Compounds for additive manufacturing of elastomer materials

Abstract

Vulcanizable formulations are provided that, when cured, provide elastomeric materials that can be used for additive manufacturing of three-dimensional objects. The formulations are based on vulcanizable mono- and multi-functional elastomeric materials in combination with vulcanizable multi-functional non-elastomeric materials, and vulcanizable materials that include at least two hydrogen bond forming groups.

Description

[Technical Field]

[0001] Related applications

[0002] This application claims the benefit of priority under U.S. Provisional Patent Application No. 63 / 210,422, 35 U.S.C. 119(e), filed on 14 June 2021, the contents of which are incorporated herein by reference in their entirety.

[0003] In some embodiments, the present invention relates to additive manufacturing (AM), and more specifically, to formulations and methods that can be used for additive manufacturing of objects made of elastomer rubber-like materials (or multiple materials), though not exclusively. [Background technology]

[0004] Synthetic rubber is typically made from artificial elastomers. Elastomers are viscoelastic polymers that generally exhibit a lower Young's modulus and higher yield strain compared to other materials. Since elastomers are typically amorphous polymers that exist above their glass transition temperature, considerable segmentation is possible. Therefore, at ambient temperatures, rubber is relatively soft, characterized by an elasticity of about 3 MPa, and is deformable.

[0005] Elastomers are typically used to crosslink polymer chains. Curing (Vulcanization) These are thermosetting polymers (or copolymers) that require elasticity. Elasticity derives from the ability of long chains to reconfigure themselves to distribute applied stress. Covalent crosslinking ensures that the elastomer returns to its original configuration when the stress is removed. Elastomers can typically be reversibly stretched from 5% to 700%.

[0006] Rubber often contains fillers or reinforcing agents, usually intended to increase its hardness. The most common reinforcing agents include micronized carbon black and / or micronized silica.

[0007] Both carbon black and silica, when added to polymer mixtures during rubber production at a concentration of typically around 30% by volume, increase the modulus of elasticity of the rubber by 2 to 3 times and impart significant toughness, particularly abrasion resistance, to otherwise weak materials. Adding more carbon black or silica particles further increases the modulus of elasticity, but may decrease tensile strength.

[0008] Additive manufacturing is generally the process by which three-dimensional (3D) objects are manufactured using computer models of those objects. Such processes are used in various fields, such as design-related fields for visualization, demonstration, and mechanical prototyping purposes, as well as for rapid manufacturing (RM).

[0009] The basic operation of any AM system consists of slicing a three-dimensional computer model into thin cross-sections, converting the results into two-dimensional positional data, and supplying that data to control equipment that manufactures the three-dimensional structure layer by layer.

[0010] Various AM technologies exist, including stereolithography, digital light processing (DLP), and three-dimensional (3D) printing, 3D inkjet printing. Such technologies generally involve one or more building materials, typically photopolymerizable (light). Curing This is carried out by the deposition and solidification of each layer of material.

[0011] In a three-dimensional printing process, for example, building material is distributed from a distribution head having a set of nozzles to deposit layers onto a support structure. Then, depending on the building material, the layers are processed using an appropriate device. Curing Alternatively, it can be solidified.

[0012] Various three-dimensional printing technologies exist, for example, disclosed in U.S. Patents 6,259,962, 6,569,373, 6,658,314, 6,850,334, 7,183,335, 7,209,797, 7,225,045, 7,300,619, 7,479,510, 7,500,846, 7,962,237 and 9,031,680 (all by the same assignee), the contents of which are incorporated herein by reference.

[0013] A printing system used in additive manufacturing may include a receiving medium and one or more print heads. The receiving medium may be, for example, an assembly tray which may include a horizontal surface for carrying material dispensed from the print heads. The print head may be, for example, an inkjet head having multiple dispensing nozzles arranged in one or more rows along the longitudinal axis of the print head. The print head may be positioned so that its longitudinal axis is substantially parallel to the indexing direction. The printing system may further include a controller, such as a microprocessor, for controlling the printing process, including the movement of the print heads according to a predefined scan plan (e.g., a CAD configuration converted to stereolithography (STL) format and programmed into the controller). The print head may include multiple spray nozzles. The spray nozzles dispense material onto the receiving medium to create layers representing the cross-section of a 3D object.

[0014] In addition to the print head, the distributed building materials Curing to Curing An energy source may be present. Curing The energy is typically radiation, such as UV radiation.

[0015] Furthermore, the printing system may include a planarizing device for flattening and / or establishing the height of each layer after deposition and at least partial solidification, and before deposition of subsequent layers.

[0016] The building material may include a modeling material and a support material, which form an object and a temporary support structure that supports the object during the molding process.

[0017] Modeling material (which may include one or more materials) is deposited to generate the desired object(s), and supporting material (which may include one or more materials) provides a support structure for specific areas of the object being fabricated, with or without modeling material elements, and is used to ensure proper vertical alignment of subsequent object layers, for example, when the object includes protruding features or shapes such as curved geometry, negative angles, or voids.

[0018] Both the modeling material and the support material are preferably liquid at the working temperature in which they are distributed, and then typically Curing When exposed to energy, it hardens (e.g., UV). Curing ) and form the required layer shape. After printing is complete, the support structure is removed to reveal the final shape of the assembled 3D object.

[0019] Some additive manufacturing processes enable the additive formation of an object using two or more modeling materials. For example, U.S. Patent Application Publication No. 2010 / 0191360 by the Assignee discloses a system comprising a solid free-assembly apparatus having multiple distribution heads, a building material feeder configured to supply multiple building materials to the assembly apparatus, and a control unit configured to control the assembly apparatus and the feeder. The system has several operating modes. In one mode, all distribution heads operate during a single building scan cycle of the assembly apparatus. In another mode, one or more distribution heads It does not operate during a single building scan cycle or part thereof.

[0020] In 3D inkjet printing processes such as Polyjet® (Stratasys Ltd., Israel), the building material is selectively ejected from one or more print heads and deposited in successive layers on an assembly tray according to a predefined configuration defined by a software file.

[0021] U.S. Patent No. 9,227,365 by the present assignee discloses a method and system for the solid freeform fabrication of shell-like objects constructed from a plurality of layers, a layered core constituting a core region, and a layered shell constituting an envelope region.

[0022] Additive manufacturing processes have been used to form rubber-like materials. For example, rubber-like materials are used in the PolyJet® systems described herein. These materials have a relatively low viscosity that enables dispensing by, for example, inkjet, and are formulated to exhibit a Tg lower than room temperature, for example, -10 °C lower than room temperature. The latter is obtained by formulating products with a relatively low degree of crosslinking and using monomers and oligomers having an inherently flexible molecular structure (e.g., acrylic elastomers).

[0023] An exemplary family of rubber-like materials that can be used in PolyJet® systems (commercially available under the trade name "Tango" family) provides various elastomeric properties including Shore scale A hardness, elongation at break, tear resistance, and tensile strength.

[0024] Another exemplary family of rubber-like materials that can be used in PolyJet® systems (commercially available as the "Agilus" family) is disclosed in International Publication No. 2017 / 208238, Curing which, in addition to the rubber-like material, contains silica nanoparticles and provides improved properties of the resulting material, particularly improved elongation at break, tear resistance, and tensile strength.

[0025] Rubber-like materials are useful for many modeling applications, including exhibition and communication models; rubber enclosures and overmoldings; soft-touch coatings and anti-slip surfaces for tools or prototypes; and knobs, grips, pulls, handles, gaskets, seals, hoses, and footwear.

[0026] Further background technology, including International Publication Nos. 2009 / 013751; International Publication Nos. 2016 / 009426; International Publication Nos. 2016 / 063282; International Publication Nos. 2016 / 125170; International Publication Nos. 2017 / 134672; International Publication Nos. 2017 / 134673; International Publication Nos. 2017 / 134674; International Publication Nos. 2017 / 134676; International Publication Nos. 2017 / 068590; International Publication Nos. 2017 / 187434; International Publication Nos. 2018 / 055521; and International Publication Nos. 2018 / 055522, is all provided by the assignee. [Overview of the Initiative]

[0027] According to one aspect of several embodiments of the present invention, an elastomer material is provided when cured. Curing A compound with properties, 50% to 70% by weight of the total weight of the aforementioned compound Curing Monofunctional elastomer materials; 20% to 40% by weight of the total weight of the aforementioned compound Curing Polyfunctional elastomer material; A total amount of 5% by weight or less of the total weight of the aforementioned compound Curing Polyfunctional non-elastomer materials; and Approximately 1% to 20% by weight of the total weight of the aforementioned compound, or approximately 1% to 10% by weight of the total Contains at least two hydrogen bond-forming groups Curing Includes materials Curing A compound is provided.

[0028] According to any of the embodiments described herein, Curing Each of the materials is UV Curing It is a material.

[0029] According to any of the embodiments described herein, Curing Each of the material properties is a (meth)acrylic material.

[0030] According to some of the embodiments described herein, the hydrogen bond forming group comprises at least one hydrogen bond donor and at least one hydrogen bond acceptor.

[0031] According to some of the embodiments described herein, at least two hydrogen bond-forming groups are separated from each other by two or fewer atoms.

[0032] According to some of the embodiments described herein, the ratio of the number of hydrogen bond-forming groups to the molecular weight of the material containing them is greater than 0.01.

[0033] According to some of the embodiments described herein, the at least two hydrogen bond-forming groups are included. Curing The material is (meth)acrylamide, preferably methacrylamide.

[0034] According to some of the embodiments described herein, the at least two hydrogen bond-forming groups are included. Curing The concentration of the active ingredient is within the range of 1% to 10% by weight, or 1% to 5% by weight, or 1% to 3% by weight, or 1.5% to 2% by weight of the total weight of the compound.

[0035] According to any of the embodiments described herein, Curing At least one of the elastomeric materials is capable of forming hydrogen bonds.

[0036] According to any of the embodiments described herein, Curing At least 50%, or at least 60%, or at least 70%, or at least 80% of the material can form hydrogen bonds. Curing Material properties (e.g., one or more) CuringIncludes (materials).

[0037] According to any of the embodiments described herein, hydrogen bonds can be formed. Curing The material contains at least one carbamate group.

[0038] According to some of the embodiments described herein, hydrogen bonds can be formed. Curing The material is urethane (meth)acrylate.

[0039] According to any of the embodiments described herein, Curing The concentration of the polyfunctional elastomer material is within the range of 10% to 20% or 10% to 15% by weight of the total weight of the compound.

[0040] According to any of the embodiments described herein, Curing The polyfunctional elastomer material contains polyfunctional urethane acrylate.

[0041] According to any of the embodiments described herein, Curing Monofunctional elastomer materials include monofunctional urethane acrylates.

[0042] According to any of the embodiments described herein, Curing A monofunctional elastomer material comprising at least two hydrogen bond-forming groups Curing The weight ratio with the material is within the range of 20:1 to 60:1, or 30:1 to 50:1.

[0043] According to any of the embodiments described herein, Curing The compound is a monofunctional non-elastomer. Curing It further contains properties.

[0044] According to some of the embodiments described herein, further monofunctional non-elastomersCuring The concentration of the active ingredient is within the range of 15% to 25% by weight of the total weight of the compound.

[0045] According to some of the embodiments described herein, polyfunctional non-elastomer Curing The material contains tertiary amine groups.

[0046] According to some of the embodiments described herein, polyfunctional non-elastomer Curing The functional materials include materials characterized by a functional value greater than 2 as defined herein.

[0047] According to some of the embodiments described herein, polyfunctional non-elastomer Curing The concentration of the active ingredient is within the range of 0.1% to 2% by weight, or 0.1% to 1% by weight, of the total weight of the compound.

[0048] According to any of the embodiments described herein, Curing The composition further comprises at least one material selected from surfactants, dispersants, plasticizers, fillers, dyes, pigments, inhibitors, and antioxidants.

[0049] According to any of the embodiments described herein, Curing The chemical composition is characterized by a tear resistance of at least 4 kg / cm or at least 4.5 kg / cm when cured.

[0050] According to any of the embodiments described herein, Curing The composition is characterized by a tensile strength of at least 2 MPa or at least 2.5 MPa when cured.

[0051] According to any of the embodiments described herein, Curing The compound is characterized by an elongation at break of at least 300% or at least 350% when cured.

[0052] According to any of the embodiments described herein, Curing The composition is characterized by a Shore A hardness of at least 30 or at least 40 when cured.

[0053] According to any of the embodiments described herein, Curing The properties of the compound are characterized by the average Tg below 15°C after curing.

[0054] According to any of the embodiments described herein, Curing The compound can be used as a modeling material compound in the additive manufacturing of three-dimensional objects, containing at least a portion of elastomer material.

[0055] According to one aspect of several embodiments of the present invention, at least a portion of the elastomer material is A method for additively manufacturing a three-dimensional object, comprising forming the object by sequentially forming multiple layers with a configured pattern corresponding to the shape of the object, The formation of at least some of the layers is described herein in any of the respective embodiments and any combination thereof. Curing The modeling material formulation, which is a ferrous elastomer compound, is distributed, and the distributed modeling material Curing Conditions (for example) Curing Exposure to energy, and thereby Curing This includes forming a modeling material, This provides a method for manufacturing three-dimensional objects.

[0056] According to any of the embodiments described herein, Curing The conditions are Curing It contains energy.

[0057] According to any of the embodiments described herein, Curing Conditions (for example, CuringEnergy includes UV irradiation.

[0058] According to some of the embodiments described herein, the UV irradiation is from an LED energy source.

[0059] According to some of the embodiments described herein, the distribution is carried out at a temperature of 40°C or lower or 35°C or lower.

[0060] According to one aspect of several embodiments of the present invention, a three-dimensional object manufactured by the additive manufacturing method described herein is provided in any one of the embodiments.

[0061] Unless otherwise defined, all technical and / or scientific terms used herein have the same meaning as those generally understood by those skilled in the art to which the present invention pertains. Similar or equivalent methods and materials to those described herein may be used in carrying out or testing embodiments of the present invention, but exemplary methods and / or materials are described below. In case of any inconsistency, the patent specification, including definitions, shall prevail. Furthermore, materials, methods, and examples are illustrative and not necessarily intended to be limiting.

[0062] Implementation of the methods and / or systems of embodiments of the present invention may include performing or completing selected tasks manually, automatically, or in combination thereof. Furthermore, according to the actual instrumentation and equipment of embodiments of the methods and / or systems of the present invention, some selected tasks may be implemented by hardware, software, or firmware, or a combination thereof, using an operating system.

[0063] For example, hardware for performing selected tasks according to embodiments of the present invention can be implemented as a chip or circuit. As software, selected tasks according to embodiments of the present invention can be implemented as a set of software instructions executed by a computer using any suitable operating system. In exemplary embodiments of the present invention, one or more tasks according to exemplary embodiments of the method and / or system described herein are performed by a data processor, such as a computing platform, for executing a set of instructions. Optionally, the data processor includes volatile memory for storing instructions and / or data, and / or non-volatile storage devices for storing instructions and / or data, such as magnetic hard disks and / or removable media. Optionally, network connectivity is also provided. A display and / or user input devices such as a keyboard or mouse are also optionally provided.

