to computerized manufacturing software that has the coordinates of the object to be formed. In this form of additive manufacturing, plastics are the most common materials used in production and include high-density polyethylene (HDPE), high-impact polystyrene (HIPS), polycarbonate (PC), polyurethane (PU), polylactic acid (PLA), acrylonitrile-butadiene-styrene (ABS), polyphenylsulfone (PPSU), and other similar plastics typically manufactured in the form of filaments. This 3D printing method has some limitations in terms of the shapes that can be manufactured, particularly for fine and elongated structures that may not be able to stand on their own during the printing process, unless a special scaffold is fabricated to support the structure and removed after fabrication.

[0006] Powder bed fusion is typically used to create 3D objects by melting granular material. In this technique, the granular material is melted to form layers, and as the printing process moves upward, other layers of granular material are repeatedly deposited and melted until the printing process is complete. In a selective sintering process, a thermal printhead applies heat to layers of powdered thermoplastic plastic, and when a layer representing the cross-section of the 3D object is completed, an automated roller adds a new layer of granular material, which is sintered to form the next cross-section of the object. The energy provided in the sintering process may be supplied by a laser source. Laser sintering processes in 3D printing can be applied to materials such as thermoplastics and metals. In addition to laser sintering processes, other laser methodologies rely on the complete melting of the granular material, as in the case of selective laser melting. Materials produced using selective laser melting are perfectly dense and typically have mechanical properties similar to those produced by conventional metal manufacturing processes.

[0007] Lamination was a 3D printing method that used paper as the material and was commercially available in the 1990s. These 3D printers cut the cross-section of adhesive-coated paper and then laminated the pieces in layers to create a 3D object. Other similar printers cut different layers of paper and bonded the layers together with adhesive deposition, and then created a 3D object by applying pressure.

[0008] Binder spraying is another commonly used 3D printing technique that consists of depositing a binder or adhesive onto a layer of material, typically in powder form. The materials used are typically metals or ceramics. As in other 3D printing processes, the object is formed by depositing a layer of material and a layer of binder, typically applied using an inkjet-type process. The strength of the object can be further improved using thermosetting impregnating polymers, which can increase the crosslinking density of the polymer binder.

[0009] Metal 3D printing is typically carried out using directed energy deposition (STD deposition), where the metal is supplied either as a wire or powder. In wire-fed STD deposition, the wire, molten by energy supplied by a laser, is fed through a nozzle and shielded during the process with an inert gas to prevent air oxidation, or selectively, the 3D printing process is carried out in an inert gas-sealed chamber. Selectively, an electron beam can be used if the sealed chamber is a vacuum chamber. In powder-fed STD deposition, a high-energy laser is used to melt the metal powder. A digital model of the part to be fabricated is provided to a software program guiding the laser head via a table that moves upward so that different cross-sections of the 3D object are formed. The process is typically carried out in a sealed chamber filled with an inert gas to prevent air oxidation of the metal. This process is commonly used for a variety of metals, including titanium, stainless steel, and aluminum.

[0010] Liquid addition manufacturing is a method in which a fluid-like substance, liquid, or extremely viscous material is placed on a surface to be formed to create an object, which is then cured or hardened by a heat-based vulcanization process.

[0011] Stereolithography is a 3D manufacturing technique based on the photopolymerization of liquid materials into solids. In this process, a light-transmitting container containing a liquid polymerizable material is exposed to light from a laser source or digital light projector, causing the liquid to harden through the chemical bonds formed. The liquid component typically contains polymerizable substances, such as acrylate moieties, that can form linear and branched polymers, resulting in the formation of a solid material when exposed to light. In this process, the light-emitting device or digital light projector selectively illuminates the transparent bottom of a tank containing the liquid polymerizable resin, and as the resin solidifies through the polymerization process, the solid material moves upward, leaving narrow gaps, which are then filled with more material and further polymerized by the light source. As the solid material moves upward during printing, the software adjusts the area of ​​illumination to continuously build different cross-sections of the object.

[0012] Other photopolymerization printing processes are based on spraying photopolymer material in ultrathin layers onto a build tray until the object is complete. Each layer is cured with UV light after spraying. Inkjet printing systems are used in the manufacture of eyeglass lenses by printing the material layer by layer using a UV light curing technique until the lens is complete. Photopolymerization reactions are also used in 3D microfabrication using multiphoton photopolymerization. This approach uses a focused laser to trace the desired 3D object into a block of gel. Curing occurs only where the laser is focused, and the remainder of the gel is removed by washing. The resin can also be solidified by projecting light from an LED source. In mask image-projection stereolithography, a 3D digital object is sliced ​​by a set of horizontal planes, with each slice corresponding to a 2D image, which is projected from a light source to cure the resin according to the 2D image. The aforementioned light is projected from below, allowing the resin to spread quickly into a uniform layer, thereby reducing the manufacturing time.

[0013] Continuous liquid interphase production (CLIP) is another form of additive manufacturing that uses digital photopolymerization (DLP) based photopolymerization to produce smooth solid objects. The CLIP process uses a pool of liquid photopolymer resin. The process typically works with a pool of material whose bottom is a UV light-transmitting window. As in conventional DLP lithography, the UV source shines light through the window, illuminating the corresponding cross-section of the object and solidifying the resin. Once the resin has solidified and the object has formed, the machine slowly raises the object, allowing additional liquid resin to fill the gap between the window and the bottom of the object. The CLIP process is characterized by having an oxygen-permeable membrane beneath the bottom of the resin pool, creating an oxygen-rich zone where photopolymerization is inhibited, however this inhibition is only effective in preventing the object from sticking to the window in that zone.

[0014] Computerized axial lithography (CAL) is a relatively new methodology for 3D printing that differs from other 3D printing techniques in that it does not create models through the deposition of layers of material, as in fused deposition modeling (FDM) or stereolithography. Instead, it generates its image by projecting a series of 2D images onto a cylinder of resin. Computerized axial lithography allows for the formation of complex 3D objects in a single operation without substrate, support structures, or mechanical devices for removing the object from the resin pool. Instead, the 3D object is produced by the superposition of light patterns projected onto a cylinder of photosensitive resin. The basic principle of CAL requires three key elements: a) its light field must have a matched pattern with the peak intensity of all light sources at all locations required to be cured; b) the lateral intensity profile of the beams must be adjusted to compensate for the limited resolution of the axial resolution of other beams; c) the polymerization inhibitor concentration (typically oxygen) must be consumed to provide the minimum threshold of polymerizable species required for the polymerization process to take place. One of the key parameters for manufacturing 3D objects using CAL technology is the exposure time of the resin to the light beams. The first solidification occurs in the region of highest intensity where the three beams intersect, and the time required to achieve solidification in this region (assuming approximately 30% conversion rate of chemical unsaturation) is typically called the three-beam hardening threshold t3. If the resin is exposed for a period longer than t3, the region exposed to two beams begins to solidify (t2). Eventually, with continued exposure, the region illuminated by a single beam also solidifies. Therefore, it is important that exposing the resin to a time window between t3 and t2 provides a useful process window for optimizing the 3D structure. Typically, the optimal hardening time is defined as the time immediately preceding the two-beam threshold (t2), but this depends on the type of resin and the characteristics of the manufacturing process.

[0015] U.S. Patent No. 4,575,330 describes a method and apparatus for manufacturing a solid object by sequentially printing thin layers of a curable material, such as a UV light photopolymer curable material, in stacks. A movable beam of UV light, controlled by a computer program, is applied to the surface or layer of the UV-curable liquid to form the solid cross-section of the object on the surface of the liquid. The object is then moved a layer away from the liquid surface, so that the next cross-section is formed and attached to the layer immediately preceding the one that defined the object. This process continues until the entire object is formed. This technique is known as stereolithography. The liquid polymerizable material typically has acrylate portions that can form linear and branched polymers, resulting in the formation of a solid material when exposed to light. The light-emitting device is typically a digital light projector that selectively illuminates the transparent bottom of a tank containing a liquid polymerizable resin, and as the resin solidifies during the polymerization process, the solid material moves upward, leaving narrow gaps, which are then filled with more material and further polymerized by the light source. As the solid material moves upward during printing, the software adjusts the area of ​​illumination to continuously build different cross-sections of the object. The physical and mechanical properties of 3D objects produced by this technique are inferior to those of objects produced by dual polymerization processes that typically require the presence of an amine curing agent.

[0016] U.S. Patent No. 5,236,637 describes two methodologies for a typically used stepwise or layer-by-layer technique. In one method, a new layer is formed on the upper surface of the growing object, and in the other method, a new layer is formed on the bottom surface of the growing object. In the first case, a new layer is formed on the upper surface of the growing object, and then after each irradiation step, the object under construction is lowered into the resin pool, a new layer of resin is coated on top, and a new irradiation step is performed. The process continues in that order until the object is completed. The requirements of such a “top-down” technique are the need to submerge the growing object in a pool of liquid resin and to rebuild a precise upper layer of liquid resin on top. This method requires that after each irradiation step, the object under construction must be removed from the bottom plate in the fabrication well, and is a time-consuming process requiring care to prevent damage or defects on each layer. In the second case, the need for a deep well into which the object is submerged is eliminated by instead lifting the object from a relatively shallow pool of resin. However, special consideration must be given to this case because it is necessary to remove the solidified layer from the bottom plate after each irradiation, and depending on the physicochemical interactions between the surfaces, this may potentially compromise the appearance and quality of the finished product. In this methodology, the physical form of the object is determined by a UV-guided photopolymerization process, and the final physical and mechanical properties of the material are determined by the degree and efficiency of UV-induced covalent bonding and crosslinking density. Generally, this methodology lacks the presence of a double polymer network, which is typically present in newer 3D printing methodologies that are typically induced by thermosetting processes involving amine curing agents and blocked isocyanates. Therefore, the physical and mechanical properties of 3D objects produced solely by UV-induced UV light are inferior to those of objects produced by dual polymerization processes that typically required the presence of amine curing agents.

[0017] U.S. Patent No. 9598606 describes an additive manufacturing method that overcomes the limitations of traditional processes by continuously manufacturing objects from a liquid interface. This method is known as "continuous liquid interface manufacturing" or "continuous liquid interface phase printing" (CLIP). (商標)) is publicly known as. In this method, an object is continuously produced from a pool of liquid polymerizable resin. The bottom of the pool is transparent to UV light, and a light source illuminates a precise cross-section of the object through the window, causing the resin to polymerize. The resulting object is slowly and steadily drawn out of the pool, bringing new liquid into contact with the polymerized surface, where further polymerization occurs on the surface guided by the UV light, subsequently forming the cross-section of the object. Below the bottom of the resin, a semipermeable membrane (also called a "dead zone") is located directly on the surface, allowing oxygen to permeate and inhibiting the polymerization of the resin, thus preventing the formation of a polymer surface on the window. The UV polymerizable resin described in this process is typically an amine-blocked diisocyanate of acrylic acid, such as methacrylic acid, which undergoes a second step of polymerization that can be induced by microwave radiation or heat during photo-induced polymerization, resulting in the formation of a secondary polyurea network that provides improved physical properties of the produced object. Typically, the amines used include PACM (4,4′-diaminodicyclohexylmethane, commercially available from Evonik Corporation), while hydroquinone bis(2-hydroxyethyl) ether (HQEE), 4,4-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA), 4,4′-methylenebis(2,6-diethylaniline) (MDEA), and 4,4-methylenebis(2-chloroaniline) (MOCA) are preferred chain extenders. PACM is characterized by providing good physical properties to the cured material; however, the blocked isocyanate resin typically reacts slowly with the blocked isocyanate, leading to an increase in viscosity over time and an unacceptable resin shelf life due to premature reaction. On the other hand, aromatic amines, such as MCDEA, MDEA, and MOCA, react too slowly to the resin, requiring longer curing times or harsher conditions, leading to productivity and quality problems.

