3D printable material for manufacturing printing dental accessory and dental

Abstract

Disclosed herein is a curable composition that can contain a high crosslinker content and cure to form a tough and color neutral material that can be effectively used for a wide range of dental applications. In various embodiments, the compositions and / or polymers resulting therefrom may be used in dental appliances, including, but not limited to, orthodontics, accessory placement devices, incremental palate dilaters, dentures, crowns, and the like.

Description

[0001] Incorporated by Reference

[0002] All publications, patents, and patent applications mentioned in this disclosure are incorporated herein by reference to the same extent as if each individual publication, patent, or patent application was specifically and individually indicated to be incorporated by reference in its entirety. This application claims priority to U.S. Provisional Patent Application No. 63 / 358,673, filed on July 6, 2022, entitled "3D Printable Materials for Making Printed Orthodontic Attachments," the contents of which are hereby incorporated by reference as if fully set forth herein.

[0003] BACKGROUND OF THE DISCLOSURE

[0004] Orthodontic devices need to meet stringent requirements for strength, flexibility, durability, size, weight, and appearance. Although high-strength devices are often required to achieve the desired treatment effect (such as tooth straightening), practical constraints (such as comfort, appearance, and patient compliance) often require that these devices must be small, lightweight, and transparent or neutral in appearance. In addition, for many dental applications, materials must be compatible with high-resolution printing methods. Since few materials can provide this combination of properties, new materials are needed to support existing and emerging dental treatment technologies.

[0005] Overview of the Disclosure

[0006] The present disclosure provides a series of curable compositions that can be used by a series of 3D printing methods and are configured for various practical applications. In many cases, the curable compositions contain high crosslinker content and produce tough, lightweight polymer materials suitable for medical applications. Many such compositions contain crosslinkers of multiple different sizes, side chain functionalities and flexibility, affecting the heterogeneity at the molecular level in the cured and uncured polymers. Because this heterogeneity may be important for toughness, color and translucency, the curable compositions of the present disclosure can be very suitable for use in dental devices, including spacers, correctors, one or more incremental palatal expanders and / or accessory placement devices.

[0007] In various aspects, the present disclosure provides a curable composition comprising a plurality of polymerizable monomers, the polymerizable monomers comprising at least 80 wt % of a crosslinking agent; and at least 10 wt % of a filler material.

[0008] In various aspects, the present disclosure provides a curable composition comprising a plurality of polymerizable monomers comprising at least 80 wt % of a crosslinker; and at least 0.5 wt % of a wetting agent.

[0009] In various aspects, the present disclosure provides a curable composition comprising a plurality of polymerizable monomers, wherein the polymerizable monomers comprise at least 80 wt % of a crosslinker; wherein the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured.

[0010] In various aspects, the present disclosure provides a curable composition comprising a first cross-linker comprising a first plurality of polymerizable functional groups, and an aryl or heteroaryl group disposed between at least two of the first plurality of polymerizable functional groups; a second cross-linker comprising a second plurality of polymerizable functional groups, and a carbamate, a diol, a carbonate, a urea, an ester, an amide, a thioether, a thioester, a guanidine, or a combination thereof disposed between at least two of the second plurality of polymerizable functional groups.

[0011] In various aspects, the present disclosure provides a method for repositioning a patient's teeth, the method comprising generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving the teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; providing a dental attachment comprising a printed device generated from a curable composition of a plurality of polymerizable monomers, the polymerizable monomers comprising at least 80 wt % of a cross-linking agent; and at least 10 wt % of a filling material; and adhering the dental attachment to the subject's teeth; connecting a dental brace to the dental attachment, wherein the dental brace is configured to move at least one of the patient's teeth toward an intermediate tooth arrangement or a final tooth arrangement.

[0012] In various aspects, the present disclosure provides a method for manufacturing an accessory placement device, the method comprising obtaining a curable composition, and using the curable composition comprising a plurality of polymerizable monomers to additively manufacture a printed article comprising the accessory placement device, the polymerizable monomers comprising at least 80 wt % of a cross-linking agent; and at least 10 wt % of a filler material.

[0013] In various aspects, the present disclosure provides a dental attachment placement device generated by an additive manufacturing process from one of the above-mentioned curable compositions, the curable composition comprising at least one first cross-linking agent having a rigid backbone between a plurality of first polymerizable functional groups; at least one second cross-linking agent having a flexible backbone between a plurality of second polymerizable functional groups; and a photoinitiator. The polymer material formed from the curable composition has a tensile strength of about 50 MPa or more, a modulus strength of 1200 MPa or more, and a strain at break of about 4% or more.

[0014] In various aspects, the present disclosure provides a dental attachment placement device generated from a curable composition by an additive manufacturing process. The dental attachment placement device includes a body; one or more additively manufactured dental attachments shaped to be connected to a person's dentition at a corresponding position, wherein the one or more additively manufactured dental attachments are shaped to engage with corresponding one or more attachment grooves of an orthodontic appliance and, when engaged with the one or more attachment grooves, apply one or more forces to the person's dentition; and one or more additively manufactured supports for removably coupling the one or more additively manufactured attachments to the body. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] The novel features of the present invention are set forth with particularity in the appended claims. A better understanding of the features and advantages of the present disclosure will be obtained by referring to the following detailed description and the accompanying drawings which set forth illustrative embodiments in which the principles of the present invention are utilized:

[0016] Figure 1A A tooth repositioning appliance according to some embodiments is shown.

[0017] Figure 1B A tooth repositioning system according to some embodiments is shown.

[0018] Figure 1C An orthodontic treatment approach using multiple appliances is shown according to some embodiments.

[0019] Figure 2 A method of designing an orthodontic appliance according to some embodiments is shown.

[0020] Figure 3 A method for digitally planning orthodontic treatment according to some embodiments is shown.

[0021] Figure 4 A process for generating and implementing a therapy according to some embodiments is shown.

[0022] Figure 5 A schematic diagram of a (eg, high temperature) additive manufacturing apparatus for curing the curable resin of the present disclosure via a 3D printing process is shown according to some embodiments.

[0023] Fig. 6A Shown is a front view of a dental attachment former according to some embodiments.

[0024] Figure 6B A top view of a dental attachment former according to some embodiments is shown.

[0025] Figure 7 A front view of an attachment former according to some embodiments is shown.

[0026] Fig. 8A A front view of a dental accessory placement structure for placing an accessory according to some embodiments is shown.

[0027] Figure 8B Shows Fig. 8A Posterior view of the dental accessory placement structure.

[0028] Figure 8C Shown is a diagram of a tooth placed on a patient's teeth. Fig. 8A and 8B Front view of a dental accessory placement structure.

[0029] Fig.8D Shows the use of Fig. 8A and Figure 8B A front view of a dental attachment placement structure attached to a patient's tooth.

[0030] Fig. 9 A front view of a dental accessory placement structure 900 is shown having a plurality of accessory placement components provided thereon, according to some embodiments.

[0031] Fig. 10A Shown is a front view of a dental attachment placement structure for etching a tooth, according to some embodiments.

[0032] Fig. 10B Shows Fig. 10A Posterior view of the dental accessory placement structure.

[0033] Fig. 10C shows a front view of an etched area on a patient's tooth that has been Fig. 10A and Fig. 10B The dental attachment placement structure is etched.

[0034] Fig.11 A front view of a dental accessory placement structure provided with a plurality of accessory placement assemblies in structure according to some embodiments is shown.

[0035] Fig. 12A Shown is a front view of a dental attachment placement structure for etching a tooth, according to some embodiments.

[0036] Fig. 12B Shows the use of Fig. 12A A front view of a dental attachment of a dental attachment placement structure attached to a patient's tooth.

[0037] Fig.13A A front view of another dental attachment placement structure for etching a tooth is shown according to some embodiments.

[0038] Fig. 13B Shows the use of Fig.13A A front view of a dental attachment placement structure of a plurality of dental attachments attached to a plurality of teeth of a patient.

[0039] Fig.14A A front view of another dental attachment placement structure for etching a tooth is shown according to some embodiments.

[0040] Fig. 14B Shows the use of Fig.14A A front view of a dental attachment of a dental attachment placement structure attached to a patient's tooth.

[0041] Fig.15A An oblique front view of a dental accessory placement structure structurally provided with an accessory placement assembly is shown according to some embodiments.

[0042] Fig. 15B Shows Fig.15A Oblique posterior view of the dental accessory placement structure.

[0043] Fig. 15C Shows Fig.15A Cross-sectional side view of a dental accessory placement structure.

[0044] Fig.16A An oblique front view of a dental accessory placement structure structurally provided with an accessory placement assembly is shown according to some embodiments.

[0045] Fig. 16B Shows Fig.16A Oblique posterior view of the dental accessory placement structure.

[0046] Fig. 16C Shows Fig.16A Cross-sectional side view of a dental accessory placement structure.

[0047] Fig.17A An oblique front view of a dental accessory placement structure structurally provided with an accessory placement assembly is shown according to some embodiments.

[0048] Fig. 17B Shows Fig.17A Oblique posterior view of the dental accessory placement structure.

[0049] Fig. 17C Shows Fig.17A Cross-sectional side view of a dental accessory placement structure.