[0064] Some embodiments of the present invention are described herein merely as examples with reference to the accompanying drawings. Details shown herein are illustrative and refer to the drawings in particular. It is emphasized that this is for illustrative purposes only regarding embodiments of the present invention. In this regard, the description made with reference to the drawings will make it clear to those skilled in the art how embodiments of the present invention may be carried out. [Brief explanation of the drawing]

[0065]

Figure 1A

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Figure 1D

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Figure 5B

Figure 5C

Figure 5D

Figure 6

Figure 7A

Figure 7B

[0066] In some embodiments, the present invention relates to additive manufacturing (AM), and more specifically, to formulations and methods that can be used for additive manufacturing of objects made of rubber-like materials (plural), but not exclusively, in some respects.

[0067] Before describing in detail at least one embodiment of the present invention, the present invention relates in its application to the components and / or elements described and / or shown in the following description and / or drawings and / or examples. It should be understood that the invention is not necessarily limited to the details of the structure and arrangement of the method. Other embodiments are possible, or the invention can be implemented or carried out in various ways.

[0068] In the conventional production of elastomer materials (elastomers, rubber-like materials), the starting material is typically a low Tg thermoplastic polymer, and the compounding and Curing or Vulcanization In contrast, additive manufacturing processes such as 3D (inkjet) printing are performed. Curing Polymers are produced in a single step from suitable monomers and / or low molecular weight (e.g., less than 1,000 g / mol or less than 500 g / mol) crosslinkers and oligomers. Therefore, it is difficult to control the molecular weight, crosslink density, and mechanical properties of rubber-like materials obtained by such processes. Consequently, PolyJet® rubber-like materials, for example, often feature a low tear resistance (TR) value and / or a slow recovery rate after deformation compared to, for example, conventional elastomers. PolyJet® rubber-like materials exhibiting high elongation often feature a low modulus of elasticity, low tear resistance, and / or low Tg and tackiness.

[0069] The inventors have designed and successfully implemented a novel formulation suitable for use in additive manufacturing (e.g., with characteristic properties that satisfy the AM process requirements described herein) that provides a rubber-like material upon curing. The novel formulation is an elastomer that can also participate in hydrogen bond formation. Curing It can form multiple hydrogen bonds with the material. Curing This includes properties of materials. As demonstrated in the following Examples section, the inventors have shown that such formulations can be used to obtain rubber-like materials that simultaneously feature improved elongation, modulus of elasticity, and tear resistance.

[0070] Referring here to the drawings, Figures 1A-1D, 2A-2C, 3A, 3B, 4, and 5A-5D show schematic diagrams of exemplary systems and structures according to several embodiments of the present invention. Figure 6 is an exemplary diagram. Curing A schematic diagram of physical crosslinking brought about by hydrogen bonding when the material, methacrylamide, is included in the formulation is shown. Figures 7A and 7B are photographs showing improved objects formed using exemplary formulations according to several embodiments of the present invention, compared to objects formed using commercially available silica particle-containing formulations. Table 1 in the following Examples section further shows the improved mechanical properties of rubber-like materials obtained by 3D inkjet printing of exemplary formulations according to this embodiment.

[0071] Throughout this specification, the terms “rubber,” “rubber-like material,” “elastomer material,” and “elastomer” are used interchangeably to describe materials characterized by elastomer properties. The terms “rubber-like material” or “rubber-like material” refer to thermoplastic polymers. Vulcanization These terms are used to describe materials characterized by rubber properties, prepared by additive manufacturing (e.g., 3D inkjet printing) rather than by conventional processes involving fermentation. These terms are used to describe materials obtained when the formulations described herein are cured or solidified.

[0072] The term "rubber-like material" is also interchangeably referred to as "elastomer material" in this specification.

[0073] Elastomers or rubbers are flexible materials typically characterized by a low Tg (e.g., below room temperature, preferably below 10°C, below 0°C, and even below -10°C).

[0074] The following describes some of the characteristics of rubbery materials used in this specification and in the art.

[0075] Shore A hardness, also known as Shore hardness or simply hardness, is a Type A durometer scale. It represents the material's resistance to permanent indentations as defined by [the relevant standard]. Shore hardness is usually determined according to ASTM D2240.

[0076] The modulus of elasticity, also known as the elastic modulus, Young's modulus, tensile modulus, or "E," represents a material's resistance to elastic deformation when a force is applied to it; in other words, it describes the tendency of an object to deform along an axis when an opposing force is applied along that axis. The modulus of elasticity is typically measured by a tensile test (e.g., according to ASTM D 624) and determined by the linear gradient of the stress-strain curve in the elastic deformation region, where stress is the force that causes deformation divided by the area over which the force is applied, and strain is the ratio of the change in several length parameters caused by deformation to the original values ​​of the length parameters. Stress is proportional to the tensile force on the material, and strain is proportional to its length.

[0077] Tensile strength represents a material's resistance to tension, i.e., its ability to withstand loads that tend to stretch, and is defined as the maximum stress (MPa) applied during the stretching of an elastomer composite before fracture. Tensile strength is typically measured by a tensile test (e.g., according to ASTM D 624) and determined as the peak of the stress-strain curve, as described herein and in the Art.

[0078] Elongation is the extension of a uniform cross-section of a material, expressed as a percentage of its original length, as follows:

[0079] Final length - Original length Growth % = ---------- × 100 Original length

[0080] Elongation is typically determined according to ASTM D412.

[0081] Z-tensile elongation is the elongation measured as described herein when printed in the Z direction.

[0082] Tear resistance (TR), also referred to herein and in the art as “tear strength,” represents the maximum force required to tear a material, expressed in N / mm or Kg / cm, where the force acts substantially parallel to the long axis of the sample. Tear resistance can be measured by the ASTM D 412 method. Using ASTM D 624, resistance to tear formation (tear initiation) and resistance to tear expansion (tear propagation) can be measured. Typically, the sample is held between two holders and a uniform tensile force is applied until deformation occurs. The tear resistance is then calculated by dividing the applied force by the thickness of the material. Materials with low tear resistance tend to have low abrasion resistance.

[0083] Tear resistance under constant elongation represents the time required for the specimen to tear when subjected to a constant elongation (less than the elongation at break). This value is determined, for example, by the "O-ring" test described in International Publication No. 2017 / 208238.

[0084] Embodiments of the present invention relate to formulations usable for additive manufacturing of three-dimensional (3D) objects or parts thereof made of rubber-like materials, additive manufacturing processes utilizing the same, and objects assembled by these processes.

[0085] Throughout this specification, the term “object” refers to the final product of additive manufacturing. This term also refers to the product obtained by the methods described herein after the removal of supporting material, where supporting material has been used as part of the building material. Therefore, “object” is essentially the same as “object” (at least 95% by weight), hardened (for example, Curing It consists of (the) modeling material.

[0086] As used throughout this specification, the term “object” refers to the entire object or a part thereof.

[0087] An object according to this embodiment is made of a rubber-like material in at least part or in part, and is also referred to herein as an "object made of a rubber-like material." An object may have several parts or parts made of a rubber-like material, or may be made entirely of a rubber-like material. The rubber-like material may be the same or different in different parts or parts, and for each part, part or whole of an object made of a rubber-like material, the rubber-like material may be the same or different within the part, part or object. When different rubber-like materials are used, they may differ in their chemical composition and / or mechanical properties, as will be further described below.

[0088] Throughout this specification, the terms "building material formulations" and "unknown" are used. Curing Building materials, Unfinished Curing The terms "building material formulation," "building material," and other variations collectively describe materials that are distributed to sequentially form layers, as described herein. Curing Materials, i.e., one or more un Curing Modeling material formulation, and undistributed to form a support Curing Materials, that is, un Curing It includes a supporting material formulation.

[0089] Throughout this specification, CuringThe terms "modeling material" or "hardened modeling material" are defined herein as distributed building materials. Curing When exposed to and optionally when support material is distributed, as described herein Curing Even when the supporting material is removed, it still represents the part of the building material that forms the object. Curing The modeling material is a single modeling material formulation used in the method described herein. Curing Materials or two or more Curing It can be a mixture of materials.

[0090] " Curing Modeling material" or Curing The term "modeling material formulation" refers to a building material that consists solely of a modeling material formulation (and not of a support material formulation). Curing It can be considered building material. That is, this phrase refers to a portion of the building material used to provide the final object.

[0091] Throughout this specification, the terms “modeling material formulation,” “model formulation,” “model material formulation,” or simply “formulation,” as interchangeably used herein, refer to a portion or all of the building material that is distributed to form an object as described herein. Modeling material formulations are (unless otherwise specified) unformulated. Curing It is a modeling formulation, Curing When exposed to energy, it forms an object or a part thereof.

[0092] In some embodiments of the present invention, the modeling material formulation is formulated for use in three-dimensional inkjet printing and can form three-dimensional objects on its own, i.e., without the need to mix or combine it with any other material.

[0093] Not yet Curing The building material may include one or more modeling formulations. Curing Sometimes different parts of an object are differentCuring Made from modeling formulations or different combinations thereof, and therefore different Curing Modeling material or Curing It can be distributed so that it is made from different mixtures of modeling materials.

[0094] The formulations that form building materials (modeling material formulations and support material formulations) are, Curing When exposed to energy, it hardens ( Curing ) One or more materials forming Curing Contains material properties.

[0095] The formulations that form building materials (modeling material formulations and support material formulations) are described herein. Curing Compounds (for example, Curing Modeling material formulation or Curing It is also called a (stressing material compound).

[0096] Throughout this specification, Curing "Materials" are as described in this specification. Curing Conditions (for example, Curing When exposed to energy, it solidifies or hardens. Curing These are compounds that form the material (typically monomers or oligomer compounds, and optionally polymer materials). Curing Polymerizable materials are typically polymerizable materials that undergo polymerization and / or crosslinking when exposed to a suitable energy source.

[0097] According to this embodiment Curing The material is, Curing Without being exposed to energy, rather another Curing Without being exposed to conditions (e.g., exposure to chemical reagents, or simply exposure to the environment), it hardens or solidifies. Curing It also includes materials that )

[0098] The term used in this specification Curing The terms "sexuality" and "solidifiable" are interchangeable.

[0099] Polymerization may be, for example, free radical polymerization, cationic polymerization, or anionic polymerization, each of which may involve, for example, radiation, heat, etc., as described herein. Curing It can be induced when exposed to energy.

[0100] In some of the embodiments described herein, Curing The photopolymerizable material is a photopolymerizable material that undergoes polymerization and / or crosslinking upon exposure to radiation, as described herein, and in some embodiments, [[ID=1 The UV material undergoes polymerization and / or crosslinking upon exposure to UV radiation, as described herein. ​ It is a material.

[0101] In some embodiments, as described herein ​ The material is a photopolymerizable material that polymerizes via photo-induced free radical polymerization. Alternatively, ​ The material is a photopolymerizable material that polymerizes via photo-induced cationic polymerization.

[0102] In some of the embodiments described herein, ​ The polymerizable material may be a monomer, oligomer, or short-chain polymer, each being polymerizable and / or crosslinkable as described herein.

[0103] In some of the embodiments described herein, ​ Material ​ When exposed to energy (e.g., radiation), hardening occurs through either chain extension or crosslinking, or a combination thereof. ​ )do.

[0104] In some of the embodiments described herein, ​ The material undergoes a polymerization reaction. ​ A monomer or mixture of monomers that, when exposed to energy, can form a polymer material during a polymerization reaction. ​ The material is a monomer as used in this specification.​ Also called material properties.

[0105] In some of the embodiments described herein, ​ The material undergoes a polymerization reaction. ​ These are oligomers or mixtures of oligomers that, when exposed to energy, can form polymer materials during polymerization reactions. ​ The material is referred to as an oligomer in this specification. ​ Also called material properties.

[0106] In some of the embodiments described herein, ​ The functional material, whether monomer or oligomer, is monofunctional. ​ Functional material or polyfunctional ​ It could be a material.

[0107] Here, monofunctional ​ The material is, ​ It contains one functional group that can undergo polymerization when exposed to energy (e.g., radiation).

[0108] multifunctionality ​ The material is, ​ It contains two or more functional groups, for example, 2, 3, 4 or more, that can undergo polymerization when exposed to energy. Polyfunctional ​ The material is, for example, a difunctional, trifunctional, or tetrafunctional material containing two, three, or four groups, each capable of polymerization. ​ It may be a functional material (also referred to herein as being characterized by a functional value such as 2, 3, or 4). Polyfunctionality ​ Two or more functional groups in a material are typically linked to each other by linking portions as defined herein. When the linking portion is an oligomer or polymer portion, the polyfunctional group is oligomer or polymer polyfunctional. ​ It is a functional material. It is polyfunctional. ​ The material is, ​ When exposed to energy, it can undergo polymerization and / or act as a crosslinking agent.

[0109] The method of this embodiment, as described herein, manufactures a three-dimensional object layer by layer by forming multiple layers with configured patterns corresponding to the shape of the object.

[0110] The final three-dimensional object is a modeling material, or a combination of modeling materials, or a combination of modeling materials and support materials, or a modification thereof (e.g., ​ These are then manufactured. All of these operations are well known to those skilled in the art of free assembly of solids.

[0111] According to one aspect of several embodiments of the present invention, an additive manufacturing method for a three-dimensional object made of the elastomer (rubber-like) material described herein is provided.

[0112] This method is generally achieved or carried out by sequentially forming multiple layers in a configured pattern corresponding to the shape of an object, and as a result, the formation of at least some of the layers or each of the layers is a building material (not) containing one or more modeling material formulations. ​ ) to distribute and the distributed modeling materials ​ Exposure to energy, and as a result, as will be explained in more detail below. ​ This includes forming a modeling material.

[0113] In some exemplary embodiments of the present invention, the object is a building material comprising two or more different modeling material formulations (unspecified). ​ The modeling material formulations are manufactured by distributing ), and each modeling material formulation comes from a different nozzle array of the inkjet printer. The modeling material formulations are optionally, preferably, deposited in layers in the same pass of the print head. The modeling material formulations and / or combinations of formulations within the layers are selected according to the desired properties of the object, which are described in more detail below.

[0114] As used herein and in the art, the term “digital material” describes a combination of two or more materials at a microscopic or voxel level, such that printed zones of a particular material are at the level of several voxels or voxel blocks. Such digital materials may exhibit novel properties influenced by the selection of material types and / or the ratio and relative spatial distribution of the two or more materials.

[0115] In example digital materials, ​ The modeling material for each voxel or voxel block obtained at any given time is ​ Sometimes the modeling material of adjacent voxels or voxel blocks is unrelated, and as a result, each voxel or voxel block can result in a different modeling material, and the new properties of the whole part can be several different at the voxel level. This is the result of the spatial combination of Dell materials.

[0116] Throughout this specification, whenever the expression “at the voxel level” is used in the context of different materials and / or properties, it means including differences between voxel blocks, as well as differences between voxels or groups of several voxels. In preferred embodiments, the properties of an entire part are the result of a spatial combination at the voxel block level of several different model materials.

[0117] ​ Elastomer compound:

[0118] According to one aspect of several embodiments of the present invention, when cured (for example, as defined herein) ​ Energy and other ​ When exposed to certain conditions, it provides an elastomer material as defined herein, as defined herein ​ A compound is provided. Such a compound is described herein. ​ Also called a ferrous elastomer compound. According to some embodiments of the present invention, ​The elastomer formulations can be used as modeling material formulations for additive manufacturing of three-dimensional objects, comprising at least a portion of an elastomer material (rubber-like material) as defined herein.

