Method and system for three-dimensional printing on textiles

Abstract

A method for forming an object on a textile by three-dimensional printing includes printing an adhesive structure having a stack of layers onto the textile in a configuration pattern corresponding to the shape of a bottom surface of the object, where for each layer of the stack, the printing includes dispensing (602) and curing (603) a first formulation along a scanning direction. The method also includes printing the object onto the stack by dispensing and curing (604) a build formulation in layers along said direction in a configuration pattern corresponding to the shape of a slice of the object. Optionally, curing includes irradiating the layers by creating a pattern of curing radiation that scans the layers along said direction, the pattern having the shape of a stripe.

Description

[Technical Field]

[0001] This application claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 63 / 436,181 (filed December 30, 2022), the entire contents of which are incorporated herein by reference.

[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 / 436,186, filed December 30, 2022, the entire contents of which are incorporated herein by reference.

[0003] This application is also related to International Design Application No. DM / 227028, the entire contents of which are incorporated herein by reference.

[0004] This application is also related to a concurrently filed, co-pending, and co-assigned PCT International patent application entitled "Composition for Three-Dimensional Printing on Textiles," having attorney docket number 97935, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 63 / 436,172. This application is also related to a concurrently filed, co-pending, and co-assigned PCT International patent application entitled "Adhesive and / or Coating Composition Usable for Three-Dimensional Printing on Textiles," having attorney docket number 97940, which claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 63 / 436,186, the entire contents of which are incorporated herein by reference.

[0005] The present invention, in some embodiments thereof, relates to three-dimensional printing, and particularly, but not exclusively, to methods and systems for three-dimensional printing on textiles. [Background technology]

[0006] Additive manufacturing (AM) is a technology that allows for the production of structures of a given shape directly from computer data through a layer-by-layer molding process. The basic operation of an AM system consists of slicing a three-dimensional computer model into thin cross sections, converting the results into two-dimensional positional data, and sending that data to control machines that build the three-dimensional structure layer by layer.

[0007] Additive manufacturing encompasses many different approaches to manufacturing, including three-dimensional (3D) printing (e.g., 3D inkjet printing), electron beam melting, stereolithography, selective laser sintering, additive manufacturing, and fused deposition modeling.

[0008] Some 3D printing processes (e.g., 3D inkjet printing) rely on inkjet deposition of build material layer by layer. Thus, build material is dispensed from a delivery head having a set of nozzles to deposit layers onto a support structure. Depending on the build material, the layers are cured, i.e., solidified, using an appropriate device.

[0009] Various three-dimensional printing techniques exist and are disclosed, for example, in U.S. Patent 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 Publication No. 20060054039, and International Publication No. WO2016 / 009426, all of which are commonly assigned and are incorporated herein by reference in their entirety. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 6,259,979 [Patent Document 2] U.S. Patent No. 6,569,373 [Patent Document 3] U.S. Patent No. 6,658,314 [Patent Document 4] U.S. Patent No. 6,850,334 [Patent Document 5] U.S. Patent No. 6,863,859 [Patent Document 6] U.S. Patent No. 7,183,335 [Patent Document 7] U.S. Patent No. 7,209,797 [Patent Document 8] U.S. Patent No. 7,225,045 [Patent Document 9] U.S. Patent No. 7,300,619 [Patent Document 10] U.S. Patent No. 7,500,846 [Patent Document 11] U.S. Patent No. 9,031,680 [Patent Document 12] U.S. Patent No. 9,227,365 [Patent Document 13] U.S. Patent Publication No. 20060054039 [Patent Document 14] International Publication No. WO2016 / 009426 [Patent Document 15] U.S. Patent Publication No. 20100191360 Summary of the Invention

[0011] According to one aspect of some embodiments of the present invention, there is provided a method for forming an object on a textile by three-dimensional printing. According to embodiments of the present invention, the method includes printing an adhesive structure having a stack of layers on the textile in a configuration pattern corresponding to the shape of a bottom surface of the object, and for each layer of the stack, the printing includes dispensing and curing a first formulation along a scanning direction. According to embodiments of the present invention, the method also includes printing the object on the stack by dispensing and curing a build (e.g., modeling material) formulation in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object. According to various exemplary embodiments of the present invention, for each layer of the stack and each layer of the object (e.g., modeling material formulation), the curing includes scanning the layer along the direction, and applying a radiation intensity I A the layer by creating a pattern of curing radiation having a shape of a stripe.

[0012] According to some embodiments of the present invention, the laminate comprises from about 10 to about 30 layers.

[0013] According to one aspect of some embodiments of the present invention, there is provided a method for forming an adhesive structure on a fabric by three-dimensional printing. According to an embodiment of the present invention, the method includes printing a first stack of uncured layers onto the fabric in a configuration pattern corresponding to the shape of a bottom surface of an object, where for each layer of the stack, the printing includes dispensing a first formulation without curing. The method also includes printing a second stack of layers on the first stack, where for each layer of the second stack, the printing includes dispensing and curing the first formulation along a scanning direction, where the curing includes scanning the layers along the direction, and a radiation intensity I B the pattern having the shape of at least two separated stripes.

[0014] According to some embodiments of the invention, the first laminate comprises fewer than 5 layers. According to some embodiments of the invention, the second laminate comprises from about 10 to about 30 layers.

[0015] According to some embodiments of the present invention, the method includes printing an object onto the second stack. According to some embodiments of the present invention, the object is printed by dispensing and curing a build compound (e.g., modeling material) in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object. According to various exemplary embodiments of the present invention, for each layer of the object, curing is performed by applying a radiation intensity I A the pattern having a shape of a stripe and having an intensity I B is the intensity I A This is about twice as much.

[0016] According to one aspect of some embodiments of the present invention, there is provided a method for forming an object on a fabric by three-dimensional printing. According to an embodiment of the present invention, the method includes printing an adhesive structure having a stack of layers on the fabric in a configuration pattern corresponding to the shape of a bottom surface of the object, wherein for each layer of the second stack, the printing comprises dispensing and curing a first formulation along a scanning direction, the curing comprising scanning the layers along the direction, and applying a radiation intensity I C and irradiating the layer by creating a pattern of curing radiation having a radiation intensity I, the pattern having a shape of at least two separated stripes. The method also includes printing an object on the laminate by applying and curing a build compound in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object, wherein for each layer of the object, curing is performed by scanning the layer along the direction. A irradiating the layer by creating a pattern of curing radiation having an intensity I C is the intensity I A This is about four times the amount.

[0017] According to some embodiments of the present invention, the laminate comprises from about 10 to about 30 layers.

[0018] According to one aspect of some embodiments of the present invention, there is provided a method for forming an adhesive structure on a fabric by three-dimensional printing, the method including obtaining parameters describing the fabric and selecting a printing protocol from the protocols described below based on the parameters.

[0019] According to some embodiments of the present invention, the method includes illuminating a top surface of the object, the illumination scanning the top surface along said direction, with a radiation intensity I B the pattern having the shape of at least two separated stripes and having an intensity I B is the intensity I A This is about twice as much.

[0020] According to some embodiments of the present invention, the method also includes printing the first formulation onto the outer surface of the object to form a liquid coating, and irradiating the coating with curing radiation to form a hardened coating. According to some embodiments of the present invention, the method includes scanning the top surface along the direction of radiation intensity I B the coating is irradiated by creating a pattern of curing radiation having an intensity I B is the intensity I A This is about twice as much.

[0021] According to some embodiments of the present invention, the method includes testing the adhesion level of an object to a fabric.

[0022] According to some embodiments of the present invention, the method is repeated on the same side of the fabric but for different orientations of the fabric.

[0023] According to one aspect of some embodiments of the present invention, there is provided a method for selecting a printing protocol for three-dimensional printing on a fabric. The method includes performing the protocol described below on different portions of the fabric and testing the adhesion level of each object to each portion of the fabric. According to some embodiments of the present invention, the method is performed repeatedly on the same side of the fabric and for different orientations of the fabric.

[0024] According to some embodiments of the present invention, the method is repeated on a different side of the fabric.

[0025] According to some embodiments of the present invention, the object includes two stacks of modeling material layers separated by a gap, and the bending resistance of the stack of modeling material layers is higher than the bending resistance of the adhesive material and the fabric.

[0026] According to some embodiments of the present invention, testing includes bending the fabric through the gap to separate at least one of the stack of modeling material layers from the fabric at a separation point adjacent the gap.

[0027] According to some embodiments of the present invention, the gap has a piecewise linear shape and the separation point is near a breakpoint of the piecewise linear shape.

[0028] According to some embodiments of the present invention, the gap forms an acute angle at the breakpoint.

[0029] According to some embodiments of the present invention, the gap has a curved shape.

[0030] According to some embodiments of the present invention, the gap width is less than 1 mm.

[0031] According to some embodiments of the present invention, the stacks separated by gaps form a three-dimensional structure with a planar aspect ratio of about 1:3 to about 1:10.

[0032] According to some embodiments of the present invention, the thickness of the stack of modeling material is greater than the thickness of the adhesive structure.

[0033] According to some embodiments of the present invention, the thickness of the stack of modeling material is at least twice as thick as the adhesive structure.

[0034] According to some embodiments of the present invention, the stack of modeling material layers has a plurality of through holes that define open cells within the stack.

[0035] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of embodiments of this invention, exemplary methods and / or materials are described below. In case of conflict, the present patent specification, including definitions, will control. Furthermore, the materials, methods, and examples are illustrative only and are not intended to be necessarily limiting.

[0036] 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 means and apparatus of an embodiment of the method and / or system of embodiments of the present invention, some selected tasks may be performed by hardware, software, or firmware, or a combination thereof using an operating system.

[0037] For example, hardware performing selected tasks according to embodiments of the present invention may be implemented as a chip or circuit. Software performing selected tasks according to embodiments of the present invention may be implemented as 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 instructions. Optionally, the data processor includes volatile memory for storing instructions and / or data and / or non-volatile memory (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 a user input device (e.g., a keyboard or mouse) are also optionally provided. [Brief explanation of the drawings]

[0038] Some embodiments of the present invention are herein described, by way of example, 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 are for purposes of illustrative discussion of embodiments of the present invention. In this regard, the description taken together with the drawings will make apparent to those skilled in the art how embodiments of the present invention may be practiced. [Figure 1] Figures 1A-1D are schematic diagrams of an additive manufacturing system according to some embodiments of the present invention, and Figures 1E-1G are schematic diagrams of a work tray including or associated with a radiation source for an additive manufacturing system according to embodiments of the present invention. [Figure 2] 2A-2C are schematic diagrams of printheads according to some embodiments of the present invention. [Figure 3] 3A and 3B are schematic diagrams illustrating coordinate transformations according to some embodiments of the present invention. [Figure 4] 4A-4F are schematic diagrams of a fixture suitable for some embodiments of the present invention. [Figure 5]5A-5C are schematic diagrams of configurations for placing fabric on lamp structures, according to some embodiments of the present invention. [Figure 6] 6A-6C are flow chart diagrams illustrating methods suitable for creating adhesive structures on textiles by three-dimensional printing, according to some embodiments of the present invention. [Figure 7] 7A-7D are schematic diagrams of two-part structures suitable for testing the adhesion level of a substance to a fabric, according to some embodiments of the present invention. [Figure 8] 8A and 8B are schematic illustrations of a procedure for bending a two-part structure, according to some embodiments of the present invention. [Figure 9] 9A and 9B show adhesion level test results obtained in experiments performed according to some embodiments of the present invention. [Figure 10] FIG. 10 shows the results of experiments conducted to investigate the effect of coatings on the tear resistance of prints, obtained in experiments carried out according to some embodiments of the present invention. [Figure 11] 11A-11D are schematic illustrations of irradiation procedures according to some embodiments of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0039] The present invention, in some embodiments thereof, relates to three-dimensional printing, and particularly, but not exclusively, to methods and systems for printing objects onto fabrics.

[0040] Before describing at least one embodiment of the present invention in detail, it is to be understood that the invention is not limited in its application to the details of construction and the arrangement of parts and / or methods and / or examples set forth in the following description and / or illustrated in the drawings. The invention is capable of other embodiments and of being practiced or carried out in various ways.

[0041] The method and system of the present embodiment fabricates a three-dimensional object layer by layer based on computer object data by forming multiple layers in a configured pattern corresponding to the shape of the object. The computer object data can 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 other formats suitable for computer-aided design (CAD).

[0042] As used herein, the term "object" refers to the entire object or a portion thereof.

[0043] 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 that target location or group of target locations should be occupied by build material and the type of build material to be applied thereto. This determination is made according to a computer image of the surface.

[0044] In preferred embodiments of the present invention, AM involves three-dimensional printing, more preferably three-dimensional inkjet printing. In these embodiments, build material is supplied from a print head having one or more arrays of nozzles to deposit the build material in layers on a receiving surface. Thus, the AM device supplies build material to target locations to be occupied while leaving other target locations empty. The device typically includes multiple nozzle arrays, each configured to supply a different build material. This is typically achieved by providing the print head with multiple fluid passages that are isolated from one another so that there is no fluid communication between them, each receiving a different build material through a separate inlet and delivering it to a different nozzle array.

[0045] Thus, different target locations can be occupied by different build materials. Types of build materials can be divided into two main categories: modeling materials and support materials. Typically, build materials are solvent-free (e.g., do not contain water or any organic solvents) and / or are supplied at temperatures above 40°C, above 50°C, or above 60°C. A support material is a support matrix or structure that supports an object or portion of an object during the manufacturing process and / or for other purposes (e.g., to provide a hollow or porous object). The support structure may additionally include modeling material elements, for example, for additional support strength.

[0046] Modeling materials are generally compositions formulated for use in additive manufacturing that can form three-dimensional objects by themselves, i.e., without being mixed or combined with other substances.

[0047] The final three-dimensional object is created from a modeling material, a combination of modeling materials, a modeling and support material, or its transformation (e.g., subsequent curing), all of which are well known to those skilled in the art of solid freeform fabrication.

[0048] In some exemplary embodiments of the present invention, an object is manufactured by dispensing two or more different build (e.g., modeling) material formulations. Each material is dispensed from a different nozzle array (belonging to the same or different print head) of the AM device. In some embodiments, two or more nozzle arrays dispensing different build (e.g., modeling) material formulations are all located within the same print head of the AM device. In some embodiments, multiple nozzle arrays dispensing different build (e.g., modeling) formulations are located within separate print heads. For example, a first nozzle array dispensing a first build (e.g., modeling) formulation is located within a first print head, and a second nozzle array dispensing a second build (e.g., modeling) formulation is located within a second print head.

[0049] In some embodiments, both the nozzle array supplying the modeling material formulation and the nozzle array supplying the support material formulation are located within the same print head, while in some embodiments, the nozzle array supplying the modeling material formulation and the nozzle array supplying the support material formulation are located within separate print heads.

[0050] Throughout the following description, whenever a material or composition (shaping, modeling and / or support) is described in the context in which it is supplied, it refers to a curable, i.e., uncured, material or composition prior to being cured or solidified (e.g., by exposure to curing conditions), unless otherwise specified.

[0051] A representative, non-limiting example of a system 110 suitable for additive manufacturing (AM) of an object 112, according to some embodiments of the present invention, is depicted in Figure 1A. The system 110 includes an additive manufacturing apparatus 114 having a supply unit 16 including multiple print heads. Preferably, each head includes one or more nozzle arrays 122, which are typically attached to an orifice plate 121 through which a liquid (uncured) build material 124 is dispensed, as shown in Figures 2A-2C described below.

[0052] Preferably (though not necessarily), device 114 is a three-dimensional printing device, in which case the print head is a print head and the build material is supplied by inkjet technology. However, this is not necessarily the case, as some applications do not require the additive manufacturing device to employ three-dimensional printing technology. Representative examples of additive manufacturing devices contemplated by various exemplary embodiments of the present invention include, but are not limited to, fused deposition modeling devices and fused material deposition devices.

[0053] Each print head is optionally and preferably supplied with material from one or more reservoirs of build material, which optionally include a temperature control unit (e.g., a temperature sensor and / or a heating device) and a material level sensor. To supply the build material, a voltage signal is applied to the print head to selectively deposit droplets of material through the print head nozzles, as in, for example, piezoelectric inkjet printing technology. Another example includes thermal inkjet print heads. These types of heads include heater elements in thermal contact with the build material, which, when activated by a voltage signal, heat the build material and form a gas bubble therein. The gas bubble generates pressure within the build material, causing a droplet of the build material to be ejected through the nozzle. Piezoelectric and thermal print heads are known to those skilled in the art of solid freeform fabrication. For any type of inkjet print head, the supply rate from the head depends on the number of nozzles, the type of nozzle, and the rate (frequency) of the applied voltage signal.

[0054] Preferably, but not necessarily, the total number of supply nozzles or nozzle arrays is selected so that half of the supply nozzles are designated to supply support material and half of the supply nozzles are designated to supply modeling material. That is, the number of nozzles ejecting modeling material is the same as the number of nozzles ejecting support material. The representative example in FIG. 1 depicts four print heads 16a, 16b, 16c, and 16d. Each of heads 16a, 16b, 16c, and 16d has a nozzle array. In this example, heads 16a and 16b can be designated for modeling material, and heads 16c and 16d can be designated for support material. Thus, head 16a can dispense one modeling material, head 16b can dispense another modeling material, and both heads 16c and 16d can dispense support material. In another embodiment, for example, heads 16c and 16d can be combined into a single head having two nozzle arrays for dispensing support material. In yet another embodiment, any one or more of the multiple print heads may have two or more nozzle arrays for supplying two or more materials (e.g., two nozzle arrays for supplying two modeling materials or a modeling material and a support material, each formulation being supplied through a different nozzle array, i.e., multiple nozzles)).

[0055] It should be understood, without intending to limit the scope of the present invention, that the number of modeling material print heads (modeling heads) and the number of support material print heads (support heads) may vary. Generally, the number of nozzle arrays supplying modeling material, the number of nozzle arrays supplying support material, and the number of nozzles in each respective array are selected so that the ratio between the maximum supply rate of support material and the maximum supply rate of modeling material is a predetermined ratio a. The value of the predetermined ratio a is preferably selected so that the height of the modeling material is equal to the height of the support material in each layer formed. Typical values ​​of a are from about 0.6 to about 1.5.

[0056] As used throughout this specification, the term "about" means ±10% or ±5%.

[0057] For example, if a=1, when the nozzle arrays are all operational, the overall supply rate of support material is approximately the same as the overall supply rate of modeling material.

[0058] Apparatus 114 may, for example, include M modeling heads, each having m arrays of p nozzles, and S support heads, each having s arrays of q nozzles, such that M×m×p=S×s×q. Each of the M×m modeling arrays and S×s support arrays may be fabricated as separate physical units that can be assembled and removed from the group of arrays. In this embodiment, each such array optionally and preferably includes its own temperature control unit and material level sensor, and receives individually controlled voltages for its operation.

[0059] The apparatus 114 may further include a solidification device 18. The solidification device 18 may include any device configured to emit light, heat, or the like to harden the deposited material. For example, the solidification device 18 may include one or more radiation sources, which may be, for example, ultraviolet, visible, or infrared lamps, other electromagnetic radiation sources, or electron beam sources, depending on the modeling material used. In some embodiments of the present invention, the solidification device 18 serves to cure or solidify the modeling material. Preferably, as depicted in FIG. 1A , two solidification devices 18 are provided on either side of the delivery head 16, such that, during operation of both devices 18, one provides radiation to positions just before material is delivered, and the other provides radiation to positions just after material is delivered to those positions. The devices 18 are preferably configured to operate independently in terms of timing and radiation intensity. However, by controlling their independent operation, a synchronized radiation protocol can be achieved, as further described below.

[0060] In some embodiments of the present invention, device 114 includes a cooling system 134, such as one or more fans.

[0061] The print head(s) and radiation source are preferably mounted on a frame or block 128, which preferably operates to reciprocate over a tray 360 that serves as a work surface. In some embodiments of the invention, the radiation source is mounted on the block so as to follow the print head to at least partially cure or solidify the material just dispensed by the print head. The tray 360 is positioned horizontally. In accordance with common practice, an XYZ Cartesian coordinate system is selected such that the XY plane is parallel to the tray 360. Preferably, the tray 360 is configured to move vertically (along the Z direction), typically downward. In various exemplary embodiments of the invention, the apparatus 114 further includes one or more planarizing devices 32, e.g., rollers 326. The planarizing device 326 serves to straighten, flatten, and / or establish the thickness of a newly formed layer before a subsequent layer is formed on top of the newly formed layer. Preferably, the planarizing device 326 includes a waste material collection device 136 for collecting excess material generated during planarization. The waste collection device 136 may include any mechanism that delivers material to a waste tank or waste cartridge.