[0050] Fig.18A A front view of a dental attachment placement structure according to some embodiments is shown.

[0051] Fig.18B Shows Fig.18A A close-up view of the attachment portion of a dental attachment placement structure.

[0052] Fig. 18C Shows Fig.18A A perspective side view of a dental accessory placement structure.

[0053] Fig.18D Shows Fig.18A Another perspective side view of a dental accessory placement structure.

[0054] Fig.18E Shows Fig.18A A perspective view of a dental accessory placement structure in a toothless state, showing multiple aspects of the various contact portions of the retention support.

[0055] Fig.18F Shows Fig.18A Close-up view of the contact portion of the retention support of a dental accessory placement structure.

[0056] Figure 18G Shows Fig.18A A top view of a dental accessory placement structure in which a portion of the frame is modified to have a zigzag or "Z" shape as an alternative to an arch shape.

[0057] Fig.18H Shows Fig.18A Another perspective side view of the frame and registration anchor of a dental accessory placement structure.

[0058] Fig.18I A flexible frame comprising one or more Fig.18A A top view of an alternative dental attachment placement structure.

[0059] Figures 18J-18K Shows an alternative Fig.18A The connecting joint of the middle arc frame section.

[0060] Figure 18L A flexible attachment support is shown. Fig.18A An alternative variant of the structure.

[0061] Figure 18M and 18N shows how to form a virtual model Fig.18A An example of the features of a dental attachment placement structure.

[0062] Fig.19A A buccal view of another dental attachment placement structure is shown in accordance with some embodiments.

[0063] Fig.19B Shows Fig.19Alingual view of a dental attachment placement structure showing an attachment frame and retention support according to some embodiments.

[0064] Fig.19C Shows Fig.19A A top view of a dental accessory placement structure showing an identifier according to some embodiments.

[0065] Fig.19D Shows Fig.19A A side view of a dental accessory placement structure showing an exemplary accessory surface of an accessory according to some embodiments.

[0066] Fig. 20A A side view of a dental attachment with a powered arm assist feature attached to a dental arch using a dental attachment placement structure is shown in accordance with some embodiments.

[0067] Fig. 20B The dental attachment placement structure is removed and the elastic band is hooked onto the auxiliary feature on the corresponding tooth. Fig. 20A A dental attachment with a powered arm assist feature.

[0068] Fig.21 A dental attachment with auxiliary features is shown connected to a dental arch using a dental attachment placement structure according to some embodiments.

[0069] Fig.22A and 22B A dental attachment with a button assist feature connected to opposing dental arches and a resilient member coupled thereto is shown according to some embodiments.

[0070] Fig.23 The functional features of a power arm with an attachment frame and retention support are shown according to some embodiments.

[0071] Fig.24 A perspective view of one example of a lattice structure that may be incorporated into one or more portions of any of the dental attachment placement structures described herein is shown.

[0072] Fig.25A A dental attachment is shown coupled to a plurality of teeth of a dental arch according to some embodiments.

[0073] Fig.25B A dental attachment placement device is shown according to some embodiments, which can be used to properly place Fig.25A Dental attachments so that they can work with dental braces to apply the correct forces on the teeth.

[0074] Fig.25CAccording to some embodiments, a method for forming Fig.25B A computer model of a dental attachment placement device of a dental attachment placement device.

[0075] Figures 26A-26E A dental attachment replacement system configured to replace a first dental attachment with a second dental attachment is shown.

[0076] Fig. 27 A dental attachment replacement system according to some embodiments is shown, which is an example of a hinge-based attachment replacement system in which the second attachment support includes a post (rather than a frame) for supporting the second dental attachment.

[0077] Fig.28 A dental accessory replacement system is shown according to some embodiments, which is another example of a hinge-based accessory replacement system, wherein the dental accessory replacement system includes a sacrificial support that couples a second accessory support to a body.

[0078] Figures 29A-29B A dental accessory replacement system according to some embodiments is shown, which is another example of a hinge-based accessory replacement system, wherein the hinge is configured to rotate a second accessory holder to either side of the body.

[0079] Fig. 30A A front view of a first framework and a second framework from a dental perspective is shown according to some embodiments.

[0080] Fig. 30B A side view of a dental attachment replacement system according to some embodiments is shown, illustrating how a second attachment holder can be rotated relative to the body to replace a first dental attachment with a second dental attachment.

[0081] Fig. 30C Another example is shown where the body includes an internal cutout that allows the second accessory holder to be further rotated to move the second accessory holder out of the way until needed.

[0082] Figures 31A-31B A dental accessory replacement system is shown according to some embodiments and includes a dial assembly in which a second accessory support member is rotatable about a post.

[0083] Fig.32 A dental attachment replacement system is shown according to some embodiments and includes a gear assembly.

[0084] Figures 33A-33C A dental attachment replacement system is shown according to some embodiments and includes a dowel joint assembly.

[0085] Figures 34A-34B A dental attachment replacement system having a dowel joint assembly is shown according to some embodiments.

[0086] Figures 35A-35C A dental attachment replacement system having a dispenser-type assembly according to some embodiments is shown.

[0087] Figures 36A-36D A portion of a dental attachment placement device is shown according to some embodiments, the device including anchors configured to removably connect with a plurality of corresponding dental attachment replacement systems.

[0088] Fig.37A A dental attachment placement device is shown having a removable dental attachment replacement system in accordance with some embodiments, wherein an anchor is removably coupled (press-fit) to a square or rectangular hole on a body.

[0089] Fig.37B A dental attachment placement device is shown having a removable dental attachment replacement system in accordance with some embodiments, wherein an anchor is removably coupled (press-fitted) to a circular hole on a body.

[0090] Fig.37C A dental attachment placement device is shown having a removable dental attachment replacement system in accordance with some embodiments, wherein an anchor is removably coupled (press-fit) to a flexible body.

[0091] Figures 38A-38C A removable dental attachment replacement system is shown according to some embodiments.

[0092] Detailed Description

[0093] The present disclosure provides a series of curable compositions that can be used through a series of 3D printing methods and configured for various practical applications. In many cases, the curable compositions contain high crosslinker content and produce tough, lightweight polymer materials suitable for medical applications. Many such compositions contain crosslinkers of different sizes, side chain functionalities and flexibility, thereby affecting a high degree of molecular level heterogeneity in the cured and uncured polymers. Because this heterogeneity can be important for toughness, color and translucency, the curable compositions of the present disclosure can be well suited for dental devices, including separators, correctors, one or more incremental palatal expanders and / or accessory placement devices.

[0094] I. Definitions

[0095] All terms, chemical names, expressions and names have their usual meanings familiar to those skilled in the art. As used herein, the terms "to comprise" and "comprising" are to be understood as non-restrictive, i.e., other components than those explicitly named may be included.

[0096] Numerical ranges should be understood to be inclusive, i.e., including the indicated lower and upper limits. In addition, unless otherwise expressly indicated, the term "about" as used herein generally refers to and includes plus or minus 10% of the indicated value. For example, "about 10%" may represent a range of 9% to 11%, and "about 1" may include a range of 0.9-1.1.

[0097] As used herein, the term "polymer" generally refers to a molecule consisting of repeating structural units linked by covalent chemical bonds, characterized by a large number of repeating units (e.g., equal to or greater than 20 repeating units, typically equal to or greater than 100 repeating units and typically equal to or greater than 200 repeating units) and a molecular weight greater than or equal to 5,000 Daltons (Da) or 5 kDa, such as greater than or equal to 10 kDa, 15 kDa, 20 kDa, 30 kDa, 40 kDa, 50 kDa or 100 kDa. A polymer is generally the polymerization product of one or more monomer precursors. The term polymer includes homopolymers, i.e., polymers consisting essentially of a single repeating monomer species. The term polymer also includes copolymers formed when two or more different types (or species) of monomers are linked in the same polymer. Copolymers can include two or more different monomer species, and include random, block, alternating, segmented, grafted, tapered and other copolymers. The term "crosslinked polymer" generally refers to a polymer having one or more connections between at least two polymer chains, which can be generated by a multivalent monomer that forms a crosslinking site when polymerized. In various embodiments, the polymers herein are telechelic polymers capable of undergoing further polymerization reactions with other polymerizable components present, for example, in a curable resin.

[0098] As used herein, the term "oligomer" generally refers to a molecule consisting of repeating structural units connected by covalent chemical bonds, characterized in that the number of repeating units is less than the number of repeating units of a polymer (e.g., equal to or less than 20 or less than 10 repeating units) and a molecular weight lower than that of a polymer, for example, less than 5,000 Da or less than 2,000 Da, in various cases from about 0.5 kDa to about 5 kDa. In some cases, an oligomer can be the polymerization product of one or more monomer precursors. In various embodiments, the oligomers herein are telechelic oligomers capable of further polymerization with other polymerizable components present in a curable resin.

[0099] As used herein, the terms "telechelic polymer" and "telechelic oligomer" generally refer to polymers or oligomers whose molecules are capable of entering into further polymerization through polymerizable reactive functional groups.