[0119] According to some embodiments of the present invention, ​ The elastomer compound is characterized by having one or more of the following features when cured.

[0120] Tear resistance of at least 4 kg / cm or at least 4.5 kg / cm, for example, 4 kg / cm to 8 kg / cm, or 4 kg / cm to 7.5 kg / cm, or 4.5 kg / cm to 8 kg / cm, or 4.5 kg / cm to 7.5 kg / cm (including any intermediate values ​​and subranges between them); Tensile strength of at least 2 MPa, or at least 2.5 MPa, for example, 2 MPa to 6 MPa, or 2 MPa to 5 MPa, or 2 MPa to 3 MPa, or 2 MPa to 4 MPa, or 3 MPa to 5 MPa (including any intermediate and partial ranges between them); Break elongation of at least 300%, or at least 350%, for example, 300% to 500%, or 300% to 450%, or 300% to 400%, or 350% to 500%, or 350% to 450%, or 350% to 400% (including any intermediate values ​​and subranges in between); Shore A hardness of at least 30, or at least 40, for example, 30–50, or 30–40, or 35–50, or 40–50, or 35–45 (including any intermediate and partial ranges in between); As described herein, a Tg of 15°C or less, or 10°C or less, or 5°C or less, or 0°C or less (e.g., average Tg), or a Tg at least 10°C, at least 15°C, or at least 20°C lower than the temperature of the AM system being operated.

[0121] According to any of the embodiments described herein, ​ The elastomer compound is characterized by one, two, three, four, or all of the above characteristics.

[0122] According to some embodiments of the present invention, ​ The elastomer compound is characterized as follows: When it hardens, Tear resistance of at least 4 kg / cm or at least 4.5 kg / cm, for example 4 kg / cm to 8 kg / cm, or 4 kg / cm to 7.5 kg / cm, or 4.5 kg / cm to 8 kg / cm, or 4.5 kg / cm to 7.5 kg / cm (including any intermediate values ​​and subranges between them); and At least 300%, or at least 350%, or even more than 400%, for example 300% to 500%, or 300% to 450%, or 300% to 400%, or 35 Elongation at break of 0% to 500%, or 350% to 450%, or 350% to 400% (including any intermediate and partial ranges in between).

[0123] According to some of the embodiments described herein, the elastomer of the embodiment of the present invention ​ The properties of the formulation are further characterized by good printability and stability, as described in the Examples section below, and by providing an object characterized by minimal deformation, curling, and / or volume shrinkage when used in additive manufacturing.

[0124] According to any of the embodiments described herein, ​ The chemical compounds are, ​ Conditions (Electromagnetic ​ When exposed to irradiation as energy, in some embodiments, when exposed to irradiation in the UV-vis range, and in some of these embodiments, when exposed to UV irradiation from an LED source, the cured material exhibits one or more of the above characteristics.

[0125] According to any of the embodiments described herein, ​ The compound is used at temperatures of 40°C or below or 35°C or below. ​ Conditions (Electromagnetic ​When exposed to irradiation (as energy), the material exhibits one or more of the above characteristics upon curing. In some of these embodiments, the irradiation is UV irradiation from an LED source.

[0126] As described herein, ​ In AM systems that use an LED source for irradiation, the ambient temperature is typically low, i.e., around 30°C to 40°C, or 30°C to 35°C. Such relatively low temperatures result in a high temperature difference between the environment and the surface of the distribution layer during the curing process, which can lead to deformation of the formed object, especially when a high degree of covalent crosslinking occurs during exposure to irradiation.

[0127] As described herein, formulations such as those described herein avoid this problem by reducing the degree of covalent crosslinking and replacing at least some of the covalent crosslinks with hydrogen crosslinking, thereby reducing the stress accumulated during curing, and consequently reducing deformation, curling, and / or shrinkage without impairing, or even improving, the mechanical properties of the resulting cured elastomer material. Therefore, formulations described herein can be successfully implemented even when the ambient temperature is relatively low as described herein (for example, when an LED light source is used for irradiation). According to one aspect of several embodiments of the present invention, ​ A ferrous elastomer compound is one or more elastomers as described herein. ​ A material that, upon curing, brings forth hydrogen bond-mediated crosslinking as described herein in any of the embodiments. ​ Contains a material that crosslinks via hydrogen bonds when cured. ​ The material is described herein as a hydrogen bond forming material. ​ Also called material or component E. In some of the embodiments described herein, such ​ The material comprises at least two hydrogen bond-forming groups as described herein.

[0128] According to some embodiments,​ The elastomer material(s) is one or more ​ Monofunctional elastomer materials (plural) (also referred to as component B herein), one or more ​ The material comprises a polyfunctional elastomer material (or multiple polyfunctional elastomer material) (hereinafter also referred to as component C) or a combination thereof.

[0129] According to some embodiments, ​ The elastomer material(s) is one or more ​ Monofunctional elastomer materials (plural) (also referred to as component B herein) and one or more ​ It comprises a polyfunctional elastomer material (plural) (also referred to herein as component C).

[0130] Hydrogen bond formation ​ Material (component E):

[0131] As used herein and as known in the art, a "hydrogen bond" is a non-covalent bond that forms a kind of dipole-dipole attraction when a hydrogen atom bonded to a strongly electronegative atom is present in the vicinity of another electronegative atom along with a lone pair of electrons.

[0132] In a hydrogen bond, the hydrogen atom is partially shared between two relatively electronegative atoms.

[0133] According to any one of the embodiments described herein, crosslinking is brought about via hydrogen bonding. ​ The material contains at least one hydrogen bond-forming group.

[0134] The term "hydrogen bond-forming group," as used herein, refers to a moiety, group, or atom capable of forming hydrogen bonds by being a hydrogen bond donor and / or hydrogen bond acceptor. A particular group may include both a hydrogen bond donor and a hydrogen bond acceptor, and thus may result in or establish a crosslink.

[0135] A hydrogen bond donor, also referred to herein as a hydrogen bond-forming donor, is a group that includes both an atom to which hydrogen is more tightly bonded and the hydrogen atom itself, while a hydrogen bond acceptor, also referred to herein as a hydrogen bond-forming acceptor, is an electronegative atom that can bond to a hydrogen atom of another group. A relatively electronegative atom to which a hydrogen atom is covalently bonded draws electron density away from the hydrogen atom, resulting in a partial positive charge (δ + This generates a partial negative charge (δ). - It can interact with atoms having ) via electrostatic interaction.

[0136] Atoms typically involved in hydrogen bonding interactions as both donors and acceptors include oxygen, nitrogen, and fluorine. These atoms typically form part of chemical groups or moies such as carbonyl, carboxylate, amide, hydroxyl, amine, imine, carbamate, alkyl fluoride, and F2. However, other electronegative atoms and chemical groups or moies containing them can also participate in hydrogen bonding.

[0137] Exemplary hydrogen bond-forming groups include, but are not limited to, amides, carboxylates, hydroxyls, alkoxys, aryloxys, ethers, amines, carbamates, hydrazines, nitrogen-containing heteroalicyclic compounds (e.g., piperidine, oxalidine), nitriles, and oxygen-containing heteroalicyclic compounds (e.g., tetrahydrofuran, morpholine), as well as any other chemical moieties containing one or more nitrogen and / or oxygen atoms.

[0138] According to some of the embodiments described herein, preferred materials are those that can form at least two hydrogen bonds by featuring one or more hydrogen bond-forming groups, for example, two of which are hydrogen donor groups and / or hydrogen acceptor groups.

[0139] In some embodiments, hydrogen bond formation ​The material contains one or more hydrogen bond-forming groups selected from amide groups and carbamate groups, each characterized by a hydrogen donor group (-NH-) and a hydrogen acceptor group or atom (=O).

[0140] According to some of the embodiments described herein, preferred materials are those characterized by at least one hydrogen bond donor group, which is an amine group (for example, an amine that forms part of an amide or carbamate).

[0141] According to some of the embodiments described herein, preferred materials are characterized by at least one hydrogen bond donor group and at least one hydrogen bond acceptor group. This is the case. Preferably, each of the donor group(s) and acceptor group(s) is separated from each other by two or fewer atoms, or one or fewer atoms. Exemplary such hydrogen bond-forming groups are amides that are unsubstituted or substituted with groups that do not contain hydrogen bond-forming groups.

[0142] In some embodiments, hydrogen bond formation ​ The properties of the material are such that the ratio of the number of hydrogen bond-forming groups to their molecular weight is higher than 0.02, for example, 0.025, 0.030, 0.035, or for example, 0.02-0.05, or 0.03-0.05, or 0.04-0.05, or 0.03-0.04.

[0143] In some of the embodiments described herein, hydrogen bond formation ​ The material comprises one or more amide groups, and in some embodiments, it is (meth)acrylamide (including acrylamide and methacrylamide), preferably methacrylamide. Methacrylamide is preferred because of its low reactivity (lower polymerization rate compared to acrylamide).

[0144] (Meth)acrylamide is preferably unsubstituted. If substituted, the substituent is preferably unable to form hydrogen bonds, i.e., does not contain hydrogen bond-forming groups as defined herein.

[0145] According to any one of the embodiments described herein, crosslinking is brought about via hydrogen bonding. ​ The concentration of the property material (component E) is within the range of 1% to 20% by weight of the total weight of the formulation, preferably 1% to 10% by weight, or 1% to 5% by weight, or 1% to 3% by weight, or 1% to 2% by weight, or 1.5% to 2% by weight (including any intermediate and partial ranges between these).

[0146] According to some embodiments, the material, which is (meth)acrylamide, is either unsubstituted or substituted with substituents that cannot form hydrogen bonds (i.e., does not contain hydrogen bond-forming groups), in an amount of 1% to 5%, or 1% to 3%, or 1% to 2%, or 1.5% to 2% of the total weight of the formulation.

[0147] According to some embodiments, the material, which is a (meth)acrylamide substituted with substituents capable of forming hydrogen bonds (i.e., containing hydrogen bond-forming groups), is present in an amount of 5% to 20% or 10% to 20% of the total weight of the formulation.

[0148] Elastomer ​ Properties (components B and C):

[0149] One or more of the modeling material formulations usable by the methods described herein are elastomers. ​ Contains material properties.

[0150] The term "elastomer" ​ "Materials" are, ​ When exposed to energy, it exhibits the properties of elastomers (rubber, or rubber-like materials) described herein and / or known in the art. ​ Materials provided, as defined herein ​ Describe the properties of the material.

[0151] Elastomer ​ The elastic material is typically linked to the portion that imparts elasticity to the polymer and / or crosslinked material, suitable ​ One or more polymerizable materials that undergo polymerization when exposed to energy ( ​ (Includes) groups. Such portions typically include alkyl, alkylene chains, hydrocarbons, alkylene glycol groups or chains (e.g., oligo or poly(alkylene glycol) as defined herein, urethane, oligourethane or polyurethane portions as defined herein, etc. (including any combination of the foregoing), and as defined herein, "elastomer" It is also called the "part".

[0152] Elastomer ​ The materials typically provide a Tg of less than 5°C, or less than 0°C, or less than -5°C, for example, -50°C to 10°C, or -50°C to 0°C, or -50°C to -5°C (including any intermediate and partial ranges in between).

[0153] Elastomer monofunctionality according to several embodiments of the present invention ​ The material can be a vinyl-containing compound represented by formula I: [ka] In the formula, at least one of R1 and R2 is and / or includes an elastomer portion as described herein.

[0154] In formula I, the (=CH2) group represents a polymerizable group, and according to some embodiments, elastomer ​ UV-resistant materials ​ UV-resistant materials ​ It is a sexual component.

[0155] For example, R1 is an elastomer portion as defined herein, or includes an elastomer portion, and R2 is ​The substituents may be, for example, hydrogen, C(1-4)alkyl, C(1-4)alkoxy, or any other substituent, as long as they do not interfere with the elastomeric properties of the material.

[0156] In some embodiments, R1 is a carboxylate and the compound is a monofunctional acrylate monomer. In some of these embodiments, R2 is methyl and the compound is a monofunctional methacrylate monomer. R1 is a carboxylate and R2 is hydrogen or methyl. ​ These materials are collectively referred to as "(meth)acrylates" in this specification.

[0157] In some of these embodiments, the carboxylate group -C(=O)-ORa comprises Ra, which is the elastomer moiety described herein.

[0158] In some embodiments, R1 is an amide, and the compound is a monofunctional acrylamide monomer. In some of these embodiments, R2 is methyl, and the compound is a monofunctional methacrylamide monomer. R1 is an amide and R2 is hydrogen or methyl. ​ The material is collectively referred to as "(meth)acrylamide" in this specification.

[0159] (Meth)acrylates and (meth)acrylamides are collectively referred to as (meth)acrylic materials in this specification.

[0160] In some embodiments, R1 is a cyclic amide, and in some embodiments, it is a cyclic amide such as a lactam, and the compound is a vinyl lactam. In some embodiments, R1 is a cyclic carboxylate such as a lactone, and the compound is a vinyl lactone.

[0161] If one or both of R1 and R2 contain a polymer or oligomer moiety, the monofunctional of formula I. sex ​ The functional compound is a monofunctional polymer or oligomer as an example. ​It is a functional material. Otherwise, it is an exemplary monomer monofunctionality. ​ It is a material.

[0162] In a polyfunctional elastomer material, two or more polymerizable groups are linked to one another via elastomer moieties, as described herein.

[0163] In some embodiments, the polyfunctional elastomer material may be represented by formula I as described herein, where R1 comprises an elastomer material terminated by a polymerizable group as described herein.

[0164] For example, a bifunctional elastomer ​ The properties of a material can be expressed by formula I*: [ka] In the formula, E is an elastomer linkage portion as described herein, and R'2 is as defined herein for R2.

[0165] In another example, trifunctional elastomer ​ The properties of the material can be expressed by formula II: [ka] In the formula, E is an elastomer linkage portion as described herein, and R'2 and R''2 are, independently, as defined herein for R2.

[0166] In some embodiments, polyfunctional (e.g., bifunctional, trifunctional, or more) elastomers are used. ​ The properties of materials can be collectively represented by equation III: [ka] During the ceremony, R2 and R'2 are as defined herein; B is a bifunctional or trifunctional branched unit as defined herein (depending on the properties of X1); X2 and X3 are, independently, absent, an elastomer portion as described herein, or selected from alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane portion, and any combination thereof; and X1 is either absent, or selected from alkyl, hydrocarbon, alkylene chain, cycloalkyl, aryl, alkylene glycol, urethane moiety, and elastomer moiety, each optionally substituted with a meth(acrylate) moiety (OC(=O)CR”2=CH2) (e.g., terminalized), or any combination thereof, or X1 is: [ka] During the ceremony, The curves represent attachment points; B' is a branching unit, which is either the same as B or different from B; X'2 and X'3 are, independently, as defined herein for X2 and X3; and R"2" and R"'2" are as defined herein for R2 and R'2.

[0167] However, at least one of X1, X2, and X3 shall be an elastomer portion as described herein, or shall include such elastomer portion.

