Adhesive / coating formulations suitable for 3D printing on textiles

Abstract

Curable additive formulations that can be used to print three-dimensional objects onto substrates such as fabrics, and methods and systems that utilize the same, are provided. These additive formulations include combinations of mono- and multi-functional materials that provide suitable adhesive materials or structures and / or suitable coverage on the printed object.

Description

[Technical Field]

[0001] (Related Applications) This application claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 63 / 436,186, filed December 30, 2022, the contents of which are incorporated herein by reference in their entirety.

[0002] This application is also related to U.S. Provisional Patent Application No. 63 / 436,172, filed December 30, 2022, and U.S. Provisional Patent Application No. 63 / 436,181, filed December 30, 2022, the contents of all of which are incorporated by reference as if fully set forth in their entireties herein.

[0003] This application is also related to International Design Application No. DM / 227028, the contents of which are incorporated by reference in their entirety as if fully set forth herein.

[0004] This application is also related to a concurrently filed, co-pending, and commonly assigned PCT International Patent Application entitled "FORMULATIONS FOR THREE-DIMENSIONAL PRINTING ON FABRIC," Attorney Docket No. 97935, which claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 63 / 436,172. This application is also related to a concurrently filed, co-pending, and commonly assigned PCT International Patent Application entitled "METHOD AND SYSTEM FOR THREE-DIMENSIONAL PRINTING ON FABRIC," Attorney Docket No. 97942, which claims the benefit of priority under 35 U.S.C. § 119(e) of U.S. Provisional Patent Application No. 63 / 436,181. The contents of all of the above applications are incorporated by reference as if fully set forth in their entirety herein.

[0005] The present invention, in some embodiments thereof, relates to three-dimensional printing, and more particularly to compositions usable for three-dimensional printing on textiles, including, but not limited to, additive compositions providing adhesive and / or coating materials, and methods of utilizing the same. [Background technology]

[0006] Additive manufacturing (AM) is a technology that allows shaped structures to be produced directly from computer data through additive forming steps. The basic operation of any AM system consists of slicing a three-dimensional computer model into thin cross-sectional sections, converting the results into two-dimensional positional data, and feeding that data to a controller that builds the three-dimensional structure layer by layer.

[0007] Additive manufacturing involves many different approaches to fabrication, such as three-dimensional (3D) printing, such as 3D inkjet printing, electron beam melting, stereolithography, selective laser sintering, thin film deposition modeling, and fused deposition modeling.

[0008] Some 3D printing processes, such as 3D inkjet printing, are performed by inkjet deposition of a build material layer by layer. Thus, the build material is ejected from an ejection head having a set of nozzles and deposited in layers onto a receiving medium. Depending on the build material, the layers can then be cured, or solidified, using an appropriate device, optionally after planarization by a leveling device.

[0009] Various three-dimensional printing techniques exist and are disclosed, for example, in U.S. Pat. Nos. 6,259,979, 6,569,373, 6,658,314, 6,850,334, 6,863,859, 7,183,335, 7,209,797, 7,225,045, 7,300,619, 7,500,846, 9,031,680, 9,227,365, U.S. Patent Application Publication No. 2006 / 0054039, WO 2016 / 009426, and WO 2022 / 024114, all of which are commonly assigned and are incorporated herein by reference in their entireties.

[0010] A printing system used for additive manufacturing may include a receiver medium and one or more print heads. The receiver medium may be, for example, a fabrication tray that may include a horizontal surface for supporting material ejected from the print head. The print head may be, for example, an inkjet head having multiple ejection nozzles arranged in one or more rows along the longitudinal axis of the print head. The print head may be arranged such that its longitudinal axis is substantially parallel to the indexing direction. The printing system may further include a controller, such as a microprocessor, that can control the printing process, including moving the print head according to a predefined scanning plan (e.g., a CAD configuration converted into a stereolithography (STL) format and programmed into the controller). The print head may include multiple jetting nozzles that eject material onto the receiver medium to generate layers representing a cross-section of the 3D object.

[0011] In addition to the print head, there may be a source of curing energy for curing the ejected build material. The curing energy is typically radiation, such as UV radiation.

[0012] Additionally, the printing system may include a leveling device for flattening and / or adjusting the height of each layer after it has been deposited and at least partially solidified and before the next layer is deposited.

[0013] Build materials include modeling materials and support materials, each capable of forming an object and a temporary support structure that supports the object during construction.

[0014] Build material (which may include one or more materials) is deposited to form the desired object or objects, and support material (which may also include one or more materials) is used in conjunction with build material elements or alone to provide support structure for specific areas of the object during construction, for example, to ensure proper vertical positioning of the next object layer when the object includes overhanging features or shapes such as curved shapes, negative angles, voids, etc.

[0015] Both the build material and the support material are preferably liquid at the operating temperature at which they are dispensed and then hardened to form the desired layer shape, typically by exposure to curing energy (e.g., UV curing). After printing is complete, the support structure is removed to reveal the final shape of the fabricated 3D object.

[0016] To be compatible with most commercially available print heads utilized in 3D inkjet printing systems, the uncured build material should be characterized by a relatively low viscosity (e.g., Brookfield viscosity of up to 50 centipoise or up to 35 centipoise, preferably 8-25 centipoise) at operating (e.g., jetting) temperatures; a surface tension of about 25 to about 55 Dyne / cm, preferably about 20 or about 25 to about 40 Dyne / cm; Newtonian liquid behavior; and high reactivity to selected curing conditions to enable rapid solidification of the jetted layer upon exposure to the curing conditions in one minute or less, preferably 20 seconds or less.

[0017] In 3D inkjet printing processes such as Polyjet® (Stratasys® Limited, Israel), build material is selectively jetted from one or more printheads and deposited in successive layers onto a fabrication tray according to a predetermined configuration defined by a software file.

[0018] WO 2022 / 024114 describes a three-dimensional printing system that includes a nozzle array for dispensing build material, a work tray, a fixture for applying fabric to the work tray, and a computerized controller for operating the nozzle array for dispensing build material onto the applied fabric. An imaging system can be arranged to image the fabric placed on the work tray, image data from the imaging system can be processed to identify patterns on the fabric, and the nozzles can dispense build material at locations selected relative to the identified features. Summary of the Invention

[0019] According to one aspect of some embodiments of the present invention, there is provided an additive formulation for use in combination with a build material formulation in three-dimensional printing of objects on a fabric. According to embodiments of the present invention, the additive formulation includes at least one monofunctional curable material characterized by at least one polar group capable of interacting with surface functional groups in the fabric and a glass transition temperature (Tg) of less than 50°C, in an amount of 85-90 wt% of the total weight of the additive formulation, and at least one multifunctional curable material characterized by a Tg of less than 50°C, in an amount of 10-15 wt% of the total weight of the additive formulation.

[0020] According to any of the embodiments described herein, the additive formulation is characterized by at least one of a viscosity ranging from about 15 to about 30 centipoise (mP·sec), or from about 15 to about 25 centipoise (mP·sec), or from about 15 to about 20 centipoise (mP·sec); a surface tension ranging from about 20 to about 40 Dyne / cm, preferably from about 20 to about 30 Dyne / cm, and more preferably from about 26 to about 28 Dyne / cm; and a fabric adhesion level of at least 20 N / cm.

[0021] According to any of the optional embodiments described herein, the additive formulation is an adhesive (priming) formulation that upon solidification provides an adhesive structure on the fabric.

[0022] According to any of the optional embodiments described herein, the additive formulation is a coating formulation that upon solidification provides a coating for an object or a portion of the object.

[0023] According to any of the embodiments described herein, each of the monofunctional curable material and the multifunctional curable material is a UV curable material.

[0024] According to any of the embodiments described herein, each of the monofunctional curable material and the multifunctional curable material is a (meth)acrylate material.

[0025] According to any of the embodiments described herein, the additive formulation further comprises a photoinitiator.

[0026] According to any of the embodiments described herein, the photoinitiator is a bis(acyl)phenyloxide (BAPO) type photoinitiator.

[0027] According to any of the embodiments described herein, the amount of photoinitiator is from about 1.5 to about 2.5 weight percent of the total weight of the additive formulation.

[0028] According to any of the embodiments described herein, the at least one monofunctional curable material is collectively represented by Formula I: YLX Formula I wherein Y is a terminal group, optionally and preferably selected from alkyl, including straight-chain and branched, substituted or unsubstituted alkyl, aryl, heteroaryl, cycloalkyl, alicyclic heterocycle, hydroxy, alkoxy, aryloxy, and amine; X is a polymerizable group, optionally and preferably a (meth)acrylate group; L is a hydrocarbon having 2 to 10 carbon atoms, preferably 2 to 8 or 2 to 6 carbon atoms in length, substituted with at least one hydroxy group and optionally interrupted by one or more heteroatoms capable of forming hydrogen bonds with the hydroxy group;

[0029] According to any of the embodiments described herein, X is a (meth)acrylate group and the monofunctional curable material is represented by Formula Ia:

[0030] [ka] wherein R1 is hydrogen or alkyl (e.g., methyl).

[0031] According to any of the embodiments described herein, Y is aryloxy (eg, phenoxy).

[0032] According to any of the embodiments described herein, L is a hydrocarbon of 2 to 6 carbon atoms substituted with at least one hydroxy group.

[0033] According to any of the embodiments described herein, the at least one multifunctional curable material comprises a difunctional curable material characterized by a Tg.

[0034] According to any of the embodiments described herein, the at least one multifunctional curable material comprises a multifunctional (eg, difunctional) aliphatic meth(acrylate) characterized by a Tg.

[0035] According to any of the embodiments described herein, the additive formulation further comprises at least one of a polymerization inhibitor, a surfactant, a dispersant, and a pigment and / or a dye.

[0036] According to any of the embodiments described herein, the additive formulation further comprises a surfactant, wherein the surfactant comprises a curable group (e.g., a UV-curable group such as a (meth)acrylate group).

[0037] According to any of the embodiments described herein, the amount of surfactant is from about 0.05 to about 0.5 wt % of the total weight of the additive formulation.

[0038] According to an aspect of some embodiments of the present invention, there is provided a method for three-dimensional printing an object on a fabric, the method comprising: forming the object by dispensing a plurality of layers in a construction pattern corresponding to a shape of the object, wherein forming each layer of at least some of the plurality of layers comprises dispensing at least one build formulation and exposing the dispensed build formulation to curing conditions to form a hardened build material, thereby printing the object; This method further Dispensing a stack of layers onto the fabric in a configuration pattern corresponding to the shape of the bottom surface of the object, prior to dispensing at least one build material formulation, wherein the dispensing for each layer of the stack is a dispensing of an additive formulation as described in any respective embodiment herein and any combination thereof, and exposing each of the layers or the stack of layers to curing conditions to form a solidified adhesive material (adhesive structure); and / or Dispensing a stack of layers onto the printed object in a configuration pattern corresponding to the shape of an outermost surface of the object or portion of the object after dispensing at least one build material formulation and exposing it to curing conditions, wherein the dispensing for each layer of the stack is the dispensing of an additive formulation as described in any respective embodiment herein and any combination thereof; and exposing each of the layers or stack of layers to curing conditions to form a solidified coating material on the printed object or portion of the printed object.

[0039] According to an aspect of some embodiments of the present invention, there is provided a method of forming a bonded structure on a fabric, the method comprising dispensing a stack of multiple layers onto the fabric in a configured pattern corresponding to a shape of the bonded structure, wherein the dispensing for at least some of the, or each, layer of the stack is a dispensing of an additive formulation as described in any respective embodiment herein and any combination thereof, and exposing each of the multiple layers or stack of multiple layers to curing conditions, thereby forming the bonded structure.

[0040] According to an aspect of some embodiments of the present invention, there is provided a method of making a fabric for three-dimensional printing of an object thereon, the method comprising: forming an adhesive structure on the fabric in a structured pattern corresponding to a shape of a bottom surface of the object; dispensing a stack of multiple layers onto the fabric in the structured pattern, wherein the dispensing for at least some or each layer of the stack is a dispensing of an additive formulation as described in any respective embodiment herein, and any combination thereof; and exposing each of the multiple layers or the stack of multiple layers to curing conditions to form a solidified adhesive material (the adhesive structure).

[0041] According to an aspect of some embodiments of the present invention, there is provided a method of forming a coating on a three-dimensional object, or portion of the object, printed on a fabric, the method comprising: dispensing a stack of multiple layers onto the printed object in a configuration pattern corresponding to a shape of an outermost surface of the object or portion of the object, wherein the dispensing for each layer of the stack is a dispensing of an additive formulation as described in any respective embodiment herein and any combination thereof; and exposing each of the multiple layers or the stack of multiple layers to curing conditions to form a solidified coating material on the printed object or portion of the object.

[0042] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Exemplary methods and / or materials are described below; however, methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of this invention. In case of conflict, the present specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be necessarily limiting.

[0043] Implementation of the method and / or system of embodiments of the present invention may involve performing or completing selected tasks manually, automatically, or a combination thereof. Furthermore, depending on the actual instrumentation and installation of the method and / or system embodiments of the present invention, some selected tasks may be performed by hardware, software, firmware, or a combination thereof using an operating system.

[0044] For example, hardware for performing selected tasks according to embodiments of the present invention may be implemented as a chip or circuit. With respect to software, selected tasks according to embodiments of the present invention may be implemented as a plurality of software instructions executed by a computer using any suitable operating system. In exemplary embodiments of the present invention, one or more tasks according to exemplary embodiments of the methods and / or systems described herein are performed by a data processor, such as a computing platform, executing a plurality of instructions. Optionally, the data processor includes volatile memory for storing instructions and / or data, and / or non-volatile storage (e.g., a magnetic hard disk and / or removable media) for storing instructions and / or data. Optionally, a network connection is also provided. A display and / or user input device, such as a keyboard or mouse, are also optionally provided.

[0045] Some embodiments of the present invention are herein described, by way of example only, with reference to the accompanying drawings. While specific reference will now be made to the drawings in detail, it is emphasized that the particulars shown are by way of example and for purposes of illustrative discussion of embodiments of the invention. In this regard, the description taken together with the drawings will make apparent to those skilled in the art how embodiments of the invention may be carried out. [Brief explanation of the drawings]

[0046] [Figure 1A] FIG. 1 is a schematic diagram of an additive manufacturing system according to some embodiments of the present invention. [Figure 1B] FIG. 1 is a schematic diagram of an additive manufacturing system according to some embodiments of the present invention. [Figure 1C] FIG. 1 is a schematic diagram of an additive manufacturing system according to some embodiments of the present invention. [Figure 1D] FIG. 1 is a schematic diagram of an additive manufacturing system according to some embodiments of the present invention. [Figure 1E]FIG. 1 is a schematic illustration of a work tray for an additive manufacturing system, the work tray including or associated with a radiation source, in an embodiment of the present invention. [Figure 1F] FIG. 1 is a schematic illustration of a work tray for an additive manufacturing system, the work tray including or associated with a radiation source, in an embodiment of the present invention. [Figure 1G] FIG. 1 is a schematic illustration of a work tray for an additive manufacturing system, the work tray including or associated with a radiation source, in an embodiment of the present invention. [Figure 2A] FIG. 1 is a schematic diagram of a print head according to some embodiments of the present invention. [Figure 2B] FIG. 1 is a schematic diagram of a print head according to some embodiments of the present invention. [Figure 2C] FIG. 1 is a schematic diagram of a print head according to some embodiments of the present invention. [Figure 3A] FIG. 1 is a schematic diagram illustrating coordinate transformation according to some embodiments of the present invention. [Figure 3B] FIG. 1 is a schematic diagram illustrating coordinate transformation according to some embodiments of the present invention. [Figure 4A] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 4B] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 4C] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 4D] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 4E] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 4F] FIG. 1 is a schematic diagram of a fixture suitable for some embodiments of the present invention. [Figure 5A] 1A-1C are schematic diagrams of configurations in which fabric is placed on a lamp structure, according to some embodiments of the present invention. [Figure 5B] 1A-1C are schematic diagrams of configurations in which fabric is placed on a lamp structure, according to some embodiments of the present invention. [Figure 5C] 1A-1C are schematic diagrams of configurations in which fabric is placed on a lamp structure, according to some embodiments of the present invention. [Figure 6A] 1 is a flowchart illustrating a method suitable for forming a three-dimensional object on a fabric by three-dimensional printing by forming an adhesive structure, according to some embodiments of the present invention. [Figure 6B] 1 is a flowchart illustrating a method suitable for forming a three-dimensional object on a fabric by three-dimensional printing by forming an adhesive structure, according to some embodiments of the present invention. [Figure 6C] 1 is a flowchart illustrating a method suitable for forming a three-dimensional object on a fabric by three-dimensional printing by forming an adhesive structure, according to some embodiments of the present invention. [Figure 6D] 1 is a flowchart illustrating a method suitable for forming three-dimensional objects on fabrics by three-dimensional printing by forming adhesive structures and / or coatings, according to some embodiments of the present invention. [Figure 7A] FIG. 1 is a schematic diagram of a two-part structure for testing the adhesion level of a substance to a fabric, according to some embodiments of the present invention. [Figure 7B] FIG. 1 is a schematic diagram of a two-part structure for testing the adhesion level of a substance to a fabric, according to some embodiments of the present invention. [Figure 7C] FIG. 1 is a schematic diagram of a two-part structure for testing the adhesion level of a substance to a fabric, according to some embodiments of the present invention. [Figure 7D] FIG. 1 is a schematic diagram of a two-part structure for testing the adhesion level of a substance to a fabric, according to some embodiments of the present invention. [Figure 8A] 1A-1C are schematic diagrams illustrating a procedure for bending a two-part structure according to some embodiments of the present invention. [Figure 8B] 1A-1C are schematic diagrams illustrating a procedure for bending a two-part structure according to some embodiments of the present invention. [Figure 9] 1 is a bar graph showing the measured adhesion levels of exemplary adhesive (primer) formulations according to some embodiments of the present invention to fabrics of different materials and / or colors. [Figure 10] 1 shows comparative plots of exemplary adhesive (primer) formulations according to some embodiments of the present invention against fabrics of different materials and / or colors under accelerated aging conditions. [Figure 11] 1 is a bar graph illustrating adhesion levels of exemplary adhesive (primer) formulations according to some embodiments of the present invention when deposited at different thicknesses on various fabrics. [Figure 12] 1 is a bar graph showing the tear resistance of objects printed on fabric using an adhesive (primer) formulation and various build material formulations when no coating formulation is dispensed (reference example) and when coating formulation VIII described herein is dispensed at different coating thicknesses (0.05 mm and 0.1 mm). [Figure 13A] FIG. 1 is a schematic diagram of an irradiation protocol, according to some embodiments of the present invention. [Figure 13B] FIG. 1 is a schematic diagram of an irradiation protocol, according to some embodiments of the present invention. [Figure 13C] FIG. 1 is a schematic diagram of an irradiation protocol, according to some embodiments of the present invention. [Figure 13D] FIG. 1 is a schematic diagram of an irradiation protocol, according to some embodiments of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0047] The present invention, in some embodiments thereof, relates to three-dimensional printing, and more particularly, but not exclusively, to compositions usable for three-dimensional printing on textiles, including as additive compositions to provide adhesive and / or coating materials, and methods of utilizing the same.

[0048] Before describing at least one embodiment of the present invention in detail, it is to be understood that the invention is not necessarily limited in its application to the details of construction and the arrangement of components and / or methods set forth in the following description and / or illustrated in the drawings and / or examples. The invention is capable of other embodiments and of being practiced or carried out in various ways.

[0049] As used herein, the term "object" refers to the entire object or a portion thereof.

[0050] An object according to some of the present embodiments is one in which at least a portion or region thereof is made of a flexible material, and is also referred to herein as an "object made of a flexible material." The object may have some regions or portions made of a flexible material, or may be entirely made of a flexible material. The flexible material may be the same or different in different regions or portions. Furthermore, for each region or portion, or for the entire object, made of a flexible material, the flexible material may be the same or different within the region, portion, or object. When different flexible materials are used, they may differ in chemical composition and / or mechanical properties and / or visual properties (e.g., color, transparency, etc.), as further described herein.

[0051] Throughout this specification, the terms "building material formulation," "uncured build material," "uncured build material formulation," "build material," and other variations thereof, collectively refer to materials dispensed to sequentially form layers as described herein. This term includes uncured materials dispensed to form objects, i.e., one or more uncured build material formulations, and uncured materials dispensed to form supports, i.e., uncured support material formulations.

[0052] Throughout this specification, the term "hardened build material," or alternatively "solidified build material," refers to the portion of the build material that forms an object as defined herein after the dispensed build material has been cured, and optionally, if a support material has been dispensed, after the hardened support material has been removed as described herein. The hardened build material may be a single hardenable material or a mixture of two or more hardenable materials, depending on the build material formulation used in the method, as described herein.

[0053] The term "hardened build material" or "hardened build material formulation" can be considered a hardened build material when the build material consists solely of the build material formulation (without the support material formulation), i.e., the term refers to the portion of the build material that is used to provide the final object.

[0054] Throughout this specification, the term "modeling material formulation," which may also be referred to interchangeably herein as a "modeling formulation," a "model formulation," a "modeling material formulation," or simply a "formulation," refers to some or all of the build material dispensed to form an object as described herein. The modeling material formulation is (unless otherwise specified) an uncured modeling formulation that forms an object or portion thereof upon exposure to curing energy.

[0055] In some embodiments of the present invention, the build material formulation is formulated for use in three-dimensional inkjet printing and is capable of forming a three-dimensional object by itself, i.e., without the need for mixing or combining with any other substances.

[0056] The uncured build material can contain one or more build compounds and can be dispensed to create different portions of an object by curing different build compounds or different combinations thereof, such that the object is created with different cured build materials or different blends of cured build materials.

[0057] The formulations that form the build material (the build material formulation and the support material formulation) include one or more curable materials that, when exposed to curing conditions (e.g., curing energy such as radiation), form a solidified (hardened) material.

[0058] The formulations that make up the build material (the build material formulation and the support material formulation) are also referred to herein as curable formulations (e.g., a curable build material formulation or a curable support material formulation).

[0059] As used herein, a "curable material" refers to a compound (typically a monomeric or oligomeric compound, and optionally a polymeric material) that, upon exposure to curing conditions (e.g., curing energy), solidifies or hardens to form a cured material, as described herein. Curable materials are typically polymerizable materials that polymerize and / or crosslink when exposed to an appropriate energy source.

[0060] According to this embodiment, hardenable materials also encompass materials that solidify or solidify (harden) not upon exposure to curing energy, but rather upon exposure to other curing conditions (e.g., upon exposure to chemical reagents or simply upon exposure to the environment).

[0061] As used herein, the terms "hardenable" and "solidifiable" are interchangeable.

[0062] The polymerization can be, for example, free radical, cationic, or anionic polymerization, each of which is inducible upon exposure to curing energy, such as radiation, heat, etc., as described herein.

[0063] In some of any of the embodiments described herein, the curable material is a photopolymerizable material, which polymerizes and / or crosslinks upon exposure to radiation as described herein, and in some embodiments, the curable material is a UV-curable material, which polymerizes and / or crosslinks upon exposure to UV radiation as described herein.

[0064] In some embodiments, the hardenable materials described herein include photopolymerizable materials that polymerize via light-induced free radical polymerization. Alternatively, the hardenable materials are photopolymerizable materials that polymerize by light-induced cationic polymerization.

[0065] In some of any of the embodiments described herein, the curable material may be a monomer, oligomer, or short chain polymer, each of which is polymerizable and / or crosslinkable as described herein.

[0066] In some of any of the embodiments described herein, when the curable material is exposed to curing energy (e.g., radiation), the curable material solidifies (cures) by either chain extension and crosslinking, or a combination thereof.

[0067] In some of the embodiments described herein, the curable material is a monomer or mixture of monomers that can undergo a polymerization reaction to form a polymeric material when exposed to a curing energy that causes a polymerization reaction. Such curable materials are also referred to herein as monomeric curable materials.

[0068] In some of the embodiments described herein, the curable material is an oligomer or mixture of oligomers that can undergo a polymerization reaction to form a polymeric material when exposed to a curing energy that causes a polymerization reaction, and such curable materials are also referred to herein as oligomeric curable materials.

[0069] In some of the embodiments described herein, the curable material, whether monomeric or oligomeric, can be a monofunctional curable material or a multifunctional curable material.

[0070] As used herein, a monofunctional curable material contains one functional group that is capable of polymerizing when exposed to curing energy (such as radiation).

[0071] A multifunctional curable material contains two or more functional groups, e.g., two, three, four, or more functional groups, that can polymerize when exposed to curing energy. The multifunctional curable material may be, for example, a difunctional, trifunctional, or tetrafunctional curable material, each containing two, three, or four polymerizable groups (sometimes referred to herein as having a functionality of two, three, or four). The two or more functional groups of a multifunctional curable material are typically connected to each other by a linkage, as defined herein. When the linkage is an oligomeric or polymeric linkage, the multifunctional group is an oligomeric or polymeric multifunctional curable material. The multifunctional curable material is polymerizable when exposed to curing energy and / or can act as a crosslinker.

[0072] The method of the present embodiment fabricates a three-dimensional object layer by layer by forming multiple layers in a configured pattern that corresponds to the shape of the object, as described herein.

[0073] The final three-dimensional object is made from a build material, a combination of build materials, or a combination of one or more build materials with one or more support materials, or modifications thereof (e.g., after curing), all of which are well known to those skilled in the art of solid freeform fabrication.

[0074] According to an aspect of some embodiments of the present invention there is provided a method for additive manufacturing of a three-dimensional object on a fabric, wherein in some embodiments the object is made of a flexible material as described herein.