[0018] The diverse methods of manufacturing objects using photopolymers described in the literature and summarized above, based on UV light as a polymerization accelerator, such as stereolithography, continuous liquid interface phase printing, and computerized axial lithography, are characterized by the fabrication of the polymer frame or scaffold of the object. Further improvements in the physical properties and performance of the object are typically achieved using a second polymerization process, generally called a curing process. This step can be initiated by different methods, such as the use of microwave radiation, or more typically by heat. To further enhance the physical properties and performance of the finished object, formulations for the diverse processes may require the presence of additional components in the resin that can be activated for reaction, assuming the scaffold of the object is manufactured in the photopolymerization process. A possible way to achieve this step is by incorporating either free or blocked isocyanates or polyisocyanates into the resin moieties, which can be activated in the presence of a suitable curing agent. Therefore, it is common to incorporate amine curing agents into the resin moieties that can be activated for reaction with a suitable substrate, such as an isocyanate, once the photopolymerization process is complete. Therefore, it is preferable that the amine curing agent reacts with its substrate after the polymer scaffold has been manufactured and not before. This is because early reactivity may lead to an increase in viscosity that hinders mass transfer during photopolymerization for manufacturing the scaffold, or a less complete solidification of the resin may occur before use. [Prior art documents] [Patent Documents]

[0019] [Patent Document 1] U.S. Patent No. 4575330 [Patent Document 2] U.S. Patent No. 5,236,637 [Patent Document 3] U.S. Patent No. 9598606 [Patent Document 4] U.S. Patent No. 7649029 [Patent Document 5] U.S. Patent No. 7767728 [Patent Document 6] U.S. Patent No. 7935476 [Patent Document 7] U.S. Patent No. 8119214 [Patent Document 8] U.S. Patent No. 8232043 [Patent Document 9] International Publication No. 2012 / 129968 [Patent Document 10] Chinese Patent Application Publication No. 102715751 Specification [Patent Document 11] Japanese Patent Publication No. 2012-210408 [Patent Document 12] U.S. Patent No. 7695643 [Patent Document 13] U.S. Patent No. 7157586 [Patent Document 14] U.S. Patent No. 6916867 [Patent Document 15] U.S. Patent No. 3,213,058 [Patent Document 16] U.S. Patent No. 7651683 [Patent Document 17] U.S. Patent No. 7651682 [Patent Document 18] U.S. Patent No. 7556490 [Patent Document 19] U.S. Patent No. 6602975 [Patent Document 20] U.S. Patent No. 5836313 [Overview of the Initiative] [Problems that the invention aims to solve]

[0020] Therefore, there is a need for amine curing agents that have sufficient stability in the resin portion to provide the following: a) sufficient shelf-life stability of the resin, which provides a sufficiently long shelf life (minimum 6 months) for resins that can be manufactured, stored, and transported to manufacturing sites; b) sufficient reactivity, which allows for the production of objects with optimal physical properties and performance during activation by a secondary polymerization process induced by the amine curing agent; c) sufficient chemical compatibility with the resin portion, which maintains the homogeneity of the resin portion and prevents solid or discoloration during the shelf life of the resin; and d) chemical properties that do not interfere with the production of solid polymer scaffolds. [Means for solving the problem]

[0021] The present invention solves the above problems related to the shelf life stability of resin mixtures, wherein the resin mixture comprises a photopolymerizable component of portion A and a polymerizable component of portion B, wherein the polymerizable component of portion B comprises an amine curing agent and a reactive composition that can polymerize with the amine curing agent, such as a blocked isocyanate or blocked polyisocyanate, and forms a second polymer network that has the function of improving the physical and mechanical properties of the finished object. Therefore, it is essential that the polymerizable portion B does not polymerize prematurely and cause: a) coagulation of the resin before use; b) an undesirable increase in viscosity that may affect the material transport or proper handling of the resin; or c) replacement of isocyanate protecting groups designed to be part of the photo-induced polymer, resulting in undesirable breakdown of different polymer networks. On the other hand, non-reactive amines may require longer curing times that impair manufacturing productivity or may require harsher conditions, such as higher temperatures, which may lead to damage to the initial object scaffold produced by the photo-induced UV polymerization process. Therefore, the novel amine curing agent needs to be able to provide sufficient shelf-life stability to the resin system, while also enabling curing at relatively low temperatures without compromising the intermediate material produced during the photopolymerization of component A of the resin.

[0022] Alternatively, the present invention relates to the use of amine curing agents useful in the manufacture of objects, by achieving the manufacture of objects by any of the diverse 3D addition manufacturing processes, for example, liquid addition manufacturing in which a viscous liquid is deposited in layers to form an object and subsequently cured by either heating or microwave radiation, and by methods requiring amine curing to form polyurea, polyurethane, polyurea-urethane polymers, such as stereolithography, continuous liquid interface manufacturing, computerized axial lithography, or any other addition manufacturing technique, wherein the polymerizable monomer may be individual diisocyanates or polyisocyanates or blocked diisocyanates or blocked polyisocyanates or blocked oligomers or blocked prepolymers having diverse functional groups (typically 2 to 6 and more typically 2 to 3), wherein the isocyanate functional groups are terminal groups, and the internal chemical chains between the isocyanate functional groups may have diverse types of chemical bonds, such as ether, urea, urethane, carbon-carbon, carbon-sulfur, carbon-nitrogen, etc.

[0023] The resulting compositions and formulations comprise a variety of primary amine curing agents, wherein the curing agent has one or two vicinal carbon atoms on the carbon atom having the primary amine group, and an alkyl group that increases size and bulk. The alkyl group is preferably a linear or branched type C alkyl group present on both vicinal carbon atoms of the carbon atom having the primary amine group. 1~6 Linear or branched type C carbon atoms, which consist of a saturated hydrocarbon group or a single vicinal carbon atom of the carbon atom having the primary amine group. 2~6 The saturated hydrocarbon group is a primary amine group, which is preferably bonded to a cyclic hydrocarbon moiety having 5 to 7 carbon atoms and preferably 6 carbon atoms (cyclohexyl group), and the cyclohexyl group having the primary amine group is a -CRR′ group [wherein R and R′ are independently hydrogen or C 1~6 The group is bonded by an alkyl group. The total number of primary amine groups present in the curing agent is 2 to 6, preferably 2.

[0024] One aspect of the present invention relates to the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [Chemical formula] [In the formula, R is H or linear or branched C 1~6 alkyl; A represents a cyclic, polycyclic or acyclic linear or branched C 6~20 polyamine; each of R 1 and R 2 is H or a linear or branched C 1~9 alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n = 1 to 6 and m = 1 to 3], and includes at least one amine curing agent. Preferably, the polyamine is a diamine or a triamine.

[0025] In one embodiment, the present invention discloses the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [Chemical formula] [In the formula, R is H or linear or branched C 1~6 alkyl; A represents a cyclic, polycyclic or acyclic linear or branched C 6~20 polyamine; R 1 and R 2 are H; n = 1 to 6 and m = 1 to 3], and includes at least one amine curing agent. Preferably, the polyamine is a diamine or a triamine.

[0026] In another embodiment, the present invention discloses the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [Chemical formula] [In the formula, R 3 is H and R 4 This is linear or branched saturated C 2~6 Alkyl or R 3 =R 4 = Linear or branched saturated C 1~6 It comprises at least one amine curing agent having [being alkyl].

[0027] In another embodiment, the present invention also discloses the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~3 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 C is linear or branched 1~9 The reaction product comprises at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3. Preferably, the polyamine is a diamine or a triamine. Preferably, R 1 and R 2 This includes linear or branched C, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, 2-methyl-butyl, hexyl, 2-hexyl, 3-hexyl, isohexyl, 4-methylpenta-1-yl, 4-methylpenta-2-yl, 2-methylpenta-2-yl, and 2-methylpenta-1-yl. 1~9 These are alkyl substituents, heteroatom-containing cyclic substituents including 2,2,6,6-tetramethylpiperidine-4-yl, or aromatic substituents including benzyl.

[0028] In another embodiment, the present invention also discloses the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is an alkyl group, and A is a cyclic, polycyclic, or acyclic linear or branched C 6~20 The reaction product comprises ii) at least one amine curing agent having [representing a polyamine, n=1 to 6, and m=1 to 3] and ii) at least one α,β-unsaturated carboxylic acid ester. Preferably, the polyamine is a diamine or a triamine. Preferably, the molar ratio of the α,β-unsaturated carboxylic acid ester to the primary amine-NH2 moiety is in the range of 4:1, preferably 3:1, and more preferably 2:1.

[0029] Another aspect of the present invention relates to a method for manufacturing an object using a 3D printing process based on a dual polymerization approach, comprising a portion A of a resin which is first polymerized by a photo-induced process, preferably using UV light, and an intermediate object (scaffold of the object) formed in this process is then further cured by a portion B of the resin which comprises the amine-curable composition together with isocyanate / polyisocyanate and blocked isocyanate / block polyisocyanate, thereby bringing about the formation of a polyurea / polyurethane / polyurea-urethane network within the polymer matrix of the object by the action of microwave radiation or heat.

[0030] The present invention also provides a catalytic hydrogenation method of a corresponding aromatic substrate for producing the amine composition used as a curing agent for portion B of the resin.

[0031] The aromatic precursors for the curing agent of the present invention are 4,4′-methylenebis(2,6-dimethylaniline), 4,4′-methylenebis(2,6-diethylaniline), 4,4′-methylenebis(2,6-di(n-propyl)aniline), 4,4′-methylenebis(2,6-di(sec-propyl)aniline), 4,4′-methylenebis(2,6-di(n-butyl)aniline), 4,4′-methylenebis(2,6-di(sec-butyl)aniline), 4, 4′-Methylenebis(2,6-di(isobutyl)aniline), 4,4′-Methylenebis(2,6-di(t-butyl)aniline), 4,4′-Methylenebis(2,6-di(n-pentyl)aniline), 4,4′-Methylenebis(2,6-di(tert-pentyl)aniline), 4,4′-Methylenebis(2,6-di(neopentyl)aniline), 4,4′-Methylenebis(2,6-di(isopentyl)aniline), 4,4′-Methylenebis(2 ,6-di(sec-pentyl)aniline), 4,4′-methylenebis(2,6-di(3-pentyl)aniline), 4,4′-methylenebis(2,6-di(sec-isopentyl)aniline), 4,4′-methylenebis(2,6-di(n-hexyl)aniline), 4,4′-methylenebis(2,6-di(2-hexyl)aniline), 4,4′-methylenebis(2,6-di(3-hexyl)aniline), 4,4′-methylenebis(2,6-di(n-hexyl)aniline) This includes 4,4′-methylenebis(2,6-di(isohexyl)aniline), 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)aniline), 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)aniline), 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)aniline), 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)aniline), etc.

[0032] The various embodiments and models described herein can be used individually or in combination with each other. [Brief explanation of the drawing]

[0033] [Figure 1]The tensile strength values ​​of various test specimens prepared using amine curing agents with different degrees of steric hindrance on vicinal carbon are shown by the dual polymerization process described herein. [Figure 2] The dual polymerization process described herein yields fracture elongation values ​​for various test specimens prepared using amine curing agents with different degrees of steric hindrance on vicinal carbon. [Modes for carrying out the invention]

[0034] definition The following definitions are provided to help those skilled in the art understand the detailed description of the invention. PUR - Polyurethane. Isocyanate index - The actual amount of polyisocyanate used divided by the theoretically required stoichiometric amount of polyisocyanate needed to react with all the active hydrogen in the reaction mixture, multiplied by 100. Also known as (NCO Eq / active hydrogen Eq) × 100. pphp - parts by weight per 100 parts by weight of polyol.

[0035] Detailed description of the invention The present invention relates to the use of amine curing agents useful in the manufacture of objects by any of a variety of 3D additive manufacturing processes, where the 3D additive manufacturing process is, for example, liquid additive manufacturing in which a viscous liquid is deposited in layers to form an object and subsequently cured by either heat or microwave radiation, or uses a manufacturing method such as stereolithography, continuous liquid interface manufacturing, computerized axial lithography, or any other additive manufacturing technique that requires amine curing of a single polymerizable polymer, or where the amine curing polymerization process is part of a dual curing system as described below. Preferably, in the dual polymerization system, for example, as used in stereolithography or CLIP methods, the first curing system or "part A" is a polymerizable component that, by the action of radiation, such as UV light, results in the formation of a solid object held together by covalent bonds formed during a radical polymerization process.

[0036] One aspect of the present invention relates to the use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 Each of these is an H or a linear or branched C 1~9 The polyamine comprises at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3. Preferably, the polyamine is a diamine or a triamine.

[0037] In a preferred embodiment, the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 The polyamine comprises at least one amine curing agent having H, n=1 to 6, and m=1 to 3. Preferably, the polyamine is a diamine or a triamine.

[0038] In another preferred embodiment, the amine composition has the following structure: [ka] [In the formula, R 3 is H and R 4 This is linear or branched saturated C 2~6 Alkyl or R 3 =R 4 = Linear or branched saturated C 1~6The compound comprises at least one amine curing agent having [alkyl]. Preferably, the at least one amine curing agent is 4,4′-methylenebis(2-ethylcyclohexylamine), 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), 4,4′-methylenebis(2 -(t-butyl)cyclohexylamine), 4,4′-methylenebis(2-(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(neopentyl)cyclohexylamine), 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4′-methylenebis s(2-(sec-isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine) , 4,4′-methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 4,4′-methylenebis(2,6-diethylcyclohexylamine), 4,4′-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexyl Methylenebis(2,6-di(tert-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4'-methylene Bis(2,6-di(sec-isopentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isohexyl Selected from the group consisting of )cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), and 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine).

