Additive fabrication of dental prostheses

Abstract

This invention provides a material formulation for additive manufacturing of denture structures, and a method for additive manufacturing of denture structures using this material formulation. The material formulation and additive manufacturing parameters provide denture structures that exhibit mechanical, physical, and biocompatible properties that meet the requirements of acceptable standards.

Description

Technical Field

[0001] Related Applications This application claims the benefit of priority of U.S. Provisional Patent Application No. 63 / 525,074, filed on July 5, 2023, under 35 U.S.C. § 119(e), the disclosure of which is incorporated herein by reference in its entirety.

[0002] This application is related to a PCT international patent application filed on the same day, entitled "METHOD AND SYSTEM FOR CORRECTING COLOR ARTIFACTS IN ADDITIVE MANUFACTURING" (Attorney Docket No. 100036), which claims priority from U.S. Provisional Patent Application No. 63 / 525,066, and the entire contents of both applications are incorporated herein by reference in their entirety.

[0003] In some embodiments, the present invention relates to additive manufacturing, and more particularly, but not limited thereto, to curable formulations that can be used for additive manufacturing of dental prostheses, including artificial teeth, denture bases, and monolithic denture structures (monolithic denture constructs).

Background Art

[0004] Additive manufacturing (AM) is a technology that enables the production of arbitrarily shaped structures directly from computer data by an additive forming process. The basic operation of any AM system consists of slicing a three-dimensional computer model into thin cross-sections, converting the result into two-dimensional position data, and supplying the data to a control device to manufacture a three-dimensional structure layer by layer.

[0005] Additive manufacturing includes many different approaches to manufacturing methods, including three-dimensional (3D) printing such as 3D inkjet printing, electron beam melting, stereolithography, selective laser sintering, laminated object manufacturing, fused deposition modeling, and others.

[0006] Some 3D printing processes, such as 3D inkjet printing, are performed by inkjet deposition of the construction material layer by layer. Thus, the construction material is extruded from an extrusion head having a series of nozzles that deposit layers onto a support structure. Depending on the construction material, the layers can then be cured or solidified. Curing may be achieved by exposure to suitable conditions and, if desired, by the use of suitable equipment.

[0007] The construction material includes an uncured model material (also called "uncured molding material" or "molding material formulation") that is selectively extruded to manufacture a desired object, and may further include an uncured support material (also called "uncured support material" or "support material formulation") that provides temporary support to specific areas of the object during construction and ensures proper vertical alignment of subsequent object layers. The support structure is configured to be removed after the object is completed.

[0008] In some known inkjet printing systems, the uncured model material is a photopolymerizable or photocurable material that is cured, hardened, or solidified by exposure to ultraviolet (UV) light after being sprayed. The uncured model material may be a photopolymerizable material formulation having a composition that, after curing, gives a solid material with mechanical properties that enable the construction and handling of the three-dimensional object being built. The modeling material formulation typically contains a reactive (curable) component and a photoinitiator. The photoinitiator may enable at least partial solidification (hardening) of the uncured support material by curing with the same UV light applied to mold the model material. The solidified material may be rigid or may have elastic properties.

[0009] The support material is formulated to allow for rapid and easy cleaning of the object from its support. The support material may be a polymer that is water-soluble and / or swells upon exposure to a liquid solution, such as water, an alkaline or acidic aqueous solution, and / or is biodegradable. The support material formulation may also contain reactive (curable) components and a photoinitiator.

[0010] To be compatible with most commercially available printheads used in 3D inkjet printing systems, the uncured construction material should be characterized by the following properties: relatively low viscosity at the operating (e.g., spray) temperature (e.g., 50 centipoise or less or cps or 35 cps or less, preferably 8 cps to 25 cps Brookfield viscosity); surface tension of about 25 dynes / cm to about 55 dynes / cm, preferably about 25 dynes / cm to about 40 dynes / cm; and Newtonian fluid behavior and high reactivity to selected curing conditions to enable rapid solidification of the sprayed layer when exposed to curing conditions of 1 minute or less, preferably 20 seconds or less.

[0011] The cured material used to form the final object typically exhibits a thermal distortion temperature (HDT) higher than room temperature to ensure its usability. Preferably, the cured material exhibits an HDT of at least 35°C. It is known that a higher HDT is desirable for the object to be stable under variable conditions. In most cases, it is also desirable for the object to withstand relatively high Izod notched impacts, e.g., greater than 50 J / m or greater than 60 J / m.

[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, 6,863,859, 7,183,335, 7,209,797, 7,225,045, 7,300,619, 7,500,846, 7,991,498, and 9,031,680, as well as U.S. Patent Application Publication 2016 / 0339643, all of which are by the same assignee and are incorporated herein by reference in their entirety.

[0013] Several additive manufacturing processes, including three-dimensional inkjet printing, enable the layering of objects using more than one material, also known as "multi-material" AM processes. For example, the assignee's U.S. Patent Application Publication 2010 / 0191360 discloses a system comprising a solid freeform fabrication apparatus having multiple print heads, a material feeder configured to supply multiple build materials to the fabrication apparatus, and a control unit configured to control the fabrication and feeder. The system has several operating modes. In one mode, all print heads operate during a single build scan cycle of the fabrication apparatus. In another mode, one or more print heads do not operate during a single build scan cycle or part thereof.

[0014] In 3D inkjet printing methods such as Polyjet (Stratasys® Ltd., Israel), the build material is selectively ejected from one or more inkjet printheads and / or nozzles according to a predetermined configuration defined by a software file and deposited in continuous layers on the build tray.

[0015] PolyJet® technology enables control over the position and composition of each voxel (volume pixel), providing immense design versatility and digital programming for multi-material structures. Other advantages of PolyJet® technology include extremely high printing resolution with layer heights of less than 14 μm, and the ability to print multiple materials simultaneously in a single object. This multi-material 3D printing process is often useful for manufacturing complex parts and structures composed of elements with different stiffnesses, properties, colors, or transparency. The PolyJet® printing process makes it possible to create a new range of materials programmed at the voxel level using only a few starting materials.

[0016] International Publication No. 2013 / 128452 by the Transferee discloses a multimaterial approach involving the separate ejection of two components, one cationic and / or radically polymerizable, which are mixed together on a print tray to produce a polymerization reaction similar to that of pre-mixing the two components before ejection, while preventing premature polymerization on the inkjet head nozzle plate.

[0017] Current PolyJet® technology offers the ability to use a wide range of curable (e.g., polymerizable) materials that provide polymer materials with various properties, ranging from rigid and hard materials (e.g., curable formulations commercially available as the Vero® family of materials) to soft and flexible materials (e.g., curable formulations commercially available as the Tango® and Agilus® families), and also includes objects made using Digital ABS, which include multimaterials consisting of two starting materials (e.g., RGD515® and RGD535 / 531®) that simulate the properties of engineering plastics. The majority of PolyJet® materials currently in use are curable materials that harden or solidify upon exposure to radiation, mainly UV radiation and / or heat, with acrylic materials being the most commonly used.

[0018] Several photocurable (photopolymerizable) 3D inkjet printing material formulations known to be usable in 3D inkjet printing are designed to provide a transparent material upon curing.

[0019] The use of light-emitting diodes (LEDs) as electromagnetic irradiation sources has become increasingly common and desirable in many fields, including additive manufacturing processes that utilize UV-curable materials. Most commercially available UV LED light sources emit UVA radiation at higher wavelengths of 365 / 395 / 405 nm. The use of such light sources has significant limitations because it cannot efficiently utilize photoinitiators that absorb shorter wavelengths, such as those of the α-hydroxyketone family that absorb at 250 nm–300 nm. These photoinitiators are typically used for surface curing, and their absence negatively impacts process quality.

[0020] Current solutions to the limitations imposed by the use of UV LEDs as irradiation sources include the use of hydrogen donors that promote surface curing, such as materials containing tertiary amines, thiols, and polyethylene glycol. However, while the use of these materials facilitates AM using UV LEDs, it comes with several drawbacks. For example, tertiary amines give cured materials an increased yellow tint; thiols are typically reactive to UV-curable materials commonly used in AM, such as acrylic materials, and therefore limit the shelf life of formulations containing them; and polyethylene glycol materials are amphiphilic materials that also act as plasticizers or elastomers, thus reducing the mechanical stability and increasing water absorption of the resulting object.

[0021] Over the past decade, efforts have been made in the field of dentures to utilize additive manufacturing methods such as 3D inkjet printing and digital light processing (DLP).

[0022] For example, U.S. Patent No. 7,476,347 and U.S. Patent Application Publication No. 2011 / 0049738 disclose a process for fabricating dentures with integrated artificial teeth and denture bases by inkjet three-dimensional printing. The methodologies taught in these patents use waxy polymerizable materials, which need to be custom synthesized, resulting in additional time and cost. These materials require the use of more than 70% filler material and are characterized by slow reaction rates and high viscosity.

[0023] U.S. Patent Application Publication No. 2019 / 0175455 describes a photocurable composition for manufacturing dental prostheses by stereolithography: a photopolymerization initiator; and a (meth)acrylic monomer component comprising at least one of the following: an acrylic monomer (X) having no aromatic ring, a ring structure other than an aromatic ring, and two or more acryloyloxy groups in one molecule, with an Mw of 200 to 800; a (meth)acrylic monomer (A) having one or more ether links and two (meth)acryloyloxy groups in one molecule, with a clear Mw; a (meth)acrylic monomer (B) having a ring structure other than an aromatic ring and one (meth)acryloyloxy group in one molecule, with a clear Mw; a (meth)acrylic monomer (C) having a hydrocarbon skeleton and two (meth)acryloyloxy groups in one molecule, with a clear Mw; and a (meth)acrylic monomer (D) having one or more aromatic rings and one (meth)acryloyloxy group in one molecule, with an Mw.

[0024] U.S. Patent Application Publication 2018 / 0049954 teaches a photocurable composition for artificial teeth and denture bases usable in 3D inkjet printing or DLP-type AM. The composition comprises a photocurable organic compound, a surface-modifying nano-sized inorganic filler, a photoinitiator, a colorant, and a stabilizer. The composition provides a characteristic set of denture bases and artificial teeth, which can then be bonded together.

[0025] Further background information includes Chung et al., Materials (Basel). 2018 Oct;11(10):1798; and U.S. Patent Nos. 9,227,365; U.S. Patent Nos. 6,242,149; U.S. Patent Application No. 2010 / 0140850; International Publication No. 2009 / 013751; International Publication No. 2016 / 063282; International Publication No. 2016 / 125170; International Publication No. 2017 / 134672; International Publication No. 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; International Publication Nos. 2018 / 055522; International Publication Nos. 2020 / 065654 and International Publication Nos. 2023 / 126943 are examples of these publications, all of which are by the assignee. [Overview of the project]

[0026] According to aspects of some embodiments of the present invention, there is provided a modeling material formulation usable for the laminated modeling of a denture structure, the modeling material formulation comprising: at least one polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (Component D2) characterized by at least 10 ethoxylated groups and / or a Tg of less than 0°C, in a total amount of 15% to 25% by weight of the total weight of the formulation; at least one polyfunctional (e.g., difunctional) urethane (meth)acrylate (Component G) characterized by a Tg of less than 100°C, in a total amount of 15% to 25% by weight of the total weight of the formulation; at least one monofunctional alicyclic (meth)acrylate, preferably monofunctional alicyclic acrylate (Component E2), in a total amount of at least 40% by weight, or at least 45% by weight, or 45% to 55% by weight of the total weight of the formulation; at least one monofunctional acrylate, preferably hydrophilic or amphiphilic, in a total amount of 3% to 10% by weight, or 5% to 10% by weight, or 3% to 8% by weight of the total weight of the formulation; and at least one dispersant (Component H). According to some of any of the embodiments described herein, the modeling material formulation according to this aspect of the present embodiment is also referred to herein as a Type B formulation.

[0027] According to some of any of the embodiments described herein, Component D2 comprises a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate characterized by at least 10 ethoxylated groups and a Tg of less than 0°C upon curing.

[0028] According to some of any of the embodiments described herein, Component D2 has a molecular weight of at least 1,000 grams / mole.

[0029] According to some of any of the embodiments described herein, Component D2 is a polyfunctional (e.g., difunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups.

[0030] According to some of the embodiments described herein, component G comprises a polyfunctional (e.g., bifunctional) urethane (meth)acrylate having a molecular weight of at least 1,000 grams / mol.

[0031] According to some of the embodiments described herein, component G is characterized by a Tg of less than 100°C, preferably in the range of 0°C to 100°C, or 50°C to 100°C (component G2).

[0032] According to some of the embodiments described herein, component G comprises a polyfunctional (e.g., bifunctional) urethane methacrylate.

[0033] According to some of the embodiments described herein, component D2 comprises a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, having a molecular weight of at least 1,000 grams / mol, and having a curing time of less than 0°C.

[0034] According to some of the embodiments described herein, component G comprises or comprises component G2, which is a polyfunctional (e.g., bifunctional) urethane (meth)acrylate having a molecular weight of at least 1,000 grams / mol and characterized by a curing time (Tg) in the range of 0°C to 100°C or 50°C to 100°C.

[0035] According to some of the embodiments described herein, the total amount of at least one component D2 and at least one component G (e.g., component G2) is in the range of about 30% to about 50% by weight, or 35% to 50% by weight, or 35% to 45% by weight, or about 40% to about 50% by weight of the total weight of the composition.

[0036] According to some of the embodiments described herein, at least one component E2 has a molecular weight (MW) of 500 grams / mol or less (e.g., 100 grams / mol to 500 grams / mol).

[0037] According to any one of the embodiments described herein, each of at least one component E2 independently features a Tg of less than 100°C or less than 50°C (e.g., 20°C to 60°C or 20°C to 50°C) at curing.

[0038] According to some of the embodiments described herein, at least one component E2 comprises a monofunctional alicyclic, preferably hydrophobic, acrylate having a molecular weight (MW) of 500 g / mol or less (e.g., 100 g / mol to 500 g / mol) and a curing temperature (Tg) of less than 100°C or less than 50°C (e.g., 20°C to 60°C, or 20°C to 50°C).

[0039] According to some of the embodiments described herein, at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of 500 grams / mol or less (e.g., 100 grams / mol to 500 grams / mol).

[0040] According to some of the embodiments described herein, at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate characterized by a Tg greater than 50°C or greater than 80°C (e.g., 50°C to 150°C) at curing.

[0041] According to some of the embodiments described herein, the amount of component H is at least 0.1% by weight, or 0.1% to 1% by weight, or 0.1% to 0.5% by weight of the total weight of the composition.

[0042] According to some of the embodiments described herein, the dispersant has a curable group.

[0043] According to some of the embodiments described herein, the dispersant is a polyfunctional aliphatic silicon (meth)acrylate.

[0044] According to any one of the embodiments described herein, the dispersant has an average MW of at least 1,000 grams / mol.

[0045] According to some of the embodiments described herein for Type B formulations: Component D2 comprises a polyfunctional (e.g., difunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, a curing time Tg of less than 0°C, and a molecular weight of at least 1,000 grams / mol; Component G comprises component G2, which is a polyfunctional (e.g., difunctional) urethane methacrylate having a molecular weight of at least 1,000 grams / mol and a curing time Tg in the range of 0°C to 100°C or 50°C to 100°C; the total amount of at least one component D2 and at least one component G2 is at least 35% by weight or at least 40% by weight, or 35% to 50% by weight, or 40% to 50% by weight of the total weight of the formulation. The composition is within the following ranges: at least one component E2 comprises a monofunctional alicyclic, preferably hydrophobic, acrylate having a molecular weight (MW) of 500 g / mol or less (e.g., 100 g / mol to 500 g / mol) and a curing time of less than 100°C or less than 50°C (e.g., 20°C to 60°C, or 20°C to 50°C); at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of 500 g / mol or less (e.g., 100 g / mol to 500 g / mol) and a curing time of greater than 50°C or greater than 80°C (e.g., 50°C to 150°C); and the amount of component H is at least 0.1% by weight of the total weight of the composition, or in the range of 0.1% to 1% by weight or 0.1% to 0.5% by weight.

[0046] According to any one of the embodiments described herein, the formulation further comprises a polymerization inhibitor (component I).

[0047] According to any one of the embodiments described herein, the formulation further comprises a photoinitiator (component J).

[0048] According to some of the embodiments described herein, the amount of the photoinitiator (component J) is in the range of 1% to 5% by weight of the total weight of the formulation.

[0049] According to any one of the embodiments described herein, the formulation further comprises a coloring agent (component P).

[0050] According to some of the embodiments described herein, the colorant (component P) includes a pigment.

[0051] According to some of the embodiments described herein, the colorant (component P) comprises a mixture of a pigment and at least one (meth)acrylic material.

[0052] According to some of the embodiments described herein, the pigment is a white pigment.

[0053] According to some embodiments of the present invention, a set of at least two molding material formulations that can be used in combination in additive manufacturing of denture structures is provided, wherein at least one of the at least two formulations is a type B formulation and is a molding material formulation described herein in any of the embodiments and any combination thereof, and at least one of the at least two formulations is a type A formulation described herein in any of the embodiments and any combination thereof.

[0054] According to some of the embodiments described herein, a Type A formulation comprises: a polyfunctional aliphatic urethane (meth)acrylate (component A) characterized by a Tg greater than 100°C at curing; a polyfunctional non-aromatic (meth)acrylate (component B) characterized by a Tg greater than 100°C at curing; a filler (component C) in the form of submicron-sized particles; and fewer than 10 ethoxylated groups, and / or characterized by a Tg in the range of 50°C to 150°C at curing. The compound comprises a polyfunctional ethoxylated aromatic (meth)acrylate (component D); a monofunctional (meth)acrylate (component E); a polyfunctional cyclic (meth)acrylate (component F); and a polyfunctional aliphatic urethane (meth)acrylate (component G) characterized by a curing temperature of less than 100°C, wherein the amount of filler is 20% by weight or less, or 15% by weight or less, of the total weight of the compound; and the amount of component D is 20% by weight or less, or 15% by weight or less, of the total weight of the compound.

[0055] According to some of the embodiments described herein, the filler particles are characterized by an average diameter of less than 1 micron.

[0056] According to some of the embodiments described herein, the filler particles include silica particles.

[0057] According to some of the embodiments described herein, the filler particles have a plurality of curable groups bonded thereto.

[0058] According to any one of the embodiments described herein, a Type A formulation comprises: Component A in an amount ranging from 15% to 25% by weight of the total weight of the formulation; Component B in an amount of 20% or less by weight, or 15% or less by weight of the total weight of the formulation; Component E in an amount ranging from 30% to 40% by weight of the total weight of the formulation; Component F in an amount ranging from 5% to 10% by weight of the total weight of the formulation; and Component G in an amount ranging from 5% to 10% by weight of the total weight of the formulation.

[0059] According to some of the embodiments described herein, component A is a bifunctional aliphatic urethane methacrylate characterized by a Tg greater than 100°C at curing; and / or component B is a bifunctional alicyclic acrylate characterized by a Tg greater than 100°C at curing; and / or component C comprises submicron-sized silica particles having curable groups bonded thereto; and / or component D is characterized by fewer than 5 ethoxylated groups and a Tg in the range of 50°C to 150°C at curing. The compound is a bifunctional ethoxylated aromatic methacrylate; and / or component E each independently comprises a monofunctional acrylate and a monofunctional methacrylate in amounts of 10% to 20% by weight or 15% to 20% by weight of the total weight of the compound; and / or component F is a trifunctional isocyanurate triacrylate; and / or component G is a bifunctional aliphatic urethane dimethacrylate having an average MW of at least 1,000 g / mol and characterized by a curing temperature of less than 100°C.

[0060] According to some of the embodiments described herein, the Type A formulation further comprises a dispersant (component H), preferably the dispersant described herein in any of the respective embodiments and any combination thereof.

[0061] According to some of the embodiments described herein, the amount of the dispersant (component H) is in the range of 0.1% to 0.5% by weight of the total weight of the type A formulation.

[0062] According to any one of the embodiments described herein, the Type A formulation further comprises a polymerization inhibitor (component I).

[0063] According to any one of the embodiments described herein, the Type A formulation further comprises a photoinitiator (component J).

[0064] According to some of the embodiments described herein, the amount of the photoinitiator (component J) is in the range of 1% to 5% by weight of the total weight of the type A formulation.

[0065] According to any one of the embodiments described herein, the Type A formulation further comprises a colorant (component P).

[0066] According to some of the embodiments described herein, the colorant (component P) includes a pigment.

[0067] According to some of the embodiments described herein, the colorant (component P) comprises a mixture of a pigment and at least one (meth)acrylic material.

[0068] According to some of the embodiments described herein, the pigment comprises nano-sized particles.

[0069] According to any one of the embodiments described herein, the colorant (component H) further comprises a pigment dispersant (component Dp).

[0070] According to some embodiments of the present invention, a kit is provided comprising a set of at least two formulations described herein (e.g., at least one type B formulation and at least one type A formulation) in any one or any combination thereof, wherein each formulation is individually packaged within the kit.

[0071] According to any one of the embodiments described herein, a set or kit of formulations further comprises a support material formulation usable for additive manufacturing of denture structures, the support material formulation comprising: an amount of a non-curable, water-soluble or water-miscible polymer material in an amount of about 40% to about 60% by weight of the total weight of the formulation; an amount of a hydrophilic monofunctional (meth)acrylate in an amount of 15% to 25% by weight of the total weight of the formulation; an amount of a hydrophilic monofunctional (meth)acrylamide in an amount of 10% to 20% by weight of the total weight of the formulation; and an amount of a polyfunctional, non-aromatic (meth)acrylate in an amount of 1% to 5% by weight of the total weight of the formulation.

[0072] According to any one of the embodiments described herein, the support material formulation further comprises a photoinitiator in an amount of 0.1% to 1% by weight of the total weight of the formulation.

[0073] According to some of the embodiments described herein, a set or kit of formulations comprises at least two Type A 3D printing material formulations described herein, the at least two formulations differing from each other by the presence and / or type of colorants. According to some of these embodiments, the kit further comprises Type B formulations.

[0074] According to some embodiments of the present invention, a method for additive manufacturing a three-dimensional denture object is provided, the method comprising extruding a plurality of layers in a configuration pattern corresponding to the shape of the denture object, thereby forming the object, wherein the forming of at least several layers comprises extruding at least one molding material formulation and exposing the extruded formulation to curing conditions, thereby forming a cured molding material, the at least one molding material formulation being a type B molding material formulation described herein in any of the respective embodiments and any combination thereof.

[0075] According to some of the embodiments described herein, the extrusion is the extrusion of a set of at least two modeling material formulations described herein (e.g., at least one type B formulation and at least one type A formulation) in any of the respective embodiments and any combination thereof.

[0076] According to some of the embodiments described herein, the discharge is further the discharge of a support material formulation.

[0077] According to some of the embodiments described herein, the support material formulation is as described herein in any of the respective embodiments and any combination thereof.

[0078] According to any one of the embodiments described herein, for at least several layers, the extrusion is such that it forms a core region and at least one outermost (coating) encapsulation region that at least partially encloses or surrounds the core region, and each of the core region and the encapsulation region is formed from different build material formulations or different combinations of at least two build material formulations.

[0079] According to some of the embodiments described herein, the core region is molded from a type B formulation.

[0080] According to some of the embodiments described herein, the outermost encapsulation region is formed from a type A formulation and / or does not contain a type B formulation.

[0081] According to any one of the embodiments described herein, for at least several layers, the extrusion is such that it further forms an internal encapsulation region that at least partially encloses or surrounds a core region, and optionally one or more intermediate encapsulation regions that at least partially enclose or surround the internal encapsulation region, the outermost (coated) encapsulation region at least partially surrounding the outermost intermediate encapsulation region, and each of the core region and the internal encapsulation region, each of the internal encapsulation region and any intermediate encapsulation region, or the outermost (coated) encapsulation region, and each of the intermediate encapsulation region and the outermost (coated) encapsulation region, if present, are formed from different material formulations or different combinations of at least two material formulations.

[0082] According to some of the embodiments described herein, the core region is molded from a type B formulation, the internal encapsulation region is molded from a type A formulation, the intermediate encapsulation region is molded from a type B formulation, and the outermost encapsulation region is molded from a type A formulation.

[0083] According to some of the embodiments described herein, the thickness of each of the internal encapsulation region, at least one intermediate encapsulation region if present, and the outermost encapsulation region is independently in the range of 0.1 mm to 1 mm or 0.3 mm to 1 mm.

[0084] According to some of the embodiments described herein, the thickness of the outermost encapsulation region is in the range of 0.5 mm to 0.7 mm, preferably 0.6 mm.

[0085] According to some of the embodiments described herein, the thickness of the internal encapsulation region is in the range of 0.5 mm to 1 mm, preferably 0.7 mm.

[0086] According to some of the embodiments described herein, the extrusion is further an extrusion of an intermediate encapsulation region, the thickness of which is in the range of 0.3 mm to 0.5 mm, preferably 0.4 mm.

[0087] According to some of the embodiments described herein, the extrusion is further an extrusion of an intermediate encapsulation region, and: the thickness of the outermost encapsulation region is in the range of 0.5 mm to 0.7 mm, preferably 0.6 mm; the thickness of the inner encapsulation region is in the range of 0.5 mm to 1 mm, preferably 0.7 mm; and the thickness of the intermediate encapsulation region is in the range of 0.3 mm to 0.5 mm, preferably 0.4 mm.

[0088] According to some of the embodiments described herein, the discharge is further an intermediate encapsulation region, and the thickness of the intermediate encapsulation region is at least 50% of the thickness of the outermost encapsulation region, for example, 50% to 100%, or 50% to 80%, or 50% to 70%.

[0089] According to some embodiments of the present invention, a method for additive manufacturing a three-dimensional denture object, the method comprising extruding a plurality of layers in a configuration pattern corresponding to the shape of the denture object, thereby forming the object, wherein the forming of at least several layers comprises extruding at least a first and second forming material formulation, and extruding the extruded formulations to curing conditions, thereby forming a cured forming material, and extruding such that a core region and at least one outermost (coating) encapsulation region enclosing or surrounding the core region, wherein the core region is formed of the second forming material formulation or a mixture of the first and second forming material formulations. The present invention provides a method for molding from a combination and for molding an encapsulated region from a first molding material formulation or a second combination of the first molding material formulation and a second molding material formulation, wherein the second combination differs from the first combination in that the first molding material formulation and the second molding material formulation are as follows: the second formulation or the first combination, upon curing, is characterized by an impact resistance at least twice, at least five times, or at least ten times higher than the impact resistance of the first formulation or the second combination; and / or the first formulation or the second combination, upon curing, is characterized by a flexural modulus at least twice, at least five times, or at least ten times higher than the flexural modulus of the second formulation or the first combination.

[0090] According to any one of the embodiments described herein, for at least several layers, the extrusion is such that it further forms an internal encapsulation region that at least partially encloses or surrounds a core region, and an intermediate encapsulation region that at least partially encloses or surrounds the internal encapsulation region and is at least partially surrounded or enclosed by the outermost encapsulation region, the internal encapsulation region being formed from a first formulation or a second combination of the first formulation and the formulation, and the intermediate encapsulation region being formed from a second formulation or a first combination of the first formulation and the second formulation.

[0091] According to some of the embodiments described herein, the thickness of each of the internal encapsulation region, at least one intermediate encapsulation region, and the outermost encapsulation region is independently in the range of 0.1 mm to 1 mm or 0.3 mm to 1 mm.

[0092] According to some of the embodiments described herein, the thickness of the outermost encapsulation region is in the range of 0.5 mm to 0.7 mm, preferably 0.6 mm.