[0168] As used herein, the term “branched unit” refers to a multiradical, preferably an aliphatic or alicyclic group. “Multiradical” means that the linking portion has two or more bond points that link two or more atoms and / or groups or parts together.

[0169] In other words, when a branched unit bonds to a single position, group, or atom of a substance, it generates two or more functional groups linked to this single position, group, or atom, and therefore has two or more functional values. This is the chemical part that "branches" into the sensory value mentioned above.

[0170] In some embodiments, the branched unit is derived from a chemical moiety having two, three or more functional groups. In some embodiments, the branched unit is a branched alkyl or branched linkage moiety as described herein.

[0171] A polyfunctional elastomer characterized by four or more polymerizable groups. ​ The material is also intended to be similar to that shown in Formula III, but may be characterized by, for example, a branched unit B having higher branching, or a structure containing an X1 portion characterized by two (meth)acrylate portions as defined herein, or similar to that shown in Formula II, but may be characterized by a structure containing another (meth)acrylate portion bonded to an elastomer portion, for example.

[0172] In some embodiments, the elastomer portion, for example, the portion represented as Ra of formula I or E of formulas I*, II, and III, can be linear or branched and preferably has three or more or four or more carbon atoms; preferably an alkylene chain of three or more or four or more carbon atoms; preferably an alkylene glycol as defined herein, oligo(alkylene glycol) or poly(alkylene glycol) as defined herein (preferably with a length of four or more atoms); preferably a urethane, oligourethane or polyurethane as defined herein (preferably with a length of four or more carbon atoms); and any combination thereof, or comprising them.

[0173] In some of the embodiments described herein, elastomer ​ The material is (meth)acrylic as described herein. ​ The material is a property material, and in some embodiments, it is an acrylate or methacrylate.

[0174] In some of the embodiments described herein, elastomer ​ The material is a monofunctional elastomer. ​ A material that is or contains the same, and in some embodiments, a monofunctional elastomer ​ The material is represented by formula I, where R1 is -C(=O)-ORa, and Ra is urethane, oligourethane, or polyurethane, or contains them.

[0175] In some embodiments, elastomer ​ The material is a polyfunctional elastomer. ​ A material that is or contains the same, and in some embodiments, a polyfunctional elastomer ​ The material is represented by formula I*, where E is urethane, oligourethane, or polyurethane, or contains them.

[0176] In some of the embodiments described herein, elastomer ​ The material is, for example, an acrylate or methacrylate (also referred to as acrylic or methacrylic elastomer) of formula I, I*, II, or III, and in some embodiments, the acrylate or methacrylate is selected such that the polymer material, when cured, is characterized by a Tg of less than 0°C or less than -10°C.

[0177] Exemplary elastomer acrylates and methacrylates ​Examples of suitable materials include, but are not limited to, 2-propenoic acid, 2-[[(butylamino)carbonyl]oxy]ethyl ester (exemplary urethane acrylate), and compounds commercially available under the trade names SR335 (lauryl acrylate) and SR395 (isodecyl acrylate) (manufactured by Sartomer). Other examples include SR350D (trifunctional trimethylolpropane trimethacrylate (TMPTMA)), SR256 (2-(2-ethoxyethoxy)ethyl acrylate), SR252 (polyethylene glycol (600) dimethacrylate), and SR561 (alkoxylated hexanediol diacrylate) (Sartomer). Examples include compounds sold under the brand name (mer) by Mer.

[0178] For example, other acrylic materials are also being considered that feature one or more acrylamide groups instead of one or more acrylate or methacrylate groups, such as those shown in formulas I, I*, II, or III.

[0179] According to any of the embodiments described herein, ​ At least one of the elastomeric materials is capable of forming hydrogen bonds, i.e., is characterized by one or more, preferably more, hydrogen bond-forming groups as defined and described herein. According to exemplary embodiments, hydrogen bonds can be formed. ​ The elastomeric material contains at least one, for example, one to twenty, carbamate groups. Exemplary such materials include urethane, oligourethane, or polyurethane, such as urethane (meth)acrylate.

[0180] According to any one of the embodiments described herein, elastomer ​ At least 50%, or at least 60%, or at least 70%, or at least 80% of the material can form hydrogen bonds as described herein. ​ Contains material properties.

[0181] According to some of any of the embodiments described herein, ​ The thermoplastic multi-functional elastomer material contains multi-functional urethane acrylate (as Component C).

[0182] According to some of any of the embodiments described herein, ​ The thermoplastic mono-functional elastomer material contains mono-functional urethane acrylate (as Component B).

[0183] In some of any of the embodiments described herein, the elastomeric ​ material contains one or more mono-functional elastomeric ​ materials (such as, for example, mono-functional elastomer acrylate as represented by Formula I) and one or more multi-functional (such as, for example, bi-functional) elastomeric ​ materials (such as, for example, bi-functional elastomer acrylate as represented by Formula I*, II or III) in any of the respective embodiments as described herein.

[0184] In some of any of the embodiments described herein, the elastomeric ​ material contains one or more mono-functional urethane (meth)acrylates and one or more multi-functional (such as, for example, bi-functional) urethane (meth)acrylates.

[0185] In some of any of the embodiments described herein, one or more mono-functional urethane (meth)acrylates contain aliphatic mono-functional urethane (meth)acrylates.

[0186] In some of any of the embodiments described herein, one or more multi-functional urethane (meth)acrylates contain aliphatic multi-functional urethane (meth)acrylates.

[0187] In some of any of the embodiments described herein, one or more multi-functional urethane (meth)acrylates contain bi-functional urethane (meth)acrylates.

[0188] In some of any of the embodiments described herein, one or more polyfunctional urethane (meth)acrylates include aliphatic difunctional urethane (meth)acrylate.

[0189] In some of any of the embodiments described herein, the elastomer ​ The total amount of the sex material(s) is the elastomer ​ Of the modeling material formulation(s) containing the sex material Is at least 40% by weight, or at least 50% by weight, or at least 60% by weight of the total weight, and can be up to 70% by weight, or even 80% by weight.

[0190] In some of any of the embodiments described herein, the elastomer ​ The total amount of the sex material(s) is the elastomer ​ Is within the range of 30% to 80% by weight, or 40% to 80% by weight, or 50% to 80% by weight, or 60% to 80% by weight, or 70% to 80% by weight of the total weight of the modeling material formulation(s) containing the sex material (including any intermediate value and sub-range therebetween).

[0191] According to some of any of the embodiments described herein, ​ The concentration of the sex polyfunctional elastomeric material is 20% by weight or less, or 15% by weight or less of the total weight of the formulation.

[0192] According to some of any of the embodiments described herein, ​ The concentration of the sex polyfunctional elastomeric material is within the range of 10% to 20% by weight, or 10% to 15% by weight of the total weight of the formulation (including any intermediate value and sub-range therebetween).

[0193] According to some of any of the embodiments described herein, ​The concentration of the monofunctional elastomer material is within the range of 40% to 70% by weight, or 50% to 70% by weight, or 55% to 65% by weight, or 60% to 70% by weight of the total weight of the compound (including any intermediate and partial ranges between these).

[0194] According to any of the embodiments described herein, ​ Monofunctional elastomer materials and ​ The weight ratio with the polyfunctional elastomer material is within the range of 1:1 to 1:10, or 1:2 to 1:10, or 1:3 to 1:7, or 1:4 to 1:7, or 1:4 to 1:6 (including any intermediate and partial ranges between these).

[0195] additional ​ sexual material

[0196] According to any of the embodiments described herein, ​ The compound is elastomer ​ Properties of materials (components B and C) and hydrogen bond crosslinking ​ In addition to the material (component E), one or more additional ​ It further contains properties.

[0197] additional ​ The material has one or more monofunctional properties. ​ Functional material (also referred to herein as component A) and / or one or more polyfunctional materials ​ It may be a material (also referred to as component D in this specification).

[0198] additional ​ The material is monofunctional. ​ material, multifunctionality ​ The materials may be synthetic materials or mixtures thereof, and each material may be a monomer, oligomer, polymer, or a combination thereof.

[0199] Preferably, but not required, one or more or each additional ​ For example, when exposed to irradiation (e.g., UV-vis irradiation) the material​ The same as the curable elastomeric material is polymerizable ​ It is polymerizable when exposed to energy.

[0200] In some embodiments, the additional ​ curable material is such that when cured, the polymerized material has a Tg higher than the Tg of the elastomeric material, e.g., higher than 0 °C, or higher than 5 °C, or higher than 10 °C. In some embodiments, it has a Tg higher than 50 °C, e.g., 50 °C to 150 °C (including any intermediate value and subrange therebetween).

[0201] Throughout this specification, "Tg" refers to the glass transition temperature defined as the position of the maximum of the E" curve, where E" is the loss modulus of the material as a function of temperature.

[0202] Broadly speaking, when heating in a temperature range including the Tg temperature, the state of the material, particularly a polymeric material, gradually changes from a glassy state to a rubbery state.

[0203] Here, the "Tg range" is the temperature range in which, at the Tg temperature defined above, the E" value is at least half (e.g., up to that value) of its value.

[0204] While not wishing to be bound by any particular theory, it is assumed that the state of the polymer material gradually changes from a glassy state to rubbery within the Tg range defined above. In this specification, the term "Tg" refers to any temperature within the Tg range defined herein.

[0205] In some embodiments, the additional ​ curable material is, for example, a non-elastomeric ​ curable material that, when cured, has a Tg and / or modulus of elasticity different from that representing the elastomeric material.

[0206] According to some of any of the embodiments described herein, ​ the curable formulation is an elastomer​ Properties and hydrogen bond crosslinking ​ In addition to the functional material, one or more additional monofunctional (non-elastomer) properties ​ It further contains properties.

[0207] According to some of the embodiments described herein, additional (non-elastomer) monofunctionality ​ The total concentration of the active ingredient is within the range of 15% to 35% by weight, or 15% to 40% by weight, or 15% to 25% by weight, or 20% to 25% by weight of the total weight of the compound.

[0208] In some embodiments, Additional ​ The material includes monofunctional acrylates or methacrylates ((meth)acrylates). Non-limiting examples include isobornyl acrylate (IBOA), isobornyl methacrylate, acryloylmorpholine (ACMO), phenoxyethyl acrylate, which is commercially available from Sartomer Company (USA) under trade name SR-339, urethane acrylate oligomers such as those commercially available under the name CN 131B, and any other acrylates and methacrylates available for use in AM methodologies. In some embodiments, ​ The non-elastomer monofunctional material (component A) is hydrophobic. ​ It is a material. In some embodiments, ​ The hydrophobic non-elastomer monofunctional material (component A) is characterized by the above Tg. ​ It is a material.

[0209] The term "hydrophobic" as used in this specification ​ The term "quality material" refers to a material characterized by a LogP of greater than 1, preferably higher than 1, when measured for water and octanol.

[0210] According to some of the embodiments described herein, the formulation has additional polyfunctional (non-elastomer) properties, which are also referred to herein as component D. ​ Contains material properties.

[0211] According to some of these embodiments, polyfunctional (non-elastomer) ​ The total concentration of the material is less than 10% by weight, or less than 8% by weight, or less than 5% by weight, or less than 2% by weight of the total weight of the compound, and in some embodiments, it is in the range of 0.1% to 1% by weight of the total weight of the compound.

[0212] According to any one of the embodiments described herein, polyfunctional (non-elastic) Tomer) ​ The material is one or more bifunctional (non-elastomer) components, also referred to herein as component D1. ​ Properties, and / or one or more polyfunctional (non-elastomer) materials with a higher functional value. ​ The material includes, for example, one of the trifunctional or tetrafunctional materials, also referred to herein as component D2.

[0213] According to some of these embodiments, bifunctional (non-elastomer) ​ The total concentration of the functional material (component D1) is 5% by weight or less, 3% by weight or less, or 2% by weight or less of the total weight of the formulation, and may be lower, or even zero, and in some embodiments, it is in the range of 0% to 5% by weight, 0% to 3% by weight, or 0% to 2% by weight of the total weight of the formulation. In some embodiments, the formulation is a bifunctional non-elastomer ​ It lacks the necessary materials.

[0214] According to some of these embodiments, higher polyfunctionality (non-elastomer) ​ The total concentration of the property material (component D2) is within the range of 0.1 to 2 or 0.1 to 1 (by weight) of the total weight of the formulation, including any intermediate and partial ranges within that range.

[0215] According to some of these embodiments, polyfunctional (non-elastomer) ​The material component D2 is an amine-modified (meth)acrylate, such as an amine-modified polyether (meth)acrylate commercially available from Sartomer under the trade name CN550. Preferably, the amine is a tertiary amine. The inventors have found that including a trace amount of such a compound substantially improves the performance of the formulation in AM.

[0216] Example formulations:

[0217] In some of the embodiments described herein, ​ Elastomers in compounding ​ Each of the materials is UV ​ The material is a property material, and in some embodiments, it is an elastomer (meth)acrylate, for example, an elastomer acrylate.

[0218] In some of the embodiments described herein, additional non-elastomers are used in the formulation. ​ Each of the materials is UV ​ It is a acrylate or methacrylate.

[0219] In some of the embodiments described herein, ​ The eluate elastomer formulation comprises one or more monofunctional elastomer acrylates (component B) as described herein, one or more polyfunctional elastomer acrylates (component C) as described herein, methacrylamide (exemplary component E), one or more monofunctional acrylates or methacrylates (component A) as described herein, and one or more polyfunctional acrylates or methacrylates (component D, preferably component D2) as described herein.

[0220] In some of the embodiments described herein, the weight ratio of one or more monofunctional elastomer acrylates (component B) to component E, as described herein, is in the range of 20:1 to 60:1 or 30:1 to 50:1, including any intermediate and partial ranges therein.

[0221] In some of the embodiments described herein, ​ Elastomer compounds are One or more monofunctional elastomer acrylates (component B), preferably monofunctional urethane acrylates, as described herein, in a total concentration ranging from approximately 50% to approximately 70% by weight or 55% to 65% by weight of the total weight of the compound; As described herein, at a total concentration within the range of approximately 10% to 15% by weight of the total weight of the formulation. One or more polyfunctional elastomer acrylates (component C), preferably polyfunctional (e.g., difunctional and / or trifunctional) urethane acrylates; Methacrylamide (as example component E) in a concentration of 1% to 2% by weight, or 1.5% to 2% by weight, of the total weight of the formulation; One or more non-elastomer monofunctional acrylates or methacrylates (component A) as described herein, at a concentration in the range of approximately 15% to approximately 25% by weight of the total weight of the formulation; and The formulation comprises one or more non-elastomer polyfunctional acrylates or methacrylates (component D) as described herein, preferably one or more highly functional (e.g., trifunctional) acrylates or methacrylates (component D2), such as amine-modified trifunctional acrylates or methacrylates, in a total concentration ranging from about 0.1% to 1% by weight of the total weight of the formulation.

[0222] According to any of the embodiments described herein, ​ The ester compound lacks silica particles or contains silica parts in an amount of 3% or less, 2% or less, or 1% or less of the total weight of the compound.

[0223] Non ​ Sex component:

[0224] In some of the embodiments described herein, ​ Elastomer compounds are​ It further contains an initiator for initiating the polymerization of the material.

[0225] all ​ In these embodiments, if the photopolymerizable material (elastomer and additional) is photopolymerizable, a photoinitiator can be used.