[0039] In another preferred embodiment, the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~3It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 C is linear or branched 1~9 The compound comprises at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3. Preferably, R 1 and R 2 This includes linear or branched C, including methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, sec-isopentyl, 2-methyl-butyl, hexyl, 2-hexyl, 3-hexyl, isohexyl, 4-methylpenta-1-yl, 4-methylpenta-2-yl, 2-methylpenta-2-yl, and 2-methylpenta-1-yl. 1~9The alkyl substituent, 2,2,6,6-tetramethylpiperidine-4-yl, heteroatom-containing cyclic substituent, or benzyl-containing aromatic substituent are preferred. Preferably, the at least one amine curing agent is N,N'-dialkylated PACM (4,4-diaminodicyclohexylmethane), N,N'-dialkylated isophoronediamine, N,N'-dialkylated MACM (4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine (MCHD) or N,N'-dialkylated ethylenediamine (EDA) or N,N'-dialkylated propylenediamine (PDA) or N,N'-dialkylated 1,4-butanediamine (BDA), or N,N'-dialkylated 1,5-pentanediamine (PeDA) or N,N'-dialkylated 1,6-hexanediamine (HMDA) or The alkyl group is selected from the group consisting of N,N′-dialkylated 4-(aminomethyl)octane-1,8-diamine, or N,N′-dialkylated 1,8-octyldiamine or N,N′,N″-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N′,N″-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof, where the alkyl group is preferably methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpenta-2-yl, 2,2,6,6-tetramethylpiperidine-4-yl, and benzyl.Most preferably, amine curing agents that can be effectively used in the 3D printing process are N,N'-dialkylated PACM (4,4-diaminodicyclohexylmethane), N,N'-dialkylated isophoronediamine, N,N'-dialkylated MACM (4,4'-methylenebis(2-methylcyclohexylamine)), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine (MCHD), or N,N'-dialkylated ethylenediamine (EDA), or N,N'-dialkylated propylenediamine (PDA), or N,N'-dialkylated 1,4-butanediamine (BDA), or N,N'-dialkylated 1,5-pentanediamine (PeDA), or N, The present invention comprises N′-dialkylated 1,6-hexanediamine (HMDA) or N,N′-dialkylated 4-(aminomethyl)octane-1,8-diamine, or N,N′-dialkylated 1,8-octyldiamine or N,N′,N″-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N′,N″-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof, wherein the alkyl group is preferably isopropyl, sec-butyl, pentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpenta-2-yl, 2,2,6,6-tetramethylpiperidine-4-yl, and benzyl.

[0040] A typical procedure for producing the aforementioned N,N′-dialkylated and N,N′,N″-trialkylated amines involves contacting the diamine or triamine with an equivalent amount of an aldehyde or ketone in the presence of hydrogen pressure and a metal catalyst such that the molar ratio of the aldehyde functional group to the primary amine functional group is in the range of 0.9 to 1.2, where the hydrogen pressure is typically 200 to 1800 psig, the catalyst is 5 to 15% palladium or platinum supported on carbon, and the reaction temperature is about 80°C to about 150°C, more preferably about 100°C to about 120°C. Examples of aldehydes and ketones produced by this procedure include formaldehyde, acetaldehyde, propionaldehyde, butanal, acetone, methyl ethyl ketone, methyl isobutyl ketone and triacetoneamine, 3-pentanone, hexanal and 2-ethylhexanal and benzaldehyde.

[0041] In another preferred embodiment, the amine composition, i) has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is an alkyl group, and A is a cyclic, polycyclic, or acyclic linear or branched C 6~20The amine composition comprises i) at least one amine curing agent having [representing a polyamine, n=1-6, and m=1-3], and ii) a reaction product of at least one α,β-unsaturated carboxylic acid ester. Preferably, the amine composition comprises i) 4,4-diaminodicyclohexylmethane (PACM) or 4,4′-methylenebis(2-methylcyclohexylamine (MACM) or 4,4′-methylenebis(2-ethylcyclohexylamine), or 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-butyl)cyclohexylamine) Methylenebis(2-(sec-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), or 4,4′-methylenebis(2-(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(neopentyl)cyclohexylamine) Methylenebis(2-(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine). (xyl)cyclohexylamine), or 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), or 4,4′-Methylenebis(2,6-dimethylcyclohexylamine), or 4,4′-Methylenebis(2,6-diethylcyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4′-Methylenebis Su(2,6-di(n-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di (Neopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2 -Hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine or 4-methylcyclohexane-1,3-diamine (MCHD) or ethylenediamine (EDA) or propylenediamine (PDA) or 1,4-butanediamine (BDA) or 1,5-pentanediamine (PeDA) or 1,6-hexanediamine (HMDA) or 4-(aminomethyl)octane-1,8-diamine or 1,8-octanediamine) The reaction product comprises ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

[0042] Most preferably, the amine composition that can be effectively used in a 3D printing process comprises: i) at least one amine curing agent selected from the group consisting of PACM (4,4-diaminodicyclohexylmethane), 4-methylcyclohexane-1,3-diamine (MCHD), ethylenediamine (EDA), propylenediamine (PDA), 1,4-butanediamine (BDA), 1,5-pentanediamine (PeDA), 1,6-hexanediamine (HMDA), 4-(aminomethyl)octane-1,8-diamine, 1,8-octyldiamine, or mixtures thereof; and ii) a reaction product with methyl acrylate, ethyl acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, or mixtures thereof.

[0043] "Part A" preferably comprises any suitable polymerizable liquid which may contain monomers or mixtures of monomers that can be photopolymerized in the presence of light and / or using a free radical initiator, wherein the radical initiator can induce polymerization of the monomers, and the initiator is either a single initiator or a mixture of suitable initiators, and the process can be induced by light in or out of the presence of such initiator.

[0044] Preferred compounds for portion A of the resin include, but are not limited to, acrylic derivatives, methacrylic derivatives, acrylamides, substituted and unsubstituted olefins (with substituents including cyclic or acyclic, OH, halogen, alkyl, aryl, aryl-alkyl, ether, ester, etc.), maleic acid and fumaric acid compounds, alkynes, CO, functionalized oligomers and prepolymers, such as acrylic esters of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMEG), polyhexamethylene glycol (PHMEG), blocked isocyanates, blocked polyisocyanates, and polyurea and / or polyurethane polyisocyanates as terminal groups, and polymers and oligomers blocked with blocking agents having photo-induced polymerizable organic functional groups of acrylic, methacrylic and other olefinic origins, which can provide 3D objects with or without air as a photoinitiator.

[0045] Examples of liquid resins, monomers, and initiators include, but are not limited to, those described in U.S. Patent No. 7,649,029 (US7649029); U.S. Patent No. 7,767,728 (US7767728); U.S. Patent No. 7,935,476 (US7935476); U.S. Patent No. 8,119,214 (US8119214); U.S. Patent No. 8,232,043 (US8232043); International Publication No. 2012 / 129968 (WO2012129968 A1); Chinese Patent Application Publication No. 102715751 (CN102715751 A); and Japanese Patent Application Publication No. 2012-210408 (JP2012210408A), which are incorporated by reference.

[0046] The photo-induced polymerization of the resin may be achieved by photo-induced cationic polymerization or acidic polymerization. Such a photopolymerization process can be achieved using a polymerizable liquid monomer having an organic functional group that can be activated by an acid or a cationic, such as an oxirane (epoxy) group or a vinyl ether group.

[0047] Therefore, in one embodiment, polymerization of portion A of the resin can be achieved by ionic and / or nonionic photoacid generators, including, but not limited to, sulfonium salts, ionium salts, and iodonium salts, such as diphenyliodide salt, triphenylsulfonium salt, diphenyl p-methoxyphenyl triflate, diphenyl p-toluenyl triflate, diphenyl p-isobutylphenyl triflate, diphenyl p-tert-butylphenyl triflate, and mixtures thereof.

[0048] The photoacid generated by light can induce polymerization of various types of monomers present in part A of the resin, including olefins such as styrene, methyl vinyl ether, 4-methoxystyrene, styrene, 2-methylpropane-1-ene, 1,3-butadiene, etc.; heterocyclic monomers (including lactones, lactams, and cyclic amines), such as oxiranes, thietans, tetrahydrofurans, oxazolines, 1,3-dioxepane, oxetan-2-one, etc., and combinations thereof.

[0049] Examples of monomers, liquid resins, and various types of initiators, not limited to those described herein, are incorporated by reference in U.S. Patent No. 7,649,029 (US7649029); U.S. Patent No. 7,767,728 (US7767728); U.S. Patent No. 7,935,476 (US7935476); U.S. Patent No. 8,119,214 (US8119214); U.S. Patent No. 8,232,043 (US8232043); International Publication No. 2012 / 129968 (WO2012129968A1); Chinese Patent Application Publication No. 102715751 (CN102715751A); and Japanese Patent Publication No. 2012-210408 (JP2012210408A).

[0050] In some embodiments, portion A of the resin comprises an acrylate-modified PEG hydrogel or a PEG hydrogel modified with other suitable functional groups that can be photopolymerized. In some embodiments, such polymerizable hydrogel material can be produced from gelatin, which may be produced by modifying collagen and subsequently modified with a photopolymerizable substrate, such as acrylic, methacrylic, or other unsaturated organic compounds.

[0051] In some embodiments, the resin portion A is made of a UV-curable silicone and / or silicone rubber material, such as LOCTITE. (商標) AA 3462; LOCTITE (商標) AA 3494; LOCTITE (商標) AA 352; LOCTITE (商標) AA 3953; LOCTITE(商標) AA 3951;Silopren (商標) UV LSR 2030, Silopren (商標) UV LSR 2060, Silopren (商標) This may include UV Gel 100 and other similar UV-curable silicone-based materials.

[0052] In some embodiments, portion A of the resin includes a biodegradable material that is particularly used in medical devices and medical applications and requires polymer degradation by biological tissue. Lactic acid and glycolic acid copolymers are examples of biodegradable materials that can dissolve in PEG methacrylate cap diester to produce components suitable for portion A of the resin.

[0053] In some embodiments, the photopolymerizable component of portion A of the resin may include a polyurethane oligomer, polyurethane polymer, or polyurethane prepolymer based on an aliphatic diisocyanate, such as IPDI (isophorone diisocyanate) or HMDI (hexamethylene diisocyanate) and a diol (ethylene glycol, diethylene glycol, 1,4-butanediol, polyethylene glycol, etc.), or a polyurethane / polyurea prepolymer based on a combination of IPDI (isophorone diisocyanate) or HMDI (hexamethylene diisocyanate), a diol, and a diamine, together with a polyfunctional acrylic acid ester, a photoinitiator, or a mixture of photoinitiators.

[0054] In some embodiments, liquid crystalline polymers of esters, ester-imides, and ester-amide oligomers may be components of portion A of the resin, which may require heating to induce melting. These liquid crystalline resins can be used together with a photocurable polymer or photocurable monomer in the presence of a photoinitiator, such as benzophenone, anthraquinone, or fluorenone, to promote polymerization when irradiated with a suitable light source.

[0055] In some embodiments, the solid particles suspended or dispersed in portion A of the liquid resin, having a size ranging from an average diameter of 1 nm to 20 μm, may include metallic, organic / polymeric, inorganic, composite, or mixtures thereof, wherein the suspended or dispersed particles may be nonconductive, semiconductive, or conductive (including metallic and nonmetallic or polymeric conductors); and the particles may be magnetic, ferromagnetic, paramagnetic, or nonmagnetic.

[0056] In some embodiments, additional components may be present in portion A of the resin as solubilized or suspended additives, including active compounds such as pigments, dyes, proteins, peptides, nucleic acids (DNA, RNA), siRNA, sugars, and low molecular weight organic compounds (drugs and drug-like compounds).

[0057] In some embodiments, portion A of the resin may contain a light absorber, such as carbon black, or a UV organic light absorber including benzotriazoles, hydroxybenzophenone, thioxanthone, triazine, titanium dioxide, etc., as described in the prior art (U.S. Patent No. 7695643, U.S. Patent No. 7157586, U.S. Patent No. 6916867, and U.S. Patent No. 3213058).

[0058] In some embodiments, the mixture of portion A and portion B of the resin may contain a radical inhibitor in liquid or gaseous form, such as oxygen gas, and a liquid inhibitor, such as an oil or lubricant (e.g., fluorinated oil, such as perfluoropolyether), may be used as an inhibitor or as a release layer to maintain the liquid interface, or in some more specific embodiments, such as photoacid-induced polymerization, the inhibitor may actually be a base, such as ammonia, trace amines (e.g., methylamine, ethylamine, dialkylamine and trialkylamine, such as dimethylamine, diethylamine, trimethylamine, triethylamine, etc.), or carbon dioxide, and mixtures thereof.

[0059] In some embodiments where the polymerizable liquid is aqueous and may be oxygenated, living cells from plants (e.g., monocots, dicots), animals (e.g., mammalian cells, avian cells, amphibian cells, reptile cells), microorganisms (e.g., prokaryotes, eukaryotes, protozoa, etc.) may be included as particles or in the form of a living emulsion in which the living cells form a discrete phase. In these cases, the polymerizable liquid can form hydrogels, for example, those described in the prior art (US Patent No. 7651683; US Patent No. 7651682; US Patent No. 7556490; US Patent No. 6602975 and US Patent No. 5836313).

[0060] As described above, in some embodiments of the present invention, the polymerizable liquid comprises a first photopolymerizable component called part A and a second component that solidifies by a different mechanism or in a different manner than the first component, and this second component is called part B. The component of part B further contributes to the manufacture of the object by reacting, polymerizing or chain extending, resulting in improved quality and performance of the finished object.