[0093] According to some of the embodiments described herein, the thickness of the internal encapsulation region is in the range of 0.5 mm to 1 mm, preferably 0.7 mm.

[0094] According to some of the embodiments described herein, the extrusion is further an extrusion of an intermediate encapsulation region, the thickness of which is in the range of 0.3 mm to 0.5 mm, preferably 0.4 mm.

[0095] According to some of the embodiments described herein, the thickness of the outermost encapsulation region is in the range of 0.5 mm to 0.7 mm, preferably 0.6 mm; the thickness of the inner encapsulation region is in the range of 0.5 mm to 1 mm, preferably 0.7 mm; and the thickness of the intermediate encapsulation region is in the range of 0.3 mm to 0.5 mm, preferably 0.4 mm.

[0096] According to some of the embodiments described herein, the thickness of the intermediate encapsulation region is at least 50% of the thickness of the outermost encapsulation region, for example, 50% to 100%, or 50% to 80%, or 50% to 70%.

[0097] According to some of the embodiments described herein, the denture structure is selected from a denture base, artificial teeth, groups of artificial teeth, and an integrated structure of the denture base and groups of artificial teeth.

[0098] According to some of the embodiments described herein, the denture structure is an integral structure comprising a denture base and an artificial tooth group.

[0099] According to some embodiments of the present invention, a denture structure obtained by the method described herein is provided in any one of each embodiment and any combination thereof.

[0100] According to some of the embodiments described herein, the denture structure is an integral structure comprising a denture base and an artificial tooth group.

[0101] According to some of the embodiments described herein, the denture structure is characterized by mechanical and physical properties in accordance with the requirements of ISO 20795-1 and biocompatible properties in accordance with the requirements of ISO 10993-1.

[0102] According to some of the embodiments described herein, the denture structure is characterized by a flexural modulus, flexural strength, Kmax, and Wf in accordance with the requirements of ISO 20795-1.

[0103] 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 conflict, the patent specification, including the definitions, shall prevail. In addition, the materials, methods, and examples are illustrative and not necessarily intended to be limiting.

[0104] 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 actual measuring instruments and apparatus of embodiments of the methods and / or systems of the present invention, several selected tasks may be implemented by hardware, software, firmware, or a combination thereof using an operating system.

[0105] For example, hardware for performing tasks selected according to embodiments of the present invention may be implemented as a chip or circuit. As software, tasks selected according to embodiments of the present invention may be performed 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 methods and / or systems 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, such as a magnetic hard disk and / or removable media, for storing instructions and / or data. Network connectivity is also provided, optionally. A display and / or a user input device, such as a keyboard or mouse, is also provided, optionally. [Brief explanation of the drawing]

[0106] Some embodiments of the present invention are described herein by reference only to the accompanying drawings. Herein, it is emphasized that the details shown, with particular reference to the drawings, are for illustrative purposes only and serve to illustrate embodiments of the present invention. In this regard, the description made in conjunction with the drawings will make it clear to those skilled in the art how embodiments of the present invention may be carried out.

[0107] [Figure 1A]Figures 1A to 1D are schematic diagrams of additive manufacturing systems according to several embodiments of the present invention. [Figure 1B] Figures 1A to 1D are schematic diagrams of additive manufacturing systems according to several embodiments of the present invention. [Figure 1C] Figures 1A to 1D are schematic diagrams of additive manufacturing systems according to several embodiments of the present invention. [Figure 1D] Figures 1A to 1D are schematic diagrams of additive manufacturing systems according to several embodiments of the present invention. [Figure 2A] Figures 2A to 2C are schematic diagrams of print heads according to several embodiments of the present invention. [Figure 2B] Figures 2A to 2C are schematic diagrams of print heads according to several embodiments of the present invention. [Figure 2C] Figures 2A to 2C are schematic diagrams of print heads according to several embodiments of the present invention. [Figure 3A] Figures 3A and 3B are schematic diagrams illustrating coordinate transformations according to several embodiments of the present invention. [Figure 3B] Figures 3A and 3B are schematic diagrams illustrating coordinate transformations according to several embodiments of the present invention. [Figure 4] Figure 4 is a photograph showing exemplary objects prepared according to several embodiments of the present invention, in particular a denture-integrated structure described herein. [Figure 5] Figure 5 is a comparative plot showing the change in mechanical properties of objects fabricated with the exemplary Type A 3D printing material formulation IX described herein, measured according to ISO 20795-1. [Figure 6A] Figures 6A and 6B are bar graphs (Figure 6B) showing the dimensional changes over time of an exemplary type A formulation IX cured material, taken from the selected region shown in Figure 6A, as measured according to ISO 20795-1. [Figure 6B]Figures 6A and 6B are bar graphs (Figure 6B) showing the dimensional changes over time of an exemplary type A formulation IX cured material, taken from the selected region shown in Figure 6A, as measured according to ISO 20795-1. [Figure 7A] Figures 7A and 7B are bar graphs (Figure 7B) showing the dimensional changes over time of an exemplary type A formulation IX cured material, taken from a selected region shown in Figure 7A, as measured according to ISO 20795-1. [Figure 7B] Figures 7A and 7B are bar graphs (Figure 7B) showing the dimensional changes over time of an exemplary type A formulation IX cured material, taken from a selected region shown in Figure 7A, as measured according to ISO 20795-1. [Figure 8A] Figures 8A and 8B show the notching device (Figure 8A) and the determination of the Kmax and Wf parameters (Figure 8B) in accordance with ISO 20795-1. [Figure 8B] Figures 8A and 8B show the notching device (Figure 8A) and the determination of the Kmax and Wf parameters (Figure 8B) in accordance with ISO 20795-1. [Figure 9A] Figures 9A and 9B are bar graphs showing the Kmax values ​​(Figure 9A) and Wf values ​​(Figure 9B) of printed objects featuring various core-shell structures molded from exemplary Type A formulation I and exemplary Type B formulation XX. [Figure 9B] Figures 9A and 9B are bar graphs showing the Kmax values ​​(Figure 9A) and Wf values ​​(Figure 9B) of printed objects featuring various core-shell structures molded from exemplary Type A formulation I and exemplary Type B formulation XX. [Figure 10A] Figures 10A and 10B are photographs showing objects featuring the core-shell structure A described herein, printed using exemplary combinations of type A formulation II and exemplary type B formulation XXV (Figure 10A) and exemplary combinations of type A formulation II and exemplary type B formulation XX (Figure 10B). [Figure 10B]Figures 10A and 10B are photographs showing objects featuring the core-shell structure A described herein, printed using exemplary combinations of type A formulation II and exemplary type B formulation XXV (Figure 10A) and exemplary combinations of type A formulation II and exemplary type B formulation XX (Figure 10B). [Figure 11] Figure 11 is a schematic diagram showing a cross-sectional view of an object portion having a core region surrounded by a plurality of encapsulation regions defining an onion-like structure, according to several embodiments of the present invention. [Modes for carrying out the invention]

[0108] In some embodiments, the present invention relates to additive manufacturing, and more specifically, but not limited to, to a curable compound usable for additive manufacturing of dental prostheses including artificial teeth, denture bases, and denture-integrated structures.

[0109] Before describing in detail at least one embodiment of the present invention, it should be understood that the present invention is not necessarily limited to its application to the configuration details and arrangement of components and / or methods described below and / or illustrated in the drawings and / or embodiments. Other embodiments of the present invention are possible, or it can be practiced or carried out in various ways.

[0110] Before describing in detail at least one embodiment of the present invention, it should be understood that the present invention is not necessarily limited to application to the details described below or to the details illustrated by the examples. Other embodiments of the present invention are possible, or it can be practiced or carried out in various ways.

[0111] Throughout this specification, the term “object” refers to the final product of additive manufacturing. This term refers to the product obtained by the method described herein after removal of support material and / or after post-processing (e.g., photobleaching as described herein) when used as part of an uncured build material.

[0112] As used throughout this specification, the term "object" refers to the object as a whole or a part thereof.

[0113] Throughout this specification, the term “hardened” or “solidified” modeling material, also referred to herein as “hardened modeling material,” means the portion of the modeling material that forms an object as defined herein when the extruded modeling material is exposed to hardening conditions (and optionally post-treatment), and optionally, when the hardened support material is removed as described herein, if support material is extruded. The hardened modeling material may be a single hardening material or a mixture of two or more hardening materials, depending on the modeling material formulation used in the method described herein.

[0114] The terms "hardened molding material," "hardened molding material," "solidified molding material," or "hardened / hardened / solidified molding material formulation" can be considered as a hardened molding material in which the construction material consists solely of the molding material formulation (and not of the support material formulation). In other words, this term refers to the portion of the construction material used to provide the final object.

[0115] Throughout this specification, the term “modeling material formulation” is interchangeable with “modeling material,” “modeling material,” “modeling material,” or simply “formulation,” and refers to a portion or all of the uncured construction material extruded to form an object, as described herein. A modeling material formulation is an uncured modeling material (unless otherwise specified) that, when exposed to conditions affecting curing, can form an object or a portion thereof.

[0116] In some embodiments of the present invention, the molding material formulation is formulated for use in three-dimensional inkjet printing and is capable of forming three-dimensional objects on its own, i.e., without being mixed or combined with other materials.

[0117] The uncured construction material may contain one or more molding material formulations and can be extruded so that different parts of an object are made of different cured molding formulations when cured, and therefore made of different hardened (e.g., cured) molding materials, or different mixtures or combinations of hardened (e.g., cured) molding materials.

[0118] The final three-dimensional object is fabricated from a molding material or a combination of molding materials, or a combination of molding materials and support materials, or a modified version thereof (e.g., after curing). All of these operations are well known to those skilled in the art of solid freeform fabrication.

[0119] In some exemplary embodiments of the present invention, an object is manufactured by extruding a construction material (uncured) comprising two or more different build material formulations, each build material formulation being extruded from different extrusion heads and / or nozzles of an inkjet printing apparatus. The build material formulations are optionally and preferably deposited in layers during the same pass of the printing head. The build material formulations and / or combinations of formulations within the layers are selected according to the desired properties of the object and according to the method parameters described herein.

[0120] The uncured construction material may contain one or more build material formulations, and different parts of the model object may be extruded so as to be made by curing different build material formulations, and thus made from different cured build material or different mixtures of cured build material, or a mixture of cured build material and cured support material.

[0121] Throughout this specification, the term “hardening support material” is also interchangeable with “curing support material” or simply “support material” and refers to the portion of the construction material that is intended to support the final object being manufactured during the fabrication process and is removed once the process is complete and the hardened molding material is obtained.

[0122] Throughout this specification, the term “support material formulation” is also interchangeable with “support formulation” and refers to a portion of the uncured construction material extruded to form a support material, as described herein. The support material formulation is an uncured formulation. If the support material formulation is a curable formulation, it forms a hardened support material upon exposure to curing conditions.

[0123] Support materials, which may be either liquid materials or hardening materials, typically gel materials, are also referred to herein as sacrificial materials, and are removable after the layer has been extruded and exposed to curing energy, thereby exposing the shape of the final object.

[0124] The support materials currently in use typically include mixtures of curable and non-curable materials.

[0125] The support materials currently in use are typically water-miscible, water-dispersible, or water-soluble.

[0126] Throughout this specification, the term “water miscible” refers to a material that is at least partially soluble or dispersible in water, i.e., a material whose molecules move into water by mixing at room temperature, for example, when mixed with an equal volume or weight of water at room temperature. This term encompasses the terms “water soluble” and “water dispersible.”

[0127] Throughout this specification, the term "water-soluble" refers to a material that, when mixed with water in equal volumes or weights at room temperature, produces a homogeneous solution.

[0128] Throughout this specification, the term "water-dispersible" refers to a material that, when mixed with water in equal volumes or weights at room temperature, produces a homogeneous dispersion.

[0129] The method and system of this embodiment manufacture a three-dimensional object in layers based on computer object data by forming multiple layers with a configuration pattern corresponding to the shape of the object. The computer object data may be any known format, but is not limited to, Standard Tessellation Language (STL) or Stereolithography Contour (SLC) format, Virtual Reality Modeling Language (VRML), Additive Manufacturing File (AMF) format, Drawing Exchange Format (DXF), Polygon File Format (PLY), or other formats suitable for computer-aided design (CAD).

[0130] Each layer is formed by an additive manufacturing apparatus that scans and patterns a two-dimensional surface. During scanning, the apparatus visits multiple target locations on the two-dimensional layer or surface and determines, for each target location or group of target locations, whether the target location or group of target locations should be occupied by a build material formulation and what type of build material formulation should be delivered there. This determination is made according to a computer image of the surface.

[0131] In preferred embodiments of the present invention, AM includes three-dimensional printing, more preferably three-dimensional inkjet printing. In these embodiments, a build material formulation is ejected from an ejection head having a set of nozzles for layering the build material formulation onto a support structure. Thus, the AM apparatus ejects the build material formulation to target locations to be occupied, leaving other target locations vacant. The apparatus typically includes a plurality of ejection heads, each configured to eject a different build material formulation. Thus, different target locations can be occupied by different build material formulations. The types of build material formulations can be classified into two main categories: build material formulations and support material formulations. Support material formulations function as a support matrix or structure for supporting an object or part of an object during the manufacturing process and / or for other purposes, e.g., to provide a hollow or porous object. The support structure may further include build material formulation elements, for example, for further support strength.

[0132] The final three-dimensional object is fabricated from a molding material, a combination of molding materials, a combination of molding materials and support materials, or a modified version thereof (e.g., after curing). All of these operations are well known to those skilled in the art of freeform fabrication of solids.

[0133] In some exemplary embodiments of the present invention, an object is manufactured by extruding one or more different material formulations. When more than one material formulation is used, each material formulation is optionally and preferably extruded from a different array of nozzles (belonging to the same or separate extrusion heads) of the AM device.

[0134] In some embodiments, the AM device's ejection head is a multi-channel ejection head, in which case different material formulations can be ejected from two or more nozzle arrays located within the same multi-channel ejection head. In some embodiments, the nozzle arrays ejecting different material formulations are located in separate ejection heads, for example, a first nozzle array ejecting a first material formulation is located in a first ejection head, and a second nozzle array ejecting a second material formulation is located in a second ejection head.

[0135] In some embodiments, the nozzle array for extruding the build material mixture and the nozzle array for extruding the support material mixture are both located within the same multi-channel extrusion head. In some embodiments, the nozzle array for extruding the build material mixture and the nozzle array for extruding the support material mixture are located within separate extrusion heads.

[0136] The building material formulations are optionally and preferably deposited in layers during the same pass of the print head. The building material formulations and combinations of building material formulations within the layers are selected according to the desired properties of the object.

[0137] As discussed herein, the inventors have designed, successfully prepared, and implemented novel construction material formulations that can be used for additive manufacturing of denture structures. The newly designed formulations, and combinations of different newly designed formulations, can be used for additive manufacturing of denture structures including denture bases and artificial teeth, preferably by three-dimensional inkjet printing.

[0138] The inventors have further designed a novel additive manufacturing process that can be usefully used in the additive manufacturing of denture structures as described herein.

[0139] Embodiments of the present invention relate to these newly designed molding material formulations and combinations of newly designed formulations, support material formulations that can be efficiently used in combination with these molding material formulations, additive manufacturing (e.g., three-dimensional inkjet printing) of denture structures using these formulations, and denture structures formed thereby.

[0140] In this specification and in the art, the term “denture structure” refers to a dental prosthesis intended to replace a missing tooth or a set of teeth. A denture structure includes an artificial tooth or a set of artificial teeth, and a base structure for supporting the artificial tooth or a set of artificial teeth. A denture structure may typically be a partial denture consisting of a denture base and one or more teeth, or a complete denture consisting of a denture base and several teeth in the mandibular arch or maxillary arch. Typically, a combination of complete dentures for both the mandibular arch and the maxillary arch is required. Denture structures are typically removable.

[0141] Embodiments of the present invention encompass the lamination of individual artificial tooth groups, denture base structures, and preferably integral structures of denture bases and artificial teeth or artificial tooth groups. In some embodiments, the integral denture structure is a complete structure including a base structure and a set of artificial teeth for the mandibular arch and / or maxillary arch.

[0142] The manufacture of such integrated denture structures is made possible by digital control of the color and mechanical properties of different parts of the structure, and consequently by additive manufacturing methods such as those described herein and their respective newly designed curable formulations.

[0143] Build material formulation: According to some embodiments of the present invention, a material formulation usable for additive manufacturing of denture structures as described herein is provided.

[0144] According to some of the embodiments described herein, the molding material formulation is a formulation that is suitable for use in three-dimensional inkjet printing and that satisfies the process requirements of three-dimensional inkjet printing as described herein.

[0145] According to some of the embodiments described herein, the molding material formulations described herein comprise one or more curable materials, also referred to herein as curable formulations. The curable formulations are characterized in that their viscosity (e.g., at room temperature) increases by at least two times, preferably at least five times, and more preferably at least one order of magnitude, upon exposure to curing conditions as described herein.

[0146] Throughout this specification, "curable material," also referred to herein as "solidifiable material," is a compound (e.g., monomer or oligomer or polymer compound) that, when exposed to curing conditions (e.g., curing energy) as described herein, solidifies or hardens to form a curable molding material as defined herein. Curable materials are typically polymerizable materials that undergo polymerization and / or crosslinking when exposed to appropriate curing conditions, typically an appropriate energy source. Curable or solidifiable materials are typically materials whose viscosity increases by at least an order of magnitude when exposed to curing conditions.

[0147] In some of the embodiments described herein, the curable material may be a monomer, oligomer, or short-chain polymer, each of which is polymerizable and / or crosslinkable as described herein.

[0148] In some of the embodiments described herein, when a curable material is exposed to curing conditions (e.g., curing energy such as radiation), the curable material polymerizes by either chain extension or crosslinking, or a combination thereof.

[0149] In some of the embodiments described herein, the curable material is a monomer or monomer mixture that, when exposed to curing conditions in which a polymerization reaction occurs, can form a polymer molding material by polymerization. Such a curable material is also referred to herein as a monomer curable material.

[0150] In some of the embodiments described herein, the curable material is an oligomer or oligomer mixture that, when exposed to curing conditions in which a polymerization reaction occurs, can form a polymer molding material by a polymerization reaction. Such a curable material is also referred to herein as an oligomer curable material.

[0151] In some of the embodiments described herein, the curable material may be a monomer or an oligomer, or it may be a monofunctional curable material or a polyfunctional curable material.

[0152] In this specification, a monofunctional curable material comprises one functional group that can undergo polymerization when exposed to curing conditions (e.g., curing energy).

[0153] A polyfunctional curable material contains two or more functional groups, for example, two, three, four, or more, that can undergo polymerization when exposed to curing conditions. A polyfunctional curable material may be a difunctional, trifunctional, or tetrafunctional curable material, for example, containing two, three, or four groups, each capable of polymerization. In a polyfunctional curable material, two or more functional groups are typically linked to one another by linking portions as defined herein. If the linking portions are oligomeric portions, the polyfunctional group is an oligomeric polyfunctional curable material.

[0154] An exemplary curable material commonly used in additive manufacturing and some of these embodiments is an acrylic material.

[0155] Throughout this specification, the term "acrylic material" collectively encompasses materials having one or more acrylate groups, methacrylate groups, acrylamide groups, and / or methacrylamide groups.

[0156] The term "(meth)acrylate" and its grammatical derivatives encompass materials having one or more acrylate groups and / or methacrylate groups.

[0157] The curable materials contained in the formulations described herein may, where appropriate, be defined by the properties of the material before hardening. Such properties include, for example, molecular weight (MW), functionality (e.g., monofunctional or polyfunctional), and viscosity.

[0158] The curable materials contained in the formulations described herein are defined separately by the properties provided by each material upon hardening. That is, the materials may be defined, where appropriate, by the properties of the material formed by exposure to curing conditions, for example, by polymerization. These properties (e.g., Tg, HDT) are those of the polymer material formed by curing any of the described curable materials alone.

[0159] As used herein, the term “curing” or “hardening” refers to the process by which a formulation is hardened. This term encompasses the polymerization of monomers and / or oligomers, and / or the crosslinking of polymer chains (either polymers present before curing or polymer materials produced by the polymerization of monomers or oligomers). Thus, the products of a curing reaction or hardening are typically polymer materials, and in some cases, crosslinked polymer materials.

[0160] As used herein, “hardening rate” refers to the rate at which hardening occurs, i.e., the extent to which a curable material undergoes polymerization and / or crosslinking within a given time (e.g., one minute). If the curable material is a polymerizable material, this term encompasses both the molar percentage of the curable material in the formulation that undergoes polymerization and / or crosslinking within a given time upon exposure to curing conditions; and / or the extent to which polymerization and / or crosslinking occurs, e.g., the extent of chain extension and / or crosslinking within a given time. The determination of the polymerization rate can be carried out by methods known to those skilled in the art.

[0161] Alternatively, the "hardening rate" can be expressed as the degree to which the viscosity of the compound changes over a given time, that is, the rate at which the viscosity of the compound increases upon exposure to hardening conditions.

[0162] In this specification, the terms “conditions affecting curing” or “conditions for inducing curing,” which are interchangeable terms used herein as “curing conditions” or “curing induction conditions,” refer to conditions that, when applied to a formulation containing a curable material, induce at least partial polymerization of monomers and / or oligomers and / or crosslinking of polymer chains. Such conditions include, for example, the application of curing energy to the curable material, as described below, and / or contact of the curable material with chemically reactive components such as catalysts, co-catalysts, and activators.

[0163] When the conditions for inducing curing include the application of curing energy, the phrase “exposure to curing conditions” means that the extruded layers, preferably each of the extruded layers, are exposed to the curing energy, which is typically carried out by applying the curing energy to the extruded layers (e.g., each of them).

[0164] "Hardening energy" typically includes the application of radiation or heat.

[0165] The radiation may be electromagnetic radiation (e.g., ultraviolet or visible light), electron beam radiation, ultrasonic radiation, or microwave radiation, depending on the material being cured. The application of radiation (or irradiation) is carried out using an appropriate radiation source. For example, as described herein, ultraviolet or visible light, infrared or xenon lamps may be used.

[0166] Curable materials, formulations, or systems that undergo curing upon exposure to radiation are also interchangeably referred to herein as “photopolymerizable,” “photoactivatable,” or “photocurable.”

[0167] In some of the embodiments described herein, the curable material is a photopolymerizable material that polymerizes or crosslinks upon exposure to radiation as described herein, and in some embodiments, the curable material is a UV-curable material that polymerizes or crosslinks upon exposure to UV-visible radiation as described herein.

[0168] In some embodiments, the curable materials described herein include polymerizable materials that polymerize by photo-induced radical polymerization.

[0169] According to some of the embodiments described herein, all curable materials in the formulation are photocurable materials, such as (meth)acrylic materials. According to some of these embodiments, the curing conditions are preferably irradiation, more preferably UV irradiation.

[0170] According to some of the embodiments described herein, the molding material formulation is such that, when hardened, it satisfies the requirements of common standards in the dental field, such as ISO 20795-1 Dental, ISO 10477 Dental, and ISO 10993-1, as described herein, also simply referred herein as ISO 20795-1, ISO 10477, and ISO 10993-1, respectively.

[0171] The fabrication material formulations usable in connection with additive manufacturing of dental structures according to some embodiments of the present invention may contain two or more, three or more, four or more, five or more, or all of the components described herein as component A, component B, component C, component D, component E, component F, component G, and component H (see Table 1 below), and in some of these embodiments, may further contain one or more of component I, component J, component P, and component Dp (see Table 1 below).

[0172] As will be described in more detail below, the material formulations usable in the context of additive manufacturing of dental structures may include two types of formulations, which are referred to herein as Type B formulations and Type A formulations, as described herein in any one of the respective embodiments and any combination thereof.

[0173] According to some of the embodiments described herein, the molding material formulation comprises the following components: A polyfunctional (e.g., bifunctional) urethane (meth)acrylate (component A) characterized by a high Tg during curing; A polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate (component B) characterized by a high Tg during curing; Particle morphology, preferably submicron-sized particles, as a filler (component C); Polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (component D); Monofunctional (meth)acrylate (component E); Polyfunctional (e.g., trifunctional) (meth)acrylate (component F); and A polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate (component G) characterized by a low Tg during curing. This includes two or more, three or more, four or more, five or more, and preferably all of them.

[0174] According to some of the embodiments described herein, component A is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a Tg greater than 100°C at curing.

[0175] According to some of the embodiments described herein, component B is a polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate characterized by a Tg greater than 100°C at curing.

[0176] According to some of the embodiments described herein, component C comprises micron-sized filler particles functionalized with a curable group, as described herein.

[0177] According to some of the embodiments described herein, component D is a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (component D1) characterized by fewer than 10 ethoxylated groups and / or a Tg in the range of 50°C to 150°C at curing, or a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (component D2) characterized by at least 10 ethoxylated groups and / or a Tg of less than 50°C or less than 0°C at curing.

[0178] According to any one of the embodiments described herein, component E comprises at least one or at least two monofunctional (meth)acrylates.

[0179] According to some of the embodiments described herein, component F is a polyfunctional (e.g., trifunctional) cyclic (meth)acrylate.

[0180] According to some of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a low Tg at curing, for example, a Tg below 100°C.

[0181] According to some of the embodiments described herein, the amount of the filler (component C) is 20% by weight or less, or 15% by weight or less, of the total weight of the composition.

[0182] Ingredient A: According to some of the embodiments described herein, component A is a polyfunctional (e.g., bifunctional) urethane (meth)acrylate characterized by a Tg greater than 100°C at curing.

[0183] According to some of the embodiments described herein, component A is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate.

[0184] According to some of the embodiments described herein, component A is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a Tg greater than 100°C at curing, as described herein.

[0185] According to some of the embodiments described herein, component A is a bifunctional urethane (meth)acrylate characterized by a curing temperature (Tg) greater than 100°C, as described herein.

[0186] According to some of the embodiments described herein, component A is a bifunctional aliphatic urethane (meth)acrylate.

[0187] According to some of the embodiments described herein, component A is a bifunctional aliphatic urethane (meth)acrylate characterized by a curing temperature (Tg) greater than 100°C, as described herein.

[0188] According to some of the embodiments described herein, component A is a bifunctional urethane methacrylate characterized by a curing temperature (Tg) greater than 100°C, as described herein.

[0189] According to some of the embodiments described herein, component A is a bifunctional aliphatic urethane methacrylate.

[0190] According to some of the embodiments described herein, component A is a bifunctional aliphatic urethane methacrylate characterized by a curing temperature (Tg) greater than 100°C, as described herein.

[0191] According to some of the embodiments described herein, component A is characterized by a curing temperature (Tg) in a range including 100°C to 200°C, 120°C to 200°C, 100°C to 150°C, or 120°C to 150°C, or any intermediate and partial ranges between these.

[0192] According to some of the embodiments described herein, the average molecular weight of component A is less than 1,000 grams / mol.

[0193] Any polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate is intended, preferably a material that is acceptable for inclusion in medical devices such as devices for prolonged contact with mucosal lumens and / or edible (e.g., food-grade) products, and / or features a toxicity profile that is considered safe for prolonged contact with mucosal lumens.

[0194] Exemplary and non-limiting materials are sold under the trade name Genomer 4297. Other urethane (meth)acrylates according to these embodiments are also intended.

[0195] Component B: According to some of the embodiments described herein, component B is a polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 100°C, as described herein.

[0196] "Non-aromatic" means a material that does not have an aryl or heteroaryl group or part as defined herein.