[0226] Non-limiting examples of suitable photoinitiators include benzophenones (aromatic ketones) such as benzophenone, methylbenzophenone, Michler ketone, and xanthones; acylphosphine oxide photoinitiators such as 2,4,6-trimethylbenzolydiphenylphosphine oxide (TMPO), 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide (TEPO), and bisacylphosphine oxide (BAPO); and benzoin and benzoin alkyl ethers, such as benzoin, benzoin methyl ether, and benzoin isopropyl ether. Examples of photoinitiators include α-aminoketones, bisacylphosphine oxide (BAPO), and those commercially available under the trade name Irgacure®.

[0227] Photoinitiators can be used alone or in combination with co-initiators. Benzophenone is an example of a photoinitiator that requires a second molecule, such as an amine, to generate a free radical. After absorbing radiation, benzophenone reacts with a ternary amine by hydrogen abstraction to produce an alpha-amino radical that initiates polymerization of the acrylate. Non-limiting examples of the class of co-initiators are alkanolamines such as triethylamine, methyldiethanolamine, and triethanolamine.

[0228] According to some embodiments, the photoinitiator is, for example, from the Irgacure® family.

[0229] The concentration of the photoinitiator in a formulation containing the photoinitiator may be within the range of approximately 0.1% to approximately 5% by weight, or approximately 1% to approximately 3% by weight (including any intermediate and partial ranges between these).

[0230] According to some of the embodiments described herein, the modeling material formulation One or more of the things, one or more additional non ​ The material further comprises one or more properties such as colorants (dyes and / or pigments), dispersants, surfactants, stabilizers, plasticizers, antioxidants, and inhibitors.

[0231] ​ Polymerization and / or before exposure to the conditions ​ The formulation includes inhibitors to prevent or slow down the process. Commonly used inhibitors, such as radical inhibitors, are intended.

[0232] In any of the exemplary modeling material formulations described herein, the concentration of the inhibitor is in the range of 0% to about 2% by weight or 0% to about 1% by weight of the total weight of the formulation or the formulation system containing it, for example, 0% by weight, 0.1% by weight, 0.2% by weight, 0.3% by weight, 0.4% by weight, 0.5% by weight, 0.6% by weight, 0.7% by weight, 0.8% by weight, 0.9% by weight or about 1% by weight (including any intermediate value between them).

[0233] Commonly used surfactants, dispersants, colorants, antioxidants, and stabilizers are intended. The exemplary concentrations of each component, if present, are in the range of about 0.01% to about 1% by weight, or about 0.01% to about 0.5% by weight, or about 0.01% to about 0.1% by weight of the total weight of the formulation containing it.

[0234] The plasticizers intended are those commonly used, preferably slow-evaporating plasticizers (characterized by a low evaporation rate, e.g., less than 1 or less than 0.5 compared to n-butyl acetate as a reference material), such as alkyl ethers of alkylene glycols (e.g., materials such as dipropylene glycol mono-n-butyl ether and dipropylene glycol monomethyl ether). While not bound by any particular theory, it is assumed and demonstrated (data not shown) that such plasticizers favorably affect (i.e., decrease) the Shore hardness of the cured material without adversely affecting other mechanical properties. In some embodiments, the addition of a plasticizer results in a Shore hardness value of 10%, 20%, 25%, or more compared to the same formulation without the plasticizer.

[0235] If present, the plasticizers described herein are present in amounts ranging from about 0.01% to about 5% by weight, or about 0.01% to about 2% by weight, or about 0.01% to about 1% by weight, or about 0.1% to about 5% by weight, or about 0.1% to about 2% by weight, or about 0.1% to about 1% by weight, or about 0.5% to about 5% by weight, or about 0.5% to about 3% by weight, or about 0.5% to about 2% by weight, or 0.5% to about 1.5% by weight of the total weight of the formulation containing them.

[0236] In any of the exemplary modeling material formulations described herein, the concentration of the surfactant is in the range of 0% to about 1% by weight of the total weight of the formulation or the formulation system containing it, for example, 0% by weight, 0.01% by weight, 0.05% by weight, 0.1% by weight, 0.5% by weight, or about 1% by weight (including any intermediate value between them).

[0237] In any of the exemplary modeling material formulations described herein, the concentration of the dispersant is in the range of 0% to about 2% by weight of the total weight of the formulation or the formulation system containing it, for example, 0% by weight, 0.1% by weight, 0.5% by weight, 0.7% by weight, 1% by weight, 1.2% by weight, 1.3% by weight, 1.35% by weight, 1.4% by weight, 1.5% by weight, 1.7% by weight, 1.8% by weight, or about 2% by weight (including any intermediate value between these).

[0238] method:

[0239] According to one aspect of several embodiments of the present invention, a method for additive manufacturing of a three-dimensional object described herein is provided. The method of this embodiment involves using an elastomer material as defined herein. It can be used to manufacture an object that has at least a part of it.

[0240] This method is generally achieved by sequentially forming multiple layers in a configured pattern corresponding to the shape of an object, and as a result, the formation of at least some of the layers or each of the layers is a building material (not) containing one or more modeling material formulations. ​ ) to distribute and the distributed modeling materials ​ Conditions, preferably ​ Exposure to energy (e.g., irradiation), as described below in more detail ​ This includes forming a modeling material.

[0241] In some exemplary embodiments of the present invention, the object is a building material comprising two or more different modeling material formulations, as described below, for example. ​ It is manufactured by distributing ). In some of these embodiments, each modeling material formulation is distributed from different arrays of nozzles belonging to the same or different distribution heads of an inkjet printer, as described herein.

[0242] In some embodiments, two or more arrays of such nozzles dispensing different modeling material formulations are both located on the same print head (i.e., a multi-channel print head) of the AM apparatus. In some embodiments, the arrays of nozzles dispensing different modeling material formulations are located on separate print heads, for example, a first array of nozzles dispensing a first modeling material formulation is located on a first print head, and a second array of nozzles dispensing a second modeling material formulation is located on a second print head.

[0243] In some embodiments, the array of nozzles distributing the modeling material formulation and the array of nozzles distributing the support material formulation are both located on the same print head. In some embodiments, the array of nozzles distributing the modeling material formulation and the array of nozzles distributing the support material formulation are located on separate print heads.

[0244] The modeling material formulations are optionally, preferably, deposited in layers during the same pass of the print head. The modeling material formulations and / or combinations of formulations within the layers are selected according to the desired properties of the object, which are described in further detail below. Such a mode of operation is also referred to herein as “multi-material,” as described herein.

[0245] In any of the embodiments of the present invention, when the layers are distributed as described herein, ​ Conditions (for example, ​ Exposure to energy occurs. In some embodiments, ​ The material is light ​ UV-resistant material, preferably UV ​ It is a material, ​ The conditions are such that the radiation source emits UV radiation.

[0246] In some of the embodiments described herein, the UV irradiation is from an LED source as described herein.

[0247] In some of the embodiments described herein, ​ The conditions include electromagnetic irradiation, and the electromagnetic irradiation is from an LED source.

[0248] In some of the embodiments described herein, ​ The conditions include UV irradiation.

[0249] In some of the embodiments described herein, the UV irradiation dose is, for example, 0.1 J / cm² per layer, as described herein. 2 Higher.

[0250] In some embodiments, the building material also includes a support material compound(s), and this method The next step is to remove the cured support material (for example, by which the adjacent cured modeling material is exposed). This can be done by mechanical and / or chemical means, as will be recognized by those skilled in the art. Optionally, some of the support material may remain in the cured mixture layer upon removal, for example, as described herein.

[0251] In some embodiments, removal of the cured support material reveals a cured mixture layer containing a cured mixture of the support material and the modeling material formulation. Such a cured mixture on the surface of an object optionally has a relatively non-reflective appearance, also referred to herein as “matte.” On the other hand, a surface lacking such a cured mixture (e.g., one on which no support material formulation was applied) is described by comparison as “glossy.”

[0252] In some of the embodiments described herein, the method is ​ If the modeling material is included in the building material, this further includes exposing it to post-treatment conditions either before or after (preferably after) the removal of the support material.

[0253] In any of the embodiments of this aspect of the present invention, for at least some of the distributed layers, the distribution is as described herein in any of the respective embodiments and any combination thereof. ​ It is a compound containing a ferrous elastomer.

[0254] In some of the embodiments described herein, the distribution temperature, i.e., the ambient temperature of the system in which the distribution takes place, is less than 40°C or less than 35°C.

[0255] system:

[0256] A representative and non-limiting example of a system 110 suitable for AM of an object 112 according to some embodiments of the present invention is shown in Figure 1A. The system 110 comprises an additive manufacturing apparatus 114 having a distribution unit 16 having a plurality of print heads. Each head preferably comprises one or more arrays of nozzles 122 typically mounted on an orifice plate 121, as shown in Figures 2A-C below, through which a liquid building material formulation 124 is distributed.

[0257] Preferably, though not required, the apparatus 114 is a three-dimensional printing apparatus, in which case the print head is a print head and the building material formulation is distributed via inkjet technology. This is not necessarily required, as in some applications the additive manufacturing apparatus does not need to use three-dimensional printing technology. Typical examples of additive manufacturing apparatuses intended according to various exemplary embodiments of the present invention include, but are not limited to, molten deposit modeling apparatuses and molten material formulation deposit apparatuses.

[0258] Each print head is supplied via one or more building material formulation reservoirs, which may optionally, preferably, include a temperature control unit (e.g., a temperature sensor and / or heating device) and a material formulation level sensor. To distribute the building material formulation, a voltage signal is applied to the print head to selectively deposit droplets of the material formulation through the print head nozzles, for example, in piezoelectric inkjet printing technology. Another example includes thermal inkjet print heads. These types of heads have a heater element that makes thermal contact with the building material formulation to heat the building material formulation and form bubbles in it when the heater element is activated by a voltage signal. The bubbles generate pressure in the building material formulation, causing droplets of the building material formulation to be released from the nozzles. Piezoelectric and thermal print heads are known to those skilled in the art of solid free assembly. For any type of inkjet print head, the distribution speed of the head depends on the number of nozzles, the type of nozzles, and the applied voltage signal speed (frequency).

[0259] Optionally, the total number of distribution nozzles or nozzle arrays is selected such that half of the distribution nozzles are designated for distributing a support material formulation and the other half are designated for distributing a modeling material formulation, i.e., the number of nozzles spraying the modeling material formulation is the same as the number of nozzles spraying the support material formulation. In a representative example in Figure 1A, four print heads 16a, 16b, 16c, and 16d are shown. Each head 16a, 16b, 16c, and 16d has a nozzle array. In this embodiment, heads 16a and 16b can be designated for modeling material formulations, and heads 16c and 16d can be designated for support material formulations. Thus, head 16a can distribute one modeling material formulation, head 16b can distribute another modeling material formulation, and both heads 16c and 16d can distribute a support material formulation. In another embodiment, heads 16c and 16d may be combined in a single head having, for example, two nozzle arrays for depositing a support material formulation. In further alternative embodiments, any one or more print heads may have two or more nozzle arrays for depositing two or more material formulations, for example, two different modeling material formulations or two nozzle arrays for depositing a modeling material formulation and a support material formulation, each formulation via a different array or number of nozzles.

[0260] However, it should be understood that the number of modeling material formulation print heads (modeling heads) and the number of support material formulation print heads (support heads) may be different, without the intention of limiting the scope of the present invention. Generally, the number of nozzle arrays for distributing the modeling material formulation, the number of nozzle arrays for distributing the support material formulation, and the number of nozzles in each array are selected to provide a predetermined ratio a between the maximum distribution rate of the support material formulation and the maximum distribution rate of the modeling material formulation. The value of the predetermined ratio a is preferably selected such that, in each formed layer, the height of the modeling material formulation is equal to the height of the support material formulation. Typical values ​​of a are about 0.6 to about 1.5.

[0261] Where used throughout this specification, the term "approximately" refers to ±10%.

[0262] For example, when a=1, the overall distribution rate of the support material formulation is generally the same as the overall distribution rate of the modeling material formulation when the entire array of nozzles is operating.

[0263] The apparatus 114 may comprise, for example, 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 can be manufactured as a separate physical unit that can be assembled and disassembled from the group of arrays. In this embodiment, each such array optionally, preferably, comprises its own temperature control unit and material formulation level sensor, and receives individually controlled voltages for its operation.

[0264] The apparatus 114 may further include a solidification device 324 which may include any device configured to emit light, heat, etc., that can harden the deposited material formulation. For example, the solidification device 324 may include one or more radiation sources, which may be, for example, an ultraviolet lamp, a visible lamp, or an infrared lamp, or another electromagnetic radiation source, or an electron beam source, depending on the modeling material formulation used. In some embodiments of the present invention, the solidification device 324 hardens the modeling material formulation ​ Alternatively, it helps to solidify things.

[0265] In addition to the solidification device 324, the apparatus 114 may optionally, preferably, provide solvent evaporation The solidification device includes an additional radiation source 328. The radiation source 328 optionally, preferably, generates infrared radiation. In various exemplary embodiments of the present invention, the solidification device 324 comprises a radiation source that generates ultraviolet radiation, and the radiation source 328 generates infrared radiation.

[0266] In some embodiments of the present invention, the apparatus 114 includes a cooling system 134 such as one or more fans.

[0267] The print head(s) and radiation source are preferably mounted within a frame or block 128 which preferably operates to reciprocate on a tray 360 that serves as a work surface. In some embodiments of the present invention, the radiation source follows the print head to at least partially disperse the material formulation that has just been dispensed by the print head. ​Alternatively, it is mounted within a block to solidify. The tray 360 is positioned horizontally. By common practice, an XYZ Cartesian coordinate system is selected such that the XY plane is parallel to the tray 360. The tray 360 is preferably configured to move vertically (along the Z direction), typically downward. In various exemplary embodiments of the present invention, the apparatus 114 further comprises one or more planaring devices 132, such as a roller 326. The planaring device 326 helps to straighten, planarize, and / or establish the thickness of a newly formed layer before forming a continuous layer on top of it. The planaring device 326 preferably comprises a waste collection device 136 for collecting excess material mixture generated during planaring. The waste collection device 136 may include any mechanism for delivering the material mixture to a waste tank or waste cartridge.

[0268] During use, the print head of unit 16 moves in a scanning direction referred to herein as the X direction, selectively distributing building material formulations in a predetermined configuration as it passes over tray 360. The building material formulations typically include one or more types of support material formulations and one or more types of modeling material formulations. Following the passage of the print head of unit 16, the modeling material formulations (or more) are irradiated by the radiation source 126. ​This continues. In the reverse pass of the head returning to the starting point of the newly deposited layer, additional distribution of building material formulation can be performed according to a predetermined configuration. In the forward and / or reverse pass of the print head, the layers thus formed may be straightened by a planarizing device 326 which preferably follows the path of the forward and / or reverse movement of the print head. As the print head returns to their starting points along the X direction, they can move to another position along the indexing direction, which is referred to herein as the Y direction, and continue building the same layer by reciprocating movement along the X direction. Alternatively, the print head may move in the Y direction between forward and reverse movement, or after two or more forward-reverse movement. A series of scans performed by the print head to complete a single layer is referred herein as a single scan cycle.