[0075] The method is generally carried out or implemented by sequentially forming a plurality of layers in a structured pattern corresponding to the shape of the object, with at least some of the layers, or each of the layers, being formed by dispensing an uncured build material comprising one or more build material formulations and exposing the dispensed build material to curing energy, thereby forming a cured build material, as described in more detail below.

[0076] In some exemplary embodiments of the present invention, objects are fabricated by dispensing a build material (uncured) comprising two or more different build material formulations, where each build material formulation is dispensed from a separate nozzle array of an inkjet printing device. The build material formulations are optionally and preferably deposited in multiple layers during the same pass of the print head. The build material formulations and / or combinations of formulations within a layer are selected according to the desired properties of the object, and as described in further detail below.

[0077] As used herein and in the art, the term "digital material" refers to a combination of two or more (e.g., model, build) materials at a microscopic scale or voxel level, such that a printed area of ​​a particular material is at the level of a few voxels or a block of voxels. Such digital materials can exhibit novel properties that are influenced by the choice of type of (e.g., model, build) material and / or the ratio and relative spatial distribution of two or more (e.g., model, build) materials.

[0078] In an exemplary digital material, the resulting hardened model material of each voxel or voxel block is independent of the resulting hardened model material of adjacent voxels or voxel blocks, and each voxel or voxel block may yield a different model material, such that the spatial combination of multiple different model materials at the voxel level results in new properties for the entire part.

[0079] In the context of digital materials, interlacing can be between single voxels, each containing a different build material (e.g., model material, build material), or between blocks of voxels. A voxel block is defined as a contiguous region occupied by n voxels that all contain the same build material (e.g., model material, build material). The boundary of this region is also defined as a set of voxels adjacent to at least one voxel containing a build material (e.g., model material, build material) that is different from the build material (e.g., model material, build material) contained in the voxels of the set. In preferred embodiments, n is less than 1000, or less than 500, or less than 100, or less than 50, or less than 10.

[0080] According to embodiments of the present invention, the method further utilizes one or more additive formulations as described herein and is carried out by dispensing these additive formulations before and / or after forming the three-dimensional object onto the fabric. According to embodiments of the present invention, the additive formulations include adhesive formulations or primer formulations that form an adhesive structure on the fabric and are dispensed before forming the object, and / or coating formulations that form a coating on the object or part of the object and are dispensed during or after forming the object.

[0081] Embodiments of the present invention relate to such additive formulations that can be used for additive manufacturing of three-dimensional objects on fabrics.

[0082] Embodiments of the present invention relate to layer-by-layer fabrication of a three-dimensional object by forming multiple layers in a construction pattern that corresponds to the shape of the object based on computer object data, which may be in any known format, including but not limited to Standard Tessellation Language (STL) or Stereolithography Contour (SLC) format, OBJ file format (OBJ), 3D Manufacturing Format (3MF), Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Interchange Format (DXF), Polygon File Format (PLY), or any other format suitable for computer-aided design (CAD).

[0083] Each layer is formed by an additive manufacturing device that scans a two-dimensional surface to pattern it. During scanning, the device visits multiple target locations on the two-dimensional layer or surface and, for each target location or group of target locations, determines whether or not to cover that target location or group of target locations with build material and what type of build material to deliver there. The decisions are made according to a computer image of the surface.

[0084] <System> A representative, non-limiting example of a system 110 suitable for additive manufacturing of an object 112, according to some embodiments of the present invention, is shown in Figure 1A. The system 110 includes an additive manufacturing apparatus 114 having a dispensing unit 16 with multiple print heads. Each head preferably includes one or more nozzle arrays 122, typically mounted in an orifice plate 121, through which a liquid build material 124 is dispensed, as shown in Figures 2A-2C described below.

[0085] Preferably, but not necessarily, apparatus 114 is a three-dimensional (3D) printing apparatus, in which case the print head is a print head and the build material is dispensed via inkjet technology. This need not be the case, as some applications may not require the additive manufacturing apparatus to use three-dimensional (3D) printing technology. Representative examples of additive manufacturing apparatuses contemplated by various exemplary embodiments of the present invention include, but are not limited to, fused deposition modeling apparatuses and fused material deposition apparatuses.

[0086] Each print head is optionally and preferably fed via one or more build material reservoirs, which may optionally include a temperature control unit (e.g., a temperature sensor and / or a heating device) and a material level sensor. To eject the build material, a voltage signal is applied to the print head, selectively depositing droplets of material through the print head nozzles, as in, for example, piezoelectric inkjet printing technology. Another example is a thermal inkjet print head. In this type of head, a heater element is in thermal contact with the build material, and a voltage signal activates the heater element to heat the build material and form a gas bubble within it. The gas bubble generates pressure within the build material, causing droplets of the build material to be ejected through the nozzles. Piezoelectric and thermal print heads are known to those skilled in the art of solid free-form molding. For any type of inkjet print head, the ejection speed of the head depends on the number of nozzles, the type of nozzle, and the applied voltage signal rate (frequency).

[0087] In some embodiments, both the nozzle arrays that eject the build material and the nozzle arrays that eject the support material are located on the same print head, while in some embodiments, the nozzle arrays that eject the build material and the nozzle arrays that eject the support material are located on separate print heads.

[0088] Preferably, but not necessarily, the total number of ejection nozzles or nozzle arrays is selected so that half of the ejection nozzles are for ejecting support material and half are for ejecting build material. That is, the number of nozzles ejecting build material is the same as the number of nozzles ejecting support material. In the representative example shown in FIG. 1A , four print heads 16 a, 16 b, 16 c, and 16 d are shown. Each head 16 a, 16 b, 16 c, and 16 d has a nozzle array. In this example, heads 16 a and 16 b may be for the build material, and heads 16 c and 16 d may be for the support material. In this manner, head 16 a may be capable of ejecting one build material, head 16 b may be capable of ejecting another build material, and heads 16 c and 16 d may both be capable of ejecting support material. In alternative embodiments, heads 16 c and 16 d may be combined into a single head with two nozzle arrays, for example, for depositing support material. In further alternative embodiments, any one or more print heads may have two or more nozzle arrays for depositing two or more materials, such as two nozzle arrays for two different build materials, or one build material and one support material, with each formulation being deposited through a different array or different number of nozzles.

[0089] However, it should be understood that this is not intended to limit the scope of the invention, and that the number of print heads (build heads) for the build material and the number of print heads (support heads) for the support material may vary. Generally, the number of nozzle arrays discharging the build material, the number of nozzle arrays discharging the support material, and the number of nozzles in each array are selected to provide a predetermined ratio a between the maximum discharging velocity of the support material and the maximum discharging velocity of the build material. The value of the predetermined ratio a is preferably selected so that the height of the build material and the height of the support material are equal in each layer formed. Typical values ​​of a are from about 0.6 to about 1.5.

[0090] As used throughout this specification, the term "about" refers to ±10%.

[0091] For example, when a=1, the total dispensing rate of the support material is approximately equal to the total dispensing rate of the build material when all nozzles in the nozzle array are operating.

[0092] The additive manufacturing device 114 may, for example, include M build heads, each with m arrays of p nozzles, and S support heads, each with s arrays of q nozzles, where M×m×p=S×s×q. Each of the M×m build arrays and S×s support arrays can be manufactured as separate physical units, and can be assembled and disassembled from a group of multiple arrays. In this embodiment, each such array optionally and preferably includes its own temperature control unit and material level sensor, and receives an individually controlled voltage for its operation.

[0093] The additive manufacturing apparatus 114 further includes a solidifying device 18. The solidifying device 18 can include any device configured to emit light, heat, or the like that can solidify the deposited material. For example, the solidifying device 18 can include one or more radiation sources. The radiation source can be, for example, an ultraviolet, visible, or infrared lamp, or other electromagnetic radiation source, or an electron beam source, depending on the build material used. In some embodiments of the present invention, the solidifying device 18 functions to harden or solidify the build material. Preferably, as shown in FIG. 1A , two solidifying devices 18 are located on either side of the dispensing head 16, so that during operation of the two solidifying devices 18, one can illuminate the target location just before the material is dispensed, and the other can illuminate the same location just after the material is dispensed. The solidifying devices 18 are configured to operate independently, both in terms of timing and irradiation intensity. Furthermore, by controlling their independent operation, synchronized irradiation protocols can be achieved, as will be further described below.

[0094] In addition to the solidification device 18, the additive manufacturing apparatus 114 optionally and preferably includes an additional radiation source 328 for evaporating the solvent. The radiation source 328 optionally and preferably generates infrared radiation. In some exemplary embodiments of the invention, the solidification device 18 includes a radiation source that generates ultraviolet radiation, and the radiation source 328 generates infrared radiation.

[0095] In some embodiments of the present invention, the additive manufacturing device 114 includes a cooling device 134, such as one or more fans.

[0096] The print head and radiation source are preferably mounted on a frame or block 128 and are operable to move back and forth over a tray 360, which preferably serves as a work surface. In some embodiments of the invention, the radiation source is mounted on the block and configured to follow the dispensing head and at least partially cure or solidify the material just dispensed by the print head. The tray 360 is positioned horizontally. According to common practice, an XYZ Cartesian coordinate system (i.e., a Cartesian coordinate system) is selected such that the XY plane is parallel to the tray 360. The tray 360 is preferably configured to move vertically (along the Z direction), typically downward. In various exemplary embodiments of the invention, the additive manufacturing apparatus 114 further includes one or more leveling devices 32, e.g., rollers 326. The leveling devices 326 function to smooth, flatten, and / or establish the thickness of a newly formed layer before a subsequent layer is formed thereon. The leveling devices 326 preferably include a waste collection device 136 for collecting excess material generated during flattening. The waste collector 136 may include any mechanism that delivers materials to a waste tank or waste cartridge.

[0097] In the schematic diagram of Figure 1A, the edges of the tray 360 are formed with straight corners, however this is not necessary and in some applications, particularly when the tray 360 is in contact with the fabric on which the object is to be printed, it may be desirable for the edges of the top surface of the tray 360 to be formed with fillets and / or chamfers (see chamfer 411 in Figures 4E and 4F).

[0098] In use, the print heads of the dispensing units 16 move in a scanning direction, referred to herein as the X direction, selectively dispensing build material in a predetermined configuration as they pass over the tray 360. The build material typically includes one or more support materials and one or more build materials. The print heads of the dispensing units 16 pass through a radiation source 126 followed by curing of the build material. Additional build material may be dispensed in a predetermined configuration as the heads move in the reverse direction back to the starting point of the deposited layer. The layer thus formed can be leveled by a leveling device 326 during the print head's forward or reverse movement. The leveling device 326 preferably follows the path of the print heads during forward and / or reverse movement. Once the print heads return to their starting points along the X direction, the print heads can be moved to another position along an index direction, referred to herein as the Y direction, to continue building the same layer by reciprocating along the X direction. Alternatively, the print head may move in the Y direction between forward and reverse moves, or after two or more forward-reverse moves. The series of scans performed by the print head to complete a single layer is referred to herein as a single scan cycle.

[0099] Once that layer is complete, the tray 360 is lowered in the Z direction to a predetermined Z level depending on the desired thickness of the next printed layer. This procedure is repeated to build the three-dimensional object 112 layer by layer.

[0100] In another embodiment, the tray 360 may be displaced in the Z direction within the layer between the forward and reverse passes of the print head of the unit 16. Such Z displacement is performed to bring the leveling device into contact with the surface in one direction and out of contact in the opposite direction.

[0101] System 110 optionally and preferably includes a supply system 330 that includes containers or cartridges of build material and supplies a plurality of build materials to fabrication device 114 .

[0102] The controller 20 controls the additive manufacturing apparatus 114, and optionally and preferably also the delivery system 330. The controller 20 typically includes electronic circuitry configured to perform control operations. The controller 20 preferably communicates with a data processor 154, which transmits digital data relating to fabrication instructions based on computer object data, such as a CAD configuration represented on a computer-readable medium in a format such as Standard Tessellation Language (STL) format. Typically, the controller 20 controls the voltage applied to each print head or each nozzle array and the temperature of the build material at each print head or each nozzle array.

[0103] Once the manufacturing data is loaded into the controller 20, the controller can operate without user intervention. In some embodiments, the controller 20 receives additional input from an operator, for example, using the data processor 154 or using a user interface 116 in communication with the controller 20. The user interface 116 can be of any type known in the art, such as, for example, but not limited to, a keyboard, a touch screen, or the like. For example, the controller 20 can receive as additional input the type and / or attributes of one or more build materials, including, but not limited to, color, characteristic strain and / or transition temperature, viscosity, electrical properties, magnetic properties, etc. Other attributes and groups of attributes are also contemplated.

[0104] Another representative, non-limiting example of a system 10 suitable for additive manufacturing of objects according to some embodiments of the present invention is shown in Figures 1B-1D, which show a top view (Figure 1B), a side view (Figure 1C), and an isometric view (Figure 1D) of system 10.

[0105] In this embodiment, the system 10 includes a tray 12 and multiple inkjet printheads 16, each having one or more nozzle arrays with one or more separate nozzles. Material used for three-dimensional printing is supplied to the printheads 16 by a build material supply system 42. The tray 12 may be disk-shaped or annular. Non-circular shapes are also contemplated, as long as the tray 12 is rotatable about a vertical axis. In the schematic diagram of FIG. 1C, the edges of the tray 12 are shown with straight corners. However, as with the tray 360 described above, in some applications, particularly when the tray 12 is in contact with a fabric on which an object is to be printed, it may be desirable to form rounded and / or chamfered edges on the top surface of the tray 12.

[0106] The tray 12 and head 16 are optionally and preferably mounted to permit relative rotational movement between the tray 12 and head 16. This can be achieved by (i) a configuration in which the tray 12 rotates relative to the head 16 about a vertical axis 14; (ii) a configuration in which the head 16 rotates relative to the tray 12 about a vertical axis 14; or (iii) a configuration in which both the tray 12 and the head 16 rotate about a vertical axis 14, but at different rotational speeds (e.g., in opposite directions). Below, several embodiments of the system 10 are described with particular emphasis on configuration (i), in which the tray is a rotating tray configured to rotate relative to the head 16 about a vertical axis 14, but it should be understood that the present application also contemplates configurations (ii) and (iii) for the system 10. Any of the embodiments of the system 10 described herein can be adapted to be applicable to either configuration (ii) or configuration (iii), and one of ordinary skill in the art would know how to make such adjustments given the details provided herein.

[0107] In the following description, the direction parallel to the tray 12 and outward from the axis 14 will be referred to as the radial direction r, the direction parallel to the tray 12 and perpendicular to the radial direction r will be referred to herein as the azimuthal direction φ, and the direction perpendicular to the tray 12 will be referred to herein as the vertical direction z.

[0108] The radial direction r of system 110 defines an index direction y of system 110, and the azimuthal direction φ defines a scan direction x of system 110. Thus, the radial direction is referred to interchangeably herein as the index direction, and the azimuthal direction is referred to interchangeably as the scan direction.

[0109] As used herein, the term "radial position" refers to a position on or above tray 12 that is a particular distance from axis 14. When the term is used in reference to a print head, the term refers to a position of the head that is a particular distance from axis 14. When the term is used in reference to a point on tray 12, the term corresponds to any point belonging to the locus of points of a circle whose radius is a particular distance from axis 14 and whose center is on axis 14.

[0110] As used herein, the term "azimuthal position" refers to a position on or above tray 12 that is at a particular azimuthal angle relative to a given reference point. A radial position, therefore, refers to any point belonging to a linear locus of points that is at a particular azimuthal angle relative to a reference point.

[0111] As used herein, the term "vertical position" refers to a position above a plane that intersects the vertical axis 14 at a particular point.

[0112] Tray 12 serves as a build platform for three-dimensional printing. The work area, on which one or more objects are printed, is typically smaller than the total area of ​​tray 12, although this need not be the case. In some embodiments of the present invention, the work area is annular. The work area is indicated by the reference numeral 26. In some embodiments of the present invention, tray 12 rotates continuously in the same direction during the formation of an object; in some embodiments of the present invention, the tray reverses its direction of rotation (e.g., oscillates) at least once during the formation of an object. Tray 12 is optionally and preferably removable. Removal of tray 12 can be performed for maintenance of system 10 or, if desired, to replace the tray before printing a new object. In some embodiments of the present invention, system 10 is provided with one or more different replacement trays (e.g., a kit of multiple replacement trays), with two or more trays designated for different types of objects (e.g., different weights), different modes of operation (e.g., different rotational speeds), etc. Tray 12 replacement can be manual or automatic, as desired. When automatic exchange is used, system 10 includes a tray exchanger 36 configured to remove tray 12 from a position beneath head 16 and replace it with a replacement tray (not shown). In the representative illustration of Figure 1B, tray exchanger 36 is shown as a drive unit 38 having a movable arm 40 configured to pull tray 12, although other types of tray exchangers are envisioned.

[0113] Exemplary embodiments of print head 16 are shown in Figures 2A-2C, which are applicable to any of the AM systems described above, including but not limited to system 110 and system 10.

[0114] 2A-2B show a print head 16 having one nozzle array 22 (FIG. 2A) and a print head 16 having two nozzle arrays 22 (FIG. 2B). The nozzles in the array are preferably arranged linearly along a straight line. In embodiments where a particular print head has two or more linear nozzle arrays, the nozzle arrays may optionally and preferably be parallel to one another. When a print head has two or more nozzle arrays (e.g., FIG. 2B), all arrays on that head may be supplied with the same build material, or at least two arrays on the same head may be supplied with different build materials.

[0115] When a system similar to system 110 is used, all print heads 16 are optionally and preferably arranged along the index direction with their positions along the scan direction offset from one another.

[0116] When a system similar to system 10 is used, all print heads 16 are optionally and preferably arranged radially (parallel to the radial direction) with their azimuthal positions offset from one another. Thus, in these embodiments, the nozzle arrays of different print heads are not parallel to one another, but rather are at an angle to one another, the angle being approximately equal to the azimuthal offset between the respective heads. For example, one head may be radially oriented and located at an azimuthal position φ1, and another head may be radially oriented and located at an azimuthal position φ2. In this example, the azimuthal offset between the two heads is φ1-φ2, and the angle between the linear nozzle arrays of the two heads is also φ1-φ2.

[0117] In some embodiments, two or more print heads can be assembled into a block of print heads, where the print heads in the block are generally parallel to one another. A block including multiple inkjet print heads 16a, 16b, 16c is shown in Figure 2C.

[0118] In some embodiments, system 10 includes a stabilizing structure 30 positioned below head 16, with tray 12 positioned between stabilizing structure 30 and head 16. Stabilizing structure 30 can serve to prevent or reduce vibrations of tray 12 that may occur when inkjet print head 16 operates. In configurations in which print head 16 rotates about axis 14, stabilizing structure 30 also preferably rotates so that stabilizing structure 30 is always directly below head 16 (with tray 12 positioned between head 16 and tray 12).

[0119] Tray 12 and / or print head 16 are optionally and preferably configured to move parallel to vertical axis 14 along vertical direction z to change the vertical distance between tray 12 and print head 16. In configurations in which the vertical distance is changed by moving tray 12 along the vertical direction, stabilizing structure 30 also preferably moves vertically with tray 12. In configurations in which the vertical position of tray 12 remains fixed and the vertical distance along the vertical direction is changed by head 16, stabilizing structure 30 is also held in a fixed vertical position.

[0120] Vertical movement can be achieved by vertical drive 28. Once a layer is completed, the vertical distance between tray 12 and head 16 can be increased (e.g., tray 12 can be lowered relative to head 16) by a predetermined vertical distance depending on the desired thickness of the next layer to be printed. This procedure is repeated to build the three-dimensional object layer by layer.

[0121] The operation of inkjet print head 16, and optionally and preferably the operation of one or more other components of system 10, such as movement of tray 12, is controlled by a controller 20. The controller may include electronic circuitry and a non-volatile storage medium readable by the circuitry that stores program instructions that, when read by the circuitry, cause the circuitry to perform control operations as described in further detail below.

[0122] The controller 20 can also communicate with a host computer 24, which transmits digital data related to fabrication instructions based on the computer object data. This digital data may be, for example, Standard Tessellation Language (STL) or Stereolithography Contour (SLC) format, Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Exchange Format (DXF), Polygon File Format (PLY), or any other format suitable for computer-aided design (CAD). The object data format is typically organized according to a Cartesian coordinate system. In such cases, the computer 24 preferably performs a procedure for converting the coordinates of each slice in the computer object data from the Cartesian coordinate system to a polar coordinate system. The computer 24 optionally and preferably transmits the fabrication instructions using the converted coordinate system. Alternatively, the computer 24 can transmit the fabrication instructions using the original coordinate system provided by the computer object data. In that case, the coordinate conversion is performed by circuitry in the controller 20.

[0123] Coordinate transformation enables three-dimensional printing on a rotating tray. In non-rotating systems with a fixed tray, the print head typically moves back and forth along a straight line above the fixed tray. In such systems, if the head's ejection speed is uniform, the print resolution is the same at any point on the tray. Unlike non-rotating systems, in system 10, not all nozzles at the head point move the same distance above tray 12 in the same amount of time. Coordinate transformation is optionally and preferably performed to ensure equal amounts of excess material at different radial locations. Representative examples of coordinate transformation according to some embodiments of the present invention are shown in Figures 3A-3B. Figures 3A-3B depict three slices of an object (each slice corresponding to a fabrication command for a different layer of the object), with Figure 3A showing the slice in a Cartesian coordinate system and Figure 3B showing the same slice after applying a coordinate transformation procedure to each slice.

[0124] Typically, controller 20 controls the voltages applied to each component of system 10 based on manufacturing instructions and based on stored program instructions described below.

[0125] Generally, controller 20 controls print head 16 to eject droplets of build material in layers to print a three-dimensional object on tray 12 while tray 12 rotates.

[0126] System 10 optionally and preferably includes one or more solidification devices 18. Solidification devices 18 may include, but are not limited to, one or more radiation sources, such as ultraviolet, visible, or infrared lamps, or other electromagnetic radiation sources, or electron beam sources, depending on the build material being used. Radiation sources may include any type of radiation emitting device, including, but not limited to, light-emitting diodes (LEDs), digital light processing (DLP) systems, resistive heat lamps, etc. Radiation sources 18 serve to cure or solidify the build material. In various exemplary embodiments of the invention, operation of solidification devices 18 is controlled by a controller 20, which activates and deactivates solidification devices 18 and optionally controls the amount of radiation generated by solidification devices 18.

[0127] In some embodiments of the present invention, system 10 further comprises one or more leveling devices 32, which may be manufactured as rollers or blades. Leveling devices 32 serve to prepare a newly formed layer before forming the next layer thereon. In some embodiments, leveling devices 32 have the shape of a conical roller, positioned so that its axis of symmetry 34 is inclined relative to the surface of tray 12 and its surface is parallel to the surface of the tray. This embodiment is shown in a side view of system 10 (FIG. 1C).

[0128] The conical roller may be in the shape of a cone or a truncated cone.

[0129] The opening angle of the conical roller is preferably selected so that the ratio between the radius of the cone at any point along its axis 34 and the distance between that point and axis 14 is constant. This embodiment allows roller 32 to efficiently flatten the layer because, as the roller rotates, the linear velocity at any point p on the roller surface is proportional to (e.g., the same as) the linear velocity of the tray at a point located directly below point p. In some embodiments, the roller has a frustoconical shape with height h, radius R1 at the point closest to axis 14, and radius R2 at the point farthest from axis 14, where parameters h, R1, and R2 satisfy the relationship R1 / R2=(Rh) / h, and R is the farthest distance of the roller from axis 14 (e.g., R can be the radius of tray 12).

[0130] The operation of the leveling device 32 is optionally and preferably controlled by the controller 20. The controller can activate and deactivate the leveling device 32 and optionally control the position of the leveling device 32 along the vertical direction (parallel to the axis 14) and / or the radial direction (parallel to the tray 12, toward or away from the axis 14).

[0131] In some embodiments of the invention, print head 16 is configured to move back and forth relative to the tray along a radial direction r. These embodiments are useful when the length of nozzle array 22 of head 16 is less than the radial width of working area 26 on tray 12. Movement of head 16 along the radial direction is optionally and preferably controlled by controller 20.

[0132] 1E-1G are schematic diagrams of a work tray 12 / 360 according to an embodiment of the present invention. The work tray includes or is associated with a radiation source 19, which emits radiation 17 to irradiate the build material from below. The radiation source 19 can emit any type of radiation 17, depending on the build material being used, including, but not limited to, electromagnetic radiation such as ultraviolet light, visible light, or infrared light, or electron beam radiation. The radiation 17 emitted by the radiation source 19 serves to solidify the build material from below. The radiation source 19 can include any device capable of emitting radiation 17, including, but not limited to, one or more LEDs, a digital light projector (DLP), a laser device, an electron beam source, or the like. The radiation source 19 can be controlled by a controller 20, which can activate and deactivate the radiation source 19 and, optionally, control the amount and / or cross-sectional area of ​​the radiation 17.

[0133] In the schematic diagram of FIG. 1E, the radiation source 19 is positioned below the work tray, in which case the work tray 12 / 360 is preferably transparent to the radiation 17 emitted from the radiation source 19. In the schematic diagram of FIG. 1F, the radiation source 19 is embedded within the tray 12 / 360, in which case the portion of the work tray positioned above the radiation source 19 is transparent to the radiation 17. In the schematic diagram of FIG. 1G, the radiation source 19 is attached to the side of the tray 12 / 360, in which case the radiation 17 enters the tray 12 / 360, is guided within the tray 12 / 360, and exits upward. The radiation 17 is guided by the material of the work tray 12 / 360 (e.g., by total internal reflection) and exits upward by a redirecting element 21 (e.g., a mirror or diffraction grating). The radiation 17 may be guided by one or more waveguides (not shown) embedded within the work tray 12 / 360.