[0197] Non-aromatic materials may be, for example, aliphatic or alicyclic.

[0198] According to some of the embodiments described herein, component B is a polyfunctional (e.g., bifunctional) alicyclic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 100°C, and is referred to herein as component B1.

[0199] According to some of the embodiments described herein, component B1 is a bifunctional alicyclic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 100°C, as described herein.

[0200] According to some of the embodiments described herein, component B1 is a bifunctional alicyclic acrylate or alicyclic diacrylate characterized by a high Tg at curing, for example, a Tg greater than 100°C, as described herein.

[0201] According to any one of the embodiments described herein, component B1 comprises an alicyclic moiety of at least 6, 7, 8, 9, 10 or more carbon atoms.

[0202] According to any one of the embodiments described herein, component B1 comprises an alicyclic moiety containing two, three or more condensed rings.

[0203] According to some of the embodiments described herein, component B or component B1 is characterized by a curing temperature (Tg) in a range including 100°C to 300°C, 150°C to 300°C, 100°C to 200°C, or 150°C to 200°C, or any intermediate and partial ranges between these.

[0204] According to some of the embodiments described herein, component B is a polyfunctional (e.g., bifunctional) aromatic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 200°C, and is referred to herein as component B2.

[0205] According to some of the embodiments described herein, component B2 is a bifunctional aromatic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 200°C, as described herein.

[0206] Component C: According to embodiments of the present invention, component C is a filler in the form of particles, preferably submicron-sized particles.

[0207] As used herein, the term “filler” refers to an inert material that modifies the properties of a polymer material and / or adjusts the quality of the final product.

[0208] Typical fillers (reinforcement materials) usable in additive manufacturing include, for example, silica, calcium carbonate, clay, carbon black, and other inorganic particles.

[0209] In some of the embodiments described herein, the filler is or comprises silica particles.

[0210] In some of the embodiments described herein, the average diameter of the filler particles (submicron particles) is less than 1 micron, preferably less than 500 nm, preferably less than 200 nm, and preferably less than 100 nm.

[0211] In any of the embodiments described herein, the filler is or comprises silica particles characterized by an average diameter of less than 1 micron, preferably less than 500 nm, preferably less than 200 nm, and preferably less than 100 nm. Such silica particles are also called silica nanoparticles.

[0212] In any of the embodiments described herein, the average diameter of the particles is in a range including 10 nm to 100 nm, or 20 nm to 100 nm, or 20 nm to 80 nm, or 10 nm to 50 nm, or any intermediate and partial ranges between these.

[0213] In some of the embodiments described herein, at least a portion of such particles may aggregate when introduced into the formulation. In some of these embodiments, the aggregates have an average size of a few micrometers (microns) or less.

[0214] Any commercially available submicron silica particle formulation, including fumed silica, colloidal silica, precipitated silica, layered silica (e.g., montmorillonite), and aerosol-assisted self-assemblies of silica particles, can be used in connection with this embodiment.

[0215] Silica particles may be characterized by hydrophobic or hydrophilic surfaces. The hydrophobic or hydrophilic properties of the particle surface are determined by the properties of the surface groups on the particle.

[0216] In a preferred embodiment, at least some or all of the silica particles are functionalized with a curable functional group (particles characterized by a curable group on the surface).

[0217] The curable functional group may be any polymerizable group as described herein. In some embodiments, the curable functional group is polymerizable by the same polymerization reaction as the curable monomer in the formulation and / or when exposed to the same curing conditions as the curable monomer. In some embodiments, the curable group is a photocurable (e.g., UV curable) group. In some embodiments, the curable group is a (meth)acrylic (acrylic or methacrylic) group as defined herein, preferably a (meth)acrylate group.

[0218] When used in connection with this embodiment, “at least a portion” means at least 10%, or at least 20%, or at least 30%, or at least 40%, or at least 50%, or at least 60%, or at least 70%, or at least 80%, or at least 90%, or at least 95%, or at least 98% of the particles.

[0219] In some embodiments, the silica particles include silica nanoparticles characterized by acrylate groups and / or methacrylate groups on their surfaces.

[0220] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, component B as described herein, preferably component B1 as described herein, and in any of the embodiments, component C as described herein are included in the formulation as a premixed composition (e.g., a dispersion of component C filler particles in component B).

[0221] According to some of these embodiments, the weight ratio of component B to component C in the premixed composition (and formulations containing it) is approximately 1:1.

[0222] According to some of the embodiments described in the specification, the total amounts of component B (e.g., component B1) and component C are in a range including about 15% to about 30% by weight, or about 15% to about 25% by weight, or about 2% to about 25% by weight, or about 20% to about 30% by weight, or any intermediate and partial ranges between these.

[0223] Component D: According to some of the embodiments described herein, component D is a polyfunctional ethoxylated (meth)acrylate.

[0224] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate comprising one or more aromatic (aryl or heteroaryl) moieties.

[0225] According to some of the embodiments described herein, component D comprises a bisphenol A moiety as a branched unit, with two or three ethoxylated moies terminated by (meth)acrylate groups.

[0226] According to some of the embodiments described herein, component D is a bifunctional ethoxylated aromatic (meth)acrylate.

[0227] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate characterized by a curing temperature (Tg) of less than 200°C.

[0228] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate characterized by a Tg in the range of 50°C to 150°C, including any intermediate and partial ranges between these values, at curing.

[0229] According to some of the embodiments described herein, component D is a bifunctional ethoxylated aromatic (meth)acrylate characterized by a Tg in the range of 50°C to 150°C, including any intermediate and partial ranges between these values, at curing.

[0230] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by a curing temperature (Tg) in the range of 50°C to 150°C, including any intermediate and partial ranges between these values.

[0231] According to some of the embodiments described herein, component D is a bifunctional ethoxylated aromatic methacrylate (ethoxylated aromatic dimethacrylate) characterized by a Tg including a curing temperature range of 50°C to 150°C, any intermediate and partial ranges between these.

[0232] According to any one of the embodiments described herein, component D comprises fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties.

[0233] According to some of the embodiments described herein, component D comprises a total of four ethoxylated moieties.

[0234] According to some of the embodiments described herein, component D is a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate characterized by a curing temperature (Tg) in the range of 50°C to 150°C, including any intermediate and partial ranges between these, and / or containing fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties, for example, 4 ethoxylated moieties. Such a component is referred to herein as component D1.

[0235] According to some of the embodiments described herein, component D1 is a polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate characterized by a Tg in the range of 50°C to 150°C at curing, including any intermediate and partial ranges between these, and containing fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties, for example, 4 ethoxylated moieties.

[0236] According to some of the embodiments described herein, component D1 is a bifunctional ethoxylated aromatic (meth)acrylate characterized by a Tg in the range of 50°C to 150°C at curing, including any intermediate and partial ranges between these, and containing fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties, for example, 4 ethoxylated moieties.

[0237] According to some of the embodiments described herein, component D1 is a polyfunctional (e.g., difunctional) ethoxylated aromatic methacrylate characterized by a curing temperature (Tg) in the range of 50°C to 150°C, including any intermediate and partial ranges between these, and containing fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties, for example, 4 ethoxylated moieties.

[0238] According to some of the embodiments described herein, component D1 is a bifunctional ethoxylated aromatic methacrylate characterized by a curing temperature (Tg) in the range of 50°C to 150°C, including any intermediate and partial ranges between these, and containing fewer than 10 ethoxylated moieties, or fewer than 8, or fewer than 6, or fewer than 5 ethoxylated moieties, for example, 4 ethoxylated moieties.

[0239] Exemplary component D1 is, but is not limited to, one sold under the trade name SR-540, although any other material may be intended.

[0240] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate that, upon curing, is characterized by a lower Tg, for example, less than 50°C, less than 20°C, or less than 0°C, for example, -100°C to 50°C, or -100°C to 0°C, or -100°C to -20°C, or -20°C to 0°C, including any intermediate and partial ranges between these, and / or contains at least 10, or at least 15, or at least 20, or at least 25, or at least 30 ethoxylated moieties, for example, 10 to 50, or 20 to 50, or 20 to 40, or 25 to 35, including any intermediate and partial ranges between these, for example, about 30 ethoxylated moieties. Such a component is referred to herein as component D2.

[0241] According to some of the embodiments described herein, component D2 is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate characterized by a Tg of less than 50°C or less than 0°C at curing, and containing at least 10, or at least 15, or at least 20, or at least 25, or at least 30 ethoxylated moieties, for example, 10 to 50, or 20 to 50, or 20 to 40, or 25 to 35, including any intermediate and partial ranges between these, for example, about 30 ethoxylated moieties.

[0242] According to some of the embodiments described herein, component D2 is a bifunctional ethoxylated aromatic (meth)acrylate characterized by a Tg of less than 50°C or less than 0°C at curing, and containing at least 10, or at least 15, or at least 20, or at least 25, or at least 30 ethoxylated moieties, for example, 10 to 50, or 20 to 50, or 20 to 40, or 25 to 35, including any intermediate and partial ranges between these, for example, about 30 ethoxylated moieties.

[0243] According to some of the embodiments described herein, component D2 is a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by a Tg of less than 50°C or less than 0°C at curing, and containing at least 10, or at least 15, or at least 20, or at least 25, or at least 30 ethoxylated moieties, for example, 10 to 50, or 20 to 50, or 20 to 40, or 25 to 35, including any intermediate and partial ranges between these, for example, about 30 ethoxylated moieties.

[0244] According to some of the embodiments described herein, component D2 is a bifunctional ethoxylated aromatic methacrylate characterized by a Tg of less than 50°C or less than 0°C at curing, and containing at least 10, or at least 15, or at least 20, or at least 25, or at least 30 ethoxylated moieties, for example, 10 to 50, or 20 to 50, or 20 to 40, or 25 to 35, including any intermediate and partial ranges between these, for example, about 30 ethoxylated moieties.

[0245] Exemplary component D2 is, but is not limited to, one sold under the trade name SR9036A, although any other material may be intended.

[0246] Component E: According to some of the embodiments described herein, component E comprises one or more monofunctional (meth)acrylate materials.

[0247] According to some of the embodiments described herein, component E comprises two or more monofunctional (meth)acrylate materials.

[0248] According to some of the embodiments described herein, component E comprises two or more monofunctional (meth)acrylate materials, at least one of which is a monofunctional methacrylate also referred to herein as component E1, and at least one which is a monofunctional acrylate also referred to herein as component E2 or E3. Optionally, component E2 is or comprises a monofunctional alicyclic acrylate comprising one or more alicyclic moieties directly or indirectly bonded to the acrylate moiety. Component E2 may be amphiphilic, hydrophilic, or hydrophobic, preferably amphiphilic or hydrophobic.

[0249] According to some of the embodiments described herein, at least one or each of components E1, E2, and E3 is a hydrophilic and / or amphiphilic material.

[0250] As used throughout this specification, the term “hydrophilic” refers to a physical property of a material or part of a material (e.g., a chemical group in a compound) that typically consists of the transient formation of bonds with water molecules by hydrogen bonding.

[0251] Hydrophilic materials dissolve more readily in water than in oil or other hydrophobic solvents. Hydrophilic materials can be determined, for example, by having a LogP of less than 0.5 when the LogP is determined in octanol and aqueous phase at room temperature.

[0252] Hydrophilic materials can be determined by having an oil-lipophilic / hydrophilic balance (HLB) of at least 10 or at least 12 according to the Davis method.

[0253] As used throughout this Specification, the term “amphiphilic” refers to a property of a material that possesses both the hydrophilicity described herein for hydrophilic materials and the hydrophobic or lipophilic properties as defined herein for hydrophobic materials.

[0254] Amphiphilic materials typically comprise both hydrophilic and hydrophobic groups as defined herein, and are substantially soluble in both water and water-immiscible solvents (oils).

[0255] Amphiphilic materials can be determined, for example, to have a LogP of 0.8 to 1.2, or about 1, when the LogP is determined in the octanol and aqueous phases at room temperature.

[0256] Amphiphilic materials can be determined by having an oil-lipid / hydrophilic balance (HLB) of 3 to 12 or 3 to 9, according to the Davis method, or in addition.

[0257] As used throughout this specification, the term “hydrophobic” refers to the physical property of a material or part of a material (e.g., a chemical group in a compound) that does not form bonds with water molecules. Hydrophobic materials dissolve more readily in oil than in water. A hydrophobic material can be determined, for example, to have a LogP greater than 1, preferably greater than 2, when the LogP is determined in the octanol and aqueous phases.

[0258] Hydrophilic materials or parts of materials (e.g., chemical groups in a compound) are typically charge-polarized and capable of hydrogen bonding.

[0259] Amphiphilic materials typically contain one or more hydrophilic groups (e.g., charge-polarizing groups) in addition to hydrophobic groups.

[0260] Hydrophilic materials or groups, and amphiphilic materials, typically contain one or more electron-donating heteroatoms that form strong hydrogen bonds with water molecules. Examples of such heteroatoms include, but are not limited to, oxygen and nitrogen. Preferably, the ratio of carbon atoms to heteroatoms in the hydrophilic material or group is 10:1 or less, and may be, for example, 8:1, more preferably 7:1, 6:1, 5:1, or 4:1, or less. It should be noted that the hydrophilicity and amphiphilicity of materials and groups can also arise from the ratio of hydrophobic to hydrophilic portions in the material or chemical group, and do not depend solely on the ratios shown above.

[0261] Hydrophilic or amphiphilic materials may have one or more hydrophilic groups or moieties. Hydrophilic groups are typically polar groups containing one or more electron-donating heteroatoms, such as oxygen and nitrogen.

[0262] Examples of hydrophilic groups include, but are not limited to, electron-donating heteroatoms, carboxylates, thiocarboxylates, oxo(=O), linear amides, hydroxyl groups, (C1-4) alkoxy groups, (C1-4) alcohols, heteroalicyclic groups (e.g., having the carbon-to-heteroatom ratio as defined herein), cyclic carboxylic acid esters such as lactones, cyclic amides such as lactams, carbamates, thiocarbamates, cyanurates, isocyanurates, thiocyanurates, ureas, thioureas, alkylene glycols (e.g., ethylene glycol or propylene glycol), and hydrophilic polymers or oligomer moieties (these terms are defined below), as well as any combination thereof (e.g., hydrophilic groups comprising two or more of the listed hydrophilic groups).

[0263] In some embodiments, the hydrophilic group is or comprises an electron-donating heteroatom, a carboxylate, a heteroalicyclic compound, an alkylene glycol, and / or a hydrophilic oligomer moiety.

[0264] The amphiphilic moiety or group is typically one or more hydrophilic groups and one or more hydrophobic groups, as described herein, or a heteroatom-containing group or moiety whose ratio of carbon atoms to heteroatoms explains the amphiphilicity.

[0265] A hydrophilic or amphiphilic monofunctional curable material according to some embodiments of the present invention may be a hydrophilic acrylate represented by the following formula A1: [ka] In formula A1, R1 and R2 are as defined herein, and at least one of R1 and R2 is a hydrophilic or amphiphilic part or group as defined herein, and / or includes such part.

[0266] In some of these embodiments, the carboxylate group, -C(=O)-ORa, comprises Ra, which is a hydrophilic or amphiphilic moiety or group as defined herein. Exemplary Ra groups relevant to these embodiments include, but are not limited to, heteroalicyclic groups (where the ratio of carbon atoms to electron-donating heteroatoms is 10:1, 8:1, 6:1, 5:1 or less, such as morpholine, tetrahydrofuran, oxalidine, and the like), hydroxyls, C(1-4) alkoxys, thiols, alkylene glycols, or hydrophilic or amphiphilic polymers or oligomeric moies as described herein.

[0267] Examples of hydrophilic or amphiphilic oligomer monofunctional curable materials include, but are not limited to, mono-(meth)acrylated urethane oligomer derivatives of polyethylene glycol, mono-(meth)acrylated polyol oligomers, mono-(meth)acrylated oligomers having hydrophilic substituents, mono-(meth)acrylated polyethylene glycol (e.g., methoxypolyethylene glycol), and monourethane acrylates.

[0268] According to some of any of the embodiments described herein, component E1 is a hydrophilic or amphiphilic monofunctional methacrylate.

[0269] According to some of any of the embodiments described herein, component E2 is a monofunctional acrylate, and in some embodiments, this is a monofunctional acrylate having an alicyclic group as Ra in formula A1.

[0270] According to some of any of the embodiments described herein, component E1 is a hydrophilic or amphiphilic monofunctional methacrylate, component E2 is a monofunctional acrylate, and in some embodiments, this is a monofunctional acrylate having an alicyclic group as Ra in formula A1.

[0271] Exemplary materials that can be used as component E1 include, for example, methacrylates characterized by a hydroxyalkyl group such as those sold under the trade name BISOMER® HPMA, but are not limited thereto.

[0272] Exemplary materials that can be used as component E2 include, for example, acrylates characterized by a monocyclic or bicyclic hydrocarbon group (cycloalkyl) such as those sold under the trade names Genomer 1120, SR-789, and SR-420, but are not limited thereto.

[0273] Component E3 is a hydrophilic or amphiphilic, preferably water-soluble monofunctional acrylate as described herein or includes this, which can be aliphatic or alicyclic. In an exemplary embodiment, component E3 is a hydrophilic heteroalicyclic acrylate. An exemplary hydrophilic monomer monofunctional acrylate is acryloyl morpholine (ACMO).

[0274] According to some of any of the embodiments described herein, each of the monofunctional materials (components E1, E2, and E3) has an average molecular weight of less than 1,000 grams / mole or less than 500 grams / mole, for example, 100 grams / mole to 500 grams / mole, or 100 grams / mole to 400 grams / mole, or 100 grams / mole to 300 grams / mole, including any intermediate values and sub-ranges therebetween.

[0275] According to some of any of the embodiments described herein, component E is included in the formulation, inter alia, to balance properties such as reactivity and / or viscosity, and components E1, E2, and / or E3, and their ratios are selected accordingly.

[0276] According to some of any of the embodiments described herein, when two or more of components E1, E2, and E3 are included in a formulation as described herein, the weight ratio between each two components can be, for example, in the range of 1:5 to 5:1, or 3:1 to 1:3, or 2:1 to 1:2, including any intermediate values and sub-ranges therebetween.

[0277] According to some of any of the embodiments described herein, at least components E1 and E2 are included in a formulation as described herein.

[0278] According to some of any of the embodiments described herein, the weight ratio of monofunctional methacrylate (component E1) to monofunctional acrylate (component E2) is in the range of 2:1 to 1:2 when both are included in a formulation as described herein.

[0279] According to some of any of the embodiments described herein, at least one or all of the monofunctional alicyclic acrylate (component E2), monofunctional methacrylate (component E1), and hydrophilic or amphiphilic monofunctional acrylate (component E3) are characterized by a Tg of less than 100 °C or less than 80 °C upon curing.

[0280] According to some of the embodiments described herein, the monofunctional alicyclic acrylate (component E2) is characterized by a curing temperature (Tg) of less than 100°C or less than 80°C.

[0281] According to some of the embodiments described herein, the monofunctional methacrylate (component E1) is characterized by a curing temperature (Tg) of less than 100°C or less than 80°C.

[0282] Ingredient F: According to some of the embodiments described herein, component F is a trifunctional (meth)acrylate.

[0283] According to some of the embodiments described herein, component F is a polyfunctional (e.g., trifunctional) (meth)acrylate characterized by a Tg of over 150°C, over 180°C, or over 200°C at curing.

[0284] According to some of the embodiments described herein, component F is a polyfunctional (e.g., trifunctional) cyclic (meth)acrylate comprising one or more cyclic moieties, such as aryl and / or alicyclic, and is also referred to herein as component F1.

[0285] According to some of the embodiments described herein, component F1 is a trifunctional cyclic (meth)acrylate comprising one or more cyclic moieties, such as aryl and / or alicyclic.

[0286] According to some of the embodiments described herein, component F1 is a trifunctional cyclic methacrylate or cyclic trimethacrylate comprising one or more cyclic moieties, such as aryl and / or alicyclic.

[0287] According to some of the embodiments described herein, component F or F1 is characterized by a high Tg at curing, for example, a Tg greater than 100°C, or greater than 150°C, or greater than 200°C, or even greater than 250°C.

[0288] According to some of the embodiments described herein, component F1 is a trifunctional cyclic methacrylate or cyclic trimethacrylate comprising one or more cyclic moieties, such as aryl and / or alicyclic, and characterized by a high Tg at curing, for example, above 100°C, above 150°C, above 200°C, or even above 250°C.

[0289] In any of the embodiments of component F or F1, the cyclic portion is a branched unit as defined herein.

[0290] In some embodiments of component F or F1, the cyclic portion is or comprises a cyanurate or isocyanurate.

[0291] In any of the embodiments of component F or F1, the cyclic portion is or comprises a cyanurate or isocyanurate, is a branched unit from which a portion containing a (meth)acrylate group extends. Examples of such materials are sold under the trade name SR-368, but are not limited to these.

[0292] Ingredient G: According to some of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a low Tg and preferably having an average MW of at least 1,000 g / mol, for example, an average MW of 1,000 g / mol to 10,000 g / mol, including any intermediate and partial ranges between these values. Such components are also referred to herein as oligomeric curable materials.

[0293] According to some of any of the embodiments described herein, component G is a bifunctional aliphatic urethane (meth)acrylate having an average MW of at least 1,000 grams / mole, for example, an average MW of 1,000 grams / mole to 10,000 grams / mole, any intermediate value and sub-range therebetween, and values including such intermediate values. According to some of any of the embodiments described herein, component G (including component G1 and component G2) is an oligomeric bifunctional aliphatic urethane (meth)acrylate.

[0294] According to some of any of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane methacrylate having an average MW of at least 1,000 grams / mole, for example, an average MW of 1,000 grams / mole to 10,000 grams / mole, any intermediate value and sub-range therebetween, and values including such intermediate values.

[0295] According to some of any of the embodiments described herein, component G is a bifunctional aliphatic urethane methacrylate having an average MW of at least 1,000 grams / mole.

[0296] According to some of any of the embodiments described herein, component G is a bifunctional aliphatic urethane acrylate having an average MW of at least 1,000 grams / mole.

[0297] According to some of any of the embodiments described herein, component G is characterized by a low Tg upon curing.

[0298] According to some of any of the embodiments described herein, component G is characterized by a Tg of less than 100 °C or less than 80 °C upon curing.

[0299] According to some of any of the embodiments described herein, component G is a nonpolar (e.g., non-hydrophilic or hydrophobic) polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate as described herein.

[0300] According to some of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a Tg of less than 0°C, e.g., -100°C to 0°C, or -100°C to 20°C, including any intermediate and partial ranges between these, and preferably having an average MW of at least 1,000 grams / mol, e.g., 1,000 grams / mol to 10,000 grams / mol, including any intermediate and partial ranges between these. Such component is also referred to herein as component G1.

[0301] According to some of the embodiments described herein, component G1 is a bifunctional aliphatic urethane (meth)acrylate characterized by a Tg of less than 0°C, e.g., -100°C to 0°C, or -100°C to -20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 g / mol, e.g., 1,000 g / mol to 10,000 g / mol, including any intermediate and partial ranges between these.

[0302] According to some of the embodiments described herein, component G1 is a polyfunctional (e.g., bifunctional) aliphatic urethane acrylate characterized by a Tg of less than 0°C, e.g., -100°C to 0°C, or -100°C to -20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 g / mol, e.g., 1,000 g / mol to 10,000 g / mol, including any intermediate and partial ranges between these.

[0303] According to some of the embodiments described herein, component G1 is a bifunctional aliphatic urethane acrylate characterized by a Tg of less than 0°C, e.g., -100°C to 0°C, or -100°C to -20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 g / mol, or at least 2,000 g / mol, or at least 3,000 g / mol, e.g., 3,000 g / mol to 10,000 or 3,000 g / mol to 8,000 g / mol, including any intermediate and partial ranges between these.

[0304] The example ingredient G1 is sold under the trade name CN9002, but any other material may be used.

[0305] According to some of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a Tg of less than 100°C, e.g., 0°C to 100°C, or 0°C to 50°C, or 0°C to 20°C, or -20°C to 50°C, or -20°C to 20°C, including any intermediate and partial ranges between these, and preferably having an average MW of at least 1,000 grams / mol, e.g., 1,000 grams / mol to 10,000 grams / mol, including any intermediate and partial ranges between these. Such a component is also referred to herein as component G2.

[0306] According to some of the embodiments described herein, component G2 is a bifunctional aliphatic urethane (meth)acrylate characterized by a Tg of less than 100°C, e.g., 0°C to 100°C, or 0°C to 50°C, or 0°C to 20°C, or -20°C to 50°C, or -20°C to 20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 grams / mol, e.g., 1,000 grams / mol to 10,000 grams / mol, including any intermediate and partial ranges between these.

[0307] According to some of the embodiments described herein, component G2 is a polyfunctional (e.g., bifunctional) aliphatic urethane methacrylate characterized by a Tg of less than 100°C, e.g., 0°C to 100°C, or 0°C to 50°C, or 0°C to 20°C, or -20°C to 50°C, or -20°C to 20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 grams / mol, e.g., 1,000 grams / mol to 10,000 grams / mol, including any intermediate and partial ranges between these.

[0308] According to some of the embodiments described herein, component G2 is a bifunctional aliphatic urethane methacrylate characterized by a Tg of less than 100°C, e.g., 0°C to 100°C, or 0°C to 50°C, or 0°C to 20°C, or -20°C to 50°C, or -20°C to 20°C, including any intermediate and partial ranges between these, and having an average MW of at least 1,000 g / mol, e.g., 1,000 g / mol to 5,000 g / mol or 1,000 g / mol to 3,000 g / mol, including any intermediate and partial ranges between these.

[0309] The example ingredient G2 is sold under the trade name CN1970EU, but any other material may be used.

[0310] Component H According to some of the embodiments described herein, the molding material formulation further comprises a dispersant (component H).

[0311] According to some of these embodiments, the dispersant is characterized by a curable group, preferably a (meth)acrylic group.

[0312] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., bifunctional) aliphatic silicon (meth)acrylate.

[0313] According to some of the embodiments described herein, the dispersant is a bifunctional aliphatic silicon (meth)acrylate.

[0314] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., bifunctional) aliphatic silicon acrylate.

[0315] According to some of the embodiments described herein, the dispersant is a bifunctional aliphatic silicon acrylate.

[0316] According to some of the embodiments described herein, the dispersant has an average MW of at least 1,000 grams / mol, or at least 2,000 grams / mol, or at least 3,000 grams / mol, and is considered an oligomeric material.

[0317] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., bifunctional) aliphatic silicon (meth)acrylate having an average MW of at least 1,000 grams / mol as described herein.

[0318] According to some of the embodiments described herein, the dispersant is a bifunctional aliphatic silicon (meth)acrylate having an average MW of at least 1,000 grams / mol, as described herein.

[0319] According to some of the embodiments described herein, the dispersant is a polyfunctional (e.g., bifunctional) aliphatic silicon acrylate having an average MW of at least 1,000 g / mol.

[0320] According to some of the embodiments described herein, the dispersant is a bifunctional aliphatic silicon acrylate having an average MW of at least 1,000 grams / mol, as described herein.

[0321] According to some of the embodiments described herein, the dispersant is characterized by a low Tg at curing, preferably below 0°C, or below -20°C, or below -50°C.

[0322] According to some of the embodiments described herein, the amount of the dispersant is in the range of 0.1% to 1% by weight or 0.1 to 0.5% by weight of the total weight of the composition, including any intermediate and partial ranges between these.