[0061] As described above, part A comprises a mixture of monomers and / or prepolymers that can be polymerized by exposure to radiation or light. The purpose of part A is to “lock” the shape of the formed object or to generate a scaffold for a fabricated object. Part A must be present in an amount that is the minimum or greater than the minimum required to maintain the shape of the formed object after initial solidification in a manner that allows the object scaffold to be handled and fabricated. In some embodiments, this amount corresponds to less than 10% by weight, less than 20% by weight, or less than 30% by weight of the total polymerizable liquid resin composition. In some embodiments, part A can react to form a crosslinked polymer network or a solid homopolymer.

[0062] Preferred compounds for portion A of the resin include, but are not limited to, acrylic derivatives, methacrylic derivatives, acrylamides, substituted and unsubstituted olefins (with substituents including cyclic or acyclic, OH, halogen, alkyl, aryl, aryl-alkyl, ether, ester, etc.), maleic acid and fumaric acid compounds, alkynes, CO, functionalized oligomers and prepolymers, such as acrylic esters of polyethylene glycol (PEG), polypropylene glycol (PPG), polytetramethylene glycol (PTMEG), polyhexamethylene glycol (PHMEG), blocked isocyanates, blocked polyisocyanates, and polyurea and / or polyurethane polyisocyanates as terminal groups, and polymers and oligomers blocked with blocking agents having photo-induced polymerizable organic functional groups of acrylic, methacrylic and other olefinic origins, which can provide 3D objects with or without air as a photoinitiator.

[0063] During the solidification of portion A, the object scaffold is located within portion A, and the second reactive resin component or portion B can solidify in a second step that may occur simultaneously with or following the solidification of portion A. Secondary polymerization is preferably required to occur without significantly distorting the original shape defined during the solidification of portion A, unless the distortion of the original shape is controlled and occurs in a desired manner. Some additive manufacturing processes, such as CLIP, are also used. (商標) In the process, the solidification of portion A may be inhibited by oxygen, amines, or other reactive species in some components of the printing device, so that the object does not adhere to the window and the resin material can always be present in the growing liquid-solid interface phase of the object.

[0064] Part B comprises a mixture of monomers and / or oligomers or prepolymers having reactive end groups that participate in a second solidification reaction after the solidification of Part A. In some embodiments, Part B can be added to Part A at the same time and thus present during exposure to radiation, or Part B can penetrate into the object being manufactured in subsequent steps during the 3D printing process. Part B can be solidified in a variety of ways, including, but not limited to, contact of the object or scaffold with heat, water, water vapor, light at a different wavelength than that used in Part A, catalysts with or without additional heat, evaporation of a solvent from the polymerizable liquid (e.g., using heat, vacuum, or a combination thereof), microwave irradiation, and combinations thereof.

[0065] Suitable reactive end group pairs for the components, monomers, or prepolymers of part B include, but are not limited to, epoxy / amine, epoxy / hydroxyl, oxetane / amine, oxetane / alcohol, isocyanate / hydroxyl, isocyanate / amine, isocyanate / carboxylic acid, anhydride / amine, amine / carboxylic acid, amine / ester, hydroxyl / carboxylic acid, hydroxyl / acid chloride, amine / acid chloride, vinyl / Si-H (hydrosilylated), Si-Cl / hydroxyl, Si-Cl / amine, hydroxyl / aldehyde, amine / aldehyde, hydroxymethyl or Alkynes / azides, along with additional reactions including alkoxymethylamide / alcohol, hydrothiolation (thiolene reaction) of thiols-enes or alkenes, Michael addition, Diels-Alder reaction, nucleophilic substitution, alkenes / sulfur (vulcanization), alkenes / peroxides, alkenes / thiols, alkynes / thiols, hydroxyls / halides, isocyanates / water (polyurethane foam), Si-OH / hydroxyl, Si-OH / water, Si-OH / Si-H (tin-catalyzed silicone), SiOH / Si-OH (tin-catalyzed silicone), perfluorovinyl (coupling to form perfluorocyclobutane), etc.

[0066] Isocyanates include protected isocyanates (oximes), dienes / dienophiles for Diels-Alder reactions, olefin metathesis polymerization, olefin polymerization using Ziegler-Natta catalysis, ring-opening polymerization (including ring-opening olefin metathesis polymerization, lactams, lactones, siloxanes, epoxides, cyclic ethers, imines, cyclic acetals, etc.).

[0067] In one embodiment, preferably, the amine composition of the present invention for part B can be used with any of the following reactive terminal group pairs, including epoxy / amine, oxetane / amine, anhydride / amine, amine / carboxylic acid, amine / ester, amine / acid chloride and Si-Cl / amine, and amine / aldehyde.

[0068] More preferably, the amine compositions of the present invention for part B can be used to cure isocyanate / polyisocyanate and / or blocked isocyanate / polyisocyanate compositions in the presence or absence of other reactive end group pairs, such as epoxy / amine, oxetane / amine, anhydride / amine, amine / carboxylic acid, amine / ester, amine / acid chloride, Si-Cl / amine, and amine / aldehyde.

[0069] In some embodiments, organic peroxides may be included in the polymerizable liquid or resin to facilitate the reaction of potentially unreacted double bonds or to complete the radical polymerization process of double bonds in the heat-induced curing portion and / or when microwave irradiation is used. The organic peroxide may be included in the resin or polymerizable liquid in any suitable amount, preferably from 0.001% by weight, 0.01% by weight, or 0.1% by weight, up to 1% by weight, 2% by weight, or 3% by weight. Commonly used peroxides include 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, dilauroyl peroxide, benzoyl peroxide, and bis(tert-butyldioxyisopropyl)benzene, and combinations thereof.

[0070] In some embodiments, the present invention relates to the additive manufacturing of elastomer, thermoplastic, and thermosetting materials of multiple shapes, using the solidification of part A, followed by the alignment of these materials in a special arrangement such that there is a hermetic seal between them, and then activating a secondary solidification step for part B, where the amine composition of the present invention is involved in the formation of an additional covalent network as described above. In this method, strong adhesion between the materials can be achieved during manufacturing.

[0071] In some embodiments, the amine of the present invention forming part B may be pre-formed in the polymer, and during the solidification of part A, the resulting material may be heated above its glass transition temperature to melt the pre-formed polymer particles.

[0072] In some embodiments, the amine of the present invention in part B may be part of a pre-formed polymer dissolved in a solvent, the polymer resulting in the solidification of the pre-formed polymer having the amine composition of the present invention during the solidification of part A into an object, followed by solvent removal under vacuum, heat, or both.

[0073] In some embodiments, portion A may have chemically protected reactive functional groups, which can be thermally activated to generate new reactive species, subsequently causing portion A to coagulate. These new reactive functional groups can react with the amine composition of the present invention to result in a second coagulation process. Preferably, an isocyanate blocking precursor is used in these cases, and the isocyanate functional groups can be effectively regenerated by heat once the object is formed after photo-induced polymerization of portion A. The amine composition of the present invention can participate in a secondary polymerization process with the heat-generated isocyanate functional groups to produce a second polymer network having polyurea / polyurethane / polyurethane-urea functional groups. Mechanistically, the formation of the isocyanate functional groups by thermal dissociation of the blocking agent may also occur in a concerted manner, and the amine composition of the present invention replaces the isocyanate protecting groups to result in a second polymer network.

[0074] In some embodiments, portion A and portion B having the amine composition of the present invention may be mixed "in situ" in a polymerization chamber to avoid premature solidification or reaction between the amine composition and the isocyanate block component. Preferably, when the resin is introduced into the printer in this manner, the solidification of portion A by the photo-induced process occurs at a faster pace than the solidification of portion B, which requires additional energy (heat) to complete the curing process. In other words, the curing rate of portion B is much slower than the photo-induced polymerization rate of portion A, and portion B can be cured once the scaffold of the object is produced by the photo-induced polymerization of portion A.

[0075] The curable compositions described in the present invention are useful in fused deposition modeling (FDM), solid-state laser sintering (SLS), and other additive manufacturing techniques, including inkjet methods. For example, a molten acrylonitrile-butadiene-styrene resin may be compounded with a second UV-curable component that can be activated after the object is formed by FDM. Novel mechanical properties have been achieved in this method.

[0076] In some embodiments, the amine curable composition reacts with the isocyanate or isocyanate precursor under conditions that, after an irradiation step (e.g., by heating or microwave irradiation), the solid polymer scaffold decomposes and forms components necessary for the polymerization of the second component. In this step, a prepolymer, diisocyanate, or polyisocyanate is generated and further reacts with the amine composition components to form a polyurethane / polyurea resin. These methods involve the use of reactive or nonreactive block groups coupled to components of the first component, which participate in a first curing event (photo-induced) and, upon deprotection, generate free components that can participate in a second coagulation and / or curing event.

[0077] A preferred "dual curing" embodiment in which the amine composition of the present invention is useful includes a method for forming a three-dimensional object comprising the following steps: a) contacting a polymerizable liquid in an optically transparent building surface in the presence of at least one of a reactive diluent, a photoinitiator, and a chain extender, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a block oligomer or reactive block oligomer, or iii) a block prepolymer or reactive block prepolymer; b) irradiating the building area with light passing through a radiolucent window to form a solid scaffold object; c) heating or microwave treatment to induce polymerization between at least one of the monomer, block oligomer or reactive block oligomer or block prepolymer or reactive block prepolymer and the amine composition to form the three-dimensional object, wherein the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 Each of these is an H or a linear or branched C 1~9 The polyamine comprises at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3. Preferably, the polyamine is a diamine or a triamine.

[0078] In a preferred embodiment of the above method, the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 The polyamine comprises at least one amine curing agent having H, n=1 to 6, and m=1 to 3. Preferably, the polyamine is a diamine or a triamine.

[0079] In another preferred embodiment of the above method, the amine composition has the following structure: [ka] [In the formula, R 3 =H and R 4 = Linear or branched saturated C 2~6 Alkyl or R 3 =R 4 = Linear or branched saturated C 1~6The compound comprises at least one amine curing agent having [alkyl]. Preferably, the at least one amine curing agent is 4,4′-methylenebis(2-ethylcyclohexylamine), 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), 4,4′-methylenebis(2 -(t-butyl)cyclohexylamine), 4,4′-methylenebis(2-(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(neopentyl)cyclohexylamine), 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4′-methylenebis s(2-(sec-isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine) , 4,4′-methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 4,4′-methylenebis(2,6-diethylcyclohexylamine), 4,4′-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexyl Methylenebis(2,6-di(tert-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4'-methylene Bis(2,6-di(sec-isopentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isohexyl Selected from the group consisting of )cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), and 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine).

[0080] In another preferred embodiment of the above method, the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~3It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 C is linear or branched 1~9 The polyamine comprises at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3. Preferably, the polyamine is a diamine or a triamine. Preferably, the above-mentioned at least one amine curing agent is N,N'-dialkylated 4,4-diaminodicyclohexylmethane, N,N'-dialkylated isophoronediamine, N,N'-dialkylated 4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine, N,N'-dialkylated ethylenediamine, N,N'-dialkylated propylenediamine, N,N'-dialkylated 1,4-butanediamine, N,N'-dialkylated 1,5-pentanediamine, N,N'-dialkylated 1,6-hexanediamine, N,N'-dialkylated 4-(aminomethyl)octane-1, The alkyl group is selected from the group consisting of 8-diamine, N,N′-dialkylated 1,8-octyldiamine, N,N′,N″-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N′,N″-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof; where the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpenta-2-yl, 2,2,6,6-tetramethylpiperidine-4-yl, and benzyl.

[0081] In another preferred embodiment of the method described above, the amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6It is an alkyl group, and A is a cyclic, polycyclic, or acyclic linear or branched C 6~20The reaction product comprises i) at least one amine curing agent having [representing a polyamine, n=1-6 and m=1-3] and ii) at least one α,β-unsaturated carboxylic acid ester. Preferably, the polyamine is a diamine or a triamine. Preferably, the amine composition is i) 4,4-diaminodicyclohexylmethane or 4,4′-methylenebis(2-methylcyclohexylamine or 4,4′-methylenebis(2-ethylcyclohexylamine), or 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), or 4, 4′-Methylenebis(2-(sec-butyl)cyclohexylamine), or 4,4′-Methylenebis(2-(isobutyl)cyclohexylamine), or 4,4′-Methylenebis(2-(t-butyl)cyclohexylamine), or 4,4′-Methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4′-Methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4′-Methylenebis(2-(neopentyl)cyclohexylamine) ), or 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(2-hexyl )cyclohexylamine), or 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), or 4,4′-Methylenebis(2,6-dimethylcyclohexylamine), or 4,4′-Methylenebis(2,6-diethylcyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4′-Methylenebis Su(2,6-di(n-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di (Neopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2 -Hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine or 4-methylcyclohexane-1,3-diamine (MCHD) or ethylenediamine (EDA) or propylenediamine (PDA) or 1,4-butanediamine (BDA) or 1,5-pentanediamine (PeDA) or 1,6-hexanediamine (HMDA) or 4-(aminomethyl)octane-1,8-diamine or 1,8-octanediamine) The reaction product comprises ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

[0082] In some embodiments, the amine composition preferably comprises i) at least one amine curing agent selected from the group consisting of PACM (4,4-diaminodicyclohexylmethane), 4-methylcyclohexane-1,3-diamine (MCHD), ethylenediamine (EDA), propylenediamine (PDA), 1,4-butanediamine (BDA), 1,5-pentanediamine (PeDA), 1,6-hexanediamine (HMDA), 4-(aminomethyl)octane-1,8-diamine, 1,8-octyldiamine, or mixtures thereof, and ii) a reaction product with methyl acrylate, ethyl acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, and mixtures thereof.