[0100] As used herein, the term "reactive diluent" generally refers to a substance that reduces the viscosity of another substance, such as a monomer or a curable resin. The reactive diluent can become part of another substance, such as a polymer obtained by a polymerization process. In some examples, the reactive diluent is a curable monomer that, when mixed with a curable resin, reduces the viscosity of the resulting formulation and is incorporated into the polymer resulting from the polymerization of the formulation.

[0101] Oligomer and polymer mixtures can be characterized and distinguished from other mixtures of oligomers and polymers by measuring molecular weight and molecular weight distribution.

[0102] The molecular weight (M) is the number average molecular weight (Mn), which is the average number n of repeating units multiplied by the molecular weight or molar mass (Mi) of the repeating unit. The number average molecular weight (Mn) is the arithmetic mean representing the total weight of the molecules present divided by the total number of molecules.

[0103] As used herein, the term "fiber" may refer to an elongated material whose length greatly exceeds its height and width. For example, a fiber may be a substantially cylindrical material having a length at least 50 times, at least 100 times, or at least 200 times its diameter. The fiber may comprise a variety of materials, including polymers, glasses, ceramics, metals, composite materials, and combinations thereof. Optionally, a fiber may include a cavity extending along a portion or all of its length.

[0104] The photoinitiators described in the present disclosure may include those that can be activated with light and initiate polymerization of the polymerizable components of the resin or formulation. As used herein, "photoinitiator" may generally refer to a compound that is capable of generating free radical species and / or promoting free radical reactions when exposed to radiation (such as UV or visible light).

[0105] As used herein, the term "biocompatibility" refers to a material that does not cause immune rejection or harmful effects (referred to herein as adverse immune responses) when it is placed in an in vivo biological environment. For example, in some embodiments, when a human or animal is exposed to or contacts a biocompatible material, the change in a biomarker indicating an immune response relative to a baseline value is less than 10% or less than 20% or less than 25% or less than 40% or less than 50%. Alternatively, the immune response can be determined histologically, wherein the local immune response is assessed by visually assessing markers (including immune cells or markers involved in immune response pathways) within and near the material. In one aspect, a biocompatible material or device does not significantly change the immune response determined by histology. In some embodiments, the present disclosure provides a biocompatible device configured to be used for a long time (e.g., within a period of about several weeks to several months) without inducing an adverse immune response. The biological effect can initially be assessed by measuring cytotoxicity, sensitization, irritation and intradermal reactivity, acute systemic toxicity, pyrogenicity, subacute / subchronic toxicity and / or implantation. Biological tests for supplementary assessment include tests for chronic toxicity.

[0106] "Bioinert" refers to a material that does not elicit an immune response in a human or animal when placed in an in vivo biological environment. For example, when a human or animal is exposed to or in contact with a bioinert material, a biomarker indicative of an immune response remains substantially constant (±5% of a baseline value). In some embodiments, the present disclosure provides a bioinert device.

[0107] As used herein, the terms "homogeneous" and "homogeneity" may refer to the uniformity of the distribution of components or properties of a composition or material. In some cases, homogeneity refers to the uniformity of distribution at a microscopic, nanometer, or chemical level. In some cases, homogeneity refers to the random distribution of components within a composition or material. In some cases, homogeneity refers to a spatially invariant chemical or physical property of a composition or material (e.g., spatially uniform hardness or color).

[0108] As used herein, the terms "inhomogeneous" and "inhomogeneity" may refer to the non-uniformity of the distribution of components or properties of a composition or material. In some cases, "inhomogeneous" refers to partitioning or patterning within a composition or material. For example, an emulsion may be inhomogeneous to the extent that two or more components separate into different phases. In some cases, inhomogeneity refers to spatial variations in the chemical or physical properties of a composition or material. In some cases, inhomogeneity refers to uneven crystallinity of a portion of a composition or material.

[0109] When a group of substituents is disclosed herein, it is understood that all individual members of the group and all subgroups, including any isomers, enantiomers and diastereomers of the group members, are disclosed separately. When Markush groups or other groupings are used herein, all individual members of the group and all combinations and possible subcombinations of the group are intended to be included in the disclosure separately. When the compounds described herein are such that a specific isomer, enantiomer or diastereomer of the compound is not specified in, for example, a formula or chemical name, the description is intended to include each isomer and enantiomer of the compound described separately or in any combination. In addition, unless otherwise specified, all isotopic variants of the compounds disclosed herein are intended to be included in the disclosure. The specific names of the compounds are intended to be exemplary, as it is known that those of ordinary skill in the art may name the same compound differently.

[0110] It should be noted that as used herein and in the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a monomer" includes a plurality of such monomers and equivalents thereof known to those skilled in the art, and so forth. Furthermore, the terms "a" (or "an"), "one or more," and "at least one" may be used interchangeably herein. It should also be noted that the terms "comprising," "including," and "having" may be used interchangeably.

[0111] As used herein, "comprising" is synonymous with "including," "containing," or "characterized by," and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, "consisting of" does not exclude any elements, steps, or ingredients not specified in the claim elements. As used herein, "consisting essentially of" does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim.

[0112] As used herein, the term "group" may refer to a reactive functional group of a compound. A group of a compound of the present invention refers to an atom or collection of atoms that is a part of a compound. The groups of the present disclosure may be attached to other atoms of the compound by one or more covalent bonds. Groups may also be characterized by their valence state. The present disclosure includes groups characterized by monovalent, divalent, trivalent, and equivalent states.

[0113] As used herein, the term "substituted" refers to compounds (eg, alkyl chains) in which a hydrogen is replaced with another reactive functional group or atom as described herein.

[0114] As used herein, dashed lines in chemical structures may be used to indicate a bond to the rest of the molecule. For example, In Used to designate the 1-position as the point of attachment of 1-methylcyclopentanoate to the rest of the molecule. Alternatively, for example In Can be used to indicate that a given moiety (the cyclohexyl moiety in this example) is attached to a molecule via a bond "capped" with a wavy line.

[0115] As used herein, "aliphatic" or "aliphatic group" refers to a straight or branched chain C 1- C 30 A hydrocarbon chain or a monocyclic C- 3- C 20 Hydrocarbon or bicyclic C8-C 20 Hydrocarbons (also referred to herein as "cycloalkyls") are attached to the rest of the molecule by a single point of attachment, wherein any individual ring in the bicyclic system has 3-7 members. For example, suitable aliphatic groups include, but are not limited to, straight or branched chain alkyls, alkenyls, alkynyls, and hybrids thereof, e.g., (cycloalkyl)alkyls, (cycloalkenyl)alkyls, or (cycloalkyl)alkenyls.

[0116] Alkyl includes straight chain, branched and cyclic alkyl, unless otherwise defined by the compound or compound genus. Alkyl includes alkyl with 1-30 carbon atoms, unless otherwise defined. Therefore, alkyl can include small alkyl with 1-3 carbon atoms, medium length alkyl with 4-10 carbon atoms and long alkyl with more than 10 carbon atoms, especially those with 10-30 carbon atoms. The term cycloalkyl specifically refers to an alkyl with a ring structure (e.g., a ring structure comprising 3-30 carbon atoms, optionally 3-20 carbon atoms and optionally 3-10 carbon atoms), including alkyl with one or more rings. Cycloalkyl includes those with 3-, 4-, 5-, 6-, 7-, 8-, 9- or 10-membered carbocyclic rings, especially those with 3-, 4-, 5-, 6-, 7- or 8-membered rings. The carbocyclic ring in the cycloalkyl can also carry an alkyl. Cycloalkyl can include bicycloalkyl and tricycloalkyl. Alkyl is optionally substituted, as described herein. Substituted alkyl groups may include those substituted by aryl groups, which may be optionally substituted. Specific alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, sec-butyl, tert-butyl, cyclobutyl, n-pentyl, branched pentyl, cyclopentyl, n-hexyl, branched hexyl and cyclohexyl, all of which are optionally substituted. Unless otherwise defined herein, substituted alkyl groups include perhalogenated or semi-halogenated alkyl groups, for example, alkyl groups in which one or more hydrogens are replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and / or iodine atoms. Therefore, substituted alkyl groups may include perfluorinated or semi-fluorinated alkyl groups, for example, alkyl groups in which one or more hydrogens are replaced by one or more fluorine atoms. Alkoxy groups are alkyl groups modified by being connected to oxygen, which may be represented by the formula RO, and may also be referred to as alkyl ether groups. Examples of alkoxy groups include, but are not limited to, methoxy, ethoxy, propoxy, butoxy and heptoxy. Alkoxy groups include substituted alkoxy groups in which the alkyl portion of the group is substituted, as provided herein in conjunction with the description of the alkyl group. As used herein, MeO- refers to CH3O-. Furthermore, as used herein, a thioalkoxy group is an alkyl group modified by being linked to a sulfur atom (instead of oxygen), and may be represented by the formula RS.