[0323] Additional ingredients: According to any one of the embodiments described herein, the molding material formulation further comprises a polymerization inhibitor (component I), such as a phenolic polymerization inhibitor, or other polymerization inhibitors commonly used in medical devices or applications and / or food products, as described herein.

[0324] According to some of the embodiments described herein, the amount of polymerization inhibitor is in the range of 0.001% by weight to 0.010% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0325] According to any one of the embodiments described herein, the molding material formulation further comprises at least one photoinitiator (component J).

[0326] According to some of the embodiments described herein, the amount of the photoinitiator is in the range of 1% to 5% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0327] According to some of the embodiments described herein, the photoinitiator comprises or is essentially derived from a phosphine oxide-based (e.g., monoacrylated (MAPO) or bisacrylated phosphine oxide-based (BAPO)) photoinitiator.

[0328] Examples of monoacyl and bisacylphosphine oxides include, but are not limited to, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, dibenzoylphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, tris(2,4-dimethylbenzoyl)phosphine oxide, tris(2-methoxybenzoyl)phosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, 2,6-dichlorobenzoyldiphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyl-bis(2,6-dimethylphenyl)phosphonate, and 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide. Commercially available phosphine oxide photoinitiators capable of initiating free radicals when irradiated in the wavelength range of approximately 380 nm to approximately 450 nm include 2,4,6-trimethylbenzoyldiphenylphosphine oxide (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (sold as IRGACURE® 819), and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide (CGI). Examples include (sold as 403), a mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one in a weight ratio of 25:75 (sold as IRGACURE® 1700), a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one in a weight ratio of 1:1 (sold as DAROCUR® 4265), and ethyl 2,4,6-trimethylbenzylphenylphosphine (LUCIRIN LR8893X).

[0329] In exemplary embodiments, the photoinitiator is or comprises bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (marketed as IRGACURE® 819).

[0330] In exemplary embodiments, the photoinitiator does not contain 2,4,6-trimethylbenzoyldiphenylphosphine oxide (marketed as TPO) and / or bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (marketed as IRGACURE® 819).

[0331] According to some of the embodiments described herein, the molding material formulation is a transparent (e.g., translucent), colorless formulation that does not contain any colorants.

[0332] According to some of the embodiments described herein, the molding material formulation further comprises one or more colorants (component P).

[0333] The coloring agent may be a pigment or a dye, and is preferably a pigment.

[0334] The pigment may be an organic pigment and / or an inorganic pigment and / or a metallic pigment, and in some embodiments, the pigment is a nanoscale pigment containing nanoparticles.

[0335] Examples of inorganic pigments include nanoparticles of titanium dioxide and / or zinc oxide and / or silica. Examples of organic pigments include nano-sized carbon black.

[0336] In some embodiments, a combination of white and colored pigments is used to prepare a colored curing material.

[0337] According to some of the embodiments described herein, the colorant comprises a mixture of a pigment and at least one (meth)acrylic material, such that the pigment is introduced into the formulation within the mixture.

[0338] According to some of the embodiments described herein, the pigment is a white pigment, and the formulation provides a white, hardened material.

[0339] According to some of the embodiments described herein, the colorant comprises a mixture of a white pigment and one or more curable materials, such as a (meth)acrylic material, and as a result, the pigment is introduced into the formulation within this mixture.

[0340] According to some of these embodiments, the amount of white pigment in the mixture is in the range of 20% to 50% by weight of the total weight of the mixture, including any intermediate and partial ranges between these.

[0341] According to some of these embodiments, the amount of the colorant, which is a mixture of a white pigment and at least one (meth)acrylic material, is in the range of 1 to 5% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0342] According to some of the embodiments described herein, the pigment is a cyan pigment, and the formulation provides a cyan hardened material.

[0343] According to some of the embodiments described herein, the colorant comprises a mixture of a cyan pigment and one or more curable materials such as a (meth)acrylic material, and as a result, the cyan pigment is introduced into the formulation within this mixture.

[0344] According to some of these embodiments, the amount of cyan pigment in the mixture is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight of the total weight of the mixture.

[0345] According to some of these embodiments, the amount of the colorant, which is a mixture of a cyan pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0346] According to some of the embodiments described herein, the pigment is a yellow pigment, and the formulation provides a yellow hardened material.

[0347] According to some of the embodiments described herein, the colorant comprises a mixture of a yellow pigment and one or more curable materials such as a (meth)acrylic material, and as a result, the yellow pigment is introduced into the formulation within this mixture.

[0348] According to some of these embodiments, the amount of yellow pigment in the mixture is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight of the total weight of the mixture, including any intermediate and partial ranges between these.

[0349] According to some of these embodiments, the amount of the colorant, which is a mixture of a yellow pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0350] According to some of the embodiments described herein, the pigment is a magenta pigment, and the formulation provides a magenta-colored hardened material.

[0351] According to some of the embodiments described herein, the colorant comprises a mixture of a magenta pigment and one or more curable materials such as a (meth)acrylic material, and as a result the magenta pigment is introduced into the formulation within this mixture.

[0352] According to some of these embodiments, the amount of magenta pigment in the mixture is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight of the total weight of the mixture, including any intermediate and partial ranges between these.

[0353] According to some of these embodiments, the amount of the colorant, which is a mixture of magenta pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0354] According to some of the embodiments described herein, the formulation comprises one or more of white, magenta, cyan, and yellow colorants, and in some of these embodiments, each pigment is introduced into the formulation in a mixture with a curable material as described herein.

[0355] According to some of the embodiments described herein, the colorant further comprises a pigment dispersant (component Dp). A preferred pigment dispersant is one having multiple groups characterized by affinity for the pigment.

[0356] According to some of the embodiments described herein, the molding material formulation comprises components H, I, and J, as described herein in any of the respective embodiments. An exemplary such formulation is a transparent, colorless formulation, which is free of colorants (and does not contain component P as described herein).

[0357] According to some of the embodiments described herein, the molding material formulation comprises components H, I, J, and P, as described herein in any of the respective embodiments. An exemplary such formulation is a white formulation comprising a white pigment as described herein.

[0358] According to some of the embodiments described herein, the molding material formulation comprises components H, I, J, P, and Dp, as described herein in any of the respective embodiments. Exemplary such formulations are cyan, magenta, and yellow formulations as described herein.

[0359] Type B molding material formulation: According to some embodiments of the present invention, a molding material formulation (curable formulation) that can be used for additive manufacturing of denture structures, and which is referred to herein as a Type B formulation, is provided.

[0360] According to some of the embodiments described herein, a Type B formulation includes a combination of a polyfunctional (meth)acrylate material characterized by a relatively high MW (e.g., greater than 1,000 grams / mol; oligomeric material) and a relatively low Tg (e.g., less than 100°C), such as component D2, component G1 and component G2 as described herein, a monofunctional material such as component E (e.g., component E1, component E2 and / or component E3), and optionally and preferably component H as described herein in any of the respective embodiments.

[0361] According to some of the embodiments described herein, the Type B formulation comprises component D2, component G, preferably component G2, and a mixture of two or more components E1, E2, and E3.

[0362] According to any one of the embodiments described herein, a Type B formulation is: A polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (component D2) characterized by at least 10 ethoxylated groups and / or a Tg below 0°C; A polyfunctional (e.g., bifunctional) urethane (meth)acrylate (component G) characterized by a Tg of less than 100℃; At least one monofunctional alicyclic (meth)acrylate, preferably a monofunctional alicyclic acrylate (component E2); Optionally, at least one monofunctional acrylate (component E3) which is preferably hydrophilic or amphiphilic; At least one dispersant (component H), Includes.

[0363] According to some embodiments, the formulation comprises at least one polyfunctional (e.g., difunctional) ethoxylated aromatic (meth)acrylate (component D2) characterized by at least 10 ethoxylated groups and / or a Tg below 0°C; and preferably component G2 as described herein, in a total amount of at least one polyfunctional (e.g., difunctional) urethane (meth)acrylate (component G) characterized by a Tg below 100°C, including 20% ​​to 50% by weight, or 30% to 50% by weight, or 35% to 45% by weight (of components D2 and G), including any intermediate and partial ranges between these.

[0364] According to some of the embodiments described herein, the formulation further comprises a mixture of two or more of component E2 and component E3, in some of these embodiments, the total amount of this mixture includes 40% to 60% by weight, or 45% to 60% by weight, or 50% to 60% by weight, or any intermediate and partial ranges between these, of the total weight of the formulation.

[0365] According to some embodiments, the composition is: A polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by at least 10 ethoxylated groups and / or a Tg below 0°C; A polyfunctional (e.g., bifunctional) urethane (meth)acrylate (e.g., component G) characterized by a Tg of less than 100℃; At least one monofunctional alicyclic (meth)acrylate (e.g., component E2), preferably a monofunctional alicyclic acrylate; Preferably, with at least one hydrophilic or amphiphilic monofunctional acrylate (e.g., component E3); At least one dispersant (e.g., component H), Includes.

[0366] According to some of the embodiments described herein, the formulation is: A total amount of 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these, containing at least one polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (e.g., component D2) characterized by at least 10 ethoxylated groups and / or a Tg below 0°C; The total amount of the compound, including any intermediate and partial ranges between 15% and 25% by weight, is at least one polyfunctional (e.g., bifunctional) urethane (meth)acrylate (e.g., component G) characterized by a Tg of less than 100°C; At least 40% by weight, or at least 45% by weight, or 45% to 55% by weight, of the total weight of the composition, including any intermediate and partial ranges between these, is at least one monofunctional alicyclic (meth)acrylate, preferably a monofunctional alicyclic acrylate (e.g., component E2); The total weight of the formulation includes 3% to 10% by weight, or 5% to 10% by weight, or 3% to 8% by weight, including any intermediate and partial ranges between these, preferably with at least one hydrophilic or amphiphilic monofunctional acrylate (e.g., component E3); In any of the embodiments, at least one dispersant as described herein (e.g., component H), Includes.

[0367] According to some of the embodiments described herein, the formulation is: The total weight of the formulation includes 15% to 25% by weight, including any intermediate and partial ranges between these, of at least one polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (component D2) characterized by at least 10 ethoxylated groups and / or a Tg below 0°C; The total amount of the compound, including 15% to 25% by weight, any intermediate and partial ranges between these, is at least one polyfunctional (e.g., bifunctional) urethane (meth)acrylate (component G) characterized by a Tg of less than 100°C; At least 40% by weight, or at least 45% by weight, or 45% to 55% by weight, of the total weight of the composition, including any intermediate and partial ranges between these, is at least one monofunctional alicyclic (meth)acrylate, preferably a monofunctional alicyclic acrylate (component E2); The total weight of the formulation includes 3% to 10% by weight, or 5% to 10% by weight, or 3% to 8% by weight, including any intermediate and partial ranges between these, preferably with at least one hydrophilic or amphiphilic monofunctional acrylate (component E3); At least one dispersant (component H), Includes.

[0368] With respect to Type B formulations, according to some of the embodiments described herein, the formulation is: In any of the embodiments and any combination thereof, component D2 is included in the total amount of the formulation in an amount of 15% to 25% by weight, including any intermediate and partial ranges between these amounts; In a total amount including 15% to 25% by weight of the total weight of the formulation, any intermediate and partial range between these, component G, preferably component G2, as described herein in any of the embodiments and any combination thereof; At least 40% by weight, or at least 45% by weight, or 45% to 55% by weight, including any intermediate and partial ranges between these, of the total weight of the formulation, with at least one or at least two components E2 as specified herein in any of the embodiments and any combination thereof; In a total amount including 3% to 10% by weight, or 5% to 10% by weight, or 3% to 8% by weight, or any intermediate and partial ranges between these, in any embodiment and any combination thereof, at least one component E3 as specified herein; Preferably, the total amount of the composition is 0.1% to 1% by weight or 0.1% to 0.5% by weight, including any intermediate and partial ranges between these, and in any one embodiment and any combination thereof, at least one dispersant described herein. Includes.

[0369] With respect to Type B formulations, according to some of the embodiments described herein, component D2 comprises a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate characterized by at least 10 ethoxylated groups, and having a Tg below 0°C at curing.

[0370] According to some of the embodiments described herein for the Type B formulation, component D2 has a molecular weight of at least 1,000 grams / mol.

[0371] According to some of the embodiments described herein for type B formulations, component D2 is a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups.

[0372] With respect to Type B formulations, according to some of the embodiments described herein, component D2 comprises a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, a curing time of less than 0°C, and a molecular weight of at least 1,000 grams / mol.

[0373] With respect to Type B formulations, according to some of the embodiments described herein, component G comprises or comprises a polyfunctional (e.g., bifunctional) urethane (meth)acrylate having a molecular weight of at least 1,000 grams / mol.

[0374] With respect to Type B formulations, according to some of the embodiments described herein, component G is characterized by a Tg of less than 100°C, preferably 0°C to 100°C, or 50°C to 100°C, including any intermediate and partial ranges between these, and is or includes component G2 as described herein.

[0375] With respect to Type B formulations, according to some of the embodiments described herein, component G comprises a polyfunctional (e.g., bifunctional) urethane methacrylate.

[0376] With respect to Type B formulations, according to some of the embodiments described herein, component D2 comprises a polyfunctional (e.g., bifunctional) ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, a curing time of less than 0°C, and a molecular weight of at least 1,000 grams / mol.

[0377] Component G comprises component G2, which is a polyfunctional (e.g., bifunctional) urethane (meth)acrylate having a molecular weight of at least 1,000 grams / mol, characterized by a Tg in the range of 0°C to 100°C or 50°C to 100°C, any intermediate and partial range between these values, when curing.

[0378] With respect to Type B formulations, according to some of the embodiments described herein, the total amount of at least one component D2 and at least one component G (e.g., component G2) is in the range of about 30% to about 50% by weight, or about 40% to about 50% by weight, of the total weight of the formulation, including any intermediate and partial ranges between these.

[0379] According to some of the embodiments described herein for type B formulations, at least one component E2 has a molecular weight (MW) of 500 grams / mol or less (e.g., 100 grams / mol to 500 grams / mol).

[0380] With respect to Type B formulations, according to some of the embodiments described herein, each of the one or more components E2 independently features a Tg of less than 100°C or less than 50°C at curing (e.g., 20°C to 60°C, or 20°C to 50°C, including any intermediate and partial ranges between these).

[0381] With respect to Type B formulations, according to some of the embodiments described herein, one or more components E2 comprises a monofunctional alicyclic, preferably hydrophobic, acrylate having a molecular weight (MW) of 500 g / mol or less (e.g., 100 g / mol to 500 g / mol) and a curing temperature (Tg) of less than 100°C or less than 50°C (e.g., 20°C to 60°C, or 20°C to 50°C, including any intermediate and partial ranges between these).

[0382] According to some of the embodiments described herein for type B formulations, component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of 500 grams / mol or less (e.g., 100 grams / mol to 500 grams / mol).

[0383] With respect to Type B formulations, according to some of the embodiments described herein, component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate characterized by a Tg of over 50°C or over 80°C at curing (e.g., 50°C to 150°C, including any intermediate and partial ranges between these).

[0384] With respect to Type B formulations, according to some of the embodiments described herein, the amount of component H is at least 0.1% by weight of the total weight of the formulation, or 0.1 to 1% by weight, or 0.1 to 0.5% by weight, including any intermediate and partial ranges between these.

[0385] According to some of the embodiments described herein for Type B formulations, component D2 comprises a polyfunctional (e.g., difunctional) ethoxylated aromatic methacrylate having a molecular weight of at least 1,000 g / mol, characterized by at least 10 ethoxylated groups, having a molecular weight of at least 1,000 g / mol, and characterized by a Tg of less than 0°C at curing; component G comprises component G2, which is a polyfunctional (e.g., difunctional) urethane (meth)acrylate having a molecular weight of at least 1,000 g / mol, characterized by a Tg of 0°C to 100°C, or in the range of 50°C to 100°C, any intermediate and partial range between these, and characterized by a molecular weight of at least 1,000 g / mol at curing; the total amount of at least one component D2 and at least one component G2 is at least 35% by weight, or at least 40% by weight, or 35-50% by weight of the total weight of the formulation. The amount is in the range of % by volume or about 40-50% by weight; at least one component E2 comprises a monofunctional alicyclic, preferably hydrophobic acrylate having a molecular weight (MW) of 500 g / mol or less (e.g., 100-500 g / mol) and a Tg at curing of less than 100°C or less than 50°C (e.g., 20°C-60°C, or 20°C-50°C, including any intermediate and partial ranges between these); at least one component E3 comprises 500 g The compound comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of less than or equal to 100 g / mol to 500 g / mol and characterized by a curing time (Tg) of over 50°C or over 80°C (e.g., 50°C to 150°C, including any intermediate and partial ranges between these); and the amount of component H is at least 0.1% by weight of the total weight of the compound, or in the range of 0.1% to 1% by weight or 0.1% to 0.5% by weight.

[0386] With respect to Type B formulations, according to some of the embodiments described herein, the formulation further comprises a polymerization inhibitor (component I) and / or a photoinitiator (component J), as described herein in any of the respective embodiments.

[0387] With respect to Type B formulations, according to some of the embodiments described herein, the formulation further comprises a colorant (component P) which preferably comprises a mixture of a pigment and at least one (meth)acrylic material, as described herein.

[0388] In the exemplary embodiment, the pigment is a white pigment.

[0389] In exemplary embodiments, the Type B formulation does not contain a pigment or colorant component P, and is, for example, a transparent or translucent formulation.

[0390] Type A molding material formulation: According to some of the embodiments described herein, a Type A molding material formulation comprises two or more, three or more, four or more, five or more, or all of the components described herein as component A, component B, component C, component D, component E, component F, and component G (see Table 1 below), and in some of these embodiments, further comprising one or more of component H, component I, component J, component P, and component Dp (see Table 1 below).

[0391] According to any one of the embodiments described herein, a Type A molding material formulation comprises the following components: A polyfunctional (e.g., bifunctional) urethane (meth)acrylate (component A) characterized by a high Tg during curing; A polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate (component B) characterized by a high Tg during curing; Filler in the form of micron-sized particles (component C); Polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (component D); Monofunctional (meth)acrylate (component E); Polyfunctional (e.g., trifunctional) (meth)acrylate (component F); and A polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate (component G) characterized by a low Tg during curing, This includes two or more, three or more, four or more, five or more, and preferably all of them.

[0392] According to some of the embodiments described herein, component A is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a Tg greater than 100°C at curing.

[0393] According to some of the embodiments described herein, component B is a polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate characterized by a Tg greater than 100°C at curing.

[0394] According to some of the embodiments described herein, component C comprises filler particles (submicron-sized particles or nanoparticles) having an average diameter of less than 1 micron and functionalized with a curable group, as described herein.

[0395] According to some of the embodiments described herein, component D is a polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate characterized by fewer than 10 ethoxylated groups and / or a Tg including any intermediate and partial range between 50°C and 150°C at curing.

[0396] According to any one of the embodiments described herein, component E comprises at least one or at least two monofunctional (meth)acrylates.

[0397] According to some of the embodiments described herein, component F is a polyfunctional (e.g., trifunctional) cyclic (meth)acrylate.

[0398] According to some of the embodiments described herein, component G is a polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate characterized by a curing temperature (Tg) of less than 100°C.

[0399] According to some of the embodiments described herein, the amount of the filler (component C) is 20% by weight or less, or 15% by weight or less, of the total weight of the composition.

[0400] According to some of the embodiments described herein, the amount of component D is 20% by weight or less, or 15% by weight or less, of the total weight of the composition.

[0401] According to some of the embodiments described herein, the amount of filler is 20% by weight or less, or 15% by weight or less, of the total weight of the composition; and the amount of component D is 20% by weight or less, or 15% by weight or less, of the total weight of the composition.

[0402] According to any one of the embodiments described herein, a type A molding material formulation is: A polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate (component A) characterized by a Tg of over 100°C during curing; A polyfunctional (e.g., bifunctional) non-aromatic (meth)acrylate (component B) characterized by a Tg of over 100°C during curing; A filler in the form of micron-sized particles (component C) and; A polyfunctional (e.g., bifunctional) ethoxylated aromatic (meth)acrylate (component D) characterized by fewer than 10 ethoxylated groups and / or a curing temperature (Tg) in the range of 50°C to 150°C; Monofunctional (meth)acrylate (component E) and; A polyfunctional (e.g., trifunctional) cyclic (meth)acrylate (component F) and; A polyfunctional (e.g., bifunctional) aliphatic urethane (meth)acrylate (component G) characterized by a curing temperature (Tg) of less than 100°C, Includes, The amount of filler (component C) is 20% by weight or less, or 15% by weight or less, of the total weight of the compound; and The amount of component D is 20% or less by weight of the total weight of the compound, or 15% or less by weight.

[0403] According to any one of the embodiments described herein, a Type A molding material formulation comprises component A as defined herein, component B1 as defined herein, component C as defined herein, component D1 as defined herein, components E1 and E2 as defined herein, component F1 as defined herein, and component G as defined herein (e.g., component G2).

[0404] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the amount of component A described herein is in the range of 15% to 25% by weight of the total weight of the composition, including any intermediate and partial ranges between these.

[0405] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the amount of each of components B and C described herein is 20% by weight or less, or 15% by weight or less, of the total weight of the composition, and includes, for example, an amount in the range of about 5% by weight to about 20% by weight, or preferably about 5% by weight to about 15% by weight, any intermediate and partial ranges between these.

[0406] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the amount of component D described herein is 20% by weight or less, or 15% by weight or less, of the total weight of the composition, preferably in the range of about 5% by weight to about 20% by weight, or preferably in the range of about 5% by weight to about 15% by weight, including any intermediate and partial ranges between these.

[0407] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the total amount of component E described herein is in the range of 30% to 40% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0408] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the amount of component F described herein is in the range of 5% to 10% by weight of the total weight of the composition, including any intermediate and partial ranges between these.

[0409] According to some of the embodiments described herein, in any of the embodiments and any combination thereof, the amount of component G described herein is in the range of about 5% to about 10% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0410] According to any one of the embodiments described herein, a type A molding material formulation is: The amount is in the range of 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these, and in any of the embodiments and any combination thereof, with respect to component A as described herein; Each component B and C described herein are added independently in an amount of 20% by weight or less, or 15% by weight or less, of the total weight of the composition, in any of the embodiments and any combination thereof; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component D as described herein is included in each embodiment and any combination thereof; In amounts including 30% to 40% by weight of the total weight of the formulation, any intermediate and partial ranges between these, with component E as described herein in any of the embodiments and any combination thereof; In amounts including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial ranges between these, with component F as described herein in any of the embodiments and any combination thereof; In amounts including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial ranges between these, in any of the embodiments and any combination thereof, Component G as described herein, Includes.

[0411] According to any one of the embodiments described herein, a type A molding material formulation is: The amount is in the range of 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these, and in any of the embodiments and any combination thereof, with respect to component A as described herein; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component B as described herein is present in any embodiment and any combination thereof; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component C as described herein is present in any embodiment and any combination thereof; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component D as described herein is included in each embodiment and any combination thereof; In a total amount including 30% to 40% by weight of the total weight of the formulation, any intermediate value and partial range between these, components E1 and E2 as described herein in any of the embodiments and any combination thereof; In any of the embodiments and any combination thereof, the amount of component F1 described herein is 5% to 10% by weight of the total weight of the formulation, including any intermediate and partial ranges between these amounts; In amounts including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial ranges between these, in any of the embodiments and any combination thereof, Component G as described herein, Includes.

[0412] According to some of the embodiments described herein, component E1 is a hydrophilic or amphiphilic monofunctional methacrylate, and component E2 is a monofunctional acrylate, which in some embodiments is a monofunctional acrylate having an alicyclic group as Ra in formula A1.

[0413] According to some of the embodiments described herein, the weight ratio of monofunctional methacrylate (E1) to monofunctional acrylate (E2) is in the range of 2:1 to 1:2, or about 1:1.

[0414] According to some of the embodiments described herein, the amount of each of the monofunctional acrylate (E2) and monofunctional methacrylate (E1) is independently in the range of 10% to 20% by weight, or 15% to 20% by weight, any intermediate and partial ranges between these, of the total weight of the composition.

[0415] According to some of the embodiments described herein, the total amount of one or more monofunctional (meth)acrylates (e.g., components E1 and E2) is in the range of 30% to 40% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0416] According to some of the embodiments described herein, at least one or both of the monofunctional acrylate (component E2) and the monofunctional methacrylate (component E1) are characterized by a curing temperature (Tg) of less than 100°C or less than 80°C.

[0417] According to an exemplary embodiment, the type A molding material formulation is: The amount is in the range of 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these, and in any of the embodiments and any combination thereof, with respect to component A as described herein; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component B, preferably component B1, as described herein in any embodiment and any combination thereof; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component C as described herein is present in any embodiment and any combination thereof; In an amount of 20% by weight or 15% by weight or less of the total weight of the formulation, component D, preferably component D1, as described herein in any embodiment and any combination thereof; A total amount of 30% to 40% by weight of the total weight of the formulation, including any intermediate and partial ranges between these, with component E as described herein, preferably a mixture of components E1 and E2, in any of the embodiments and any combination thereof; In amounts including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial ranges between these, component F, preferably component F1, as described herein in any of the embodiments and any combination thereof; In amounts including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial ranges between these, in any of the embodiments and any combination thereof, Component G as described herein, Includes.

[0418] According to an exemplary embodiment, the type A molding material formulation is: Component A is a difunctional aliphatic urethane methacrylate characterized by a curing temperature (Tg) of over 100°C, as described herein; Component B is a bifunctional alicyclic acrylate characterized by a curing temperature of over 100°C, as described herein; Component C includes silica particles having curable groups bonded thereto, such as those described herein; Component D1 is a bifunctional ethoxylated aromatic methacrylate characterized by fewer than 5 ethoxylated groups and a curing temperature range of 50°C to 150°C, as described herein; Component E consists of a monofunctional acrylate (component E2) and a monofunctional methacrylate (component E1), each independently present in an amount of 10% to 20% by weight or 15% to 20% by weight of the total weight of the formulation; Component F1 is a trifunctional isocyanurate triacrylate, and component F is a trifunctional isocyanurate triacrylate; Component G is a bifunctional aliphatic urethane dimethacrylate, such as those described herein, characterized by a curing time Tg of less than 100°C and an average MW of at least 1,000 grams / mol. Includes.

[0419] According to an exemplary embodiment, the molding material composition is: Component A is a bifunctional aliphatic urethane methacrylate characterized by a curing temperature of over 100°C, as described herein, in an amount ranging from 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these; Component B is a bifunctional alicyclic acrylate characterized by a curing temperature (Tg) of over 100°C, as described herein, in an amount of 20% by weight or less, or 15% by weight or less, of the total weight of the formulation; Component C is a component containing silica particles having a curable group bound to it, in an amount of 20% by weight or less, or 15% by weight or less, of the total weight of the compound; Component D is a difunctional ethoxylated aromatic methacrylate, comprising Component D1 in an amount of 20% or less by weight, or 15% or less by weight, of the total weight of the formulation, characterized by fewer than 5 ethoxylated groups as described herein, and having a curing temperature (Tg) in the range of 50°C to 150°C, any intermediate and partial range between these values; As component E, each independently comprises a monofunctional acrylate (component E2) and a monofunctional methacrylate (component E1) in amounts including 10% to 20% by weight or 15% to 20% by weight, including any intermediate and partial ranges between these amounts, of the total weight of the formulation, and a total amount including 30% to 40% by weight, including any intermediate and partial ranges between these amounts; Component F1 is a trifunctional isocyanurate triacrylate, and is present in an amount of 5% to 10% by weight of the total weight of the formulation, including any intermediate and partial ranges between these amounts; As component G - an amount including 5% to 10% by weight of the total weight of the formulation, any intermediate and partial range between these, a bifunctional aliphatic urethane dimethacrylate characterized by a curing time of less than 100°C and an average MW of at least 1,000 g / mol, as described herein, Includes.