[0083] In some embodiments, the block prepolymer or reactive block prepolymer preferably comprises at least one of a diisocyanate prepolymer, a polyisocyanate prepolymer, and a polyisocyanate oligomer. In some embodiments, the block prepolymer or reactive block prepolymer preferably comprises a diisocyanate prepolymer or polyisocyanate prepolymer, which is produced by condensing an isocyanate or polyisocyanate with a polyol or polyamine or a combination thereof to produce a polyurethane or polyurea, and the polyurethane / polyurea prepolymer has an isocyanate functional group as a terminal group. In some embodiments, the isocyanate functional group can be completely or partially blocked with an isocyanate blocking agent.

[0084] In some embodiments, the block prepolymer or reactive block prepolymer preferably includes a polyisocyanate oligomer produced by the reaction of at least one diisocyanate (e.g., diisocyanate, e.g., hexamethylene diisocyanate (HMDI), isophorone diisocyanate (IPDI), bis-(4-isocyanatocyclohexyl)methane, triisocyanate, etc.) with at least one polyol (e.g., polyether polyol or polyester polyol or polybutadiene diol or polybutadiene polyol).

[0085] In some embodiments, preferably the reactive block prepolymer is blocked by reaction of the polyisocyanate with a blocking agent selected from the group consisting of 2-(tert-butylamino)ethyl methacrylate (TBAEMA), 2-(tert-pentylamino)ethyl methacrylate (TPAEMA), 2-(tert-hexylamino)ethyl methacrylate (THAEMA), 3-(tert-butylamino)propyl methacrylate (TBAPMA), other similar acrylate compounds, and mixtures thereof.

[0086] In some embodiments, preferably, the acrylate-based isocyanate blocking agent can also be used as a diluent. In some embodiments, any other blocking agent for isocyanates may also be used. A preferred embodiment of the blocking agent includes TBAEMA. Additional preferred blocking agents can be used to carry out the present invention through esterification or amidation reactions of methacrylic acid with suitable sterically hindered N-substituted amine-alcohols and diamines. Similar examples include maleimides or substituted maleimides on other known blocking agents for use in the present invention.

[0087] Other known preferred isocyanate blocking agents include phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol, t-butylphenol, hydroxybenzoic acid, hydroxybenzoic acid esters, 2,5-di-t-butyl-4-hydroxytoluene, lactam-type blocking agents, active methylene-type blocking agents such as diethyl malonate, dimethyl malonate, ethyl acetate, methyl acetate, acetylacetone, alcohol-type blocking agents such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-amyl alcohol, t-amyl alcohol, lauryl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, methoxyethanol, glycolic acid, glycolic acid esters, lactic acid, lactic acid esters, methylolurea, methylol Melamine, diacetone alcohol, ethylene chlorohydrin, ethylene bromohydrin, 1,3-dichloro-2-propanol, ω-hydroperfluoroalcohol, acetocyanohydrin, mercaptan-type blocking agents, e.g., butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, t-dodecyl mercaptan, 2-mercapto-benzothiazole, thiophenol, methylthiophenol, ethylthiophenyl, acid amide-type blocking agents, e.g., acetanilide, acetanisidineamide, acrylamide , methacrylamide, acetate amide, stearic acid amide, benzamide, imide-type blocking agents, e.g., succinimide, phthalimide, maleimide, amine-type blocking agents, e.g., diphenylamine, phenylnaphthylamine, xylidine, N-phenylxylidine, carbazole, aniline, naphthylamine, butylamine, dibutylamine, butylphenylamine, imidazole-type blocking agents, e.g., imidazole, 2-ethylimidazole, urea-type blocking agents, e.g., urea, thiourea, ethyleneurea, ethylenethiourea, 1,This includes, but is not limited to, 3-diphenylurea, carbamate-type blocking agents such as N-phenylcarbamate phenyl ester, 2-oxazolidone, imine-type blocking agents such as ethyleneimine, oxime-type blocking agents such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, cyclohexanone oxime, and sulfite-type blocking agents such as sodium bisulfite, potassium bisulfite, etc.

[0088] In some embodiments, the diisocyanate prepolymer, polyisocyanate prepolymer, or polyisocyanate oligomer is preferably blocked with an aldehyde blocking agent, such as 2-formyloxyethyl (meth)acrylate.

[0089] In some embodiments, preferably the reactive diluent of part A includes acrylates, methacrylates, styrene, acrylic acid, vinyl amides, vinyl ethers, vinyl esters, acrylonitriles, styrene, divinylbenzene, vinyltoluene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl (meth)acrylate, amine (meth)acrylate, and their derivatives and combinations thereof.

[0090] In some embodiments, the chain extender preferably comprises at least one diol, diamine, or dithiol chain extender selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; corresponding diamines and dithiol analogs thereof; lysine ethyl esters, arginine ethyl esters, β-alanine-based diamines, and at least one diisocyanate, and a random copolymer or block copolymer produced from at least one diol, diamine, or dithiol chain extender.

[0091] In some embodiments, the polymerizable liquid preferably comprises: 5% by weight, 20% by weight, 40% to 60% by weight, 80% by weight, or 90% by weight of the block prepolymer or reactive block prepolymer; 10% by weight, 20% to 30% by weight, 40% by weight, or 50% by weight of the reactive diluent; 5% by weight, 10% to 20% by weight, or 30% by weight of the chain extender; and 0.1% by weight, 0.2% to 1% by weight, 2% by weight, or 4% by weight of the photoinitiator. Any additional components, such as dyes, fillers, surfactants, etc., may be included.

[0092] The polymerizable liquid having the amine composition of the present invention provides sufficient stability, and the mixture of components in the resin can be relatively stable, and the need to pre-formulate them and modify the apparatus to provide separate reservoirs and mixing volumes can be eliminated.

[0093] During the thermosetting process, the blocking agent is cleaved, the diisocyanate prepolymer is reformed, and it rapidly reacts with the chain extender or additional soft segments to form a thermoplastic or thermosetting polyurethane, polyurea, or copolymer having both urea functional groups and urethane functional groups.

[0094] An example of a dual-curing resin consists of an acrylic block polyurethane (ABPU), such as a UV-curable methacrylate block polyurethane, a reactive diluent, a photoinitiator, and a chain extender. The function of the reactive diluent is to provide a UV photopolymerization source (preferably 10-50% by weight of the mixture), such as an acrylate or methacrylate ester, which helps to reduce the viscosity of the ABPU polymer or oligomer. The photoinitiator, preferably present in about 1% by weight, may be one of the commonly used UV initiators, such as acetophenones (e.g., diethoxyacetophenone), phosphine oxides, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide (PPO), Irgacure 369, etc.

[0095] After UV curing to form an intermediate molded product having a block polyurethane oligomer as a scaffold and the chain extender, the ABPU resin is subjected to thermal curing, during which high molecular weight polyurethane / polyurea is formed by a spontaneous reaction between the block polyurethane / polyurea oligomer and the chain extender contained in the amine composition of the present invention.

[0096] The component having the blocked isocyanate functional group, which may include an isocyanate-blocked polyurethane / polyurea prepolymer or oligomer, can react with the chain extender contained in the amine composition of the present invention by either substitution or displacement of the blocking agent (preferably TBAEMA) during heating of the pre-formed object. The required curing time may vary depending on the temperature, size, shape, and density of the product, but is preferably between 1 and 6 hours, depending on the specific ABPU system, chain extender, and temperature.

[0097] Blocking the terminal isocyanate functional groups of the polyurethane / polyurea prepolymer / oligomer using sterically hindered amine-alcohols allows for thermal replacement (deprotection) or substitution of the blocking agent at relatively mild temperatures within a range of about 100°C, enabling further polymerization of portion B containing the amine curing agent of the present invention.

[0098] The amine curing agent of the present invention can be used together with other chain extenders, such as diols, diamines, triols, triamines, or combinations thereof, for example, ethylene glycol, 1,4-butanediol, methylenedicyclohexylamine (PACM as a trade name from Evonik Corporation), hydroquinone bis(2-hydroxyethyl) ether (HQEE), 4,4-methylenebis(3-chloro-2,6-diethylaniline) (MCDEA), 4,4′-methylenebis(2,6-diethylaniline) (MDEA), and 4,4-methylenebis(2-chloroaniline) (MOCA).

[0099] For the synthesis of acrylic block polyurethane / polyurea prepolymers, TBAEMA may be used to block the isocyanate end groups of the prepolymer. The polyurethane prepolymer or oligomer can preferably be produced from a polyol having two hydroxyl functional groups. The polyol may be a polyether, particularly polytetramethylene oxide (PTMO), polypropylene glycol (PPG), polyester, polycaprolactone (PCL), polycarbonate, polybutadienediol, or polybutadiene polyol. The molecular weight range of these polyols may be 500 to 6000 daltons, and preferably 500 to 2000 daltons.

[0100] The polyurethane prepolymer or oligomer is preferably produced by reacting the polyol with an isocyanate, such as diisocyanate, such as toluene diisocyanate (TDI), methylenediphenyl diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), hydrogenated MDI (HMDI), or paraphenyl diisocyanate (PPDI), in the presence of a polyurethane catalyst, such as tin(II) octoate, at an isocyanate index greater than 100 and preferably 200 or more to ensure isocyanate terminal groups. Blocking the terminal isocyanates is preferably achieved by adding sufficient TBAEMA to cap the isocyanate functional groups, as described in the Examples section.

[0101] Objects produced using these methodologies with the amine curing agent of the present invention include (a) linear thermoplastic polyurethane, polyurea, or polyurethane / polyurea copolymer, (b) crosslinked thermosetting polyurethane, polyurea, or polyurethane / polyurea copolymer, or (c) a combination of (a) and (b), optionally blended with deblocked blocked groups copolymerized with the reactive diluent, to form interpenetrating polymer networks, semi-interpenetrating polymer networks, or sequentially interpenetrating polymer networks.

[0102] The photoinitiator used to promote the radical polymerization of portion A may remain in the formed three-dimensional object in amounts ranging from 0.1 or 0.2% by weight to 1% by weight, 2% by weight, or 4% by weight, or the photoinitiator may be present in smaller amounts, only trace amounts, or as fragments of the original photoinitiator structure.

[0103] In some examples of embodiments, the three-dimensional product may contain a reacted photoinitiator fragment.

[0104] Non-reactive blocking groups that do not participate in the photo-induced radical polymerization can also be used. Furthermore, portion A of the resin may contain non-blocked isocyanates. In addition, chain extenders, such as triols, tetraols and polyols, as well as triamines, tetraamines and polyamines, can also be used.

[0105] During the thermal curing process, the blocking agent is cleaved, and the chain extender polyalcohol, polyamine, or both react to form a polyurethane / polyurea, which is a thermoplastic or thermosetting polyurethane, polyurea, or a mixed polymer, depending on the selection of the chain extender.

[0106] In some embodiments, preferably, the amine composition of the present invention in part B can be used in combination with any type of diglycidyl ether and especially diglycidyl ether and triglycidyl ether, which can immobilize the amine composition and optionally other functionalized trialkoxy-aminoalkyl-siloxane together with a silica precursor, such as tetraethyl orthosilicate (TEOS). Thus, once the free radical polymerization of part A is complete, the diverse components, including silica and functionalized silica precursors, can be completed in the second step by incorporating water and adding an acid or by generating the acid in situ by the action of light (photoacid generation).

[0107] In some embodiments, other components may preferably be included, in or out of the presence of a solvent or diluent, such as phenolic resins (phenolic resol or novolac), polyimides (made from dianhydrides or diacides and diimines), and derivatives of natural products such as glycerin, and natural oil polyols.

[0108] In some embodiments, preferably silicone or poly(dimethylsiloxane) (PDMS) may be used as a flexible segment in the formation of these materials. For example, (meth)acrylate-functionalized ABPU could be formed by first reacting an oligomer PDMS diol or diamine with two equivalents of diisocyanate to form a PDMS urethane prepolymer. This material could be further reacted with TBAEMA or other reactive blocking agents described herein to form a reactive blocked PDMS prepolymer, which could then be blended with chain extenders and reactive diluents as described in the Examples section.

[0109] In some embodiments, the material may preferably include, be derived from, or essentially consist of, a UV-curable PDMS oligomer blended with a two-component thermosetting PDMS oligomer system.

[0110] In some embodiments, photopolymerization preferably involves UV light cleaving the initiator into active radical fragments. These active radical fragments then react with monomers. During the growth phase, the active monomers react with additional monomers that bind to the growing polymer chain. Finally, termination can be induced by either recombination or disproportionation.