[0117] Alkenyl includes straight chain, branched and cyclic alkenyl. Alkenyl includes those with 1, 2 or more double bonds, and those in which two or more double bonds are conjugated double bonds. Unless otherwise defined herein, alkenyl includes those with 2 to 20 carbon atoms. Alkenyl includes small alkenyl with 2 to 3 carbon atoms. Alkenyl includes alkenyl with medium length of 4 to 10 carbon atoms. Alkenyl includes long alkenyl with more than 10 carbon atoms, particularly those with 10-20 carbon atoms. Cycloalkenyl includes those in which double bonds are located in the ring or in the alkenyl connected to the ring. The term cycloalkenyl specifically refers to alkenyl with a ring structure, including alkenyl with 3, 4, 5, 6, 7, 8, 9 or 10-membered carbocyclic rings, particularly those with 3, 4, 5, 6, 7 or 8-membered rings. The carbocyclic ring in the cycloalkenyl group can also carry an alkyl group. Cycloalkenyl can include bicyclic and tricyclic alkenyl groups. Alkenyl can be optionally substituted. Unless otherwise defined herein, the substituted alkenyl includes those substituted by alkyl or aryl, and these groups can be optionally substituted.Specific alkenyl includes vinyl, prop-1-enyl, prop-2-enyl, cycloprop-1-enyl, but-1-enyl, but-2-enyl, cyclobut-1-enyl, cyclobut-2-enyl, penta-1-enyl, penta-2-enyl, branched penta-enyl, cyclopent-1-enyl, hex-1-enyl, branched hexenyl, cyclohexenyl, all of which are optionally substituted.The substituted alkenyl can include perhalogenated or semihalogenated alkenyl, for example, one or more hydrogens are replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and / or iodine atoms.The substituted alkenyl includes perfluoro or semifluoro alkenyl, for example, one or more hydrogen atoms are replaced by one or more fluorine atoms.

[0118] Aryl includes groups with one or more 5, 6, 7 or 8-membered aromatic rings (including heterocyclic aromatic rings). The term "heteroaryl" specifically refers to an aryl with at least one 5, 6, 7 or 8-membered heterocyclic aromatic ring. Aryl can include one or more fused aromatic rings, including one or more fused heteroaromatic rings, and / or a combination of one or more aromatic rings and one or more non-aromatic rings that can be fused or connected by covalent bonds. Heterocyclic aromatic rings can include one or more N, O or S atoms in the ring. Heterocyclic aromatic rings can include those with one, two or three N atoms, those with one or two O atoms, and those with one or two S atoms or those with a combination of one or two or three N, O or S atoms. Aryl is optionally substituted. Substituted aryl includes those substituted by alkyl or alkenyl, and these groups can be optionally substituted. Specific aryl comprises phenyl, biphenyl, pyrrolidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furyl, thienyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl and naphthyl, all of which are optionally substituted. The aryl replaced comprises perhalogenated or semi-halogenated aryl, for example, the aryl that one or more hydrogens are replaced by one or more fluorine atoms, chlorine atoms, bromine atoms and / or iodine atoms. The aryl replaced comprises perfluoro or semi-fluoro aryl, for example, the aryl that one or more hydrogens are replaced by one or more fluorine atoms. Aryl includes, but is not limited to, aromatic or heterocyclic aromatic groups corresponding to any of the following: benzene, naphthalene, naphthoquinone, diphenylmethane, fluorene, anthracene, anthraquinone, phenanthrene, tetracene, tetracene dione, pyridine, quinoline, isoquinoline, indole, isoindole, pyrrole, imidazole, oxazole, thiazole, pyrazole, pyrazine, pyrimidine, purine, benzimidazole, furan, benzofuran, dibenzofuran, carbazole, acridine, acridone, phenanthridine, thiophene, benzothiophene, dibenzothiophene, xanthene, xanthone, flavonoid, coumarin, azulene, or anthracycline. As used herein, groups corresponding to the above-listed groups explicitly include aromatic or heterocyclic aromatic groups in the aromatic and heterocyclic aromatic groups listed herein, including monovalent, divalent, and multivalent groups, which are provided in the compounds of the present disclosure in a covalently bonded configuration at any suitable point of attachment. In some embodiments, the aryl group comprises 5 to 30 carbon atoms. In some embodiments, the aryl group comprises an aromatic or heteroaromatic six-membered ring and one or more additional five-membered or six-membered aromatic or heteroaromatic rings. In a number of embodiments, the aryl group comprises five to eighteen carbon atoms in the ring. The aryl group optionally has one or more aromatic or heterocyclic aromatic rings having one or more electron donating groups, electron withdrawing groups and / or targeting ligands provided as substituents.

[0119] Arylalkyl is an alkyl substituted with one or more aryl groups, wherein the alkyl group optionally carries other substituents, and the aryl group is optionally substituted. Specific alkylaryl is an alkyl substituted with phenyl, for example, phenylmethyl. Alkylaryl can be alternatively described as an aryl substituted with one or more alkyl groups, wherein the alkyl group optionally carries other substituents, and the aryl group is optionally substituted. Specific alkylaryl is an alkyl substituted with phenyl, for example, methylphenyl. The arylalkyl substituted includes perhalogenated or semihalogenated arylalkyl, for example, an arylalkyl with one or more alkyl and / or aryl groups substituted with one or more hydrogens by one or more fluorine atoms, chlorine atoms, bromine atoms and / or iodine atoms.

[0120] As used herein, the terms "alkylene" and "alkylene group" are used synonymously and refer to a divalent group "-CH2-" derived from an alkyl group as defined herein. The present disclosure includes compounds having one or more alkylene groups. The alkylene group in some compounds acts as a linking group and / or a spacer group. The compounds of the present disclosure may have substituted and / or unsubstituted C1-C 20 Alkylene, C1-C 10 Alkylene and C1-C6 alkylene.

[0121] As used herein, the terms "cycloalkylene" and "cycloalkylene group" are used synonymously and refer to a divalent group derived from a cycloalkyl group as defined herein. The present disclosure includes compounds having one or more cycloalkylene groups. The cycloalkyl group in some compounds acts as a linking group and / or a spacer group. The compounds of the present disclosure may have substituted and / or unsubstituted C3-C 20 Cycloalkylene, C3-C 10 Cycloalkylene and C3-C5 cycloalkylene.

[0122] As used herein, the terms "arylene" and "arylene group" are used synonymously and refer to a divalent group derived from an aryl group as defined herein. The present disclosure includes compounds having one or more arylene groups. In some embodiments, the arylene group is a divalent group derived from an aryl group by removing hydrogen atoms from two intracyclic carbon atoms of the aromatic ring of the aryl group. The arylene group in some compounds acts as a linking group and / or a spacer group. The arylene group in some compounds acts as a chromophore, a fluorophore, an aromatic antenna, a dye, and / or an imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C3-C 30 Arylene, C3-C 20 Arylene, C3-C 10 Arylene group and C1-C5 arylene group.

[0123] As used herein, the terms "heteroarylene" and "heteroarylene group" are used synonymously and refer to a divalent group derived from a heteroaryl group as defined herein. The present disclosure includes compounds having one or more heteroarylene groups. In some embodiments, the heteroarylene group is a divalent group derived from a heteroaryl group by removing hydrogen atoms from two intracyclic carbon atoms or intracyclic nitrogen atoms of a heteroaromatic ring or aromatic ring of a heteroaryl group. The heteroarylene group in some compounds acts as a linking group and / or a spacer group. The heteroarylene group in some compounds acts as a chromophore, an aromatic antenna, a fluorophore, a dye and / or an imaging group. The compounds of the present disclosure include substituted and / or unsubstituted C3-C 30 Heteroarylene, C3-C 20 Heteroarylene, C1-C 10 heteroarylene and C3-C5 heteroarylene.

[0124] As used herein, the terms "alkenylene" and "alkenylene group" are used synonymously and refer to a divalent group derived from an alkenyl group as defined herein. The present invention includes compounds having one or more alkenylene groups. The alkenylene group in some compounds acts as a linker and / or spacer group. The compounds of the present disclosure include substituted and / or unsubstituted C2-C 20 Alkenylene, C2-C 10 Alkenylene and C2-C5 alkenylene.

[0125] As used herein, the terms "cycloalkenylene" and "cycloalkenylene group" are used synonymously and refer to a divalent group derived from a cycloalkenyl group as defined herein. The present disclosure includes compounds having one or more cycloalkenylene groups. The cycloalkenylene groups in some compounds act as linking groups and / or spacer groups. The compounds of the present disclosure include substituted and / or unsubstituted C3-C 20 Cycloalkenylene, C3-C 10 Cycloalkenylene and C3-C5 cycloalkenylene.

[0126] As used herein, the terms "alkynylene" and "alkynylene group" are used synonymously and refer to a divalent group derived from an alkynyl group as defined herein. The present disclosure includes compounds having one or more alkynylene groups. The alkynylene group in some compounds acts as a linker and / or spacer group. The compounds of the present disclosure include substituted and / or unsubstituted C2-C 20 Alkynylidene, C2-C 10 Alkyne and C2-C5 alkynyl.

[0127] As used herein, the terms "halo" and "halogen" are used interchangeably and refer to a halogen radical, such as fluorine (-F), chlorine (-Cl), bromine (-Br), or iodine (-I).