[0062] 1A, the edge(s) of the tray 360 is shown with straight corners. However, this is not necessarily the case, as in some applications, particularly when the tray 360 is in contact with a fabric on which an object is to be printed, it may be desirable for the edge(s) on the top surface of the tray 360 to be formed as a fillet and / or chamfer (see chamfer 411 in FIGS. 4E and 4F).

[0063] In use, the multiple print heads of unit 16 move in a scanning direction (referred to herein as the X direction) and selectively dispense build material in a predetermined configuration as they pass over tray 360. The build material typically includes one or more types of support material and one or more types of modeling material. After the print heads of unit 16 pass, the modeling material(s) is cured by radiation source 26. During the head's retreating pass back to the starting point for the just-dispensed layer, additional build material may be dispensed according to a predetermined configuration. During the print head's forward and / or retreating pass, the layer thus formed may be straightened by flattening device 326. The flattening device 326 preferably follows the path of the multiple print heads during their forward and / or retreating movements. Once the print heads return to their starting points along the X direction, they will move to another position along the indexing direction (referred to herein as the Y direction) and continue to build the same layer by reciprocating motion along the X direction. Alternatively, the print head may move in the Y direction between forward and reverse movements, or after two or more forward and reverse movements. As used herein, the series of scans made by the print head to complete a single layer is referred to as a single scan cycle.

[0064] Once a layer is completed, the tray 360 is lowered in the Z direction to a predetermined Z height according to the desired thickness of the next layer to be printed. This procedure is repeated to build up the three-dimensional object 112 layer by layer.

[0065] In another embodiment, the tray 360 would be displaced in the Z direction during forward and backward passes of the print head of unit 16 through the layer. Such Z displacement is performed to allow the planarizing device to contact the surface in one direction and prevent contact in the other direction.

[0066] System 110 optionally and preferably includes a supply system 330 that includes multiple build material containers or cartridges to supply multiple build materials to manufacturing device 114 .

[0067] The controller 20 controls the manufacturing equipment 114 and, optionally and preferably, also the supply 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 related to manufacturing instructions based on computer object data (e.g., a CAD configuration expressed on a computer-readable medium in Standard Tessellation Language (STL) format, etc.). Typically, the controller 20 controls the voltage applied to each print head or nozzle array and the temperature of the build material within each print head or nozzle array.

[0068] Once the manufacturing data is loaded into the controller 20, the controller 20 can operate without user intervention. In some embodiments, the controller 20 receives additional input from an operator, for example, using a data processor 154 or 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, but not limited to, a keyboard, a touchscreen, etc.). For example, the controller 20 can receive as additional input one or more of the type and / or attributes of the build material (such as, 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.

[0069] Another representative, non-limiting example of a system 10 suitable for additive manufacturing (AM) of an object according to some embodiments of the present invention is depicted in Figures 1B-1D, which show a top view (Figure 1B), a side view (Figure 1C), and an isometric view (Figure 1D) of the system 10.

[0070] In this embodiment, the system 10 includes a tray 12 and multiple inkjet print heads 16, each having one or more nozzle arrays with one or more separate nozzles. Material for three-dimensional printing is supplied to the heads 16 by a build material supply system 42. The tray 12 can be disk-shaped or annular. Non-circular shapes are also contemplated, provided they are rotatable about a vertical axis. In the schematic diagram of FIG. 1C, the edge(s) of the tray 12 have straight corners. However, as with 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 for the edge(s) of the top surface of the tray 12 to be formed with fillets and / or chamfers.

[0071] 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 accomplished by (i) configuring the tray 12 to rotate about a vertical axis 14 relative to the head 16, (ii) configuring the head 16 to rotate about a vertical axis 14 relative to the tray 12, or (iii) configuring both the tray 12 and the head 16 to rotate about a vertical axis 14 but at different rotational speeds (e.g., rotation in opposite directions). While 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 about a vertical axis 14 relative to the head 16, 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, given the details provided herein, will know how to make such an adjustment.

[0072] In the following description, the direction parallel to the tray 12 and pointing outward from the axis 14 is referred to as the radial direction γ, the direction parallel to the tray 12 and perpendicular to the radial direction γ is referred to as the azimuth direction φ, and the direction perpendicular to the tray 12 is referred to as the vertical direction z.

[0073] The radial direction γ in system 10 corresponds to the index direction y in system 110, and the azimuthal direction φ corresponds to the scan direction x in system 110. Thus, in this specification, the radial direction is referred to interchangeably as the index direction, and the azimuthal direction is referred to interchangeably as the scan direction.

[0074] 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, it 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, it corresponds to any point belonging to a locus of points that is a circle whose radius is a particular distance from axis 14 and whose center is on axis 14.

[0075] As used herein, the term "azimuthal position" means a position on or above tray 12 that is at a particular azimuthal angle relative to a given reference point. Thus, a radial position means any point belonging to a locus of points that is a line that makes a particular azimuthal angle relative to a reference point.

[0076] As used herein, the term "vertical position" means a position on a plane that intersects the vertical axis 14 at a particular point.

[0077] Tray 12 serves as a build platform for three-dimensional printing. The work area where one or more objects are printed is typically, but not necessarily, smaller than the total area of ​​tray 12. In some embodiments of the present invention, the work area is annular. The work area is indicated at 26. In some embodiments of the present invention, tray 12 rotates continuously in the same direction throughout the formation of an object; in some embodiments of the present invention, the tray reverses its rotational direction (e.g., oscillatory) at least once during the formation of an object. Tray 12 is optionally and preferably removable. Removal of tray 12 may be performed for maintenance of system 10 or, if necessary, 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 replacement trays), where two or more trays are designated for different types of objects (e.g., different weights), different modes of operation (e.g., different rotational speeds), etc. Replacement of tray 12 can be performed manually or, if desired, automatically. When automated changeover is employed, system 10 includes a tray change device 36 configured to remove tray 12 from its position beneath head 16 and replace it with a replacement tray (not shown). In the representative drawing of Figure 1B, tray change device 36 is depicted as a drive 38 with a movable arm 40 configured to pull tray 12, although other types of tray change devices are contemplated.

[0078] Exemplary embodiments of print head 16 are depicted in Figures 2A-2C. These embodiments may be employed in any of the AM systems described above, including but not limited to system 110 and system 10.

[0079] 2A and 2B show print heads 16 with one nozzle array 22 (FIG. 2A) and two nozzle arrays 22 (FIG. 2B). The nozzles within an array are preferably aligned in a straight line. In embodiments where a particular print head has more than one linear nozzle array, the nozzle arrays can optionally, and preferably, be parallel to one another. When a print head has more than one nozzle array (e.g., FIG. 2B), all arrays in the head can be supplied with the same build material, or at least two arrays in the same head can be supplied with different build materials.

[0080] When a system similar to system 110 is employed, all print heads 16 are oriented along an index direction and their positions along the scan direction are offset from one another.

[0081] When employing a system similar to system 10, all print heads 16 are optionally and preferably oriented radially (parallel to the radial direction) and have azimuthal offsets relative to one another. Thus, in these embodiments, the nozzle arrays of different print heads are not parallel to one another, but are angled relative to one another, with the angle approximately equal to the azimuthal offset between the respective heads. For example, one head can be oriented radially and positioned at an azimuthal position φ1, while another head can be oriented radially and positioned 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.

[0082] 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 typically parallel to one another. A block containing several inkjet print heads 16 a, 16 b, 16 c is depicted in FIG. 2C.

[0083] In some embodiments, system 10 includes a stabilizing structure 30 positioned below head 16 such that tray 12 is between stabilizing structure 30 and head 16. Stabilizing structure 30 may help prevent or reduce vibration of tray 12 that may occur during operation of inkjet print head 16. In configurations in which print head 16 rotates about axis 14, stabilizing structure 30 preferably also rotates so that stabilizing structure 30 is always directly below head 16 (so that tray 12 is located between head 16 and tray 12).

[0084] Tray 12 and / or print head 16 are optionally and preferably configured to move along a vertical direction z, parallel to vertical axis 14, to vary the vertical distance between tray 12 and print head 16. In configurations in which the vertical distance is varied 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 is kept fixed while moving head 16 along the vertical direction to vary the vertical distance, stabilizing structure 30 is also maintained at a fixed vertical position.

[0085] Vertical movement can be established by vertical drive 28. Once one layer is completed, the vertical distance between tray 12 and head 16 can be increased by a predetermined vertical step (e.g., by lowering tray 12 relative to head 16) depending on the desired thickness of the next layer to be printed. This procedure is repeated, building up the three-dimensional object layer by layer.

[0086] The operation of inkjet printhead 16, and optionally and preferably, the operation of one or more other components of system 10 (e.g., movement of tray 12), is also controlled by controller 20. The controller may include electronic circuitry and a non-volatile memory medium readable by the circuitry, which stores program instructions that, when read by the circuitry, cause the circuitry to perform control operations, as described in more detail below.

[0087] The controller 20 can also communicate with a host computer 24, which transmits digital data related to manufacturing instructions based on computer object data in, 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 other formats suitable for computer-aided design (CAD). Object data formats are typically structured according to a Cartesian coordinate system. In these cases, the computer 24 preferably performs a procedure to convert 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 manufacturing instructions in the converted coordinate system. Alternatively, the computer 24 can transmit the manufacturing instructions in the original coordinate system provided in the computer object data, in which case the coordinate conversion is performed by circuitry in the controller 20.

[0088] Coordinate transformation enables three-dimensional printing on a rotating tray. In non-rotating systems with a stationary tray, the print head typically moves back and forth along a straight line above the stationary tray. In such systems, if the head feed rate is uniform, the printing resolution is the same at any point on the tray. In system 10, unlike non-rotating systems, not all of the nozzles at the head point to cover the same distance on tray 12 in the same amount of time. Coordinate transformation is optionally and preferably performed to equalize the amount of excess material at different radial locations. A representative example of coordinate transformation according to some embodiments of the present invention is provided in FIGS. 3A and 3B, which show three slices of an object (each slice corresponding to a manufacturing command for a different layer of the object), where FIG. 3A shows the slice in a Cartesian coordinate system and FIG. 3B shows the same slice after applying a coordinate transformation procedure to each slice.

[0089] Typically, controller 20 controls the voltages applied to the various components of system 10 based on manufacturing instructions and stored program instructions, as described below.

[0090] In general, controller 20 controls print head 16 to dispense droplets of build material in layers as tray 12 rotates so as to print three-dimensional objects onto tray 12 .

[0091] System 10 optionally and preferably includes one or more solidification devices 18, which may include, for example, one or more radiation sources (which may be, but are not limited to, ultraviolet, visible, or infrared lamps, other electromagnetic radiation sources, or electron beam sources), depending on the modeling material being used. The 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 lamps, etc. The radiation sources 18 serve to cure or solidify the modeling material. In various exemplary embodiments of the invention, the operation of solidification devices 18 is controlled by a controller 20, which may activate or deactivate solidification devices 18 and, optionally, control the amount of radiation emitted by solidification devices 18.

[0092] In some embodiments of the present invention, system 10 further includes one or more flattening devices 32, which can be fabricated as rollers or blades. Flattening device 32 serves to straighten a newly formed layer before a subsequent layer is formed on top of it. In some embodiments, flattening device 32 has the shape of a conical roller, which is 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 depicted in a side view of system 10 (FIG. 1C).

[0093] The conical roller can be conical or frustoconical.

[0094] The opening angle of the conical roller is preferably selected so that the ratio of the cone's radius at any point along its axis 34 to the distance between that point and axis 14 is constant. This embodiment allows roller 32 to efficiently flatten the layer because, while the roller is rotating, any point p on the roller's surface has a linear velocity that is proportional to (e.g., the same as) the linear velocity of the tray at a point vertically below point p. In some embodiments, the roller has a truncated cone 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, where R is the maximum distance of the roller from axis 14 (e.g., R can be the radius of tray 12).

[0095] The operation of the flattening device 32 is optionally and preferably controlled by a controller 20, which activates and deactivates the flattening device 32 and optionally also controls the position of the flattening device 32 along a vertical direction (parallel to the axis 14) and / or along a radial direction (parallel to the tray 12 and toward or away from the axis 14).

[0096] In some embodiments of the present invention, print head 16 is configured to move back and forth relative to the tray along radial direction γ. 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.

[0097] 1E-1G are schematic diagrams of a work tray 12 / 360 according to an embodiment of the present invention, the work tray including or associated with a radiation source 19 that emits radiation 17 to irradiate the build material from below. The radiation source 19 can emit any type of radiation 17 depending on the modeling material being used. Examples of radiation 17 include, but are not limited to, electromagnetic radiation (e.g., ultraviolet, visible light, infrared, etc.), electron beam radiation, etc. The radiation 17 emitted from 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, such as, but not limited to, one or more light-emitting diodes (LEDs), a digital light projector (DLP), a laser device, an electron beam source, etc. The radiation source 19 can be controlled by a controller 20, which activates and deactivates the radiation source 19 and, optionally, controls the amount and / or cross-sectional area of ​​the radiation 17.

[0098] In the schematic diagram of FIG. 1E, the radiation source 19 is located below the work tray, in which case the work tray 12 / 360 is preferably transparent to the radiation 17 emitted by the radiation source 19. In the schematic diagram of FIG. 1F, the radiation source 19 is embedded in the tray 12 / 360, in which case the portion of the work tray 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 is coupled into the tray 12 / 360 and guided within the tray 12 / 360 until it exits upward. The radiation 17 can be guided by the material of the work tray 12 / 360 (e.g., by total internal reflection) and exit upward by a redirecting element 21 (e.g., a mirror or diffraction grating). The radiation 17 can also be guided by one or more waveguides (not shown) embedded in the work tray 12 / 360.

[0099] In some embodiments, radiation source 19 is activated by controller 20 only when dispensing the bottom layer(s) of build material (e.g., the first one, two, three, four, or five layers) and is deactivated thereafter. Alternatively, the build material dispensed to form the bottom layer of build material can be transparent to radiation 17, allowing radiation 17 to penetrate the bottom layer and solidify the layers above it. In some embodiments, it is contemplated that a build material that absorbs radiation 17 can be selected for the bottom layer to mask radiation 17 from reaching the layers above it.

[0100] In some embodiments, the radiation source 19 is activated in a spatially selective manner, such that some areas on the tray emit radiation and other areas do not. For example, the radiation source 19 is activated in a spatially selective manner, irradiating only those areas on the work tray onto which the build material has been applied. Spatially selective irradiation can be achieved, for example, by providing the radiation source 19 as an array of LEDs and selectively activating individual LEDs.

[0101] Some embodiments contemplate fabricating an object by dispensing different materials from different nozzle arrays (belonging to the same or different printheads). These embodiments, among other things, provide 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 spatial location of deposition of each material in a layer is defined, causing different materials to occupy different three-dimensional spatial locations, or causing two or more different materials to occupy substantially the same three-dimensional location or adjacent three-dimensional locations, allowing spatial combination of materials after deposition within the layer, thereby forming a composite material at each location.

[0102] Any post-deposition combination or mixing of modeling materials is contemplated. For example, when a material is applied, it will maintain its original properties. However, if it is applied simultaneously with another modeling material or other applied material applied at the same or nearby location, a composite material will be formed that has different properties than the applied material.

[0103] In some embodiments of the present invention, the system provides digital material for at least one of the layers.

[0104] As used herein and in the art, the term "digital material" refers to the combination of two or more materials at the pixel or voxel level, such that pixels or voxels of different materials interlace with one another over an area. Such digital materials may exhibit novel properties that are influenced by the choice of material type and / or the proportions and relative spatial distribution of the two or more materials.

[0105] As used herein, a "voxel" of a layer refers to a physical three-dimensional elementary volume within the layer that corresponds to a single pixel in a bitmap describing the layer. The dimensions of a voxel are approximately the same as the dimensions of the area created by the build material when it is dispensed, flattened, and solidified at the location corresponding to the respective pixel.

[0106] In the context of digital materials, interlacing can be between single voxels, each containing a different build material, or between blocks of voxels. In the latter case, a block of voxels is defined as a contiguous region occupied by n voxels that all contain the same build material, and the boundary of this region is defined as a set of voxels that are adjacent to at least one voxel that contains a build material other than the build material contained in the voxels in the set. In preferred embodiments, n is less than 1000, less than 500, less than 100, less than 50, or less than 10.

[0107] In an exemplary digital material, the modeling material obtained by hardening of each voxel or voxel block is independent of the modeling material obtained by hardening of adjacent voxels or voxel blocks; each voxel or voxel block is a different modeling material, and the overall new properties are the result of a spatial combination at the voxel level of several different modeling materials.

[0108] Thus, the present embodiment allows for the deposition of a wide range of material combinations and the fabrication of objects comprised of multiple different combinations of materials in different portions of the object according to the properties required to characterize each portion of the object.

[0109] Further details regarding the principles and operation of an AM system suitable for this embodiment are described in U.S. Publication No. 20100191360, the entire contents of which are incorporated herein by reference.

[0110] Some embodiments of the system 10 and / or system 110 of the present invention are configured to print one or more objects onto a fabric.

[0111] As used herein, the term "fabric" includes any product 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, fabric items, carpets, fabric hats, fabric bags, socks, towels, curtains, etc.

[0112] The present embodiment contemplates printing on woven or non-woven fabrics.

[0113] As used herein, the term "woven" refers to a structure that results when at least two sets of yarns are interlaced (e.g., at right angles to each other) in a predetermined interlacing pattern, with at least one set parallel to the longitudinal axis of the fabric, in accordance with ASTM D123-03.

[0114] As used herein, the term "non-woven" means a fabric structure formed by bonding or interlocking (or both) fibers, in accordance with ASTM D123-03, where the bonding or interlocking is achieved by mechanical, chemical, thermal, or solvent means and combinations thereof.

[0115] Preferably (but not necessarily), when a printing system (e.g., system 10 or 110) is employed to print an object onto a fabric, flattening device 32 is not used or is used only after the object has reached a predetermined height above the fabric.

[0116] Preferably (but not necessarily), when a printing system (e.g., system 10 or 110) is employed to print an object onto 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.

[0117] In some embodiments of the present invention, the work tray of the system (e.g., tray 12 or 360) has a reflectivity of at least 50%, at least 60%, at least 70%, or at least 80% or more to the radiation emitted by the radiation source of solidification device 18. The advantage of making the work tray reflective or partially reflective is that reflected radiation reaching the fabric from the underside thereof can solidify the build material on the underside of the fabric and also penetrate pores in the fabric and solidify droplets of build material within those pores, thereby improving adhesion of the printed object to the fabric.

[0118] This embodiment also contemplates providing one or more fluid passages 52 in the work tray. A fluid supply system 54 can generate a fluid flow through the fluid passages 52. The fluid is optionally and preferably at a controlled temperature, thereby controlling the temperature of the work tray. If the fluid supply system 54 generates a fluid flow at a temperature lower than that of the applied build material, the fluid absorbs heat from the build material. The fluid supply system 54 can also generate a fluid flow at a temperature higher than that of the fabric to facilitate smoothing out wrinkles in the fabric before applying the build material to the fabric. The present invention also contemplates combinations of these embodiments, where the fluid is maintained at an elevated temperature before applying the build material and at a reduced temperature during the fabrication of the object. The fluid can be in a gaseous or liquid phase (e.g., air, helium, water, oil, etc.). Preferably, the fluid supply system 54 is controlled by the controller 20.

[0119] Some embodiments of the systems 10 and / or 110 of the present invention include a fixture 402 configured to secure a fabric 420 in a predetermined position on a work tray (e.g., tray 12 or 360) of the system and in a predetermined orientation relative to a nozzle array (e.g., array 122) of the system. Some embodiments of the fixture 402 of the present invention are also configured to stretch the fabric 420.

[0120] Fixture 402 is depicted in more detail in Figures 4A-4F. Figures 4A and 4B show an embodiment in which fixture 402 includes a frame 403 and one or more magnetic or metallic elements 405, with elements 405 preferably permanently attached to or adjacent tray 12 / 360 (e.g., on a stationary platform 361 surrounding tray 12 / 360), and one of tray 12 / 360 and elements 405 including a permanent magnet to ensure mutual magnetic attraction between element 405 and frame 403. Frame 403 can be entirely magnetic or metallic, or it can include magnetic or metallic elements (not shown, see Figures 4E and 4F) in lateral positions that match the positions of elements 405 around it. Figure 4A shows the jig 402 in an open position before the fabric 420 is placed on the work tray 12 / 360, and Figure 4B shows the jig 402 in a closed position, in which the frame 403 is magnetically attached to an element 405 (not shown in Figure 4B) to secure the fabric 420 (optionally and preferably stretch the fabric) to the work tray 12 / 360. The jig 402 can also include a pair of frames 403 that can be magnetically attached to one another, in which case the fabric 420 is stretched between the frames of the jig 402 before being placed on the work tray 12 / 360. In these embodiments, the element 405 is not required.