[0420] According to any one of the embodiments described herein, the Type A molding material formulation includes, as component G, component G1 as described herein in any one of the respective embodiments.

[0421] According to some of the embodiments described herein, the Type A molding material formulation is a formulation that does not contain methyl methacrylate and / or methyl acrylate, and / or the cured molding material does not contain poly(methyl methacrylate) (PMMA).

[0422] Throughout this specification, "devoid of" means less than 1%, less than 0.1%, less than 0.01%, less than 0.001%, or none (zero).

[0423] According to some of the embodiments described herein, the Type A molding material formulation further comprises a dispersant (component H) as described herein in any of the respective embodiments.

[0424] According to some of the embodiments described herein, the amount of the dispersant is in the range of 0.1% to 0.5% by weight of the total weight of the composition, including any intermediate and partial ranges between these.

[0425] According to any one of the embodiments described herein, the Type A molding material formulation further comprises a polymerization inhibitor (component I), such as a phenolic polymerization inhibitor, or other polymerization inhibitors commonly used in medical devices or applications and / or food products, as described herein.

[0426] According to some of the embodiments described herein, the amount of polymerization inhibitor is in the range of 0.001% by weight to 0.010% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0427] According to any one of the embodiments described herein, the molding material formulation further comprises at least one photoinitiator (component J).

[0428] According to some of the embodiments described herein, the amount of the photoinitiator is in the range of 1% to 5% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0429] According to any one of the embodiments described herein, the Type A molding material formulation further comprises one or more colorants (component P).

[0430] The coloring agent may be a pigment or a dye, and is preferably a pigment.

[0431] The pigment may be an organic pigment and / or an inorganic pigment and / or a metallic pigment, and in some embodiments, the pigment is a nanoscale pigment containing nanoparticles.

[0432] Examples of inorganic pigments include nanoparticles of titanium dioxide and / or zinc oxide and / or silica. Examples of organic pigments include nano-sized carbon black.

[0433] In some embodiments, a combination of white and colored pigments is used to prepare a colored curing material.

[0434] According to some of the embodiments described herein, the colorant comprises a mixture of a pigment and at least one (meth)acrylic material, such that the pigment is introduced into the formulation within the mixture.

[0435] According to some of the embodiments described herein, the pigment is a white pigment, and the formulation provides a white, hardened material.

[0436] According to some of the embodiments described herein, the colorant comprises a mixture of a white pigment and one or more curable materials, such as a (meth)acrylic material, and as a result, the pigment is introduced into the formulation within this mixture.

[0437] According to some of these embodiments, the amount of white pigment in a mixture with one or more curable materials is in the range of 20% to 50% by weight of the total weight of the mixture, including any intermediate and partial values ​​between these ranges.

[0438] According to some of these embodiments, the amount of the colorant, which is a mixture of a white pigment and at least one (meth)acrylic material, is in the range of 1 to 5% by weight of the total weight of the formulation (e.g., Type A), and includes any intermediate and partial ranges between these.

[0439] According to some of the embodiments described herein, the pigment is a cyan pigment, and the formulation provides a cyan hardened material.

[0440] According to some of the embodiments described herein, the colorant comprises a mixture of a cyan pigment and one or more curable materials such as a (meth)acrylic material, and as a result, the cyan pigment is introduced into the formulation within this mixture.

[0441] According to some of these embodiments, the amount of cyan pigment in a mixture with one or more curable materials is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight, including any intermediate and partial ranges between these.

[0442] According to some of these embodiments, the amount of the colorant, which is a mixture of a cyan pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation (e.g., Type A), including any intermediate and partial ranges between these.

[0443] According to some of the embodiments described herein, the pigment is a yellow pigment, and the formulation provides a yellow hardened material.

[0444] According to some of the embodiments described herein, the colorant comprises a mixture of a yellow pigment and one or more curable materials such as a (meth)acrylic material, and as a result, the yellow pigment is introduced into the formulation within this mixture.

[0445] According to some of these embodiments, the amount of yellow pigment in a mixture with one or more curable materials is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight, including any intermediate and partial ranges between these.

[0446] According to some of these embodiments, the amount of the colorant, which is a mixture of a yellow pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation (e.g., Type A), including any intermediate and partial ranges between these.

[0447] According to some of the embodiments described herein, the pigment is a magenta pigment, and the formulation provides a magenta-colored hardened material.

[0448] According to some of the embodiments described herein, the colorant comprises a mixture of a magenta pigment and one or more curable materials such as a (meth)acrylic material, and as a result the magenta pigment is introduced into the formulation within this mixture.

[0449] According to some of these embodiments, the amount of magenta pigment in a mixture with one or more curable materials is in the range of 0.01% to 1% by weight, or 0.05% to 0.5% by weight, or 0.1% to 0.2% by weight, including any intermediate and partial ranges between these.

[0450] According to some of these embodiments, the amount of the colorant, which is a mixture of magenta pigment and at least one (meth)acrylic material, is in the range of 0.1% to 1% by weight of the total weight of the formulation (e.g., Type A), including any intermediate and partial ranges between these.

[0451] According to some of the embodiments described herein, the formulation comprises one or more of white, magenta, cyan, and yellow colorants, and in some of these embodiments, each pigment is introduced into the formulation in a mixture with a curable material as described herein.

[0452] According to some of the embodiments described herein, the colorant further comprises a pigment dispersant (component Dp). A preferred pigment dispersant is one having multiple groups characterized by affinity for the pigment.

[0453] According to some of the embodiments described herein, the molding material formulation comprises component H, component I, and component J, as described herein in any of the respective embodiments. An exemplary such formulation is a transparent, colorless formulation, which is free of colorants.

[0454] According to some of the embodiments described herein, the molding material formulation comprises components H, I, J, and P, as described herein in any of the respective embodiments. An exemplary such formulation is a white formulation comprising a white pigment as described herein.

[0455] According to some of the embodiments described herein, the molding material formulation comprises components H, I, J, P, and Dp, as described herein in any of the respective embodiments. Exemplary such formulations are cyan, magenta, and yellow formulations as described herein.

[0456] Formula sets and kits: In some of the embodiments described herein, a kit is provided comprising one or more molding material formulations described herein in any of the respective embodiments and any combination thereof.

[0457] In some of the embodiments described herein, a kit is provided comprising two or more molding material formulations described herein in any one of the embodiments and any combination thereof. In some of these embodiments, each formulation is individually packaged within the kit.

[0458] In some of the embodiments described herein, a kit is provided comprising one or more, or two or more, type B 3D printing material formulations described herein in any of the respective embodiments and any combination thereof.

[0459] In exemplary embodiments, the kit includes a combination of two or more Type B formulations that differ from each other in the presence and / or type of colorants or pigments.

[0460] In exemplary embodiments, the kit includes two or more of the clear, white, cyan, magenta, and yellow type B formulations described herein in any of the embodiments.

[0461] In some of the embodiments described herein, the kit further comprises one or more, or two or more, type A 3D printing material formulations described herein in any of the respective embodiments and any combination thereof.

[0462] In exemplary embodiments, the kit comprises a combination of two or more Type A formulations that differ from each other in the presence and / or type of colorants or pigments.

[0463] In exemplary embodiments, the kit includes two or more of the clear, white, cyan, magenta, and yellow Type A formulations described herein in any of the embodiments.

[0464] In exemplary embodiments, the kit comprises a clear (transparent) type B formulation and / or a white type B formulation, and may optionally further comprise one or more clear, white, cyan, magenta, and yellow type A formulations described herein in any of the respective embodiments.

[0465] In exemplary embodiments, the kit includes a clear (transparent) Type B formulation and, in any of the respective embodiments, one or more clear, white, cyan, magenta, and yellow Type A formulations as described herein.

[0466] In exemplary embodiments, the kit includes a clear (transparent) type B formulation and, in any of the respective embodiments, the white, cyan, magenta, and yellow type A formulations described herein.

[0467] In exemplary embodiments, the kit includes a white type B formulation and one or more clear, white, cyan, magenta, and yellow type A formulations as described herein in any of the respective embodiments.

[0468] In exemplary embodiments, the kit includes a white type B formulation and, in any of the respective embodiments, the clear, cyan, magenta, and yellow type A formulations described herein.

[0469] The kits described herein can be used for additive manufacturing of the denture structures described herein, in particular the integral denture structures described herein.

[0470] In some embodiments, each formulation is individually packaged within the kit.

[0471] In exemplary embodiments, the formulation is packaged within the kit in a suitable packaging material, preferably an impermeable material (e.g., a water and gas impermeable material), and more preferably an opaque material. In some embodiments, the kit further includes instructions for using the formulation in an additive manufacturing process, preferably a 3D inkjet printing process as described herein. The kit may further include instructions for using the formulation in the process according to the methods described herein.

[0472] According to any one of the embodiments relating to the kit, the kit may further include a support material formulation. For example, any support material formulation usable in AM such as 3D inkjet printing is intended.

[0473] According to some of these embodiments, the support material formulation is one described herein in any of the respective embodiments.

[0474] According to some of these embodiments, a set of formulations is provided, comprising one or more Type B molding material formulations and one or more Type A molding material formulations, and optionally a support material formulation as described herein. The set of formulations can be packaged in a kit as described herein. The set of formulations can be used for additive manufacturing of denture structures as described herein in any of the respective embodiments.

[0475] In exemplary embodiments, the set of formulations includes a combination of two or more Type B formulations that differ from each other in the presence and / or type of colorants or pigments.

[0476] In exemplary embodiments, the set of formulations includes two or more of the clear, white, cyan, magenta, and yellow Type B formulations described herein in any of the embodiments.

[0477] In some of the embodiments described herein, the set of formulations further comprises one or more, or two or more, type A molding material formulations described herein in any of the respective embodiments and any combination thereof.

[0478] In exemplary embodiments, the set of formulations includes a combination of two or more Type A formulations that differ from each other in the presence and / or type of colorants or pigments.

[0479] In exemplary embodiments, the set of formulations includes two or more of the clear, white, cyan, magenta, and yellow Type A formulations described herein in any of the embodiments.

[0480] In exemplary embodiments, the set of formulations includes a clear (transparent) type B formulation and / or a white type B formulation, and may optionally further include one or more clear, white, cyan, magenta, and yellow type A formulations described herein in any of the respective embodiments.

[0481] In exemplary embodiments, the set of formulations includes a clear (transparent) type B formulation and, in any of the embodiments, one or more clear, white, cyan, magenta, and yellow type A formulations as described herein.

[0482] In exemplary embodiments, the set of formulations includes a clear (transparent) type B formulation and, in any of the embodiments, the white, cyan, magenta, and yellow type A formulations described herein.

[0483] In exemplary embodiments, the set of formulations includes a white type B formulation and, in any of the embodiments, one or more clear, white, cyan, magenta, and yellow type A formulations as described herein.

[0484] In exemplary embodiments, the set of formulations includes a white type B formulation and, in any of the embodiments herein, the clear, cyan, magenta, and yellow type A formulations described herein.

[0485] Supporting material formulation: The inventors have designed and successfully implemented a support material formulation suitable for use in combination with the molding material formulations described herein.

[0486] According to some embodiments of this aspect of the present invention, the support material formulation is: An amount of non-curable, water-soluble or water-miscible polymer material, including any intermediate and partial ranges between approximately 40% and 60% by weight of the total weight of the formulation; A hydrophilic monofunctional (meth)acrylate in an amount of 15% to 25% by weight of the total weight of the formulation, including any intermediate and partial ranges between these amounts; Hydrophilic monofunctional (meth)acrylamide in an amount of 10% to 20% by weight of the total weight of the formulation, including any intermediate and partial ranges between these amounts; A polyfunctional non-aromatic (e.g., aliphatic or alicyclic) (meth)acrylate in an amount of 1% to 5% by weight of the total weight of the composition, including any intermediate and partial ranges between these amounts, Includes.

[0487] According to some of these embodiments, the non-curable polymer material includes a polyol.

[0488] In this specification and in the art, the term "polyol" refers to a polymer material characterized by two or more free hydroxyl groups, typically about 10 to several tens or hundreds of free hydroxyl groups. Representative examples of polyols include, but are not limited to, polyester polyols, polyether polyols, and urethane polyols. Preferably, the polyol is a polyether polyol such as poly(alkylene glycol).

[0489] Polyols can be linear polyols or non-linear polyols (e.g., branched polyols).

[0490] According to some of the embodiments described herein, the polyol is poly(alkylene glycol), for example, poly(ethylene glycol) or poly(propylene glycol), or a mixture thereof. In some embodiments, the polyol is poly(propylene glycol) or includes the same.

[0491] According to some of the embodiments described herein, the polyol includes alkoxylated branched-chain polyols, such as those commercially available as Polyol 3165.

[0492] According to some of the embodiments described herein, the polyol has an average molecular weight of less than 1,200 grams / mol or less than 1,000 grams / mol.

[0493] Polyols can have an average molecular weight in the range of about 200 to about 1,100, or about 400 to about 1,100, including any intermediate and subrange values ​​between these.

[0494] According to some of the embodiments described herein, the support material formulation further comprises a non-curable, water-soluble or water-miscible nonpolymer material such as a diol, triol, glycerol, or the like. In exemplary embodiments, this is a diol such as propanediol.

[0495] According to some of the embodiments described herein, the support material formulation comprises a mixture of polymeric and nonpolymeric materials described herein, and in some of these embodiments, this comprises a mixture of poly(alkylene glycol), branched-chain polyols, and diols. In some embodiments, the total amount of these materials is in the range of about 40% to about 80% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0496] According to some of the embodiments described herein, the formulation comprises one or more monofunctional curable materials.

[0497] According to some of the embodiments described herein, one or more monofunctional curable materials, or each of them, are hydrophilic materials having, for example, formula A1, as defined herein.

[0498] According to some embodiments, at least one of the monofunctional curable materials is a monofunctional (meth)acrylate, preferably a monofunctional acrylate having formula A1, where R1 is a carboxylate. In some of these embodiments, R' is a poly(alkylene glycol) as defined herein. An exemplary hydrophilic monofunctional acrylate is hexa(ethylene glycol)acrylate (6-PEA).

[0499] According to some embodiments, at least one of the monofunctional curable materials is a monofunctional (meth)acrylamide, preferably a monofunctional acrylate having formula A1 where R1 is an amide. According to some embodiments, at least one of the monofunctional curable materials is a monofunctional acrylamide. In some of these embodiments, Ra is a short alkyl group having a carbon atom length of 2-8, or 2-6, or 2-4, which is terminated by a hydrophilic group as defined herein. An exemplary such hydrophilic group is a hydroxyalkyl group, for example, hydroxyethyl.

[0500] According to some of the embodiments described herein, one or more monofunctional curable materials, or each of them, are water-miscible or water-soluble materials as defined herein.

[0501] According to some of the embodiments described herein, the formulation comprises a polyfunctional (e.g., bifunctional) aliphatic or alicyclic (meth)acrylate.

[0502] According to some embodiments, the formulation comprises a bifunctional aliphatic or alicyclic (meth)acrylate.

[0503] According to some of the embodiments described herein, the formulation comprises a polyfunctional (e.g., bifunctional) aliphatic or alicyclic acrylate.

[0504] According to some of the embodiments described herein, the formulation comprises a bifunctional aliphatic or alicyclic acrylate, i.e., an aliphatic or alicyclic diacrylate.

[0505] According to some of the embodiments described herein, the formulation comprises a polyfunctional (e.g., bifunctional) alicyclic (meth)acrylate.

[0506] According to some of the embodiments described herein, the formulation comprises a bifunctional alicyclic (meth)acrylate.

[0507] According to some of the embodiments described herein, the formulation comprises a polyfunctional alicyclic acrylate.

[0508] According to some of the embodiments described herein, the formulation comprises a bifunctional alicyclic acrylate and an alicyclic diacrylate.

[0509] According to some of the embodiments described herein, the formulation comprises a polyfunctional (e.g., bifunctional) alicyclic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 100°C.

[0510] According to some of the embodiments described herein, the formulation comprises a bifunctional alicyclic (meth)acrylate characterized by a high Tg at curing, for example, a Tg above 100°C.

[0511] According to some of the embodiments described herein, the formulation comprises a bifunctional alicyclic acrylate or alicyclic diacrylate characterized by a high Tg at curing, for example, a Tg greater than 100°C.

[0512] According to some of the embodiments described herein, the alicyclic diacrylate comprises an alicyclic moiety of at least six, seven, eight or more carbon atoms.

[0513] According to any one of the embodiments described herein, the alicyclic diacrylate includes an alicyclic portion comprising two, three or more fused rings.

[0514] According to some of the embodiments described herein, in any of the embodiments, the polyfunctional (meth)acrylate described herein is characterized by a curing temperature (Tg) of 100°C to 300°C, or 150°C to 300°C, or 100°C to 200°C, or 150°C to 200°C, including any intermediate and partial ranges between these.

[0515] According to any one embodiment of this aspect of the present invention, the support material formulation further comprises a photoinitiator and optionally one or more dispersants, inhibitors, and the like as described herein in any one embodiment of the 3D material formulation.

[0516] According to some embodiments, the amount of the photoinitiator is in the range of 0.1% to 1% by weight of the total weight of the formulation, including any intermediate and partial ranges between these.

[0517] method: According to some embodiments of the present invention, a method for additive manufacturing of three-dimensional objects as described herein is provided. The method of this embodiment can be used for the manufacture of denture structures as defined herein.

[0518] The method generally involves sequentially molding multiple layers in a structural pattern corresponding to the shape of an object, wherein the molding of at least several layers, or each of the layers, includes extruding a construction material (uncured) containing one or more molding material formulations, as described in more detail below, and exposing the extruded molding material to curing conditions, preferably curing energy (e.g., irradiation), thereby molding a cured molding material.

[0519] According to these embodiments, the construction material includes, as a build material formulation, one or more of the Type B build material formulations described herein in any one of the embodiments and any combination thereof. According to some of these embodiments, the construction material further includes, as one or more build material formulations, one or more of the Type A build material formulations described herein in any one of the embodiments and any combination thereof. According to these embodiments, the construction material includes, as a build material formulation, a set of formulations described herein in any one of the embodiments and any combination thereof.

[0520] In some exemplary embodiments of the present invention, an object is manufactured by extruding a construction material (uncured) comprising two or more different build material formulations, for example, as described below. In some of these embodiments, each build material formulation is extruded from different nozzle arrays belonging to the same or different extrusion heads of an inkjet printing apparatus, as described herein.

[0521] In some embodiments, two or more such nozzle arrays extruding different 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 nozzle arrays extruding different material formulations are located on separate print heads, for example, a first nozzle array extruding a first material formulation is located on a first print head, and a second nozzle array extruding a second material formulation is located on a second print head.

[0522] In some embodiments, the nozzle array for extruding the build material mixture and the nozzle array for extruding the support material mixture are both located on the same print head. In some embodiments, the nozzle array for extruding the build material mixture and the nozzle array for extruding the support material mixture are located on separate print heads.

[0523] The printing material formulations are optionally and preferably deposited in layers during the same pass of the print head. The printing material formulations and / or combinations of formulations within the layers are selected according to the desired properties of the object and as described in further detail below. Such a mode of operation is also referred to herein as “multimaterial”.

[0524] As used herein and in the art, the term “digital material” refers to a combination of two or more materials at a microscopic or voxel level such that the printed zone of a particular material is at the level of a few voxels or at the level of a voxel block. 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.

[0525] In exemplary digital materials, the material of each voxel or voxel block obtained by curing is independent of the material of adjacent voxels or voxel blocks obtained by curing. As a result, each voxel or voxel block may result in a different model material, and the new properties of the entire part are a result of the spatial combination of several different model materials at the voxel level.

[0526] As used herein and in the art, the term “digital material formulation” refers to a combination of two or more material formulations at the pixel or voxel level, where pixels or voxels of different material formulations are interwoven with each other throughout the region. Such digital material formulations may exhibit novel properties influenced by the selection of material formulation types, and / or the ratios and relative spatial distributions of the two or more material formulations.

[0527] As used herein, a “voxel” of a layer represents the basic three-dimensional physical volume within the layer, corresponding to a single pixel of the bitmap describing the layer. The size of a voxel is approximately the size of the area formed by the build material when the build material is extruded, leveled, and solidified at the location corresponding to each pixel.

[0528] Throughout this specification, whenever the expression “at the voxel level” is used in relation to different materials and / or properties, it means that it includes not only differences between voxel blocks but also differences between voxels or groups of voxels. In preferred embodiments, the properties of the entire part are the result of a spatial combination of several different model materials at the voxel block level.

[0529] In some embodiments of the present invention, once the layer is extruded as described herein, it is exposed to curing conditions (e.g., curing energy) as described herein. In some embodiments, the curable material is a photocurable material, preferably a UV-curable material, and the curing conditions are such that the radiation source emits UV radiation.

[0530] In some of the embodiments described herein, the UV irradiation is from an LED light source described herein.

[0531] In some of the embodiments described herein, the curing conditions include electromagnetic irradiation, which is from an LED light source.

[0532] In some of the embodiments described herein, the curing conditions include UV irradiation.

[0533] In some embodiments, if the construction material also includes a support material formulation, the method proceeds to removing the hardened support material (e.g., thereby exposing the adjacent hardened molding material). This can be carried out by mechanical and / or chemical means, as will be recognized by those skilled in the art. Some of the support material may optionally remain in the hardened mixture layer upon removal, for example, as described herein.

[0534] In some embodiments, upon removal of the hardening support material, a hardened mixture layer is revealed, containing a hardened mixture of the support material and the molding material formulation. Such a hardened mixture on the surface of an object may optionally have a relatively non-reflective appearance, also referred to herein as “matte”; a surface lacking such a hardened mixture (e.g., where no support material formulation was applied) is described as comparatively “glossy.”

[0535] In some of the embodiments described herein, the method further comprises exposing the cured modeled material to post-treatment conditions either before or after (preferably after) the removal of the support material, if such support material was included in the build material, the post-treatment conditions may optionally include exposure to heat and / or irradiation, if immersion in an organic solvent, preferably a polar organic solvent such as alcohol, and more preferably a biocompatible polar organic solvent such as glycerol.

[0536] According to some of the embodiments described herein, one or more or all of the extruded molding material formulations are molding material formulations described herein in any of the respective embodiments and any combination thereof.

[0537] According to some of the embodiments described herein, the extrusion is the extrusion of two or more molding material formulations, each independently being a formulation described herein in any of the respective embodiments and any combination thereof. In some of these embodiments, the extrusion is the extrusion of a digital material described herein.

[0538] In exemplary embodiments, two or more formulations of the Type A formulations described herein are used in any one of the embodiments, and these formulations differ from one another in the presence and / or type of colorants, enabling the manufacture of a single object (e.g., a denture integral structure described herein) characterized by multiple colors and hues.

[0539] According to some of the embodiments described herein, the dispensing is further dispensing of a support material formulation, for example, a support material formulation described herein in any of the respective embodiments and any combination thereof.

[0540] According to some of the embodiments described herein, once the support material is removed, the object is subjected to a post-curing treatment or other post-treatment.

[0541] In an exemplary post-processing procedure, the printed object is subjected to support material removal (e.g., using a water jet), and then sequentially treated with a solution of a strong base (e.g., sodium hydroxide) (e.g., using a water jet); with glycerol (preferably while heating and UV irradiating the object for 2-4 hours); and optionally with alcohol (e.g., isopropyl alcohol). The object can be washed with tap water between contacts with each of these components. The object can then be oven-dried or air-dried for at least 2 hours.

[0542] According to some of the embodiments described herein, additive manufacturing is three-dimensional inkjet printing.

[0543] According to some of the embodiments described herein, the denture structure is selected from a denture base, artificial teeth, groups of artificial teeth, and an integrated structure of the denture base and groups of artificial teeth.

[0544] According to some of the embodiments described herein, the denture structure is an integral structure comprising a denture base and an artificial tooth group.

[0545] As demonstrated in the following Examples section, the inventors have designed additive manufacturing processes or methods that use digital materials to produce the denture structures described herein that meet the requirements of the respective ISO standards. Such additive manufacturing processes or methods use two or more material formulations that are extruded to form an object portion having a core region surrounded by multiple encapsulating regions that define an onion-like structure (also known as a layered structure or core-shell structure) of the object portion, either in at least a portion of a layer or in at least a portion of an object.

[0546] As used herein, a “onion-like structure” is defined as a structure comprising a core region and a plurality of encapsulating regions, each encapsulating a different volume size, where each encapsulating region encapsulates the core region, and for any pair of encapsulating regions, one encapsulating region of the pair is encapsulated by the other encapsulating region of that pair. For convenience, encapsulating regions can be considered as a series of encapsulating regions ordered according to the size of the encapsulated volume they encapsulate. In this view, the i-th encapsulating region of the series encapsulates the core and a volume Vi that includes all i-1 encapsulating regions whose encapsulated volume is less than Vi.

[0547] Figure 11 shows a typical non-limiting example of an object portion 800 in an embodiment in which the object portion has a core region 800a surrounded by three encapsulation regions 800b, 800c, and 800d that define an onion-like structure. Region 800b encapsulates the core region 800a, region 800c encapsulates regions 800b and 800a, and region 800d encapsulates regions 800c, 800b, and 800a, so the structure of the four regions is onion-like.

[0548] It should be noted that the object portion may consist of only the core region 800a and one encapsulation region (e.g., 800d), or the core region 800a and two encapsulation regions (e.g., 800c and 800d), or four or more encapsulation regions (e.g., further including encapsulation regions 800e, 800f, etc. (not shown in Figure 11)).

[0549] In this specification, the encapsulation region (e.g., 800b, 800c, and 800d in Figure 11) is also referred to as the "shell," and the outermost encapsulation region shown as 800d in Figure 11 is also referred to as the outermost shell or coating.

[0550] According to some embodiments of the present invention, a method for additive manufacturing a denture object as described herein is provided, wherein, for at least several layers, the extrusion is of at least two molding material formulations, namely a first molding material formulation and a second molding material formulation, and the method is provided such that a core region (e.g., 800a) and at least one encapsulation region (e.g., 800b, 800c, 800d in Figure 11) at least partially enclose or surround the core region.

[0551] According to some of these embodiments, an object or part thereof formed from such layers and characterized by an onion-like structure as described herein comprises a core region 800a and a single encapsulation region, which is therefore the outermost encapsulation region or coating (i.e., structure 800 does not include encapsulation regions 800b and 800c).

[0552] Alternatively, and preferably, an object or part thereof formed from such layers and characterized by an onion-like structure as described herein includes a core region 800a, also referred herein as the internal encapsulation region or shell 1, which at least partially encloses or surrounds the core region 800a, and an encapsulation region 800c, also referred herein as the intermediate encapsulation region or shell 2, which at least partially encloses or surrounds the internal encapsulation region 800b and is at least partially surrounded or enclosed by the outermost encapsulation region (coating) 800d.

[0553] According to any one of the embodiments described herein, the thickness of each of the internal encapsulation region (e.g., 800b), the intermediate encapsulation region (e.g., 800c), and the outermost encapsulation region (e.g., 800d), if present, is independently a thickness that includes any intermediate and partial range between 0.1 mm and 2 mm, or 0.2 mm and 1.5 mm, or 0.3 mm and 1 mm.