[0128] The term "heterocycle" refers to a ring structure containing at least one other type of atom in the ring in addition to carbon. Examples of such heteroatoms include nitrogen, oxygen and sulfur. Heterocyclic rings include heterocyclic alicyclic rings and heterocyclic aromatic rings. Examples of heterocyclic rings include, but are not limited to, pyrrolidinyl, piperidinyl, imidazolidinyl, tetrahydrofuranyl, tetrahydrothienyl, furanyl, thienyl, pyridyl, quinolyl, isoquinolyl, pyridazinyl, pyrazinyl, indolyl, imidazolyl, oxazolyl, thiazolyl, pyrazolyl, pyridyl, benzoxadiazolyl, benzothiadiazolyl, triazolyl and tetrazolyl. The atoms of the heterocyclic ring can be bonded to a variety of other atoms and reactive functional groups, for example, provided as a substituent.

[0129] The term "carbocycle" refers to a ring structure containing only carbon atoms in the ring. The carbon atoms of the carbocyclic ring may be bonded to a variety of other atoms and reactive functional groups, for example, to provide as substituents.

[0130] The term "alicyclic ring" refers to a ring or multiple condensed rings that are not aromatic rings. Alicyclic rings include carbocyclic rings and heterocyclic rings.

[0131] The term "aromatic ring" refers to a ring or multiple condensed rings containing at least one aromatic ring group. The term aromatic ring includes aromatic rings containing carbon, hydrogen and heteroatoms. Aromatic rings include carbocyclic and heterocyclic aromatic rings. Aromatic rings are an integral part of an aryl group.

[0132] The term "fused ring" or "fused ring structure" refers to multiple alicyclic rings and / or aromatic rings provided in a fused ring configuration, eg, fused rings that share at least two intra-ring carbon atoms and / or heteroatoms.

[0133] As used herein, the term "alkoxyalkyl" refers to a substituent of the formula alkyl-O-alkyl.

[0134] As used herein, the term "polyhydroxyalkyl" refers to substituents having 2 to 12 carbon atoms and 2 to 5 hydroxyl groups, for example, 2,3-dihydroxypropyl, 2,3,4-trihydroxybutyl or 2,3,4,5-tetrahydroxypentyl groups.

[0135] As used herein, the term "polyalkoxyalkyl" refers to groups of the formula alkyl-(alkoxy) n -alkoxy substituents, wherein n is an integer from 1 to 10, for example, from 1 to 4, and in some embodiments from 1 to 3.

[0136] As used herein, the term "heteroalkyl" generally refers to alkyl, alkenyl or alkynyl as defined herein, wherein at least one carbon atom of the alkyl is replaced by a heteroatom. In some cases, the heteroalkyl can contain 1 to 18 non-hydrogen atoms (carbon and heteroatoms) in the chain, or 1 to 12 non-hydrogen atoms, or 1 to 6 non-hydrogen atoms, or 1 to 4 non-hydrogen atoms. Heteroalkyl can be straight or branched / saturated or unsaturated. Unsaturated heteroalkyl has one or more double bonds and / or one or more triple bonds. Heteroalkyl can be unsubstituted or substituted. Exemplary heteroalkyl includes but is not limited to alkoxyalkyl (e.g., methoxymethyl) and aminoalkyl (e.g., alkylaminoalkyl and dialkylaminoalkyl). Heteroalkyl can be optionally substituted by one or more substituents.

[0137] As used herein, the term "carbonyl" refers to, for example, 1-6 In the context of a carbonyl substituent, this generally refers to a carbon chain of a given length (e.g., C 1-6 ), where each carbon atom of a given carbon chain can form a carbonyl bond as long as it is chemically feasible with respect to the valence state of that carbon atom. Thus, in some cases, “C 1-6 A "carbonyl" substituent refers to a carbon chain of 1 to 6 carbon atoms with a terminal carbon containing a carbonyl functionality or an internal carbon containing a carbonyl functionality (in which case the substituent may be described as a ketone). As used herein, the term "carboxyl", e.g., in C 1-6 In the context of a carboxyl substituent, this generally refers to a carbon chain of a given length (e.g., C 1-6 ), wherein the terminal carbon contains a carboxyl functionality, unless otherwise defined herein.

[0138] For any group containing one or more substituents described herein, it is understood that such group does not contain any substitution or substitution pattern that is sterically impractical and / or synthetically unfeasible. In addition, the compounds of the present disclosure include all stereochemical isomers resulting from the substitution of these compounds.

[0139] Unless otherwise defined herein, optional substitutions for any alkyl, alkenyl, and aryl groups include substitution with one or more of the following substituents, among others:

[0140] Halogen, including fluorine, chlorine, bromine or iodine;

[0141] Halides, including -CN, -OCN (cyanate), -NCO (isocyanate), -SCN (thiocyanate), and -NCS (isothiocyanate);

[0142] -COOR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

[0143] -COR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

[0144] -CON(R)2, wherein each R independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0145] -OCON(R)2, wherein each R independently of each other R is hydrogen or alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted; and wherein R and R may form a ring, which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0146] -N(R)2, wherein each R independently of each other R is hydrogen or alkyl or acyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl, phenyl or acetyl, all of which are optionally substituted; and wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms;

[0147] -SR, wherein R is hydrogen or alkyl or aryl, more particularly wherein R is hydrogen, methyl, ethyl, propyl, butyl or phenyl, which is optionally substituted;

[0148] -SO2R or -SOR, wherein R is alkyl or aryl, more particularly wherein R is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted;

[0149] –OCOOR, where R is alkyl or aryl;

[0150] -SO2N(R)2, wherein each R independently of each other R is hydrogen or alkyl or aryl, all of which are optionally substituted, and wherein R and R may form a ring which may contain one or more double bonds and may contain one or more additional carbon atoms; and

[0151] -OR, wherein R is H, alkyl, aryl or acyl, all of which are optionally substituted. In a specific example, R can be acyl, yielding -OCOR'', wherein R'' is hydrogen or alkyl or aryl, more specifically wherein R'' is methyl, ethyl, propyl, butyl or phenyl, all of which are optionally substituted.

[0152] Specific substituted alkyl groups include haloalkyl groups, particularly trihalomethyl groups and particularly trifluoromethyl groups. Specific substituted aryl groups include mono-, di-, tri-, tetra- and penta-halo-substituted phenyl groups; mono-, di-, tri-, tetra-, penta-, hexa- and hepta-halo-substituted naphthyl groups; 3- or 4-halo-substituted phenyl groups, 3- or 4-alkyl-substituted phenyl groups, 3- or 4-alkoxy-substituted phenyl groups, 3- or 4-RCO-substituted phenyl groups, 5- or 6-halo-substituted naphthyl groups. More specifically, substituted aryl groups include acetylphenyl groups, particularly 4-acetylphenyl groups; fluorophenyl groups, particularly 3-fluorophenyl groups and 4-fluorophenyl groups; chlorophenyl groups, particularly 3-chlorophenyl groups and 4-chlorophenyl groups; methylphenyl groups, particularly 4-methylphenyl groups; and methoxyphenyl groups, particularly 4-methoxyphenyl groups.

[0153] For any of the above groups containing one or more substituents, it is understood that such groups do not contain any substitutions or substitution patterns that are sterically impractical and / or synthetically infeasible. In addition, as further described herein, the compounds of the present disclosure may include all stereochemical isomers (and racemic mixtures) resulting from the substitution of these compounds.

[0154] II. Curable Compositions

[0155] The present disclosure provides a series of curable compositions, and solid polymer materials printed therefrom. In many cases, the curable compositions of the present disclosure include a variety of cross-linking agents with different molecular weights, sizes and / or non-polymerizable functional groups, so that the polymer generated by the curable composition has a high degree of molecular level heterogeneity, which is very important for toughness and appropriate appearance. In some cases, the curable composition is photocurable, chemically curable, heat curable or any combination thereof. In some cases, the composition is photocurable.

[0156] In some embodiments, the curable composition comprises a resin matrix including a plurality of polymerizable monomers, and the polymerizable monomers comprise at least 80 weight percent (wt%) of a crosslinking agent. In some cases, the curable composition comprises at least 10wt% of a filler material. In some cases, the filler material is an inorganic material. In some cases, the curable composition comprises a wetting agent. In some cases, the curable composition comprises a photoinitiator. In some cases, the curable composition comprises a pigment. In some cases, the curable composition comprises a glass transition temperature modifier. In some cases, the curable composition comprises a reactive diluent. In some cases, the curable composition comprises a UV blocker.

[0157] In some cases, the curable composition is configured to exhibit a specific color when cured (e.g., when the curing is at least 95% complete). The color of the curable or cured composition can generally be described by L*, a*, and b* values, which can represent brightness, red-greenness, and blue-yellowness, respectively, wherein the L* value ranges from 0 to 100, wherein 0 represents no brightness (i.e., black), and 100 represents diffuse white; the a* value can range from -128 to 128, wherein -128 represents green, 128 represents red, and values ​​between -128 and 128 represent a combination of green and red; the b* value can range from -128 to 128, wherein -128 represents blue, 128 represents yellow, and values ​​between -128 and 128 represent a combination of blue and yellow. In some cases, the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured. In some cases, the curable composition is configured to exhibit a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured. In some cases, the curable composition is configured to exhibit a color that matches the shade of a subject's teeth. In some cases, the curable composition is configured to have a transmittance of 40% to 100% for 550nm and 650nm light when cured into an object of 1mm to 12mm thickness. In some cases, the curable composition is configured to have a transmittance of 40% to 75% for 550nm and 650nm light when cured into an object of 1mm to 12mm thickness. In some cases, the curable composition is configured to have a transmittance of 60% to 100% for 550nm and 650nm light when cured into an object of 1mm to 12mm thickness. In some cases, the curable composition is configured to have a light transmittance of 50% to 90% with translucency to 550 nm and 650 nm light when cured into a 1 mm to 12 mm thick object.