[0134] In some embodiments, the radiation source 19 is activated by the controller 20 only when the bottom layer(s) of build material is dispensed, e.g., the first one, two, three, four, or five layers, and is then deactivated. Alternatively, the build material dispensed to form the bottom layer may be transparent to the radiation 17, allowing the radiation 17 to pass through the bottom layer and solidify the layers above. In some embodiments, it is contemplated that the build material of the bottom layer may be selected to absorb the radiation 17, thereby shielding the layers above from the radiation 17.

[0135] In some embodiments, the radiation source 19 is activated in a spatially selective manner so that certain areas on the tray emit radiation and other areas do not. For example, the radiation source 19 is activated in a spatially selective manner so that only the areas on the work tray where the build material is being dispensed are irradiated. Spatially selective irradiation can be achieved, for example, by providing the radiation source 19 as an LED array and selectively activating individual LEDs.

[0136] In some embodiments, it is envisioned that an object may be created by ejecting different materials from different nozzle arrays (belonging to the same or different printheads). These embodiments provide, among other things, the ability to select materials from a predetermined number of materials and define a desired combination of the selected materials and their properties. According to this embodiment, the deposition location of each material within a layer is defined so that different materials occupy different three-dimensional spatial locations, or so that two or more different materials occupy substantially the same three-dimensional location or adjacent three-dimensional locations, thereby allowing these materials to be spatially combined within the layer after deposition to form a composite material at each single location or locations.

[0137] Any combination or mixing of model (build) materials after deposition is contemplated. For example, when a particular formulation is dispensed, the solidified material may retain its original properties. However, when a particular formulation is dispensed simultaneously with another build material formulation, or with another dispensed material dispensed at the same or nearby location, a composite material may be formed that has different properties than the material formed from the particular formulation by itself.

[0138] In some embodiments of the present invention, the system dispenses digital material as described herein for at least one of the layers.

[0139] Further details of the principles and operation of an AM system suitable for this embodiment are provided in US Patent Application Publication No. 2010 / 0191360, the contents of which are incorporated herein by reference.

[0140] In some embodiments of the present invention, system 10 and / or system 110 are configured to print one or more objects onto fabric.

[0141] As used herein, "fabric" includes any manufactured article made at least in part from natural or man-made fiber materials. Examples of types of fabric include, but are not limited to, clothing, shoes, toys, cloth items, carpets, cloth hats, cloth bags, socks, towels, linens, curtains, etc.

[0142] In this embodiment, printing on woven or nonwoven fabric is assumed.

[0143] As used herein, the term "woven" refers to a structure in accordance with ASTM D123-03, in which at least two sets of strands are interlaced, e.g., perpendicular to each other, according to a predetermined interlacing pattern, with at least one set parallel to an axis along the length of the fabric.

[0144] As used herein, the term "nonwoven" means a woven structure made by bonding or entangling fibers, or both, by mechanical, chemical, thermal, or solvent means, and combinations thereof, in accordance with ASTM D123-03.

[0145] Preferably, but not necessarily, when a printing system (e.g., system 10 or system 110) is used to print an object on fabric, leveling device 32 is not used or is used only after the object reaches a predetermined height on the fabric.

[0146] Preferably, but not necessarily, when a printing system (e.g., system 10 or system 110) is used to print an object on fabric, the height of the printed object is less than 10 cm, more preferably less than 9 cm, more preferably less than 8 cm, more preferably less than 8 cm, more preferably less than 7 cm, more preferably less than 6 cm, more preferably less than 5 cm, more preferably less than 4 cm, more preferably less than 3 cm, more preferably less than 2 cm, more preferably less than 1 cm.

[0147] In some embodiments of the invention, the work tray of the system (e.g., tray 12 or tray 360) has a reflectivity of at least 50%, or at least 60%, or at least 70%, or at least 80%, or more, to the radiation emitted by the radiation source of solidification device 18. An advantage of making the work tray reflective or partially reflective is that reflected radiation reaching the fabric from below can solidify the build material underneath the fabric and can penetrate the pores of the fabric and solidify droplets of build material within those pores, thereby improving adhesion of the printed object to the fabric.

[0148] This embodiment also contemplates providing one or more fluid flow paths 52 in the work tray. A fluid delivery system 54 can generate a fluid flow within the fluid flow path 52. The fluid can optionally and preferably be temperature-controlled, thereby controlling the temperature of the work tray. If the fluid delivery system 54 generates a fluid flow at a temperature lower than that of the dispensed build material, the fluid absorbs heat from the build material. The fluid delivery system 54 can also generate a fluid flow at a temperature higher than that of the fabric, facilitating smoothing of the fabric before dispensing the build material onto the fabric. The inventors also contemplate combining these embodiments, in which the fluid is at a higher temperature before dispensing the build material and at a lower temperature during fabrication. The fluid can be in a gas or liquid phase (e.g., air, helium, water, oil, etc.). Preferably, the fluid delivery system 54 is controlled by the controller 20.

[0149] In some embodiments of the present invention, system 10 and / or system 110 includes a fixture 402 configured to affix fabric 420 in a predetermined position on a work tray (e.g., tray 12 or tray 360) of the system and to fix fabric 420 in a predetermined orientation relative to a nozzle array (e.g., array 122) of the system. In some embodiments of the present invention, fixture 402 is also configured to stretch fabric 420.

[0150] The fixture 402 is shown in detail in Figures 4A-4F. Figures 4A and 4B illustrate an embodiment in which the fixture 402 comprises a frame 403 and one or more magnetic or metallic elements 405. The elements 405 are preferably permanently attached to the tray 360 / 12 or nearby (e.g., on a stationary platform 361 surrounding the tray 360 / 12), and at least one of the tray 360 / 12 and the elements 405 comprises a permanent magnet to ensure mutual magnetic attraction between the elements 405 and the frame 403. The frame 403 may be entirely composed of a magnetic or metallic material, or may comprise metallic or magnetic elements (not shown, see Figures 4E and 4F) around its periphery, in which case the metallic or magnetic elements are positioned lateral to correspond to the positions of the elements 405. Figure 4A illustrates the fixture 402 in an open state before a fabric 420 is placed on the work tray 360 / 12. 4B shows the fixture 402 in a closed state, in which the frame 403 is magnetically attached to an element 405 (not shown in FIG. 4B) to secure the fabric 420 on the work tray 360 / 12 and, optionally and preferably, stretch the fabric 420. The fixture 402 may also include a pair of frames 403 that are magnetically attachable to one another. In that case, the fabric 420 is stretched between the frames of the fixture 402 before being placed on the work tray 360 / 12. In these embodiments, the element 405 is not required.

[0151] 4E and 4F show side views of jig 402. In the illustrated embodiment, frame 403 includes magnetic or metallic elements 407 attached to its periphery, with the magnetic or metallic elements 407 positioned at lateral locations corresponding to the locations of elements 405. Elements 407 and 405 may be flat, as shown in FIG. 4E, or may include protruding elements 409 or roughened surfaces, as shown in FIG. 4F. The protruding elements or roughened surfaces may be provided on metallic or magnetic elements attached to frame 403, metallic or magnetic elements attached to platform 361, or metallic or magnetic elements attached to both frame 403 and platform 361. If frame 403 is entirely metallic or magnetic and has no other metallic or magnetic elements 407 attached thereto, the protruding elements 409 or roughened surfaces may be formed on frame 403 at lateral locations corresponding to the locations of elements 405.

[0152] 4C and 4D show an embodiment in which the jig 402 includes a rotatable frame 406 and a flat fabric holder 408. Here, the frame 406 is sized and shaped such that when the frame 406 rotates to engage the surface of the fabric holder 408, the frame 406 surrounds the fabric holder 408 and captures the fabric 420 between the frame 406 and the fabric holder 408. The fabric holder 408 may be in the form of a continuous surface or a frame. If the fabric holder 408 is a continuous surface, once the fabric 420 is placed on the fabric holder 408 and, optionally and preferably, stretched, the fabric 420 is accessible from only one side (typically the top side). If the fabric holder 408 is in the form of a frame, once the fabric 420 is placed on the fabric holder 408 and, optionally and preferably, stretched over the holder, the fabric 420 is accessible from both sides. FIG. 4C shows the fixture 402 in an open position ready to receive the fabric 420, and FIG. 4D shows the fixture 402 in a closed position with the fabric 420 secured to the tray 12 / 360.

[0153] An advantage of having a jig with a flat fabric holder 408 is that the jig 402 can receive the fabric 420 while the jig 402 is placed on the work tray 12 / 360, or the jig 402 can receive the fabric 420 before the jig 402 is placed on the work tray 12 / 360.

[0154] 5A-5C are schematic diagrams illustrating an arrangement in which the fabric 420 is positioned on a ramp structure 450. The ramp structure 450 includes a flat ramp 452 and one or more spacer beams 454 that maintain the ramp 452 vertically spaced apart from the work tray 12 / 360. The ramp structure 450 may be positioned above the tray 12 / 360 or may be connected to the tray 12 / 360 by a connector (not shown), such as, but not limited to, a snap connector. If the ramp structure 450 is connected to the tray, the connector is preferably located outside the printing area of ​​the AM system so as not to interfere with the printing process when the AM system is operated without the ramp 450. While the fabric 420 can be secured using any of the techniques described above, in the example illustrated in FIGS. 5A-5C, the fabric 420 is secured to the ramp structure 450 rather than the tray 12 / 360.

[0155] An advantage of using the ramp structure 450 is that it allows three-dimensional objects to be printed on fabric that is larger than the work tray. In use, the fabric 420 is secured to the upper surface of the ramp 452. If the dimensions of the fabric 420 are larger than the dimensions of the ramp structure, the fabric 420 is folded over at the end of the ramp structure 450, so that the horizontal portion 420a of the fabric 420 is supported on the upper surface of the ramp 452 and the hanging portion 420b of the fabric 420 is folded below the ramp 452 into the space above the work tray 12 / 360, as shown in FIG. 5A . Preferably, the fabric 420 is secured to the ramp structure 450 before being placed on or connected to the work tray 12 / 360. However, embodiments are also contemplated in which the fabric 420 is secured to the ramp 452 while the ramp structure 450 is on the work tray 12 / 360.

[0156] Once the fabric 420 is secured to the work tray 12 / 360 (FIGS. 4A-4F) or the lamp 452 (FIGS. 5A-5C), the computerized controller 20 (FIGS. 1A and 1B) operates the nozzle array 122 (FIGS. 2A-2C) to dispense build material onto the secured fabric 420 in a structured pattern corresponding to the object shape. In embodiments where a lamp structure 450 is used, the computerized controller 20 controls the nozzle array 122 to cease all dispensing when the nozzles are positioned above the gap between the lamp structure 450 and the platform 361, thereby ensuring that droplets of build material land only on the horizontal portions 402a of the fabric 420.

[0157] When the ramp structure 450 is used, it may be found that the vertical position of the ramp 452 in the Z-axis direction is higher than the vertical position of the work tray 12 / 360. In this case, the computerized controller 20 adjusts the vertical position of the work tray 12 / 360 to compensate for the height of the ramp structure 452 above the work tray 12 / 360. This adjustment process is illustrated in FIGS. 5A-5C. The initial vertical position of the work tray 12 / 360 is preferably selected so that the upper surface of the ramp 452 is at the vertical position that the work tray 12 / 360 would be in if the ramp structure were not being used. For example, as shown in FIG. 5C, the initial vertical position of the work tray 12 / 360 can be selected so that the upper surface of the ramp 452 is at the same vertical position as the upper surface of the platform 361. Once the initial vertical position adjustment is made, the printing process continues layer by layer as described above, and as one layer is completed, the work tray 12 / 360 is lowered in the Z-direction depending on the desired thickness of the next layer.

[0158] 1A-1C, systems 10 and 110 optionally and preferably include a position tracking system 50. In some embodiments of the present invention, position tracking system 50 is configured to determine the position of fixture 402 relative to work tray 12 or work tray 360 when fixture 402 is placed on the tray. Position tracking system 50 may include, for example, an optical scanner, an imaging device, a magnetic sensor, and / or a radio frequency sensor. A computerized controller 20 receives position tracking signals from system 50, performs an alignment procedure based on the position tracking signals, and activates nozzle array 122 accordingly. An advantage of this embodiment is that precise positioning of fixture 402 on the tray is not required, as the alignment procedure performed by controller 20 ensures that nozzles are activated to dispense build material at the appropriate locations on fabric 420.

[0159] The position tracking system 50 can determine the position of the fixture 402 in several ways. In some embodiments of the invention, the system 50 captures an image of the tray or a portion thereof (e.g., if the system 50 includes a pixelated imager or optical scanner) and performs an image processing procedure to identify the position of the fixture 402 relative to the tray. In some embodiments of the invention, the position tracking system 50 can use marks 414 to determine the position of the fixture 402. The marks can be formed or attached, for example, to the frame 406 of the fixture 402, or to a fabric holder 408 as shown in FIGS. 4A, 4C, and 4D, or to a work tray, or to a stationary platform 361 as shown in FIG. 4A. The marks 414 are identifiable by the position tracking system 50 and are used by the system 50 to determine the position of the fixture 402. For example, if system 50 includes an optical scanner or imaging device, mark 414 may be, but is not limited to, a printed pattern such as a bar code, or an optical signal source (e.g., a light emitting diode that emits radiation that does not harden the build material dispensed by the nozzle array). If system 50 includes a magnetic or radio frequency sensor, mark 414 may include, but is not limited to, a source of radio frequency or magnetic field, such as, but not limited to, a miniature coil.

[0160] The present disclosure also contemplates embodiments in which the position tracking system 50 is used to identify a pattern (e.g., a printed pattern, a woven pattern, a knit pattern) on the fabric 420 itself. In these embodiments, the controller 20 can perform an alignment procedure based on the identified pattern on the fabric 420, without the need to use the tracking system 50 to determine the position of the fixture 402 (although such determination is contemplated in some embodiments).

[0161] The process of fabricating the three-dimensional object on the fabric 420 optionally and preferably includes the use of one or more liquid formulations other than the build material for three-dimensional printing. The liquid formulations may be curable or non-curable. The liquid formulations are also referred to herein interchangeably as "liquid additives," "additive formulations," or "liquid additive formulations." The liquid additive formulations may be deposited onto the fabric by a dispensing head of the system 10 or system 110. Embodiments are also contemplated in which the liquid formulations are deposited by an additive dispensing system 340 (see FIGS. 1A and 1B). The additive dispensing system may be in fluid communication with a container 342 (shown only in FIG. 1A) that contains the liquid formulation and controlled by the controller 20. In some embodiments of the present invention, the one or more additive formulations are applied by directing an aerosol or mist of the liquid additive onto the fabric. In these embodiments, the system 340 is in the form of an aerosol dispenser or sprinkler that generates an aerosol or mist of the liquid additive and directs it toward the fabric. In some embodiments of the present invention, one or more liquid additives are applied by depositing droplets of the additive at discrete addressable locations on the fabric. In these embodiments, one or more print heads 16 can be configured to dispense a respective additive formulation, and one or more reservoirs or cartridges of the delivery system 330 can contain a respective additive formulation. When there are two or more additive formulations (e.g., formulations that are normally non-reactive but react with each other in situ after deposition), deposition at discrete addressable locations on the fabric is preferably laterally interleaved to allow for the formation of interfaces between adjacent droplets of different additive formulations.

[0162] The additive dispensing system 340 can be mounted on the same print block as the head 16, as shown in FIG. 1A, and thus can move horizontally with the head 16. Alternatively, the system 340 can be mounted separately from the head 16 (e.g., see FIG. 1B), in which case the head 16 and the system 340 can be configured to move independently. In some embodiments, the build tray 12 / 360, or a portion thereof, moves beneath the stationary print block 128 to which the stationary additive dispensing system 340 (e.g., a sprinkler array) and / or head 16 are mounted. In some other embodiments, the tray 360 is configured to move in the Z direction, the head 16 is mounted to a print block 128 configured to horizontally scan the surface of the tray 360 in a first direction (e.g., the X-axis), and the additive dispensing system 340 is configured to horizontally scan the surface of the tray 360 in a second direction (e.g., the Y-axis). In some embodiments, both the print block 128 and the additive dispensing system 340 are configured to horizontally scan the surface of the tray 360 in the same direction (eg, the X axis).

[0163] Types of liquid additive formulations contemplated by some embodiments of the present invention include, but are not limited to, priming formulations (e.g., curing formulations, adhesive formulations, pore size control formulations, etc.), finishing or coating formulations (e.g., radiation protection formulations, gloss finish formulations, matte finish formulations, etc.), masking formulations, etc. Other types of additives that may be used with some embodiments of the present invention include temporary protection formulations, water repellent formulations, waterproofing formulations, hydrophobic formulations, etc.

[0164] If the additive formulation is a primer formulation or an adhesive formulation, it is applied before dispensing the build material. Thus, for example, an adhesive formulation can be applied to the fabric followed by dispensing a build (e.g., model, shaping) material formulation, ensuring adhesion of the build material formulation and / or solidified build material to the fabric by the adhesive formulation.

[0165] Another example is the application of a pore size adjusting liquid to increase the pore sizes of the fabric, after which a build material can be dispensed to form piercing elements (e.g., element 506) within the enlarged pores. A further example is the application of a stiffening substance to stabilize the fabric prior to dispensing.

[0166] If the additive formulation is a finishing or coating formulation, it is applied after the build material formulation is dispensed. For example, a glossy or matte finishing formulation can be applied to the dispensed build material formulation and / or the solidified build material to impart a desired appearance to the solidified material. Similarly, paints such as metallic paints (e.g., chrome, gold) can be applied in the form of a finishing formulation to at least a portion of an object printed with the build material. Finishing formulations that serve to protect fabrics or printed objects against, for example, discoloration, radiation, abrasion, chemical damage, moisture absorption, etc. are also contemplated. Representative examples of such protective formulations include, but are not limited to, UV-resistant materials (such as those commercially available from Krylon®) and polyurethanes (such as polyurethane solutions from Rust-Oleum).

[0167] If the additive formulation is a masking formulation, it is preferably applied before the build material formulation is dispensed. The masking formulation serves to prevent selected areas of the fabric from contacting the dispensed build material formulation. Thus, it is selectively applied to locations that should not be occupied by the printed object. The masking formulation is preferably removable (e.g., removable by washing). For example, the masking formulation may include the solution disclosed in U.S. Pat. No. 5,308,647, the contents of which are incorporated herein by reference. If a finishing process is performed, the masking formulation may be applied after printing but before the finishing process to protect other locations of the object or fabric from the finishing process.

[0168] It is also envisaged to use the support material layer as a protective coating in places that should not be occupied by the object to be printed.

[0169] Any of the additive formulations described above can optionally and preferably comprise an inactive (e.g., non-curing) formulation that can be activated in situ, i.e., activated while spread on the fabric. In these embodiments, the formulation is applied to the fabric and then activated. In exemplary embodiments, the formulation is a curable formulation that undergoes polymerization of monomers and / or oligomers, crosslinking of polymer chains, or modification of the optical properties of the formulation upon exposure to curing conditions (e.g., radiation, heat) as described herein.

[0170] Formulations that are activated by a chemical reaction are also contemplated. Such a reaction can occur between the formulation and one or more build materials and / or between two or more applied formulations. For example, in some embodiments of the present invention, one or more build material formulations are dispensed onto a textile and allowed to at least partially penetrate into the pores of the textile while in a liquid phase (before being exposed to curing conditions and solidifying). A formulation that reacts with the build material formulation is then applied. A chemical reaction between the build material formulation (e.g., one or more curable materials therein) and the applied formulation alters at least one property (e.g., mechanical property and / or optical property) of the solidified build material. In some embodiments, the formulation induces polymerization of one or more curable materials in the dispensed build material formulation.

[0171] In embodiments where two or more formulations react with each other, it is preferred to deposit them separately so that their reaction is induced on the fabric. Depending on the product of such reaction, the two or more formulations can be dispensed before the build material formulation, after the build material formulation, or simultaneously with or intermittently during the dispense of the build material formulation.

[0172] For example, if the reaction product forms an adhesive that allows build materials to adhere together, and / or if the reaction product alters pore size (e.g., a reaction product that locally shrinks fibers in a fabric, thereby increasing the pore size between the fibers), and / or if the reaction product forms a mask in areas of the fabric where it is desired to prevent build material contact, the formulation can be dispensed before the dispense of the build material formulation. If the reaction product alters the appearance of the solidified build material (e.g., increases or decreases gloss, modifies color) or covers the solidified build material with a (usually transparent) cover (e.g., a protective cover), the formulation can be deposited after the dispense of the build material formulation. If it is desired to interleave the reaction product vertically or laterally with the solidified build material, e.g., to strengthen the build material, increase the flexibility of the final object, etc., the formulation can be deposited simultaneously with or intermittently during the dispense of the build material formulation.

[0173] A representative example of an additive formulation suitable for use as a primer (eg, adhesive) and / or coating formulation according to exemplary embodiments of the present invention is described in more detail in Example 3 of the Examples section below.

[0174] The present disclosure also contemplates the use of non-liquid additives. For example, the additive applied may be in a solid phase. In these embodiments, the additive can be transferred from the substrate to the textile by contacting the textile with a substrate bearing the additive and applying pressure, radiation, and / or heat to the substrate. The substrate typically takes the form of, but is not necessarily limited to, a film containing or coated with the additive. For example, if the additive includes a curable substance (e.g., including, but not limited to, an oily substance such as wax), a sheet containing the curable substance can be placed on the textile and heated and / or pressed against the textile to transfer the curable substance to the textile.

[0175] The solid phase additive may be applied to the same side of the fabric as the building material formulation is dispensed and / or may be applied to the opposite side of the fabric from the building material formulation is dispensed. Application of the solid phase additive to the fabric is typically performed before dispensing, although embodiments are envisioned in which the solid phase additive is applied to the fabric after the object is formed on the fabric.

[0176] <Method> The method of the present embodiment can be performed by a computerized controller (eg, controller 20) of system 10 or system 110.

[0177] Unless otherwise specified, it should be understood that the operations described below can be performed either simultaneously or sequentially in many combinations or orders of execution. In particular, the order of the flow diagrams should not be considered limiting. For example, two or more operations that appear in a particular order in the following description or flow diagrams may be performed in a different order (e.g., in the reverse order) or substantially simultaneously. Furthermore, some operations described below are optional and may not be performed.

[0178] The method of the present embodiment can be used as a printing protocol to improve adhesion of three-dimensional printed objects to fabrics and / or to improve the appearance and / or mechanical properties of the printed objects.

[0179] In some embodiments, the method is for forming an adhesive structure or adhesive material within a textile, thereby preparing the textile for 3D printing of an object thereof. The adhesive structure is formed by sequentially dispensing, in layers, additive formulations suitable for functioning as a primer formulation or adhesive formulation, as described in any individual embodiment herein. Preferably, but not necessarily, the entire adhesive structure is composed of a single formulation, which is an additive formulation as described herein.

[0180] Typically, once an adhesive structure is formed on the fabric, a three-dimensional object composed of one or more build materials is printed onto the adhesive structure, as described below.

[0181] According to one aspect of some embodiments of the present invention, there is provided a method for forming a bonded structure on a fabric. The method is generally carried out by dispensing a stack of layers onto the fabric in a structured pattern corresponding to the shape of the bonded structure, wherein at least some or each of the layers of the stack are dispensed with an additive (e.g., primer / adhesive) formulation as described in any of the embodiments herein. The method includes exposing each layer or stack of layers to curing conditions as described herein, thereby forming the bonded structure.

[0182] According to an aspect of some embodiments of the present invention, there is provided a method of preparing a fabric for three-dimensional printing of an object thereon, the method generally being carried out by forming an adhesive structure on the fabric in a configuration pattern corresponding to the shape of the bottom surface of the object, thereby forming the adhesive structure by a method as described in any one or any combination of embodiments herein.

[0183] According to one aspect of some embodiments of the present invention, there is provided a method for forming a coating on a three-dimensional object, or a portion of the object, printed on a fabric. The method is generally carried out by dispensing a stack of layers onto the printed object in a structured pattern corresponding to the shape of the outermost surface of the object or portion thereof to which the coating is desired, wherein for each layer of the stack, an additive (e.g., coating) formulation is dispensed, as described in any of the embodiments and any combination thereof herein. The method further includes exposing each layer or stack of layers to curing conditions, thereby forming a solidified coating material on the printed object or portion thereof.

[0184] According to an aspect of some embodiments of the present invention, there is provided a method for three-dimensional printing an object onto a fabric, the method comprising dispensing a plurality of layers in a construction pattern corresponding to a shape of the object, thereby forming the object, wherein forming each layer in at least some of the layers comprises dispensing one or more build (e.g., modeling) formulations and exposing the dispensed formulations to curing conditions to thereby form a hardened build (e.g., modeling) material, thereby printing the object.

[0185] According to some of these embodiments, the build material formulation comprises or consists of one or more build material formulations, such as those described in Example 4 of the Examples section below.

[0186] According to these embodiments, the method further includes forming an adhesive structure on the fabric or preparing the fabric by forming an adhesive structure as described in any of the embodiments herein prior to dispensing the one or more build (e.g., modeling) material formulations, and / or forming a coating on the printed object or portion thereof as described in any of the embodiments herein after dispensing the one or more build (e.g., modeling) material formulations and exposing it to curing conditions.

[0187] According to some of these embodiments, the method further includes dispensing a stack of layers onto the fabric in a configuration pattern corresponding to the shape of the bottom surface of the object, where each layer of the stack is dispensed with an additive (e.g., primer / adhesive) formulation as described in any of the embodiments herein, prior to dispensing one or more build (e.g., shaping) material formulations. Further, the method includes exposing each layer or stack of layers to curing conditions, thereby forming a solidified adhesive material (adhesive structure) as described in any of the embodiments herein.