[0554] According to some of the embodiments described herein, the thickness of the outermost encapsulation region (e.g., 800d) is in the range of about 0.4 mm to about 1 mm, or about 0.4 mm to about 0.8 mm, or about 0.4 mm to about 0.7 mm, or about 0.5 mm to about 0.8 mm, or about 0.5 mm to about 0.7 mm, including any intermediate and partial ranges between these. In exemplary embodiments, the thickness is about 0.6 mm.

[0555] According to some of the embodiments described herein, the thickness of the internal encapsulation region (e.g., 800b), if present, is in the range of about 0.4 mm to about 1 mm, or about 0.5 mm to about 1 mm, including any intermediate and partial ranges between these. In exemplary embodiments, the thickness is about 0.7 mm. In exemplary embodiments, the thickness is about 1 mm.

[0556] According to some of the embodiments described herein, the thickness of the intermediate encapsulation region (e.g., 800c), if present, is in the range of about 0.3 mm to about 0.6 mm, or about 0.3 mm to about 0.5 mm, including any intermediate and partial ranges between these. In exemplary embodiments, the thickness is about 0.4 mm.

[0557] According to some of the embodiments described herein, The thickness of the outermost encapsulation region (e.g., 800d) is in the range of 0.5 mm to 0.7 mm, preferably 0.6 mm; The thickness of the internal encapsulation region (e.g., 800b) is in the range of 0.5 mm to 1 mm, preferably 0.7 mm; and The thickness of the intermediate encapsulation region (e.g., 800c) is in the range of 0.3 mm to 0.5 mm, preferably 0.4 mm.

[0558] According to some of the embodiments described herein, the thickness of the intermediate encapsulation region (e.g., 800c) is at least 50% of the thickness of the outermost encapsulation region (e.g., 800d), for example, 50% to 100%, or 50% to 80%, or 50% to 70%, including any intermediate and partial ranges between these. Alternatively, or in addition, the ratio of the thickness of the intermediate encapsulation region (e.g., 800c) to the thickness of the outermost encapsulation region (e.g., 800d) is at least 1:1.5, for example, 1:1.5 or 1:1.6, or 1:1.7, or 1:1.8, or 1:1.0, or 1:2, or 1:2.5, or the range of about 1:1.5 to about 1:2.5, or about 1:1.5 to about 1:2, including any intermediate and partial ranges between these.

[0559] In this specification, "thickness" means the average thickness of the encapsulation region.

[0560] According to any of these embodiments and some combinations thereof, a core region (e.g., 800a) is molded from one build material formulation or one combination of build material formulations, and an encapsulation region (e.g., 800d) is molded from another build material formulation or another combination of formulations different from the one used to mold the core region (e.g., 800a). If internal and / or intermediate encapsulation regions (e.g., 800b and optionally 800c) are molded, the composition of each region (e.g., build material formulation type or combination of two or more build material formulations) is different from the region it encapsulates and the region that encapsulates it.

[0561] According to an exemplary embodiment, the extrusion is such that a core region (e.g., 800a) is formed from a second molding material formulation or a first combination of the first molding material formulation and the second molding material formulation, and an encapsulation region (e.g., the outermost encapsulation region 800d) is formed from a first molding material formulation or a second combination of the first molding material formulation and the second molding material formulation, the second combination being different from the first combination.

[0562] If the object or part of the object also includes an internal encapsulation region 800b and an intermediate encapsulation region 800c, the internal encapsulation region may be formed from a first formulation or a second combination of the first formulation and the formulation, and the intermediate encapsulation region may be formed from a second formulation or a first combination of the first formulation and the second formulation. Alternatively, the internal encapsulation region may be formed from a third formulation or a third combination of two or more formulations. Alternatively, the intermediate encapsulation region may be formed from a fourth formulation or a fourth combination of the first formulation and the second formulation.

[0563] According to any of these embodiments and any combination thereof, the first and second molding material formulations used to form the onion-like structure, and optionally a third, fourth, and subsequent formulations, if selected, can be chosen from any molding material formulations that satisfy the biocompatibility requirements of the denture structures described herein.

[0564] According to some of the embodiments described herein, the molding material formulations or combinations thereof are selected to differ from one another depending on the mechanical properties of the hardened material formed therefrom.

[0565] In some embodiments, the molding material formulations or combinations thereof differ from one another by the impact resistance of the mineralized material molded from each formulation or combination itself, as defined herein. In some of these embodiments, the impact resistance of one formulation or combination molding one region differs from the impact resistance of other formulations or combinations molding the region encapsulating or being encapsulated by this region by a factor of at least 2, or at least 5, or at least 10, for example, 2 to 50, or 5 to 50, or 5 to 20, or 10 to 50, or 10 to 30, or 5 to 30, or 10 to 20, including any intermediate and partial ranges between these.

[0566] In some embodiments, the molding material formulations or combinations thereof differ from one another by the flexural modulus and / or flexural strength of the cured material of each formulation or combination itself, as defined herein. In some of these embodiments, the flexural modulus and / or flexural strength of one formulation or combination forming one region differs from the flexural modulus and / or flexural strength of other formulations or combinations forming the region encapsulating or being encapsulated by this region by a factor of at least 2, or at least 5, or at least 10, for example, 2 to 50, or 5 to 50, or 5 to 20, or 10 to 50, or 10 to 30, or 5 to 30, or 10 to 20, including any intermediate and partial ranges between these.

[0567] In some embodiments, the molding material formulations or combinations thereof differ from one or more, or all, of the impact resistance, flexural modulus, and / or flexural strength of the cured material of each formulation or combination itself, as defined herein.

[0568] According to exemplary embodiments, the extrusion of an onion-like structure is the extrusion of a first and second molding material formulation, which are selected as follows: the second formulation or first combination forming a core region (e.g., 800a) and optionally an intermediate encapsulation region (e.g., 800c) is characterized in that, upon curing, it has an impact resistance at least twice, at least five times, or at least ten times higher than that of the first formulation or second combination forming an outermost encapsulation region (e.g., 800d) and optionally an inner encapsulation region (e.g., 800b), as described herein.

[0569] According to exemplary embodiments, the extrusion of an onion-like structure is the extrusion of a first and second molding material formulation, which are selected as follows: The second formulation or first combination forming the core region (e.g., 800a) and optionally the intermediate encapsulation region (e.g., 800c) is characterized in that, upon curing, has a flexural modulus and / or flexural strength at least twice, at least five times, or at least ten times higher than that of the first formulation or second combination forming the outermost encapsulation region (e.g., 800d) and optionally the internal encapsulation region (e.g., 800b), as described herein.

[0570] According to exemplary embodiments, the extrusion of an onion-like structure is the extrusion of a first and second molding material formulation, which are selected as follows: The second formulation or first combination forming the core region (e.g., 800a) and optionally the intermediate encapsulation region (e.g., 800c) is characterized in that, upon curing, has impact resistance and flexural modulus at least twice, or at least five times, or at least ten times higher than that of the first formulation or second combination forming the outermost encapsulation region (e.g., 800d) and optionally the internal encapsulation region (e.g., 800b), as described herein.

[0571] When a combination of two or more build material formulations (for example, a combination of a first build material formulation and a second build material formulation) is used to form a core region or one or more encapsulated regions, the combination is embodied by voxelization, which is optionally and preferably by producing some voxels that form each region from one of the build material formulations and other voxels from another of the build material formulations. The voxelized combination may follow any distribution in which the voxels occupied by the first formulation are interwoven within the voxels occupied by the second formulation, including but not limited to a random distribution.

[0572] According to some of the embodiments described herein, the method described herein is carried out such that at least one of the first and second molding material formulations described herein is a Type B formulation described herein in any of the embodiments and any combination thereof. According to some of these embodiments, at least one more of the first and second molding material formulations is a Type B formulation described herein in any of the embodiments and any combination thereof.

[0573] According to some of the embodiments described herein, the second formulation is a Type B formulation described herein in any of the respective embodiments and any combination thereof, and the first formulation is a Type A formulation described herein in any of the respective embodiments and any combination thereof.

[0574] According to some embodiments, the method described herein involves extrusion of a Type A formulation and a Type B formulation as described herein to form a core region and at least one encapsulation region as described herein for at least several layers, wherein each of the core region and the encapsulation region is formed from a Type A material formulation or a Type B material formulation, or from a different combination of a Type A molding material formulation and a Type B molding material formulation.

[0575] According to some of the embodiments described herein, the core region (e.g., 800a) is molded from a type B formulation.

[0576] According to some of the embodiments described herein, the outermost encapsulation region (e.g., 800d) is molded from a type A formulation.

[0577] For example, if a further encapsulation region is molded in any of the embodiments of structure 800 as described herein, each of the core region and the internal encapsulation region, each of the internal encapsulation region and any intermediate encapsulation region, or each of the outermost (coated) encapsulation region, and each of the intermediate encapsulation region and any outermost (coated) encapsulation region, are molded from a type A formulation or a type B formulation, or a different combination of a type A formulation and a type B formulation.

[0578] According to an exemplary embodiment, a core region (e.g., 800a) is molded from a type B formulation, an internal encapsulation region (e.g., 800b) is molded from a type A formulation or a combination of one or more type A formulations, an intermediate encapsulation region (e.g., 800c) is molded from a type B formulation, and an outermost encapsulation region (e.g., 800d) is molded from a type A formulation or a combination of one or more type A formulations.

[0579] According to exemplary embodiments, the Type A formulations described herein are, optionally and preferably, transparent or partially transparent. The Type A formulations described herein are particularly useful for fabricating the outermost regions of object assemblies. In some embodiments of the present invention, the Type A formulations described herein are used to fabricate the outermost regions of object assemblies, which are integral structures including a denture base having the shape of a gingiva and a set of artificial teeth.

[0580] According to exemplary embodiments, the Type B formulations described herein are suitable for use as opaque or partially opaque formulations in some embodiments of the present invention. The Type B formulations described herein are preferably and preferably more opaque and less transparent than the Type A formulations described below. The Type B formulations described herein are particularly useful for fabricating one or more internal regions of an object assembly. In some embodiments of the present invention, the Type B formulations described herein are used for fabricating one or more internal regions of an object assembly that is a single-piece structure including a denture base having the shape of a gingiva and a set of artificial teeth. Preferably, but not necessarily, the Type B formulations described herein are used for fabricating one or more internal regions of a single-piece structure denture base.

[0581] object: According to some embodiments of the present invention, a denture structure obtained by additive manufacturing as described herein is provided.

[0582] According to some embodiments, the denture structure is an integrated structure comprising a denture base and a group of artificial teeth.

[0583] According to some embodiments of the present invention, a three-dimensional printed object is provided which is an integrated structure of a denture base and an artificial tooth group.

[0584] According to some of the embodiments described herein, the denture structure is known in the art and features mechanical and physical properties in accordance with the requirements of ISO 20795-1 and ISO 10477, as well as biocompatible properties in accordance with the requirements of ISO 10993-1, as described herein in any of the embodiments.

[0585] system: Representative and non-limiting examples of a system 110 suitable for AM of an object 112 according to some embodiments of the present invention are shown in Figure 1A. The system 110 includes an additive manufacturing apparatus 114 having an ejection unit 16 including a plurality of printing heads. Each head preferably includes one or more nozzle arrays 122 typically mounted on an orifice plate 121, as shown in Figures 2A to 2C below, through which a liquid build material formulation 124 is ejected.

[0586] Preferably, though not required, the apparatus 114 is a three-dimensional printing apparatus, in which case the printing head is a printing head and the build material formulation is ejected by inkjet technology. This is not necessarily required, as in some applications, additive manufacturing apparatuses do not need to employ three-dimensional printing technology. Representative examples of additive manufacturing apparatuses intended by various exemplary embodiments of the present invention include, but are not limited to, fused deposition modeling apparatuses and molten material formulation deposition apparatuses.

[0587] Each print head is supplied by one or more build material formulation reservoirs, which may optionally and preferably include a temperature control unit (e.g., a temperature sensor and / or heating device) and a build material formulation level sensor. To eject the build material formulation, a voltage signal is applied to the print head so that droplets of the build material formulation are selectively deposited by the print head nozzles, for example, in piezoelectric inkjet printing technology. Another example is a thermal inkjet print head. In these types of heads, there is a heater element that is in thermal contact with the build material formulation to heat the build material formulation and form bubbles in it, by activating the heater element with a voltage signal. The bubbles generate pressure in the build material formulation, causing droplets of the build material formulation to be ejected through the nozzles. Piezoelectric and thermal print heads are known to those skilled in the art of solid free fabrication. With respect to either type of inkjet print head, the ejection speed of the head depends on the number of nozzles, the type of nozzles, and the rate (frequency) of the applied voltage signal.

[0588] Desired and preferably, the total number of ejection nozzles or nozzle arrays is selected such that half of the ejection nozzles are designed to eject support material formulations and the other half are designed to eject build material formulations, i.e., the number of nozzles ejecting build material formulations is the same as the number of nozzles ejecting support material formulations. A representative example in Figure 1A shows four printing heads 16a, 16b, 16c, and 16d. Each of the heads 16a, 16b, 16c, and 16d has a nozzle array. In this example, heads 16a and 16b can be designed for build material formulations, and heads 16c and 16d can be designed for support material formulations. Thus, head 16a can eject one build material formulation, head 16b can eject another build material formulation, and both heads 16c and 16d can eject support material formulations. In an alternative embodiment, for example, heads 16c and 16d may be combined into a single head having two nozzle arrays for depositing support material formulations. In further alternative embodiments, each of the one or more print heads may have one or more nozzle arrays for depositing one or more material formulations, for example, two different build material formulations, or two nozzle arrays for depositing a build material formulation and a support material formulation, with each formulation being deposited using different arrays or nozzle counts.

[0589] However, it should be understood that the number of build material formulation printing heads (build heads) and the number of support material formulation printing heads (support heads) may differ, without the intention of limiting the scope of the present invention. Generally, the number of nozzle arrays for ejecting build material formulations, the number of nozzle arrays for ejecting support material formulations, and the number of nozzles in each respective array are selected to provide a predetermined ratio, a, of the maximum ejection rate of the support material formulation to the maximum ejection rate of the build material formulation. The value of the predetermined ratio, a, is preferably selected to ensure that in each layer being molded, the height of the build material formulation is equal to the height of the support material formulation. Typical values ​​of a are about 0.6 to about 1.5.

[0590] When used throughout this specification, the term "approximately" represents ±10%.

[0591] For example, when a=1, the overall extrusion rate of the support material mixture is roughly the same as the overall extrusion rate of the build material mixture when all nozzle arrays are operating.

[0592] The apparatus 114 may comprise, for example, M build 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 build arrays and S × s support arrays can be manufactured as a separate physical unit that can be assembled and disassembled from the array group. In this embodiment, each such array optionally and preferably comprises its own temperature control unit and material composition level sensor, and receives individually controlled voltages for its operation.

[0593] The apparatus 114 may further comprise a solidification device 324 which may include any device configured to emit light, heat, or the like that can harden the deposited material mixture. For example, the solidification device 324 may comprise one or more radiation sources, which may be, for example, ultraviolet, visible, or infrared lamps, or other electromagnetic radiation sources, or electron beam sources, depending on the molding material mixture being used. In some embodiments of the present invention, the solidification device 324 is useful for curing or solidifying the molding material mixture.

[0594] In addition to the solidification device 324, the apparatus 114 optionally and preferably comprises an additional radiation source 328 for solvent evaporation. The radiation source 328 optionally and 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.

[0595] In some embodiments of the present invention, the apparatus 114 comprises a cooling system 134, such as one or more fans or the like.

[0596] The print head and radiation source are preferably mounted on a frame or block 128 that is operable to reciprocate on a tray 360 which serves as a work surface. In some embodiments of the present invention, the radiation source is mounted on a block to follow the print head in order to at least partially cure or solidify the material formulation that has just been extruded by the print head. The tray 360 is positioned horizontally. Following 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 leveling devices 132, e.g., rollers 326. The leveling device 326 helps to straighten, flatten, and / or establish the thickness of a newly formed layer before forming a continuous layer on it. The leveling device 326 preferably comprises a waste collection device 136 for collecting excess material formulation generated during leveling. The waste recovery device 136 may include a mechanism for delivering the material mixture to a waste tank or a waste cartridge.

[0597] During use, the print head of unit 16 moves in a scanning direction, referred to herein as the X direction, and selectively ejects a build material formulation in a predetermined configuration as it passes over the tray 360. The build material formulation typically includes one or more types of support material formulations and one or more types of build material formulations. Following the passage of the print head of unit 16, the build material formulation is cured by the radiation source 126. In the reverse passage of the head, returning to the starting point of the newly deposited layer, additional ejection of the build material formulation may be performed according to a predetermined configuration. In the forward and / or reverse passage of the print head, the thus formed layer may preferably be straightened by a leveling device 326 that follows the path of the forward and / or reverse movement of the print head. As the print head returns to the starting point along the X direction, they may continue to build the same layer by moving to another position along the index direction, referred herein as the Y direction, and reciprocating along the X direction. Alternatively, the print head may move in the Y direction between the forward and reverse movements, or after more than one forward-reverse movement. In this specification, a series of scans performed by the print head to complete a single layer is referred to as a single scan cycle.

[0598] Once a layer is complete, the tray 360 descends in the Z direction to a predetermined Z level, depending on the desired thickness of the next layer to be printed. This procedure is repeated until the three-dimensional object 112 is formed layer by layer.

[0599] In another embodiment, the tray 360 may be displaced in the Z direction within the layer between the forward and backward paths of the print head of unit 16. Such Z displacement is performed to bring the leveling equipment into contact with the surface in one direction and to prevent contact in the other direction.

[0600] System 110 optionally and preferably includes a construction material formulation supply system 330 that supplies a plurality of construction material formulations to the manufacturing apparatus 114, comprising a construction material formulation container or cartridge.

[0601] The control unit 152 also controls the manufacturing apparatus 114 and, optionally and preferably, the supply system 330. The control unit 152 typically comprises electronic circuitry configured to perform control operations. The control unit 152 preferably communicates with a data processor 154 that transmits digital data relating to manufacturing instructions based on computer object data, for example, a CAD configuration represented in Standard Tessellation Language (STL) format or similar on a computer-readable medium. Typically, the control unit 152 controls the voltage applied to each print head or each nozzle array, and the temperature of the construction material formulation in each print head or each nozzle array.

[0602] 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 an operator, for example, using a data processor 154 or a user interface 116 that communicates with the unit 152. The user interface 116 may be, but is not limited to, a keyboard, touchscreen, and similar, or any type known in the art. For example, the control unit 152 may receive, but is not limited to, the type and / or attributes of one or more construction material formulations, such as color, characteristic strain and / or transition temperature, viscosity, electrical properties, and magnetic properties, as additional input. Other attributes and attribute groups are also contemplated.

[0603] Another representative non-limiting example of system 10 suitable for AM of an object 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 projection view (Figure 1D) of system 10.

[0604] In this embodiment, the system 10 comprises a tray 12 and a plurality of inkjet print heads 16, each print head having one or more nozzle arrays, each having one or more isolated nozzles. The material used for three-dimensional printing is supplied to the heads 16 by a construction material supply system 42. The tray 12 may have a disc shape or be annular. Non-circular shapes are also contemplated, provided that they can rotate around a vertical axis.

[0605] The tray 12 and head 16 are mounted, optionally and preferably, 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 but at different rotational speeds (e.g., rotation in opposite directions). While some embodiments of System 10 are described below with particular emphasis on configuration (i), which is a rotating tray configured to rotate about a vertical axis 14 relative to the head 16, it should be understood that this application also intends configurations (ii) and (iii) of System 10. Any one of the embodiments of System 10 described herein can be adapted to be applicable to either configuration (ii) and (iii), and those skilled in the art, given the details described herein, will know how to make such adaptations.

[0606] 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.

[0607] The radial direction r in system 10 defines the indexing direction y in system 110, and the azimuth direction φ defines the scan direction x in system 110. Therefore, the radial direction is referred to interchangeably with the indexing direction in this specification, and the azimuth direction is referred to interchangeably with the scan direction in this specification.

[0608] 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 circle whose radius is a specific distance from the axis 14 and whose center is the axis 14.

[0609] As used herein, the term “azimuth position” refers to a position on or above the tray 12 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 points which is a straight line forming a specific azimuth angle with respect to the reference point.

[0610] As used herein, the term “vertical position” refers to a position on a plane that intersects the vertical axis 14 at a particular point.

[0611] Tray 12 functions as a construction 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, but does not necessarily have to be. 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 entire molding of the object, and in some embodiments of the present invention, the tray reverses its direction of rotation at least once (e.g., oscillating) during the molding of the object. Tray 12 is optionally and preferably removable. Removal of tray 12 can be done for maintenance of system 10 or, optionally, 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., replacement tray kits), and two or more trays are designed for different types of objects (e.g., different weights), different operating modes (e.g., different rotation speeds), etc. Replacement of tray 12 can be done manually or automatically, as desired. If automatic replacement is employed, the system 10 includes a tray changer 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 typical example in Figure 1B, the tray changer 36 is illustrated as a drive unit 38 with a movable arm 40 configured to pull the tray 12, but other types of tray changers are also conceivable.

[0612] Exemplary embodiments of the print head 16 are shown in Figures 2A to 2C. These embodiments are not limited to those shown and can be used in any of the AM systems described above, including system 110 and system 10.

[0613] Figures 2A and 2B illustrate a printhead 16 having one (Figure 2A) and two (Figure 2B) nozzle arrays 22. The nozzles in the arrays are preferably arranged linearly along a straight line. In embodiments in which a particular printhead has two or more linear nozzle arrays, the nozzle arrays may, optionally and preferably, be parallel to each other. When a printhead has two or more nozzle arrays (e.g., Figure 2B), the same build material formulation can be supplied to all arrays of the head, or different build material formulations can be supplied to at least two arrays of the same head.

[0614] If a system similar to system 110 is employed, all print heads 16 are, if desired and preferably, oriented along the indexing direction with their positions along the scanning direction offset from each other.

[0615] When a system similar to system 10 is employed, all print heads 16 are optionally and preferably oriented radially (parallel to the radial direction) with their azimuth positions offset from one another. 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 this 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.

[0616] In some embodiments, two or more printheads can be assembled into a printhead block, in which case the printheads in the block are typically parallel to each other. A block including several inkjet printheads 16a, 16b, 16c is shown in Figure 2C.

[0617] 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 may function to prevent or reduce vibrations of the tray 12 that may occur while the inkjet print head 16 is operating. In configurations in which the print head 16 rotates around an axis 14, it is preferable that the stabilization structure 30 also rotates so that the stabilization structure 30 is always directly below the head 16 (with the tray 12 between the head 16 and the tray 12).

[0618] The tray 12 and / or printhead 16 are optionally and preferably configured to move along a vertical direction z parallel to the vertical axis 14 in order to change the vertical distance between the tray 12 and the printhead 16. In a configuration in which the vertical distance is changed by moving the tray 12 vertically, the stabilization structure 30 also preferably moves vertically with the tray 12. In a configuration in which the vertical distance is changed vertically by the head 16 while the vertical position of the tray 12 remains fixed, the stabilization structure 30 is also maintained in a fixed vertical position.

[0619] Vertical motion can be established by the vertical drive unit 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 next layer to be printed (for example, by lowering the tray 12 relative to the head 16). This procedure is repeated to form a three-dimensional object in layers.

[0620] The operation of the inkjet print head 16, and optionally and preferably the operation of one or more other components of the system 10, such as the movement of the tray 12, are controlled by the controller 20. The controller may have electronic circuits and a non-volatile storage medium readable by the circuits, which, when read by the circuits, stores program instructions that cause the circuits to perform control operations, as described in more detail below.

[0621] The controller 20 can also communicate with a host computer 24 that transmits digital data relating to manufacturing 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 other formats suitable for computer-aided design (CAD). The object data format is typically configured 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 transmits manufacturing instructions described in the converted coordinate system, if desired and preferably. Alternatively, the computer 24 can transmit manufacturing instructions described in the original coordinate system provided by the computer object data, in which case the coordinate conversion is performed by the controller 20's circuitry.

[0622] Coordinate transformation enables three-dimensional printing on a rotating tray. In a non-rotating system with a stationary tray, the print head typically reciprocates along a straight line on the stationary tray. In such a system, the print resolution is the same at any point on the tray, provided that the head ejection speed is uniform. 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 and preferably, to ensure equal amounts of excess material composition at different radial positions. Representative examples of coordinate transformations according to some embodiments of the present invention are shown in Figures 3A and 3B, which show three slices of an object (each slice corresponding to a manufacturing instruction for a different layer of the object), with Figure 3A showing the slices in Cartesian coordinates and Figure 3B showing the same slices after applying the coordinate transformation procedure to each slice.

[0623] Typically, the controller 20 controls the voltage applied to each component of the system 10 based on manufacturing instructions and stored program instructions, as described below.

[0624] Generally, the controller 20 controls the print head 16 to print a three-dimensional object on the tray 12 by ejecting droplets of the building material mixture in layers while the tray 12 rotates.

[0625] System 10 optionally and preferably comprises one or more radiation sources 18, which may be, for example, ultraviolet, visible, or infrared lamps, other electromagnetic radiation sources, or electron beam sources, depending on the material formulation used. The radiation sources may include, but are not limited to, any type of radiation device, including light-emitting diodes (LEDs), digital light processing (DLP) systems, resistor lamps, and the like. The radiation sources 18 function to cure or solidify the material formulation. In various exemplary embodiments of the present invention, the operation of the radiation sources 18 is controlled by a controller 20, which may activate and deactivate the radiation sources 18 and, optionally, also control the amount of radiation produced by the radiation sources 18.

[0626] In some embodiments of the present invention, the system 10 further comprises one or more leveling devices 32, which can be manufactured as rollers or blades. The leveling devices 32 function to straighten a newly formed layer before forming a continuous layer on it. In some embodiments, the leveling device 32 has the shape of a conical roller, with its axis of symmetry 34 inclined with respect to the surface of the tray 12 and its surface positioned parallel to the tray surface. This embodiment is shown in a side view of the system 10 (Figure 1C).

[0627] A conical roller may have the shape of a cone or a frustum of a cone.

[0628] The opening angle of the conical roller is preferably selected such that there is a constant ratio between the radius of the cone at any position along its axis 34 and the distance between this position and the axis 14. As the roller rotates, any point p on the roller surface has a linear velocity proportional to (e.g., the same as) the linear velocity of the tray at a point vertically below point p, so that this embodiment allows the roller 32 to efficiently level the layers. In some embodiments, the roller has the shape of a frustocone with height h, radius R1 at the closest distance from the axis 14, and radius R2 at the 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 from the axis 14 to the roller (e.g., R may be the radius of the tray 12).

[0629] The operation of the leveling device 32 is optionally and preferably controlled by a controller 20, which activates and deactivates the leveling device 32 and optionally controls its position along the vertical (parallel to the axis 14) and / or radial (parallel to the tray 12 and toward or away from the axis 14).

[0630] In some embodiments of the present invention, the print head 16 is configured to reciprocate relative to the tray along the 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 and preferably controlled by a controller 20.

[0631] As used herein, the term "about" refers to ±10% or ±5%.

[0632] The terms "comprises," "comprising," "includes," "including," and "having," as well as their conjugations, all mean "to include but not limited to these."

[0633] The term "consisting of" means "to include or be limited to."

[0634] The term "consisting essentially of" means that the composition, method, or structure may include additional components, steps, and / or parts, provided that these additional components, steps, and / or parts do not substantially alter the basic and novel features of the claimed composition, method, or structure.