[0121] 4E and 4F show side views of jig 402. In the illustrated embodiment, frame 403 is provided with magnetic or metallic element 407, which is attached at a lateral position that matches the position of element 405 around frame 403. Element 407 and element 405 can be flat, as shown in FIG. 4E, or can have protruding element 409 or a roughened surface, as shown in FIG. 4F. This protruding element 409 or roughened surface can be provided on the magnetic or metallic element attached to frame 403, on platform 361, or on both frame 403 and platform 361. If frame 403 is entirely magnetic or metallic, no additional magnetic or metallic element 407 needs to be attached to it, and protruding element 409 or a roughened surface can be formed on frame 403 at a lateral position that matches the position of element 405.

[0122] 4C and 4D show an embodiment in which the fixture 402 includes a rotating frame 406 and a planar fabric holder 408, the frame 406 being sized and shaped so that when the frame 406 is rotated to engage the planar surface of the fabric holder 408, the frame 406 surrounds the fabric holder 408 and traps the fabric 420 between the frame 406 and the fabric holder 408. The fabric holder 408 can be in the form of a continuous surface or a frame. When the fabric holder 408 is a continuous surface, the fabric 420 placed (optionally and preferably stretched) on the fabric holder 408 is accessible from only one side of the fabric 420 (typically from above). When the fabric holder 408 is in the form of a frame, the fabric 420 placed (optionally and preferably stretched) on the fabric holder 408 is accessible from both sides of the fabric 420. FIG. 4C shows the fixture 402 open and ready to accept the fabric 420, and FIG. 4D shows the fixture 402 closed, securing the fabric 420 to the tray 12 / 360.

[0123] An advantage of having a fixture that also includes a planar fabric holder 408 is that it allows the fixture 402 to receive the fabric 420 while the fixture 402 is placed on the work tray 12 / 360 or before the fixture 402 is placed on the work tray 12 / 360.

[0124] 5A-5C are schematic diagrams of a configuration in which the fabric 420a is placed on a ramp structure 450, which includes a planar ramp 452 and one or more spacer beams 454 that maintain the ramp 452 vertically spaced from the work tray 12 / 360. The ramp structure 450 can be placed on the tray 12 / 360 or can be connected to the tray 12 / 360 by a connector (not shown) (e.g., but not limited to, a snap connector). If the ramp structure 450 is connected to the tray, the connector is preferably outside the printing area of ​​the AM system, preventing the connector from interfering with the printing process when the AM system is operated without the ramp 450. The fabric 420 can be secured using any of the techniques described above, except that the fabric is secured to the ramp structure 450 rather than the tray 12 / 360.

[0125] An advantage of the ramp structure 450 is that it allows printing of three-dimensional objects on fabrics 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, as shown in FIG. 5A , the fabric 420 is folded over the edge of the ramp structure 450, with the horizontal portion 420a of the fabric 420 supported on the upper surface of the ramp 452 and the hanging portion 420b of the fabric 420 folded into the space below the ramp 452 but above the work tray 12 / 360. Preferably, the fabric 420 is secured to the ramp structure 450 before the ramp structure 450 is 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.

[0126] Once fabric 420 is secured to work tray 12 / 360 (FIGS. 4A-4F) or lamp 452 (FIGS. 5A-5C), computerized controller 20 (FIGS. 1A and 1B) operates nozzle array 122 (FIGS. 2A-2C) to dispense build material(s) onto secured fabric 420 in a structured pattern corresponding to the shape of the object. In embodiments employing lamp structure 450, computerized controller 20 controls nozzle array(s) 122 to terminate any dispensing when a nozzle is above the gap between lamp structure 450 and platform 361, thereby ensuring that droplets of build material(s) land only on horizontal portions 402a of fabric 420.

[0127] It will be appreciated that if the ramp structure 450 is employed, the vertical position of the ramp 452 along the Z direction will be higher than the vertical position of the work tray 12 / 360. In this case, the computerized control device 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 depicted 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 located at the same vertical position as the upper surface of the platform 361 if the ramp structure is not employed. 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 located at the same vertical position as the upper surface of the platform 361. Once the initial vertical position has been adjusted, the printing process continues with multiple layers as described in more detail above, and once a layer is completed, the work tray 12 / 360 is lowered in the Z direction depending on the desired thickness of the next layer.

[0128] 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 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. Computerized controller 20 receives position tracking signals from system 50, performs a registration procedure based on the position tracking signals, and operates nozzle array 122 accordingly. An advantage of this embodiment is that precise positioning of fixture 402 on the tray is not required, because the registration procedure performed by controller 20 can ensure that nozzles are activated to dispense build material at the appropriate locations on fabric 420.

[0129] The position tracking system 50 can determine the position of the fixture 402 in more than one way. In some embodiments of the present 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 an optical scanner) and performs image processing to determine the position of the fixture 402 relative to the tray. In some embodiments of the present invention, the position tracking system 50 can determine the position of the fixture 402 using marks 414. The marks 414 can be formed on or attached to, for example, the frame 406 of the fixture 402, the fabric holder 408 as shown in FIGS. 4A, 4C, and 4D, the work tray, or the stationary platform 361 as shown in FIG. 4A. The marks 414 can be identified by the position tracking system 50 and used by the system 50 to determine the position of the fixture 402. For example, if the system 50 includes an optical scanner or an image generator, the marks 414 can be a printed pattern. Examples of printed patterns include, but are not limited to, bar codes or optical signal sources (e.g., light-emitting diodes that emit radiation that does not solidify the build material dispensed by the nozzle array). If system 50 includes a magnetic or radio frequency sensor, the mark may include a radio frequency or magnetic field source. Examples of radio frequency or magnetic field sources include, but are not limited to, miniature coils, etc.

[0130] 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 tracking system 50 need not be used to determine the position of the jig 402 (although such determination is contemplated in some embodiments), because the control device 20 can perform a registration procedure based on the identified pattern on the fabric 420.

[0131] The process for fabricating three-dimensional objects on the fabric 420 may optionally and preferably include the use of one or more liquid formulations other than the three-dimensional printing build material. The liquid formulation may be curable or non-curable. Herein, the liquid formulation may alternatively be referred to as a "liquid additive," "additive formulation," or "liquid additive formulation." The liquid additive formulation may be dispensed onto the fabric by a dispense head of the system 10 or system 110. Embodiments are also contemplated in which the liquid formulation is dispensed by an additive dispense system 340 (FIGS. 1A and 1B), which is in fluid communication with a container 342 (shown only in FIG. 1A) containing the liquid formulation and is controllable by the controller 20. In some embodiments of the present invention, the one or more additive formulations may be applied by directing an aerosol or mist of the liquid additive toward the fabric. In these embodiments, the system 340 may be in the form of an aerosol dispenser or sprinkler for generating and directing an aerosol or mist of the liquid additive toward the fabric. In some embodiments of the present invention, one or more additive formulations are applied by depositing droplets of the additive at separate accessible locations on the fabric. In these embodiments, one or more of the plurality of print heads 16 can be configured to supply each additive formulation, and one or more of the plurality of containers or cartridges of the supply system 330 can contain each additive formulation. When there are two or more additive formulations (e.g., formulations that react with each other in situ after deposition but not otherwise), deposition at separate accessible locations on the fabric is preferably done in a laterally interleaved manner to create boundaries between adjacent droplets of different additive formulations.

[0132] The additive delivery system 340 can be mounted on the same print block as the head 16, as shown in FIG. 1A, and thus 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 system 340 can be configured for independent movement. In some embodiments, the build tray 12 / 360, or a portion thereof, moves below the static print block 128 to which the static additive delivery system 340 (e.g., sprinkler array) and / or head 16 is mounted. In some other embodiments, the tray 360 is configured for movement in the Z direction, with the head 16 mounted on the 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 delivery system 340 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 delivery system 340 are configured to horizontally scan the surface of the tray 360 in the same direction (eg, the X-axis).

[0133] Types of liquid additive formulations contemplated by some embodiments of the present invention include, but are not limited to, primer formulations (e.g., reinforcing formulations, adhesive formulations, pore sizing formulations, etc.), finishing or coating formulations (e.g., radiation protection formulations, gloss finish formulations, matte finish formulations, etc.), masking formulations, etc. Other types of additive formulations that may be used by some embodiments of the present invention include temporary protection formulations, water repellent formulations, waterproofing formulations, hydrophobic formulations, etc.

[0134] If the additive formulation is a base formulation, it is applied before the application of the building (e.g., modeling) material formulation. Thus, for example, an adhesive formulation can be applied to the fabric, followed by the application of the building (e.g., modeling) material formulation, where the adhesive formulation ensures adhesion of the uncured building (e.g., modeling) material formulation or the cured building (e.g., model, modeling) material to the fabric. Another example is the application of a pore-sizing solution that increases the size of the pores in the fabric. The building (e.g., modeling) material formulation can then be applied to form protruding elements (e.g., elements 506) within the increased-sized pores. Another example is the application of a reinforcing substance to stabilize the fabric before the material is applied.

[0135] If the additive formulation is a finish or coating formulation, it is applied after the application of the build material. For example, a gloss or matte finish formulation can be applied to the applied build material to provide a desired appearance to the applied material. Similarly, paints such as metallic paints (e.g., chrome, gold) can be applied in the form of a finish formulation over at least a portion of an object printed with the build material. Finish formulations for protecting fabrics or printed objects from, for example, fading, 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 (e.g., UV-resistant materials commercially available from Krylon®) and polyurethanes (e.g., polyurethane solutions available from Rust-Oleum).

[0136] If the additive formulation is a masking formulation, it is preferably applied before the application of the build material formulation. The masking formulation serves to prevent selected portions of the fabric from contacting the applied build material, and is therefore selectively applied in locations that should not be occupied by the object being printed. The masking formulation is preferably removable (e.g., washes off with water). For example, the masking formulation can include the solution disclosed in U.S. Pat. No. 5,308,647, the contents of which are incorporated herein by reference. The masking formulation can also be applied after printing and before finishing (if applied) to protect the object or other parts of the fabric from the finishing formulation (if applied).

[0137] It is also envisioned that a layer of support material may be used as a protective coating in areas not occupied by the object to be printed.

[0138] Any of the above additive formulations can optionally and preferably include an unactivated (e.g., uncured) formulation that can be activated in situ (i.e., while applied to a textile). In these embodiments, the formulation is applied to a textile 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.

[0139] Formulations that are activated by a chemical reaction are also contemplated. Such a reaction can occur between the formulation and one or more of the plurality of 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 applied onto the fabric and at least partially penetrate the pores of the fabric while they are in a liquid phase (before being cured by exposure to curing conditions). A formulation that reacts with the applied build material formulation is then applied. The chemical reaction between the build material formulation (e.g., one or more curable materials therein) and the applied formulation changes at least one property (e.g., mechanical and / or optical property) of the build material. In some embodiments, the formation involves polymerization of one or more curable materials within the applied build material formulation.

[0140] In embodiments where two or more formulations react with one another, it is preferred to deposit the two or more formulations separately and allow the reaction between them to occur on the fabric. Depending on the product of such reaction, the formulations can be deposited before, after, simultaneously with, or intermittently with the application of the build material formulation.

[0141] For example, a compound can be deposited prior to dispensing the build material compound if the reaction product forms an adhesive that allows the build material to adhere, if the reaction product alters pore size (e.g., the reaction product locally shrinks the fibers of the fabric, increasing the interfiber pore size), and / or if the reaction product forms a mask in areas of the fabric that are desired to be protected from contact with the build material. A compound can be deposited after dispensing the build material compound if the reaction product alters the appearance of the cured build material (e.g., increases or decreases gloss, changes color), or encases the cured build material with a (typically transparent) cover (e.g., a protective cover). If it is desired to interlace a reaction product vertically or laterally with the cured build material, for example, to strengthen the build material, improve flexibility of the final product, etc., the compound can be deposited simultaneously with or intermittently with dispensing the build material compound.

[0142] Representative examples of formulations suitable to serve as primer and / or coating formulations according to some embodiments of the present invention are described in more detail in the Examples section below.

[0143] The present disclosure also contemplates the use of non-liquid additives. For example, the applied additive can be in a solid phase. In these embodiments, the additive can be applied by contacting the fabric with a substrate bearing the additive and applying pressure, radiation, and / or heat to the substrate to transfer the additive from the substrate to the fabric. The substrate is typically (but not necessarily) in the form of a film containing or coated with the additive. For example, if the additive includes a reinforcing substance (such as, but not limited to, an oily substance (e.g., wax)), a sheet containing the reinforcing substance can be placed on the fabric and heated and / or pressed against the fabric to transfer the reinforcing substance to the fabric.

[0144] The solid phase additive can be applied to the same side of the fabric as the build material formulation and / or to the side opposite the side to which the build material formulation is applied. Application of the solid phase additive to the fabric is typically performed before the build material formulation is applied, although embodiments are contemplated in which the solid phase additive is applied to the fabric after the object is formed on the fabric.

[0145] Reference is now made to Figures 6A-6C, which are flow chart diagrams describing methods suitable for forming adhesive structures on fabrics by three-dimensional printing, according to various exemplary embodiments of the present invention.

[0146] Unless otherwise specified, it should be understood that the steps described below can be performed simultaneously or sequentially in any combination or order of execution. In particular, the order of the flowchart diagrams should not be considered limiting. For example, two or more steps that appear in a particular order in the following description or flowchart diagrams can be performed in a different order (e.g., in reverse order) or substantially simultaneously. Furthermore, some steps described below are optional and may not be performed.

[0147] The method of the present embodiment can be performed by a computerized controller (eg, controller 20) of system 10 or system 110.

[0148] The method of the present embodiments can be used as a printing protocol to improve adhesion of three-dimensionally printed objects to textiles. The adhesive structure is formed by sequentially applying layers of formulations suitable as base formulations. Preferably (but not required), the entire adhesive structure is made from a single formulation. Representative examples of formulations suitable for these embodiments are described in the Examples section below. Other types of formulations are also contemplated.

[0149] Typically, after an adhesive structure is formed on a fabric as described below, a three-dimensional object made of one or more modeling materials is printed onto the adhesive structure. The inventors have discovered that performing the method described below with reference to FIG. 6A provides adequate adhesion between the object and any fabric. The inventors have discovered that if the fabric has low absorbency for the applied formulation, performing the method described below with reference to FIG. 6B can provide a further improvement in the level of adhesion, and if the fabric has higher absorbency for the applied formulation, performing the method described below with reference to FIG. 6C can provide a further improvement in the level of adhesion.

[0150] The absorbency level of the fabric can be determined prior to printing using any procedure known in the art. For example, a droplet of the provided 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. In this case, a larger contact angle corresponds to a more hydrophobic and less absorbent fabric. Alternatively, or in addition, the fabric can be immersed in a liquid (e.g., water) and the time it takes for the fabric to absorb the liquid can be correlated with the absorbency level of the fabric.

[0151] Referring to Figure 6A, the method begins at 600 and optionally and preferably proceeds to 601. At 601, computer object data is received. The computer object data can be in any of the formats described above and can describe at least the bottom-most surface of an object to be fabricated on an adhesive structure. Typically, however, the computer object data describes the entire shape of the object.

[0152] The method continues at 602 where a base compound is applied to create a layer. The application is onto the fabric or onto a previously applied layer (if such a layer has already been created by the method described above). The compound is selectively applied according to computer object data of the bottom surface of the object to be created on the adhesive structure. Thus, the compound is applied to the lateral coordinates that the object is expected to occupy after printing, and not to other locations.

[0153] The method proceeds to 603 where the illumination intensity I A The formulation is irradiated with curing radiation of intensity I to form a hardened adhesive material that constitutes a layer of the adhesive structure. 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 UV light. A A typical value of is about 2.5 W / cm 2 to approximately 5.5 W / cm 2 is.

[0154] For any layer of the adhesive structure, step 603 is preferably performed according to a protocol in which a pattern of curing radiation is created on the layer. In this protocol, the pattern has the shape of a single stripe and advances along the scanning direction (x or φ). A representative example of an irradiation protocol suitable for step 603 is depicted in Figures 11A and 11B. These figures show a layer 610 of base compound on fabric 420 and a pattern 612 of curing radiation in the shape of a single linear stripe that advances along the direction x when fabric 420 is on tray 360 (Figure 11A) or along the direction φ when fabric 420 is on tray 12 (Figure 11B).

[0155] The radiation pattern is generated by a radiation-emitting device (e.g., device 18 of system 10 or system 110), and the irradiation protocol shown in Figures 11A and 11B can be employed with appropriate control of these devices. For example, if the system is configured for linear reciprocating relative motion between the feed head and the tray (e.g., system 110), step 603 can be performed by activating only the solidification devices that follow the print head and deactivating the solidification devices that precede the print head (e.g., referring to Figure 1D, if head 16 moves to the left, device 18 to the right of head 16 is activated and device 18 to the left of head 16 is deactivated (similarly for head 16 moving to the right)). This ensures that the protocol shown in Figure 11A can be performed. If the system is configured for rotational relative motion between the feed head and the tray (e.g., system 10), step 603 can be performed by activating only the solidification devices that are rotationally in front of the print head and deactivating the solidification devices that are rotationally behind the print head. This ensures execution of the protocol shown in Figure 11B. Control of the solidification device is typically performed by a controller of the three-dimensional printing system (e.g., controller 20 of system 10 or system 110).

[0156] The method optionally and preferably returns from 603 to 602 to form the next layer of the bonded structure. This looping is repeated a predetermined number of times. Preferably, this looping is repeated until the number of layers in the bonded structure reaches N1. The number of layers N1 is about 10 to about 30, or about 15 to about 30, for example, about 20.

[0157] After the iterations are complete, a stack of layers is formed, and the method optionally and preferably proceeds to 604, where a three-dimensional object is printed layer by layer on the top layer of the stack based on the computer object data. Preferably, the object is printed using one or more modeling materials (e.g., but not limited to, one or more of the modeling materials described above). In some embodiments of the invention, at least one of the modeling material formulations applied in 604 is a flexible modeling material (e.g., but not limited to, the flexible modeling material described in Example 3 in the Examples section below). The object is printed by applying one or more modeling formulations in layers in a structured pattern corresponding to the shape of a slice of the object, and exposing each layer of modeling formulation to curing radiation. This exposure is preferably performed according to the same exposure protocol as described above with respect to step 603.

[0158] In some embodiments, the method continues at 605, where a formulation suitable for use as a coating formulation is applied to the surface of the object and cured to form a hardened coating. In some embodiments, the coating formulation is the same as the base formulation applied at 602. The coating is formed by applying the formulation in layers over the object and exposing each layer of formulation to curing radiation. In some embodiments, the coating formulation is also applied to at least partially surround one or more of the layers formed at 604. Such surrounding or partially surrounding coatings can be formed substantially simultaneously with the formation of each layer of the object by applying the modeling formulation and coating formulation using different nozzle arrays on the delivery head 16. Alternatively, as indicated by the looping back arrow from 605 to 604, a surrounding or partially surrounding coating can be formed for each layer after the layer of modeling formulation has been applied. An advantage of forming a surrounding or partially surrounding coating is that it also provides a coating on the sides of the object. For example, a coating that surrounds the print object on all sides can be provided by dispensing the coating formulation so that it completely surrounds each of the layers formed in 604. Irradiation in 605 is preferably carried out according to the same irradiation protocol as described above with respect to step 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.

[0159] In some embodiments of the present invention, the method proceeds to 606, where the top layer of the object or coating (if applied) is A and different strength I B Preferably, no formulation is dispensed during 606. Intensity I B I A It is preferable that the temperature is about twice as high as the above.

[0160] The irradiation protocol adopted by the controller in 606 is optionally and preferably different from the irradiation protocol adopted in 603. Specifically, 606 is performed according to a protocol in which a pattern of curing radiation is produced on the layer. In this protocol, the pattern has the shape of two stripes and advances along the scanning direction (x or φ). Representative examples of irradiation protocols suitable for step 606 are depicted in FIGS. 11C and 11D. These figures show a layer 614 of the object 112 on a fabric 420 and a pattern 616 of curing radiation in the shape of two linear stripes that advance along the direction x when the fabric 420 is on tray 360 (FIG. 11C) or along the direction φ when the fabric 420 is on tray 12 (FIG. 11D). Such a pattern of curing radiation can be produced by operating both devices at the same power used during step 603. In particular, if the system is configured for reciprocating relative motion along a line (e.g., system 110), step 606 is performed by actuating both a solidification device that follows the print head and a solidification device that precedes the print head, and if the system is configured for rotational relative motion (e.g., system 10), step 606 is performed by actuating both a solidification device that is rotationally in front of the print head and a solidification device that is rotationally behind the print head. Control of the solidification devices is typically performed by a controller for the three dimensional printing system (e.g., controller 20 of system 10 or system 110).