[0188] According to some of these embodiments, the method includes dispensing a stack of layers onto the printed object or portion thereof in a configuration pattern corresponding to the shape of the outermost surface of the object or portion thereof, as described herein, where the dispensing of each layer of the stack is with an additive (e.g., coating) formulation as described in any of the embodiments herein. The method further includes exposing each layer or stack of layers to curing conditions, thereby forming a solidified coating material on the printed object or portion thereof. In some embodiments, the coating formulation is also dispensed to at least partially surround one or more layers formed with the build (e.g., modeling) material formulation. Such a fully or partially surrounding coating can be formed substantially simultaneously with the formation of each layer of the object by dispensing the build (e.g., modeling) material formulation and the coating formulation using different nozzle arrays of the dispensing head 16. Alternatively, a fully or partially surrounding coating can be formed on each layer after the layer of the build (e.g., modeling) material formulation has been dispensed. An advantage of forming a fully or partially surrounding coating is that the coating is also provided on the side surfaces of the object. For example, a coating that surrounds the object to be printed on all sides can be provided by dispensing a coating formulation to completely surround each layer formed with the build (e.g., modeling) material formulation.

[0189] According to some embodiments, the method further includes, prior to dispensing one or more build (e.g., modeling) material formulations, dispensing a stack of layers onto the fabric in a configuration pattern corresponding to the shape of the bottom-most surface of the object, where each layer of the stack is dispensed with an additive (e.g., primer / adhesive) formulation as described in any of the embodiments herein, and exposing each layer or stack of layers to curing conditions, thereby forming a solidified adhesive material as described in any of the embodiments herein. Such a stack of layers can function as an adhesive structure to aid in the adhesion of the build (e.g., modeling) material to the fabric. After dispensing one or more build (e.g., modeling) material formulations and exposing them to curing conditions, the method can dispense a stack of layers onto the printed object or portion thereof in a configuration pattern corresponding to the shape of the outermost surface of the object or portion thereof, as described herein, where each layer of the stack is dispensed with an additive (e.g., coating) formulation as described in any of the embodiments herein. Each layer or stack of layers can then be exposed to curing conditions, thereby forming a solidified coating material on the printed object or portion thereof.

[0190] The methods described herein can be used to fabricate any type of object on a fabric using any formulation suitable for three-dimensional printing. Representative examples of formulations suitable for this embodiment include, but are not limited to, formulations sold under the Vero® family of trade names, such as VeroVivid® Cyan, VeroVivid®, VeroClear®, VeroContactFlex, and VeroUltraClear, and formulations sold under the Agilus® family of trade names, such as Agilus30®, Agilus® White, Agilus® Clear, Agilus® Black, Agilus® Cyan, Agilus® Magenta, and Agilus® Yellow, all of which are commercially available from Stratasys® Limited, Israel. In some embodiments of the present invention, at least one formulation dispensed to fabricate an object on a fabric provides a flexible material. A representative example of such a formulation is described in Example 4 in the Examples section below.

[0191] In some embodiments, these methods are performed according to the embodiments described herein with respect to Figures 6A-6D.

[0192] 6D, the method begins at 840 and optionally and preferably continues to 601, where computer object data is received. The computer object data may be in any of the formats described above and may describe at least the bottom surface of the object to be fabricated on the adhesive structure, although typically the computer object data describes the overall shape of the object.

[0193] Optionally, but not necessarily, the method continues at 841, where the primer (adhesive) formulation of the present embodiment is dispensed to form a layer of primer (adhesive) formulation, which will later become the adhesive structure layer. Dispensing occurs onto the fabric, or onto a previously dispensed layer, if any, already formed in the method. In some embodiments, the formulation is selectively dispensed according to computer object data of the bottom surface of the object to be fabricated on the adhesive structure. Thus, the formulation is optionally and preferably dispensed at the lateral coordinate that the object is expected to occupy after printing, and not at other locations.

[0194] The method continues at 842 where the primer (adhesive) formulation is exposed to curing conditions (eg, irradiated).

[0195] In some embodiments, operations 841 and 842 are performed according to respective embodiments as described below with respect to one of Figures 6A-6C.

[0196] The method optionally and preferably loops back from 842 to 841 to form the next layer of the bonded structure. This loop is repeated a predetermined number of times. Preferably, this loop is repeated until the number of layers of the bonded structure is N1, where N1 is about 10 to about 30 layers, or about 15 to about 30 layers, e.g., about 20 layers.

[0197] Upon completion of the loop, a stack of layers is formed. The method then optionally and preferably continues to 843, where a three-dimensional object is printed layer by layer on top of the stack based on the computer object data. The object is preferably printed using one or more build materials (such as, but not limited to, one or more of the build materials described above). The object is printed by dispensing one or more build compounds in layers in a configuration pattern according to the shape of the slices of the object, and irradiating to cure the build compound in each layer. Irradiation is preferably performed according to the same irradiation protocol as described in connection with operation 606 herein.

[0198] Optionally, but not necessarily, the method continues at 844 with the dispensing of a formulation suitable for use as a coating formulation, as described in any of the embodiments herein. In some embodiments, the coating formulation is the same as the basecoat formulation dispensed at 841. In some embodiments, the coating formulation is dispensed to at least partially surround one or more layers formed at 843. Such a fully or partially surrounding coating can be formed substantially simultaneously with the formation of each layer of the object, for example, by dispensing the build formulation and the coating formulation using different nozzle arrays of the dispensing head 16. Alternatively, as shown by the loop-back arrow from 844 back to 843, a fully or partially surrounding coating can be formed for each layer after the build formulation layer is dispensed. An advantage of forming a fully or partially surrounding coating is that the coating is also provided on the sides of the object. For example, a coating that surrounds all sides of the object to be printed can be provided by dispensing a coating formulation to completely surround each layer formed at 843.

[0199] The method continues at 845 where the coating formulation is exposed to curing conditions (e.g., irradiated). Once the coating has been dispensed to fully or partially surround the layer of build (e.g., modeling) material formulation, the exposing at 845 is optionally and preferably performed substantially simultaneously with the exposing of the build (e.g., modeling) material formulation.

[0200] In some embodiments, operations 844 and 845 are performed according to respective embodiments as described below with respect to one of Figures 6A-6C.

[0201] A coating on the upper surface of the object is optionally and preferably formed by dispensing the formulation onto the object in layers and irradiating each layer of the formulation with curing radiation. Irradiation is preferably according to the same irradiation protocol as described above with respect to operation 841, and may also follow the irradiation protocol described herein in connection with operation 606. The thickness of the solidified coating is preferably from about 0.01 mm to about 0.5 mm, for example, about 0.05 mm or about 0.1 mm.

[0202] In some embodiments of the present invention, the object is a test object that is printed to test the level of adhesion provided by the adhesive structure. In these embodiments, an operation is performed to test the level of adhesion of the object to the fabric. Representative examples of test objects and testing procedures suitable for this embodiment are provided below and illustrated in block 607 of Figures 6A-6C.

[0203] According to some embodiments, the method includes one or both of operations 841 and 842 and one or both of operations 844 and 845.

[0204] The method ends at 846.

[0205] According to some of the embodiments of any of the embodiments described herein, performing the method described below with reference to FIG. 6A provides suitable adhesion between an object and any fabric.

[0206] According to some of the embodiments described herein, if the fabric has low absorbency for the dispensed formulation, the adhesion level can be further improved by carrying out the method described below with reference to FIG. 6B.

[0207] According to some of the embodiments described herein, if the fabric has high absorbency for the dispensed formulation, the adhesion level can be further improved by carrying out the method described below with reference to FIG. 6C.

[0208] The absorbency level of the fabric can be determined before printing using any procedure known in the art. For example, a droplet of the jetted formulation can be applied to the fabric and the absorbency level can be determined based on the contact angle between the droplet and the fabric. A larger contact angle corresponds to a more hydrophobic fabric and therefore a lower absorbency of the fabric. Alternatively or additionally, the fabric can be immersed in a liquid (e.g., water) and the length of time it takes for the fabric to absorb the liquid can be correlated to the absorbency level of the fabric.

[0209] 6A, the method begins at 600 and optionally and preferably continues to 601, where computer object data is received. The computer object data may be in any of the formats described above and may describe at least the bottom surface of the object to be fabricated on the adhesive structure, although typically the computer object data describes the overall shape of the object.

[0210] The method continues at 602 where a primer (additive) formulation according to the present embodiments is dispensed to form a layer. Dispensing occurs on the fabric, or on a previously dispensed layer, if any, already formed by the method. The formulation is selectively dispensed according to computer object data of the bottom surface of the object to be fabricated on the adhesive structure. Thus, the formulation is dispensed at the lateral coordinates that the object is expected to occupy after printing, and not at other locations.

[0211] The method continues at 603, where the formulation is exposed to an irradiation intensity I A to form a solidified adhesive material that constitutes the adhesive structure layer. The wavelength of the curing radiation depends on the type of formulation used. For example, if the formulation is UV-curable, the radiation may be ultraviolet. A A typical value of is about 2.5 W / cm 2 to approximately 5.5 W / cm 2 is.

[0212] For any layer of the adhesive structure, operation 603 is preferably performed according to a protocol in which a curing radiation pattern having the shape of a single stripe is generated on the layer and advanced along the scanning direction (x or φ). Representative examples of radiation protocols suitable for operation 603 are shown in Figures 13A and 13B, which show a layer 610 of basecoat formulation on a fabric 420 and a curing radiation pattern 612 in the form of a single linear stripe propagating along direction x when the fabric 420 is on tray 360 (Figure 13A), or a curing radiation pattern 612 in the form of a single linear stripe propagating along direction φ when the fabric 420 is on tray 12 (Figure 13B).

[0213] The irradiation pattern is generated by a radiation-emitting device (e.g., device 18 of system 10 or 110), and the irradiation protocols shown in Figures 13A and 13B can be used by appropriately controlling these devices. For example, if a system is configured for linear, back-and-forth relative movement between the dispensing head and the tray (e.g., system 110), operation 603 can be performed by activating only the solidification devices that follow the print head and not activating the solidification devices that the print head follows (e.g., referring to Figure 1D, when head 16 moves left, devices 18 to the right of head 16 are activated and devices 18 to the left of head 16 are not activated, and vice versa). This ensures execution of the protocol shown in Figure 13A. If a system is configured for rotational relative movement between the dispensing head and the tray (e.g., system 10), operation 603 can be performed by activating only the solidification devices that are rotationally ahead of the print head and not activating the solidification devices that are rotationally behind the print head. This ensures execution of the protocol shown in Figure 13B. Control over the solidification device is typically provided by a controller of the three dimensional printing system (e.g., controller 20 of system 10 or system 110).

[0214] The method optionally and preferably loops back from 603 to 602 to form the next layer of the bonded structure. This loop is repeated a predetermined number of times. Preferably, this loop is repeated until the number of layers of the bonded structure reaches N1, where N1 is about 10 to about 30 layers, or about 15 to about 30 layers, such as about 20 layers.

[0215] Upon completion of the loop, a stack of layers is formed. The method then optionally and preferably continues to 604, where a three-dimensional object is printed layer by layer on top of the stack based on the computer object data. The object is preferably printed using one or more build materials (such as, but not limited to, one or more of the build materials described above). The object is printed by dispensing one or more build compounds in layers in a configuration pattern that corresponds to the shape of the slices of the object, and irradiating to cure the build compound in each layer. Irradiation is preferably performed according to the same irradiation protocol as described in connection with operation 603 above.

[0216] In some embodiments, the method continues at 605, where a formulation suitable for use as a coating formulation described herein is dispensed onto the exterior surface of the object and cured to form a solidified coating. In some embodiments, the coating formulation is the same as the primer formulation dispensed at 602. The coating is formed by dispensing the formulation in layers onto the object and irradiating each layer of the formulation with curing radiation. In some embodiments, the coating formulation is also dispensed to at least partially surround one or more layers formed at 604. Such full or partial surrounding coatings can be formed substantially simultaneously with the formation of each layer of the object, for example, by dispensing the build formulation and the coating formulation using different nozzle arrays on the dispensing head 16. Alternatively, a full or partial surrounding coating can be formed for each layer after the build formulation layer is dispensed, as shown by the loop-back arrow from 605 back to 604. An advantage of forming a full or partial surrounding coating is that it also provides a coating to the sides of the object. For example, a coating that surrounds the object to be printed on all sides can be provided by dispensing the coating formulation so as to completely surround each layer formed in 604. Irradiation in 605 is preferably carried out according to the same irradiation protocol as described in connection with operation 603. The thickness of the solidified coating is preferably from about 0.01 mm to about 0.5 mm, for example about 0.05 mm or about 0.1 mm.

[0217] In some embodiments of the invention, the method proceeds to 606, where the object or the top layer of the coating (if present) is coated with a coating having an intensity I A Intensity I, which is different from B Preferably, no formulation is dispensed during 606. Intensity I B is preferably of intensity I A It is twice as much.

[0218] The irradiation protocol used by the controller in 606 is optionally and preferably different from the irradiation protocol used in 603. Specifically, in 606, a curing irradiation pattern having the shape of two stripes is formed on the layer and advanced along the scanning direction (x or φ). Representative examples of irradiation protocols suitable for operation 606 are shown in FIGS. 13C and 13D, which show a layer 614 of the object 112 on the fabric 420 and a curing irradiation pattern 616 in the form of two straight stripes propagating along the direction x when the fabric 420 is on the tray 360 (FIG. 13C), or a curing irradiation pattern 616 in the form of two straight stripes propagating along the direction φ when the fabric 420 is on the tray 12 (FIG. 13D). Such an irradiation curing pattern can be generated by operating both solidification devices at the same power as used during operation 603. Specifically, if the system is configured for reciprocating relative motion along a straight line (e.g., system 110), operation 606 can be performed by activating both a solidification device following the print head and a solidification device followed by the print head. Alternatively, if the system is configured for rotational relative motion (e.g., system 10), operation 606 can be performed by activating both a solidification device rotationally ahead of the print head and a solidification device rotationally behind the print head. Control of the solidification devices is typically performed by a controller of the three dimensional printing system (e.g., controller 20 of system 10 or system 110).

[0219] Alternatively, operation 606 can be performed by doubling the power of one solidification device and deactivating the other solidification device, resulting in the same illumination pattern as shown in Figures 13A and 13B, but at twice the intensity.

[0220] In some embodiments of the invention, the object is a test object that is printed to test the level of adhesion that the adhesive structure provides. In these embodiments, the method proceeds to 607, where the level of adhesion of the object to the fabric is tested. Representative examples of test objects and testing procedures suitable for this embodiment are provided below. If a test object is used, operation 605 can be omitted.

[0221] The method ends at 608.

[0222] 6B, the method described in this flowchart is suitable for implementation where the fabric has a relatively low level of absorption. The method begins at 620 and optionally and preferably continues to 601, where computer object data is received, as detailed above.

[0223] The method continues at 621 where a primer / adhesive formulation as described herein is dispensed to form a first stack of uncured layers. Dispensing occurs either onto the fabric or onto a previously dispensed layer, selectively performed according to computer object data for the bottom surface of the object, as detailed above. For each layer of the first stack, the formulation is dispensed without curing. Thus, all solidification devices are not activated during operation 621. The number of layers dispensed without curing during operation 621 is less than five, and more preferably less than four. In a preferred embodiment, the first stack consists of two layers.

[0224] The method continues to 622 where a primer formulation is dispensed onto the first stack to form a layer. The method continues to 623 where the formulation is dispensed onto the first stack at the aforementioned irradiation intensity I B It is irradiated with an intensity of I B A typical value of is about 5 W / cm 2 to about 10 W / cm 2 For any layer of the adhesive structure, operation 623 is preferably performed according to a protocol in which a curing radiation pattern 616 having the shape of two stripes is generated on the layer and advanced along the scanning direction (x or φ), as already described in detail in connection with operation 606 and illustrated in Figures 13C and 13D.

[0225] The method optionally and preferably loops back from 623 to 622 to form the next layer of the bonded structure. This loop is repeated a predetermined number of times. Preferably, this loop is repeated until the number of layers of the bonded structure reaches N2, where N2 is about 10 to about 30 layers, or about 15 to about 30 layers. As discussed below, the present disclosure contemplates performing two or more of the methods described in FIGS. 6A-6C on the same fabric or the same type of fabric. When both method 600 and method 620 are performed on the same fabric, the value of N2 is optionally and preferably less than the value of N1. For example, if N1=15, then N2 may be 10; if N1=20, then N2 may be 18; etc.

[0226] Upon completion of the loop including 622 and 623, a second stack of layers is formed and the method optionally and preferably continues to 604, where a three-dimensional object is printed onto the top layer of the second stack. The object is preferably printed using one or more build materials (such as, but not limited to, one or more of the build materials described above). The object is printed by dispensing one or more build compounds in layers in a structured pattern according to the shape of the slices of the object, and irradiating the build compound in each layer with curing radiation. The irradiation is preferably performed according to the same irradiation protocol as described in connection with operation 603 above.

[0227] In some embodiments, the method continues at 605, where a formulation suitable for use as a coating formulation is dispensed onto the exterior surface of the object and cured, as previously described. Also, in some embodiments, the method continues at 606, where a top layer of the object or coating is cured to a strength I B The curing radiation is scanned at .

[0228] In some embodiments of the invention, the method continues to 607 where the level of adhesion of the object to the fabric is tested mutatis mutandis as described above, as will be described below.

[0229] The method ends at 628.

[0230] 6C, the method described in this flowchart is suitable for implementation where the fabric has a relatively high level of absorption. The method begins at 640 and optionally and preferably continues to 601, where computer object data is received, as detailed above.

[0231] The method continues at 641 where a primer / adhesive formulation as described herein is dispensed to form a layer onto the fabric, or if such a layer has already been formed by this method, onto the previously dispensed layer, with the formulation being selectively dispensed according to computer object data for the bottom surface of the object, as detailed above.

[0232] The method continues at 642, where the formulation is exposed to the aforementioned curing radiation at an irradiation intensity I C The irradiation intensity I C is usually the aforementioned irradiation intensity I B It is higher than, for example, about twice as high. C A typical value of is about 10 W / cm 2 to approximately 22 W / cm 2 is.

[0233] For any layer of the bonded structure formed by method 640, operation 642 is preferably performed according to a protocol in which a curing radiation pattern 616 is generated on the layer. Here, as already described in detail in connection with operation 606 and shown in Figures 13C and 13D, the pattern has the shape of two stripes and is advanced along the scanning direction (x or φ). Operation 642 can be performed by activating both curing devices of the system, each of which applies a radiation intensity I C606). In order to provide a solidification device that is in a state where the solidification device ...

[0234] Upon completion of the loop including 641 and 642, a stack of layers has been formed and the method optionally and preferably continues to 604, where a three-dimensional object is printed on the top layer of the previously formed stack. The object is preferably printed using one or more build materials (such as, but not limited to, one or more of the build materials described above). The object is printed by dispensing one or more build compounds in layers in a structured pattern according to the shape of the slices of the object, and irradiating the build compound in each layer with curing radiation. The irradiation is performed according to the same irradiation protocol as described in connection with operation 603 above.

[0235] In some embodiments, the method continues at 605, where a formulation suitable for use as a coating formulation is dispensed onto the exterior surface of the object and cured, as previously described. Also, in some embodiments, the method continues at 606, where a top layer of the object or coating is cured to a strength I B The curing radiation is scanned at .

[0236] The method ends at 647.

[0237] In some embodiments of the present invention, an operator first determines which of the above methods is more appropriate for the fabric and selects the appropriate method. Thus, the operator obtains parameters describing the fabric and selects one of methods 600, 620, 640, and 840 based on the obtained parameters. The parameters may be the fabric's absorption level or an indicator thereof. For example, the parameters may be the type of fabric, and the operator may use a lookup table to determine the fabric's absorption level. If the absorption level is less than a predetermined threshold, the operator can perform method 620. If the absorption level is greater than a predetermined threshold, the operator can perform method 640. The operator can select method 600 as a default method and perform method 600 when the fabric's absorption level is unknown.

[0238] The present embodiments also contemplate performing one or more of methods 600, 620, 640, and 840 multiple times on the same fabric or fabric type. For example, one or more of these methods can be repeated for different fabric directions on the same side of the fabric and / or for different sides of the fabric. These embodiments are particularly useful for testing, where each method may include a test operation 607 during each run of the method to determine the direction and / or side that provides the highest adhesion.

[0239] In this embodiment, it is also contemplated that two or more of methods 600, 620, 640, and 840 may be performed on the same fabric or fabric of the same type. These embodiments are also useful for testing, in which a prototyping operation 607 may be performed during each run of the method to determine which printing protocol provides the highest adhesion for the fabric under consideration. When two or more methods are performed using the same fabric, different methods form bonded structures on different portions of the fabric. This type of testing may also be combined with testing adhesion levels for different directions and / or different sides of the fabric. Thus, in this combined testing, two or more of methods 600, 620, 640, and 840 may be performed on the same fabric or fabric of the same type, and may also be performed on at least two different directions and / or two different sides of the same fabric or fabric of the same type. For each method, a prototyping operation 607 may be performed during each run of the method to determine which printing protocol, direction, and / or side provides the highest adhesion level.

[0240] In some embodiments of the present invention, the method is performed to fabricate objects such as, but not limited to, lenticular objects, prismatic objects, objects that reflect visible light, objects that are transparent to visible light but reflect non-visible light, fluorescent objects, and waveguides. In some embodiments, the fabricated object is capable of changing optical, mechanical, and / or geometric properties in response to environmental changes, such as, but not limited to, temperature changes, humidity changes, electromagnetic changes in the environment, etc. For example, the object may be made of a photosensitive material that changes its color in response to changes in light conditions or temperature.

[0241] In some embodiments of the present invention, the method is performed to fabricate an object that includes an agent, such as, but not limited to, a pharmaceutical and / or cosmetic product. For example, the agent can be adsorbed onto the surface of the object (e.g., by applying the agent as an additive to a build material), or the object can be in the form of a capsule containing the agent. Representative examples of pharmaceutical agents that can be incorporated into the object include, but are not limited to, antibacterial and antiviral agents.

[0242] In some embodiments of the present invention, the method is performed to fabricate an object comprising a heating element capable of emitting heat or a cooling element capable of absorbing heat, in some embodiments the method is performed to fabricate an object comprising a circuit, and in some embodiments the method is performed to fabricate an object comprising a cavity for receiving a foreign object, such as, but not limited to, an electrical circuit, a magnetic element, a light emitting element, a chip, or a capsule containing a pharmaceutical or cosmetic product.

[0243] When testing 607 is performed by each method, the object is preferably a test object having a shape selected to facilitate testing.

[0244] Test objects are fabricated by printing build material to form two-component structures. Plan views of a representative example of a two-component structure 720 suitable for this embodiment are shown in FIGS. 7A-7C, and a side view of a representative example of the two-component structure 720 is shown in FIG. 7D. The two-component structure 720 is formed from a first stack 722 of build material layers, which is laterally offset from a second stack 724 of build material layers. These layers are stacked along a vertical direction z defined relative to the printing system (see FIGS. 1A and 1C), with stacks 722 and 724 offset from each other along a horizontal direction perpendicular to the vertical direction. FIGS. 7A-7C show plan views of the structure 720, with only the top layers 720 and 724 of each stack visible. In FIGS. 7A-7C, the vertical direction z is depicted as a circled dot, indicating that it points outward from the plane of the drawing. A side view of the two-part structure 720, adhesive structure 740, and fabric 742 is shown in FIG. 7D, with the vertical direction z also depicted as an upward arrow.

[0245] In some embodiments of the present invention, at least one of stacks 722 and 724, and more preferably both stacks 722 and 724, include a plurality of through-holes 734 that define open cells within stacks 722 and 724. For example, stacks 722 and 724 may have a honeycomb structure. Although through-holes 734 are shown as hexagonal in FIGS. 7A-7C, they may be any other shape. An advantage of having through-holes 734 in stacks 722 and 724 is that they reduce the likelihood of the periphery of structure 720 curling relative to its center during the printing process.

[0246] Stacks 722 and 724 are separated by a gap 726. The width of gap 726 is preferably constant along the gap, although it is contemplated that in some embodiments, gap 726 may have a non-uniform width. The width of gap 726 is preferably less than 1 mm, for example, from about 0.4 mm to about 0.9 mm. In our experiments, widths of 0.5 mm, 0.7 mm, and 0.9 mm have been used. While FIG. 7D illustrates the case where an adhesive structure 740 is also formed below gap 726, this is not necessarily the case. In some embodiments, it may be desirable to configure a material layer that has the same lateral shape as structure 720 and is vertically aligned with structure 720. In these embodiments, there are two stacks of material layers, one stack vertically aligned below stack 722 and the other stack vertically aligned below stack 724. A representative representation of two adhesive structures 740a, 740b separated by a gap is shown in FIG. 8A, described below.

[0247] Two-component structure 720 is preferably elongated with a planar width-to-length aspect ratio of about 1:3 to about 1:10. The length of two-component structure 720 is defined as the combined length of stack 722, gap 726, and stack 724. Preferably, the length of structure 720 is about 50 mm to about 200 mm, and the width of structure 720 is preferably about 10 mm to about 20 mm.