[0269] Once a layer is complete, the tray 360 is lowered in the Z direction to a predetermined Z level, depending on the desired thickness of the subsequent layer to be printed. This procedure is repeated to form a layered three-dimensional object 112.

[0270] In another embodiment, the tray 360 may be displaced in the Z direction within the layer between the forward and reverse passage of the print head of unit 16. Such Z displacement is performed to prevent the planarizing device from contacting the surface in one direction and not in the other.

[0271] System 110 optionally preferably includes a building material formulation supply system 330 that includes a building material formulation container or cartridge and supplies a plurality of building material formulations to the assembly apparatus 114.

[0272] The control unit 152 controls the assembly apparatus 114 and optionally, preferably, also controls the supply system 330. The control unit 152 typically includes electronic circuitry configured to perform control operations. The control unit 152 preferably communicates with a data processor 154 that transmits digital data relating to assembly instructions based on computer object data, such as CAD configurations, which are represented on a computer-readable medium in a form such as Standard Tessellation Language (STL) format. Typically, the control unit 152 controls the voltage applied to each print head or each nozzle array and the temperature of the building material formulation in each print head or each nozzle array.

[0273] Once the manufacturing data is loaded into the control unit 152, it can operate without user intervention. In some embodiments, the control unit 152 receives additional input from the operator, for example, using a data processor 154 or using a user interface 116 that communicates with the unit 152. The user interface 116 can be any type known in the art, such as a keyboard or a touchscreen, but is not limited. For example, the control unit 152 may receive, as additional input, one or more types and / or attributes of building material formulations, such as color, characteristic strain and / or transition temperature, viscosity, electrical properties, and magnetic properties, but is not limited. Other attributes and attribute groups are also possible.

[0274] Another representative and non-limiting example of system 10 suitable for AM of objects according to some embodiments of the present invention is shown in Figures 1B to 1D. Figures 1B to 1D show a top view (Figure 1B), a side view (Figure 1C), and an isometric view (Figure 1D) of system 10.

[0275] In this embodiment, the system 10 comprises a tray 12 and a plurality of inkjet print heads 16, each inkjet print head having one or more arrays of nozzles, each having one or more separated nozzles. The material used for three-dimensional printing is supplied to the heads 16 by a building material supply system 42. The tray 12 may have a disc shape or it may be annular. Non-circular shapes are also conceivable, as long as it can be rotated about a vertical axis.

[0276] The tray 12 and head 16 are optionally mounted to allow relative rotational motion between the tray 12 and the head 16. This can be achieved 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 the vertical axis 14 at different rotational speeds (e.g., rotation in opposite directions). Several embodiments of System 10 are described below 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, but it should be understood that this application also intends configurations (ii) and (iii) of System 10. Any embodiment of System 10 described herein can be adapted to be applicable to either configuration (ii) and (iii), and those skilled in the art who are provided with the details described herein will know how to make such adaptations.

[0277] 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 r, the direction parallel to the tray 12 and perpendicular to the radial direction r is referred to as the azimuth direction φ in this specification, and the direction perpendicular to the tray 12 is referred to as the vertical direction z in this specification.

[0278] The radial direction r in system 10 defines the index direction y in system 110, and the azimuth direction φ defines the scanning direction x in system 110. Thus, the radial direction is referred to herein interchangeably with the index direction, and the azimuth direction is referred herein interchangeably with the index direction. This is referred to interchangeably with the scanning direction.

[0279] As used herein, the term “radial position” refers to a position on or above the tray 12 at a specific distance from the axis 14. When used in relation to a print head, the term refers to a position of the head at a specific distance from the axis 14. When used in relation to a point on the tray 12, the term corresponds to any point that belongs to the locus of a point whose radius is a specific distance from the axis 14 and whose center is a circle located on the axis 14.

[0280] As used herein, the term “azimuth position” refers to a position on or above tray 12 that is at a specific azimuth angle with respect to a given reference point. Therefore, a radial position refers to any point that belongs to the locus of a point which is a straight line forming a specific azimuth angle with respect to the reference point.

[0281] As used herein, the term “vertical position” refers to a position on a plane that intersects the vertical axis 14 at a specific point.

[0282] Tray 12 functions as a building platform for three-dimensional printing. The work area on which one or more objects are printed is typically smaller than the total area of ​​tray 12, although it is not necessarily required. In some embodiments of the present invention, the work area is annular. The work area is shown in 26. In some embodiments of the present invention, tray 12 rotates continuously in the same direction throughout the formation of the object, and in some embodiments of the present invention, the tray reverses its direction of rotation at least once (e.g., oscillatingly) during the formation of the object. Tray 12 is optionally, preferably, removable. Removing tray 12 may be 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), with two or more trays designated for different types of objects (e.g., different weights), different operating modes (e.g., different rotation speeds), etc. Replacing tray 12 can be done manually or automatically as necessary. When automatic replacement is used, the system 10 includes a tray replacement device 36 configured to remove the tray 12 from its position below the head 16 and replace it with a replacement tray (not shown). In the representative diagram of Figure 1B, the tray replacement device 36 is shown as a drive 38 having a movable arm 40 configured to pull the tray 12, but other types of tray replacement devices are also possible.

[0283] Exemplary embodiments of the print head 16 are shown in Figures 2A to 2C. These embodiments can be used in any of the AM systems described above, including but not limited to systems 110 and 10.

[0284] Figures 2A and 2B show a print head 16 having one (Figure 2A) and two (Figure 2B) nozzle arrays 22. The nozzles in the arrays are preferably aligned linearly along a straight line. In embodiments in which a particular print head has two or more linear nozzle arrays, the nozzle arrays may optionally, preferably, be parallel to each other. When a print head has two or more arrays of nozzles (for example, Figure 2B), the same building material formulation can be supplied to all arrays of the head, or different building material formulations can be supplied to at least two arrays of the same head.

[0285] When a system similar to system 110 is used, all print heads 16 are optionally, preferably, oriented along the indexing direction with their positions along the scanning direction offset from each other.

[0286] If a system similar to system 10 is used, all print heads 16 are optional Preferably, their azimuth positions are offset from each other and they are oriented radially (parallel to the radial direction). Thus, in these embodiments, the nozzle arrays of different print heads are not parallel to each other, but rather at an angle to each other, and that angle is approximately equal to the azimuth offset between the respective heads. For example, one head can be oriented radially and positioned at azimuth position φ1, and another head can be oriented radially and positioned at azimuth position φ2. In this example, the azimuth offset between the two heads is φ1-φ2, and the angle between the linear nozzle arrays of the two heads is also φ1-φ2.

[0287] In some embodiments, two or more print heads can be assembled into a print head block, in which case the print heads of the block are typically parallel to each other. A block containing several inkjet print heads 16a, 16b, 16c is shown in Figure 2C.

[0288] In some embodiments, the system 10 includes a stabilization structure 30 positioned below the head 16 such that the tray 12 is between the stabilization structure 30 and the head 16. The stabilization structure 30 can help prevent or reduce vibrations of the tray 12 that may occur while the inkjet print head 16 is in operation. In a configuration in which the print head 16 rotates around an axis 14, the stabilization structure 30 also preferably rotates so that the stabilization structure 30 is always directly below the head 16 (having the tray 12 between the head 16 and the tray 12).

[0289] The tray 12 and / or print head 16 are optionally, preferably, configured to move along a vertical direction z parallel to the vertical axis 14 so as to change the vertical distance between the tray 12 and the print head 16. In a configuration where the vertical distance is changed by moving the tray 12 along the vertical direction, it is preferable that the stabilization structure 30 also moves vertically with the tray 12. In a configuration where the vertical distance is changed by the head 16 along the vertical direction, the vertical position of the tray 12 remains fixed, and the stabilization structure 30 is also maintained in a fixed vertical position.

[0290] Vertical motion can be established by the vertical drive 28. Once a layer is completed, the vertical distance between the tray 12 and the head 16 can be increased by a predetermined vertical step, depending on the desired thickness of the subsequent layers to be printed (for example, the tray 12 is lowered relative to the head 16). This procedure is repeated to form a three-dimensional object in layers.

[0291] The operation of the inkjet print head 16, and optionally the operation of one or more other components of the system 10, such as the movement of the tray 12, is controlled by the controller 20. The controller may have an electronic circuit and a non-volatile memory medium readable by the circuit, which stores program instructions that cause the circuit to perform control operations when read by the circuit, as will be described in more detail below.

[0292] The controller 20 can also communicate with the host computer 24, which transmits digital data relating to assembly instructions based on computer object data, in the form of, for example, Standard Tessellation Language (STL) or Stereolithography Contour (SLC) format, Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Exchange Format (DXF), Polygon File Format (PLY), or any other format suitable for computer-aided design (CAD). The object data format is typically 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 a Cartesian coordinate system to a polar coordinate system. The computer 24 optionally, preferably, transmits the assembly instructions with respect to the converted coordinate system. Alternatively, the computer 24 may transmit the assembly instructions with respect to the original coordinate system provided by the computer object data, in which case the coordinate conversion is performed by the circuitry of the controller 20.

[0293] Coordinate transformation enables three-dimensional printing on a rotating tray. In a non-rotating system with a fixed tray and a print head, the print head typically moves back and forth along a straight line above the fixed tray. In such a system, if the head distribution speed is uniform, the print resolution is the same at any point on the tray. In system 10, unlike the non-rotating system, not all nozzles at the head point cover the same distance on the tray 12 simultaneously. Coordinate transformation is performed optionally, preferably, to ensure equal amounts of excess material formulation at different radial positions. Representative examples of coordinate transformations according to some embodiments of the present invention are shown in Figures 3A and 3B, showing three slices of an object (each slice corresponding to an assembly instruction for different layers of the object), where Figure 3A shows the slices in Cartesian coordinates, and Figure 3B shows the same slices after applying the coordinate procedure transformation to each slice.

[0294] Typically, the controller 20 controls the voltage applied to each component of the system 10 based on assembly instructions and stored program instructions, as described below.

[0295] Generally, the controller 20 controls the print head 16 to distribute droplets of a layered building material mixture while the tray 12 is rotating, for example, to print a three-dimensional object onto the tray 12.

[0296] System 10 optionally includes one or more radiation sources 18, which may be, optionally and preferably, depending on the modeling material formulation used, for example, ultraviolet lamps, visible lamps, infrared lamps, other electromagnetic radiation sources, or electron beam sources. The radiation sources may include, but are not limited to, any type of radiation-emitting device, including light-emitting diodes (LEDs), digital photoprocessing (DLP) systems, and resistive lamps. The radiation sources 18 emit radiation from the modeling material formulation. ​ Or it helps in solidification. In various exemplary embodiments of the present invention, the operation of the radiation source 18 is controlled by a controller 20 which can activate and deactivate the radiation source 18 and optionally control the amount of radiation generated by the radiation source 18.

[0297] In some embodiments of the present invention, the system 10 further comprises one or more planaring devices 32 which can be manufactured as rollers or blades. The planaring devices 32 help to straighten a newly formed layer before forming a continuous layer on top of it. In some embodiments, the planaring device 32 has the shape of a conical roller whose axis of symmetry 34 is inclined with respect to the surface of the tray 12 and whose surface is positioned parallel to the surface of the tray. This embodiment is shown in a side view of the system 10 (Figure 1C).

[0298] A conical roller can have the shape of a cone or a frustocone.

[0299] The opening angle of the conical roller is preferably selected such that there exists a constant ratio between the radius of the cone at any position along its axis 34 and the distance between that position and the axis 14. As the roller rotates, any point p on the surface of the roller has a linear velocity proportional to (e.g., the same as) the linear velocity of the tray at the point directly below point p, so this embodiment allows the roller 32 to efficiently flatten the layers. In some embodiments, the roller has a frustoconical shape with height h, radius R1 at its closest distance from the axis 14, and radius R2 at its furthest distance from the axis 14, where the parameters h, R1 and R2 satisfy the relation R1 / R2=(Rh) / h, and R is the furthest distance of the roller from the axis 14 (e.g., R can be the radius of the tray 12).

[0300] The operation of 32 may optionally, preferably, activate and deactivate the planarization device 32. It is controlled by a controller 20, and its position can optionally be controlled along the vertical (parallel to the axis 14) and / or radial (parallel to the tray 12 and positioned toward or away from the axis 14).

[0301] In some embodiments of the present invention, the print head 16 is configured to reciprocate relative to the tray along a radial direction r. These embodiments are useful when the length of the nozzle array 22 of the head 16 is shorter than the radial width of the work area 26 on the tray 12. The radial movement of the head 16 is optionally, preferably, controlled by a controller 20.

[0302] object:

[0303] According to some of the embodiments described herein, a three-dimensional object is provided which is characterized in at least part by a cured elastomer material.

[0304] In some of these embodiments, the cured elastomer material is characterized by one or more of the following features:

[0305] Tear resistance of at least 4 kg / cm or at least 4.5 kg / cm, for example, 4 kg / cm to 8 kg / cm, or 4 kg / cm to 7.5 kg / cm, or 4.5 kg / cm to 8 kg / cm, or 4.5 kg / cm to 7.5 kg / cm (including any intermediate values ​​and subranges between them); Tensile strength of at least 2 MPa, or at least 2.5 MPa, for example, 2 MPa to 6 MPa, or 2 MPa to 5 MPa, or 2 MPa to 3 MPa, or 2 MPa to 4 MPa, or 3 MPa to 5 MPa (including any intermediate and partial ranges between them); Elongation at break of at least 300%, or at least 350%, for example, 300% to 500%, or 300% to 450%, or 300% to 400%, or 350% to 500%, or 350% to 450%, or 350% to 400% (including any intermediate values ​​and subranges in between); and Shore A hardness of at least 30, or at least 40, for example, 30–50, or 30–40, or 35–50, or 40–50, or 35–45 (including any intermediate and partial ranges in between).

[0306] In some embodiments, the object is stable (maintaining its shape, dimensions, and mechanical properties for at least two days, preferably longer, for example, at least one week, one month, or one year).

[0307] During the term of the patent, from this application until it matures, many related ​ It is expected that properties will be developed. ​ Properties and / or ​ The term "elastomer materials" is intended to encompass, a priori, all such new technologies.

[0308] As used herein, the term “approximately” refers to ±10% or ±5%.

[0309] The terms "comprises," "comprising," "includes," "including," and "having," as well as their conjugations, all mean "including but not limited to."

[0310] The term "consisting of" means "including and limited to".

[0311] The phrase "consisting essentially of" means that the composition, method, or structure may include additional components, steps, and / or parts, but only if the additional components, steps, and / or parts do not substantially alter the basic and novel features of the claimed composition, method, or structure.

[0312] As used herein, the singular forms "a," "an," and "the" include plural references unless otherwise explicitly indicated by the context. For example, the terms "a compound" or "at least one compound" may include multiple compounds, including mixtures thereof.

[0313] Throughout this application, various embodiments of the present invention may be presented in range form. It should be understood that the range form description is merely for convenience and brevity and should not be interpreted as an inflexible limitation to the scope of the invention. Therefore, the range description should be considered to specifically disclose all possible subranges and the individual numbers within those ranges. For example, a range description such as 1-6 should be considered to specifically disclose subranges such as 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, and the individual numbers within those ranges, e.g., 1, 2, 3, 4, 5, and 6. This applies regardless of the width of the range.