[0161] Alternatively, step 606 doubles the power of one solidification device and deactivates the other solidification device, in which case the radiation pattern will be as shown in Figures 11A and 11B, except that its intensity will be doubled.

[0162] In some embodiments of the invention, the object is a test object printed to test the level of adhesion provided by the adhesive structure. 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 described below. If the object is to be used for testing, step 605 can be skipped.

[0163] The method ends at 608.

[0164] Referring to Figure 6B, the method set forth in this flow chart is suitable for implementation when the fabric has a relatively low level of absorption. The method begins at 620 and optionally and preferably proceeds to 601. At 601, computer object data is received, as described in more detail above.

[0165] The method continues at 621, where the formulation is dispensed to create a first stack of uncured layers. Dispensing occurs on the fabric or on a previously dispensed layer, and is selectively performed according to computer object data of the bottom surface of the object, as described in more detail above. For each layer of the first stack, the formulation is dispensed without being cured. Therefore, all solidification devices are deactivated during step 621. The number of layers dispensed without being cured during step 621 is less than five, more preferably less than four. In a preferred embodiment, the first stack consists of two layers.

[0166] The method proceeds to 622, where a base compound is applied onto the first laminate to create a layer. The method proceeds to 623, where the curing radiation is applied at a radiation intensity I B The formulation is irradiated with a typical intensity IB of about 5 W / cm. 2 to about 10 W / cm 2For any layer of the adhesive structure, step 623 is preferably performed according to a protocol in which a pattern 616 of curing radiation is created on the layer, in which the pattern has the shape of two stripes, advancing along the scanning direction (x or φ) as described in more detail above in connection with step 606 and as depicted in Figures 11C and 11D.

[0167] The method optionally and preferably returns from 623 to 622 to form the next layer of the bonded structure. This looping is repeated a predetermined number of times. Preferably, this looping is repeated until the number of layers in the bonded structure is N2, which is about 15 to about 30. As described in more detail below, the present disclosure contemplates performing two or more of the methods described in FIGS. 6A-6C on the same fabric or 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, when N1=15, N2 can be 10, and when N1=20, N2 can be 18.

[0168] After the iterative steps including 622 and 623 have been completed, a second stack of layers is formed, and the method optionally and preferably proceeds to 604, where a three-dimensional object is printed layer by layer on the top layer of the second stack based on the computer object data. Preferably, the object is printed using one or more modeling materials (e.g., but not limited to, one or more of the modeling materials described above). The object is printed by applying one or more modeling compositions in layers in a structured pattern corresponding to the shape of a slice of the object, and exposing each layer of modeling composition to curing radiation. This exposure is preferably performed according to the same exposure protocol as described above with respect to step 603.

[0169] In some embodiments, the method continues at 605, where a formulation, preferably for use as a coating formulation, is applied to the outer surface of the object and cured, as described in more detail above. In some embodiments, the method continues at 606, where a top layer of the object or coating is applied to a surface of the object with a strength of I, as described in more detail above. B The curing radiation is scanned at .

[0170] In some embodiments of the invention, the method proceeds to 607 where the level of adhesion of the object to the fabric is tested, if desired, as described above, and more fully below.

[0171] The method ends at 628.

[0172] Referring to Figure 6C, the method set forth in this flow chart is suitable for implementation when the fabric has a relatively high level of absorption. The method begins at 640 and optionally and preferably proceeds to 601. At 601, computer object data is received, as described in more detail above.

[0173] The method continues at 641 where a base formulation is applied to form a layer, either onto the fabric or onto a previously applied layer (if such a layer has already been formed by the method), with the formulation being selectively applied according to computer object data of the bottom surface of the object, as described in more detail above.

[0174] The method proceeds to 642, where the curing radiation is applied at a radiation intensity I C The formulation is irradiated with an intensity of I C is typically the aforementioned radiant intensity I B Higher (e.g., twice as high) than Intensity I C A typical value of is about 10 W / cm 2 to approximately 22 W / cm 2 is.

[0175] For any layer of the bonded structure formed by method 640, step 642 is preferably performed according to a protocol in which a pattern 616 of curing radiation is created on the layer. In this protocol, the pattern has the shape of two stripes, advancing along the scanning direction (x or φ) as described in more detail above in connection with step 606 and as depicted in Figures 11C and 11D. Step 642 can be performed by activating both solidification devices of the system, but step 642 also involves applying a radiation intensity I C To provide this, each solidification device is operated with a greater power than in step 606 (typically twice as much as in 606). Specifically, if the system is configured for reciprocating relative motion along a straight line (e.g., system 110), step 642 is performed by activating both the solidification device that follows the print head and the solidification device that precedes the print head; if the system is configured for rotational relative motion (e.g., system 10), step 642 is performed by activating both the solidification device that is in front of the print head in the direction of rotation and the solidification device that is behind the print head in the direction of rotation. Control of the solidification devices is typically performed by a controller for the three dimensional printing system (e.g., controller 20 of system 10 or system 110).

[0176] After the iterative steps including 641 and 642 have been completed, a stack of layers has been formed, and the method optionally and preferably proceeds to 604, where a three-dimensional object is printed layer by layer on top of the previously formed stack. Preferably, the object is printed using one or more modeling materials (e.g., but not limited to, one or more of the modeling materials described above). The object is printed by applying one or more modeling compounds in layers in a structured pattern corresponding to the shape of a slice of the object, and exposing each layer of modeling compound to curing radiation. This exposure is preferably performed according to the same exposure protocol as described above with respect to step 603.

[0177] In some embodiments, the method continues at 605, where a formulation, preferably for use as a coating formulation, is applied to the surface of the object and cured, as described in more detail above. In some embodiments, the method continues at 606, where a top layer of the object or coating is applied to a surface of the object with a strength of I, as described in more detail above. B The curing radiation is scanned at .

[0178] The method ends with 647.

[0179] In some embodiments of the present invention, an operator first determines which of the above methods is more suitable for the fabric and selects the appropriate method. Therefore, parameters describing the fabric are obtained, and one of methods 600, 620, and 640 can be selected based on the obtained parameters. The parameter is the absorbency level of the fabric or an indicator thereof. For example, the parameter may be the type of fabric, and the operator can determine the absorbency level of the fabric using a lookup table. If the absorbency level is below a predetermined threshold, the operator can perform method 620, and if the absorbency level is above the predetermined threshold, the operator can perform method 640. The operator can select method 600 as the default method, which is performed when the absorbency level of the fabric is unknown.

[0180] The present embodiments also contemplate performing one or more of methods 600, 620, and 640 more than once on the same fabric or type of fabric. For example, one or more of these methods can be repeated on the same side of the fabric with different orientations of the fabric and / or on different sides of the fabric. These embodiments are particularly useful for testing, where testing step 607 is performed with each run of each method, allowing for determination of the orientation and / or side that provides the highest level of adhesion.

[0181] This embodiment also contemplates performing two or more of methods 600, 620, and 640 on the same fabric or fabric type. These embodiments are also useful for testing, in which case a test step 607 is performed for each run of the respective method, allowing for a determination of which printing protocol provides the highest adhesion level for the fabric under investigation. When two or more methods are performed using the same fabric, different methods may be used to form adhesive structures on different portions of the fabric. This type of testing can also be combined with testing adhesion levels for different orientations and / or sides of the fabric. Thus, in this combined testing, two or more of methods 600, 620, and 640 are performed on the same fabric or fabric type, and these methods are further performed on at least two different orientations and / or two sides of the same fabric or fabric type. Each time a method is run, a test step 607 is performed, allowing for a determination of the printing protocol, orientation, and / or side that provides the highest adhesion level.

[0182] Methods 600, 620, and 640 can be used to create any type of object on a textile using any formulation suitable for three-dimensional printing. Examples of formulations suitable for this embodiment include, but are not limited to, formulations sold under the trade names Vero™ family (e.g., VeroVivid™ Cyan, VeroVivid™, VeroClear™, Vero ContactFlex, and VeroUltraClear) and Agilus™ family (e.g., Agilus30™, Agilus™ White, Agilus™ Clear, Agilus™ Black, Agilus™ Cyan, Agilus™ Magenta, and Agilus™ Yellow), all of which are sold by Stratasys® Ltd., Israel. In some embodiments of the present invention, at least one of the formulations provided to create the textile object provides a flexible material. Representative examples of such formulations are described in the Examples section below.

[0183] In some embodiments of the present invention, a method is performed to fabricate an object selected from the group consisting of a lens-like object, a prism-like object, an object reflective to visible light, an object transparent to visible light but reflective to non-visible light, a fluorescent object, and a waveguide. In some embodiments, the fabricated object can change optical, mechanical, and / or geometric properties in response to changes in the environment (such as, but not limited to, changes in temperature, humidity, or electromagnetic content of the environment). For example, the object can be fabricated from a photosensitive material that changes color in response to changes in light conditions or temperature.

[0184] In some embodiments of the present invention, methods are implemented to create objects that include an agent (e.g., but not limited to, a pharmaceutical agent and / or a cosmetic agent). For example, the agent can be adsorbed onto the surface of the object (e.g., by applying the agent to a build material with an additive), or the object can be in the form of a capsule that contains the agent. Representative examples of pharmaceutical agents that can be incorporated into the object include, but are not limited to, antibacterial and antiviral agents.

[0185] In some embodiments of the present invention, the methods are performed to create objects that include a heating element capable of emitting heat or a cooling element capable of absorbing heat, in some embodiments, the methods are performed to create objects that include circuits, and in some embodiments, the methods are performed to create objects that include a cavity that houses an external object (e.g., but not limited to, an electrical circuit, a magnetic element, a light emitting element, a chip, or a capsule containing a pharmaceutical or cosmetic agent).

[0186] When testing 607 is employed by each method, the object is preferably a test object having a shape selected to facilitate testing.

[0187] The test object is constructed by printing a modeling material to form a two-part structure. Top views of a representative two-part structure 720 suitable for this embodiment are shown in FIGS. 7A-7C, and a side view of a representative two-part structure 720 is shown in FIG. 7D. The two-part structure 720 is constructed from a first stack 722 of modeling material layers, which is laterally offset from a second stack 724 of modeling material layers. The layers are stacked along a vertical direction z, defined for the printing system (see FIGS. 1A and 1C), and the stacks 722 and 724 are spaced apart from each other along a horizontal direction orthogonal to the vertical direction. FIGS. 7A-7C show top views of the structure 720; therefore, only the top layer of each of the stacks 722 and 724 is shown. In FIGS. 7A-7C, the vertical direction z is shown as a circled dot, indicating that it points out of the plane of the drawing. A side view of the two-part structure 720, adhesive structure 740, and fabric 742 is depicted in Figure 7D, which shows the vertical direction z as an upward arrow.

[0188] In some embodiments of the present invention, at least one of laminates 722 and 724, and more preferably both laminates 722 and 724, includes a plurality of through-holes 734 that define open cells in laminates 722 and 724. For example, laminates 722 and 724 can have a honeycomb structure. Although through-holes 734 are shown as hexagonal in Figures 7A-7C, they can have any other shape. An advantage of laminates 722 and 724 having through-holes 734 is that it can reduce the likelihood of the periphery of structure 720 curling toward its center during the printing process.

[0189] Laminates 722 and 724 are separated by gap 726. While gap 726 preferably has a uniform width along the gap, gaps 726 with non-uniform widths are contemplated in some embodiments. Gap 726 preferably has a width of less than 1 mm, for example, between about 0.4 mm and 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 adhesive structure 740 is formed below gap 726, this is not necessarily the case. This is because, in some embodiments, it may be desirable to configure material layers to have the same lateral shape as structure 720 and to be vertically aligned with each other. 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 diagram of two adhesive structures 740a, 740b separated by a gap is depicted in FIG. 8A, discussed below.

[0190] Two-part structure 720 is preferably elongated, with an aspect ratio of width to length in the planar direction of about 1:3 to about 1:10. The length of two-part structure 720 is defined as the total length of stack 722, gap 726, and stack 724. The length of structure 720 is preferably about 50 mm to about 200 mm, and the width of structure 720 is preferably about 10 mm to about 20 mm.

[0191] Gap 726 is optionally and preferably non-linear. In these embodiments, laminates 722 and 724 can be viewed as a male-female pair. For example, laminate 722 can be defined as a male laminate and laminate 724 can be defined as a female laminate. In some embodiments of the invention, gap 726 has a piecewise linear shape, as depicted in FIGS. 7A and 7B , and in some embodiments of the invention, gap 726 has a curved shape, as depicted in FIG. 7C . If the gap has a piecewise linear shape, it preferably forms an acute angle at one or more of its breakpoints 728. If the gap has a piecewise linear shape, it preferably has at least one vertex 728. In the representative examples depicted in FIGS. 7A-7C , the gap has a V-shape ( FIG. 7A ), a W-shape ( FIG. 7B ), and an arc-shape ( FIG. 7C ), although other piecewise linear or curved shapes for gap 726 are also contemplated. An advantage of having a gap with a break point or apex is that it can facilitate partial separation of laminate 722 and / or laminate 724 from the fabric during bend testing. Specifically, a point 732 on the periphery of male laminate 722 adjacent to gap 726 and immediately proximate (e.g., closest to) break point 728 or apex 730 can be a separation point in the sense that the adhesion between structure 720 and the fabric is weakest near separation point 732.

[0192] In various exemplary embodiments of the invention, the bending resistance of each of the laminates 722, 724 is greater than the bending resistance of the bonded structure 740 and greater than the bending resistance of the fabric 742. This can be achieved by selecting a modeling material for the structure 720 that is stiffer than the bonded structure 740 and the fabric 742 and / or by making the thickness of the laminates 722, 724 along the vertical direction z greater than the thickness of the bonded structure 740 and the fabric 742. The thickness of the laminates 722, 724 is preferably at least two times, and more preferably at least three times, the thickness of the bonded structure 740. In some embodiments, the thickness of the laminates 722, 724 is at least two times, and more preferably at least three times, the thickness of the fabric 742.

[0193] 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 laminates 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 laminate 740, and a thickness of 2.2 mm was used for the laminates 722 and 724.

[0194] The testing procedure typically involves bending the fabric 742 at the gap 726 to separate at least one of the laminates 722 and 724 from the fabric at separation point 732. Because both the test object and the adhesive structure are created by printing, the adhesive force between the adhesive structure and the modeling material that forms the test object printed thereon is stronger than the adhesive force between the adhesive structure and the fabric.

[0195] A preferred procedure for performing step 704 is depicted in Figures 8A and 8B. Structure 720 is placed against a pair of support posts 750. Preferably, structure 720 contacts post pair 750 and fabric 742 is spaced 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 placed on a jig 754, and fabric 742 can contact them in either a horizontal (Figure 8A) or vertical (Figure 8B) orientation.

[0196] A force-applying pin 752 engages the fabric 742 at a location proximate to the location of the gap 726 (not shown in FIGS. 8A and 8B ), and pin 752 applies a force F to the fabric 742 perpendicular to the fabric (approximately in the direction of the support post pair 750). In the configuration shown in FIG. 8A (where the fabric 742 is oriented horizontally), F is directed downward, while in the configuration shown in FIG. 8B (where the fabric 742 is oriented vertically), F is directed horizontally. Force F causes the fabric 742 to bend into the space between the post pair 750. Because the bending resistance of laminates 722 and 724 is higher, they begin to separate from the fabric 742 (with laminate 740 being more strongly attached to structure 720 than fabric 742) at the point of weakest adhesion near the gap.

[0197] It is understood that the above procedure provides a qualitative assessment of the adhesion level of the material 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 monitored, 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 material to the fabric can then be determined based on the monitored values. For example, a maximum load at which a sharp change occurs in the correlation between force and displacement can be identified and defined as the adhesion level. Typically, displacement increases approximately linearly with force until the force reaches the maximum load. When the displacement is greater than the displacement at the maximum load, the linear increase in displacement with force is no longer observed. At this stage, a negative correlation between force and displacement often occurs. Therefore, the maximum load can be identified as the force at which the linear increase in displacement with force ends.

[0198] In experiments conducted in accordance with exemplary embodiments of the present invention, after forming an object on a fabric as described above, the printed fabric was placed in a washing machine to test the adhesion of the printed object to the fabric. To prevent rubbing or abrasion of the printed object, the printed fabric samples were rolled in a mesh bag and washed in a standard washing machine. A "delicate" wash cycle was used, with a spin speed of 600 RPM and a temperature of 30°C.

[0199] As used herein, the term "about" means ±10% or ±5%.

[0200] The word "exemplary" is used herein to mean "serving as an example, instance, or illustration." An embodiment described as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments and / or to exclude the incorporation of features from other embodiments.

[0201] As used herein, the word "optionally" is used to mean "present in some embodiments and not present in other embodiments." Any particular embodiment of the present invention may include multiple "optional" features, so long as the features do not interfere.

[0202] The words "comprises," "comprising," "includes," "including," and "having," and their conjugations, mean "including but not limited to."

[0203] The term "consisting of" means "including and limited to."

[0204] The term "consisting essentially of" means that a compound, 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 compound, method, or structure.

[0205] As used herein, the singular forms "a," "an," and "the" include plural references unless the context clearly dictates otherwise. For example, "a compound" or "at least one compound" includes multiple compounds (and mixtures thereof).

[0206] 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 should not be construed as an inflexible limitation on the scope of the invention. Thus, the description of a range should be construed as including all the possible subranges specifically disclosed and individual numerical values ​​within that range. For example, the description of a range such as 1 to 6 should be construed as including the specifically disclosed subranges (e.g., 1 to 3, 1 to 4, 1 to 5, 2 to 4, 2 to 6, 3 to 6, etc.) and individual numerical values ​​within that range (e.g., 1, 2, 3, 4, 5, and 6). This applies regardless of the broadness of the range.

[0207] Whenever a range of numerical values ​​is given herein, it is meant to include the recited numbers (decimals or integers) within the given range. The phrases "a range between a first recited number and a second recited number" and "a range from a first recited number to a second recited number" are used interchangeably herein and are meant to include the first and second recited numbers and all decimals and integers therebetween.

[0208] Throughout this specification, whenever the phrase "weight percent" or "wt %" or "% wt" appears in the context of an embodiment of a formulation (e.g., a modeling formulation), it means the weight percent of the total weight of the respective uncured formulation.

[0209] "Acrylic materials" is used herein to collectively refer to materials having one or more acrylate, methacrylate, acrylamide, and / or methacrylamide groups.

[0210] Similarly, "acrylic group" is used collectively to 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).

[0211] As used herein, the term "(meth)acrylic" encompasses acrylic and methacrylic materials. Urethane acrylates are also contemplated.

[0212] As used herein, the phrase "linking moiety" or "linking group" refers to a group that links two or more moieties or groups in a compound. Linking moieties are typically derived from difunctional or trifunctional compounds and can be considered as difunctional or trifunctional radical groups, bonded via two or three atoms to two or three other atoms, respectively.

[0213] Examples of linking moieties include hydrocarbon groups or chains, as defined herein, optionally interrupted by one or more heteroatoms, and / or any of the chemical groups listed below when defined as a linking group.

[0214] When a chemical group is referred to herein as an "end group," it is to be understood as a substituent that is attached to another group via one atom of the chemical group.

[0215] Throughout this specification, the term "hydrocarbon" refers collectively to a chemical group composed primarily of carbon and hydrogen atoms. Hydrocarbons can be composed of alkyls, alkenes, alkynes, aryls, and / or cycloalkyls, each of which can be substituted or unsubstituted and can be interrupted by one or more heteroatoms. The number of carbon atoms can range from 2 to 30, but is preferably fewer, e.g., 1 to 10, 1 to 6, or 1 to 4. Hydrocarbons can be linking or terminal groups.

[0216] Bisphenol A is an example of a hydrocarbon with two aryl groups and one alkyl group. Dimethylencyclohexane is an example of a hydrocarbon with two alkyl groups and one cycloalkyl group.

[0217] As used herein, the term "amine" refers to both the group --NR'R" and --NR'--, where R' and R" are each independently hydrogen, alkyl, cycloalkyl, or aryl, as defined below.

[0218] 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 R' and R'' are each independently alkyl, cycloalkyl, or aryl.

[0219] Alternatively, R' and R'' can each independently be hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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-amido, N-amido, guanyl, guanidine, and hydrazine.

[0220] The term "amine" is used herein to represent the group --NR'R" when the amine is a terminal group as defined below, and the group --NR'-- when the amine is a linking group or part of a linking moiety.

[0221] 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. When a numerical range is given herein (e.g., "1 to 20"), it means that the group (in this case, the alkyl group) contains 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc., up to 20 carbon atoms. Alkyl groups can be substituted or unsubstituted. A substituted alkyl can have one or more substituents, whereby each substituent can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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.