[0158] In many cases, most of the polymerizable functional groups of the curable composition include ethylenically unsaturated functional groups. In some cases, about 50 to about 100 mole percent (mol%) of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. In some cases, about 70 to about 100mol% of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. In some cases, about 80 to about 100mol% of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. In some cases, about 90 to about 100mol% of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. In some cases, about 95 to about 100mol% of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. In some cases, about 60 to about 90mol% of the functional groups of a variety of polymerizable monomers are ethylenically unsaturated functional groups. For example, a curable composition consistent with the present disclosure can be completely composed of a crosslinking agent based on acrylate and / or methacrylate.

[0159] In some cases, the curable composition includes about 50 wt % to about 100 wt %, about 70 to about 100 wt %, about 80 to about 100 wt %, about 90 to about 100 wt %, about 95 to 100 wt %, or about 60 to about 90 wt % of the polymerizable monomer.

[0160] In some cases, about 50 to about 100 mol%, about 70 to about 100 mol%, about 80 to about 100 mol%, about 90 to about 100 mol%, about 95 to 100 mol%, or about 60 to about 90 mol% of the plurality of polymerizable functional groups of the curable composition are acrylates, methacrylates, acrylamides, methacrylamides, vinyl ethers, styryls, or combinations thereof. In some cases, about 50 to about 100 mol%, about 70 to about 100 mol%, about 80 to about 100 mol%, about 90 to about 100 mol%, about 95 to 100 mol%, or about 60 to about 90 mol% of the polymerizable functional groups of the curable composition are acrylates, methacrylates, or combinations thereof.

[0161] In some cases, the polymerizable monomers of about 50 to about 100 mole percent of the curable composition include a molecular weight of at least 250Da. In some cases, the polymerizable monomers of about 70 to about 100 mole percent of the curable composition include a molecular weight of at least 250Da. In some cases, the polymerizable monomers of about 90 to about 100 mole percent of the curable composition include a molecular weight of at least 250Da. In some cases, the polymerizable monomers of about 50 to about 100 mole percent of the curable composition include a molecular weight of at least 500Da. In some cases, the polymerizable monomers of about 70 to about 100 mole percent of the curable composition include a molecular weight of at least 500Da. In some cases, the polymerizable monomers of about 80 to about 100 mole percent of the curable composition include a molecular weight of at least 500Da.

[0162] 1) Cross-linking agent

[0163] Many cases of curable compositions disclosed herein include high crosslinker loadings. In some cases, the crosslinker is at least 85wt% of polymerizable monomers. In some cases, the crosslinker is at least 90wt% of polymerizable monomers. In some cases, the crosslinker is at least 95wt% of polymerizable monomers. In some cases, the crosslinker accounts for at least 97.5wt% of polymerizable monomers. In some cases, the crosslinker accounts for at least 99wt% of polymerizable monomers. This high crosslinker loading can lead to high viscosity and low vapor pressure in the curable composition, as well as high toughness, elastic modulus and swelling resistance in the material printed therefrom.

[0164] In many cases, the crosslinking agent comprises a plurality of crosslinking agents. Since the combination of crosslinking agents can impart performance that a single crosslinking agent composition cannot achieve, the curable composition can comprise two or more crosslinking agents with different structures and characteristics. In some cases, the use of a plurality of structurally different crosslinking agents can lead to heterogeneity at the molecular level, which is very important for optical transparency, low scattering, low refraction and toughness. It is important to use a plurality of structurally different crosslinking agents because the heterogeneity caused by the use of a plurality of types allows multiple phases within the material. Different components can provide a hard phase or a soft phase, as well as a range of distances between crosslinks. This allows for a material that is both rigid and tough. In addition, in some cases, the use of a plurality of structurally different crosslinking agents can reduce crystallization. For example, although a high concentration of urethane acrylate can promote the formation of lamellae and crystalline domains, the addition of an aromatic crosslinking agent (e.g., bisphenol α-glycidyl methacrylate) can promote heterogeneity at the molecular level, thereby destroying ordered stacking.

[0165] Therefore, in some cases, the curable composition comprises at least two, at least three, at least four, at least five or at least six cross-linking agents. In some cases, the curable composition comprises two to five cross-linking agents. In some cases, the curable composition comprises three to four cross-linking agents. In some cases, the weight percentage of the cross-linking agents of at least one subset in the curable composition does not differ by more than ten times. In some cases, the weight percentage of the cross-linking agents of at least one subset in the curable composition does not differ by more than 5 times. In some cases, the weight percentage of the cross-linking agents of at least one subset in the curable composition does not differ by more than 3 times. In some cases, the weight percentage of the cross-linking agents in the curable composition does not differ by more than 10 times. In some cases, the weight percentage of the cross-linking agents in the curable composition does not differ by more than 5 times. In some cases, the weight percentage of the cross-linking agents in the curable composition does not differ by more than 3 times. For example, the curable composition may comprise 15.8wt% to 36.8wt% of two, three, four, five, six cross-linking agents.

[0166] In some cases, curable composition comprises a variety of cross-linking agents with different molecular weights. In some cases, the cross-linking agent in a variety of cross-linking agents comprises a molecular weight that differs by at least 100Da, at least 150Da, at least 200Da, at least 250Da, at least 350Da, at least 500Da, at least 750Da or at least 1000Da. In some cases, about 50 to about 100mol%, about 70 to 100mol%, about 80 to 100mol%, about 90 to 100mol%, about 95 to 100mol% or about 60 to 90mol% of the cross-linking agent comprises at least 200Da, at least 250Da, at least 350Da, at least 500Da, at least 750Da or at least 1000Da of molecular weight in curable composition. In some cases, about 50 and about 100 mole percent of the cross-linking agent comprises a molecular weight of at least 250Da in curable composition. In some cases, about 90 and about 100 mole percent of the cross-linking agent in the curable composition comprises a molecular weight of at least 250Da. In some cases, the curable composition comprises at least one cross-linking agent having a molecular weight less than 1000Da. In some cases, the curable composition comprises at least one cross-linking agent having a molecular weight less than 750Da. In some cases, the curable composition comprises at least one cross-linking agent having a molecular weight less than 500Da. In some cases, the curable composition comprises at least one cross-linking agent having a molecular weight less than 300Da. In some cases, the cross-linking agent having a molecular weight less than 1000Da, less than 750Da, less than 500Da or less than 300Da accounts for at least 10wt% of the curable composition.

[0167] In some cases, the crosslinking agent comprises two polymerizable functional groups. In some cases, the crosslinking agent comprises three polymerizable functional groups. In some cases, the crosslinking agent comprises four or more polymerizable functional groups. In some cases, the crosslinking agent comprises two to four polymerizable functional groups. In some cases, the various crosslinking agents of the curable composition each comprise two polymerizable functional groups. In some cases, about 50 to about 100wt% of the crosslinking agent in the various crosslinking agents comprises two polymerizable functional groups. In some cases, about 70 to about 100wt% of the crosslinking agent in the various crosslinking agents comprises two polymerizable functional groups. In some cases, about 90 to about 100wt% of the crosslinking agent in the various crosslinking agents comprises two polymerizable functional groups. In some cases, about 95 to about 100wt% of the crosslinking agent in the various crosslinking agents comprises two polymerizable functional groups. In some cases, about 50 to about 100 mole percent (mol%) of the crosslinking agent in the various crosslinking agents comprises two polymerizable functional groups. In some cases, about 70 and about 100 mol% of the crosslinking agents in the plurality of crosslinking agents contain two polymerizable functional groups. In some cases, about 90 and about 100 mol% of the crosslinking agents in the plurality of crosslinking agents contain two polymerizable functional groups. In some cases, about 95 and about 100 mol% of the crosslinking agents in the plurality of crosslinking agents contain two polymerizable functional groups.

[0168] Because the cross-linking agent length can affect the accumulation of molecular level, for example, hydrogen bond, van der Waals interaction and polymer entanglement, the cross-linking agent of the present disclosure can include a certain range of length. In some cases, the cross-linking agent includes at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, at least 22 or at least 30 atoms between polymerizable functional groups (for example, decanediol dimethacrylate (DDDMA) can be considered to contain 10 atoms between its methacrylate groups). In some cases, the cross-linking agent includes at least 8 atoms between polymerizable functional groups. In some cases, the multiple cross-linking agents of curable composition each include at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, at least 22 or at least 30 atoms. In some cases, the multiple cross-linking agents each include at least 8 atoms between polymerizable functional groups.

[0169] In some cases, the cross-linking agent comprises an aryl, heteroaryl, carbamate, diol, carbonate, urea, ester, amide, thioether, thioester, guanidine or a combination thereof within the backbone (e.g., disposed between at least two polymerizable functional groups). In some cases, the cross-linking agent comprises an alkane backbone, an alkane diol backbone, an oligoethylene glycol backbone, a biphenyl backbone, a glycidyl backbone, a carbamate backbone or a combination thereof.