[0111] In some embodiments, the photoinitiator may preferably include the following: (a) Benzoyl chromophore compounds, for example [ka]

[0112] (b) Morpholine aminoketones, e.g.: [ka]

[0113] (c) Benzoylphosphine oxide, for example: [ka]

[0114] (d) Amines: Many photoinitiators may be used in combination with amines. In this case, the excited photoinitiator is used to extract hydrogen atoms from the amine, thereby generating active radicals. These radicals can then initiate polymerization and are thus incorporated into the resulting polymer network.

[0115] (e) Other systems: These types of photoinitiators, which may be used to produce such materials and thereby generate fragments that are covalently bonded to the formed polymer network, include: triazines, ketones, peroxides, diketones, azides, azo derivatives, disulfide derivatives, disilane derivatives, thiol derivatives, diselenium derivatives, diphenylditelluride derivatives, digermannine derivatives, distannan derivatives, carbon-germanium compounds, carbon-silicon derivatives, sulfur-carbon derivatives, sulfur-silicon derivatives, peracid esters, barton ester derivatives, hydroxamic acids and thiohydroxamic acids and esters, organoborates, organometallic compounds, titanocenes, chromium complexes, alumate complexes, carbon-sulfur or sulfur-sulfur compounds, oxyamines, aldehydes, acetals, silanes, phosphorus-containing compounds, borane complexes, thioxanthone derivatives, coumarins, anthraquinones, fluorenones, ferrocenium salts.

[0116] In some embodiments of the above method, preferably, the light that passes through the radioactive window to form the solid scaffolding object is ultraviolet light.

[0117] The amine compositions of the present invention are suitable for countless products, such as medical devices and implantable medical devices, such as stents, drug delivery depots, catheters, bladders, breast implants, testicular implants, pectoral implants, ophthalmic implants, contact lenses, dental aligners, microfluidics, seals, shrouds, and other applications requiring high biocompatibility, functional structures, microneedle arrays, fibers, rods, waveguides, micromechanical devices, microfluidic devices; fasteners; electronic device housings; gears, propellers, and impellers; wheels, mechanical equipment housings; tools; structural elements; hinges, including integrally molded hinges; boat and ship hulls and decks; wheels; bottles, jars, and other containers; pipes, liquid tubes, and fittings; footwear soles, heels, insoles, and midsoles; bushings, O-rings, and gaskets; shock absorbers, leaks It can be used in any type of 3D printing manufacturing method that requires the second solidifiable component of the dual-curing system to essentially 3D print a number of other 3D objects, including: hose assemblies, cushions; electronic device housings; shin guards, foul cups, knee pads, elbow pads, foam liners, padding or inserts; helmets, helmet straps, headgear, shoe spikes, gloves, other wearable or athletic equipment; brushes, combs, rings, jewelry, buttons, snaps, fasteners, watch bands or watch housings; mobile phone or tablet casings; computer keyboards or keyboard buttons or parts; remote control buttons or parts; automotive dashboard parts, buttons, dials; automotive body components, panels; other automotive, aircraft or boat components; cookware, heat-resistant dishes, kitchenware, steamers and a number of other 3D objects.

[0118] The preferred items of the present invention are the following items 1 to 25.

[0119] Use of an amine composition for manufacturing an object by a 3D printing process based on dual polymerization, wherein the amine composition has the following structure: [Chemical Formula] [where R is H or linear or branched C 1~6 alkyl; A represents a cyclic, polycyclic or acyclic linear or branched C 6~20 polyamine; each of R 1 and R 2 is H, a linear or branched C 1~9 alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n = 1 to 6 and m = 1 to 3] and includes at least one amine curing agent, said use.

[0120] Item 2. The use according to item 1, wherein the amine composition has the following structure: [Chemical Formula] [where R is H or linear or branched C 1~6 alkyl; A represents a cyclic, polycyclic or acyclic linear or branched C 6~20 polyamine; R 1 and R 2 are H; n = 1 to 6 and m = 1 to 3] and includes at least one amine curing agent.

[0121] Item 3. The use according to item 2, wherein the at least one amine curing agent has the following structure: [Chemical Formula] [where R 3 is H and R 4 is linear or branched saturated C 2~6 alkyl, or R 3 = R 4 = linear or branched saturated C 1~6 alkyl].

[0122] Item 4. At least one of the aforementioned amine curing agents is 4,4′-methylenebis(2-ethylcyclohexylamine), 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), 4,4′-methylenebis(2-(t-butyl)cyclohexylamine) Methylenebis(2-(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(neopentyl)cyclohexylamine), 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine) Methylenebis(2-(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-2-yl) 4,4′-methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 4,4′-methylenebis(2,6-diethylcyclohexylamine), 4,4′-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(tert-pentyl 4,4′-methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine) Hexylamine), 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), 4, Use of item 3, selected from the group consisting of 4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), and 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine).

[0123] Item 5. The amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~3 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20Represents polyamines; R 1 and R 2 C is linear or branched 1~9 Use of Item 1, comprising at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3.

[0124] Item 6. The above-mentioned at least one amine curing agent is N,N'-dialkylated 4,4-diaminodicyclohexylmethane, N,N'-dialkylated isophoronediamine, N,N'-dialkylated 4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine, N,N'-dialkylated ethylenediamine, N,N'-dialkylated propylenediamine, N,N'-dialkylated 1,4-butanediamine, N,N'-dialkylated 1,5-pentanediamine, N,N'-dialkylated 1,6-hexanediamine, N,N'-dialkylated 4-(aminomethyl)octane-1,8-diamine. The use of item 5, where the alkyl group is selected from the group consisting of mine, N,N′-dialkylated 1,8-octyldiamine, N,N′,N″-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N′,N″-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof; where the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpenta-2-yl, and 2,2,6,6-tetramethylpiperidine-4-yl.

[0125] Item 7. The amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is an alkyl group, and A is a cyclic, polycyclic, or acyclic linear or branched C 6~20The use of item 2 comprises a reaction product of at least one amine curing agent having [representing a polyamine, n=1-6 and m=1-3] and ii) at least one α,β-unsaturated carboxylic acid ester.

[0126] Item 8. The amine composition is i) 4,4-diaminodicyclohexylmethane or 4,4′-methylenebis(2-methylcyclohexylamine or 4,4′-methylenebis(2-ethylcyclohexylamine), or 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), or 4,4 '-Methylenebis(2-(isobutyl)cyclohexylamine), or 4,4'-Methylenebis(2-(t-butyl)cyclohexylamine), or 4,4'-Methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4'-Methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4'-Methylenebis(2-(neopentyl)cyclohexylamine), or 4,4'-Methylenebis(2-(isopentyl)cyclohexylamine), or 4,4'-Methylenebis(2-(sec-pentyl)cyclohexylamine) 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2 -(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-dimethylcyclohexylamine), or 4,4′-methylenebis(2,6-Diethylcyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-butyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4′-Methylenebis(2,6- Di(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4′-methylenebis Su(2,6-di(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4,4′ -Methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine), or 4-methylcyclohexane-1,The use of item 7, comprising the reaction product of 3-diamine (MCHD), or ethylenediamine (EDA), or propylenediamine (PDA), or 1,4-butanediamine (BDA), or 1,5-pentanediamine (PeDA), or 1,6-hexanediamine (HMDA), or 4-(aminomethyl)octane-1,8-diamine, or 1,8-octyldiamine, or any mixture thereof, and ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

[0127] Item 9. The following steps: a) Contact a polymerizable liquid in an optically transparent surface to be built in the presence of at least one of a reactive diluent, a photoinitiator, and a chain extender, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a block oligomer or a reactive block oligomer, or iii) a block prepolymer or a reactive block prepolymer; b) Irradiate the surface to be built with light passing through a radiolucent window to form a solid scaffold object; c) Heat or microwave the solid scaffold object to induce polymerization between at least one of the monomer, block oligomer or a reactive block oligomer or a block prepolymer or a reactive block prepolymer and the amine composition to form a three-dimensional object. A method for forming a three-dimensional object comprising the following: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R2 Each of these is H, linear or branched C 1~9 The method comprising at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3.

[0128] Item 10. The amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20 Represents polyamines; R 1 and R 2 The method of item 9, comprising at least one amine curing agent having [where is H; n=1 to 6 and m=1 to 3].

[0129] Item 11. The amine composition has the following structure: [ka] [In the formula, R 3 is H and R 4 This is linear or branched saturated C 2~6 Alkyl or R 3 =R 4 = Linear or branched saturated C 1~6 The method of item 10, comprising at least one amine curing agent having [being alkyl].

[0130] Item 12. At least one of the amine curing agents is 4,4′-methylenebis(2-ethylcyclohexylamine), 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), 4,4′-methylenebis(2-(t-butyl)cyclohexylamine) Methylenebis(2-(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(neopentyl)cyclohexylamine), 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine) Methylenebis(2-(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), 4,4′-methylenebis(2-(isohexyl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2-(4-methylpenta-2-yl) 4,4′-methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), 4,4′-methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), 4,4′-methylenebis(2,6-dimethylcyclohexylamine), 4,4′-methylenebis(2,6-diethylcyclohexylamine), 4,4′-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(tert-pentyl )Cyclohexylamine), 4,4′-Methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4′-Methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4′-Methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4′-Methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4′-Methylenebis(2,6-di(sec-isopentyl)cyclohexylamine) Methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), 4,4 The method of item 11, selected from the group consisting of '-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), and 4,4'-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine).

[0131] Item 13. The amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~3 It is alkyl; A is cyclic, polycyclic or acyclic linear or branched C 6~20Represents polyamines; R 1 and R 2 C is linear or branched 1~9 The method of item 9, comprising at least one amine curing agent having an alkyl substituent, a cyclic substituent having a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3.

[0132] Item 14. The above-mentioned at least one amine curing agent is N,N'-dialkylated 4,4-diaminodicyclohexylmethane, N,N'-dialkylated isophoronediamine, N,N'-dialkylated 4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine, N,N'-dialkylated ethylenediamine, N,N'-dialkylated propylenediamine, N,N'-dialkylated 1,4-butanediamine, N,N'-dialkylated 1,5-pentanediamine, N,N'-dialkylated 1,6-hexanediamine, N,N'-dialkylated 4-(aminomethyl)octane-1,8-diamine. The method of item 13, wherein the alkyl group is selected from the group consisting of mine, N,N′-dialkylated 1,8-octyldiamine, N,N′,N″-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N′,N″-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof; wherein the alkyl group is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpenta-2-yl and 2,2,6,6-tetramethylpiperidine-4-yl.

[0133] Item 15. The amine composition has the following structure: [ka] [In the formula, R is H or linear or branched C] 1~6 It is an alkyl group, and A is a cyclic, polycyclic, or acyclic linear or branched C 6~20The method of item 10, comprising a reaction product of ii) at least one amine curing agent having [representing a polyamine, n=1 to 6 and m=1 to 3] and ii) at least one α,β-unsaturated carboxylic acid ester.

[0134] Item 16. The amine composition is i) 4,4-diaminodicyclohexylmethane or 4,4′-methylenebis(2-methylcyclohexylamine) or 4,4′-methylenebis(2-ethylcyclohexylamine), or 4,4′-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-butyl)cyclohexylamine), and This is 4,4′-methylenebis(2-(isobutyl)cyclohexylamine), or 4,4′-methylenebis(2-(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(neopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-pentyl (2-(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(2-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4′-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4 ′-Methylenebis(2-(isohexyl)cyclohexylamine), or 4,4′-Methylenebis(2-(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-Methylenebis(2-(2-methylpenta-1-yl)cyclohexylamine), or 4,4′-Methylenebis(2,6-dimethylcyclohexylamine), or 4,4′-Methylenebis(2,6-diethylcyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(n-butyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4′-Methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4′-Methylenebis Lenbis(2,6-di(t-butyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4′ -Methylenebis(2,6-di(3-pentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4 ,4′-methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-1-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(4-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-2-yl)cyclohexylamine), or 4,4′-methylenebis(2,6-di(2-methylpenta-1-yl)cyclohexylamine), or 4-methylcyclohexane-1,The method of item 15 comprises a reaction product of 3-diamine (MCHD), or ethylenediamine (EDA), or propylenediamine (PDA), or 1,4-butanediamine (BDA), or 1,5-pentanediamine (PeDA), or 1,6-hexanediamine (HMDA), or 4-(aminomethyl)octane-1,8-diamine, or 1,8-octyldiamine, or any mixture thereof, and ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

[0135] Item 17. Any method according to items 9 to 16, wherein the block prepolymer or reactive block prepolymer comprises at least one of diisocyanate prepolymers, polyisocyanate prepolymers, and polyisocyanate oligomers.

[0136] Item 18. The method of Item 17, wherein the block prepolymer or reactive block prepolymer is produced by condensing an isocyanate or polyisocyanate with a polyol or polyamine or a combination thereof to produce a polyurethane or polyurea, and the polyurethane / polyurea prepolymer comprises a diisocyanate prepolymer or polyisocyanate prepolymer having isocyanate functional groups as terminal groups.