[0222] An alkyl group, as defined above, can be a terminal group attached to a single adjacent atom, or a linking group, as defined above, connecting two or more moieties through at least two carbons in the chain. When alkyl is a linking group, it is also referred to herein as an "alkylene" or "alkylene chain."

[0223] As used herein, alkenes and alkynes are alkyls, as defined herein, containing one or more double or triple bonds, respectively.

[0224] The term "cycloalkyl" refers to an all-carbon monocyclic or fused ring (i.e., rings that share adjacent pairs of carbon atoms) group in which one or more rings do not have a completely conjugated pi-electron system. Examples include, but are not limited to, cyclohexane, adamantane, norbornyl, isobornyl, and the like. Cycloalkyl groups can be substituted or unsubstituted. A substituted cycloalkyl can have one or more substituents, each of which can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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. A cycloalkyl group can be a terminal group, as defined above, attached to a single adjacent atom, or a linking group, as defined above, connecting two or more moieties at two or more positions.

[0225] The term "heteroalicyclic" refers to a monocyclic or fused ring group containing one or more atoms, such as nitrogen, oxygen, or sulfur, within the ring. These rings may contain one or more double bonds, provided that the rings do not have a completely conjugated pi-electron system. Representative examples include piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino, oxalidine, and the like.

[0226] Heteroalicyclics can be substituted or unsubstituted. Substituted heteroalicyclics can have one or more substituents, each of which can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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. Heteroalicyclic groups can be terminal groups, as defined above, attached to a single adjacent atom, or linking groups, as defined above, attaching two or more moieties at two or more positions.

[0227] The term "aryl" refers to an all-carbon monocyclic or fused-ring polycyclic (i.e., rings that share 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, each of which can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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. Aryl groups may be terminal groups, as defined above, attached to a single adjacent atom, or linking groups, as defined above, joining two or more moieties at two or more positions.

[0228] The term "heteroaryl" refers to a monocyclic or fused-ring (i.e., rings that share adjacent pairs of atoms) group having one or more atoms (e.g., nitrogen, oxygen, 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, purine, and the like. Heteroaryl groups can be substituted or unsubstituted. Substituted heteroaryls may have one or more substituents, each of which may independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, 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 above, bonded to a single adjacent atom, or a linking group, as defined above, linking two or more moieties at two or more positions. Representative examples include pyridine, pyrrole, oxazole, indole, purine, and the like.

[0229] The terms "halide" and "halo" refer to fluorine, chlorine, bromine, or iodine.

[0230] The term "haloalkyl" refers to an alkyl group, as defined above, further substituted with one or more halide groups.

[0231] The term "sulfate" refers to an -OS(=O)2-OR' terminal group, as defined above, or an -OS(=O)2-O- linking group, as defined above, where R' is as defined above.

[0232] The term "thiosulfate" refers to an -OS(=S)(=O)-OR' terminal group or an -OS(=S)(=O)-O- linking group, as these terms are defined above, and R' is as defined above.

[0233] The term "sulfite" refers to an -OS(=O)-O-R' terminal group or an -OS(=O)-O- linking group, as these terms are defined above, where R' is as defined above.

[0234] The term "thiosulfite" refers to an -OS(=S)-O-R' terminal group or an -OS(=S)-O- linking group, as these terms are defined above, where R' is as defined above.

[0235] The term "sulfinate" refers to an -S(=O)-OR' terminal group or an -S(=O)-O- group linking group, as these terms are defined above, where R' is as defined above.

[0236] The term "sulfoxide" or "sulfinyl" refers to an -S(=O)R' terminal or -S(=O)- linked group as defined above, where R' is as defined above.

[0237] The term "sulfonate" refers to an -S(=O)2-R' terminal or -S(=O)2- linked group as defined above, where R' is as defined above.

[0238] The term "S-sulfonamido" refers to the -S(=O)2-NR'R'' terminal group or the -S(=O)2-NR'- linking group, as these terms are defined above, and R' and R' are as defined herein.

[0239] The term "N-sulfonamido" refers to an R'S(=O)2-NR''- terminal group or an -S(=O)2-NR'- linked group, as these terms are defined above, with R' and R' as defined herein.

[0240] The term "disulfide" refers to an --S--SR' terminal group or an --SS-- linked group, as these terms are defined above, and R' is as defined herein.

[0241] The term "phosphonate" refers to a -P(=O)(OR')(OR'') terminal group or a -P(=O)(OR')(O)- linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0242] The term "thiophosphonate" refers to a -P(=S)(OR')(OR'') terminal group or a -P(=S)(OR')(O)- linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0243] The term "phosphinyl" refers to a -PR'R'' terminal group or a -PR'- linking group, as these terms are defined above, with R' and R'' as defined herein.

[0244] The term "phosphine oxide" refers to a -P(=O)(R')(R'') terminal group or a -P(=O)(R') linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0245] The term "phosphine sulfide" refers to a -P(=S)(R')(R'') terminal group or a -P(=S)(R') linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0246] The term "phosphite" refers to an -O-PR'(=O)(OR'') terminal group or an -O-PH(=O)(O)- linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0247] The term "carbonyl" or "carbonate" as used herein refers to a -C(=O)-R' terminal group or a -C(=O)- linking group as defined above, where R' is as defined herein.

[0248] The term "thiocarbonyl," as used herein, refers to a -C(=S)-R' terminal or C(=S)-linking group, as defined above, where R' is as defined herein.

[0249] As used herein, the term "oxo" refers to a group in which an oxygen atom is attached by a double bond to an atom (eg, a carbon atom) at the indicated position (=O).

[0250] As used herein, the term "thioxo" refers to a group in which a sulfur atom is attached by a double bond to an atom (eg, a carbon atom) at the indicated position (=S).

[0251] The term "oxime" refers to the =N-OH terminal group or the =NO- linking group, as defined above.

[0252] The term "hydroxyl" refers to an --OH group.

[0253] 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.

[0254] The term "aryloxy" refers to both an --O-aryl and an --O-heteroaryl group, as defined herein.

[0255] The term "thiohydroxy" or "thiol" refers to an -SH group. The term "thiolate" refers to an -S- group.

[0256] The term "thioalkoxy" refers to both an -S-alkyl group and an -S-cycloalkyl group, as defined herein.

[0257] The term "thioaryloxy" refers to both an -S-aryl and an -S-heteroaryl group, as defined herein.

[0258] "Hydroxyalkyl", also referred to herein as "alcohol", refers to an alkyl, as defined herein, substituted with a hydroxy group.

[0259] The term "cyano" refers to the group --C.ident.N.

[0260] The term "isocyanate" refers to the group --N.dbd.C.dbd.O.

[0261] The term "isothiocyanate" refers to the group --N.dbd.C.dbd.S.

[0262] The term "nitro" refers to the group --NO.sub.2.

[0263] The term "acyl halide" refers to the group --(C.dbd.O)R'''' where R'''' is a halide as defined above.

[0264] The term "azo" or "diazo" refers to an --N.dbd.NR' terminal group or an --N.dbd.N- linking group, as defined above, where R' is as defined above.

[0265] The term "peroxo" refers to an -O-OR' terminal group or an -OO- linking group, as defined above, where R' is as defined above.

[0266] As used herein, the term "carboxylate" encompasses C-carboxylates and O-carboxylates.

[0267] The term "C-carboxylate" refers to a -C(=O)-OR' terminal group or a -C(=O)-O- linking group, as defined above, where R' is as defined herein.

[0268] The term "O-carboxylate" refers to an -OC(=O)R' terminal group or an -OC(=O)- linking group, as defined above, where R' is as defined herein.

[0269] Carboxylate groups can be linear or cyclic. In the cyclic case, R' and the carbon atom bond together to form a ring, as in C-carboxylates, and the group is also called a lactone. Alternatively, R' and O bond together to form a ring, as in O-carboxylates. Cyclic carboxylates can function as linking groups, for example, when atoms in the resulting ring are bonded to other groups.

[0270] As used herein, the term "thiocarboxylate" encompasses C-thiocarboxylates and O-thiocarboxylates.

[0271] The term "C-thiocarboxylate" refers to a -C(=S)-OR' terminal group or a -C(=S)-O- linking group, as these terms are defined above, and R' is as defined herein.

[0272] The term "O-thiocarboxylate" refers to an -OC(=S)R' terminal group or an -OC(=S)- linking group, as these terms are defined above, where R' is as defined herein.

[0273] Thiocarboxylates can be linear or cyclic. In the cyclic case, R' and the carbon atom bond together to form a ring, as in C-thiocarboxylates, and the group is also called a thiolactone. Alternatively, R' and O bond together to form a ring, as in O-thiocarboxylates. Cyclic thiocarboxylates can function as linking groups, for example, when atoms in the resulting ring are bonded to other groups.

[0274] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0275] The term "N-carbamate" refers to an R'''OC(=O)-NR'- terminal group or an -OC(=O)-NR'- linking group, as defined above, where R' and R'' are as defined herein.

[0276] The term "O-carbamate" refers to an -OC(=O)-NR'R'' terminal group or an -OC(=O)-NR'- linking group, as defined above, where R' and R'' are as defined herein.

[0277] Carbamates can be linear or cyclic. In the case of cyclic carbamates, R' and a carbon atom bond together to form a ring, as in O-carbamates, or R' and O bond together to form a ring, as in N-carbamates. Cyclic carbamates can function as linking groups, for example, when atoms within the resulting ring are bonded to other groups.

[0278] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0279] As used herein, the term "thiocarbamate" includes N-thiocarbamates and O-thiocarbamates.

[0280] The term "O-thiocarbamate" refers to an -OC(=S)NR'R'' terminal group or an -OC(=S)NR'- linking group, as defined above, where R' and R'' are as defined herein.

[0281] The term "N-thiocarbamate" refers to an R"OC(=S)NR'- terminal group or an -OC(=S)NR'- linking group, as these terms are defined above, and R' and R" are as defined herein.

[0282] Thiocarbamates can be linear or cyclic, as described herein for carbamates.

[0283] As used herein, the term "dithiocarbamate" includes S-dithiocarbamates and N-dithiocarbamates.

[0284] The term "S-dithiocarbamate" refers to an -SC(=S)-NR'R'' terminal group or an -SC(=S)NR'- linking group, as these terms are defined above, with R' and R'' as defined herein.

[0285] The term "N-dithiocarbamate" refers to an R"SC(=S)NR'- terminal group or an -SC(=S)NR'- linking group, as defined above, where R' and R" are as defined herein.

[0286] The term "urea," also referred to herein as "ureido," refers to the -NR'C(=O)-NR''R''' terminal group or the -NR'C(=O)-NR''- linking group, as defined above, where R' and R'' are as defined herein and R''' is as defined herein for R' and R''.

[0287] 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, where R', R'' and R''' are as defined herein.

[0288] As used herein, the term "amide" encompasses C-amides and N-amides.

[0289] The term "C-amido" refers to a -C(=O)-NR'R'' terminal group or a -C(=O)-NR'- linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0290] The term "N-amido" refers to the R'C(=O)-NR''- terminal group or the R'C(=O)-N- linking group, as these terms are defined above, and R' and R'' are as defined herein.

[0291] Amides can be linear or cyclic. In the cyclic case, R' and the carbon atom bond together to form a ring; in C-amides, the group is also called a lactam. Cyclic amides can function as linking groups, for example, when an atom in the resulting ring is bonded to another group.

[0292] The term "guanyl" refers to the R'R''NC(=N)-terminal group or the -R'NC(=N)-linking group defined above, where R' and R'' are as defined herein.

[0293] The term "guanidine" refers to the -R'NC(=N)-NR''R''' terminal group or the -R'NC(=N)NR''- linking group defined above, where R', R'' and R''' are as defined herein.

[0294] The term "hydrazine" refers to the -NR'-NR''R''' terminal group or the -NR'-NR''- linking group defined above, where R', R'' and R'''' are as defined herein.

[0295] As used herein, the term "hydrazide" refers to a -C(=O)-NR'NR''R''' terminal group or a -C(=O)-NR'-NR''- linking group, as defined above, where R', R'' and R''' are as defined herein.

[0296] As used herein, the term "thiohydrazide" refers to a -C(=S)-NR'NR''R''' terminal group or a -C(=S)-NR'-NR''- linking group, as defined above, where R', R'' and R''' are as defined herein.

[0297] As used herein, the term "alkylene glycol" refers to a group selected from the group consisting of -O-[(CR' R'') z -O] y -R''' end group or -O-[(CR' R'') z -O] y -refers to a linking group, where R', R'', and R''' are as defined herein, 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).

[0298] The term "silanol" refers to a -Si(OH)R'R'' group, or a -Si(OH)2R' or -Si(OH)3 group, where R' and R'' are as defined herein.

[0299] The term "silyl" refers to the group -SiR'R''R''' where R', R'', and R''' are as defined herein.

[0300] As used herein, the term "urethane" or "urethane moiety" or "urethane group" refers to an Rx-OC(=O)-NR'R" terminal group or an -Rx-OC(=O)-NR'- linked group, where R' and R" are as described herein, and Rx is alkyl, cycloalkyl, aryl, alkylene glycol, or any combination thereof. Preferably, R' and R" are both hydrogen.

[0301] The term "polyurethane" or "oligourethane" refers to a moiety that contains at least one urethane group as defined herein in the repeating backbone unit or that contains at least one urethane linkage, -OC(=O)-NR'-, in the repeating backbone unit.

[0302] Throughout this specification, when the phrase "weight percent" or "wt. %" or "% wt." is given in the context of an embodiment of a formulation (e.g., a modeling formulation), it means the weight percent relative to the total weight of the respective uncured formulation.

[0303] As used herein, "ethoxylated" materials refer to acrylic or methacrylic compounds containing one or more alkylene glycol groups, or preferably one or more alkylene glycol chains, as defined herein. Ethoxylated (meth)acrylate materials can be monofunctional, or preferably multifunctional, i.e., difunctional, trifunctional, tetrafunctional, etc.

[0304] In polyfunctional materials, typically each (meth)acrylate group is attached to an alkylene glycol group or alkylene glycol chain, which are linked to each other via branching units such as branched alkyl, cycloalkyl, aryl (e.g., bisphenol A), etc.

[0305] 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 alkylene glycol groups. Some or all of the alkylene glycol groups can be bonded to each other to form an alkylene glycol chain. For example, an ethoxylated material comprising 30 ethoxylated groups can comprise a chain of 30 alkylene glycol groups bonded to each other, two chains each having, for example, 15 alkylene glycol groups bonded to each other (the two chains are bonded to each other via a branching moiety), or three chains each having, for example, 10 alkylene glycol groups bonded to each other (the three chains are bonded to each other via a branching moiety). Shorter and longer chains are also contemplated.

[0306] The ethoxylated material can contain one, two, or more alkylene glycol chains of any length.

[0307] As used herein, the term "branching unit" refers to multiple radicals, preferably aliphatic or alicyclic groups. "Multiple radicals" means that the unit has two or more points of attachment, linking two or more atoms and / or groups or moieties.

[0308] In some embodiments, the branching unit is derived from a chemical moiety having two, three, or more functional groups, hi some embodiments, the branching unit is a branched alkyl, cycloalkyl (alicyclic), or aryl (e.g., phenyl), as defined herein.

[0309] 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.

[0310] Generally, as the temperature increases within a 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.

[0311] As used herein, a "Tg range" is the temperature range at which the E value is at least half (eg, up to) the Tg temperature defined above.

[0312] Without intending to be bound by any particular theory, it is believed that within the Tg range defined above, the state of the polymeric material gradually changes from a glassy state to a rubbery state, with 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).

[0313] Throughout this specification, when a hardenable material is defined by the properties of the hardened material obtained therefrom, it should be understood that the properties are the properties of the hardened material obtained from the hardenable material itself.

[0314] Throughout this specification, unless otherwise specified, viscosity values ​​refer to the viscosity of a material or formulation measured using a Brookfield viscometer at 25°C. Measurements are given in centipoise, which is equivalent to mPa·sec.

[0315] 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, which are, for clarity, described in the context of a single embodiment, may also be provided separately or in any suitable subcombination or other embodiments of the invention, as appropriate. 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.

[0316] Various embodiments and aspects of the present invention as delineated above and as claimed in the claims below are found experimentally supported in the following examples.

[0317] Example Reference is now made to the following examples, which together with the above descriptions, serve to illustrate, in a non-limiting manner, some embodiments of the present invention.

[0318] Throughout this specification, the terms "build material formulation," "uncured build material," "uncured build material formulation," "build material," and other variations refer collectively to the materials dispensed to sequentially form the layers described herein. This term encompasses uncured materials dispensed to form an object, i.e., one or more uncured build material formulations, and uncured materials dispensed to form a support, i.e., uncured support material formulations.

[0319] Throughout this specification, the phrases "cured build material" or "hardened build material" refer to the portion of build material that forms an object as defined herein upon hardening of the dispensed build material, as described herein, and, optionally, removal of the hardened support material, if dispensed. The hardened build material can be a single hardenable material or a mixture of two or more hardenable materials, depending on the build material formulation used in the methods described herein.

[0320] The phrase "hardened build material" or "hardened build material formulation" can be considered to be a hardened build material where the build material is comprised solely of the build material formulation and not the support formulation, i.e., the phrase refers to the portion of the build material that is used to provide the final object.

[0321] Throughout this specification, the phrase "build material formulation," also referred to interchangeably herein as "build formulation," "model formulation," "model material formulation," or simply "formulation," refers to some or all of the build material dispensed to form the objects described herein. A build material formulation (unless otherwise indicated) is an uncured build formulation that forms an object or portion thereof upon exposure to curing energy.

[0322] 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 three-dimensional objects by itself, i.e., without the need to mix or combine with other substances.

[0323] The uncured build material can include one or more build formulations and can be distributed so that upon curing, different parts of the object are made of different cured build formulations or different combinations thereof, i.e., different cured build materials or mixtures of different cured build materials.

[0324] The formulations that form the build material (modeling material formulation and support material formulation) include one or more hardenable materials that form a hardened / cured material upon exposure to curing energy.

[0325] The formulations that form the build material (modeling material formulations and support material formulations) are also referred to herein as curable formulations (e.g., curable modeling material formulations or curable support material formulations).

[0326] Throughout this specification, a "curable material" refers to a compound (typically a monomeric or oligomeric compound, but optionally a polymeric material) that solidifies or cures to form a cured material upon exposure to the curing conditions (e.g., curing energy) described herein. Curable materials are typically polymerizable materials that undergo polymerization and / or crosslinking upon exposure to an appropriate energy source.

[0327] In this embodiment, the hardenable material also includes materials that harden or solidify without exposure to curing energy, but by exposure to other curing conditions (e.g., exposure to chemical reagents or simply exposure to the environment).

[0328] As used in the examples below, the terms "curable" and "hardenable" are used interchangeably.

[0329] The polymerization can be, for example, free radical, cationic, or anionic polymerization, each of which can be induced upon exposure to curing energy, such as, for example, radiation, heat, etc., as described herein.

[0330] In some of the embodiments described herein, the curable material is a photopolymerizable material that polymerizes and / or crosslinks upon exposure to radiation as described herein, and in some embodiments, the curable material is a UV-curable material that polymerizes and / or crosslinks upon exposure to UV light as described herein.

[0331] In some embodiments, the hardenable materials described herein are photopolymerizable materials that polymerize by light-induced free radical polymerization. Alternatively, the hardenable materials are photopolymerizable materials that polymerize by light-induced cationic polymerization.

[0332] In some of the embodiments described herein, the curable material may be a monomer, oligomer, or short chain polymer, each of which may be polymerized and / or crosslinked as described herein.

[0333] In some of the embodiments described herein, the hardenable material, upon exposure to curing energy (eg, radiation), hardens / cures by either chain extension and crosslinking, or a combination thereof.

[0334] 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 curing energy, such curable materials are also referred to herein as monomeric curable materials.

[0335] 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, such curable materials are also referred to herein as oligomeric curable materials.

[0336] In some of the embodiments described herein, the curable material, whether monomeric or oligomeric, can be a monofunctional or multifunctional curable material.

[0337] As used herein, a monofunctional curable material contains one functional group that can polymerize upon exposure to curing energy (eg, radiation).

[0338] A multifunctional curable material contains two or more functional groups, e.g., two, three, four or more, that can polymerize upon exposure to curing energy. The multifunctional curable material can be, for example, a difunctional, trifunctional, or tetrafunctional curable material, each containing two, three, or four polymerizable functional groups (also referred to herein as having a functionality of two, three, or four, etc.). The two or more functional groups in a multifunctional curable material are typically linked to each other by a linking moiety, as defined herein. When the linking moiety is an oligomeric or polymeric moiety, the multifunctional group is an oligomeric or polymeric multifunctional curable material. The multifunctional curable material can polymerize upon exposure to curing energy and / or act as a crosslinker.