[0170] In some cases, the crosslinking agent comprises epoxy acrylate (e.g., bisphenol A epoxy acrylate), epoxy methacrylate (e.g., bisphenol A epoxy methacrylate), novolac epoxy acrylate (e.g., cresol novolac epoxy acrylate or phenol novolac epoxy acrylate), modified epoxy acrylate (e.g., phenyl epoxy acrylate, aliphatic alkyl epoxy acrylate, soybean oil epoxy acrylate, DP296, E207 / 25TP, E207 / 25HD or E207 / 30PE), urethane acrylates, aliphatic urethane acrylates (e.g., aliphatic difunctional acrylates, aliphatic trifunctional acrylates, aliphatic multifunctional acrylates), aromatic urethane acrylates (e.g., aromatic difunctional acrylates, aromatic trifunctional acrylates, aromatic multifunctional acrylates), urethane methacrylates, aliphatic urethane methacrylates, aromatic urethane methacrylates, polyester acrylates (e.g., trifunctional polyester acrylates, tetrafunctional polyester acrylates, difunctional polyester acrylates), ester acrylates, hexafunctional polyester acrylates), silicone acrylates (e.g., silicone urethane acrylates, silicone polyester acrylates), melamine acrylates, dendritic acrylates, acrylic acrylates, caprolactone monomer acrylates (e.g., caprolactone methacrylates, caprolactone acrylates), oligomeric amine acrylates (e.g., amino acrylates, aminated polyester acrylates), diphenol acrylates, diphenol methacrylates, alkyl acrylates, alkyl methacrylates, alkanediol acrylates, alkanediol methacrylates, derivatives thereof, or combinations thereof. Non-limiting examples of aliphatic urethane acrylates include difunctional aliphatic acrylates (e.g., Miramer PU210, Miramer PU2100, Miramer PU2560, Miramer SC2404, Miramer SC2565, Miramer UA5216, Miramer U307, Miramer U3195, or Photocryl DP102), trifunctional aliphatic acrylates (e.g., Miramer PU320, Miramer PU340, Miramer PU3450, Miramer U375, or Photocryl DP225), tetrafunctional aliphatic acrylates (e.g., Miramer U3304), hexafunctional aliphatic acrylates (e.g., Miramer MU9800), multifunctional aliphatic acrylates (e.g., Miramer MU9800, or Miramer SC2152), or combinations thereof.

[0171] 2) Filling material

[0172] The curable composition may include a filling material that does not participate in polymerization, but is fixed in the curing resin after curing, thereby affecting its material properties. For example, adding a filling material to a curable composition can reduce vapor pressure and increase viscosity before curing, and improve the strength, storage modulus and stiffness of the polymer material printed therefrom. In addition, in some cases, the filling material can inhibit the propagation of cracks or deformations, preventing small fractures from spreading throughout the printed material. For practical applications such as dental appliances, filling materials can reduce overall quality and thickness requirements and extend service life. This enhancement is particularly important for orthodontic appliances (e.g., dental attachments), which may need to be used continuously or repeatedly for a long time. For example, a tooth alignment plan may rely on a single set of dental attachments to maintain shape, strength and integrity over many years of treatment. In many cases, the filling material is an inorganic material. In certain cases, the filling material is a radiopaque material that can increase the detectability of the curable composition by an imaging system while minimizing the appearance and color.

[0173] Filling material can be unevenly distributed in the whole curable composition or the material printed by it. In some cases, filling material is evenly dispersed in the whole curable composition. This uniform dispersion can be realized, for example, by stirring or mixing the curable composition before or during solidification. In some cases, filling material is evenly distributed along the first size or the first group of sizes, and unevenly distributed along the second size or the second group of sizes. For example, filling material can be randomly dispersed in the whole length and width of the curable composition, and unevenly distributed along the height of the curable composition. Filling material can be, for example, patterned along transverse or longitudinal waves or along concentration gradients. Filling material can also be concentrated in the inner space of the curable composition or the material printed by it or along its surface. In some cases, filling material is patterned in the curable composition. In this case, filling material can be concentrated along longitudinal or transverse waves, complex patterns, gradients or their combinations. In some cases, filling material can be provided as braid (for example, overlapping, non-parallel fibers), clusters, sheets or their combinations.

[0174] Curable composition can include filler material in certain weight percentage range.Filler material can be the minor component of curable composition, for example, accounting for less than 5 weight percentage (wt%), or can account for most of weight of curable composition.In some cases, filler material is present in the curable composition with at least 0.05wt%, at least 0.5wt%, at least 1wt%, at least 2wt%, at least 3wt%, at least 5wt%, at least 8wt%, at least 10wt%, at least 12wt%, at least 15wt%, at least 20wt%, at least 25wt%, at least 30wt%, at least 40wt%, at least 50wt%, at least 60wt%, at least 70wt%, at least 75wt% or at least 80wt% amount. In some cases, the filler material is present in the curable resin in an amount of up to 80 wt%, up to 75 wt%, up to 70 wt%, up to 60 wt%, up to 50 wt%, up to 40 wt%, up to 30 wt%, up to 25 wt%, up to 20 wt%, up to 15 wt%, up to 10 wt%, up to 8 wt%, up to 5 wt%, up to 3 wt%, up to 2 wt%, up to 1 wt% or up to 0.5 wt%. In some cases, the filler material is present in the curable composition in an amount of 0.05 to 60wt%, 1 to 5wt%, 1 to 10wt%, 1 to 20wt%, 2 to 5wt%, 2 to 10wt%, 2 to 20wt%, 3 to 6wt%, 3 to 10wt%, 3 to 20wt%, 5 to 10wt%, 5 to 25wt%, 8 to 20wt%, 10 to 60wt%, 12 to 25wt%, 15 to 30wt%, 15 to 40wt%, 20 to 35wt%, 25 to 50wt%, 30 to 50wt%, 35 to 65wt%, 40 to 65wt%, 40 to 80wt%, 50 to 75wt% or 60 to 80wt%. In some cases, the filler material is present in the curable composition in an amount of 10 to 60wt%. In some cases, the filler material is present in the curable composition in an amount of 20 to 60wt%. In some cases, the filler material is present in the curable composition in an amount of 20 to 40 wt %. In some cases, the filler material is present in the curable composition in an amount of 30 to 50 wt %.

[0175] The filler material may include a mass of about 0.05 to about 500 μg per discrete unit (e.g., at least 80%, 95%, or 99% of the constituent particles, fibers, glass fragments, etc.). The filler material may include a mass of about 0.05 μg to about 5 μg, about 0.1 μg to about 10 μg, about 0.25 μg to about 15 μg, about 0.5 μg to about 30 μg, about 1 μg to about 50 μg, about 10 μg to about 100 μg, or about 50 μg to about 500 μg per discrete unit. The average width or diameter of the filler material may be from about 2 to about 500 microns, from about 2 to about 200 microns, from about 2 to about 100 microns, from about 2 to about 50 microns, from about 2 to about 25 microns, from about 5 to about 500 microns, from about 5 to about 200 microns, from about 5 to about 100 microns, from about 5 to about 50 microns, from about 5 to about 50 microns, from about 5 to about 25 microns, from about 10 to about 500 microns, from about 10 to about 200 microns, from about 10 to about 100 microns, from about 10 to about 50 microns, from about 10 to about 50 microns, from about 10 to about 25 microns, from about 25 to about 500 microns, from about 25 to about 200 microns, from about 25 to about 100 microns, from about 25 to about 50 microns, from about 50 to about 500 microns, from about 50 to about 200 microns, from about 50 to 100 microns, or from about 100 microns to about 500 microns.

[0176] In some cases, the filler material includes a prepolymerized material. As non-limiting examples, the prepolymerized material may include a carbohydrate, such as hyaluronic acid, chitosan, or cellulose acetate butyrate (CAB); a synthetic polymer, such as polyurethane, polyacrylate, polymethacrylate, polyethylene, polystyrene, polyvinyl, polyester, or polyether; or a combination thereof. The prepolymerized material may be linear or branched, and may include a defined three-dimensional structure, such as a star, dendritic, sheet, granular structure, brush-like structure, or a combination thereof.

[0177] In some cases, the filling material is an inorganic filling material. As a non-limiting example, the inorganic filling material may include silicon dioxide, glass, ceramic, metal oxide, crystal, carbon nanomaterial (e.g., carbon nanotube, fullerene, graphene, graphite, diamond), inorganic semiconductor (e.g., gallium arsenide, silicon, boron phosphide or arsenide) or a combination thereof. In some cases, the filling material includes nanoparticles or micron particles. In some cases, the filling material is provided as nanoparticles or micron particles. In some cases, the filling material is provided as a powder.