[0635] As used herein, the singular forms "a," "an," and "the" refer to multiple subjects unless the context clearly indicates otherwise. For example, the term "a compound" or "at least one compound" may refer to multiple compounds, including mixtures thereof.

[0636] Throughout this application, various embodiments of the invention may be presented in range form. It should be understood that range form is merely for convenience and conciseness and should not be interpreted as an inflexible limitation on the scope of the invention. Therefore, range descriptions should be considered to specifically disclose all possible subranges and individual numerical values ​​within that range. For example, a range description such as 1-6 should be considered to specifically disclose 1-3, 1-4, 1-5, 2-4, 2-6, 3-6, other subranges, and individual numerical values ​​within that range, such as 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.

[0637] Wherever a numerical range is indicated herein, it is always intended to include any of the cited numbers (fractions or integers) within that range. The phrases “ranging / ranges between” and “ranging / ranges from” between the first and second indicated numbers are used interchangeably herein and mean including the first and second indicated numbers, as well as all fractions and integers between them.

[0638] In this specification, the terms “method” and “process” are used interchangeably to refer to methods, means, techniques and procedures for achieving a given task, including but not limited to those known by experts in the fields of chemistry, pharmacology, biology, biochemistry and medicine, or readily developed from known methods, means, techniques and procedures.

[0639] Throughout this specification, whenever the terms “weight percent,” “% by weight,” or “% wt.” are used in reference to embodiments of a formulation (e.g., a molding material formulation), they mean a weight percentage of the total weight of the respective uncured formulation.

[0640] Throughout this specification, the term "acrylic material" is used to describe collectively materials characterized by one or more acrylate groups, methacrylate groups, acrylamide groups, and / or methacrylamide groups.

[0641] Similarly, the term "acrylic group" is used to collectively describe curable groups that are acrylate groups, methacrylate groups, acrylamide groups and / or methacrylamide groups, preferably acrylate groups or methacrylate groups (also referred to herein as (meth)acrylate groups).

[0642] Throughout this specification, the term "(meth)acrylic" encompasses both acrylic and methacrylic materials.

[0643] Throughout this specification, the terms “linking moiety” or “linking group” refer to a group that connects two or more moies or groups in a compound. Linking moies can typically be thought of as two-radical or three-radical moies derived from bifunctional or trifunctional compounds, which are connected to two or three other moies, respectively, via two or three of those atoms.

[0644] Examples of linking portions include hydrocarbon portions or chains, which may optionally be interposed by one or more heteroatoms as defined herein, and / or any of the chemical groups listed below when defined as linking groups.

[0645] In this specification, when a chemical group is referred to as a “terminal group,” it should be interpreted as a substituent connected to another group via this one atom.

[0646] Throughout this specification, the term “hydrocarbon” refers collectively to chemical groups composed primarily of carbon and hydrogen atoms. Hydrocarbons can consist of alkyl, alkene, alkyne, aryl, and / or cycloalkyl groups, each of which may be substituted or unsubstituted and may be interposed by one or more heteroatoms. The number of carbon atoms can range from 2 to 30, preferably fewer, for example, 1 to 10, or 1 to 6, or 1 to 4. Hydrocarbons may be linking groups or terminal groups.

[0647] 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.

[0648] 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, as defined below.

[0649] 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.

[0650] Alternatively, R' and R'' may each independently be a 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, or hydrazine.

[0651] The term "amine" is used herein to describe the -NR'R'' group when the amine is a terminal group as defined below, and to describe the -NR'- group when the amine is a linking group or part of a linking moiety.

[0652] 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. Whenever a numerical range, such as "1 to 20," is specified herein, it implies that the alkyl group may contain 1 carbon atom, 2 carbon atoms, 3 carbon atoms, or 20 or fewer carbon atoms. Alkyl groups may be substituted or unsubstituted. The substituted alkyl may have one or more substituents, so that each substituent can independently be, 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.

[0653] An alkyl group may be a terminal group bonded to a single adjacent atom, as defined above, or a linking group that connects to two or more parts via at least two carbon atoms in its chain, as defined above. When alkyl is a linking group, it is also referred to herein as an "alkylene" or "alkylene chain."

[0654] As used herein, alkenes and alkynes are alkyl groups as defined herein, and each contains one or more double or triple bonds.

[0655] The term "cycloalkyl" refers to a monocyclic or fused ring group (i.e., a ring sharing adjacent carbon atom pairs) in which one or more rings do not have a fully conjugated π-electron system. Examples include, but are not limited to, cyclohexane, adamantine, norbornyl, isobornyl, and similar groups. Cycloalkyl groups may be substituted or unsubstituted. A substituted cycloalkyl group may have one or more substituents, so that each substituent can independently be, 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 bonded to a single adjacent atom as defined above, or a linking group connecting two or more parts at two or more positions as defined above.

[0656] The term "heteroalicyclic" refers to a monocyclic or fused ring group containing 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. Representative examples include piperidine, piperazine, tetrahydrofuran, tetrahydropyran, morpholino, oxalidine, and similar compounds.

[0657] Heteroalicyclic groups may be substituted or unsubstituted. A substituted heteroalicyclic group may have one or more substituents, thereby each substituent independently being, 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 bonded to a single adjacent atom as defined above, or a linking group connecting two or more parts at two or more positions as defined above.

[0658] 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 be substituted or unsubstituted. A substituted aryl may have one or more substituents, thereby each substituent independently being, 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 can be a terminal group bonded to a single adjacent atom, as defined above, or a linking group connecting two or more parts at two or more positions, as defined above.

[0659] The term "heteroaryl" refers to a monocyclic or fused ring (i.e., a ring sharing adjacent pairs of atoms) group that has one or more atoms, such as nitrogen, oxygen, and sulfur, within its ring, and further possesses 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 be substituted or unsubstituted. Substitutive heteroaryls may have one or more substituents, so that each substituent can independently be, for example, hydroxyalkyl, trihaloalkyl, cycloalkyl, alkenyl, alkynyl, aryl, heteroaryl, heteroalicyclic, amine, halide, sulfonate, sulfoxide, phosphonate, hydroxy, alkoxy, aryloxy, thiohydroxy, thioalkoxy, thioaryloxy, cyano, nitro, azo, sulfonamide, C-carboxylate, O-carboxylate, N-thiocarbamate, O-thiocarbamate, urea, thiourea, 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, or a linking group connecting two or more parts at two or more positions as defined above. Typical examples include pyridine, pyrrole, oxazole, indole, purine, and similar groups.

[0660] The terms "halides" and "halo" refer to fluorine, chlorine, bromine, or iodine.

[0661] The term "haloalkyl" refers to an alkyl group as defined above, which is further substituted with one or more halides.

[0662] The term "sulfate" refers to the terminal group -OS(=O)2-OR' as defined above, or the linking group -OS(=O)2-O- as defined above, and R' is as defined above.

[0663] The term "thiosulfate" refers to the terminal group -OS(=S)(=O)-OR' or the linking group -OS(=S)(=O)-O- as defined above, and R' is as defined above.

[0664] The term "sulfite" refers to the terminal group -OS(=O)-O-R' or the linking group -OS(=O)-O- as defined above, where R' is as defined above.

[0665] The term "thiosulfite" refers to the terminal group -OS(=S)-O-R' or the linking group -OS(=S)-O- as defined above, where R' is as defined above.

[0666] The term "sulfinate" refers to the terminal group -S(=O)-OR' or the linking group -S(=O)-O- as defined above, and R' is as defined above.

[0667] The terms "sulfoxide" or "sulfinyl" refer to the terminal group -S(=O)R' or the linking group -S(=O)- as defined above, where R' is as defined above.

[0668] The term "sulfonate" refers to the terminal group -S(=O)2-R' or the linking group -S(=O)2- as defined above, where R' is as defined herein.

[0669] The term "S-sulfonamide" refers to the terminal group -S(=O)2-NR'R'' or the linking group -S(=O)2-NR'- as defined above, where R' and R'' are as defined herein.

[0670] The term "N-sulfonamide" refers to the terminal group R'S(=O)2-NR''- or the linking group -S(=O)2-NR'- as defined above, where R' and R'' are as defined herein.

[0671] The term "disulfide" refers to the terminal group -S-SR' or the linking group -SS- as defined above, where R' is as defined herein.

[0672] The term "phosphonate" refers to the terminal group -P(=O)(OR')(OR'') or the linking group -P(=O)(OR')(O)- as defined above, where R' and R'' are as defined herein.

[0673] The term "thiophosphonate" refers to the terminal group -P(=S)(OR')(OR'') or the linking group -P(=S)(OR')(O)- as defined above, where R' and R'' are as defined herein.

[0674] The term "phosphinyl" refers to the terminal group -PR'R'' or the linking group -PR'- as defined above, where R' and R'' are as defined above.

[0675] The term "phosphine oxide" refers to the terminal group -P(=O)(R')(R'') or the linking group -P(=O)(R')- as defined above, where R' and R'' are as defined herein.

[0676] The term "phosphine sulfide" refers to the terminal group -P(=S)(R')(R'') or the linking group -P(=S)(R')- as defined above, where R' and R'' are as defined herein.

[0677] The term "phosphite" refers to the terminal group -O-PR'(=O)(OR'') or the linking group -O-PH(=O)(O)- as defined above, where R' and R'' are as defined herein.

[0678] As used herein, the terms “carbonyl” or “carbonate” refer to the terminal group -C(=O)-R' or the linking group -C(=O)- as defined above, where R' is as defined herein.

[0679] As used herein, the term “thiocarbonyl” refers to the terminal group -C(=S)-R' or the linking group -C(=S)- as defined above, where R' is as defined herein.

[0680] As used herein, the term "oxo" refers to an (=O) group in which an oxygen atom is bonded by a double bond to the atom at the indicated position (e.g., a carbon atom).

[0681] As used herein, the term "thiooxo" refers to a (=S) group in which a sulfur atom is bonded by a double bond to the atom at the indicated position (e.g., a carbon atom).

[0682] The term "oxime" refers to the terminal group = N-OH or the linking group = NO- as defined above.

[0683] The term "hydroxyl" refers to the -OH group.

[0684] The term "alkoxy" refers to both -O-alkyl groups and -O-cycloalkyl groups as defined herein. The term "alkoxide" refers to a -R'O- group as defined herein, where R' is the -R'O- group.

[0685] The term "aryloxy" refers to both the -O-aryl group and the -O-heteroaryl group as defined herein.

[0686] The terms "thiohydroxy" or "thiol" refer to the -SH group. The term "thiolate" refers to the -S- group.

[0687] The term "thioalkoxy" refers to both -S-alkyl groups and -S-cycloalkyl groups as defined herein.

[0688] The term "thioaryloxy" refers to both the -S-aryl group and the -S-heteroaryl group as defined herein.

[0689] "Hydroxyalkyl" is also referred to as "alcohol" in this specification and refers to an alkyl group as defined herein that is substituted with a hydroxyl group.

[0690] The term "cyano" refers to the -C≡N group.

[0691] The term "isocyanate" refers to the -N=C=O group.

[0692] The term "isothiocyanate" refers to the -N=C=S group.

[0693] The term "nitro" refers to the -NO2 group.

[0694] The term "acyl halide" describes the -(C=O)R'''' group, where R'''' is a halide as defined above.

[0695] The terms "azo" or "diazo" refer to the terminal group -N=NR' or the linking group -N=N- as defined above, where R' is as defined above.

[0696] The term "peroxo" refers to the terminal group -O-OR' or the linking group -OO- as defined above, and R' is as defined above.

[0697] As used herein, the term "carboxylate" encompasses C-carboxylates and O-carboxylates.

[0698] The term "C-carboxylate" refers to the terminal group -C(=O)-OR' or the linking group -C(=O)-O- as defined above, where R' is as defined herein.

[0699] The term "O-carboxylate" refers to the terminal group -OC(=O)R' or the linking group -OC(=O)- as defined above, where R' is as defined herein.

[0700] Carboxylates can be linear or cyclic. In the cyclic form, in C-carboxylates, R' and a carbon atom bond to form a ring, which is also called a lactone. Alternatively, in O-carboxylates, R' and O bond to form a ring. Cyclic carboxylates can function as linking groups, for example, when atoms within the formed ring are bonded to another group.

[0701] As used herein, the term "thiocarboxylate" encompasses C-thiocarboxylate and O-thiocarboxylate.

[0702] The term "C-thiocarboxylate" refers to the terminal group -C(=S)-OR' or the linking group -C(=S)-O- as defined above, where R' is as defined herein.

[0703] The term "O-thiocarboxylate" refers to the terminal group -OC(=S)R' or the linking group -OC(=S)- as defined above, where R' is as defined herein.

[0704] Thiocarboxylates can be linear or cyclic. In the cyclic form, in C-thiocarboxylates, R' and a carbon atom bond to form a ring; this group is also called a thiolactone. Alternatively, in O-thiocarboxylates, R' and O bond to form a ring. Cyclic thiocarboxylates can function as linking groups, for example, if atoms within the formed ring are bonded to another group.

[0705] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0706] The term "N-carbamate" refers to the terminal group R''OC(=O)-NR'- or the linking group -OC(=O)-NR'- as defined above, where R' and R'' are as defined herein.

[0707] The term "O-carbamate" refers to the terminal group -OC(=O)-NR'R'' or the linking group -OC(=O)-NR'- as defined above, where R' and R'' are as defined herein.

[0708] Carbamates can be linear or cyclic. In the cyclic form, in O-carbamates, R' bonds with a carbon atom to form a ring, or in N-carbamates, R' bonds with O to form a ring. Cyclic carbamates can function as linking groups, for example, if atoms within the formed ring are bonded to another group.

[0709] As used herein, the term "carbamate" includes N-carbamates and O-carbamates.

[0710] As used herein, the term "thiocarbamate" encompasses N-thiocarbamates and O-thiocarbamates.

[0711] The term "O-thiocarbamate" refers to the terminal group -OC(=S)-NR'R'' or the linking group -OC(=S)-NR'- as defined above, where R' and R'' are as defined herein.

[0712] The term "N-thiocarbamate" refers to the terminal group R''OC(=S)NR'- or the linking group -OC(=S)NR'- as defined above, where R' and R'' are as defined herein.

[0713] Thiocarbamates may be linear or cyclic, as described herein for carbamates.

[0714] As used herein, the term “dithiocarbamate” encompasses S-dithiocarbamates and N-dithiocarbamates.

[0715] The term "S-dithiocarbamate" refers to the terminal group -SC(=S)-NR'R'' or the linking group -SC(=S)NR'- as defined above, where R' and R'' are as defined herein.

[0716] The term "N-dithiocarbamate" refers to the terminal group R''SC(=S)NR'- or the linking group -SC(=S)NR'- as defined above, where R' and R'' are as defined herein.

[0717] The term "urea" is also referred to as "ureid" in this specification, and these terms refer to the terminal group -NR'C(=O)-NR''R''' or the linking group -NR'C(=O)-NR''- as defined above, where R' and R'' are as defined herein, and R'''' is as defined herein for R' and R''.

[0718] The term "thiourea" is also referred to as "thioureide" in this specification and refers to the terminal group -NR'-C(=S)-NR''R''' or the linking group -NR'-C(=S)-NR''-, where R', R'' and R''' are as defined herein.

[0719] As used herein, the term "amide" encompasses both C-amides and N-amides.

[0720] The term "C-amide" refers to the terminal group -C(=O)-NR'R'' or the linking group -C(=O)-NR'- as defined above, where R' and R'' are as defined herein.

[0721] The term "N-amide" refers to the terminal group R'C(=O)-NR''- or the linking group R'C(=O)-N- as defined above, where R' and R'' are as defined herein.

[0722] Amides can be linear or cyclic. In the cyclic form, R' and a carbon atom bond to form a ring in a C-amide, and this group is also called a lactam. Cyclic amides can function as linking groups, for example, if atoms within the formed ring are bonded to another group.

[0723] The term "guanyle" refers to the terminal group R'R''NC(=N)- or the linking group -R'NC(=N)- as defined above, where R' and R'' are as defined herein.

[0724] The term "guanidine" refers to the terminal group -R'NC(=N)-NR''R''' or the linking group -R'NC(=N)-NR''- as defined above, where R', R'' and R''' are as defined herein.

[0725] The term "hydrazine" refers to the terminal group -NR'-NR''R''' or the linking group -NR'-NR''- as defined above, where R', R'' and R''' are as defined herein.

[0726] As used herein, the term “hydrazide” refers to the terminal group -C(=O)-NR'-NR''R''' or the linking group -C(=O)-NR'-NR''- as defined above, where R', R'' and R''' are as defined herein.

[0727] As used herein, the term “thiohydrazide” refers to the terminal group -C(=S)-NR'-NR''R''' or the linking group -C(=S)-NR'-NR''- as defined above, where R', R'' and R''' are as defined herein.

[0728] The term "cyanurate" refers to the following terminal group [ka] or the following linking base [ka] This refers to R' and R'' as defined herein.

[0729] The term "isocyanurate" refers to the following terminal group [ka] or the following linking base [ka] This refers to R' and R'' as defined herein.

[0730] The term "thiocyanurate" refers to the following terminal groups [ka] or the following linking base [ka] This refers to R' and R'' as defined herein.

[0731] As used herein, the term "alkylene glycol" refers to the terminal group -O-[(CR'R'') z -O] y -R''', or the linking group -O-[(CR'R'')] z -O] y - refers to R', R'' and R''' as defined herein, z is an integer from 1 to 10, preferably 2 to 6, more preferably 2 or 3, and y is an integer of 1 or more. Preferably, both R' and R'' are hydrogen. When z is 2 and y is 1, the group is ethylene glycol. When z is 3 and y is 1, the group is propylene glycol. When y is 2 to 4, alkylene glycol is referred to herein as oligo(alkylene glycol).

[0732] 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, or otherwise.

[0733] In polyfunctional materials, typically, each (meth)acrylate group is linked to an alkylene glycol group or alkylene glycol chain, and these alkylene glycol groups or chains are linked to one another by branched units such as branched alkyl, cycloalkyl, aryl (e.g., bisphenol A), and others.

[0734] In some embodiments, the ethoxylated material comprises at least one or at least two ethoxylated groups, i.e., at least one or at least two alkylene glycol moieties or alkylene glycol groups. Some or all of the alkylene glycol groups can be linked together to form an alkylene glycol chain. For example, an ethoxylated material comprising 30 ethoxylated groups may include a chain of 30 linked alkylene glycol groups, each consisting of, for example, two chains of 15 linked alkylene glycol moieties, with the two chains connected by a branching portion, or a chain of 30 linked alkylene glycol groups, each consisting of, for example, 10 linked alkylene glycol groups, with the three chains connected by a branching portion. Shorter and longer chains are also intended.

[0735] The ethoxylated material may contain one, two, or more alkylene glycol chains of any length.

[0736] As used herein, the term “branched unit” refers to a multiradical, preferably an aliphatic or alicyclic group. “Multiradical” means having two or more bond points such that the unit is linked between two or more atoms and / or groups or parts.

[0737] In some embodiments, the branching unit is derived from a chemical moiety having two, three, or more functional groups. In some embodiments, the branching unit is a branched alkyl or cycloalkyl (alicyclic) or aryl (e.g., phenyl) as defined herein.

[0738] As used herein, the term “impact strength” or simply “impact,” as interchangeably used herein and in the art, refers to a material’s resistance to fracture by mechanical impact and is expressed as the amount of energy absorbed by the material before it completely breaks. Impact strength can be measured, for example, using the ASTM D256-06 standard Izod impact test (also known as “Izod notched impact” or “Izod impact”) and / or as described below, and is expressed in J / m.

[0739] As used herein, HDT represents the temperature at which each compound or combination of compound deforms under a given load at several specific temperatures. Suitable test procedures for determining the HDT of a compound or combination of compound are the ASTM D-648 series, in particular the ASTM D-648-06 and ASTM D-648-07 methods. In various exemplary embodiments of the present invention, the core and shell of a structure differ in their HDTs measured by the ASTM D-648-06 method, as well as by the ASTM D-648-07 method. In some embodiments of the present invention, the core and shell of a structure differ in their HDTs measured by any of the methods in the ASTM D-648 series. In most of the examples herein, HDT at a pressure of 0.45 MPa was used.

[0740] In this specification, "Tg" of a material represents the glass transition temperature, defined as the position of the maximum value of the E'' curve, and E'' is the loss modulus of the material as a function of temperature.

[0741] Roughly speaking, as the temperature increases within a temperature range that includes the Tg temperature, the state of a material, especially a polymer material, gradually changes from a glassy state to a rubbery state.

[0742] In this specification, the "Tg range" is a temperature range in which the E'' value is at least half (for example, less than or equal to) its value at the Tg temperature as defined above.

[0743] While we do not wish to be bound by any particular theory, it is assumed that the state of polymer materials gradually changes from a glassy state to a rubbery state within the Tg range defined above. The lowest temperature in the Tg range is referred to herein as Tg(low), and the highest temperature in the Tg range is referred to herein as Tg(high).

[0744] Throughout this specification, whenever a curable material is defined by the properties of the hardened material obtained from it, it should be understood that these properties refer to the hardened material itself.

[0745] "Tensile strength" refers to the maximum stress that a material can withstand while being stretched or pulled before it breaks. Tensile strength may be determined, for example, according to ASTM D-638-03.

[0746] "Tensile modulus" refers to the stiffness of a material, defined as the relationship between stress (force per unit area) and strain (proportional deformation) within the material in the linear elastic region of uniaxial deformation. The tensile modulus may be determined, for example, according to ASTM D-638-04.

[0747] "Bending strength" or "bending stress" refers to the stress in the material just before it yields during a bending test. Unless otherwise specified, bending strength may be determined according to, for example, ASTM D-790-03.

[0748] The "flexural modulus" or "flexural Y modulus" refers to the stress-to-strain ratio in bending deformation, which is determined from the slope of the stress-strain curve produced by a bending test such as ASTM D790. Unless otherwise specified, the flexural modulus may be determined according to, for example, ASTM D-790-04.

[0749] According to some embodiments, the bending strength and bending modulus are determined in accordance with ISO 20795-1(8.5).

[0750] Throughout this specification, unless otherwise specified, viscosity values ​​are provided for the viscosity of a material or formulation as measured with a Brookfield viscometer at 25°C. Measurements are provided in centipoise units, corresponding to units of mPa / second.

[0751] "Transparent curable formulation" means a curable formulation as defined herein that provides a transparent material when cured. Such formulations are also referred to herein as "clear" formulations and include formulations that do not contain the pigments described herein.

[0752] The term "transparent" describes the properties of a hardened material that reflect the transmission of light. A transparent material is typically characterized by its ability to transmit at least 70% of the light passing through it, or by having a transmittance of at least 70%. The transmittance of a material can be determined using methods well known in the art.

[0753] The transparent curable formulations described herein may remain transparent even before hardening.

[0754] The transparent curable formulations described herein may be colorless and / or have color characteristics determined by the L*a*b* scale, as described below for the hardening material.

[0755] For clarity, it is understood that certain features of the invention described in relation to separate embodiments may be provided in combination in a single embodiment. Conversely, for brevity, various features of the invention described in relation to a single embodiment may be provided separately, in any suitable subcombination, or as appropriate in other described embodiments of the invention. Certain features described in relation to various embodiments should not be considered essential features of those embodiments unless the embodiments would not function without those elements.

[0756] The various embodiments and aspects of the present invention, detailed above and claimed in the following claims section, are experimentally supported in the following examples. [Examples]

[0757] The following examples illustrate, in conjunction with the above description, some non-limiting embodiments of the present invention.

[0758] Example 1 design The inventors have sought a curable formulation usable for additive manufacturing, particularly 3D inkjet printing, of dental prostheses including artificial tooth groups, denture bases, and preferably integrated structures combining denture bases and teeth. The inventors have focused on 3D inkjet printing using a system such as the one shown in Figure 1D, which employs an LED radiation source as the curing energy source and can carry out the PolyJet printing process. The PolyJet printing process allows for the combination of different formulations with different colors and / or different mechanical properties, and is particularly useful for manufacturing full-color integrated structures combining denture bases and teeth, and for manufacturing any denture component in a personalized manner.

[0759] The inventors have sought curable formulations that, in addition to meeting the requirements of 3D printing processes (e.g., exhibiting desired viscosity, surface tension, printability, and reactivity), also meet regulatory dental requirements and, in particular, exhibit the biocompatibility and mechanical properties described in ISO 20795-1 Dental, ISO 10477 Dental; and ISO 10993-1 (Biological evaluation of medical devices (for mucosal contact with long-term exposure)).

[0760] During the painstaking testing, the inventors designed, successfully prepared, and implemented 3D printing material and support material formulations that met the requirements of the 3D printing process, regulatory requirements, and desired color control. All materials selected for these tests, including curable materials, photoinitiators, dispersants, polymerization inhibitors, and colorants, were chosen for their biocompatibility during post-curing and photobleaching, according to their toxicity profiles.

[0761] As described in further detail below, the inventors have identified formulations and printing modes that meet all of the above requirements and can be successfully used to manufacture full-color, one-piece denture structures.

[0762] Example 2 Exemplary Type A molding material formulation Table 1 below shows exemplary curable materials and other components that are considered to be included in molding material formulations because they are used in medical formulations or have relatively high NOEAL (No Observed Adverse Effect Level) values.

[0763] [Table 1] (Continued from Table 1) JPEG2026525243000010.jpg62156

[0764] Various combinations of these components were used at various concentrations (expressed as a weight percentage of the total weight of the formulation) to prepare the formulations shown in Table 2 (for example, by mixing all materials at a temperature of 50°C or below).

[0765] [Table 2]

[0766] Formulation I is a clear, colorless, and preferably transparent formulation that does not contain any pigment. Such a formulation can be used as a base for CMY (cyan, magenta, and yellow) formulations as described herein.

[0767] Formulation II is a white formulation, and pigment P is a white paste containing 40% white pigment in a mixture of curable (meth)acrylate materials.

[0768] In addition to the formulations shown in Table 2, the following formulations were cast.

[0769] Formulation IX, also referred to herein as WC formulation, comprises 80% by weight of formulation II and a total of 20% by weight of formulation I, or a mixture of equal weights (5% by weight each) of formulation I, formulation X, formulation XI, and formulation XII.

[0770] Formulation X - A cyan-colored formulation comprising cyan pigments and their respective pigment dispersants as described herein.

[0771] Formulation XI - A magenta-colored formulation comprising magenta pigments and their respective pigment dispersants as described herein.

[0772] Formulation XII - A yellow formulation comprising a yellow pigment and a respective pigment dispersant as described herein.

[0773] Formulations X, XI, and XII have the composition of Formulation I, to which a paste containing a curable material in an amount of 0.1% to 0.5% by weight, a selected pigment in an amount of 0.05% to 0.5% by weight, and a pigment dispersant are added.

[0774] The cyan, magenta, and yellow pigments (component P) in all formulations are preferably nano-sized pigments (not dyes) with an average particle size of less than 1 micrometer, exhibiting good thermal stability and selected from pigments suitable for use in food and / or medical devices.

[0775] The pigment dispersant (component Dp) is preferably a surfactant approved for use in food-contact printing inks, a high molecular weight block copolymer based on polyurethane chemistry, and preferably characterized by functional groups having high affinity for each pigment. The pigment dispersant Dp may be the same or different for each pigment.

[0776] Table 3 below shows the process parameters for each of the formulations shown in Table 2.

[0777] Tables 4A to 4B below show the mechanical and physical properties required by and measured according to the ISO 20795-1 standard, as well as the respective properties of each of the formulations shown in Table 2.