[0137] Item 19. The method of Item 17, wherein the block prepolymer or reactive block prepolymer comprises a polyisocyanate oligomer produced by the reaction of at least one diisocyanate with at least one polyol.

[0138] Item 20. The method of Item 17, wherein the reactive block prepolymer is blocked by reaction of a polyisocyanate with a blocking agent selected from the group consisting of 2-(tert-butylamino)ethyl methacrylate, 2-(tert-pentylamino)ethyl methacrylate, 2-(tert-hexylamino)ethyl methacrylate, 3-(tert-butylamino)propyl methacrylate, and mixtures thereof.

[0139] Item 21. The method of Item 17, wherein the diisocyanate prepolymer, polyisocyanate prepolymer, or polyisocyanate oligomer is blocked with 2-formyloxyethyl (meth)acrylate.

[0140] Item 22. Any method of Items 9 to 21, wherein the reactive diluent comprises acrylates, methacrylates, styrenes, acrylic acids, vinylamides, vinyl ethers, vinyl esters, acrylonitriles, styrenes, divinylbenzenes, vinyltoluenes, methyl acrylates, ethyl acrylates, butyl acrylates, methyl (meth)acrylates, amine (meth)acrylates, and their derivatives and combinations thereof.

[0141] Item 23. Any method of items 9 to 21, wherein the chain extender comprises at least a diol, diamine or dithiol, selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; corresponding diamines and dithiol analogs thereof; lysine ethyl esters, arginine ethyl esters, β-alanine-based diamines, and random copolymers or block copolymers produced from at least one diisocyanate and at least one diol, diamine or dithiol.

[0142] Item 24. Any method according to items 9 to 21, wherein the photoinitiator is a benzoyl chromophore compound, a morpholine aminoketone, or a benzoylphosphine oxide.

[0143] Item 25. Any method described in items 9-21, wherein the light is ultraviolet light. [Examples]

[0144] Example 1 General range These examples are provided to demonstrate aspects of the present invention and are not intended to limit the scope of the appended claims. The polymers produced were essentially flexible polyurethane materials (FPU) and elastomer polyurethane materials (EPU).

[0145] Example 2 Synthesis of acrylate-block polyurethane prepolymer for resin side The procedure for producing the acrylate block polyurethane prepolymer can be carried out using the following steps. The prepolymer used is a commercially available product from COIM, Inc., known as IMUTHANE® APC-504, manufactured from isophorone diisocyanate and PTMEG (polytetramethylene glycol), with an equivalent weight of 506 equivalents / mol. For this purpose, IMUTHANE® APC-504 (375.7 g, 354 mmol) was added under nitrogen to a reaction vessel equipped with a mechanical stirrer, dropping funnel, and condenser. Isobornyl methacrylate (352 g) was then added, and the mixture was mechanically mixed until a uniform and homogeneous liquid was observed. Once the prepolymer was dissolved, the blocking agent tert-butylamino-ethyl methacrylate (131 g, 708 mmol) was added dropwise to the reaction vessel, and the reaction mixture was stirred for another 60 minutes. The progress of the reaction was monitored by ATR-FTIR (attenuated total internal reflection-FTIR). Approximately 2260 cm⁻¹ -1The absence of the isocyanate absorption band indicated complete consumption of the isocyanate and completion of the reaction. The concentration of the acrylic block polyurethane prepolymer in the isobornyl methacrylate diluent was approximately 59%.

[0146] Example 3 Synthesis of hardening agents An aliphatic curing agent was prepared from 4,4′-methylenebis(2,6-diethylaniline) by catalytic hydrogenation. For this purpose, a 40 wt% solution of 4,4′-methylenebis(2,6-diethylaniline) and a mixture of a catalyst prepared from 5 wt% Ru on 3 wt% lithium aluminate and 4 wt% Rh on 3 wt% lithium aluminate were charged into a stainless steel reactor. The reactor was purged with nitrogen, then hydrogen, and the temperature was increased to 180°C. The hydrogen pressure was increased to approximately 800 psig. This reaction was continued until absorption by hydrogenation was complete, and the catalyst was filtered to obtain a THF solution mainly of 4,4′-methylenebis(2,6-diethylcyclohexylamine). After removing THF using a rotary evaporator, 4,4′-methylenebis(2,6-diethylcyclohexylamine) was obtained in a yield of approximately 96% as a pale amber liquid.

[0147] Example 4 Synthesis of hardening agents Another aliphatic curing agent was prepared from 4,4′-methylenebis(2,6-diethylaniline) by catalytic hydrogenation. For this purpose, a 40 wt% solution of 4,4′-methylenebis(2,6-diisopropylaniline) and a mixture of a catalyst prepared from 5 wt% Ru on 3 wt% lithium aluminate and 4 wt% Rh on 3 wt% lithium aluminate were charged into a stainless steel reactor. The reactor was purged with nitrogen and then hydrogen, and the temperature was increased to 180°C. The hydrogen pressure was increased to approximately 800 psig. The reaction was continued until absorption by hydrogenation was complete, and the catalyst was filtered to obtain a THF solution mainly of 4,4′-methylenebis(2,6-diisopropylcyclohexylamine). After removing THF using a rotary evaporator, 4,4′-methylenebis(2,6-diisopropylcyclohexylamine) was obtained in a yield of approximately 98% as a pale orange liquid.

[0148] Example 5 Amine curing test of acrylic block isocyanate-based prepolymers Tests to evaluate the gelling performance of the different curing agents described above were carried out at an isocyanate / amine index of 1.0, which means that equal equivalent amounts of amine and block isocyanate were combined and reacted. The procedure for the reaction of the isocyanate block polyurethane prepolymer with 4,4′-methylenebis(2-methylcyclohexylamine) is described. A 59 wt% solution (18.2 g, equivalent weight = 1214.2 g / eq) of the acrylic block polyurethane prepolymer in isobornyl methacrylate prepared in Example 2 was mixed with 1.79 g (equivalent weight = 119 eq / eq) of 4,4′-methylenebis(2-methylcyclohexylamine) at a high shear rate (2000 rpm) for 40 seconds. Approximately 18 g of this mixture was added to a container and placed in a thermocell chamber preheated to 40°C in a viscometer. The spindle of the viscometer was lowered and placed in the center of the chamber, and the test was started. When the aforementioned resin was heated to 40°C, its viscosity decreased until it leveled out, and then began to increase until the end of the test. The initial viscosity (η) of this experiment iThe value was selected 30 minutes after the start of the test, from the lowest value during heating. The viscosity change was monitored over time for the curing agents of Example 3 and Example 4 following a similar procedure.

[0149] Table I: Time required to double the viscosity of various hardeners from their initial value [Table 1]

[0150] Table I shows that increasing the steric hindrance at the vicinal carbon atoms results in a longer curing time for the resin. Furthermore, increasing the steric hindrance leads to an overall decrease in the viscosity of the resin-curing agent mixture.

[0151] Example 6 Dual polymerization: Evaluation of the physical properties of specimens obtained by radical polymerization followed by amine thermosetting. Radical polymerization of the acrylic block polyurethane prepolymer / amine curing agent mixture was achieved by exposing the resin / amine mixture to UV light supplied by a UV lamp that was switched on and reached maximum brightness for at least 10 minutes before use. The procedures for the dual polymerization and stepwise polymerization were as follows: The resin of Example 2 was mixed with 0.5 wt% of a photoinitiator (PPO, 0.125 g). The resin and initiator were mixed in a high-speed mixer (2000 rpm) for 40 seconds. A polyethylene mold 5″×5″×1 / 8″ was coated with a release agent, and 25 g of polymerizable material was prepared by mixing it with an equivalent amount of the resin (the resin of Example 2 and PPO) and the amine curing agent. The mold was placed on a flat surface with an adjustable platform, and the polymerizable material was introduced into the mold near the UV lamp. Irradiation of the plate was continued until the surface was fully cured, as measured by touching different parts of the polymer mass with a wooden tongue depressor, and the surface was tack-free, indicating completion of photopolymerization. The mold was then placed in an oven preheated to 125°C for 2-4 hours. After heat curing, the plate was easily removed from the mold using a metal tab. The plate must remain in the mold during the curing process, otherwise the specimen will warp during this process. Physical testing of the dual-cured plate was performed according to ASTM standards. The D638 test was used to compare the performance of various amines when thermosetting the radically polymerized resin from the previous step described above. The test measured modulus, tensile strength, and elongation at break percentage, and the following bar graph shows the results for the various amines.

[0152] Figures 1 and 2 show the tensile strength and elongation at break values ​​of various specimens produced by the dual polymerization process described above using amine curing agents with different degrees of steric hindrance on their vicinal carbons. It can be seen that acceptable values ​​were obtained in all cases. In particular, increasing the steric hindrance on the vicinal carbons improves tensile strength when using 4,4'-methylenebis(2,6-dimethylcyclohexylamine) instead of many other conventional amines, such as 4,4'-methylenebis(cyclohexylamine) and 4,4'-methylenebis(2-methylcyclohexylamine) (curing agents 1 and 2 in Figures 1 and 2, respectively).

[0153] Example 7 Synthesis of curing agents produced by blocking primary amines with α,β-unsaturated esters. Another aliphatic curing agent was prepared from ethyl acrylate and PACM. Ethyl acrylate (EA, 103.6 g, 1.035 mol, 2.10 equivalents) was slowly added to PACM (103.71 g, 0.4930 mol) in THF. A slight reaction exothermic reaction was observed during the addition of EA. Monosubstituted PACM and disubstituted EA-block PACM products were identified by GC-MS analysis of the product mixture. [ka]

[0154] A similar curing agent was also prepared from PACM and diethyl maleate (DEM) by contacting stoichiometric amounts of these reagents in ethanol or THF, typically in a 2:1 DEM:PACM molar ratio, to obtain 1,1′,4,4′-tetraethyl N,N′-(methylenedi-4,1-cyclohexanediyl)bis(aspartate). [ka]

[0155] Example 8 (Predictive) Another aliphatic curing agent was prepared from ethyl acrylate and 4-methylcyclohexane-1,3-diamine (MCHD). Ethyl acrylate (EA, 103.6 g, 1.035 mol, 2.10 equivalents) was slowly added to 4-methylcyclohexane-1,3-diamine (63.1 g, 0.4930 mol) in THF. A slight reaction exothermic reaction was observed during the addition of EA. The monosubstituted block MCHD and the disubstituted EA block MCHD products were identified by GC-MS analysis of the product mixture. [ka]

[0156] Similar curing agents can be prepared from 4-methylcyclohexane-1,3-diamine and diethyl maleate by contacting stoichiometric amounts of these reagents in ethanol or THF, typically in a 2:1 DEM:MCHD molar ratio, to obtain the corresponding diamine-diethyl maleate adducts. [ka]

[0157] Example 9 (Predictive) Table II: Time required for viscosity to double from initial value in curing agents produced by amine blocking with acrylates and maleates. [Table 2]

[0158] Test specimens for evaluating physical properties are manufactured as in Example 5, and they also show improvements in physical properties, including tensile strength and elongation at break.

Claims

1. 1. Use of an amine composition for producing an object by a dual polymerization based 3D printing process, wherein the amine composition has the following structure: 【Chemical 1】 wherein R is H or a linear or branched C １～６ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ each of which is H, linear or branched C １～９ and n=1 to 6 and m=1 to 3.

2. The amine composition has the following structure: 【Chemistry 2】 wherein R is H or a linear or branched C １～６ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ is H; n=1 to 6 and m=1 to 3.

3. The at least one amine curing agent has the following structure: 【Chemistry 3】 [In the formula, R ３ is H and R ４ is a linear or branched saturated C ２～６ alkyl or R ３ =R ４ = Linear or branched saturated C １～６ The use according to claim 2, wherein the aryl group is alkyl.

4. the at least one amine curing agent is selected from the group consisting of 4,4'-methylenebis(2-ethylcyclohexylamine), 4,4'-methylenebis(2-(n-propyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4'-methylenebis(2-(n-butyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4'-methylenebis(2-(isobutyl)cyclohexylamine), 4,4'-methylenebis(2-(t-butyl)cyclohexylamine), amine), 4,4'-methylenebis(2-(n-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(neopentyl)cyclohexylamine), 4,4'-methylenebis(2-(isopentyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-isopentyl)cyclohexylamine 4,4'-methylenebis(2-(n-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(neohexyl)cyclohexylamine), 4,4'-methylenebis(2-(isohexyl)cyclohexylamine), 4,4'-methylenebis(2-(4-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2-(4-methylpent-2-yl)cyclohexylamine), cyclohexylamine), 4,4'-methylenebis(2-(2-methylpent-2-yl)cyclohexylamine), 4,4'-methylenebis(2-(2-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2,6-dimethylcyclohexylamine), 4,4'-methylenebis(2,6-diethylcyclohexylamine), 4,4'-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(n-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(tert-pentyl )cyclohexylamine), 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine cyclohexylamine), 4,4'-methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isohexyl)cyclohexylamine), 4,4'- The use according to claim 3, wherein the hydroxybenzoate is selected from the group consisting of methylenebis(2,6-di(4-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(4-methylpent-2-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(2-methylpent-2-yl)cyclohexylamine), and 4,4'-methylenebis(2,6-di(2-methylpent-1-yl)cyclohexylamine).