[0248] Gap 726 is optionally and preferably not linear. In these embodiments, stack 722 and stack 724 can be viewed as a male-female pair. For example, stack 722 can be defined as a male stack, and stack 724 can be defined as a female stack. In some embodiments of the invention, gap 726 has a piecewise linear shape, as shown in FIGS. 7A and 7B . In some embodiments of the invention, gap 726 has a curved shape, as shown in FIG. 7C . If the gap has a piecewise linear shape, it preferably forms an acute angle at one or more breakpoints 728. If the gap has a piecewise linear shape, it preferably has at least one vertex 728. In the representative examples shown in FIGS. 7A-7C , the gap has a V-shape ( FIG. 7A ), a W-shape ( FIG. 7B ), and an arc-shape ( FIG. 7C ). However, other piecewise linear or curved shapes are also contemplated for gap 726. The advantage of having a gap with a break point or apex is that it facilitates partial peeling of stack 722 and / or stack 724 from the fabric during a bend test. Specifically, a point 732 located on the periphery of male stack 722 adjacent to gap 726 and near (e.g., closest to) break point 728 or apex 730 can be the peel point because the adhesion between structure 720 and the fabric is weakest near peel point 732.

[0249] In various exemplary embodiments of the invention, stacks 722 and 724 each have a bending resistance that is higher than the bending resistance of the bonded structure and higher than the bending resistance of fabric 742. This relationship can be achieved by selecting a material for building structure 720 that is stiffer than bonded structure 740 and fabric 742, and / or by making the thickness of stacks 722, 724 along the vertical direction z greater than the thickness of bonded structure 740 and fabric 742. Preferably, the thickness of stacks 722 and 724 is at least two times greater, and more preferably at least three times greater, than the thickness of bonded structure 740. In some embodiments, the thickness of stacks 722 and 724 is at least two times greater, and more preferably at least three times greater, than the thickness of fabric 742.

[0250] A typical thickness of the bonded structure 740 is about 0.1 mm to about 1 mm, more preferably about 0.2 mm to about 0.9 mm, and more preferably about 0.2 mm to about 0.8 mm. A typical thickness of the stacks 722 and 724 is about 1 mm to about 4 mm, more preferably about 1.6 mm to about 3 mm, and more preferably about 2 mm to about 3 mm. In experiments conducted by the inventors, thicknesses of 0.3 mm and 0.6 mm were used for the stacks 740, and a thickness of 2.2 mm was used for the stacks 722 and 724.

[0251] The testing procedure typically involves bending fabric 742 at gap 726 so that at least one of stacks 722 and 724 peels from the fabric at peel point 732. Because both the test object and the adhesive structure are fabricated by printing, the adhesion between the adhesive structure and the build material forming the test object printed on the adhesive structure is stronger than the adhesion between the adhesive structure and the fabric.

[0252] A preferred procedure for performing operation 704 is shown in Figures 8A and 8B. Structure 720 is positioned so that it contacts a pair of posts 750. Preferably, structure 720 contacts post pair 750, and fabric 742 is spaced apart from post pair 750. Figure 8B is an exploded view from a perspective showing the side of fabric 742 that does not include structure 720. Posts 750 are positioned on a jig 754, and fabric 742 can contact posts 750 in a horizontal orientation (Figure 8A) or a vertical orientation (Figure 8B).

[0253] Force-applying pin 752 is positioned to engage fabric 742 near the location of gap 726 (not shown in FIGS. 8A-8B ), and pin 752 applies force F perpendicular to fabric 742 (generally in the direction of strut pair 750). In the configuration shown in FIG. 8A (horizontal orientation of fabric 742), F acts downward, while in the configuration shown in FIG. 8B (vertical orientation of fabric 742), F acts horizontally. Force F causes fabric 742 to bend toward the space between strut pair 750. Due to the high bending resistance of stacks 722 and 724, stacks 722 and 724 begin to peel from fabric 742 (with stack 740 being more strongly adhered to structure 720 than to fabric 742) at the weakest point of adhesion near the gap.

[0254] It can be seen that the above procedure provides a qualitative assessment of the adhesion level of the substance to the fabric. If a more quantitative assessment of the adhesion level is desired, the magnitude of the force F and the strain of the fabric 742 can be measured, for example, by a device 756 (FIG. 8B) that measures the displacement of the pin 752 and the force applied by the pin. The adhesion level of the substance to the fabric can then be determined based on the measured values. For example, the measured values ​​can be analyzed to identify a maximum load at which an abrupt change occurs in the correlation between force and displacement, and this maximum load can be defined as the adhesion level. Typically, displacement increases approximately linearly with force until the force reaches the maximum load. Once the displacement exceeds the displacement at the maximum load point, the displacement no longer increases linearly with force. At this stage, there is often a negative correlation between displacement and force. Therefore, the maximum load can be identified as the force at which the linear increase in displacement with force ends.

[0255] <Additive formulation> According to an aspect of some embodiments of the present invention there is provided an additive formulation for use in combination with a build material formulation in three-dimensional printing of objects on fabric.

[0256] According to any of the embodiments described herein, the additive formulation is characterized by one or more of a viscosity in the range of about 15 to about 25, or about 15 to about 20 centipoise or mPa / sec, a surface tension in the range of about 20 to about 40, or about 26 to about 30, or about 26 to about 28 Dyne / cm, and an adhesion level to the respective fabric of at least 20 N / cm.

[0257] According to any of the optional embodiments described herein, the additive formulation is an adhesive (primer) formulation that upon solidification provides an adhesive material or structure on the fabric.

[0258] According to any of the optional embodiments described herein, the additive formulation is a coating or finishing formulation that upon solidification provides a coating for an object or portion thereof.

[0259] According to any of the optional embodiments described herein, the additive formulation is both an adhesive (primer) formulation that upon solidification provides an adhesive material or structure on the fabric, and a coating or finishing formulation that upon solidification provides a coating for an object or portion thereof.

[0260] According to any of the embodiments described herein, the additive formulation includes a combination of one or more monofunctional curative materials and one or more multifunctional curative materials.

[0261] According to any of the embodiments described herein, the one or more monofunctional curable materials comprise at least one monofunctional curable material characterized by at least one polar group capable of interacting with surface functional groups of the textile and a Tg of less than 50°C.

[0262] According to some of these embodiments, the amount of the at least one monofunctional curative material having at least one polar group capable of interacting with surface functional groups in the textile and characterized by a Tg less than 50°C is 85 to 90 wt% of the total formulation weight, including any intermediate values ​​and subranges therebetween.

[0263] According to any of the embodiments described herein, the one or more multifunctional curable materials include at least one multifunctional curable material characterized by a Tg of less than 50°C.

[0264] According to some of these embodiments, the amount of the at least one multifunctional curable material characterized by a Tg less than 50°C is 10 to 15 wt% of the total formulation weight, including any intermediate values ​​and subranges therebetween.

[0265] According to any of the embodiments of the present invention, the additive formulation comprises at least one monofunctional curative material having at least one group capable of interacting with surface functional groups in the textile and characterized by a Tg less than 50°C, in an amount of 85-90% of the total formulation (including intermediate values ​​and subranges therebetween), and at least one multifunctional curative material characterized by a Tg less than 50°C, in an amount of 10-15% of the total formulation (including intermediate values ​​and subranges therebetween).

[0266] Fabrics typically contain multiple exposed surface groups, which are typically hydroxyl groups or other polar groups, but may also contain hydrophobic and / or aromatic groups. The groups capable of interacting with such surface functional groups generally include groups capable of forming temporary bonds with those functional groups, such as hydrogen bonds, hydrophobic interactions, aromatic interactions, or other similar interactions. For example, if the surface functional groups of the fabric are hydrophobic, the groups capable of interacting with these functional groups may be alkyl, cycloalkyl, and aryl groups, as defined herein, or hydrocarbon groups, preferably all-carbon groups having 2, 3, 4, or more carbon atoms. If the surface functional groups of the fabric are aromatic, the groups capable of interacting with these functional groups may be or include aromatic groups, such as aryl and / or heteroaryl groups, as defined herein. These groups may interact with the surface groups through aromatic interactions, such as π-π stacking. If the surface functional groups of the fabric are hydroxyl groups or any other polar groups (e.g., carboxylate groups or amine groups), the groups capable of interacting with these functional groups are generally polar groups, capable of electrostatically interacting with the surface groups, such as through hydrogen bonds.

[0267] According to some embodiments, the at least one monofunctional curable material is characterized by at least one polar group capable of interacting with surface functional groups in the textile. Such materials are also referred to herein as "component A."

[0268] The term "polar group" refers to a charge polarizable group capable of exhibiting temporary charge polarization.

[0269] Exemplary polar groups typically contain one or more electron-donating heteroatoms that form strong hydrogen bonds with the surface polar groups, including, but not limited to, oxygen and nitrogen.

[0270] Exemplary polar groups include, but are not limited to, electron-donating heteroatoms (e.g., oxygen or nitrogen), carboxylates, thiocarboxylates, oxo (=O), linear amides, hydroxy groups, alkoxy groups (1 to 4 carbon atoms), alcohols (1 to 4 carbon atoms), heteroalicyclic (e.g., having a ratio of carbon atoms to heteroatoms as defined herein), cyclic carboxylates such as lactones, cyclic amides such as lactams, carbamates, thiocarbamates, cyanurates, isocyanurates, thiocyanurates, ureas, thioureas, alkylene glycols (e.g., ethylene glycol or propylene glycol), and the like.

[0271] In an exemplary embodiment, the monofunctional curable material comprises one or more hydroxy groups and an electron donating heteroatom.

[0272] According to some embodiments, the one or more monofunctional curable materials, for example component A, are collectively represented by Formula I: YLX Formula I where: Y is a terminal group, optionally and preferably selected from alkyl groups (including linear and branched, substituted or unsubstituted alkyls), aryl groups, heteroaryl groups, cycloalkyl groups, alicyclic heterocyclic groups, hydroxy groups, alkoxy groups, aryloxy groups, and amine groups; X is a polymerizable group, optionally and preferably a (meth)acrylate group (-OC(=O)-CR1=CR2R3), where R1 is hydrogen for acrylates and methyl for methacrylates, and R2 and R3 are typically each hydrogen; L is a linking moiety consisting of a hydrocarbon having 2 to 10 carbon atoms, preferably 2 to 8 or 2 to 6 carbon atoms, substituted with at least one polar group (e.g., a hydroxy group), and optionally interrupted by one or more heteroatoms (e.g., heteroatoms capable of forming hydrogen bonds with the hydroxy group, such as oxygen or nitrogen).

[0273] In an exemplary embodiment, at least one monofunctional curable material is a monofunctional (meth)acrylate, where X is a (meth)acrylate group, and the monofunctional curable material is represented by Formula Ia:

[0274] [ka] where R1 is hydrogen (in the case of acrylates) or alkyl (e.g., methyl in the case of methacrylates).

[0275] In an exemplary embodiment, R1 is hydrogen.

[0276] In some embodiments, Y is an alicyclic heterocyclic group, a hydroxy group, an alkoxy group. , aryloxy groups, and amine groups, and in exemplary embodiments, Y is an alkoxy group or an aryloxy group (eg, a phenoxy group).

[0277] In some embodiments, L is a hydrocarbon group of 2 to 6 carbon atoms or 2 to 4 carbon atoms substituted with one or more hydroxy groups.

[0278] An exemplary monofunctional acrylate material, Component A, is provided in the Examples section below.

[0279] According to embodiments described herein, the additive formulation includes one or more multifunctional curative materials characterized by a Tg of less than 50° C., also referred to herein as “Component D.”

[0280] According to some embodiments, the at least one multi-functional curable material comprises a di-functional curable material characterized by an indicated Tg.

[0281] According to some embodiments, the at least one multifunctional curable material comprises a multifunctional (e.g., difunctional) aliphatic or non-aromatic (e.g., aliphatic or cycloaliphatic) meth(acrylate) characterized by an indicated Tg.

[0282] According to some embodiments, the at least one multifunctional curable material comprises a multifunctional (e.g., difunctional) aliphatic or non-aromatic (e.g., aliphatic or cycloaliphatic) urethane meth(acrylate) characterized by an indicated Tg.

[0283] According to any of the embodiments described herein, the one or more multifunctional curable materials are characterized by a Tg of -20 to 50°C, or -20 to 40°C, or -20 to 30°C, or -20 to 20°C, or -10 to 40°C, or -10 to 30°C, or -10 to 20°C, or 0 to 50°C, or 0 to 40°C, or 0 to 30°C, including any intermediate values ​​and subranges therebetween.

[0284] Exemplary multifunctional curable materials include the family of materials sold under the Miramer trade name, for example, Miramer® PU2100NT.

[0285] According to any of the embodiments described herein, the additive formulation is a biocompatible formulation, where all components, or at least components present in an amount greater than 0.1%, or greater than 0.5%, or greater than 1%, are biocompatible.

[0286] According to any of the embodiments described herein, each of the curable materials in the formulation is a biocompatible material.

[0287] According to any of the embodiments described herein, each curable material in the formulation is free of materials that are considered not biocompatible, such as free of metal catalysts (e.g., catalyst-free), and free of other materials that may be present in residual amounts with the curable materials as a result of the synthetic process for preparing these curable materials.

[0288] According to any of the embodiments described herein, each of the multifunctional curable materials is a multifunctional (e.g., difunctional) acrylate or a multifunctional (e.g., difunctional) urethane acrylate.

[0289] According to any of the embodiments described herein, each of the monofunctional curable materials is a monofunctional acrylate.

[0290] According to any of the embodiments described herein, at least one, or all, of the curable materials in the formulation are photocurable materials (e.g., UV-curable materials such as acrylic materials), and the additive formulation further includes at least one photoinitiator (Component J).

[0291] According to any of the embodiments described herein, the amount of photoinitiator ranges from 1 to 3 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0292] According to some of the optional embodiments described herein, the photoinitiator(s) comprise or consist essentially of a phosphine oxide type (e.g., a monoacrylated phosphine oxide type (MAPO) or a bisacrylated phosphine oxide type (BAPO) photoinitiator).

[0293] Exemplary monoacyl and bisacyl phosphine oxides include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis(2,6-dimethylphenyl)phosphonate, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide. Commercially available phosphine oxide photoinitiators capable of free radical initiation when irradiated in the wavelength range from about 380 nm to about 450 nm include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available as IRGACURE® 819), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (commercially available as CGI 403), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (commercially available as CGI 403), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (commercially available as CGI 403). Examples of suitable methylbenzylphosphine oxides include a 25:75 by weight mixture of trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (commercially available as IRGACURE® 1700), a 1:1 by weight mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (commercially available as DAROCUR® 4265), and ethyl 2,4,6-trimethylbenzylphenylphosphinate (LUCIRINLR8893X).

[0294] According to any of the embodiments described herein, the photoinitiator comprises or consists essentially of a bis-acrylated phosphine oxide (BAPO) photoinitiator.

[0295] In an exemplary embodiment, the photoinitiator comprises or consists essentially of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available as IRGACURE® 819).

[0296] In exemplary embodiments, the photoinitiator does not include monoacrylated (MAPO) phosphine oxide photoinitiators, and in some embodiments does not include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commercially available as TPO).

[0297] According to any of the embodiments described herein, the additive formulation may further comprise additional non-curing components, such as, for example, inhibitors, surfactants, dispersants, colorants (coloring components), and stabilizers. Commonly used surfactants, dispersants, colorants, and stabilizers are contemplated. Exemplary concentrations of each component, if present, range from about 0.01 to about 1 wt. %, or from about 0.01 to about 0.5 wt. %, or from about 0.01 to about 0.1 wt. %, based on the total weight of the formulation including it, including any intermediate values ​​and subranges therebetween. Exemplary components are described below.

[0298] In any of the embodiments described herein, the formulation includes a cure inhibitor, i.e., an agent that inhibits or suppresses cure in the absence of cure conditions, also referred to herein as Component I. In some embodiments, the inhibitor is a free radical polymerization inhibitor. In some embodiments, the amount of inhibitor (e.g., Component I, e.g., a free radical inhibitor) ranges from 0.01 to 2 wt. %, or 0.01 to 1 wt. %, or 0.05 to 0.5 wt. %, or 0.1 to 0.2 wt. %, including any intermediate values ​​and subranges therebetween, depending on the type of inhibitor used. Commonly used inhibitors, such as radical inhibitors, are contemplated.

[0299] According to any of the embodiments described herein, the additive formulation further comprises an inhibitor (Component I) as described herein, such as a phenolic-type inhibitor, or any other inhibitor commonly used in medical devices or applications, and / or foods.

[0300] According to any of the embodiments described herein, the amount of inhibitor ranges from 0.05 to 0.5% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0301] In an exemplary embodiment, the free radical inhibitor is a member of the Genorad® series (eg, Genorad 20), or the like.

[0302] In exemplary embodiments, such free radical inhibitors are used in amounts of 0.1 to 3 wt %, or 0.1 to 2 wt %, or 0.1 to 1 wt %, or 0.1 to 0.5 wt %, including intermediate values ​​and subranges therebetween.

[0303] According to any of the optional embodiments described herein, the additive formulation further comprises one or more dispersants or surfactants (Component H).

[0304] According to any of the embodiments described herein, the amount of dispersant ranges from 0.01 to 1 wt. %, or from 0.1 to 0.5 wt. %, of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0305] Exemplary dispersants and surfactants include those commercially available as BYK surface additives.

[0306] According to some of these embodiments, the dispersant is such that it is characterized by a curable group, preferably a (meth)acrylic group.

[0307] According to any of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicon (meth)acrylate.

[0308] According to any of the embodiments described herein, the dispersing agent is a difunctional aliphatic silicon (meth)acrylate.

[0309] According to any of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicone acrylate.

[0310] According to any of the embodiments described herein, the dispersant is a difunctional aliphatic silicone acrylate.

[0311] According to any of the embodiments described herein, the dispersant has an average molecular weight (MW) of at least 1,000 grams / mole, or at least 2,000 grams / mole, or at least 3,000 grams / mole, and is considered an oligomeric material.

[0312] According to any of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicon (meth)acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0313] According to any of the embodiments described herein, the dispersing agent is a difunctional aliphatic silicon (meth)acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0314] According to any of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicone acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0315] According to any of the embodiments described herein, the dispersing agent is a difunctional aliphatic silicone acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0316] According to any of the embodiments described herein, the dispersant, once solidified, is characterized by a low Tg, preferably below 0°C, or below -20°C, or below -50°C.

[0317] According to any of the embodiments described herein, the amount of dispersant ranges from 0.1 to 0.5 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0318] According to any of the embodiments described herein, the additive formulation is a clear (e.g., transparent), colorless formulation, which does not contain any colorants or pigments.

[0319] According to any of the embodiments described herein, the additive formulation further comprises one or more colorants or pigments (ingredient P).

[0320] The colorant is a pigment or a dye, preferably a pigment.

[0321] The pigments may be organic and / or inorganic and / or metallic pigments, and in some embodiments, the pigments are nanoscale pigments, including nanoparticles.

[0322] Exemplary inorganic pigments include nanoparticles of titanium oxide and / or zinc oxide and / or silica. Exemplary organic pigments include nano-sized carbon black.

[0323] In some embodiments, a combination of white and colored pigments is used to prepare the colored cured material.

[0324] According to any of the embodiments described herein, the colorant comprises a pigment and at least one (meth)acrylic material, wherein the pigment is introduced into the formulation in a mixture.

[0325] According to any of the embodiments described herein, the pigment is a white pigment and the formulation provides a white cured product.

[0326] According to any of the embodiments described herein, the colorant comprises a white pigment and one or more curable materials, such as a (meth)acrylic material, and the white pigment is introduced into the formulation within this mixture.

[0327] According to some of these embodiments, the amount of white pigment in the mixture ranges from 20 to 50 weight percent of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0328] According to some of these embodiments, when the colorant is a mixture of a white pigment and at least one (meth)acrylic material, the amount of colorant ranges from 1 to 5 wt. % of the total weight of the formulation.

[0329] According to any of the embodiments described herein, the pigment is a cyan pigment and the formulation provides a cyan cure.

[0330] According to any of the embodiments described herein, the colorant comprises a cyan pigment and one or more curable materials, such as (meth)acrylic materials, and the cyan pigment is introduced into the formulation within this mixture.

[0331] According to some of these embodiments, the amount of cyan pigment in the mixture ranges from 0.01 to 1 wt %, or 0.05 to 0.5 wt %, or 0.1 to 0.2 wt %, of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0332] According to some of these embodiments, when the colorant is a mixture of a cyan pigment and at least one (meth)acrylic material, the amount of colorant is in the range of 0.1 to 1 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0333] According to any of the embodiments described herein, the pigment is a yellow pigment and the formulation provides a yellow cured product.

[0334] According to any of the embodiments described herein, the colorant includes a yellow pigment and one or more curable materials, such as (meth)acrylic materials, and the yellow pigment is introduced into the formulation within the mixture.

[0335] According to some of these embodiments, the amount of yellow pigment in the mixture ranges from 0.01 to 1 wt. %, or 0.05 to 0.5 wt. %, or 0.1 to 0.2 wt. % of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0336] According to some of these embodiments, when the colorant is a mixture of a yellow pigment and at least one (meth)acrylic material, the amount of colorant is in the range of 0.1 to 1 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0337] According to any of the embodiments described herein, the pigment is a magenta pigment and the formulation provides a magenta cured product.

[0338] According to any of the embodiments described herein, the colorant comprises a magenta pigment and one or more curable materials, such as (meth)acrylic materials, and the magenta pigment is introduced into the formulation within the mixture.

[0339] According to some of these embodiments, the amount of magenta pigment in the mixture ranges from 0.01 to 1 wt. %, or 0.05 to 0.5 wt. %, or 0.1 to 0.2 wt. % of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0340] According to some of these embodiments, when the colorant is a mixture of a magenta pigment and at least one (meth)acrylic material, the amount of colorant is in the range of 0.1 to 1 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0341] According to any of the embodiments described herein, the formulation includes one or more white, magenta, cyan, and yellow colorants, and in some of these embodiments, each pigment is introduced into the formulation in admixture with the curable material described herein.

[0342] According to any of the embodiments described herein, the colorant further comprises a pigment dispersant (component Dp). Preferred pigment dispersants include those having multiple groups that characterize their affinity for the pigment.

[0343] According to any of the embodiments described herein, the additive formulation includes components H, I, and J, as described herein in any of the respective embodiments. An exemplary such formulation is a clear, colorless formulation that does not contain any colorant.

[0344] According to any of the embodiments described herein, the additive formulation includes components H, I, J, P, and optionally component Dp, as described herein in any of the respective embodiments. An exemplary such formulation is a white formulation including a white pigment as described herein.

[0345] According to any of the embodiments described herein, the additive formulation includes components H, I, J, P, and optionally component Dp, as described herein in any of the respective embodiments.

[0346] <Kit> According to some of the embodiments described herein, kits are provided that include one or more additive formulations as described in any of the respective embodiments herein and any combination thereof.

[0347] According to some of the embodiments described herein, there is provided a kit comprising two or more additive formulations, and any combination thereof, as described in any of the respective embodiments and any combination thereof herein, in some of these embodiments, each formulation is packaged separately within the kit.

[0348] In an exemplary embodiment, the kit includes a combination of two or more formulations that differ from one another by the presence and / or type of colorant or pigment.

[0349] In an exemplary embodiment, the kit includes a combination of two or more formulations, one of which can be used as an adhesive formulation and another of which can be used as a coating formulation, as described herein.

[0350] The kits described herein, including one or more additive formulations, can be used for additive manufacturing of three-dimensional objects on fabrics.

[0351] In exemplary embodiments, the formulation is packaged in a kit in a suitable packaging material, preferably an impermeable material (e.g., a material impermeable to water and gas), and more preferably an opaque material. In some embodiments, the kit further includes instructions for using the formulation in an additive manufacturing process, preferably a 3D inkjet printing process as described herein. The kit further includes instructions for using the formulation in a process according to the methods described herein.

[0352] According to some of the optional kit embodiments, the kit may further include one or more additive formulations described herein.

[0353] In an exemplary embodiment, the kit further includes a formulation such as that described in Example 4 of the Examples section below, which may be used as a build material formulation as described herein.

[0354] <Objects and Manufactured Products> According to some embodiments of the present invention, there is provided a three-dimensional object obtained by the additive manufacturing process described herein using at least one additive formulation as described in any of the respective embodiments herein and any combination thereof.

[0355] According to some embodiments, the object is formed on a substrate, such as a fabric described herein.

[0356] According to some embodiments of the present invention, there is provided an article of manufacture comprising a substrate as described herein and a three-dimensional object applied to at least a portion of a surface of the substrate.

[0357] In some of these embodiments, the substrate is a fabric, and the article of manufacture can be any article that includes or is made from a fabric, including, for example, clothing.

[0358] As used herein, the term "about" refers to ±10%, or ±5%.

[0359] The words "comprises," "comprising," "includes," "including," "having," and their conjugations are used to mean "including, but not limited to."

[0360] The term "consisting of" means "including and limited to."

[0361] The term "consisting essentially of" means that a composition, method, or structure may include additional ingredients, steps, and / or components, but only if the additional ingredients, steps, and / or components do not materially alter the basic and novel characteristics of the claimed composition, method, or structure.

[0362] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. For example, the term "a compound" or "at least one compound" can encompass multiple compounds, including mixtures thereof.

[0363] Throughout this application, various embodiments of the present invention may be presented in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as a fixed limitation on the scope of the invention. Accordingly, the description of a range should be considered to have specifically disclosed all possible subranges along with individual numerical values ​​within that range. For example, a description of a range such as 1 to 6 should be considered to have specifically disclosed subranges such as 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc., as well as individual numerical values ​​within that range, e.g., 1, 2, 3, 4, 5, and 6. This applies regardless of the broadness of the range.

[0364] Whenever a range of numerical values ​​is given herein, it is meant to include any stated number (fractional or integer) within the given range. The phrases "ranging between" a first specified number and a second specified number and "ranging from" a first specified number "to" a second specified number are used interchangeably herein and are meant to include the first specified number and the second specified number, and all fractional and integer numbers therebetween.