[0778] Table 5 below shows the mechanical and physical properties required by and measured according to the ISO 10477 standard, as well as the respective properties of each of the formulations shown in Table 2.

[0779] Table 6 below shows the biocompatibility characteristics required by and measured according to the ISO 10993-1 standard, as well as the characteristics of each of the formulations shown in Table 2.

[0780] [Table 3]

[0781] [Table 4]

[0782] [Table 5]

[0783] From the data shown in Tables 3, 4A, and 4B, the following can be inferred: If the mixture of components B1 and C is used in an amount greater than 25% by weight, or if the silica filler is used in an amount greater than 15% by weight, as in formulation III, the process parameters will not be met (see Table 3); =When component D1 is used in amounts greater than 15% by weight, it adversely affects process parameters and color, as in formulation V; If component C and / or component A are absent, the mechanical properties required by ISO 20795-1 will not be met, as in formulations VII and VIII. The addition of component B1 improves mechanical strength but results in darkening of the color, as in formulation VII; Using component F2 instead of F1 improves the mechanical properties, as in formulation IV, but the process parameters are not met and the color darkens.

[0784] Therefore, formulations I, II, and IX are deemed to meet the requirements of the process and ISO 20795-1, and are further characterized as meeting the requirements of ISO 10477 and ISO 10993-1, as follows:

[0785] [Table 6]

[0786] As indicated, all formulations meet the requirements of ISO 10477.

[0787] [Table 7]

[0788] As indicated, all formulations meet the requirements of ISO 10993-1.

[0789] Example 3 Stability of Exemplary Type A Molding Material Formulations Additional tests were conducted to evaluate the time-dependent stability of the selected formulations.

[0790] Figure 5 shows a comparative plot illustrating the change in the mechanical properties of an object prepared using formulation IX in water at 37°C for one month, according to ISO 20795-1. The change is less than 10%, which meets the requirements of the ISO 20795-1 standard.

[0791] Table 7 below shows the mechanical properties of an object prepared using formulation IX before and after immersion in water at 37°C for one month and exposure to mercury lamp irradiation for two hours, in accordance with ISO 20795-1. The change is less than 10%, which satisfies the requirements of the ISO 20795-1 standard. The change in mechanical properties is minor, or even nonexistent, thus satisfying the requirements of the ISO 20795-1 standard.

[0792] [Table 8]

[0793] Figures 6A and 6B show the dimensional changes of the internal portion (printed in matte mode as described herein) of an exemplary denture integral structure prepared using at least some of formulations I, II, IX, X, XI, and XII by immersion in water at 37°C. Figure 6B is a bar graph showing the measured dimensions of exemplary points in the central portion of the denture and the left and right gingival contact areas, as indicated by the circles in Figure 6A.

[0794] In accordance with the requirements of ISO 20795-1, changes of less than 200 micrometers were observed after immersion in water for three weeks.

[0795] Figures 7A and 7B show the dimensional changes of the external portion (printed in gloss mode) of an exemplary denture integral structure prepared using at least some of the formulations I, II, IX, X, XI, and XII described herein, by immersion in water at 37°C. Figure 7B is a bar graph showing the measured dimensions of exemplary points of the exemplary upper teeth, indicated by circles in the upper image of Figure 7A, and the exemplary molars and gingiva, indicated by circles in the lower image of Figure 7A.

[0796] In accordance with the requirements of ISO 20795-1, immersion in water for three weeks resulted in changes of less than 125 micrometers in the peripheral area and less than 3 microns in the tooth portion.

[0797] The stability of the formulation during storage was tested by measuring the change in viscosity at 70°C over 21 days at 65°C. The obtained data is shown in Table 8 below, and the fact that there was no substantial change in viscosity indicates the chemical stability of the formulation.

[0798] [Table 9]

[0799] Example 4 Support material formulation The inventors have found that currently available support material formulations do not function optimally in relation to denture structures, and accordingly, have designed and successfully implemented novel formulations that can be used to provide support materials. The support material formulations can be used in combination with any of the shaping material formulations according to this embodiment. More specifically, the inventors have identified the need to include a polyfunctional curable material in the support material formulation in addition to the hydrophilic monofunctional curable material commonly used in such formulations.

[0800] Exemplary support material formulations according to some embodiments of the present invention are: Hydrophilic monofunctional (meth)acrylate, preferably PEGylated acrylate such as PEA6; 15% to 25% by weight; Hydrophilic monofunctional (meth)acrylamide such as HEAA; 10% to 20% by weight; Polyfunctional (e.g., bifunctional) aliphatic / alicyclic (meth)acrylates; 1% to 5% by weight; and Non-curable water-soluble or water-miscible polymer materials described herein (e.g., polyols or polyol mixtures); 40% to 60% by weight, Includes.

[0801] The formulation preferably further comprises a photoinitiator in a concentration of 0.1% to 1% by weight, and optionally a polymerization inhibitor and / or a surfactant.

[0802] The stability of the exemplary formulations is shown in Table 8 above.

[0803] Example 5 Exemplary Type B molding material formulations The inventors have embarked on designing additional molding material formulations with the aim of not only meeting the required flexural strength and flexural modulus, water absorption and water solubility in accordance with ISO 20795-1, but also meeting the recommended (optional) fracture toughness properties such as the maximum strength expansion factor or Kmax and total work of fracture or Wf, which determine the resistance of printed objects to crack propagation in accordance with ISO 20795-1.

[0804] Figures 8A and 8B show the notching apparatus (Figure 8A) and the measurement of Kmax and Wf parameters (Figure 8B) performed in accordance with ISO 20795-1.

[0805] In short, the process involves two stages of notching: a 3mm rough pre-cut (typically included in printed models) and a fine crack ranging from 100μm to 400μm. The object is then immersed in 37°C water for 7 days, or for rapid evaluation, at 67°C for 21 hours, followed by cooling in 23°C water for approximately 60 minutes. Next, a three-point bending test is performed at a low speed (1mm / min).

[0806] Various combinations of the components shown in Table 1 (see Example 1) were used at various concentrations (expressed as a weight % of the total weight of the formulation) to prepare the formulations shown in Table 9 (for example, by mixing all materials at a temperature of 50°C or lower). This was intended to provide a hardening material characterized by a lower degree of crosslinking (compared to, for example, the formulation shown in Example 2), while balancing the above characteristics by using a curable material characterized by a relatively low Tg during curing, and by including a curable material that maintains the reactivity and required viscosity of the formulation. For reference, formulation I (Type A formulation) described in Example 2 is presented.

[0807] [Table 10]

[0808] Formulation XX is a white formulation, and pigment P is a white paste containing 40% white pigment in a mixture of curable (meth)acrylate materials. All other formulations are clear formulations.

[0809] Table 10 below shows the process parameters for each of the formulations shown in Table 9, and the mechanical properties of the resulting hardened materials, measured according to the permissible ASTM standards, for printed objects as described herein.

[0810] [Table 11]

[0811] Most Type B formulations are cast to reduce the total amount and degree of crosslinking of rigid materials, while components A, B, C, and F1, and importantly, component C, are absent. They also contain polyfunctional oligomer materials such as components G2 and D2, characterized by relatively low to moderate Tg values ​​(e.g., less than 100°C), and it is found that the total amount of component E is substantially increased, along with component E2, preferably characterized by a Tg of less than 100°C, and a newly introduced component E3 added to enhance reactivity, in order to maintain the desired viscosity.

[0812] Example 6 Core-shell structure The inventors conceived of combining the Type A and Type B formulations described herein in a digital printing mode, with the aim of further improving the mechanical and aesthetic properties of the resulting denture structure.

[0813] Therefore, various combinations of Type A and Type B formulations were used in various configurations of the core-shell structure, which are described in more detail above and illustrated in Figure 11.

[0814] Table 11 below shows exemplary configurations, and Figures 9A and 9B show the Kmax and Wf obtained for the tested configurations. Shell 1, if present, is the innermost shell or encapsulation region enclosing the core region, which can be enclosed by Shell 2, if present, or by the outermost coating shell or encapsulation region; Shell 2, if present, is an intermediate inner shell or encapsulation region enclosing Shell 1 and being enclosed by the outermost coating shell or encapsulation region; and Shell 3 is the enclosing outermost shell or encapsulation region.

[0815] [Table 12] (Continued from Table 11) JPEG2026525243000022.jpg34160

[0816] As can be seen in Figures 9A and 9B, structure A provided the best performance.

[0817] Figure 10A shows a photograph of a shelled object fabricated according to structure A using formulation II (white) as the type A formulation (see Table 2) and formulation XXV as the type B formulation, showing the collapse of the resulting structure, which is likely due to the formation of a mixed layer of type A and type B formulations.

[0818] Figure 10B shows a photograph of a shelled object prepared according to structure A using formulation II (white) as the type A formulation (see Table 2) and formulation XX* (clear, without white pigment) as the type B formulation, showing the improved structure obtained therefrom, which is likely due to the improved reactivity of formulation XX* (possibly due to the addition of component E3).

[0819] Table 12 below shows the mechanical and physical properties required by and measured according to the ISO 20795-1 standard, as well as the properties of objects printed in structural configurations A, A1, A2, A3, A4, or A5 according to Table 11, using the Type A formulations shown in Table 2 and the Type B formulations shown in Table 9. Unless otherwise specified, all printed objects were manufactured using the system shown in Figure 1D. All objects were printed in matte mode using the support material formulations described herein. After removal of the support material (typically by using a water jet and immersion in an alkaline solution), the objects were post-processed by immersion in a biocompatible polar solvent such as glycerol at 80°C in a UV oven for several hours (e.g., 1 to 2 hours).

[0820] [Table 13]

[0821] All tested structures meet the requirements of ISO 10993-1.

[0822] From the data shown in Table 12, the following can be inferred.

[0823] The combination of Type A and Type B formulations in either a core-shell structure provides improved mechanical properties and satisfies additional desired requirements outlined above that would not be met if the Type A formulation were used alone.

[0824] Structure A1, and further structure A3, are superior to structures A, A2, A4, and A5, as can be seen when comparing the same combination of compound XX and compound I or compound II in these structures. These data show that (i) the Kmax and Wf values ​​increase in direct correlation with the thickness of the innermost shell or encapsulation region; and (ii) the ratio of the thickness of the intermediate inner shell or encapsulation region to the thickness of the outermost coating shell or encapsulation region affects mechanical properties including flexural modulus, strength, and fracture toughness (Kmax and Wf), and should not exceed a ratio of 1:2 (i.e., the thickness of the intermediate inner shell should be at least 50% of the thickness of the outermost coating shell, e.g., 50% to 100% or 50% to 70%).

[0825] Formulations XXI and XXV exhibit inferior properties when combined with Formulation I in Structure A, and the presence of a surfactant in an amount greater than 0.1%, a preference for component G2 over component G1, and the presence of a reactive, rigid (high Tg) curable material such as component E3 improves performance.

[0826] Formulations XXII, XXIII, and XXIV provide inferior properties even when combined with formulation I in structure A, further supporting the preference of component G2 over component G1, the superiority of component E2 over component E1, and the optional inclusion of less than 10% of a reactive, rigid (high Tg) curable material such as component E3.

[0827] Figure 4 is a photograph of an exemplary one-piece structure of a denture base and artificial teeth prepared by 3D inkjet printing using an AM system, such as the one illustrated in Figure 1D, and the exemplary white type A formulation, transparent type A formulation, and colored type A formulation described herein, in combination with formulation XX as a type B formulation in structure A1. As can be seen, an integral structure with precise color control of each part of the structure was successfully prepared.

[0828] While the present invention has been described in relation to its specific embodiments, it is obvious that many alternatives, modifications, and variations will be apparent 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.

[0829] 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 indicated to be incorporated herein by reference. Furthermore, no citation or specification of any reference in this application should be construed as an admission that such reference is available as prior art of the present invention. Section headings, to the extent in which they are used, should not necessarily be construed as restrictive. Furthermore, any priority document of this application is incorporated herein by reference in its entirety.

Claims

1. A molding material formulation that can be used for additive manufacturing of denture structures, wherein the molding material formulation is: The above formulation comprises, in an amount of 15% to 25% by weight of the total weight, at least one polyfunctional ethoxylated aromatic (meth)acrylate (component D2) characterized by at least 10 ethoxylated groups and / or a Tg of less than 0°C; The above formulation comprises, in a total weight of 15% to 25% by weight, at least one polyfunctional urethane (meth)acrylate (component G) characterized by a Tg of less than 100°C; At least 40% by weight, or at least 45% by weight, or 45% to 55% by weight of the total weight of the aforementioned compound, contains at least one monofunctional alicyclic (meth)acrylate (component E2); The above formulation contains at least one monofunctional acrylate (component E3) in an amount of 3% to 10% by weight, or 5% to 10% by weight, or 3% to 8% by weight, of the total weight of the formulation; A compound comprising at least one dispersant (component H), Build material formulation.

2. The component D2 comprises a polyfunctional ethoxylated aromatic (meth)acrylate characterized by at least 10 ethoxylated groups and a curing temperature (Tg) of less than 0°C. The compound according to claim 1.

3. The aforementioned component D2 has a molecular weight of at least 1,000 grams / mol. The compound according to claim 1 or claim 2.

4. The component D2 is a polyfunctional ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups. The formulation according to any one of claims 1 to 3.

5. The aforementioned component G comprises a polyfunctional urethane (meth)acrylate having a molecular weight of at least 1,000 grams / mol. The formulation according to any one of claims 1 to 4.

6. The aforementioned component G is characterized by a Tg in the range of 0°C to 100°C or 50°C to 100°C (component G2). The formulation according to any one of claims 1 to 5.

7. The aforementioned component G includes a polyfunctional urethane methacrylate. The formulation according to any one of claims 1 to 6.

8. The component D2 comprises a polyfunctional ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, a curing time (Tg) of less than 0°C, and a molecular weight of at least 1,000 grams / mol. The compound according to any one of claims 1 to 7.

9. The aforementioned component G includes component G2, which is a polyfunctional urethane methacrylate characterized by a curing time (Tg) in the range of 0°C to 100°C or 50°C to 100°C, and having a molecular weight of at least 1,000 grams / mol. The formulation according to any one of claims 1 to 8.

10. The total amount of at least one component D2 and at least one component G or component G2 is in the range of about 30% to about 50% by weight of the total weight of the compound. The compound according to any one of claims 1 to 9.

11. The at least one component E2 has a molecular weight (MW) of 500 grams / mol or less, or between 100 grams / mol and 500 grams / mol. The compound according to any one of claims 1 to 10.

12. Each of the at least one component E2 is independently characterized by a curing temperature (Tg) of less than 100°C, less than 50°C, 20°C to 60°C, or 20°C to 50°C. The formulation according to any one of claims 1 to 11.

13. The at least one component E2 comprises a monofunctional alicyclic acrylate having a molecular weight (MW) of 500 g / mol or less, or 100 g / mol to 500 g / mol, and characterized by a curing temperature (Tg) of less than 100°C, less than 50°C, or 20°C to 60°C, or 20°C to 50°C. The formulation according to any one of claims 1 to 12.

14. The at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of 500 grams / mol or less, or between 100 grams / mol and 500 grams / mol. The formulation according to any one of claims 1 to 13.

15. The at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate characterized by a curing temperature (Tg) of over 50°C, over 80°C, or between 50°C and 150°C. The formulation according to any one of claims 1 to 14.

16. The amount of the dispersant (component H) is at least 0.1% by weight, or 0.1% to 1% by weight, or 0.1% to 0.5% by weight of the total weight of the compound. The formulation according to any one of claims 1 to 15.

17. The dispersant has a curable group, The compound according to claim 16.

18. The dispersant is a polyfunctional aliphatic silicon (meth)acrylate. The formulation according to claim 17.

19. The aforementioned component D2 comprises a polyfunctional ethoxylated aromatic methacrylate characterized by at least 10 ethoxylated groups, having a molecular weight of at least 1,000 grams / mol, and having a curing time of less than 0°C; and The aforementioned component G comprises component G2, which is a polyfunctional urethane methacrylate having a molecular weight of at least 1,000 grams / mol and characterized by a curing time (Tg) in the range of 0°C to 100°C or 50°C to 100°C; The total amount of the at least one component D2 and the at least one component G2 is in the range of 30% to 50% by weight of the total weight of the compound; The at least one component E2 comprises a monofunctional alicyclic acrylate having a molecular weight (MW) of 500 g / mol or less, or 100 g / mol to 500 g / mol, and characterized by a curing temperature (Tg) of less than 100°C, less than 50°C, or 20°C to 60°C, or 20°C to 50°C; The at least one component E3 comprises a monofunctional hydrophilic or amphiphilic acrylate having a molecular weight (MW) of 500 g / mol or less, or 100 g / mol to 500 g / mol, and characterized by a curing temperature (Tg) of over 50°C, over 80°C, or 50°C to 150°C; and The amount of component H is at least 0.1% by weight of the total weight of the compound, or in the range of 0.1% to 1% by weight, or 0.1% to 0.5% by weight. The compound according to claim 1.

20. The aforementioned formulation further comprises a photoinitiator (component J), The formulation according to any one of claims 1 to 19.

21. The amount of the photoinitiator (component J) is in the range of 1% to 5% by weight of the total weight of the compound. The formulation according to claim 20.

22. The aforementioned formulation further comprises a coloring agent (component P). The formulation according to any one of claims 1 to 21.

23. The aforementioned coloring agent (component P) includes a pigment. The formulation according to claim 22.

24. The coloring agent (component P) comprises a mixture of a pigment and at least one (meth)acrylic material. The compound according to claim 22 or claim 23.

25. The aforementioned pigment is a white pigment. The compound according to claim 23 or claim 24.

26. A set of at least two fabrication material formulations that can be used in combination in additive manufacturing of denture structures, At least one of the two formulations is a Type B formulation, which is a molding material formulation according to any one of claims 1 to 25, and at least one of the two formulations is a Type A formulation, which is: A polyfunctional aliphatic urethane (meth)acrylate (component A) characterized by a curing temperature (Tg) exceeding 100°C; A polyfunctional non-aromatic (meth)acrylate (component B1) characterized by a curing temperature (Tg) exceeding 100°C; A filler (component C) characterized by a particle morphology with an average diameter of less than 1 micron; A polyfunctional ethoxylated aromatic (meth)acrylate (component D1) characterized by fewer than 10 ethoxylated groups and / or a curing temperature (Tg) in the range of 50°C to 150°C; Monofunctional (meth)acrylate (component E) and; A polyfunctional cyclic (meth)acrylate (component F) and; It comprises a polyfunctional aliphatic urethane (meth)acrylate (component G) characterized by a curing temperature (Tg) of less than 100°C, The amount of the filler is 20% by weight or less, or 15% by weight or less, of the total weight of the compound; and The amount of component D is 20% by weight or less, or 15% by weight or less, of the total weight of the compound. A set of ingredients.

27. The aforementioned filler particles include silica particles. A set of the formulations according to claim 26.

28. The aforementioned filler particles have multiple curable groups bonded to them, A set of the formulations according to claim 26 or claim 27.

29. The aforementioned Type A formulation is: The amount of component A is in the range of 15% to 25% by weight of the total weight of the aforementioned compound; The aforementioned compound is composed of the aforementioned component B in an amount of 20% by weight or less, or 15% by weight or less, of the total weight of the aforementioned compound; The above-mentioned component E in an amount of 30% to 40% by weight of the total weight of the above-mentioned compound; The component F in an amount of 5% to 10% by weight of the total weight of the aforementioned compound; The compound comprises the above-mentioned component G in an amount of 5% to 10% by weight of the total weight of the above-mentioned compound, A set of formulations according to any one of claims 26 to 28.

30. The aforementioned component A is a bifunctional aliphatic urethane methacrylate characterized by a curing temperature (Tg) of over 100°C; and / or The aforementioned component B is a bifunctional alicyclic acrylate (component B1) characterized by a Tg of over 100°C during curing; and / or The aforementioned component C comprises silica particles having an average diameter of less than 1 micron and having curable groups bonded thereto; and / or The aforementioned component D is a bifunctional ethoxylated aromatic methacrylate (component D1) characterized by having fewer than five ethoxylated groups and a curing temperature (Tg) in the range of 50°C to 150°C; and / or Each of the components E independently comprises a monofunctional acrylate and a monofunctional methacrylate (component E2) in an amount of 10% to 20% by weight or 15% to 20% by weight of the total weight of the formulation; and / or The aforementioned component F is a trifunctional isocyanurate triacrylate; and / or The aforementioned component G is a bifunctional aliphatic urethane dimethacrylate having an average MW of at least 1,000 grams / mol, a curing time (Tg) of less than 100°C, and an average MW of at least 1,000 grams / mol. A set of formulations according to any one of claims 26 to 29.

31. The aforementioned Type A formulation further comprises a dispersant (component H), A set of formulations according to any one of claims 26 to 30.

32. The dispersant (component H) has a curable group, A set of the compound according to claim 31.

33. The dispersant (component H) is a polyfunctional aliphatic silicon (meth)acrylate. A set of the formulations according to claim 32.

34. The amount of the dispersant (component H) is in the range of 0.1% to 0.5% by weight of the total weight of the type A formulation. A set of formulations according to any one of claims 31 to 33.

35. The aforementioned Type A formulation further comprises a photoinitiator (component J), A set of formulations according to any one of claims 26 to 34.

36. The amount of the photoinitiator (component J) is in the range of 1% to 5% by weight of the total weight of the type A formulation. A set of the formulations described in claim 35.

37. The aforementioned Type A formulation further comprises a coloring agent (component P). A set of formulations according to any one of claims 26 to 36.

38. The aforementioned coloring agent (component P) includes a pigment. A set of the formulations described in claim 37.

39. The coloring agent (component P) comprises a mixture of a pigment and at least one (meth)acrylic material. A set of the formulations according to claim 37 or claim 38.

40. The aforementioned pigment contains nano-sized particles, A set of the formulations according to claim 38 or claim 39.

41. The aforementioned coloring agent (component P) further comprises a pigment dispersant (component Dp). A set of formulations according to any one of claims 38 to 40.

42. A kit comprising a set of formulations according to any one of claims 26 to 41, wherein each of the at least two formulations is individually packaged within the kit. kit.

43. The set or kit further comprises a support material formulation usable for additive manufacturing of denture structures, the support material formulation being: A non-curable, water-soluble or water-miscible polymer material in an amount of approximately 40% to 60% by weight of the total weight of the aforementioned compound; A hydrophilic monofunctional (meth)acrylate in an amount of 15% to 25% by weight of the total weight of the aforementioned compound; A hydrophilic monofunctional (meth)acrylamide in an amount of 10% to 20% by weight of the total weight of the aforementioned compound; The compound comprises a polyfunctional non-aromatic (meth)acrylate in an amount of 1% to 5% by weight of the total weight of the aforementioned compound, A set of formulations according to any one of claims 26 to 41, or a kit according to claim 42.

44. The support material formulation further comprises a photoinitiator in an amount of 0.1% to 1% by weight of the total weight of the formulation. A set or kit of the formulations described in claim 43.

45. The set or kit comprises at least two Type A molding material formulations as described in any one of claims 26 to 41, wherein the at least two formulations differ from each other in the presence and / or type of a colorant (component P). A set of formulations according to any one of claims 26 to 41, 43, and 44, or a kit according to any one of claims 42 to 44.

46. A method for additive manufacturing a three-dimensional denture object, wherein the method is: This includes extruding multiple layers in a configuration pattern corresponding to the shape of the denture object, thereby forming the object. Each of the molding of at least several of the aforementioned layers includes extruding at least one molding material formulation and exposing the extruded formulation to curing conditions to thereby form a cured molding material. The at least one molding material formulation is the molding material formulation described in any one of claims 1 to 25. method.

47. The extrusion is the extrusion of a set of at least two molding material formulations according to any one of claims 26 to 41. The method according to claim 46.

48. The aforementioned discharge is further the discharge of a support material formulation. The method according to claim 46 or claim 47.

49. For at least several layers of the aforementioned layers, the extrusion is such that it forms a core region and at least one outermost encapsulation region that at least partially encloses or surrounds the core region, and each of the core region and the encapsulation region is formed from a different material formulation or a different combination of the at least two material formulations. The method according to any one of claims 46 to 48.

50. The core region is formed from the type B compound. The method according to claim 49.

51. The outermost encapsulation region is formed from the type A formulation. The method according to claim 49 or claim 50.

52. For at least several layers of the aforementioned layers, the extrusion is such that it further forms an internal encapsulation region that at least partially encloses or surrounds the core region, and optionally one or more intermediate encapsulation regions that at least partially enclose or surround the internal encapsulation region, the outermost encapsulation region at least partially surrounding the outermost intermediate encapsulation region, and each of the core region and the internal encapsulation region, each of the internal encapsulation region and the intermediate encapsulation region if present, or each of the outermost encapsulation region and the intermediate encapsulation region if present, and each of the outermost encapsulation region are formed from different molding material formulations or different combinations of the at least two molding material formulations. The method according to claim 49.

53. The core region is molded from the type B formulation, the internal encapsulation region is molded from the type A formulation, the intermediate encapsulation region is molded from the type B formulation, and the outermost encapsulation region is molded from the type A formulation. The method according to claim 52.

54. A method for additive manufacturing a three-dimensional denture object, wherein the method is: This includes extruding multiple layers in a configuration pattern corresponding to the shape of the denture object, thereby forming the object. The molding of at least several of the aforementioned layers includes extruding at least a first molding material compound and a second molding material compound, and exposing the extruded compound to curing conditions to thereby form a cured molding material. The extrusion process forms a core region and at least one outermost encapsulation region that at least partially encloses or surrounds the core region. The core region is formed from the second molding material compound or a first combination of the first molding material compound and the second molding material compound, and the encapsulation region is formed from the first molding material compound or a second combination of the first molding material compound and the second molding material compound, the second combination being different from the first combination, The first molding material formulation and the second molding material formulation are The second formulation or the first combination, upon curing, is characterized by having an impact resistance at least twice, at least five times, or at least ten times higher than the impact resistance of the first formulation or the second combination; and / or The first formulation or the second combination is characterized by having a flexural modulus at least twice, at least five times, or at least ten times higher than that of the second formulation or the first combination upon curing. method.

55. For at least several layers of the aforementioned layers, the extrusion is such that it further forms an internal encapsulation region that at least partially encloses or surrounds the core region, and an intermediate encapsulation region that at least partially encloses or surrounds the internal encapsulation region and is at least partially surrounded or enclosed by the outermost encapsulation region, wherein the internal encapsulation region is formed from the first formulation or the second combination of the first formulation and the formulation, and the intermediate encapsulation region is formed from the second formulation or the first combination of the first formulation and the second formulation. The method according to claim 54.

56. The denture structure is selected from a denture base, artificial teeth, a group of artificial teeth, and an integrated structure of the denture base and the group of artificial teeth. The method according to any one of claims 46 to 55.

57. The aforementioned denture structure is an integrated structure of a denture base and an artificial tooth group. The method according to any one of claims 46 to 56.

58. Obtained by the method described in any one of claims 46 to 57, Denture structure.

59. The aforementioned denture structure is an integrated structure of a denture base and an artificial tooth group. The denture structure according to claim 58.

60. The aforementioned denture structure is characterized by mechanical and physical properties in accordance with the requirements of ISO 20795-1 and biocompatible properties in accordance with the requirements of ISO 10993-1. The denture structure according to claim 58 or claim 59.

61. The aforementioned denture structure is characterized by a flexural modulus, flexural strength, Kmax, and Wf in accordance with the requirements of ISO 20795-1. A denture structure according to any one of claims 58 to 60.

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