[0339] Experimental Method Tear resistance (TR) was measured according to ASTM D 624 and is expressed in N / m.

[0340] Shore A hardness was measured using a Shore A durometer according to ASTM-2240.

[0341] Printability was measured by testing the compatibility of the formulation with a 3D inkjet system (e.g., those depicted in Figure 1A or Figures 1B-D, and / or systems equipped with LEDs as the curing energy source) in terms of viscosity, reactivity, jettability, etc.

[0342] Curling and deformation were confirmed by visual inspection (see, for example, Figures 7A-B). Unless otherwise noted, formulations were prepared by mixing all ingredients at room temperature. Powdered ingredients, such as photoinitiators, were dissolved at 85°C for 30 minutes.

[0343] Viscosity was measured using a Brookfield viscometer and is given in centipoise (equivalent to mPa·sec).

[0344] Surface tension was measured using a Cruss K6 Force Tensiometer and is reported in dynes / cm.

[0345] Adhesion was measured according to Test Procedure 607 above and expressed as the maximum force required to peel (N / cm).

[0346] Jettability was assessed, for example, by recording the jetting pattern using a high speed camera and analytical gravitational force and / or by using a jetting station to test jetting parameters relevant to the printing process.

[0347] Example 1 Adhesion test of aged samples

[0348] Adhesion levels were measured using the protocol described above with reference to Figures 6A-C. Figure 9A shows the adhesion level and adhesion stability results for five different types of fabrics using the priming formulation described in Example 2 below. Fabrics 1-4 (blue, orange, jeans, and beige, respectively) were bonded using Method 640, while Fabric 5 (pink) was bonded using Method 620. As shown, adhesion levels of greater than 15 N / cm were achieved for all tested fabrics. Stability was assessed using an accelerated aging method. It was found that the same adhesion levels could be maintained for at least two years. Figure 9B shows the adhesion levels when an exemplary formulation described in Example 2 below was applied to various test fabrics at different thicknesses of adhesive material (structures), as shown in Figure 9A.

[0349] FIG. 10 shows the results of experiments to investigate the effect of coatings on the tear resistance of objects. Tear resistance measurements were performed on six different build materials printed onto bonded structures formed using the protocol described above with reference to FIGS. 6A-C. The objects were coated using the same formulations used to form the bonded structures. Results are shown for coating thicknesses of 0.05 mm and 0.1 mm and compared to a reference case in which no coating was applied. Build materials used in these experiments include the flexible build material described in Example 3 below. As shown, the coating improves tear resistance for all types of build materials.

[0350] Example 2 Formulated with additives (e.g. priming and / or coating)

[0351] This example describes exemplary curable additive formulations that can be used in combination with the build material formulations described herein and are suitable for use as priming formulations to provide a priming material that forms a bonded structure upon curing, and as coating formulations to provide a coating material that forms a solidified coating upon curing.

[0352] Exemplary additive formulations function as curable adhesive additive formulations that are dispensed from a print head to form a pattern of adhesive that promotes adhesion of a build material formed from a subsequently dispensed build material formulation, and as coating formulations that are dispensed from a print head after a build material formulation is dispensed to form a build object to form a pattern of coating that improves properties such as tear resistance and durability (e.g., color retention, washability, etc.) of the print object.

[0353] Exemplary additive formulations include curable materials characterized by functional groups capable of interacting with common fabric surface functional groups, preferably polar functional groups capable of interacting (e.g., via hydrogen bond formation) with hydroxy groups typically present on the surface of fabrics, and further characterized by a Tg of less than 100°C, less than 80°C, or less than 50°C to provide a cured material that exhibits flexibility suitable for application to fabrics.

[0354] Examples of such materials can be summarized by Formula I:

[0355] [ka] wherein Y is a terminal group and can be, for example, linear and branched alkyl, substituted or unsubstituted alkyl, aryl, heteroaryl, cycloalkyl, heteroalicyclic, hydroxy, alkoxy, aryloxy, and amine, 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, substituted with at least one hydroxy group and optionally with one or more heteroatoms, such as O heteroatoms, capable of forming hydrogen bonds with the hydroxy groups.

[0356] When X is a (meth)acrylate group, such exemplary materials can be collectively represented by Formula Ia:

[0357] [ka] wherein Y and L are as defined herein, and R1 is hydrogen for acrylate polymerizable moieties and methyl for methacrylate polymerizable moieties.

[0358] An exemplary curable material used was a hydrophilic monofunctional epoxy (meth)acrylate material with hydroxy groups, such as 2-hydroxy-3-phenoxypropyl acrylate sold under the trade name DA-141, which has the following structure:

[0359] [ka]

[0360] The additive formulation is selected to exhibit the desired performance, i.e., sufficient adhesion level to fabric (at least 20 N / cm) and / or sufficient tear resistance to the coated object (at least 10,000 N / m), as well as jettability (e.g., viscosity at the jetting temperature (e.g., 70°C) of 15-30, preferably 15-25 or 15-20 centipoise (mPa·sec) and surface tension at the jetting temperature of 20-40, preferably 20-30, more preferably 26-30).

[0361] Furthermore, the additive formulations are suitable for use in systems including LED irradiation sources (e.g., wavelength 395 nm) as described in Figure 1A or Figures 1B-D, and are preferably designed to be biocompatible.

[0362] According to some of the embodiments described herein, the additive formulation is characterized by one or more of a viscosity in the range of 15-30, or 15-25, or 15-20 centipoise; a surface tension in the range of 20-40, preferably 20-30, more preferably 26-30, or 26-28 dynes / cm; and an adhesion to the respective fabric of at least 20 N / cm.

[0363] According to some of the embodiments described herein, the additive formulation is an adhesive (priming) formulation that upon curing provides an adhesive material or structure on the fabric.

[0364] According to some of the embodiments described herein, the additive formulation is a coating or finish formulation that, upon curing, provides a coating on an object or portion thereof.

[0365] According to some of the embodiments described herein, the additive formulation is both an adhesive (priming) formulation that, upon curing, provides an adhesive material or structure on the fabric, and a coating or finishing formulation that, upon curing, provides a coating on an object or portion thereof.

[0366] According to some of the embodiments described herein, the additive formulation comprises a combination of one or more monofunctional curable materials and one or more multifunctional curable materials.

[0367] According to some of the embodiments described herein, the one or more monofunctional curable materials comprise at least one monofunctional curable material having at least one polar group capable of interacting with surface functional groups of the textile and having a glass transition temperature (Tg) of less than 50°C.

[0368] According to some of the embodiments described herein, the additive formulation comprises a combination of one or more monofunctional curable materials and one or more multifunctional curable materials.

[0369] According to some of the embodiments described herein, the one or more monofunctional curable materials comprise at least one monofunctional curable material having at least one polar group capable of interacting with surface functional groups of the textile and having a glass transition temperature (Tg) of less than 50°C.

[0370] According to some of these embodiments, the amount of the at least one monofunctional curable material having at least one polar group capable of interacting with the surface functional groups of the textile and having a Tg of less than 50°C is 85-90 wt% of the total weight of the formulation.

[0371] According to some of the embodiments described herein, the one or more multifunctional curable materials include at least one multifunctional curable material having a Tg of less than 50°C.

[0372] According to some of these embodiments, the amount of the at least one multifunctional curable material having a Tg less than 50°C is 10 to 15 wt% of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0373] According to some 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 having a Tg less than 50°C in an amount of 85 to 90 wt% (including intermediate values ​​and subranges therebetween) of the total weight of the formulation, and at least one multifunctional curative material having a Tg less than 50°C in an amount of 10 to 15 wt% (including intermediate values ​​and subranges therebetween) of the total weight of the formulation.

[0374] Fabrics typically contain a plurality of exposed surface groups, which are typically hydroxyl or other polar groups, but may also be or contain hydrophobic and / or aromatic groups. The groups capable of interacting with such surface functional groups typically include groups capable of forming temporary bonds with such functional groups, such as hydrogen bonds, hydrophobic interactions, aromatic interactions, and similar temporary bonds. 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, which are preferably all carbon groups and have 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 contain aromatic groups, such as aryl and / or heteroaryl groups, as defined herein, and may interact with the surface groups through aromatic interactions, such as π-π stacking. When the surface functional groups of the fabric are hydroxyl groups or other polar groups (e.g., carboxylate or amine groups), the groups capable of interacting with these functional groups are typically polar groups, capable of electrostatically interacting with the surface groups, for example, via hydrogen bonding.

[0375] According to some embodiments, the at least one monofunctional curable material has at least one polar group capable of interacting with the surface functional groups of the textile. Such materials are also referred to herein as "component A."

[0376] The phrase "polar group" refers to a charge polarizable group that is capable of exhibiting a transient charge polarization.

[0377] Exemplary polar groups typically include one or more electron-donating heteroatoms that form strong hydrogen bonds with surface polar groups, including, but not limited to, oxygen and nitrogen.

[0378] Examples of polar groups include, but are not limited to, electron-donating heteroatoms (e.g., oxygen or nitrogen), carboxylates, thiocarboxylates, oxo (=O), linear amides, hydroxy, (C1-4)alkoxy, (C1-4)alcohols, heteroalicyclic compounds (e.g., having a carbon atom to heteroatom ratio 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).

[0379] In an exemplary embodiment, the monofunctional curable material comprises one or more hydroxy groups and electron-donating heteroatoms.

[0380] According to some embodiments, the one or more monofunctional curable materials can be collectively represented by Formula I:

[0381] [ka] During the ceremony: Y is a terminal group, optionally and preferably selected from linear and branched alkyl, substituted or unsubstituted alkyl, aryl, heteroaryl, cycloalkyl, heteroalicyclic, hydroxy, alkoxy, aryloxy, and amine; 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 usually each hydrogen); and L is a hydrocarbon-linked moiety having 2 to 10 carbon atoms, preferably 2 to 8 carbon atoms, 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 hydroxy groups, such as oxygen or nitrogen).

[0382] In an exemplary embodiment, the at least one monofunctional curable material is a monofunctional (meth)acrylate, X is a (meth)acrylate group, and the monofunctional curable material is represented by Formula Ia:

[0383] [ka] where R1 is hydrogen (in the case of acrylates) or alkyl (e.g., methyl in the case of methacrylates).

[0384] In an exemplary embodiment, R1 is hydrogen.

[0385] In some embodiments, Y is a group containing an electron-donating heteroatom, such as heteroalicyclic, hydroxy, alkoxy, aryloxy, and amine; in exemplary embodiments, Y is alkoxy or aryloxy (e.g., phenoxy).

[0386] In some embodiments, L is a hydrocarbon of 2 to 6 carbon atoms or 2 to 4 carbon atoms substituted with one or more hydroxy groups.

[0387] Exemplary monofunctional acrylate materials (Component A) are shown in the Examples section below.

[0388] According to embodiments described herein, the additive formulation includes one or more multifunctional curable materials characterized by a Tg of less than 50°C.

[0389] According to some embodiments, the at least one multifunctional curable material comprises a difunctional curable material characterized by an indicated Tg.

[0390] 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) methacrylate having the indicated Tg.

[0391] 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 methacrylate having the indicated Tg.

[0392] According to some of the embodiments described herein, the one or more multifunctional curable materials are characterized by a Tg of -20°C to 50°C, -20°C to 40°C, -20°C to 30°C, -20°C to 20°C, -10°C to 40°C, -10°C to 30°C, -10°C to 20°C, 0°C to 50°C, 0°C to 40°C, 0°C to 30°C, including any intermediate values ​​and subranges therebetween.

[0393] Exemplary multifunctional curable materials include the family of materials sold under the trade name Miramer, such as Miramer PU2100NT.

[0394] According to some of the embodiments described herein, the additive formulation is a biocompatible formulation in which all of the components, or at least the components present in an amount greater than 0.1%, greater than 0.5%, or greater than 1%, are biocompatible.

[0395] According to some of the embodiments described herein, each curable material in the formulation is a biocompatible material.

[0396] According to some of the embodiments described herein, each curable material in the formulation does not contain materials that are considered to be biocompatible, such as metal catalysts (e.g., catalyst-free), or other materials that may be present in residual amounts with the curable materials as a result of the synthetic processes used to prepare these curable materials.

[0397] According to some of the embodiments described herein, each of the multifunctional curable materials is a multifunctional (eg, difunctional) acrylate or a multifunctional (eg, difunctional) urethane acrylate.

[0398] According to some of the embodiments described herein, each of the monofunctional curable materials is a monofunctional acrylate.

[0399] According to some 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).

[0400] According to some 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.

[0401] According to some of the embodiments described herein, the photoinitiator comprises or consists essentially of a phosphine oxide type (e.g., monoacrylated (MAPO) type or bisacrylated phosphine oxide type (BAPO) type photoinitiator.

[0402] 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, benzoylbis(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 greater than about 380 nm to about 450 nm include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (sold as IRGACURE® 819), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (CGI 403), and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one mixed in a 25:75 weight ratio (sold as IRGACURE® 1700), and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one mixed in a 1:1 weight ratio (sold as DAROCUR® 4265), and ethyl 2,4,6-trimethylbenzylphenylphosphinate (LUCIRIN LR8893X).

[0403] According to some of the embodiments described herein, the photoinitiator comprises or consists essentially of a bisacrylated phosphine oxide type (BAPO) photoinitiator.

[0404] In an exemplary embodiment, the photoinitiator is bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (sold as IRGACURE® 819).

[0405] In exemplary embodiments, the photoinitiator does not include monoacrylated (MAPO) phosphine oxide type photoinitiators, and in some embodiments does not include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (commercially available as TPO).

[0406] According to some of the embodiments described herein, the additive formulation further comprises additional non-curing components, such as, for example, inhibitors, surfactants, dispersants, colorants (colorants), and stabilizers. Commonly used surfactants, dispersants, colorants, and stabilizers are contemplated. Exemplary concentrations of each component, when present, range from about 0.01 to about 1 wt. % of the total weight of the formulation including them, or from about 0.01 to about 0.5 wt. %, or from about 0.01 to about 0.1 wt. %, including any intermediate values ​​and subranges therebetween. Exemplary components are described below.

[0407] In some of the embodiments described herein, the formulation includes a cure inhibitor, i.e., an agent that inhibits or reduces 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. %, 0.01 to 1 wt. %, 0.05 to 0.5 wt. %, or 0.1 to 0.2 wt. %, depending on the type of inhibitor used, including any intermediate values ​​and subranges therebetween. Commonly used inhibitors, such as radical inhibitors, are contemplated.

[0408] According to some of the embodiments of any of the methods described herein, the additive formulation further comprises an inhibitor (component I) described herein, such as a phenolic inhibitor, or any other inhibitor commonly used in medical devices or applications and / or foods.

[0409] According to some 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.

[0410] In exemplary embodiments, free radical inhibitors include, for example, the Genorad® family of free radical inhibitors (eg, Genorad 20).

[0411] In exemplary embodiments, such free radical inhibitors are used in amounts of 0.1 to 3% by weight, or 0.1 to 2% by weight, or 0.1 to 1% by weight, or 0.1 to 0.5% by weight, including any intermediate values ​​and subranges therebetween.

[0412] According to some of the embodiments described herein, the additive formulation further comprises one or more dispersants or surfactants (Component H).

[0413] According to some 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.

[0414] Exemplary dispersants and surfactants are those commercially available as BYK Surface Additives.

[0415] According to some of these embodiments, the dispersant is characterized by a curable group, preferably a (meth)acrylic group.

[0416] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., difunctional) aliphatic silicon (meth)acrylate.

[0417] According to some of the embodiments described herein, the dispersant is a difunctional aliphatic silicon (meth)acrylate.

[0418] According to some of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicone acrylate.

[0419] According to some of the embodiments described herein, the dispersant is a difunctional aliphatic silicone acrylate.

[0420] According to some of the embodiments described herein, the dispersant has an average molecular weight of at least 1,000, or at least 2,000, or at least 3,000 grams / mole, and is considered an oligomeric material.

[0421] According to some of the embodiments described herein, the dispersing agent is a polyfunctional (e.g., difunctional) aliphatic silicon (meth)acrylate having an average molecular weight of at least 1,000 grams / mole, as described herein.

[0422] According to some of the embodiments described herein, the dispersing agent is a difunctional aliphatic silicon (meth)acrylate having an average molecular weight of at least 1,000 grams / mole, as described herein.

[0423] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., difunctional) aliphatic silicone acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0424] According to some of the embodiments described herein, the dispersant is a difunctional aliphatic silicone acrylate, as described herein, having an average molecular weight of at least 1,000 grams / mole.

[0425] According to some of the embodiments described herein, the dispersant is characterized by a low Tg upon cure, preferably a Tg below 0°C, below -20°C, or below 50°C.

[0426] According to some 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.

[0427] According to some of the embodiments described herein, the additive formulation is a clear (e.g., transparent), colorless formulation that does not contain colorants or pigments.

[0428] According to some of the embodiments described herein, the additive formulation further comprises one or more colorants or pigments (ingredient P).

[0429] The colorant can be a pigment or a dye, preferably a pigment.

[0430] The pigments can be organic and / or inorganic and / or metallic pigments, and in some embodiments, the pigments are nanoscale pigments comprising nanoparticles.

[0431] Exemplary inorganic pigments include nanoparticles of titanium oxide, and / or zinc oxide, and / or silica. Exemplary organic pigments include nanosized carbon black.

[0432] In some embodiments, a combination of white and colored pigments is used to prepare the colored cured material.

[0433] According to some of the embodiments described herein, the colorant comprises a mixture of a pigment and at least one (meth)acrylic material within which the pigment is introduced into the formulation.

[0434] According to some of the embodiments described herein, the pigment is a white pigment and the formulation provides a white cured material.

[0435] According to some of the embodiments described herein, the colorant comprises a mixture of a white pigment and one or more curable materials (e.g., (meth)acrylic materials) within which the pigment is introduced into the formulation.

[0436] 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.

[0437] 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.

[0438] According to some of the embodiments described herein, the pigment is a cyan pigment and the formulation provides a cyan colored cured product.

[0439] According to some of the embodiments described herein, the colorant comprises a mixture of a cyan pigment and one or more curable materials, such as (meth)acrylic materials, and the cyan pigment is introduced into the formulation within the mixture.

[0440] 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, including any intermediate values ​​and subranges therebetween.

[0441] 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, is in the range of 0.1 to 1 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0442] According to some of the embodiments described herein, the pigment is a yellow pigment and the formulation provides a yellow cured product.

[0443] According to some of the embodiments described herein, the colorant comprises a mixture of a yellow pigment and one or more curable materials (e.g., (meth)acrylic materials), and the yellow pigment is introduced into the formulation within the mixture.

[0444] 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.

[0445] 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.

[0446] According to some of the embodiments described herein, the pigment is a magenta pigment and the formulation provides a magenta colored cured product.

[0447] According to some of the embodiments described herein, the colorant comprises a mixture of a magenta pigment and one or more curable materials, such as a (meth)acrylic material, and the magenta pigment is introduced into the formulation in this mixture.

[0448] According to some of these embodiments, the amount of magenta pigment in the mixture ranges from 0.01 to 1 weight percent, or from 0.05 to 0.5 weight percent, or from 0.1 to 0.2 weight percent of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0449] 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 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0450] According to some of the embodiments described herein, the formulation includes one or more of a white, magenta, cyan, and yellow colorant, and in some of these embodiments, each pigment is introduced into the formulation as a mixture with the curable material described herein.

[0451] According to some of the embodiments described herein, the colorant further comprises a pigment dispersant (component Dp). Preferred pigment dispersants are those having multiple groups that characterize their affinity for the pigment.

[0452] According to some of the embodiments described herein, the additive formulation includes components H, I, and J according to any of the embodiments described herein. Examples of such formulations include clear, colorless formulations that do not contain colorants.

[0453] According to some of the embodiments described herein, an additive formulation includes components H, I, J, and P as described in any of the embodiments described herein, and optionally Dp. Examples of such formulations include white formulations that include the white pigments described herein.

[0454] According to some of the embodiments described herein, the additive formulation includes components H, I, J, P, and optionally Dp, as described in any of the embodiments described herein.

[0455] Example 3 Flexible Building Materials

[0456] In this embodiment, the object has at least a part or portion made of a flexible material and is also referred to herein as an "object made of a flexible material." The object may have multiple parts 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 parts or portions, and in each part, portion, or entire object made of a flexible material, the flexible material may be the same or different within that part, 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 below.

[0457] Exemplary build material formulations exhibit desirable Shore A hardness values ​​(e.g., 70-100) and printability, preferably providing a biocompatible cured material suitable for 3D printing onto fabrics, such as apparel fabrics.

[0458] Exemplary build material formulations include materials that are free of elements that may adversely affect the biocompatibility of the cured material.