[0314] Whenever a numerical range is indicated in this specification, it means that any cited number (fraction or integer) within the indicated range is included. The phrases “ranging / ranges between” and “ranging / ranges from…to” between the first and second indicators are used interchangeably in this specification and mean that the first and second indicators, as well as all fractions and integers between them, are included.

[0315] In this specification, the terms “method” and “process” are used interchangeably and refer to modes, means, techniques and procedures for achieving a given task, for example, but not limited to, modes, means, techniques and procedures that are known to those skilled in the art in the fields of chemistry, pharmacology, biology, biochemistry and medicine, or modes, means, techniques and procedures that can be readily developed from modes, means, techniques and procedures known to those skilled in the art.

[0316] Throughout this specification, whenever the phrase “weight percent,” “weight %,” or “% wt.” is used in the context of embodiments of a formulation (e.g., a modeling formulation), each of these terms is used. ​ This refers to a weight percentage of the total weight of the ingredients.

[0317] Throughout this specification, the term "acrylic material" is used to collectively describe materials characterized by one or more acrylate groups, methacrylate groups, acrylamide groups, and / or methacrylamide groups.

[0318] Similarly, the acrylic group is an acrylate group, a methacrylate group, an acrylamide group and / or a methacrylamide group, preferably an acrylate group or a methacrylate group (also referred to herein as a (meth)acrylate group). ​ It is used to collectively describe the properties of a group.

[0319] Throughout this specification, the term "(meth)acrylic" encompasses acrylic and methacrylic materials.

[0320] Throughout this specification, the terms “linking portion” or “linking group” refer to a group that links two or more portions or groups in a compound. Linking portions are typically found in bifunctional or tertiary compounds. It can be considered as a diradical or triradical moiety derived from a potential compound, with two or three atoms of the compound linked to two or three other parts via each of those two or three atoms.

[0321] Exemplary linking portions include hydrocarbon portions or chains optionally interrupted by one or more heteroatoms as defined herein, and / or any of the chemical groups listed below, where defined as linking groups.

[0322] When a chemical group is referred to as a “terminal group” in this specification, it should be interpreted as a substituent bonded to another group via one of its atoms.

[0323] Throughout this specification, the term “hydrocarbon” refers collectively to chemical groups composed primarily of carbon and hydrogen atoms. Hydrocarbons may consist of alkyl, alkene, alkyne, aryl and / or cycloalkyl groups, each of which may be substituted or unsubstituted and may be interrupted by one or more heteroatoms. The number of carbon atoms may be in the range of 2 to 30, preferably lower, for example, 1 to 10, or 1 to 6, or 1 to 4. Hydrocarbons may be linking groups or terminal groups.

[0324] Bisphenol A is an example of a hydrocarbon composed of two aryl groups and one alkyl group. Dimethylenecyclohexane is an example of a hydrocarbon composed of two alkyl groups and one cycloalkyl group.

[0325] As used herein, the term "amine" refers to both the -NR'R” group and the -NR'- group, where R' and R” are independently hydrogen, alkyl, cycloalkyl, and aryl, respectively, and these terms are defined below.

[0326] Therefore, the amine group may be a primary amine in which both R' and R'' are hydrogen, a secondary amine in which R' is hydrogen and R'' is alkyl, cycloalkyl, or aryl, or a tertiary amine in which each of R' and R'' is independently alkyl, cycloalkyl, or aryl.

[0327] Alternatively, R' and R'' may 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-amide, N-amide, guanyl, guanidine, and hydrazine.

[0328] The term "amine" is used herein to describe the -NR'R” group if the amine is a terminal group as defined below herein, and is used herein to describe the -NR'- group if the amine is a linking group, a linking moiety, or part thereof.

[0329] The term "alkyl" refers to saturated aliphatic hydrocarbons containing linear and branched groups. Preferably, alkyl groups have 1 to 30 or 1 to 20 carbon atoms. Numerical range; for example, whenever "1 to 20" is used herein, it means that the group (in this case, alkyl group) may contain 20 or fewer carbon atoms, such as 1 carbon atom, 2 carbon atoms, 3 carbon atoms, etc. Alkyl groups may be substituted or unsubstituted. A substituted alkyl group may have one or more substituents, each substituent being These can be, independently, 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.

[0330] An alkyl group may be a terminal group to which this term is bonded to a single adjacent atom as defined herein above, or a linking group which links two or more parts via at least two carbon atoms in its chain as defined herein above. When alkyl is a linking group, it is also referred herein to as an "alkylene" or "alkylene chain".

[0331] Alkenes and alkynes as used herein are alkyl groups as defined herein, each containing one or more double or triple bonds.

[0332] The term "cycloalkyl" refers to a monocyclic or fused ring (i.e., a ring sharing adjacent pairs of carbon atoms) group that does not have a fully conjugated π-electron system of one or more rings. Examples include, but are not limited to, cyclohexane, adamantine, norbornyl, and isobornyl. Cycloalkyl groups may or may not be substituted. A substituted cycloalkyl group may have one or more substituents, each substituent independently of, for example, a 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 may be a terminal group to which this phrase is bonded to a single adjacent atom as defined above herein, or a linking group that links two or more parts at two or more positions as defined above herein.

[0333] The term "heteroalicyclic" refers to a monocyclic or fused ring group that contains one or more atoms, such as nitrogen, oxygen, and sulfur, within the ring. The ring may also contain one or more double bonds. However, the ring does not have a fully conjugated π-electron system. Typical examples include piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino, and oxalidine.

[0334] Heteroalicyclic groups may or may not be substituted. A substituted heteroalicyclic group may have one or more substituents, each substituent independently of, for example, a 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. A heteroalicyclic group may be a terminal group to which this phrase is bonded to a single adjacent atom as defined above herein, or a linking group to which two or more parts are linked at two or more positions as defined above herein.

[0335] The term "aryl" refers to a monocyclic or polycyclic (i.e., a ring sharing adjacent pairs of carbon atoms) all-carbon group having a fully conjugated π-electron system. The aryl group may or may not be substituted. A substituted aryl may have one or more substituents, each substituent independently of, for example, a 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. An aryl group may be a terminal group bonded to a single adjacent atom as defined above herein, or a linking group that links two or more parts at two or more positions as defined above herein.

[0336] The term "heteroaryl" refers to a monocyclic or fused ring (i.e., a ring sharing adjacent pairs of atoms) group that contains one or more atoms such as nitrogen, oxygen, and sulfur within the ring and has a fully conjugated π-electron system. Examples of heteroaryl groups include, but are not limited to, pyrrole, furan, thiophene, imidazole, oxazole, thiazole, pyrazole, pyridine, pyrimidine, quinoline, isoquinoline, and purine. Heteroaryl groups may or may not be substituted. A substituted heteroaryl group may have one or more substituents, each substituent independently of, for example, a 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. A heteroaryl group may be a terminal group bonded to a single adjacent atom as defined above herein, or a linking group linking two or more parts at two or more positions as defined above herein. Typical examples include pyridine, pyrrole, oxazole, indole, and purine.

[0337] The terms "halogen" and "halo" refer to fluorine, chlorine, bromine, or iodine.

[0338] The term "haloalkyl" refers to an alkyl group as defined above, further substituted with one or more halides.

[0339] The term "sulfate" refers to an -OS(=O)2-OR terminal group as defined above herein, or an -OS(=O)2-O-linked group as defined above herein, where R' is as defined above.

[0340] The term "thiosulfate" refers to an -OS(=S)(=O)-OR' terminal group or an -OS(=S)(=O)-O- linking group, these terms are defined herein as above, and R' is as defined herein as above.

[0341] The term "sulfite" refers to an -OS(=O)-O-R' terminal group or an -OS(=O)-O- group linking group, these terms are defined herein as above, and R' is as defined herein as above.

[0342] The term "thiosulfite" refers to the --OS(=S)-O-R' terminal group or -O- R' represents an S(=S)-O- group linking group, and these terms are defined herein as above, and R' is as defined herein as above.

[0343] The term "sulfinate" refers to an -S(=O)-OR' terminal group or an -S(=O)-O- group linking group, these terms are defined herein as above, and R' is as defined herein as above.

[0344] The terms "sulfoxide" or "sulfinyl" represent an -S(=O)R' terminal group or an -S(=O)- linking group, which are defined herein as above, and R' is as defined herein as above.

[0345] The term "phosphonate" refers to an -S(=O)2-R' terminal group or -S(=O)2-linking group, which are defined herein as above, and R' is as defined herein.

[0346] The term "S-sulfonamide" refers to the -S(=O)2-NR'R” terminal group or -S(=O)2-NR'- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0347] The term "N-sulfonamide" refers to an R'S(=O)2-NR''-terminal group or -S(=O)2-NR'-linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0348] The term "disulfide" refers to an -S-SR' terminal group or an -SS- linking group, which are defined herein as above, and R' is as defined herein.

[0349] The term "phosphonate" refers to a -P(=O)(OR')(OR) terminal group or -P(=O)(OR')(O)- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0350] The term "thiophosphonate" refers to a -P(=S)(OR')(OR) terminal group or -P(=S)(OR')(O)- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0351] The term "phosphenyl" refers to the -PR'R" terminal group or -PR'- linking group, which are defined herein as above, and R' and R'' are as defined herein as above.

[0352] The term "phosphine oxide" refers to a -P(=O)(R')(R) terminal group or -P(=O)(R')- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0353] The term "phosphine sulfide" refers to a -P(S)(R')(R) terminal group or -P(=S)(R')- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0354] The term "phosphite" refers to an -O-PR'(=O)(OR) terminal group or an -O-PH(=O)(O)- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0355] As used herein, the terms “carbonyl” or “carbonate” refer to a -C(=O)-R' terminal group or -C(=O)-linking group, which are defined herein as above, and R' is as defined herein.

[0356] As used herein, the term “thiocarbonyl” refers to a -C(=S)-R' terminal group or -C(=S)-linking group, which are defined herein as above, and R' is as defined herein.

[0357] As used herein, the term "oxo" refers to an (=O) group, in which the oxygen atom is double-bonded to an atom (e.g., a carbon atom) at the indicated position.

[0358] As used herein, the term "thiooxo" refers to a (=S) group, where the sulfur atom is double-bonded to an atom (e.g., a carbon atom) at the indicated position.

[0359] The term "oxime" refers to an =N-OH terminal group or an =NO- linking group, and these terms are defined herein as above.

[0360] The term "hydroxyl" refers to the -OH group.

[0361] The term "alkoxy" refers to both -O-alkyl and -O-cycloalkyl groups as defined herein. The term "alkoxide" refers to -R'O - It represents the base, and R' is as defined herein.

[0362] The term "aryloxy" refers to both -O-aryl groups and -O-heteroaryl groups as defined herein.

[0363] The terms "thiohydroxy" or "thiol" represent the -SH group. The term "thiolate" represents the -S group. - It represents the base.

[0364] The term "thioalkoxy" refers to both -S-alkyl groups and -S-cycloalkyl groups as defined herein.

[0365] The term "thioaryloxy" refers to both the -S-aryl group and the -S-heteroaryl group as defined herein.

[0366] "Hydroxyalkyl" is also referred to herein as "alcohol" and represents an alkyl group as defined herein that is substituted with a hydroxyl group.

[0367] The term "cyano" represents a -C≡N group.

[0368] The term "isocyanate" represents the -N=C=O group.

[0369] The term "isothiocyanate" represents the -N=C=S group.

[0370] The term "nitro" refers to the -NO2 group.

[0371] The term "acyl halogen" represents the -(C=O)R'' group, where R'' is a halogen as defined above.

[0372] The terms "azo" or "diazo" refer to the -N=NR' terminal group or -N=N- linking group. These terms are defined above in this specification, and R' is as defined above in this specification.

[0373] The term "peroxo" refers to an -O-OR' terminal group or an -OO- linking group, these terms as defined herein above, and R' as defined herein above.

[0374] As used herein, the term "carboxylate" includes C-carboxylates and O-carboxylates.

[0375] The term "C-carboxylate" refers to a -C(=O)-OR' terminal group or -C(=O)-O-linking group, these terms are defined herein as above, and R' is as defined herein.

[0376] The term "O-carboxylate" refers to an -OC(=O)-R' terminal group or -OC(=O)- linking group, as defined herein above, where R' is as defined herein.

[0377] Carboxylates can be linear or cyclic. When cyclic, in C-carboxylates, R' and a carbon atom are linked together to form a ring, which is also called a lactone. Alternatively, in O-carboxylates, R' and O are linked together to form a ring. Cyclic carboxylates can function as linking groups, for example, if atoms within the formed ring are linked to another group.

[0378] As used herein, the term "thiocarboxylate" encompasses C-thiocarboxylate and O-thiocarboxylate.

[0379] The term "C-thiocarboxylate" refers to a -C(=S)-OR' terminal group or -C(=S)-O-linking group, these terms as defined herein above, and R' as defined herein.

[0380] The term "thio-O-carboxylate" refers to an -OC(=S)-R' terminal group or -OC(=S)-linking group, which are defined herein as above, and R' is as defined herein.

[0381] Thiocarboxylates can be linear or cyclic. When cyclic, in C-thiocarboxylates, R' and a carbon atom are linked together to form a ring, which is also called a thiolactone. Alternatively, in O-thiocarboxylates, R' and O are linked together to form a ring. Cyclic thiocarboxylates can function as linking groups, for example, if atoms within the formed ring are linked to another group.

[0382] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0383] The term "N-carbamate" refers to the R''OC(=O)-NR'-terminal group or -OC(=O)-NR'-linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0384] The term "O-carbamate" refers to the -OC(=O)-NR'R” terminal group or -OC(=O)-NR'- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0385] Carbamates can be linear or cyclic. When cyclic, R' and carbon atoms are linked together to form a ring in O-carbamates, or R' and O are linked together to form a ring in N-carbamates. Cyclic carbamates can function as linking groups, for example, if atoms within the formed ring are linked to another group.

[0386] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0387] As used herein, the term "thiocarbamate" includes N-thiocarbamates and O-thiocarbamates.

[0388] The term "O-thiocarbamate" refers to the -OC(=S)-NR'R” terminal group or -OC(=S)-NR'- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0389] The term "N-thiocarbamate" refers to an R''OC(=S)NR'-terminal group or -OC(=S)NR'-linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0390] Thiocarbamates may be linear or cyclic, as described herein for carbamates.

[0391] As used herein, the term "dithiocarbamate" includes S-dithiocarbamates and N-dithiocarbamates.

[0392] The term "S-dithiocarbamate" refers to the -SC(=S)-NR'R” terminal group or -SC(=S)NR'- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0393] The term "N-dithiocarbamate" refers to an R''SC(=S)NR'-terminal group or -SC(=S)NR'-linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0394] The term "urea," also referred to herein as "ureid," represents the -NR'C(=O)-NR"R"' terminal group or the -NR'C(=O)-NR"- linking group, which are defined herein as above, wherein the formulas, R' and R'' are as defined herein, and R''' is as defined herein for R' and R''.

[0395] The term "thiourea," also referred to herein as "thioureide," represents a -NR'-C(=S)-NR"R"' terminal group or an -NR'-C(=S)-NR"- linking group, where R', R" and R"' are as defined herein.