[0365] As used herein, the terms "method" or "process", which are used interchangeably herein, refer to ways, means, techniques, and procedures for accomplishing a given task, and include, but are not limited to, such methods, means, techniques, and procedures that are known to or readily developed by those skilled in the art of chemistry, pharmacology, biology, biochemistry, and medicine from known methods, means, techniques, and procedures.

[0366] Throughout this specification, whenever the expressions "weight percent," "wt. %," and "% wt." are used in the context of embodiments of formulations (e.g., shaping formulations), they refer to weight percent relative to the total weight of the respective uncured formulation.

[0367] Throughout this specification, acrylic materials are used to collectively refer to materials characterized by one or more acrylate, methacrylate, acrylamide, and / or methacrylamide groups.

[0368] Similarly, acrylic groups are used to collectively refer to curable groups that include acrylate groups, methacrylate groups, acrylamide groups, and / or methacrylamide groups, preferably acrylate groups or methacrylate groups (also referred to herein as (meth)acrylate groups).

[0369] Throughout this specification, the term "(meth)acrylic" encompasses acrylic and methacrylic materials. Urethane acrylates are also contemplated.

[0370] Throughout this specification, the phrase "linking moiety" or "linking group" refers to a group that connects two or more moieties or groups in a compound. Linking moieties are usually derived from bifunctional or trifunctional compounds and can be considered as bi- or tri-radical moieties, each bonded through its two or three atoms to two or three other moieties.

[0371] Exemplary linking moieties include hydrocarbon moieties or hydrocarbon chains (optionally interrupted by one or more heteroatoms as defined herein) and / or any of the chemical groups listed below when defined as linking groups.

[0372] When a chemical group is referred to herein as a "terminal group," it should be interpreted as a substituent that is connected through one atom of it to another group.

[0373] Throughout this specification, the term "hydrocarbon" refers generally to a chemical group composed primarily of carbon and hydrogen atoms. The hydrocarbon can be composed of alkyl, alkene, alkyne, aryl, and / or cycloalkyl, each of which may be substituted or unsubstituted and may be interrupted by one or more heteroatoms. The number of carbon atoms may range from 2 to 30, but is preferably fewer, e.g., 1 to 10, or 1 to 6, or 1 to 4. The hydrocarbon can be a linking group or a terminal group.

[0374] Bisphenol A is an example of a hydrocarbon consisting of two aryl groups and one alkyl group. Dimethylencyclohexane is an example of a hydrocarbon consisting of two alkyl groups and one cycloalkyl group.

[0375] As used herein, the term "amine" refers to both the -NR'R" and -NR'- groups, where R' and R" are each independently hydrogen, alkyl, cycloalkyl, or aryl, as defined below.

[0376] Thus, the amine group can be a primary amine where R' and R" are both hydrogen; a secondary amine where R' is hydrogen and R" is alkyl, cycloalkyl, or aryl; or a tertiary amine where each of R' and R" is independently alkyl, cycloalkyl, or aryl.

[0377] Alternatively, R′ and R″ can each independently be hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, carbonyl, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, and hydrazine.

[0378] The term "amine," as defined herein, is used herein to represent the group --NR'R" when the amine is a terminal group, and the group --NR'-- when the amine is part of a linking group or moiety.

[0379] The term "alkyl" refers to saturated aliphatic hydrocarbons, including straight-chain and branched-chain groups. Preferably, alkyl groups have 1 to 30 or 1 to 20 carbon atoms. Whenever a numerical range is provided herein, e.g., "1 to 20," it indicates that the group, in this case, the alkyl group, can contain up to 20 carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. Alkyl groups can be substituted or unsubstituted. Substituted alkyls can have one or more substituents. Each substituent can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, and hydrazine.

[0380] An alkyl group, as defined herein, may be a terminal group attached to a single adjacent atom, or may be a linking group, as defined herein, connecting two or more moieties through at least two carbon atoms in the chain. When alkyl is a linking group, it is also referred to herein as an "alkylene" or an "alkylene chain."

[0381] Alkenes and alkynes, as used herein, are alkyls as defined herein and each contain one or more double or triple bonds.

[0382] The term "cycloalkyl" refers to an all-carbon monocyclic ring or fused ring (i.e., rings that share adjacent pairs of carbon atoms) group in which one or more of the rings does not have a completely conjugated pi-electron system. Examples include, but are not limited to, cyclohexane, adamantine, norbornyl, isobornyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. Substituted cycloalkyls can have one or more substituents. whereby each substituent independently can be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amido, N-amido, guanyl, guanidine, and hydrazine. A cycloalkyl group, as defined herein, can be a terminal group attached to a single adjacent atom, or a linking group, as defined herein, linking two or more moieties at two or more positions thereof.

[0383] The term "alicyclic heterocycle" refers to a monocyclic or fused ring group containing one or more atoms, such as nitrogen, oxygen, or sulfur, within the ring. The ring may also contain one or more double bonds, provided that the ring does not have a completely conjugated pi-electron system. Representative examples include piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino, oxalidine, and the like.

[0384] The alicyclic heterocyclic group may be substituted or unsubstituted. A substituted alicyclic heterocycle may have one or more substituents, whereby each substituent may independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, O-carbamate, N-carbamate, C-amide, N-amide, guanyl, guanidine, and hydrazine. The alicyclic heterocyclic group may be a terminal group, as defined herein, bonded to a single adjacent atom, or a linking group, as defined herein, linking two or more moieties at two or more positions thereof.

[0385] The term "aryl" refers to an all-carbon monocyclic or fused-ring polycyclic (i.e., rings sharing adjacent pairs of carbon atoms) group having a completely conjugated π-electron system. Aryl groups can be substituted or unsubstituted. A substituted aryl can have one or more substituents, whereby each substituent can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, N-carbamate, O-carbamate, C-amide, N-amide, guanyl, guanidine, and hydrazine. An aryl group, as defined herein, may be a terminal group attached to a single adjacent atom, or may be a linking group, as defined herein, linking two or more moieties at two or more positions thereof.

[0386] The term "heteroaryl" refers to a monocyclic or fused ring (i.e., rings sharing adjacent pairs of atoms) group containing one or more atoms, such as nitrogen, oxygen, or sulfur, in the ring and having a completely conjugated π-electron system. Examples of heteroaryl groups include, but are not limited to, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, isoquinoline, and purine. Heteroaryl groups may be substituted or unsubstituted. Substituted alicyclic heterocycles may have one or more substituents. Thus, each substituent can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, alicyclic heterocycle, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, O-carbamate, N-carbamate, C-amide, N-amide, guanyl, guanidine, and hydrazine. The heteroaryl group may be a terminal group, as defined herein, bonded to a single adjacent atom, or a linking group, as defined herein, linking two or more moieties at two or more positions. Representative examples include pyridine, pyrrole, oxazole, indole, purine, and the like.

[0387] The terms "halide" and "halo" refer to fluorine, chlorine, bromine, or iodine.

[0388] The term "haloalkyl" refers to an alkyl group, as defined herein, further substituted with one or more halide groups.

[0389] The term "sulfate" refers to an -OS(=O)2-OR' terminal group or an -OS(=O)2-O- linking group, as defined herein, where R' is as defined herein.

[0390] The term "thiosulfate" refers to an -OS(=S)(=O)-OR' terminal group or an -OS(=S)(=O)-O- linking group, as defined herein, where R' is as defined herein.

[0391] The term "sulfite" refers to an -OS(=O)-O-R' terminal group or an -OS(=O)-O- linking group, where R' is as defined herein.

[0392] The term "thiosulfite" refers to an -OS(=S)-O-R' terminal group or an -OS(=S)-O- linking group, where R' is as defined herein.

[0393] The term "sulfinate" refers to an -S(=O)-OR' terminal group or an -S(=O)-O- linking group, as defined herein, where R' is as defined herein.

[0394] The terms "sulfoxide" or "sulfinyl" refer to an -S(=O)R' terminal group or an -S(=O)- linking group, as defined herein, where R' is as defined herein.

[0395] The term "sulfonate" refers to an -S(=O)2-R' terminal group or an -S(=O)2- linking group, as defined herein, where R' is as defined herein.

[0396] The term "S-sulfonamide" refers to an -S(=O)2-NR'R" terminal group or an -S(=O)2-NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0397] The term "N-sulfonamide" refers to an R'S(=O)2-NR"- terminal group or an -S(=O)2NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0398] The term "disulfide" refers to an -S-SR' terminal group or an -SS- linking group, where R' is as defined herein.

[0399] The term "phosphonate" refers to a -P(=O)(OR')(OR") terminal group or a -P(=O)(OR')(O)- linking group, as defined herein, where R' and R" are as defined herein.

[0400] The term "thiophosphonate" refers to a -P(=S)(OR')(OR") terminal group or a -P(=S)(OR')(O)- linking group, as defined herein, where R' and R" are as defined herein.

[0401] The term "phosphinyl," as defined herein, refers to a -PR'R" terminal group or a -PR'- linking group, where R' and R" are as defined above.

[0402] The term "phosphine oxide," as defined herein, refers to a -P(=O)(R')(R") terminal group or a -P(=O)(R')- linking group, where R' and R" are as defined herein.

[0403] The term "phosphine sulfide," as defined herein, refers to a -P(=S)(R')(R") terminal group or a -P(=S)(R')- linking group, where R' and R" are as defined herein.

[0404] The term "phosphite," as defined herein, refers to an -O-PR'(=O)(OR") end group or an -O-PH(=O)(O)- linking group, where R' and R" are as defined herein.

[0405] The term "carbonyl" or "carbonate" as used herein refers to a -C(=O)-R' terminal group or a -C(=O)- linking group, where R' is as defined herein.

[0406] The term "thiocarbonyl," as used herein, refers to a -C(=S)-R' terminal group or a -C(=S)- linking group, where R' is as defined herein.

[0407] The term "oxo," as used herein, represents the (=O) group, in which an oxygen atom is connected by a double bond to an atom (eg, a carbon atom) at the indicated position.

[0408] The term "thiooxo," as used herein, represents the (=S) group in which a sulfur atom is connected by a double bond to an atom (eg, a carbon atom) at the indicated position.

[0409] The term "oxime," as defined herein, refers to an =N-OH terminal group or an =NO- linking group.

[0410] The term "hydroxyl" refers to the group --OH.

[0411] The term "alkoxy" refers to both an -O-alkyl group and an -O-cycloalkyl group, as defined herein. The term alkoxide refers to an -R'O- group, where R' is as defined herein.

[0412] The term "aryloxy" refers to both an --O-aryl group and an --O-heteroaryl group, as defined herein.

[0413] The terms "thiohydroxy" or "thiol" refer to an -SH group. The term "thiolate" refers to an -S- group.

[0414] The term "thioalkoxy" refers to both an --S-alkyl group and an --S-cycloalkyl group, as defined herein.

[0415] The term "thioaryloxy" refers to both an --S-aryl group and an --S-heteroaryl group, as defined herein.

[0416] The term "hydroxyalkyl," also known as "alcohol," refers to an alkyl, as defined herein, substituted with a hydroxy group.

[0417] The term "cyano" refers to the group --C.ident.N.

[0418] The term "isocyanate" refers to the group --N.dbd.C.dbd.O.

[0419] The term "isothiocyanate" refers to the group --N.dbd.C.dbd.S.

[0420] The term "nitro" refers to the group --NO.sub.2.

[0421] The term "acyl halide" refers to the group --(C.dbd.O)R"" where R"" is a halide, as defined herein.

[0422] The terms "azo" or "diazo" refer to an -N=NR' terminal group or an -N=N- linking group, as defined herein, where R' is as defined herein.

[0423] The term "peroxo" refers to an -O-OR' terminal group or an -OO- linking group, where R' is as defined herein.

[0424] As used herein, the term "carboxylate" includes C-carboxylate and O-carboxylate.

[0425] The term "C-carboxylate" refers to a -C(=O)-OR' terminal group or a -C(=O)-O- linking group, as defined herein, where R' is as defined herein.

[0426] The term "O-carboxylate" refers to an -OC(=O)R' terminal group or an -OC(=O)- linking group, where R' is as defined herein.

[0427] Carboxylate groups can be linear or cyclic. In the cyclic case, R' and a carbon atom are bonded to form a C-carboxylate ring. This group is also called a lactone. Alternatively, R' and O are bonded to form an O-carboxylate ring. Cyclic carboxylates can function as linking groups, for example, when an atom in the resulting ring is linked to another group.

[0428] As used herein, the term "thiocarboxylate" includes C-thiocarboxylates and O-thiocarboxylates.

[0429] The term "C-thiocarboxylate" refers to a -C(=S)-OR' terminal group or a -C(=S)-O- linking group, as defined herein, where R' is as defined herein.

[0430] The term "O-thiocarboxylate" refers to an -OC(=S)R' terminal group or an -OC(=S)- linking group, where R' is as defined herein.

[0431] Thiocarboxylates can be linear or cyclic. In the cyclic case, R' and a carbon atom are bonded to form a C-thiocarboxylate ring. This group is also called a thiolactone. Alternatively, R' and an O are bonded to form an O-thiocarboxylate ring. Cyclic thiocarboxylates can function as linking groups, for example, when an atom in the resulting ring is linked to another group.

[0432] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0433] The term "N-carbamate" refers to an R"OC(=O)-NR'- terminal group or an -OC(=O)-NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0434] The term "O-carbamate" refers to an -OC(=O)-NR'R" terminal group or an -OC(=O)-NR'- linking group, where R' and R" are as defined herein.

[0435] Carbamates can be linear or cyclic. In the cyclic case, R' and a carbon atom are bonded to form a ring, O-carbamate. Alternatively, R' and O are bonded to form a ring, N-carbamate. Cyclic carbamates can function as linking groups, for example, when an atom in the resulting ring is linked to another group.

[0436] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0437] As used herein, the term "thiocarbamate" includes N-thiocarbamates and O-thiocarbamates.

[0438] The term "O-thiocarbamate" refers to an -OC(=S)NR'R" terminal group or an -OC(=S)NR'- linking group, where R' and R" are as defined herein.

[0439] The term "N-thiocarbamate" refers to an R"OC(=S)NR'- terminal group or an -OC(=S)NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0440] The thiocarbamates can be linear or cyclic, as described herein for carbamates.

[0441] As used herein, the term "dithiocarbamate" includes S-dithiocarbamates and N-dithiocarbamates.

[0442] The term "S-dithiocarbamate" refers to an -SC(=S)NR'R" terminal group or an -SC(=S)NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0443] The term "N-dithiocarbamate" refers to an R"SC(=S)NR'- terminal group or an -SC(=S)NR'- linking group, as defined herein, where R' and R" are as defined herein.

[0444] The term "urea," also referred to herein as "ureido," refers to an -NR'C(=O)-NR"R"' terminal group or an -NR'C(=O)-NR"- linking group, as defined herein, where R' and R" are as defined herein and R"' is the same as defined for R' and R".

[0445] The term "thiourea," also referred to herein as "thioureido," refers to an -NR'-C(=S)-NR"R"' terminal group or an -NR'-C(=S)-NR"- linking group, as defined herein, where R', R" and R"' are as defined herein.

[0446] As used herein, the term "amide" includes C-amides and N-amides.

[0447] The term "C-amido" refers to a -C(=O)-NR'R" terminal group or a -C(=O)-NR'- linking group, where R' and R" are as defined herein.

[0448] The term "N-amido" refers to the R'C(=O)-NR"- terminal group or R'C(=O)-N- linking group, where R' and R" are as defined herein.

[0449] Amides can be linear or cyclic. In the cyclic case, R' and the carbon atom bond to form a C-amide ring. This group is also called a lactam. Cyclic amides can function as linking groups, for example, when an atom in the resulting ring is linked to another group.

[0450] The term "guanyl" refers to the R'R"NC(=N)-terminus group or the -R'NC(=N)- linking group, where R' and R" are as defined herein.

[0451] The term "guanidine" refers to the -R'NC(=N)-NR"R"' terminal group or the -R'NC(=N)-NR"- linking group, where R', R" and R"' are as defined herein.

[0452] The term "hydrazine," as defined herein, refers to an -NR'-NR"R"' terminal group or an -NR'-NR"- linking group, where R', R" and R"' are as defined herein.

[0453] As used herein, the term "hydrazide" refers to a -C(=O)-NR'-NR"R"' terminal group or a -C(=O)-NR'-NR"- linking group, where R', R" and R"' are as defined herein.

[0454] As used herein, the term "thiohydrazide" refers to a -C(=S)-NR'-NR"R"' terminal group or a -C(=S)-NR'-NR"- linking group, where R', R" and R"' are as defined herein.

[0455] As used herein, the term "alkylene glycol" refers to -O-[(CR'R") z -O] y -R"' terminal group or -O-[(CR'R") z -O] y-represents a linking group. Here, R', R", and R"' are as defined herein. Here, z is an integer of 1 to 10, preferably 2 to 6, more preferably 2 or 3, and y is an integer of 1 or greater. Preferably, R' and R" are both hydrogen. When z is 2 and y is 1, the group is ethylene glycol. When z is 3 and y is 1, the group is propylene glycol. When y is 2 to 4, the alkylene glycol is referred to herein as an oligo(alkylene glycol).

[0456] The term "silanol" refers to a -Si(OH)R'R" group, or a -Si(OH)R' group, or a -Si(OH) group, where R' and R" are as defined herein.

[0457] The term "silyl" refers to the group -SiR'R"R"', where R', R" and R"' are as defined herein.

[0458] As used herein, the terms "urethane," "urethane moiety," or "urethane group" refer to an Rx-OC(=O)-NR'R" terminal group or an -Rx-OC(=O)-NR'- linking group, where R' and R" are as defined herein and Rx is alkyl, cycloalkyl, aryl, alkylene glycol, or any combination thereof. Preferably, R' and R" are both hydrogen.

[0459] The term "polyurethane" or "oligourethane" refers to a moiety that contains, in its repeating backbone unit, at least one urethane group, as described herein, or at least one urethane linkage (-OC(=O)-NR'-).

[0460] Throughout this specification, the expressions "weight percent," "wt. %," and "% wt.", when used in the context of formulation (e.g., shaping formulation) embodiments, always refer to weight % relative to the total weight of the respective uncured formulation.

[0461] As used herein, "ethoxylated" materials refer to acrylic or methacrylic compounds, as defined herein, that contain one or more alkylene glycol groups, or preferably one or more alkylene glycol chains. Ethoxylated (meth)acrylate materials can be monofunctional, or preferably multifunctional, i.e., difunctional, trifunctional, tetrafunctional, etc.

[0462] In polyfunctional materials, each (meth)acrylate group is typically linked to an alkylene glycol group or alkylene glycol chain, which are in turn linked to each other through branching units such as branched alkyl, cycloalkyl, aryl (e.g., bisphenol A), etc.

[0463] In some embodiments, the ethoxylated material comprises at least one or at least two ethoxylated groups, i.e., at least one or at least two alkylene glycol moieties or groups. Some or all of the alkylene glycol groups can be linked to each other to form an alkylene glycol chain. For example, an ethoxylated material comprising 30 ethoxylated groups can comprise one chain of 30 alkylene glycol groups linked to each other, or two chains of, e.g., 15 alkylene glycol moieties linked to each other, connected via a branch, or three chains of, e.g., 10 alkylene glycol moieties linked to each other, connected via a branch. Shorter or longer chains are also contemplated.

[0464] The ethoxylated material can contain one, two or more alkylene glycol chains of any length.

[0465] As used herein, the term "branching unit" refers to a multi-radical, preferably an aliphatic or alicyclic group. "Multi-radical" means that the branching unit has two or more points of attachment such that the branching unit interconnects two or more atoms and / or groups or moieties.

[0466] In some embodiments, the branching unit may be derived from a chemical moiety having two, three, or more functional groups, hi some embodiments, the branching unit is a branched alkyl, or cycloalkyl (alicyclic), or aryl (e.g., phenyl), as defined herein.

[0467] Throughout this specification, the "Tg" of a material refers to the glass transition temperature, defined as the location of the maximum in the E" curve, where E" is the loss modulus of the material as a function of temperature.

[0468] Roughly speaking, as the temperature is increased within a certain temperature range that includes the Tg temperature, the state of a material, particularly a polymeric material, gradually changes from a glassy state to a rubbery state.

[0469] As used herein, a "Tg range" is a temperature range in which the E" value is at least half (e.g., may reach) the E" value at the Tg temperature defined above.

[0470] Without being bound by any particular theory, it is believed that the state of a polymeric material gradually changes from a glassy state to a rubbery state within the Tg range defined above, the lowest temperature in the Tg range being referred to herein as Tg(low) and the highest temperature in the Tg range being referred to herein as Tg(high).

[0471] Throughout this specification, whenever a curable material is defined by the properties of the hardened material obtained therefrom, it should be understood that these properties refer to the hardened material obtained from the curable material itself.

[0472] Throughout this specification, unless otherwise stated, viscosity values ​​are given as the viscosity of a material or formulation measured at 25°C using a Brookfield viscometer. Measurements are given in centipoise, which is equivalent to mPa·sec.

[0473] It is understood that certain features of the invention, which are for clarity described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various features of the invention that are for brevity described in the context of a single embodiment may also be provided separately or in any suitable subcombination, or as appropriate to any other described embodiment of the invention. Certain features described in the context of various embodiments should not be considered essential features of those embodiments unless the embodiment is inoperable without those elements.

[0474] Various embodiments and aspects of the present invention as described herein and as claimed in the claims section below find experimental support in the following examples. [Example]

[0475] Reference is now made to the following examples, which together with the above descriptions illustrate some embodiments of the present invention in a non-limiting fashion.

[0476] [Experimental Method] Tear resistance (TR) was determined according to ASTM D624 and is expressed in N / m.

[0477] Shore A hardness was determined using a Shore A durometer according to ASTM-2240.

[0478] The printability of the formulations was determined by evaluating their suitability for 3D inkjet systems (e.g., systems such as those depicted in FIG. 1A or 1B-1D, and / or systems equipped with an LED curing energy source) in terms of viscosity, reactivity, jettability, etc.

[0479] Curling and deformation were visually inspected (see, for example, Figures 7A-7B).

[0480] Formulations were prepared by mixing all ingredients at room temperature unless otherwise noted. Powdered ingredients, such as photoinitiators, were dissolved at 85°C for 30 minutes.

[0481] Viscosity was measured using a Brookfield viscometer and is reported in centipoise, which is equivalent to mPa·sec.

[0482] Surface tension was measured using a Kruss K6 Force Tensiometer and expressed in dyne / cm.

[0483] Adhesion was measured as described herein for Test Procedure 607 and expressed as maximum force required to peel (N / cm).

[0484] Jetting properties were evaluated, for example, by recording the jetting patterns using a high speed camera and analytical weight and / or by using a jetting station that tests the jetting parameters relevant to the printing process.

[0485] [Example 1] -design- The present inventors have sought to develop curable formulations that can be effectively used as additive formulations to form adhesive and / or coating materials.

[0486] More specifically, the inventors have designed a formulation that can function as a curable adhesive additive formulation. Such a formulation is ejected from a print head to form a pattern of adhesive material. The adhesive material promotes adhesion of a subsequently ejected build material, which is comprised of a build material formulation. This formulation can also function as a coating formulation. The coating formulation is ejected from a print head after the ejection of the build material formulation to form a pattern of coating material. The coating material improves properties such as tear resistance and durability of the printed object (e.g., the object's color retention, washability).

[0487] The present inventors have devised the use of curable materials characterized by functional groups capable of interacting with common fabric functional groups (preferably polar protic functional groups capable of interacting (e.g., via hydrogen bond formation) with hydroxy groups commonly present on fabric surfaces), which are further characterized by a Tg of less than 100°C, or less than 80°C, or less than 50°C, providing a cured product with flexibility suitable for application on fabrics.

[0488] Such exemplary materials can be summarized by Formula I: YLX Formula I wherein Y is a terminal group and can be, for example, an alkyl group (including straight-chained and branched, substituted or unsubstituted alkyl), an aryl group, a heteroaryl group, a cycloalkyl group, an alicyclic heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, and an amine group; X is a polymerizable group, preferably a (meth)acrylate group as described herein; and L is a hydrocarbon having 2 to 10 carbon atoms, preferably 2 to 8 or 2 to 6 carbon atoms in length, substituted with at least one hydroxy group and, optionally, with one or more heteroatoms (e.g., heteroatoms capable of forming hydrogen bonds with the hydroxy groups, such as oxygen or nitrogen).

[0489] When X is a (meth)acrylate group, such exemplary materials can be collectively represented by Formula Ia:

[0490] [ka] wherein Y and L are as defined herein, and R1 is hydrogen in the case of an acrylate polymerizable moiety or methyl in the case of a methacrylate polymerizable moiety.

[0491] For this purpose, we selected a hydrophilic monofunctional epoxy (meth)acrylate material characterized by a hydroxy group as an exemplary curable material, such as 2-hydroxy-3-phenoxypropyl acrylate, which is commercially available under the trade name "DA-141" and has the following structure:

[0492] [ka]

[0493] The inventors have tested various combinations of this representative curable material with other curable materials and identified formulations that exhibit the desired performance.

[0494] The inventors have realized that the desired performance should include sufficient "adhesion" to fabrics at a level of at least 20 N / cm and / or sufficient "tear resistance" to the coated object of at least 10,000 N / m, and further include "dischargeability" (e.g., viscosity of 15-30 centipoise, or 15-25 centipoise, or 15-20 centipoise at the discharge temperature (e.g., 70°C), surface tension of 20-40, preferably 20-30 or 26-30, at the discharge temperature).

[0495] Furthermore, the formulation is designed to be suitable for use in the system shown in FIG. 1A or the systems shown in FIGS. 1B-1D, each of which includes an LED radiation source (e.g., 395 nm wavelength), and is preferably designed to be biocompatible.

[0496] Table 1 below shows the test materials.