[0459] Exemplary formulations are described in Figure 1A or Figures 1B-D and are suitable for use in systems including an LED illumination source (eg, 395 nm wavelength).

[0460] Exemplary build material formulations are also referred to herein as "build formulations" or "flexible formulations" or "flexible build material formulations" or "build material formulations that provide a flexible material upon curing," and other variations thereof.

[0461] 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.

[0462] The build material formulation of this embodiment is designed to be suitable for additive manufacturing (e.g., 3D inkjet printing) of three-dimensional objects on fabrics, and provides a flexible material upon curing.

[0463] According to some of the embodiments described herein, the build material formulation is such that the cured material formed therefrom is characterized by mechanical properties corresponding to a flexible material and / or meets the requirements of a material to be printed on a textile, 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, or greater than 12,000 N / m, or greater than 15,000 N / m, e.g., 10,000-25,000 N / m).

[0464] According to some embodiments, the build material formulation, upon hardening, provides one or more of the following:

[0465] The Tg as defined herein is less than 50°C, for example, 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.

[0466] The Shore A hardness as defined herein is at least 80, for example, 80 to 120, 80 to 100, and preferably 80 to 90.

[0467] The tear strength is 10,000 or more, 12,000 or more, 15,000 or more N / m, for example, 10,000 to 25,000 N / m, 12,000 to 25,000 N / m, 15,000 to 25,000 N / m, including any intermediate values ​​and subranges therebetween.

[0468] According to some of the embodiments described herein, the build material formulation is a biocompatible formulation in which all components, or at least components present in an amount greater than 0.1%, greater than 0.5%, or greater than 1%, are biocompatible.

[0469] According to some of the embodiments described herein, each curable material in the formulation is a biocompatible material.

[0470] According to some of the embodiments described herein, each curable material in the formulation does not contain materials that are considered to be biocompatible, such as metal catalysts (e.g., catalyst-free), or other materials that may be present in residual amounts with the curable materials as a result of the synthetic processes used to prepare these curable materials.

[0471] The build material formulations in some embodiments of the present invention include a combination of mono- and multi-functional materials characterized by a low Tg (eg, less than 150°C, or less than 100°C).

[0472] According to some embodiments of any of the present invention, the total amount of monofunctional and multifunctional materials characterized by low Tg as described herein is at least 60 wt%, or at least 65 wt%, or at least 70 wt%, or at least 75 wt%, or at least 80 wt%, or at least 85 wt%, or even at least 90 wt% of the total weight of the formulation, such as a total amount of 60-95 wt%, or 60-90 wt%, or 70-90 wt%, or 70-95 wt%, or 80-95 wt%, or 80-90 wt%, or 60-85 wt%, or 60-80 wt%, or 70-85 wt%, or 70-80 wt%, of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0473] According to some of the embodiments described herein, the build material formulation includes the following components:

[0474] at least one monofunctional curable material having a Tg less than 150°C in an amount of 40 to 60 wt% of the total weight of the formulation, including any intermediate values ​​and subranges therebetween;

[0475] at least one multifunctional curative material having a Tg greater than 100°C, or greater than 150°C, in an amount of 4 to 10 wt% of the total weight of the formulation, including any intermediate values ​​and subranges therebetween; and

[0476] At least one multifunctional curative material having a Tg of less than 150°C, or less than 100°C, in an amount of 25 to 35 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0477] Monofunctional curable materials:

[0478] According to some of the embodiments described herein, the formulation includes one or more monofunctional curable materials, each characterized by a Tg of less than 150°C.

[0479] According to some of the embodiments described herein, the formulation comprises two or more monofunctional materials.

[0480] 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 two second monofunctional curable materials (referred to herein as component A2) characterized by a Tg of less than 50°C, or less than 20°C. * and / or B. * (also called

[0481] According to some of the embodiments described herein, the formulation comprises a first monofunctional curable material (component A1) characterized by a Tg of 50 to 150°C. * ) and a second monofunctional curable material (component A2) characterized by a Tg of less than 50°C, or less than 20°C. * and B * ) and two or more of the following.

[0482] According to some of the embodiments described herein, each of the one or more monofunctional curable materials described herein is a monofunctional (meth)acrylate.

[0483] According to some 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.

[0484] According to some of the embodiments described herein, the one or more monofunctional curable materials may be a first monofunctional (meth)acrylate (referred to herein as component A1) characterized by a Tg of 50 to 150°C. * and a second monofunctional (meth)acrylate (referred to herein as component A2) characterized by a Tg of less than 50°C, or less than 20°C. * (also called)

[0485] According to some embodiments, the first monofunctional curable material described herein, such as the first monofunctional (meth)acrylate, or component A1 * is a hydrophobic material as described herein.

[0486] According to some embodiments, a second monofunctional curable material, such as a second monofunctional (meth)acrylate, or component A2, as described herein, is used. * is a hydrophilic and / or amphiphilic material as described herein.

[0487] The term "hydrophilic" as used throughout this specification refers to the physical property of a material or a portion of a material (e.g., a chemical group in a compound) that temporarily forms bonds with water molecules, typically via hydrogen bonds.

[0488] A hydrophilic material dissolves more readily in water than in oil or other hydrophobic solvents, as can be determined, for example, by a LogP of less than 0.5 when measured in an octanol phase and an aqueous phase.

[0489] The hydrophilic material may alternatively or additionally be characterized by a lipophilic / hydrophilic balance (HLB) of at least 10, or at least 12, according to Davis.

[0490] The term "amphiphilic" as used throughout this specification refers to hydrophilic materials.

[0491] It refers to the properties of a material that combines both hydrophilicity as described herein and hydrophobicity or lipophilicity as defined herein for hydrophobic materials.

[0492] 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).

[0493] An amphiphilic material can be determined by, for example, measuring the LogP in an octanol phase and an aqueous phase and finding that the LogP is 0.8 to 1.2, or about 1.

[0494] Amphiphilic materials may alternatively or additionally be characterized by a lipophilic / hydrophilic balance (HLB) of 3-12, or 3-9, according to the Davis method.

[0495] The term "hydrophobic" as used throughout this specification refers to the physical property of a material or part of a material (eg, a chemical group in a compound) that does not form bonds with water molecules.

[0496] Hydrophobic materials dissolve more readily in oil than in water or other hydrophilic solvents, as can be determined by a LogP greater than 1, for example, when measuring the LogP in octanol and water phases.

[0497] Hydrophobic materials may alternatively or additionally be determined by a lipophilic / hydrophilic balance (HLB) of less than 3 according to the Davis method.

[0498] Hydrophilic materials or portions of materials (eg, chemical groups in a chemical compound) are typically charge polarized and capable of forming hydrogen bonds.

[0499] Amphiphilic materials typically contain one or more hydrophilic groups (eg, charge-polarized groups) in addition to hydrophobic groups.

[0500] Hydrophobic materials or portions of materials (eg, chemical groups in a chemical compound) are typically non-polarizable and cannot form hydrogen bonds.

[0501] Hydrophilic materials or hydrophilic groups, and amphiphilic materials, typically 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. The ratio of carbon atoms to heteroatoms in a hydrophilic material or hydrophilic group is preferably 10:1 or less, e.g., 8:1, more preferably 7:1, 6:1, 5:1, or 4:1 or less. Note that the hydrophilic and amphiphilic properties of materials and groups may also result from the ratio of hydrophobic to hydrophilic moieties in the material or chemical group, and are not solely dependent on the ratio.

[0502] A hydrophilic or amphiphilic substance can have one or more hydrophilic groups or moieties. Hydrophilic groups are typically polar groups and are composed of one or more electron-donating heteroatoms such as oxygen or nitrogen.

[0503] Exemplary hydrophilic groups include, but are not limited to, electron-donating heteroatoms, carboxylates, thiocarboxylates, oxo (=O), linear amides, hydroxy, (C1-4)alkoxy, (C1-4)alcohols, heteroalicyclic groups (e.g., having a carbon atom to heteroatom ratio 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 defined herein below, and any combination thereof (e.g., a hydrophilic group comprising two or more of the indicated hydrophilic groups).

[0504] In some embodiments, the hydrophilic group is or includes an electron donating heteroatom, a carboxylate, a heteroalicyclic compound, an alkylene glycol, and / or a hydrophilic oligomeric moiety.

[0505] Amphiphilic moieties or groups typically contain one or more hydrophilic groups and one or more hydrophobic groups as described herein, or may be heteroatom-containing groups or groups where the ratio of the number of carbon atoms to the number of heteroatoms determines the amphiphilicity.

[0506] Hydrophobic groups include, for example, all carbon groups such as alkyl, alkenyl, alkynyl, aryl, and cycloalkyl.

[0507] The monomeric monofunctional (meth)acrylate materials according to this embodiment can be collectively represented by Formula A:

[0508] [ka] wherein 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 that can be hydrophilic or hydrophobic, as described herein.

[0509] When the material is a cycloaliphatic monomeric monofunctional (meth)acrylate material, R can be, for example, an cycloaliphatic moiety such as, but not limited to, isobornyl, or other substituted or unsubstituted cycloalkyl as described herein, or a heterocycloaliphatic moiety such as, for example, morpholine, tetrahydrofuran, oxalidine, or other substituted or unsubstituted heterocycloaliphatic as described herein, where substituents, if present in the case of cycloalkyl or heterocycloaliphatic, do not include aryl or heteroaryl as defined herein. Examples of cycloaliphatic monomeric monofunctional acrylates include, but are not limited to, isobornyl acrylate (IBOA), acryloylmorpholine (ACMO), and materials sold under the tradename SR-218.

[0510] When the material is an aliphatic monomeric monofunctional (meth)acrylate material, Ra can be, for example, a substituted or unsubstituted alkyl or alkylene, or other short chain hydrocarbon as defined herein, and does not include aryl or heteroaryl as defined herein, if any, substituents.

[0511] When the material is an aromatic monomeric monofunctional (meth)acrylate material, Ra can be, for example, aryl or heteroaryl as defined herein, such as substituted or unsubstituted phenyl, substituted or unsubstituted naphthalenyl, etc., and when substituted, can be alkyl or cycloalkyl, such as substituted or unsubstituted benzyl, substituted with one, two, three or more substituents, each of which may be the same or different, or one or more substituted or unsubstituted aryl or substituted or unsubstituted heteroaryl as defined herein. Examples of aromatic monomeric monofunctional (meth)acrylates include those commercially available as CN131B.

[0512] Ingredient A2 * Additional exemplary monomeric monofunctional (meth)acrylates having the Tg shown for the second monofunctional (meth)acrylate, and optionally hydrophilic or amphiphilic, include, but are not limited to, those commercially available under the trade names SR-256, SR-217, SR-285, SR-336, SR-420, and SR-238.

[0513] According to some of the embodiments described herein, component A1 * is a monofunctional (meth)acrylate, such as an acrylate with an alicyclic moiety.

[0514] According to some of the embodiments described herein, component A2 * is a monofunctional (meth)acrylate, such as an acrylate, having an aromatic moiety (e.g., phenoxy).

[0515] According to some of the embodiments described herein, one or more or all of the monofunctional (meth)acrylate materials, such as component A1 * and A2 * and optionally component B * The compound has a molecular weight of 1,000 grams / mole or less, or 500 grams / mole or less.

[0516] According to some of the embodiments described herein, the monofunctional acrylate or methacrylate in the formulation, such as component A1 described herein, * and 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.

[0517] According to some 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 each other in chemical composition, i.e., one type comprises one or more materials having Formula A described herein, i.e., this type comprises acrylates and / or methacrylates described herein, collectively referred to as Component A. * The other type is referred to as component B * The material includes one or more materials that are urethane acrylates, referred to as acrylic acrylates.

[0518] 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, as described herein (e.g., Component A * , component A1 * and A2 * or first and second monofunctional curable materials), and at least one monofunctional urethane (meth)acrylate material characterized by a Tg of less than 150°C (e.g., component B * ) and

[0519] According to some of these embodiments, one or more monofunctional (meth)acrylate materials, Component A * is one monofunctional (meth)acrylate, preferably an acrylate (referred to herein as component A1) characterized by a Tg of 50 to 150°C, or 50 to 100°C, as described herein. *, or also referred to as first monofunctional curable material or first monofunctional (meth)acrylate), and one or more monofunctional (meth)acrylates, preferably acrylates, characterized by a Tg of less than 50° C. or less than 20° C., as described herein (referred to herein as component A2 * or a second monofunctional curable material or and a second monofunctional (meth)acrylate.

[0520] According to some of these embodiments, component A * monofunctional (meth)acrylate materials, such as component A1 * and component A2 * Alternatively, the total amount of the first and second monofunctional materials may range from 20 to 40 weight percent, or from 25 to 35 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0521] According to some of these embodiments, a second monofunctional curable material (e.g., a monofunctional (meth)acrylate (e.g., component A2) having a Tg of less than 50°C or less than 20°C) is used. * The amount of )) ranges from 5 to 10% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0522] According to some of these embodiments, a first monofunctional curable material (e.g., a monofunctional (meth)acrylate) (e.g., component A1) characterized by a Tg of 50 to 150°C, or 50 to 100°C. * ) ranges 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.

[0523] According to some 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 Tg, i.e., one type comprises one or more materials each characterized by a Tg of 50-150°C, or 50-100°C (including any intermediate values ​​and subranges therebetween), and another type comprises one or more materials each characterized by a Tg below 50°C, or below 20°C, e.g., −50-50°C, or 20-50°C, or 50-20°C, or 20-20°C (including any intermediate values ​​and subranges therebetween).

[0524] According to some of these embodiments, each monofunctional curable material is a (meth)acrylate material, including acrylate, methacrylate, and urethane acrylate materials.

[0525] According to some of these embodiments, the total amount of one or more monofunctional curable materials characterized by a Tg of 50-150°C, or 50-100°C, ranges from 20-30% by weight, or 20-25% by weight of the total formulation, including any intermediate values ​​and subranges therebetween.

[0526] 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 weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0527] 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 * ), wherein one or more are monofunctional urethane acrylates or urethane methacrylates characterized by the indicated Tg (e.g., component B * )

[0528] According to some 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, or two or more, components A and B. * and one or more components B * Includes:

[0529] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150°C described herein is a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C described herein. * ) and a second monofunctional (meth)acrylate material characterized by a Tg of less than 50°C or less than 20°C (e.g., component A2 * ) and one or more monofunctional urethane (meth)acrylate materials characterized by a Tg of less than 150°C as described herein (e.g., Component B * ) and at least

[0530] According to some of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) has a Tg of less than 20°C, less than 10°C, or less than 0°C.

[0531] According to some of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) is an aliphatic urethane (meth)acrylate.

[0532] According to some of the embodiments described herein, at least one monofunctional urethane (meth)acrylate material (e.g., Component B * ) is an aliphatic urethane (meth)acrylate having a Tg of less than 20°C, less than 10°C, or less than 0°C.

[0533] According to some 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).

[0534] Component B * Exemplary monofunctional urethane (meth)acrylates having the above Tg that can be used as the urethane (meth)acrylate include, for example, those sold under the trademark Genomer, such as Genomer 1122, which is also sold as a tin-free material. Any other monofunctional aliphatic urethane (meth)acrylate is also contemplated.

[0535] According to some of the embodiments described herein, the amount of the at least one monofunctional urethane (meth)acrylate material described herein ranges from 20 to 30 weight percent of the total weight of the formulation, in any of the respective embodiments, including all intermediate values ​​and subranges therebetween.

[0536] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg less than 150°C is present in a total amount of 40 to 60 wt% (including any intermediate values ​​and subranges therebetween) and includes:

[0537] a first monofunctional (meth)acrylate material (optionally hydrophobic and / or alicyclic) characterized by a Tg of 50 to 150°C, as described in any of the embodiments herein (e.g., component A1 * );

[0538] 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 in any of the embodiments herein (e.g., component A2 * ); and

[0539] 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 in any of the embodiments herein. * ).

[0540] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150° C. can be any of the embodiments described herein (e.g., Component A1 * ), a first monofunctional (meth)acrylate material (optionally hydrophobic and / or cycloaliphatic) characterized by a Tg of 50 to 150°C in an amount of 10 to 30 wt% of the total weight of the formulation (including any intermediate values ​​and subranges therebetween).

[0541] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150° C. is used in each of the embodiments described herein (e.g., component A2). * ), in an amount of 5 to 10 wt. % of the total weight of the formulation (including any intermediate values ​​and subranges therebetween).

[0542] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg of less than 150° C. is preferably a monofunctional curable material, as described in each of the embodiments described herein (e.g., Component B * ), in an amount of 10 to 30 weight percent (including any intermediate values ​​and subranges therebetween) of the total weight of the formulation, of at least one (preferably uncatalyzed) monofunctional (preferably aliphatic) urethane (meth)acrylate material characterized by a Tg of less than 20°C, or less than 10°C, or less than 0°C.

[0543] According to some of the embodiments described herein, the at least one monofunctional curable material characterized by a Tg less than 150°C is present in a total amount of 40 to 60 wt% (including any intermediate values ​​and subranges therebetween) and comprises the following components:

[0544] A first monofunctional (meth)acrylate material (optionally hydrophobic and / or alicyclic) characterized by a Tg of 50 to 150°C according to any of the embodiments described herein (e.g., Component A1 * ) at 10 to 30 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween;

[0545] 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, according to the embodiments described herein (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 therebetween; and

[0546] 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, according to the embodiments described herein. * ) in an amount of 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0547] According to this embodiment, the build material formulation further comprises two or more multi-functional curable materials.

[0548] According to some of the embodiments described herein, the total amount of all multifunctional curable materials is at least 15% by weight of the total weight of the formulation, or in the range of 15-25% by weight, including any intermediate values ​​and subranges therebetween.

[0549] The two or more multifunctional curing materials may be, for example, Component C described herein. * and one or more multifunctional curable materials characterized by a higher Tg, for example, a Tg greater than 100°C or greater than 150°C, including, for example, component D described herein. * and one or more multifunctional curable materials characterized by a lower Tg, for example, a Tg less than 150°C or less than 100°C, including

[0550] According to some of the embodiments described herein, the at least one multifunctional curable material having a Tg greater than 100° C., or greater than 150° C., comprises a difunctional curable material.

[0551] According to some of the embodiments described herein, the at least one multifunctional curable material having a Tg greater than 100°C or greater than 150°C is at least one multifunctional (e.g., difunctional) (meth)acrylate (Component C * ) is included.

[0552] According to some of the embodiments described herein, the average molecular weight of the at least one multifunctional curable material having a Tg greater than 100°C, or greater than 150°C, is 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 therebetween.

[0553] In multifunctional materials, typically each of the curable groups (e.g., (meth)acrylate) are linked to one another via a linking moiety, which can be, for example, a branching 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).

[0554] Higher Tg (e.g., component C * The polyfunctional (e.g., difunctional) curable material characterized by (meth)acrylate ...

[0555] According to some of the embodiments described herein, a higher Tg (e.g., component C *), are non-aromatic (e.g., alicyclic or aliphatic) polyfunctional (e.g., difunctional) (meth)acrylates that include alicyclic and / or aliphatic moieties linking the curable groups (e.g., (meth)acrylate groups).

[0556] In some of these embodiments, the linking moiety is or includes an all-carbon alicyclic moiety, optionally a polyalicyclic moiety containing 2, 3, 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.

[0557] In some embodiments, the linking moiety comprises a polycyclic alicyclic moiety, as described herein, in which two or more rings are fused to one another.

[0558] Such multifunctional curable materials (e.g., Component C) * An example of the diacrylate is tricyclododecane dimethanol diacrylate (for example, SR833S and / or SR368 manufactured by Sartomer Corporation).

[0559] According to some of the embodiments described herein, one or more multifunctional curable materials (e.g., component C) having a Tg greater than 100°C or greater than 150°C are used. * ) provides a clear material when cured.

[0560] According to some of the embodiments described herein, the formulation includes one or more multifunctional (e.g., difunctional) (meth)acrylates having a Tg greater than 100°C, or greater than 150°C, such as 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).

[0561] According to some of the embodiments described herein, the formulation may be heated to above 100°C or above 150°C (e.g., component C) as described herein. *), for example, 100-200°C, or 150-200°C, or 160-200°C, and a molecular weight of less than 500 grams / mole. In some of these embodiments, the multifunctional (e.g., difunctional) 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. In some of these embodiments, the curable material provides a transparent material upon curing.

[0562] According to some of the embodiments described herein, the formulation is heated to above 100°C or above 150°C (e.g., component C * ), for example, 100-200°C, or 150-200°C, or 160-200°C, and which upon curing provide a transparent material. In some of these embodiments, the multifunctional (e.g., difunctional) curable material is a non-aromatic material having a non-aromatic linking moiety between the curable groups, and in some embodiments, the linking moiety is an aliphatic or alicyclic moiety.