5. The amine composition has the following structure: 【Chemistry 4】 wherein R is H or a linear or branched C １～３ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ is a linear or branched C １～９ 2. The use of claim 1, comprising at least one amine curing agent having an alkyl substituent, a cyclic substituent with a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3.

6. The at least one amine curing agent is selected from the group consisting of N,N'-dialkylated 4,4-diaminodicyclohexylmethane, N,N'-dialkylated isophoronediamine, N,N'-dialkylated 4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine, N,N'-dialkylated ethylenediamine, N,N'-dialkylated propylenediamine, N,N'-dialkylated 1,4-butanediamine, N,N'-dialkylated 1,5-pentanediamine, N,N'-dialkylated 1,6-hexanediamine, and N,N'-dialkylated 4-(aminomethyl)octane-1,8-diamine. , N,N'-dialkylated 1,8-octyldiamine, N,N',N"-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N',N"-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof; wherein the alkyl groups are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpent-2-yl, and 2,2,6,6-tetramethylpiperidin-4-yl.

7. The amine composition comprises i) an amine having the following structure: 【Chemistry 5】 wherein R is H or a linear or branched C １～６ alkyl, and A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ wherein n=1 to 6 and m=1 to 3] and ii) at least one α,β-unsaturated carboxylic acid ester.

8. the amine composition is i) 4,4-diaminodicyclohexylmethane or 4,4'-methylenebis(2-methylcyclohexylamine or 4,4'-methylenebis(2-ethylcyclohexylamine), or 4,4'-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-butyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-butyl)cyclohexylamine), or 4,4 '-methylenebis(2-(isobutyl)cyclohexylamine), or 4,4'-methylenebis(2-(t-butyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(neopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(isopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-pentyl)cyclohexylamine) cyclohexylamine), or 4,4'-methylenebis(2-(3-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(2-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4'-methylenebis(2 -(isohexyl)cyclohexylamine), or 4,4'-methylenebis(2-(4-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2-(4-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2-(2-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2-(2-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-dimethylcyclohexylamine), or 4,4'-methylenebis(2,4,4'-methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4'-methylenebis(2,6- di(t-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4'-methylenebis bis(2,6-di(3-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4,4' -methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(4-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(4-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-methylpent-1-yl)cyclohexylamine), or 4-methylcyclohexane-1,8. The use according to claim 7, comprising the reaction product of 3-diamine (MCHD), or ethylenediamine (EDA), or propylenediamine (PDA), or 1,4-butanediamine (BDA), or 1,5-pentanediamine (PeDA), or 1,6-hexanediamine (HMDA), or 4-(aminomethyl)octane-1,8-diamine, or 1,8-octyldiamine, or any mixture thereof, with ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

9. a) contacting a polymerizable liquid in the presence of at least one of a reactive diluent, a photoinitiator, and a chain extender in an optically transparent build surface, wherein the polymerizable liquid comprises at least one of i) a monomer, ii) a block oligomer or a reactive block oligomer, or iii) a block prepolymer or a reactive block prepolymer; b) irradiating the build surface with light passing through a radiation-transparent window to form a solid scaffold object; and c) heating or microwaving the solid scaffold object to induce polymerization of the at least one of the monomer, the block oligomer, the reactive block oligomer, the block prepolymer, or the reactive block prepolymer with an amine composition to form a three-dimensional object.

1. A method of forming a three-dimensional object, comprising: 【Chemistry 6】 wherein R is H or a linear or branched C １～６ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ each of which is H, linear or branched C １～９ and n=1 to 6 and m=1 to 3.

10. The amine composition has the following structure: 【Chemistry 7】 wherein R is H or a linear or branched C １～６ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ is H; n=1-6, and m=1-3.

11. The amine composition has the following structure: 【Chemistry 8】 [In the formula, R ３ is H and R ４ is a linear or branched saturated C ２～６ alkyl or R ３ =R ４ = Linear or branched saturated C １～６ 11. The method of claim 10, comprising at least one amine curing agent having a C1-C1 alkyl group.

12. the at least one amine curing agent is selected from the group consisting of 4,4'-methylenebis(2-ethylcyclohexylamine), 4,4'-methylenebis(2-(n-propyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-propyl)cyclohexylamine), 4,4'-methylenebis(2-(n-butyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-butyl)cyclohexylamine), 4,4'-methylenebis(2-(isobutyl)cyclohexylamine), 4,4'-methylenebis(2-(t-butyl)cyclohexylamine), amine), 4,4'-methylenebis(2-(n-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(tert-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(neopentyl)cyclohexylamine), 4,4'-methylenebis(2-(isopentyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(3-pentyl)cyclohexylamine), 4,4'-methylenebis(2-(sec-isopentyl)cyclohexylamine 4,4'-methylenebis(2-(n-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(2-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(3-hexyl)cyclohexylamine), 4,4'-methylenebis(2-(neohexyl)cyclohexylamine), 4,4'-methylenebis(2-(isohexyl)cyclohexylamine), 4,4'-methylenebis(2-(4-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2-(4-methylpent-2-yl)cyclohexylamine), cyclohexylamine), 4,4'-methylenebis(2-(2-methylpent-2-yl)cyclohexylamine), 4,4'-methylenebis(2-(2-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2,6-dimethylcyclohexylamine), 4,4'-methylenebis(2,6-diethylcyclohexylamine), 4,4'-methylenebis(2,6-di(n-propyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-propyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(n-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isobutyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(t-butyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(n-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(tert-pentyl)cyclohexylamine cyclohexylamine), 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-pentyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine) hexylamine), 4,4'-methylenebis(2,6-di(n-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(2-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(3-hexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(neohexyl)cyclohexylamine), 4,4'-methylenebis(2,6-di(isohexyl)cyclohexylamine), 4, The method of claim 11, wherein the hydroxyl group is selected from 4'-methylenebis(2,6-di(4-methylpent-1-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(4-methylpent-2-yl)cyclohexylamine), 4,4'-methylenebis(2,6-di(2-methylpent-2-yl)cyclohexylamine), and 4,4'-methylenebis(2,6-di(2-methylpent-1-yl)cyclohexylamine).

13. The amine composition has the following structure: 【Chemistry 9】 wherein R is H or a linear or branched C １～３ A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ represents a polyamine; R １ and R ２ is a linear or branched C １～９ 10. The method of claim 9, comprising at least one amine curing agent having an alkyl substituent, a cyclic substituent with a heteroatom, or an aromatic substituent; and n=1 to 6 and m=1 to 3.

14. The at least one amine curing agent is selected from the group consisting of N,N'-dialkylated 4,4-diaminodicyclohexylmethane, N,N'-dialkylated isophoronediamine, N,N'-dialkylated 4,4'-methylenebis(2-methylcyclohexylamine), N,N'-dialkylated 4-methylcyclohexane-1,3-diamine, N,N'-dialkylated ethylenediamine, N,N'-dialkylated propylenediamine, N,N'-dialkylated 1,4-butanediamine, N,N'-dialkylated 1,5-pentanediamine, N,N'-dialkylated 1,6-hexanediamine, and N,N'-dialkylated 4-(aminomethyl)octane-1,8-diamine. , N,N'-dialkylated 1,8-octyldiamine, N,N',N"-trialkylated 4-(aminomethyl)octane-1,8-diamine, N,N',N"-trialkylated tris(2-aminoethyl)amine, tris(3-aminopropyl)amine, and mixtures thereof; wherein the alkyl groups are selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, pentyl, neopentyl, isopentyl, sec-pentyl, sec-isopentyl, 4-methylpent-2-yl, and 2,2,6,6-tetramethylpiperidin-4-yl.

15. The amine composition comprises i) an amine having the following structure: 【Chemistry 10】 wherein R is H or a linear or branched C １～６ alkyl, and A is a cyclic, polycyclic or acyclic, linear or branched C ６～２０ wherein n=1 to 6 and m=1 to 3; and ii) the reaction product of at least one amine curing agent having the formula (I) and (II) above; and ii) at least one α,β-unsaturated carboxylic acid ester.

16. the amine composition is i) 4,4-diaminodicyclohexylmethane or 4,4'-methylenebis(2-methylcyclohexylamine) or 4,4'-methylenebis(2-ethylcyclohexylamine), or 4,4'-methylenebis(2-(n-propyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-propyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-butyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-butyl)cyclohexylamine), or 4, 4'-methylenebis(2-(isobutyl)cyclohexylamine), or 4,4'-methylenebis(2-(t-butyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(tert-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(neopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(isopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-pentyl)cyclohexylamine) xylamine), or 4,4'-methylenebis(2-(3-pentyl)cyclohexylamine), or 4,4'-methylenebis(2-(sec-isopentyl)cyclohexylamine), or 4,4'-methylenebis(2-(n-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(2-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(3-hexyl)cyclohexylamine), or 4,4'-methylenebis(2-(neohexyl)cyclohexylamine), or 4,4'-methylenebis( 2-(isohexyl)cyclohexylamine), or 4,4'-methylenebis(2-(4-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2-(4-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2-(2-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2-(2-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-dimethylcyclohexylamine), or 4,4'-methylenebis(2,4,4'-methylenebis(2,6-di(n-propyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-propyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(isobutyl)cyclohexylamine), or 4,4'-methylenebis(2,6- di(t-butyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(tert-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(neopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(isopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-pentyl)cyclohexylamine), or 4,4'-methylenebis bis(2,6-di(3-pentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(sec-isopentyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(n-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(3-hexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(neohexyl)cyclohexylamine), or 4,4' -methylenebis(2,6-di(isohexyl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(4-methylpent-1-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(4-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-methylpent-2-yl)cyclohexylamine), or 4,4'-methylenebis(2,6-di(2-methylpent-1-yl)cyclohexylamine), or 4-methylcyclohexane-1,16. The method of claim 15, comprising the reaction product of 3-diamine (MCHD), or ethylenediamine (EDA), or propylenediamine (PDA), or 1,4-butanediamine (BDA), or 1,5-pentanediamine (PeDA), or 1,6-hexanediamine (HMDA), or 4-(aminomethyl)octane-1,8-diamine, or 1,8-octyldiamine, or any mixture thereof, with ii) methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, dimethyl maleate, diethyl maleate, dipropyl maleate, dibutyl maleate, dipentyl maleate, dihexyl maleate, dimethyl fumarate, diethyl fumarate, dipropyl fumarate, dibutyl fumarate, dipentyl fumarate, dihexyl fumarate, or any mixture thereof.

17. 17. The method of any one of claims 9 to 16, wherein the blocked prepolymer or reactive blocked prepolymer comprises at least one of a diisocyanate prepolymer, a polyisocyanate prepolymer, and a polyisocyanate oligomer.

18. 18. The method of claim 17, wherein the blocked prepolymer or reactive blocked prepolymer comprises a diisocyanate prepolymer or polyisocyanate prepolymer prepared by condensing an isocyanate or polyisocyanate with a polyol or polyamine or a combination of both to produce a polyurethane or polyurea, the polyurethane / polyurea prepolymer being terminated with isocyanate functionality.

19. 18. The method of claim 17, wherein the blocked prepolymer or reactive blocked prepolymer comprises a polyisocyanate oligomer prepared by the reaction of at least one diisocyanate with at least one polyol.

20. 18. The method of claim 17, wherein the reactive blocked prepolymer is blocked by reaction of a polyisocyanate with a blocking agent selected from the group consisting of 2-(tert-butylamino)ethyl methacrylate, 2-(tert-pentylamino)ethyl methacrylate, 2-(tert-hexylamino)ethyl methacrylate, 3-(tert-butylamino)propyl methacrylate, and mixtures thereof.

21. The method of claim 17, wherein the diisocyanate prepolymer, polyisocyanate prepolymer, or polyisocyanate oligomer is blocked with 2-formyloxyethyl (meth)acrylate.

22. 17. The method of any one of claims 9 to 16, wherein the reactive diluent comprises acrylate, methacrylate, styrene, acrylic acid, vinylamide, vinyl ether, vinyl ester, acrylonitrile, styrene, divinylbenzene, vinyltoluene, methyl acrylate, ethyl acrylate, butyl acrylate, methyl (meth)acrylate, amine (meth)acrylate, and derivatives thereof and combinations thereof.

23. 17. The method of any one of claims 9 to 16, wherein the chain extender comprises at least a diol, diamine, or dithiol selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,2-cyclohexanedimethanol, 1,4-cyclohexanedimethanol; the corresponding diamine and dithiol analogs thereof; lysine ethyl ester, arginine ethyl ester, β-alanine-based diamines, and random or block copolymers prepared from at least one diisocyanate and at least one diol, diamine, or dithiol.

24. 17. The method of any one of claims 9 to 16, wherein the photoinitiator is a benzoyl chromophore-based compound, a morpholine amino ketone, or a benzoyl phosphine oxide.

25. 17. The method of any one of claims 9 to 16, wherein the light is ultraviolet light.

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