[0497] [Table 1]

[0498] [Example 2] Tables 2A and 2B below show the chemical compositions of exemplary test formulations. Components H1, H2 and I are typically present in amounts less than 0.5 wt. % based on the total weight of the formulation.

[0499] [Table 2]

[0500] [Table 3]

[0501] The viscosity and surface tension of the test formulations, as well as the maximum adhesive strength after solidification of the dispensed material, were measured as described above. The resulting data are shown in Table 3 below. VeroClear® was used as the build material formulation. The formulations were dispensed onto different fabrics, as shown in Figures 9 and 10, for example. The presented data represent the average adhesive strength values ​​obtained.

[0502] [Table 4]

[0503] As can be seen from the table, Formulations II, VII, and IX provided the best adhesion. Formulations II and IX, on the other hand, were characterized by high surface tension and were therefore deemed to have poor jettability. These data indicate that to achieve best performance, the amount of component A in the formulation should be in the range of 85-90 wt. %, that component A and component D should be combined in a weight ratio of 3:1 to 10:1, preferably 6:1 to 10:1, with the amount of component D being in the range of 10-15 wt. %, and that it is preferable to use a formulation featuring a curable group (component H2) as a dispersant / surfactant (preferably only 0.1-0.5 wt. %).

[0504] [Example 3] The performance of exemplary adhesive formulation VIII was tested on various fabrics featuring different materials and / or different colors, using different printing systems, and / or printing conditions, and / or post-printing treatments (e.g., washing). VeroClear® was used as the build material formulation. The procedure described above with reference to Figures 6A-6D was applied.

[0505] Figure 9 shows the measured adhesion levels for various fabrics and shows that sufficient adhesion was obtained for all fabrics.

[0506] Figure 10 shows the durability of adhesive formulations applied to five different fabrics, determined when held at conditions reflecting accelerated aging, i.e., 60°C and 10% humidity. Under these conditions, one day corresponds to approximately 10 days at ambient conditions (room temperature and humidity). For Fabrics 1-4 (blue, orange, jeans, and beige, respectively), the bonded structures were formed by Method 640, and for Fabric 5 (pink), the bonded structure was formed by Method 620. As shown, adhesion levels of greater than 15 N / cm were achieved for all tested fabrics. Furthermore, satisfactory adhesion levels are maintained even after the equivalent of two years.

[0507] FIG. 11 shows the adhesion level of exemplary formulation VIII described herein when it is deposited on the various test fabrics identified above at different thicknesses of adhesive material (structure).

[0508] 12 shows the tear resistance of objects printed in gloss mode on a tray using various build material formulations without coating formulation dispensed (reference) and with exemplary coating formulation VIII dispensed at different coating thicknesses. The data obtained demonstrates improved tear resistance of the printed objects.

[0509] [Example 4] Exemplary Flexible Build Material Formulations Exemplary build material formulations have desirable Shore A hardness values ​​(e.g., 70-100) and printability, preferably to provide a biocompatible cured product suitable for 3D printing onto fabrics, such as clothing fabrics.

[0510] Exemplary build material formulations include materials that are free of elements that may adversely affect the biocompatibility of the cured product.

[0511] The exemplary formulation is suitable for use in the system described in Figures 1B-1D, which includes an LED radiation source (eg, 395 nm wavelength).

[0512] Exemplary build material formulations are also referred to herein as "build formulations" or "flexible formulations" or "flexible build formulations" or "build material formulations that provide a flexible material upon solidification," including other variations thereof.

[0513] The build material formulation is a hardenable formulation that includes a combination of hardenable materials as defined herein and thus hardens or solidifies upon exposure to curing conditions, as defined herein.

[0514] The build material formulation of the present embodiment is designed to be suitable for forming three-dimensional objects into fabrics by additive manufacturing (e.g., 3D inkjet printing), and provides a flexible material upon solidification.

[0515] According to any of the embodiments described herein, the build material formulation is designed so that the cured product formed therefrom is characterized by mechanical properties corresponding to a flexible material and / or meets the requirements of the material to be printed on the fabric, such as, for example, an appropriate Shore A hardness (e.g., 80-100, or 80-90) and / or high tear resistance (e.g., greater than 10,000 N / m, greater than 12,000 N / m, or greater than 15,000 N / m, e.g., 10,000-25,000 N / m).

[0516] According to some embodiments, the build material formulation, upon solidification, Tg, as defined herein, is less than 50°C, e.g., 0 to 50°C, 0 to 45°C, 0 to 40°C, 0 to 30°C, 10 to 40°C, 20 to 40°C, 10 to 30°C, or 10 to 30°C, including any intermediate values ​​and subranges therebetween; a Shore A hardness, determined as defined herein, of at least 80, for example 80 to 120, or 80 to 100, preferably 80 to 90; and a tear resistance of at least 10,000 N / m, at least 12,000 N / m, or at least 15,000 N / m, e.g., 10,000 to 25,000 N / m, 12,000 to 25,000 N / m, or 15,000 to 25,000 N / m, including any intermediate values ​​and subranges therebetween; The formulation is such that it provides one or more of the following:

[0517] According to any of the embodiments described herein, the build material formulation is a biocompatible formulation, where all components, or at least components present in an amount greater than 0.1%, or greater than 0.5%, or greater than 1%, are biocompatible.

[0518] According to any of the embodiments described herein, each of the curable materials in the formulation is a biocompatible material.

[0519] According to any of the embodiments described herein, each curable material in the formulation is free of materials that are considered not biocompatible, such as free of metal catalysts (e.g., catalyst-free), and free of any other materials that may be present in residual amounts with the curable materials as a result of the synthetic process for preparing these curable materials.

[0520] Some build material formulations of the present embodiments include a combination of mono- and multi-functional materials characterized by a low Tg, for example, less than 150°C, or less than 100°C.

[0521] According to any of the embodiments of the present invention, the total amount of monofunctional and multifunctional materials characterized by a low Tg as described herein is at least 60 wt%, at least 65 wt%, at least 70 wt%, at least 75 wt%, at least 80 wt%, at least 85 wt%, or even at least 90 wt% of the total weight of the formulation, such as 60-95 wt%, 60-90 wt%, 70-90 wt%, 70-95 wt%, 80-95 wt%, 80-90 wt%, 60-85 wt%, 60-80 wt%, 70-85 wt%, 70-80 wt%, including any intermediate values ​​and subranges therebetween.

[0522] According to any of the embodiments described herein, the build material formulation comprises: at least one monofunctional curable material characterized by a Tg of less than 150°C, in a total amount of 40 to 60 wt%, based on the total weight of the formulation, including any intermediate values ​​and subranges therebetween; at least one multifunctional curative material characterized by a Tg greater than 100°C or greater than 150°C in an amount of 4 to 10 wt%, including any intermediate values ​​and subranges therebetween, based on the total weight of the formulation; and at least one multifunctional curable material characterized by a Tg of less than 150°C or less than 100°C in a total amount of 25 to 35 wt%, including any intermediate values ​​and subranges therebetween, based on the total weight of the formulation.

[0523] -Monofunctional curing material- According to any of the embodiments described herein, the formulation includes one or more monofunctional curable materials, each characterized by a Tg of less than 150°C.

[0524] According to any of the embodiments described herein, the formulation comprises two or more monofunctional materials.

[0525] According to some of these embodiments, the one or more monofunctional curable materials include at least one first monofunctional curable material (referred to herein as Component A1) characterized by a Tg of 50 to 150°C. * and the one or more other monofunctional curable materials comprise at least one second monofunctional curable material (referred to herein as component A2) characterized by a Tg of less than 50°C, or less than 20°C. * and / or B * (also referred to as "commonly used").

[0526] According to any of the embodiments described herein, the formulation may contain one (or more) first monofunctional curable material (component A1) characterized by a Tg between 50 and 150°C. * ) and two or more second monofunctional curable materials (component A2) characterized by a Tg of less than 50°C or less than 20°C. * and B * ) is included.

[0527] According to any of the embodiments described herein, each of the one or more monofunctional curable materials described herein is a monofunctional (meth)acrylate.

[0528] According to any of the embodiments described herein, each of the monofunctional materials has an average molecular weight of less than 1,000 grams / mole, or less than 500 grams / mole.

[0529] According to any of the embodiments described herein, the one or more monofunctional curable materials may comprise one or more first monofunctional (meth)acrylates (referred to herein as Component A1) characterized by a Tg in the range of 50 to 150°C, including any intermediate values ​​and subranges therebetween. * and one or more second monofunctional (meth)acrylates (referred to herein as component A2) characterized by a Tg of less than 50° C. or less than 20° C. * (also referred to as "internal stimuli").

[0530] According to some embodiments, the first monofunctional curable material described herein (e.g., the first monofunctional (meth)acrylate, i.e., component A1) * ) is a hydrophobic material, as described herein.

[0531] According to some embodiments, a second monofunctional curable material (e.g., a second monofunctional (meth)acrylate, i.e., component A2) described herein is used. * ) is a hydrophilic and / or amphiphilic material, as described herein.

[0532] As used throughout this specification, the term "hydrophilic" refers to the physical property of a material or a portion of a material (e.g., a chemical group in a compound) that describes the temporary formation of bonds with water molecules, typically via hydrogen bonds.

[0533] A hydrophilic material is more soluble in water than in oil or other hydrophobic solvents, as can be determined, for example, by a LogP of less than 0.5 when the LogP is determined in the octanol and water phases.

[0534] Hydrophilic materials may alternatively or additionally have a lipophilicity / hydrophilicity balance (HLB) of at least 10, or alternatively at least 12, as determined by the Davies method.

[0535] As used throughout this specification, the term "amphiphilic" refers to the property of a material that combines both hydrophilicity, as described herein for hydrophilic materials, and hydrophobicity or lipophilicity, as defined herein for hydrophobic materials.

[0536] Amphiphilic materials typically contain both hydrophilic groups, as defined herein, and hydrophobic groups, as defined herein, and are substantially soluble in both water and water-immiscible solvents (oils).

[0537] An amphiphilic material can be characterized, for example, by having a LogP of 0.8 to 1.2, or about 1, when the LogP is determined in octanol and aqueous phases.

[0538] Alternatively or additionally, amphiphilic materials can be determined by having a lipophilic / hydrophilic balance (HLB) of 3 to 12, or 3 to 9, as determined by the Davis method.

[0539] As used throughout this specification, the term "hydrophobic" refers to the physical property of a material or part of a material (e.g., a chemical group in a compound) that does not form bonds with water molecules.

[0540] A hydrophobic material is more soluble in oil than in water or other hydrophilic solvents, as can be determined, for example, by a LogP greater than 1 when the LogP is determined in the octanol and water phases.

[0541] Hydrophobic materials may alternatively or additionally be determined by having a lipophilic / hydrophilic balance (HLB) of less than 3 according to the Davis method.

[0542] Hydrophilic materials or portions of materials (eg, chemical groups in chemical compounds) are generally charge-polarized and capable of forming hydrogen bonds.

[0543] Amphiphilic materials generally contain one or more hydrophilic groups (eg, charge polarizable groups) in addition to hydrophobic groups.

[0544] A hydrophobic material or portion of a material (eg, a chemical group in a chemical compound) is generally non-polarizable and unable to form hydrogen bonds.

[0545] Hydrophilic materials or hydrophilic groups, and amphiphilic materials, generally contain one or more electron-donating heteroatoms that form strong hydrogen bonds with water molecules. Such heteroatoms include, but are not limited to, oxygen and nitrogen. Preferably, the ratio of the number of carbon atoms to the number of heteroatoms in the hydrophilic material or hydrophilic group is 10:1 or less, e.g., 8:1, more preferably 7:1, 6:1, 5:1, or 4:1, or even less. Note that the hydrophilic and amphiphilic properties of materials and groups may also depend on the ratio between the hydrophobic and hydrophilic moieties in the material or chemical group, and are not solely dependent on the above ratio.

[0546] A hydrophilic or amphiphilic material may have one or more hydrophilic groups or moieties. Hydrophilic groups are generally polar groups containing one or more electron-donating heteroatoms such as oxygen or nitrogen.

[0547] Exemplary hydrophilic groups include, but are not limited to, electron-donating heteroatoms, carboxylates, thiocarboxylates, oxo (=O), linear amides, hydroxy, alkoxy (1-4 carbon atoms), alcohols (1-4 carbon atoms), alicyclic heterocycles (e.g., having a carbon atom to heteroatom ratio as defined herein), cyclic carboxylates such as lactones, cyclic amides such as lactams, carbamates, thiocarbamates, cyanurates, isocyanurates, thiocyanurates, ureas, thioureas, alkylene glycols (e.g., ethylene glycol or propylene glycol), and hydrophilic polymeric or oligomeric moieties, as well as any combination of these hydrophilic groups as defined herein (e.g., hydrophilic groups comprising two or more of the exemplified hydrophilic groups).

[0548] In some embodiments, the hydrophilic group is or includes an electron donating heteroatom, a carboxylate, an alicyclic heterocycle, an alkylene glycol, and / or a hydrophilic oligomeric moiety.

[0549] An amphiphilic moiety or group generally comprises one or more hydrophilic groups and one or more hydrophobic groups as described herein, or it may be a heteroatom-containing group or moiety that is amphiphilic due to the ratio of the number of carbon atoms to the number of heteroatoms.

[0550] Hydrophobic groups include all carbon groups, such as alkyl groups, alkenyl groups, alkynyl groups, aryl groups, cycloalkyl groups, and the like.

[0551] The monomeric monofunctional (meth)acrylate materials according to this embodiment can be collectively represented by Formula A.

[0552] [ka] where R1 is a carboxylate, -C(=O)-O-Ra, R2 is hydrogen (in the case of an acrylate) or methyl (in the case of a methacrylate), and Ra is an aliphatic, alicyclic, or aromatic moiety, which can be hydrophilic or hydrophobic, as described herein.

[0553] When the material is a cycloaliphatic monomer monofunctional (meth)acrylate material, Ra is a cycloaliphatic moiety such as isobornyl or any other substituted or unsubstituted cycloalkyl described herein, or a cycloaliphatic heterocycle moiety as described herein, such as morpholine, tetrahydrofuran, oxalidine, or any other substituted or unsubstituted cycloaliphatic heterocycle described herein, where substituents on the cycloalkyl or cycloaliphatic heterocycle, if any, do not include aryl or heteroaryl, as defined herein. Exemplary cycloaliphatic monomer monofunctional acrylates include, but are not limited to, isobornyl acrylate (IBOA), acryloylmorpholine (ACMO), and materials commercially available under the trade name SR-218.

[0554] When the material is an aliphatic monomeric monofunctional (meth)acrylate material, Ra can be, for example, a substituted or unsubstituted alkyl or alkylene, or any other short hydrocarbon as defined herein, where the substituents, if present, do not include aryl or heteroaryl, as defined herein.

[0555] When the material is an aromatic monomeric monofunctional (meth)acrylate material, Ra can be or include, for example, aryl or heteroaryl, as defined herein, such as substituted or unsubstituted phenyl, substituted or unsubstituted naphthalenyl, etc., where substitution, if any, can be one, two, three, or more substituents, each the same or different, or alkyl or cycloalkyl substituted with one or more substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl, as described herein, such as substituted or unsubstituted benzyl. Exemplary aromatic monomeric monofunctional (meth)acrylates include, for example, the material commercially available as CN131B.

[0556] Ingredient A2 *or a second monofunctional (meth)acrylate characterized by the Tg shown, and optionally hydrophilic or amphiphilic, include, but are not limited to, those sold under the trade names SR-256, SR-217, SR-285, SR-336, SR-420, and SR-238.

[0557] According to any of the embodiments described herein, component A1 * is a monofunctional (meth)acrylate having an alicyclic moiety, for example, an acrylate.

[0558] According to any of the embodiments described herein, component A2 * is a monofunctional (meth)acrylate, e.g., acrylate, having an aromatic moiety (e.g., phenoxy).

[0559] According to any of the embodiments described herein, a monofunctional (meth)acrylate material, such as component A1 * and A2 * and optionally component B * , one or more or all of which are such that the MW of the compound is 1,000 grams / mole or less, or 500 grams / mole or less.

[0560] According to any of the embodiments described herein, the monofunctional acrylate or monofunctional methacrylate in the formulation, such as component A1 described herein, * and component A2 * The total amount of ranges from 20 to 40 weight percent or 25 to 35 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0561] According to any of the embodiments described herein, the at least one monofunctional curable material in the formulation comprises at least two types of monofunctional curable materials that differ from one another in chemical composition, i.e., one type comprises one or more materials having the formula A described herein, which type comprises acrylates and / or methacrylates, collectively referred to herein as Component A * Another class includes one or more materials that are urethane acrylates, collectively referred to herein as Component B. * It is called.

[0562] According to some of these embodiments, the at least one monofunctional curable material characterized by a Tg of less than 150°C is at least one monofunctional (meth)acrylate material characterized by a Tg of less than 150°C (e.g., Component A * , which is component A1 * and ingredient A2 * , i.e., the first monofunctional curable material and the second monofunctional curable material described herein), and at least one monofunctional urethane (meth)acrylate material characterized by a Tg of less than 150°C (e.g., Component B * ) and includes.

[0563] According to some of these embodiments, Component A, which is one or more monofunctional (meth)acrylate materials, * is characterized by a Tg of 50 to 150°C, or 50 to 100°C, as described herein, and is defined herein as component A1 * , alternatively referred to as first monofunctional curable material or first monofunctional (meth)acrylate, preferably an acrylate, characterized by a Tg of less than 50°C or less than 20°C, as described herein, and * and one or more monofunctional (meth)acrylates, preferably acrylates, also referred to as second monofunctional curable material or second monofunctional (meth)acrylates.

[0564] According to some of these embodiments, Component A is a monofunctional (meth)acrylate material. * For example, component A1 * and component A2 * , that is, the total amount of the first and second monofunctional materials ranges from 20 to 40 weight percent or 25 to 35 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0565] According to some of these optional embodiments, a second monofunctional curing material (e.g., a monofunctional (meth)acrylate) (e.g., component A2) characterized by a Tg of less than 50°C or less than 20°C is added. * ) ranges from 5 to 10% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0566] According to some of these optional embodiments, a first monofunctional curable material (e.g., a monofunctional (meth)acrylate) is characterized by a Tg of 50 to 150°C, or 50 to 100°C (e.g., component A1 * ), in an amount ranging from 20 to 30 weight percent, or 20 to 25 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0567] According to any of the embodiments described herein, the at least one monofunctional curable material of the formulation includes at least two types of monofunctional curable materials that differ from one another in their Tg, with one type including one or more materials characterized by a Tg of 50-150°C, or 50-100°C, including any intermediate values ​​and subranges therebetween, and another type including one or more materials each characterized by a Tg below 50°C, or below 20°C, such as in the ranges of -50-50°C, -20-50°C, -50-20°C, or -20-20°C, including any intermediate values ​​and subranges therebetween.

[0568] According to some of these embodiments, each of the monofunctional curable materials is a (meth)acrylate material, including acrylate, methacrylate, and urethane acrylate materials.

[0569] According to some of these embodiments, the total amount of one or more monofunctional curable materials characterized by a Tg of 50 to 150°C, or 50 to 100°C, ranges from 20 to 30 wt%, or 20 to 25 wt%, of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0570] According to some of these embodiments, the total amount of one or more monofunctional curable materials characterized by a Tg of less than 50°C, or less than 20°C, ranges from 20 to 40 wt. %, or 25 to 35 wt. %, of the total formulation weight, including any intermediate values ​​and subranges therebetween.

[0571] According to some of these embodiments, the one or more monofunctional curable materials characterized by a Tg of less than 50°C, or less than 20°C, include two or more such monofunctional curable materials, one or more of which is a monofunctional acrylate or methacrylate characterized by the indicated Tg (e.g., component A2 * ), one or more of which are monofunctional urethane acrylates or urethane methacrylates characterized by the indicated Tg (e.g., component B * )

[0572] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150° C. described herein may comprise one or more components A, B, C, C, D, E, E, F, F, G, H, G, I ... * and one or more components B * Includes:

[0573] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150°C as described herein may be at least a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C as described herein. * ) and a second monofunctional (meth)acrylate material (e.g., component A2) characterized by a Tg of less than 50°C, or less than 20°C. * ) and one or more monofunctional urethane (meth)acrylate materials (e.g., Component B) characterized by a Tg of less than 150°C as described herein. * ) and

[0574] According to any of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) are characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C.

[0575] According to any of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) is an aliphatic urethane (meth)acrylate.

[0576] According to any of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) is an aliphatic urethane (meth)acrylate characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C.

[0577] According to any of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) is a catalyst-free material (e.g., a tin-free material).

[0578] Characterized by the indicated Tg, component B * Exemplary monofunctional urethane (meth)acrylates that can be used include those commercially available under the trade name Genomer®, such as Genomer® 112, which is also sold as a tin-free material. Any other monofunctional aliphatic urethane (meth)acrylate is also contemplated.

[0579] According to any of the embodiments described herein, the amount of the at least one monofunctional urethane (meth)acrylate material, as described in any of the respective embodiments herein, is in the range of 20 to 30 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0580] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg below 150°C is in a total amount of 40 to 60 wt%, including any intermediate values ​​and subranges, and a first monofunctional (meth)acrylate material (optionally hydrophobic and / or cycloaliphatic) characterized by a Tg of 50 to 150°C, as described in any of the respective embodiments herein (e.g., Component A1 * ) and a second monofunctional (meth)acrylate material (optionally hydrophilic or amphiphilic, and / or aromatic) characterized by a Tg of less than 50°C, or less than 20°C, as described herein in any of the respective embodiments (e.g., component A2 * ) and at least one (preferably catalyst-free) monofunctional (preferably aliphatic) urethane (meth)acrylate material (e.g., component B) characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C, as described herein in any of the respective embodiments. * ) and includes.

[0581] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150°C may be a first monofunctional (meth)acrylate material (optionally hydrophobic and / or cycloaliphatic) characterized by a Tg of 50 to 150°C, as described herein in any of the respective embodiments (e.g., Component A1 * ) in an amount of 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges.

[0582] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150° C. may be combined with a second monofunctional (meth)acrylate material (optionally hydrophilic or amphiphilic, and / or aromatic) characterized by a Tg of less than 50° C., or less than 20° C., as described herein in any of the respective embodiments (e.g., component A2). * ) in an amount of 5 to 10% by weight of the total weight of the formulation, including any intermediate values ​​and subranges.

[0583] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150°C may be at least one (preferably uncatalyzed) monofunctional (preferably aliphatic) urethane (meth)acrylate material (e.g., Component B) characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C, as described herein in any of the respective embodiments. * ) in an amount of 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges.

[0584] According to any of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg below 150°C is in a total amount of 40 to 60 wt%, inclusive of any intermediate values ​​and subranges, and in an amount of 10 to 30 wt%, inclusive of any intermediate values ​​and subranges, of the total weight of the formulation. The first monofunctional (meth)acrylate material (optionally hydrophobic and / or cycloaliphatic) characterized by a Tg of 50 to 150°C (e.g., component A1), as described herein in any of the respective embodiments, is in an amount of 10 to 30 wt%, inclusive of any intermediate values ​​and subranges, of the total weight of the formulation. * ), and a second monofunctional (meth)acrylate material (optionally hydrophilic or amphiphilic, and / or aromatic) characterized by a Tg of less than 50°C, or less than 20°C, as described herein in any of the respective embodiments (e.g., component A2 * ), and at least one (preferably uncatalyzed) monofunctional (preferably aliphatic) urethane (meth)acrylate material (e.g., Component B), in an amount of 10 to 30 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges, characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C, as described herein in any of the respective embodiments. * ) and includes.

[0585] According to this embodiment, the build material formulation further includes two or more multifunctional curable materials.

[0586] According to any of the embodiments described herein, the total amount of all multifunctional curable materials is at least 15%, or 15 to 25% by weight, including any intermediate values ​​and subranges, of the total weight of the formulation.

[0587] The two or more multifunctional curative materials are characterized by a high Tg, for example, greater than 100°C, or greater than 150°C, such as component C described herein. * and one or more multifunctional curable materials, characterized by a low Tg, e.g., less than 150°C, or less than 100°C, e.g., component D described herein. * and one or more multifunctional curable materials, including

[0588] According to any of the embodiments described herein, the at least one multifunctional curable material characterized by a Tg greater than 100°C, or greater than 150°C, comprises a difunctional curable material.

[0589] According to any of the embodiments described herein, the at least one multifunctional curable material characterized by a Tg greater than 100°C, or greater than 150°C, comprises at least one multifunctional (e.g., difunctional) (meth)acrylate (Component C * ) is included.

[0590] According to any of the embodiments described herein, the at least one multifunctional curable material characterized by a high Tg of greater than 100°C, or greater than 150°C, has an average molecular weight of less than 500 grams / mole, for example, in the range of 200 to 500 grams / mole, or 200 to 400 grams / mole, including any intermediate values ​​and subranges.

[0591] In multifunctional materials, typically each of the curable (e.g., (meth)acrylate) groups are interconnected via a linking moiety, which can be, for example, a branched unit such as a linear (in the case of difunctional materials) or branched alkyl, cycloalkyl, aryl (e.g., bisphenol A), etc. (in the case of di-, tri-, and higher-functional materials).

[0592] Multifunctional (e.g., bifunctional) curable materials characterized by high Tg (e.g., component C * ) can be, for example, an aromatic or non-aromatic (e.g., alicyclic or aliphatic) polyfunctional (e.g., difunctional) (meth)acrylate, which includes at least one aromatic or non-aromatic (e.g., alicyclic or aliphatic) linking moiety between curable groups (e.g., (meth)acrylate groups).