[0563] According to some of the embodiments described herein, one or more other multifunctional curable materials are included in the formulation, each characterized by a lower Tg, i.e., a Tg less than 150° C., preferably less than 100° C. Such exemplary materials are collectively referred to herein as Component D. * It is also called.

[0564] According to some 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 difunctional curable material characterized by a Tg of less than 150°C, or less than 100°C.

[0565] According to some 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 multifunctional (e.g., difunctional) methacrylate.

[0566] According to some 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° C. to 150° C., or 50° C. to 100° C., including any intermediate values ​​and subranges therebetween. * (called "the

[0567] According to some 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, are used. * , or component D1 * and / or D2 * ) comprises at least one multifunctional (e.g., difunctional) ethoxylated (meth)acrylate as described herein.

[0568] In ethoxylated multifunctional materials, typically each of the curable (e.g., (meth)acrylate) groups is attached to an alkylene glycol group or chain that either joins two curable groups (in the case of difunctional materials) or to each other via a linking moiety (in the case of tetra-, tri-, tetra-, etc. functional materials). The linking moiety can be, for example, a branching 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).

[0569] According to some 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 comprising aromatic (e.g., bisphenol A) branching units as described herein.

[0570] According to some 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 is used. * ) is or includes a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate having at least 10 ethoxylated groups (e.g., 10 to 40, or 20 to 40, including any intermediate values ​​and subranges therebetween). According to some embodiments, the material is characterized by a Tg of 0°C to -50°C, or -20°C to -50°C, including any intermediate values ​​and subranges therebetween.

[0571] Ingredient D1 * Examples of such materials that can be used as curing agents include ethoxylated aromatic polyfunctional materials having two or more alkylene (glycol) chains extending from a bisphenol A branching unit, the alkylene (glycol) chains containing a total of 10 or more (e.g., 10 to 40, or 20 to 40) alkylene glycol units, and the alkylene glycol units terminated with a curable group (e.g., a (meth)acrylate group). Examples of such compounds are sold under the trademarks Miramer (e.g., Miramer M2301) or SR9036A. Other ethoxylated aromatic polyfunctional (e.g., difunctional) (meth)acrylates are also contemplated.

[0572] According to some 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, is used. *) is or includes a polyfunctional (e.g., difunctional) ethoxylated (meth)acrylate having fewer than 10 (e.g., 2-4) ethoxylated groups, and in some embodiments is a polyfunctional (e.g., difunctional) aromatic ethoxylated (meth)acrylate having fewer than 10 (e.g., 2-4) ethoxylated groups, as described herein.

[0573] According to some 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 used. * ) is a first multifunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D1) having at least 10 (e.g., 10 to 40) ethoxylated groups, as described in any of the embodiments herein. * ) and a second multifunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) having fewer than 10 (e.g., 2-4) ethoxylated groups, as described in any of the embodiments herein. * Includes:

[0574] According to some of the embodiments described herein, a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate (e.g., component D1) having 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.

[0575] According to some of the embodiments described herein, a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate having fewer than 10 (e.g., 2-4) ethoxylated groups (e.g., component D2 * ) ranges from 10 to 20% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0576] According to some of the embodiments described herein, a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate (e.g., component D1) having at least 10 (e.g., 10 to 40) ethoxylated groups is used. * ) ranges from 10 to 30 wt. % of the total weight of the formulation, including any intermediate values ​​and subranges therebetween, and is preferably a polyfunctional (e.g., difunctional) ethoxylated (e.g., aromatic) (meth)acrylate (e.g., component D2) having 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.

[0577] An exemplary build material formulation according to some embodiments of the present invention includes the following ingredients:

[0578] 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 embodiments of this specification. * );

[0579] 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 embodiments herein. * );

[0580] 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 embodiments herein. * );

[0581] At least one aliphatic multifunctional (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 in any of the embodiments herein. * );

[0582] 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 characterized by a Tg of less than 0°C or less than -20°C, as described in any of the embodiments herein. * ); and

[0583] As described in any of the embodiments herein, a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by less than 10 (e.g., 2 to 4) ethoxylated groups and having a Tg in the range of 50 to 100°C. * ).

[0584] According to some of these exemplary embodiments, a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C is used. * ) ranges from 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0585] According to some 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 weight percent of the total weight of the formulation, including intermediate values ​​and subranges therebetween.

[0586] According to some 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 used. * ) ranges from 10 to 30% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0587] According to some 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.

[0588] According to some of these exemplary embodiments, a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate having at least 10 (e.g., 10 to 40) ethoxylated groups (e.g., component D1 * ) ranges from 10 to 30 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0589] According to some of these exemplary embodiments, a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate having fewer than 10 (e.g., 2-4) ethoxylated groups (e.g., component D2 * ) ranges from 10 to 20% by weight of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0590] According to some of these exemplary embodiments, a first monofunctional (meth)acrylate material (e.g., component A1) characterized by a Tg of 50 to 150°C is used. * ) in an amount ranging from 10 to 30 wt. % of the total weight of the formulation; 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 characterized by a Tg of less than 20° C. (e.g., component B * ) in an amount ranging from 10 to 30% by weight of the total weight of the formulation; at least one non-aromatic (e.g., cycloaliphatic) polyfunctional (e.g., difunctional) (meth)acrylate (e.g., component C) characterized by a Tg of greater than 100°C, or greater than 150°C, and optionally having a molecular weight of less than 500 grams / mole; * ) in an amount ranging from 4 to 10% by weight of the total weight of the formulation; polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylates (e.g., component D1) characterized by at least 10 (e.g., 10 to 40) ethoxylated groups;* ) in an amount ranging from 10 to 30% by weight of the total weight of the formulation; polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylates having less than 10 (e.g., 2 to 4) ethoxylated groups (e.g., component D2 * ) ranges from 10 to 20% by weight of the total weight of the formulation (all ranges including any intermediate values ​​and subranges therebetween).

[0591] According to some of the embodiments described herein, each of the multifunctional curable materials is a multifunctional (eg, difunctional) acrylate.

[0592] According to some of the embodiments described herein, each of the monofunctional curable materials is a monofunctional acrylate.

[0593] According to some 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 further comprises at least one photoinitiator (Component J). * ) is included.

[0594] According to some 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.

[0595] According to some of the embodiments described herein, the photoinitiator comprises or consists essentially of a phosphine oxide type (e.g., monoacrylated (MAPO) type or bisacrylated phosphine oxide type (BAPO) type photoinitiator.

[0596] 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, etc. 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoylbis(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 greater than about 380 nm to about 450 nm include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (sold as IRGACURE® 819), bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (CGI 403), a 25:75 weight ratio mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (sold as IRGACURE® 1700), a 1:1 weight ratio mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (sold as DAROCUR® 4265), and ethyl 2,4,6-trimethylbenzylphenylphosphinate (LUCIRIN LR8893X).

[0597] According to some of the embodiments described herein, the photoinitiator comprises or consists essentially of a bisacrylated phosphine oxide type (BAPO) photoinitiator.

[0598] In an exemplary embodiment, the photoinitiator is or includes bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (sold as IRGACURE® 819).

[0599] In exemplary embodiments, the photoinitiator does not include a monoacrylate (MAPO) phosphine oxide type photoinitiator, and in some embodiments does not include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (sold as TPO).

[0600] According to some of the embodiments described herein, the build material formulation further comprises additional non-curable components, such as, for example, inhibitors, surfactants, dispersants, colorants (colorants), and stabilizers. Commonly used surfactants, dispersants, colorants, and stabilizers are contemplated. Exemplary concentrations of each component, when present, are from about 0.01 to about 1, or from about 0.01 to about 0.5, or the component is from about 0.01 to about 0.1 weight percent of the total weight of the formulation. Exemplary components are described below.

[0601] In some of the embodiments described herein, the formulation includes a cure inhibitor, i.e., an agent that inhibits or reduces cure in the absence of cure conditions, herein referred to 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. %, depending on the type of inhibitor used, including any intermediate values ​​and subranges therebetween. Commonly used inhibitors, such as radical inhibitors, are contemplated.

[0602] According to some of the embodiments described herein, the build material formulation contains an inhibitor (component I) described herein. * ), such as phenolic type inhibitors, or other inhibitors commonly used in medical devices or applications, and / or in foods.

[0603] According to some 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.

[0604] In an exemplary embodiment, the free radical inhibitor is from the Genorad® family (eg, Genorad 20).

[0605] In exemplary embodiments, such free radical inhibitors are used in amounts of 0.1 to 3% by weight, or 0.1 to 2% by weight, or 0.1 to 1% by weight, or 0.1 to 0.5% by weight (including any intermediate values ​​and subranges therebetween).

[0606] According to some of the embodiments described herein, the build material formulation contains one or more dispersants or surfactants (Component H * ) further includes.

[0607] According to some of the embodiments described herein, the amount of dispersant ranges from 0.01 to 0.1 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0608] Exemplary dispersants and surfactants are those commercially available as BYK Surface Additives.

[0609] According to some of the embodiments described herein, the build material formulation is a clear (e.g., transparent), colorless formulation that does not contain colorants or pigments.

[0610] According to some of the embodiments described herein, the build material formulation contains one or more colorants or pigments (ingredient P * ) further includes.

[0611] The colorant can be a pigment or a dye, preferably a pigment.

[0612] The pigments can be organic and / or inorganic and / or metallic pigments, and in some embodiments, the pigments are nanoscale pigments comprising nanoparticles.

[0613] Examples of inorganic pigments include nanoparticles of titanium oxide, zinc oxide, and / or silica. Examples of organic pigments include nano-sized carbon black.

[0614] In some embodiments, a combination of white and colored pigments is used to prepare the colored cured material.

[0615] According to some of the embodiments described herein, the colorant comprises a mixture of a pigment and at least one (meth)acrylic material, and the pigment is introduced into the formulation within this mixture.

[0616] According to some of the embodiments described herein, the pigment is a white pigment and the formulation provides a white cured material.

[0617] According to some of the embodiments described herein, the colorant comprises a mixture of a white pigment and one or more curable materials, such as (meth)acrylic materials, in which the pigment is introduced into the formulation.

[0618] 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.

[0619] 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 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0620] According to some of the optional embodiments described herein, the pigment is a cyan pigment and the formulation provides a cyan colored cured product.

[0621] According to some of the optional embodiments described herein, the colorant comprises a mixture of a cyan pigment and one or more curable materials, such as a (meth)acrylic material, and the cyan pigment is introduced into the formulation within the mixture.

[0622] 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, including any intermediate values ​​and subranges therebetween.

[0623] 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.

[0624] According to some of the embodiments described herein, the pigment is a yellow pigment and the formulation provides a yellow cured product.

[0625] According to some of the embodiments described herein, the colorant comprises a mixture of a yellow pigment and one or more curable materials, such as (meth)acrylic materials, and the yellow pigment is introduced into the formulation in this mixture.

[0626] 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.

[0627] 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.

[0628] According to some of the embodiments described herein, the pigment is a magenta pigment and the formulation provides a magenta colored cured product.

[0629] According to some of the embodiments described herein, the colorant comprises a mixture of a magenta pigment and one or more curable materials, such as (meth)acrylic materials, and the magenta pigment is introduced into the formulation in this mixture.

[0630] According to some of these embodiments, the amount of magenta pigment in the mixture ranges from 0.01 to 1 weight percent, or from 0.05 to 0.5 weight percent, or from 0.1 to 0.2 weight percent of the total weight of the mixture, including any intermediate values ​​and subranges therebetween.

[0631] 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 weight percent of the total weight of the formulation, including any intermediate values ​​and subranges therebetween.

[0632] According to some of the embodiments described herein, the formulation includes one or more of a white, magenta, cyan, and yellow colorant, and in some of these embodiments, each pigment is introduced into the formulation as a mixture with the curable material described herein.

[0633] According to some of the embodiments described herein, the colorant may comprise a pigment dispersant (component Dp * Preferred pigment dispersants are those having multiple groups that exhibit affinity for the pigment.

[0634] According to some of the embodiments described herein, the build material formulation comprises component H * , I * , and J * An example of such a formulation is a clear, colorless formulation that does not contain any colorants.

[0635] According to some of the embodiments described herein, the build material formulation comprises component H according to any of the embodiments described herein. * , I * , J * , and P* , and optionally Dp * Examples of such formulations include white formulations that include the white pigments described herein.

[0636] According to some of the embodiments described herein, the build material formulation comprises component H according to any of the embodiments described herein. * , I * , J * , P * , and optionally Dp * Examples of such formulations include the cyan, magenta, and yellow formulations described herein.

[0637] While the present invention has been described in conjunction with specific embodiments, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art. Accordingly, the present invention is intended to embrace all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.

[0638] It is the intention of the applicants that all publications, patents, and patent applications referenced herein be incorporated herein in their entireties as if specifically and individually set forth herein. Furthermore, citation or identification of a reference herein shall not be construed as an admission that such reference is available as prior art to the present invention. To the extent section headings are used, they should not be construed as necessarily limiting. Additionally, the priority documents of this specification are incorporated herein by reference in their entireties.

Claims

1. 1. A method for forming an object on a fabric by three-dimensional printing, comprising: printing an adhesive structure having a stack of layers on a fabric in a structural pattern corresponding to the shape of the bottom surface of the object, wherein for each layer of the stack, the printing comprises dispensing and curing a first formulation along a scanning direction; printing an object onto the laminate by dispensing and curing a build compound in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object; For each layer of the stack and each layer of the object, the curing is performed by scanning the layer along the direction of the radiation intensity I Ａ irradiating said layer with a pattern of curing radiation having a thickness of 100 nm to 150 nm, said pattern having the shape of a stripe;

2. The method of claim 1 , wherein the stack comprises from about 10 to about 30 layers.

3. 1. A method for forming an adhesive structure on a fabric by three-dimensional printing, comprising: printing a first laminate of uncured layers onto the fabric in a configuration pattern corresponding to the shape of the bottom surface of the object, wherein for each layer of the laminate, the printing comprises dispensing a first formulation without curing; and printing a second stack of layers onto the first stack; for each layer of the second laminate, the printing includes dispensing and curing the first formulation along a scanning direction; The curing is performed by scanning the layer along the direction of the radiation intensity I Ｂ irradiating said layer with a pattern of curing radiation having a curing rate of at least two separated stripes;

4. The method of claim 3 , wherein the first laminate comprises less than five layers.

5. The method of claim 3 or 4, wherein the second laminate comprises from about 10 to about 30 layers.

6. The method of claim 3 or 4, comprising printing the object onto the second laminate.

7. The printing of the object is performed by dispensing and curing a build compound in layers along the direction in a structured pattern corresponding to the shape of a slice of the object, and for each layer of the object, the curing is performed by scanning the layer along the direction with a radiation intensity I Ａ irradiating the layer by creating a pattern of curing radiation having an intensity I Ｂ is the intensity I Ａ 7. The method of claim 6, wherein the concentration is about twice as high as the concentration of the hydroxyl group.

8. 1. A method for forming an object on a fabric by three-dimensional printing, comprising: a process for printing an adhesive structure on a fabric, the adhesive structure comprising a stack of layers, in a structured pattern corresponding to the shape of the bottom surface of the object, wherein for each layer of the stack, the printing comprises dispensing and curing a first formulation along a scanning direction, the curing scanning the layers along said direction, with a radiation intensity I Ｃ irradiating the layer by creating a pattern of curing radiation having a curing rate of at least two separated stripes; printing an object onto the laminate by dispensing and curing a build compound in layers along said direction in a structured pattern corresponding to the shape of a slice of the object, wherein for each layer of the object, said curing scans said layer along said direction; Ａ irradiating the layer by creating a pattern of curing radiation having an intensity I Ｃ is the intensity I Ａ The process is about four times faster than A method comprising:

9. The method of claim 8 , wherein the stack comprises from about 10 to about 30 layers.

10. 1. A method for forming an adhesive structure on a fabric by three-dimensional printing, comprising: obtaining parameters describing the fabric; (i) printing a first laminate of uncured layers onto a fabric in a configuration pattern corresponding to the shape of a bottom surface of an object, wherein for each layer of the laminate, the printing comprises dispensing a first formulation without curing; and printing a second stack of layers onto the first stack; for each layer of the second laminate, the printing includes dispensing and curing the first formulation along a scanning direction; The curing is performed by scanning the layer along the direction of the radiation intensity I Ｂ irradiating the layer by creating a pattern of curing radiation having a thickness of at least two separated stripes; (ii) performing one of the methods according to claim 8 or 9, A method wherein (i) is performed if the parameter indicates an absorption level below a predetermined threshold, and (ii) is performed if the parameter indicates an absorption level above a predetermined threshold.

11. illuminating a top surface of the object, the illumination scanning the top surface along the direction, with a radiation intensity I Ｂ wherein the pattern has the shape of at least two separate stripes, and the intensity I Ｂ is the intensity I Ａ 10. The method of claim 1, 2, 8, or 9, wherein the concentration is about twice as high as the concentration of the hydroxybenzoates.

12. 10. The method of any of claims 1, 2, 8 and 9, further comprising printing the first formulation onto an exterior surface of the object to form a liquid coating, and exposing the coating to the curing radiation to form a hardened coating.

13. Scanning the top surface along the direction, the radiation intensity I Ｂ irradiating the coating by creating a pattern of curing radiation having an intensity I Ｂ is the intensity I Ａ The method of claim 12, wherein the concentration is about twice as high as the concentration of the hydroxybenzoates.

14. 10. The method of any of claims 1, 2, 8 and 9, including testing the adhesion level of the object to a fabric.

15. 15. The method of claim 14, repeated on the same side of the fabric but for different orientations of the fabric.

16. 15. The method of claim 14, wherein the method is repeated on different sides of the fabric.

17. 1. A method for selecting a printing protocol for three-dimensional printing on a fabric, comprising: performing a first method on a first portion of the fabric; performing a second method on a second portion of the fabric; carrying out the method of claim 8 or 9 on a third portion of the fabric; testing the adhesion level of each object to each of said portions of fabric; Including, The first method comprises: printing an adhesive structure having a stack of layers on a fabric in a structural pattern corresponding to the shape of the bottom surface of the object, wherein for each layer of the stack, the printing comprises dispensing and curing a first formulation along a scanning direction; printing an object onto the laminate by dispensing and curing a build compound in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object; For each layer of the stack and each layer of the object, the curing is performed by scanning the layer along the direction of the radiation intensity I Ａ irradiating the layer by creating a pattern of curing radiation having a shape of a stripe; The second method comprises: printing a first laminate of uncured layers onto the fabric in a configuration pattern corresponding to the shape of the bottom surface of the object, wherein for each layer of the laminate, the printing comprises dispensing a first formulation without curing; and printing a second stack of layers onto the first stack; for each layer of the second laminate, the printing includes dispensing and curing the first formulation along a scanning direction; The curing is performed by scanning the layer along the direction of the radiation intensity I Ｂ irradiating the layer by creating a pattern of curing radiation having a curing radiation having a shape of at least two separated stripes; printing the object onto the second laminate, wherein the printing of the object is performed by dispensing and curing a build compound in layers along the direction in a configuration pattern corresponding to the shape of a slice of the object, and for each layer of the object, the curing is performed by scanning the layer along the direction with a radiation intensity I Ａ irradiating the layer by creating a pattern of curing radiation having an intensity I Ｂ is the intensity I Ａ This method is about twice as fast as the previous method.

18. 18. The method of claim 17, which is performed repeatedly on the same side of the fabric for different fabric orientations.

19. 18. The method of claim 17, wherein the method is repeated on different sides of the fabric.

20. 15. The method of claim 14, wherein the object includes two stacks of modeling material layers separated by a gap, the stack of modeling material layers having a bending resistance greater than the bending resistance of the adhesive material and the fabric.

21. 21. The method of claim 20, wherein the testing includes bending the fabric at the gap to separate at least one of the stack of modeling material layers from the fabric at a separation point adjacent the gap.

22. 22. The method of claim 21, wherein the gap has a piecewise linear shape and the separation point is near a breakpoint of the piecewise linear shape.

23. The method of claim 22 , wherein the gap forms an acute angle at the breakpoint.

24. The method of claim 20 , wherein the gap has a curved shape.

25. 21. The method of claim 20, wherein the gap width is less than 1 mm.

26. 21. The method of claim 20, wherein the gap-separated stacks form a three-dimensional structure having a planar aspect ratio of about 1:3 to about 1:

10.

27. The method of claim 20 , wherein the thickness of the stack of modeling material is greater than the thickness of the adhesive structure.

28. 30. The method of claim 27, wherein the thickness of the stack of modeling material is at least twice as thick as the adhesive structure.

29. 21. The method of claim 20, wherein the stack of modeling material layers has a plurality of through holes defining open cells within the stack.

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