[0396] As used herein, the term "amide" encompasses C-amides and N-amides.

[0397] The term "C-amide" refers to a -C(=O)-NR'R” terminal group or -C(=O)-NR'- linking group, which are defined herein as above, and R' and R'' are as defined herein.

[0398] The term "N-amide" refers to an R'C(=O)-NR”-terminal group or an R'C(=O)-N-linking group, which are defined herein as above, and R' and R” are as defined herein.

[0399] Amides can be linear or cyclic. When cyclic, in C-amides, R' and a carbon atom are linked together to form a ring, which is also called a lactam. Cyclic amides can function as linking groups, for example, if atoms within the formed ring are linked to another group.

[0400] The term "guanyle" refers to an R'R”NC(=N)-terminal group or an -R'NC(=N)-linking group, which are defined herein as above, and R' and R” are as defined herein.

[0401] The term "guanidine" refers to the -R'NC(=N)-NR"R"' terminal group or the -R'NC(=N)-NR"- linking group, which are defined herein as above, and R', R" and R"' are as defined herein.

[0402] The term "hydrazine" refers to the -NR'-NR”R”' terminal group or the -NR'-NR”- linking group, which are defined herein as above, and R', R” and R”' are as defined herein.

[0403] As used herein, the term “hydrazide” refers to a -C(=O)-NR'-NR”R”' terminal group or a -C(=O)-NR'-NR”- linking group, which are defined herein as above, and R', R” and R”' are as defined herein.

[0404] As used herein, the term “thiohydrazide” refers to a -C(=S)-NR'-NR”R”' terminal group or a -C(=S)-NR'-NR”- linking group, which are defined herein as above, and R', R” and R”' are as defined herein.

[0405] The term "cyanurate" is [ka] terminal group or [ka] These represent linking groups, where R' and R'' are as defined herein.

[0406] The term "isocyanurate" refers to [Chem.] a terminal group or [Chem.] a linking group, where R’ and R” are as defined herein.

[0407] The term "thiocyanurate" refers to [Chem.] a terminal group or [Chem.] a linking group, where R’ and R’’ are as defined herein.

[0408] As used herein, the term "alkylene glycol" refers to -O-[(CR’R”) z -O] y -R’’’ terminal group or -O-[(CR’R”)<00,00008>-O] y - a linking group, where R’, R” and R’’’ are as defined herein, z is an integer from 1 to 10, preferably an integer from 2 to 6, more preferably 2 or 3, and y is an integer greater than or equal to 1. Preferably, both R’ and R” are hydrogen. When z is 2 and y is 1, this group is ethylene glycol. When z is 3 and y is 1, this group is propylene glycol. When y is from 2 to 4, the alkylene glycol is referred to herein as oligo(alkylene glycol).

[0409] In this specification, “ethoxylated” material refers to an acrylic or methacrylic compound comprising one or more alkylene glycol groups, or preferably one or more alkylene glycol chains, as defined herein. Ethoxylated (meth)acrylate materials may be monofunctional, or preferably polyfunctional, i.e., difunctional, trifunctional, tetrafunctional, etc.

[0410] In polyfunctional materials, typically, each (meth)acrylate group is linked to an alkylene glycol group or chain, and these alkylene glycol groups or chains are linked to each other via branched units such as branched alkyl, cycloalkyl, or aryl (e.g., bisphenol A).

[0411] In some embodiments, the ethoxylated material contains 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 linked together to form alkylene glycol chains. For example, an ethoxylated material containing 30 ethoxylated groups may contain chains of 30 linked alkylene glycol groups, each consisting of, for example, two chains of 15 linked alkylene glycol moieties, two chains linked together via branched portions, or each consisting of, for example, three chains of 10 linked alkylene glycol groups, the three chains linked together via branched portions. Shorter and longer chains are also possible.

[0412] The ethoxylated material may contain one, two, or more alkylene glycol chains of any length.

[0413] As used herein, the term “branched unit” refers to a multiradical, preferably an aliphatic or alicyclic group. “Multiradical” means that the unit has two or more bonds that link two or more atoms and / or groups or parts together.

[0414] In some embodiments, the branched unit is derived from a chemical moiety having two, three or more functional groups. In some embodiments, the branched unit is a branched alkyl or cycloalkyl (alicyclic) or aryl (e.g., phenyl) as defined herein.

[0415] For clarity, certain features of the Invention described in the context of separate embodiments may be provided in combination in a single embodiment. Conversely, various features of the Invention described in the context of a single embodiment for brevity may also be provided separately, in any suitable partial combination, or as appropriate in any other described embodiment of the Invention. Certain features described in the context of different embodiments should not be considered essential features of those embodiments unless the embodiments are unable to function without those elements.

[0416] The various embodiments and aspects of the present invention described above and claimed in the following claims section will find experimental support in the following examples. [Examples]

[0417] Herein, along with the above description, we refer to the following examples which non-limitingly illustrate some embodiments of the present invention.

[0418] Experimental method

[0419] Shore A hardness was determined according to ASTM D2240.

[0420] The elastic modulus was determined from the strength-strain curve in accordance with ASTM D412.

[0421] Tensile strength is determined according to ASTM D412 and expressed in MPa units.

[0422] The elongation at break is determined according to ASTM D412 and expressed as a percentage.

[0423] Tear resistance (TR) is determined according to ASTM D624 and expressed in kg / cm.

[0424] Printability, in terms of viscosity, reactivity, ejection, etc., depends on the 3D inkjet system (e.g., those shown in Figures 1B to 1BD; and / or ​ This was determined by testing the compatibility of the formulation with a system equipped with an LED energy source.

[0425] Adhesion / tackiness was determined by visual inspection of adhesion to system components (e.g., receiving trays, rollers, etc.).

[0426] Stability was determined by measuring one or more of the above mechanical properties one, two, three days, or beyond after printing. A change of less than 20% or less than 10% in mechanical properties indicates good stability, while a higher change indicates poor stability.

[0427] Curling and deformation were visually confirmed (see, for example, Figures 7A and 7B).

[0428] Unless otherwise specified, all components were prepared by mixing them at room temperature. Powdered components such as photoinitiators were dissolved at 85°C for 30 minutes.

[0429] result

[0430] The present inventors have found that silica particles, preferably, can be added to elastomer formulations usable in additive manufacturing such as 3D inkjet printing. ​ We previously discovered that the properties of the resulting cured rubber-like material are improved by introducing silica particles functionalized with property groups. Such formulations are described, for example, in International Publication No. 2017 / 208238 and are commercially available under the trade names of the "Agilus" family.

[0431] Such formulations actually provide a curing material characterized by high elongation along with relatively high tear resistance, but the inventors have found that the polyfunctionality present in the formulation​ We have discovered that advanced covalent crosslinking resulting from functionalized silica particles combined with a material can lead to deformation, high curling, and / or volume shrinkage of the resulting three-dimensional object under specific printing conditions. We have further discovered that such formulations, when used in systems such as those shown in Figures 1B-1D, provide materials with inferior properties (LEDs). ​ (It is used as an energy source and features a lower printing temperature compared to other systems.)

[0432] In the search for formulations that provide a rubber-like material when cured, the inventors can engage in "physical crosslinking," that is, they can form crosslinks through hydrogen bond formation. ​ While the idea of ​​using a physical material was conceived, it was considered that such "physical" crosslinking, in contrast to covalent crosslinking, would result in improved elongation and improved tear resistance while minimizing, or even eliminating, deformation, curling, and / or volume shrinkage.

[0433] The present inventors have found that multiple hydrogen bonds can be formed in materials such as methacrylamide, although this is not limited to these materials. ​ We have discovered that by using the property material in combination with an elastomer material that can participate in hydrogen bond formation, as described in more detail herein, we can provide a rubber-like material that exhibits improved performance upon curing, and that a formulation suitable for use in a system equipped with an LED irradiation source as shown in Figures 1B to 1D can be obtained.

[0434] Table 1A below shows the components of an exemplary reference elastomer formulation. Reference 1 refers to a formulation of the Agilus family, and in this specification refers to Agilus silica or Agilus S Also known as i, as described, for example, in International Publication No. 2017 / 208238, reference 2 refers to formulations of the Tango family. Table 1B shows the components of various formulations tested in the search for improved formulations.

[0435] Component A is one or more of the components described herein. ​ It is a non-elastomer monofunctional material;

[0436] Component B is one or more elastomer monofunctional materials as described herein;

[0437] Component C is one or more of the components described herein. ​ The material is a polyfunctional elastomer, preferably a bifunctional material.

[0438] Component D is one or more ​ These are non-elastomer, bifunctional materials; D1 refers to such bifunctional materials, while D2 refers to materials with three or more functionalities.

[0439] Component E is one or more components capable of forming hydrogen bonds as described herein. ​ It is a material.

[0440] Component F represents silica particles containing the functionalized silica particles described herein.

[0441] [Table 1]

[0442] [Table 2]

[0443] Table 2 shows the reference formulations. ​ Using a 3D inkjet printing system like the one shown in Figure 1A, equipped with a mercury lamp as an energy source, the exemplary tested elastomer formulations ​ The mechanical properties of objects printed using a J55 inkjet printing system (Stratasys, Ltd., Israel), as shown in Figures 1B to 1D, which is equipped with an LED as an energy source, are shown.

[0444] [Table 3]

[0445] *When Reference Formulation 1 was printed on the same system as the example formulation tested, the printability and tackiness were poor (failed).

[0446] *Objects made from the Reference 1 formulation are characterized by substantial curling and deformation, which are negligible in the exemplary formulation according to this embodiment.

[0447] Figures 7A and 7B show exemplary photographs illustrating the deformation and curling observed in an object made from the reference elastomer formulation (left object) and their absence in an object made from the exemplary elastomer formulation according to this embodiment (right object).

[0448] As can be seen from Table 2 and other data obtained, the formulation according to this embodiment is characterized by improved elongation and tear resistance compared to the reference formulation. Formulations lacking component E were unsuitable. Formulations containing component D at concentrations higher than 5% were inferior, and the same was observed for formulations lacking component D2.

[0449] These data indicate that the best performance in terms of both the mechanical properties of the resulting object and its compatibility with 3D inkjet systems is achieved with formulations containing the following components. A-15-20% B-55-65% C-10-15% D1-0-5% D2-1-2% E-1.5-2% F-<1%

[0450] While the present invention has been described in conjunction with its specific embodiments, it will be apparent that many alternatives, modifications, and variations are obvious to those skilled in the art. Therefore, it is intended to encompass all such alternatives, modifications, and variations that fall within the spirit and broad scope of the appended claims.

[0451] It is the applicant's(s) intention that all publications, patents, and patent applications referenced herein are incorporated herein by reference in their entirety, as if each individual publication, patent, or patent application were specifically and individually referenced when it is mentioned that they are incorporated herein by reference. Furthermore, any citation or specification of any reference in this application should not be construed as an acknowledgment that such reference is available as prior art of the present invention. Section headings, to the extent that they are used, should not necessarily be construed as restrictive. Furthermore, any priority document(s) of this application are incorporated herein by reference in their entirety.

Claims

1. A curable compound that provides an elastomer material when cured, A curable monofunctional elastomer material comprising 50% to 70% by weight of the total weight of the compound, which is a urethane (meth)acrylate capable of forming hydrogen bonds, A curable polyfunctional elastomer material comprising 10% to 20% by weight of the total weight of the aforementioned compound, which is a urethane (meth)acrylate capable of forming hydrogen bonds, A total amount of a curable polyfunctional non-elastomer material in an amount of 5% by weight or less of the total weight of the aforementioned compound, A curable material comprising at least two hydrogen bond-forming groups in an amount of 1% to 20% by weight of the total weight of the aforementioned compound, wherein the at least two hydrogen bond-forming groups are (meth)acrylamide separated from each other by two or fewer atoms, and Includes, Each of the curable materials is a (meth)acrylic material. Curable formulation.

2. The curable compound according to claim 1, wherein the at least two hydrogen bond-forming groups include at least one hydrogen bond-donating group and at least one hydrogen bond-accepting group.

3. The curable compound according to claim 1, wherein the ratio of the number of at least two hydrogen bond-forming groups to the molecular weight of the material containing the hydrogen bond-forming groups is higher than 0.

01.

4. The curable compound according to claim 1, wherein the curable material containing at least two hydrogen bond-forming groups is methacrylamide.

5. The curable compound according to claim 1, wherein the concentration of the curable material containing at least two hydrogen bond-forming groups is within the range of 1% to 10% by weight of the total weight of the compound.

6. The curable compound according to claim 1, wherein at least 50% of the curable material comprises a urethane (meth)acrylate capable of forming hydrogen bonds.

7. The curable compound according to claim 1, wherein the curable polyfunctional elastomer material, urethane (meth)acrylate, comprises polyfunctional urethane acrylate.

8. The curable compound according to claim 1, wherein the curable monofunctional elastomer material, urethane (meth)acrylate, comprises monofunctional urethane acrylate.

9. The curable compound according to claim 1, wherein the weight ratio of the curable monofunctional elastomer material, urethane (meth)acrylate, to the curable material containing at least two hydrogen bond-forming groups is in the range of 20:1 to 60:

1.

10. The curable compound according to claim 1, further comprising a monofunctional non-elastomer curable material.

11. The curable compound according to claim 10, wherein the concentration of the further monofunctional non-elastomer curable material is in the range of 15% to 25% by weight of the total weight of the compound.

12. The curable compound according to claim 1, wherein the curable polyfunctional non-elastomer material contains a tertiary amine group.

13. The curable compound according to claim 1, wherein the curable polyfunctional non-elastomer material includes a material characterized by a functional value higher than 2.

14. The curable compound according to claim 13, wherein the concentration of the curable polyfunctional non-elastomer material is within the range of 0.1% to 2% by weight of the total weight of the compound.

15. The curable compound according to claim 1, further comprising at least one material selected from surfactants, dispersants, fillers, dyes, pigments, inhibitors, and antioxidants.

16. The curable compound according to claim 1, characterized by a tear resistance of at least 4 kg / cm when cured.

17. The curable compound according to claim 1, characterized by a tensile strength of at least 2 MPa when cured.

18. The invention, characterized by at least 300% elongation at break when cured, according to claim 1. The curable compound as described.

19. The curable compound according to claim 1, characterized by a Shore A hardness of at least 30 when cured.

20. The curable compound according to claim 1, characterized by an average Tg of 15°C or lower when cured.

21. A curable compound according to any one of claims 1 to 20, which can be used as a modeling material compound in additive manufacturing of three-dimensional objects, comprising at least a portion thereof an elastomer material.

22. A method for manufacturing a three-dimensional object that contains an elastomer material in at least part thereof, comprising forming the object by sequentially forming multiple layers in a configured pattern corresponding to the shape of the object, Each of the formations of at least some of the layers includes distributing a modeling material formulation as defined in any one of claims 1 to 20, exposing the distributed modeling material to curing energy, thereby forming a cured modeling material, A method for manufacturing the aforementioned three-dimensional object.

23. The method according to claim 22, wherein the curing energy includes UV irradiation.

24. The method according to claim 23, wherein the UV irradiation is from an LED energy source.

25. The method according to claim 22, wherein the distribution is carried out at a temperature of 40°C or lower or 35°C or lower.

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