[0593] According to any of the embodiments described herein, a multifunctional (e.g., bifunctional) curable material (e.g., component C) characterized by a high Tg is * ) are non-aromatic (e.g., alicyclic or aliphatic) polyfunctional (e.g., difunctional) (meth)acrylates, which contain alicyclic and / or aliphatic moieties connecting between curable groups (e.g., (meth)acrylate groups).

[0594] In some of these embodiments, the linking moiety is or includes an all-carbon alicyclic moiety, optionally a polyalicyclic moiety consisting of two, three, or more rings, hi some embodiments, the alicyclic moiety has at least 6, at least 7, at least 8, at least 9, or at least 10 carbon atoms.

[0595] In some embodiments, the linking moiety comprises a polyalicyclic moiety, as described herein, in which two or more rings are fused to one another.

[0596] Such multifunctional curable materials (e.g., component C) * An example of a diacrylate is tricyclododecane dimethanol diacrylate (e.g., SR833S and / or SR368 available from Sartomer).

[0597] According to any of the embodiments described herein, one or more multifunctional curable materials (e.g., component C) characterized by a Tg greater than 100°C, or greater than 150°C, may be used. * ) provides a transparent material upon solidification.

[0598] According to any of the embodiments described herein, the formulation includes one or more multifunctional (e.g., difunctional) (meth)acrylates characterized by a Tg greater than 100°C, or greater than 150°C, e.g., a Tg between 100 and 200°C, or between 150 and 200°C, or between 160 and 200°C, including any intermediate values ​​and subranges therebetween.

[0599] According to any of the embodiments described herein, the formulation may comprise one or more multifunctional (e.g., difunctional) (meth)acrylates (e.g., component C) characterized by a Tg of greater than 100° C., or greater than 150° C., e.g., a Tg of 100-200° C., or 150-200° C., or 160-200° C., including any intermediate values ​​and subranges therebetween, and having a molecular weight of less than 500 grams / mole, as described herein. * In some of these embodiments, the polyfunctional (e.g., bifunctional) curable material is a non-aromatic material having a non-aromatic linking moiety between the curable groups, in some embodiments the linking moiety is an aliphatic or alicyclic moiety. In any of the embodiments, the curable material provides a transparent material upon solidification.

[0600] According to any of the embodiments described herein, the formulation may comprise one or more multifunctional (e.g., difunctional) (meth)acrylates (e.g., component C) characterized by a Tg of greater than 100° C., or greater than 150° C., e.g., a Tg of 100-200° C., or 150-200° C., or 160-200° C., including any intermediate values ​​and subranges therebetween, that upon solidification provide a transparent material. * In some of these embodiments, the polyfunctional (e.g., bifunctional) curable material is a non-aromatic material having a non-aromatic linking moiety between the curable groups, which in some embodiments is an aliphatic or alicyclic moiety.

[0601] According to any of the embodiments described herein, one or more other multifunctional curative materials are included in the formulation, each characterized by a low Tg, i.e., a Tg below 150° C., preferably below 100° C. Examples of such materials are also collectively referred to herein as Component D * It is called.

[0602] According to any of the embodiments described herein, one or more of the or each of the at least one multifunctional curable material characterized by a Tg of less than 150°C, or less than 100°C, is a bifunctional curable material characterized by a Tg of less than 150°C, or less than 100°C.

[0603] According to any of the embodiments described herein, one or more of, or each, of the at least one multifunctional curable material characterized by a Tg of less than 150°C, or less than 100°C, is a multifunctional (e.g., difunctional) meth(acrylate).

[0604] According to any of the embodiments described herein, the formulation includes two (or more) multifunctional curable materials characterized by a Tg of less than 150° C., or less than 100° C. According to some of these embodiments, one of these materials is a first multifunctional curable material (referred to herein as component D1) characterized by a Tg of less than 0° C., or less than −20° C. * and a second multifunctional curable material (referred to herein as component D2) characterized by a Tg in the range of 50 to 150°C, or 50 to 100°C, including any intermediate values ​​and subranges therebetween. * (such as those referred to as "innovative technologies").

[0605] According to any of the embodiments described herein, one or more multifunctional curable materials (e.g., Component D) characterized by a Tg of less than 150°C, or less than 100°C, may be used. * , or component D1 * and / or D2 * ) comprises at least one multifunctional (e.g., difunctional) ethoxylated (meth)acrylate, as described herein.

[0606] In ethoxylated multifunctional materials, typically, each curable (e.g., (meth)acrylate) group is linked to an alkylene glycol group or chain that either links two curable groups (in the case of difunctional materials) or is linked to each other (in the case of di-, tri-, tetra-, etc. functional materials) via a linking moiety, which can be, for example, a branched unit such as a linear (in the case of difunctional materials) or branched alkyl, cycloalkyl, aryl (e.g., bisphenol A), etc. (in the case of di-, tri-, and higher functional materials).

[0607] According to any of the embodiments described herein, one or more of the, or each, multifunctional (e.g., difunctional) ethoxylated (e.g., (meth)acrylate) materials is a multifunctional (e.g., difunctional) aromatic ethoxylated (meth)acrylate, which includes aromatic (e.g., bisphenol A) branching units, as described herein.

[0608] According to any of the embodiments described herein, a first multifunctional curable material (e.g., component D1) characterized by a Tg of less than 0°C or less than -20°C may be used. * ) is or includes a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate characterized by at least 10 (e.g., 10 to 40, or 20 to 40, including any intermediate values ​​and subranges therebetween) ethoxyl groups. According to some embodiments, the material is characterized by a Tg between 0 and -50°C, or between -20 and -50°C.

[0609] Ingredient D1 *Exemplary such materials that can be used include any ethoxylated aromatic polyfunctional material characterized by bisphenol A branching units from which extend two or more alkylene (glycol) chains, the chains containing a total of 10 or more (e.g., 10 to 40, or 20 to 40) alkylene glycol units, which terminate in a curable group (e.g., a (meth)acrylate group). Exemplary such compounds are commercially available under the tradename Miramer (e.g., Miramer® M2301) or SR9036A. Other ethoxylated aromatic polyfunctional (e.g., difunctional) (meth)acrylates are also contemplated.

[0610] According to any of the embodiments described herein, a second multifunctional curable material (e.g., component D2) characterized by a Tg in the range of 50 to 150°C, or 50 to 100°C, may be used. * ) is or includes a polyfunctional (e.g., difunctional) ethoxylated (meth)acrylate characterized by fewer than 10 (e.g., 2-4) ethoxylated groups. In some embodiments, it is a polyfunctional (e.g., difunctional) aromatic ethoxylated (meth)acrylate described herein characterized by fewer than 10 (e.g., 2-4) ethoxylated groups.

[0611] According to any of the embodiments described herein, at least one multifunctional curable material (e.g., Component D) characterized by a Tg of less than 150°C, or less than 100°C, is included. * ) is a first multifunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups, as described herein in any of the respective embodiments. * ) and a second multifunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by fewer than 10 (e.g., 2-4) ethoxylated groups, as described herein in any of the respective embodiments. * ) and includes.

[0612] According to any of the embodiments described herein, a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups is used. * ) ranges from 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0613] According to any of the embodiments described herein, polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylates (e.g., component D2) characterized by less than 10 (e.g., 2-4) ethoxylated groups are used. * ) ranges from 10 to 20% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0614] According to any of the embodiments described herein, a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups is used. * ) ranges from 10 to 30 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween, and includes polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylates (e.g., component D2) characterized by less than 10 (e.g., 2 to 4) ethoxylated groups. * ) ranges from 10 to 20% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0615] An exemplary build material formulation according to some of the present embodiments is: A first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C, as described in any of the respective embodiments herein. * )and, a second monofunctional (meth)acrylate material (e.g., component A2) characterized by a Tg of less than 50°C, or less than 20°C, as described in any of the respective embodiments herein; * )and, At least one catalyst-free monofunctional urethane (meth)acrylate material (e.g., Component B), characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C, as described in any of the respective embodiments herein. * )and, at least one aliphatic polyfunctional (e.g., difunctional) (meth)acrylate (e.g., component C), characterized by a Tg greater than 100°C or greater than 150°C, and optionally having a molecular weight less than 500 grams / mole, as described herein in any of the respective embodiments; * )and, At least one polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (e.g., component D1), characterized by at least 10 (e.g., 10 to 40) ethoxylated groups and a Tg of less than 0°C or less than -20°C, as described in any of the respective embodiments herein. * )and, Polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylates (e.g., component D2), characterized by fewer than 10 (e.g., 2-4) ethoxylated groups and a Tg in the range of 50-100°C, as described in any of the respective embodiments herein. * ) and includes.

[0616] According to any of these exemplary embodiments, a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C is provided. * ) ranges from 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0617] According to any of these exemplary embodiments, a second monofunctional (meth)acrylate material (e.g., component A2) characterized by a Tg of less than 50°C or less than 20°C is used. * ) ranges from 5 to 10% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0618] According to any of these exemplary embodiments, at least one catalyst-free monofunctional urethane (meth)acrylate material (e.g., Component B) characterized by a Tg of less than 20°C is included. * ) ranges from 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0619] According to any of these exemplary embodiments, at least one non-aromatic (e.g., cycloaliphatic) polyfunctional (e.g., difunctional) (meth)acrylate (e.g., component C) characterized by a Tg greater than 100°C, or greater than 150°C, and optionally having a molecular weight less than 500 grams / mole. * ) ranges from 4 to 10 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0620] According to any of these exemplary embodiments, a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups is used. * ) is 10 to 30 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0621] According to any of these exemplary embodiments, a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by fewer than 10 (e.g., 2-4) ethoxylated groups is used. * ) ranges from 10 to 20% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0622] According to any of these exemplary embodiments, a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C is provided. * ) in an amount ranging from 10 to 30 wt. % of the total weight of the formulation, and a second monofunctional (meth)acrylate material (e.g., component A2) characterized by a Tg of less than 50°C or less than 20°C. *) in an amount ranging from 5 to 10 wt. % of the total weight of the formulation, and at least one catalyst-free monofunctional urethane (meth)acrylate material (e.g., component B) characterized by a Tg of less than 20°C. * ) in an amount ranging from 10 to 30 wt. % of the total weight of the formulation, and at least one non-aromatic (e.g., cycloaliphatic) polyfunctional (e.g., bifunctional) (meth)acrylate (e.g., component C) characterized by a Tg greater than 100°C or greater than 150°C and optionally having a molecular weight less than 500 grams / mole. * ) in an amount ranging from 4 to 10 wt. % of the total weight of the formulation, and a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups. * ) in an amount ranging from 10 to 30 wt. % of the total weight of the formulation, and a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by less than 10 (e.g., 2 to 4) ethoxylated groups. * ) ranges from 10 to 20% by weight of the total weight of the formulation.

[0623] According to any of the embodiments described herein, each of the multifunctional curable materials is a multifunctional (e.g., difunctional) acrylate.

[0624] According to any of the embodiments described herein, each of the monofunctional curable materials is a monofunctional acrylate.

[0625] According to any of the embodiments described herein, at least one or all of the curable materials in the formulation are photocurable materials (e.g., UV-curable materials such as acrylic materials), and the build material formulation contains at least one photoinitiator (Component J). * ) further includes.

[0626] According to any of the embodiments described herein, the amount of photoinitiator is in the range of 1 to 3 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0627] According to some of the optional embodiments described herein, the photoinitiator comprises or consists essentially of a phosphine oxide type (e.g., monoacrylated (MAPO) or bisacrylated phosphine oxide type (BAPO)) photoinitiator.

[0628] Exemplary monoacyl and bisacyl phosphine oxides include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis(2,6-dimethylphenyl)phosphonate, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide. Commercially available phosphine oxide photoinitiators capable of free radical initiation when irradiated in the wavelength range from about 380 nm to about 450 nm include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available as IRGACURE® 819), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (commercially available as CGI403 ... and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (commercially available as CGI403). Examples of suitable methyl 2,4,6-trimethylbenzylphenylphosphine oxide include a 25:75 by weight mixture of bis(2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (commercially available as IRGACURE® 1700), a 1:1 by weight mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (commercially available as DAROCUR® 4265), and ethyl 2,4,6-trimethylbenzylphenylphosphinate (LUCIRIN LR8893X).

[0629] According to any of the embodiments described herein, the photoinitiator comprises or consists essentially of a bis-acrylated phosphine oxide (BAPO) photoinitiator.

[0630] In an exemplary embodiment, the photoinitiator comprises or consists essentially of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (commercially available as IRGACURE® 819).

[0631] In exemplary embodiments, the photoinitiator does not include monoacrylated (MAPO) phosphine oxide photoinitiators, and in some embodiments does not include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commercially available as TPO).

[0632] According to any of the embodiments described herein, the build material formulation may include additional non-curable components, such as inhibitors, surfactants, dispersants, colorants (coloring components), and stabilizers. Commonly used surfactants, dispersants, colorants, and stabilizers are contemplated. Exemplary concentrations of each component, if present, range from about 0.01 to about 1 wt. %, or from about 0.01 to about 0.5 wt. %, or from about 0.01 to about 0.1 wt. %, based on the total weight of the formulation including it. Exemplary components are described below.

[0633] In any of the embodiments described herein, the formulation includes a set inhibitor, i.e., an agent that inhibits or reduces the amount of set in the absence of set conditions, referred to herein as Component I * In some embodiments, the inhibitor is a free radical polymerization inhibitor. In some embodiments, the inhibitor (e.g., component I) * The amount of inhibitor (e.g., free radical inhibitor) ranges from 0.01 to 2 wt.%, or 0.01 to 1 wt.%, or 0.05 to 0.5 wt.%, or 0.1 to 0.2 wt.%, including any intermediate values ​​and subranges therebetween, depending on the type of inhibitor used. Commonly used inhibitors, such as free radical inhibitors, are contemplated.

[0634] According to any of the embodiments described herein, the build material formulation may contain an inhibitor (component I) as described herein. *), such as phenolic type inhibitors, or any other inhibitors commonly used in medical devices or applications, and / or in food products.

[0635] According to any of the embodiments described herein, the amount of inhibitor ranges from 0.05 to 0.5% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0636] In an exemplary embodiment, the free radical inhibitor is a member of the Genorad® series (eg, Genorad® 20).

[0637] In exemplary embodiments, such free radical inhibitors are used in amounts of 0.1 to 3 wt %, or 0.1 to 2 wt %, or 0.1 to 1 wt %, or 0.1 to 0.5 wt %, including intermediate values ​​and subranges therebetween.

[0638] According to any of the embodiments described herein, the build material formulation may contain one or more dispersants or surfactants (Component H * ) further includes.

[0639] According to any of the embodiments described herein, the amount of dispersant ranges from 0.01 to 0.1 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0640] Exemplary dispersants and surfactants include those commercially available as BYK surface additives.

[0641] According to any of the embodiments described herein, the build material formulation is a clear (e.g., transparent), colorless formulation, and does not contain any colorants or pigments.

[0642] According to any of the embodiments described herein, the build material formulation may contain one or more colorants or pigments (component P * ) further includes.

[0643] The colorant is a pigment or a dye, preferably a pigment.

[0644] The pigments may be organic and / or inorganic and / or metallic pigments, and in some embodiments, the pigments are nanoscale pigments, including nanoparticles.

[0645] Exemplary inorganic pigments include nanoparticles of titanium oxide and / or zinc oxide and / or silica. Exemplary organic pigments include nano-sized carbon black.

[0646] In some embodiments, a combination of white and colored pigments is used to prepare the colored cured material.

[0647] According to any of the embodiments described herein, the colorant comprises a pigment and at least one (meth)acrylic material, and the pigment is introduced into the formulation within this mixture.

[0648] According to any of the embodiments described herein, the pigment is a white pigment and the formulation provides a white cured product.

[0649] According to any of the embodiments described herein, the colorant comprises a white pigment and one or more curable materials, such as a (meth)acrylic material, and the pigment is introduced into the formulation within this mixture.

[0650] According to some of these embodiments, the amount of white pigment in the mixture ranges from 20 to 50 weight percent of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0651] According to some of these embodiments, the amount of colorant, which is a mixture of a white pigment and at least one (meth)acrylic material, ranges from 1 to 5 wt. % of the total weight of the formulation.

[0652] According to any of the embodiments described herein, the pigment is a cyan pigment and the formulation provides a cyan cure.

[0653] According to any of the embodiments described herein, the colorant comprises a cyan pigment and one or more curable materials, such as (meth)acrylic materials, and the cyan pigment is introduced into the formulation within this mixture.

[0654] According to some of these embodiments, the amount of cyan pigment in the mixture ranges from 0.01 to 1 wt %, or from 0.05 to 0.5 wt %, or from 0.1 to 0.2 wt %, of the total weight of the mixture.

[0655] According to some of these embodiments, the amount of colorant, which is a mixture of a cyan pigment and at least one (meth)acrylic material, ranges from 0.1 to 1 wt % of the total weight of the formulation.

[0656] According to any of the embodiments described herein, the pigment is a yellow pigment and the formulation provides a yellow cured product.

[0657] According to any of the embodiments described herein, the colorant comprises a yellow pigment and one or more curable materials, such as (meth)acrylic materials, and the yellow pigment is introduced into the formulation within this mixture.

[0658] According to some of these embodiments, the amount of yellow pigment in the mixture ranges from 0.01 to 1 wt %, or 0.05 to 0.5 wt %, or 0.1 to 0.2 wt %, of the total weight of the mixture.

[0659] According to some of these embodiments, the amount of colorant, which is a mixture of a yellow pigment and at least one (meth)acrylic material, ranges from 0.1 to 1 wt % of the total weight of the formulation.

[0660] According to any of the embodiments described herein, the pigment is a magenta pigment and the formulation provides a magenta cured product.

[0661] According to any of the embodiments described herein, the colorant comprises a magenta pigment and one or more curable materials, such as (meth)acrylic materials, and the magenta pigment is introduced into the formulation within this mixture.

[0662] According to some of these embodiments, the amount of magenta pigment in the mixture ranges from 0.01 to 1 wt %, or from 0.05 to 0.5 wt %, or from 0.1 to 0.2 wt %, of the total weight of the mixture.

[0663] According to some of these embodiments, the amount of colorant, which is a mixture of a magenta pigment and at least one (meth)acrylic material, ranges from 0.1 to 1 wt % of the total weight of the formulation.

[0664] According to any of the embodiments described herein, the formulation includes one or more white, magenta, cyan, and yellow colorants, and according to some of these embodiments, each pigment is introduced into the formulation in a mixture with the curable material described herein.

[0665] According to any of the embodiments described herein, the colorant may comprise a pigment dispersant (component Dp * Preferred pigment dispersants include those having multiple groups that characterize their affinity for the pigment.

[0666] According to any of the embodiments described herein, the shaping formulation comprises a component H, as described herein in any of the respective embodiments. * , I * , and J * An exemplary such formulation is a water-clear formulation that does not contain any colorants.

[0667] According to any of the embodiments described herein, the build material formulation comprises a component H, as described herein in any of the respective embodiments. * , I * , J * , P * and optionally component Dp *An exemplary such formulation is a white formulation comprising the white pigment described herein.

[0668] According to any of the embodiments described herein, the build material formulation comprises a component H, as described herein in any of the respective embodiments. * , I * , J * , P * , and optionally component Dp * An exemplary such formulation is the cyan, magenta, and yellow formulation described herein.

[0669] While the present invention has been described in conjunction with specific embodiments thereof, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.

[0670] It is the intention of the applicants that all publications, patents, and patent applications mentioned herein be incorporated by reference in their entireties to the same extent as if each individual publication, patent, and patent application was specifically and individually indicated to be incorporated by reference herein. Furthermore, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention. To the extent used as section headings, they should not be construed as necessarily limiting. Additionally, any priority documents to this application are incorporated herein by reference in their entireties.

Claims

1. 1. An additive formulation for use in combination with a build material formulation in three-dimensional printing of objects on fabric, comprising: at least one monofunctional curing material characterized by at least one polar group capable of interacting with surface functional groups in the fabric and a glass transition temperature (Tg) of less than 50°C, in an amount of 85-90 wt% of the total weight of the additive formulation; at least one multifunctional curing material characterized by a Tg of less than 50°C, in an amount of 10 to 15 wt% of the total weight of the additive formulation; 10. An additive formulation comprising:

2. viscosity in the range of 15 to 20 centipoise; A surface tension in the range of 26 to 28 Dyne / cm; and Adhesion level to fabric is at least 20 N / cm; 10. The additive formulation of claim 1, characterized by at least one of:

3. 3. The additive formulation of claim 1 or claim 2, which is an adhesive (primer) formulation and, upon setting, provides an adhesive structure on the fabric.

4. 3. The additive formulation of claim 1 or claim 2, which is a coating formulation and which upon solidification provides a coating for the object or a portion of the object.

5. The additive formulation of any one of claims 1 to 4, wherein each of the monofunctional curable material and the multifunctional curable material is a UV curable material.

6. The additive formulation of any one of claims 1 to 5, wherein each of the monofunctional curable material and the multifunctional curable material is a (meth)acrylate material.

7. 7. The additive formulation of claim 5 or claim 6, further comprising a photoinitiator.

8. 8. The additive formulation of claim 7, wherein the photoinitiator is a bis(acyl)phenyloxide (BAPO) type photoinitiator.

9. 9. The additive formulation of claim 7 or claim 8, wherein the amount of the photoinitiator is 1.5 to 2.5 wt % of the total weight of the additive formulation.

10. The at least one monofunctional curable material is collectively represented by Formula I: Y-L-X Formula I During the ceremony, Y is a terminal group, optionally and preferably selected from alkyl, including linear and branched, substituted or unsubstituted alkyl, aryl, heteroaryl, cycloalkyl, alicyclic heterocycle, hydroxy, alkoxy, aryloxy, and amine; X is a polymerizable group, optionally and preferably a (meth)acrylate group; L is a hydrocarbon having 2 to 10 carbon atoms, preferably 2 to 8 or 2 to 6 carbon atoms in length, substituted with at least one hydroxy group and optionally interrupted by one or more heteroatoms capable of forming hydrogen bonds with the hydroxy group; The additive formulation according to any one of claims 1 to 9.

11. X is a (meth)acrylate group and the monofunctional curable material is represented by Formula Ia: 【Chemistry 1】 In the formula, R １ 11. The additive formulation of claim 10, wherein is hydrogen or alkyl.

12. 12. The additive formulation of claim 10 or claim 11, wherein Y is aryloxy.

13. The additive formulation of any one of claims 10 to 12, wherein L is a hydrocarbon having 2 to 6 carbon atoms substituted with at least one hydroxy group.

14. The additive formulation of any one of claims 1 to 13, wherein the at least one multifunctional curable material comprises a difunctional curable material characterized by said Tg.

15. The additive formulation of any one of claims 1 to 14, wherein the at least one multifunctional curable material comprises a multifunctional aliphatic meth(acrylate) characterized by said Tg.

16. The additive formulation of any one of claims 1 to 15, further comprising at least one of a polymerization inhibitor, a surfactant, a dispersant, and a pigment and / or a dye.

17. 17. The additive formulation of any one of claims 1 to 16, further comprising a surfactant, said surfactant comprising a curable group (e.g. a UV curable group such as a (meth)acrylate group).

18. 18. The additive formulation of claim 17, wherein the amount of the surfactant is 0.05 to 0.5 wt % of the total weight of the additive formulation.

19. 1. A method for three-dimensional printing of an object onto a fabric, comprising: The method includes forming the object by dispensing a plurality of layers in a structured pattern corresponding to a shape of the object; forming each layer of at least some of the plurality of layers includes dispensing at least one build formulation and exposing the dispensed build formulation to curing conditions to form a hardened build material, thereby printing the object; The method further comprises: Prior to dispensing the at least one build material formulation, - dispensing a stack of layers onto the fabric in a structured pattern corresponding to the shape of the bottom surface of the object, the dispensing for each layer of the stack being a dispense of an additive formulation according to any one of claims 1 to 18; - exposing each of said layers or said stack of layers to curing conditions to form a solidified adhesive material (adhesive structure); and / or After dispensing the at least one build material formulation and exposing it to the curing conditions, - dispensing a stack of layers onto the printed object in a structural pattern corresponding to the shape of the outermost surface of the object or part of the object, wherein for each layer of the stack, the dispensing is a dispensing of an additive formulation according to any one of claims 1 to 18; - forming a solidified coating material on the printed object or part of the printed object by exposing each of the layers or the stack of layers to curing conditions; A method comprising:

20. 1. A method for forming a bonded structure on a fabric, comprising: - dispensing a stack of layers onto the fabric in a structural pattern corresponding to the shape of the adhesive structure, wherein the dispensing for at least some or each layer of the stack is a dispensing of an additive formulation according to any one of claims 1 to 18; forming the bonded structure by exposing each of the layers or the stack of layers to curing conditions; A method comprising:

21. 1. A method of making a fabric for three-dimensional printing of an object thereon, comprising: The method includes forming an adhesive structure on the fabric in a structured pattern corresponding to a shape of a bottom surface of the object; The formation of the adhesive structure is - dispensing a stack of layers onto the fabric in said configuration pattern, said dispensing for at least some layers or for each layer of said stack being a dispensing of an additive formulation according to any one of claims 1 to 18; - exposing each of the layers or the stack of layers to curing conditions to form a solidified adhesive material (adhesive structure); A method comprising:

22. 1. A method of forming a coating on a printed three-dimensional object or part of said object on a fabric, comprising: - dispensing a stack of layers onto the printed object in a configuration pattern corresponding to the shape of an outermost surface of the object or part of the object, wherein for each layer of the stack, the dispensing is a dispensing of an additive formulation according to any one of claims 1 to 18; forming a solidified coating material on the printed object or portion of the object by exposing each of the layers or the stack of layers to curing conditions; A method comprising:

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