[0178] The filler material may include a mass of about 0.05 to about 500 μg per discrete unit (e.g., per particle, fiber, glass fragment, etc.). The filler material may include a mass of about 0.05 μg to about 5 μg, about 0.1 μg to about 10 μg, about 0.25 μg to about 15 μg, about 0.5 μg to about 30 μg, about 1 μg to about 50 μg, about 10 μg to about 100 μg, or about 50 μg to about 500 μg per discrete unit. The average width or diameter of the filler material is about 2 to about 500 microns, about 2 to about 200 microns, about 2 to about 100 microns, about 2 to about 50 microns, about 2 to about 25 microns, about 5 to about 500 microns, about 5 to about 200 microns, about 5 to about 100 microns, about 5 to about 50 microns, about 5 to about 50 microns, about 5 to about 25 microns, about 10 to about 500 microns, about 10 to about 200 microns, about 10 to about 100 microns, about 10 to about 50 microns, about 10 to about 50 microns, about 10 to about 25 microns, about 25 to about 500 microns, about 25 to about 200 microns, about 25 to about 100 microns, about 25 to about 50 microns, about 50 to about 500 microns, about 50 to about 200 microns, about 50 to about 100 microns, or about 100 to about 500 microns.

[0179] 3) Wetting agent

[0180] In some cases, the curable composition includes a wetting agent. Since the wetting agent can change the surface properties of the printed material, the inclusion of the wetting agent can enhance the applicability of 3D printing. In some cases, the wetting agent can increase hydrophilicity and wettability, and therefore may be important for medical devices configured for use in humid environments (such as those experienced by orthodontic appliances). In many cases, the wetting agent reduces the surface tension of water along the surface of the printed material, promotes the formation of a water coating, and thereby reduces the contact between the printed material and the surrounding tissue (e.g., between a dental attachment and the buccal mucosa).

[0181] The wetting agent may include a hydrophilic material, such as a siloxane, a polyamide, a polylactone, a phosphate ester, a polylactam, or a combination thereof. In certain cases, the wetting agent comprises a siloxane. In some cases, the siloxane is a polyether-modified polydimethylsiloxane.

[0182] In some cases, the curable composition comprises from about 0.01 to about 3 wt % of a wetting agent. In some cases, the curable composition comprises from about 0.05 to about 1.5 wt %, from about 0.1 to about 1.5 wt %, from about 0.3 to about 1.5 wt %, from about 0.1 to about 1 wt %, from about 0.1 to about 0.5 wt %, from about 0.2 to about 1 wt %, from about 0.3 to about 0.7 wt %, or from about 0.4 to about 1 wt % of a wetting agent.

[0183] 4) Pigments

[0184] The curable composition may further comprise a pigment. Since appearance may be important for medical devices that are visible during use (such as many orthodontic appliances disclosed herein), careful selection of base matrix materials (e.g., polymerizable substances) and additives is generally required for patient satisfaction and compliance. However, optimizing appearance and mechanical properties simultaneously may be challenging. For example, although some polyurethanes provide mechanical properties (e.g., hardness) suitable for dental attachments, many of them also contribute to forming a strong opaque amber or green visual profile, which is generally considered to be undesirable for orthodontic appliances (on the contrary, orthodontic appliances are generally preferably transparent or neutral colors). The surprising results disclosed herein include a combination of polymerizable substances, physical property modifying materials (e.g., fillers and wetting agents) and pigments that provide the desired physical and visual properties for medical applications.

[0185] In some embodiments, the curable composition comprises a pigment. In some cases, the pigment comprises an inorganic or organic metal substance. In some cases, the pigment comprises an organic substance, for example, anthraquinone, diazo, isoindolinone, benzimidazolone, diketopyrrolopyrrole, isoindolinone, naphthol, phthalocyanine or dioxazine. In some cases, the pigment is a metal oxide, for example, titanium dioxide, zinc oxide, iron oxide (for example, wüstite (FeO), magnetite (Fe3O4), α-phase hematite (α-Fe2O3), β-phase hematite (β-Fe2O3), magnetic hematite (γ-Fe2O3) or ε-phase iron oxide (ε-Fe2O3)), cobalt oxide, yttrium oxide, aluminum oxide or or a combination thereof. In some cases, the pigment is a metal salt, for example, a yttrium salt (e.g., yttrium acetate, yttrium chloride, yttrium formate, yttrium carbonate, yttrium sulfamate, yttrium silicate, yttrium lactate, yttrium nitrate, yttrium bromide, yttrium hydroxide, yttrium molybdate, yttrium sulfate, yttrium silicate, yttrium fluoride or yttrium oxalate), barium sulfate (BaSO4), bismuth vanadate, nickel antimony, ammonium manganese pyrophosphate (NH4MnP2O7), zinc sulfide (ZnS), lithopone, beige titanium dioxide (TiO2 and iron oxide), or a combination thereof. These pigment materials can be crystalline or amorphous. In some cases, the pigment is an opaque crystalline material with a high crystallinity of more than 50% by volume.

[0186] In some cases, the curable composition comprises from about 0.001 to about 3 wt% of a pigment. In some cases, the curable composition comprises from about 0.005 to about 2 wt% of a pigment. In some cases, the curable composition comprises from about 0.005 to about 0.5 wt% of a pigment. In some cases, the curable composition comprises from about 0.01 to about 0.3 wt% of a pigment. In some cases, the curable composition comprises from about 0.005 to about 0.1 wt% of a pigment.

[0187] In some cases, the curable composition is configured to present a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured. In some cases, the curable composition is configured to present a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured. In some cases, the curable composition is configured to present high transparency when cured. In some cases, the curable composition is configured to present opacity when cured. In some cases, the curable composition has at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% average transmittance in the visible spectrum (about 380 to about 700 nanometers) after curing. In some cases, when cured into an object 1 to 12 mm thick, the curable composition has a total light transmittance of at most about 60%, at most about 50%, at most about 40%, at most about 30%, at most about 20%, at most about 10%, or at most about 5% in the visible spectrum (about 380 to about 700 nanometers). In some cases, when cured into an object 1 to 12 mm thick, the curable composition has a total light transmittance of 40% to 100%, 40% to 75%, 60% to 100%, or 50% to 90% for 550nm light. In some cases, when cured into an object 1 to 12 mm thick, the curable composition has a total light transmittance of 40% to 100%, 40% to 75%, 60% to 100%, or 50% to 90% for 650nm light.

[0188] 5) Reactive diluent

[0189] The curable composition may include a uniform or non-uniformly dispersed or patterned reactive diluent. The degree of non-uniform distribution (e.g., emulsification) or uniformity can be controlled by methods or devices disclosed herein, for example, by stirring before printing. In some cases, the degree of heterogeneity in the curable composition can be controlled by adding a solvent or a reactive diluent. In various cases, the reactive diluent may include an acrylate or methacrylate moiety for incorporation into an oligomer or polymer backbone, which is connected to a straight or cyclic (e.g., monocyclic, dicyclic or tricyclic) side chain moiety. Typically, any aliphatic, alicyclic or aromatic molecule (also including liquid crystal monomers) with a monofunctional polymerizable reactive functional group can be used. In some cases, the polymerizable reactive functional group is an acrylate or methacrylate group. In some cases, the reactive diluent is a eugenol, guaiacol or vanillin derivative, for example, high salicylic acid methacrylate (HSMA), syringyl methacrylate (SMA), isobornyl methacrylate (IBOMA) or isobornyl acrylate (IBOA). In some cases, the reactive diluents used herein may have low vapor pressure, low viscosity, or a combination thereof. However, in some embodiments, low amounts (e.g., 5% w / w or less) of reactive diluents may be used. In some embodiments, no reactive diluent is used.

[0190] In some embodiments, the reactive diluent includes acrylate, methacrylate, acrylamide or methacrylamide monomers. In some cases, the reactive diluent includes acrylate or methacrylate monomers. In some cases, the acrylate or methacrylate monomers are selected from n-butyl acrylate, isodecyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, 2-ethylhexyl acrylate, 2-(2-ethoxyethoxy) ethyl acrylate, n-hexyl acrylate, 2-methoxyethyl acrylate, n-octyl methacrylate, 2-phenylethyl acrylate, n-propyl acrylate and tetrahydrofurfuryl acrylate.

[0191] 6) Photoinitiator

[0192] In various embodiments, the curable composition herein is a photocurable composition. Such photocurable compositions described herein may include one or more photoinitiators. When activated with light of an appropriate wavelength (e.g., UV / VIS), such photoinitiators can initiate polymerization reactions between telechelic polymers, monomers, and other potential polymerizable components that may be present in the photocurable resin (e.g., during photocuring) to form a polymeric material as further described herein. Typically, the photoinitiators described in the present disclosure may include those that can be photoactivated and initiate polymerization of the polymerizable components of the formulation. As used herein, "photoinitiator" may generally refer to compounds that can generate free radical species and / or promote free radical reactions when exposed to radiation (e.g., UV or visible light).

[0193] In some embodiments, the photocurable composition herein comprises 0.05 to 1 wt%, 0.05 to 2 wt%, 0.05 to 3 wt%, 0.05 to 4 wt%, 0.05 to 5 wt%, 0.1 to 1 wt%, 0.1 to 2 wt%, 0.1 to 3 wt%, 0.1 to 4 wt%, 0.1 to 5 wt%, 0.1 to 6 wt%, 0.1 to 7 wt%, 0.1 to 8 wt%, 0.1 to 9 wt%, or 0.1 to 10 wt% of a photoinitiator based on the total weight of the composition. In some embodiments, the photoinitiator is a free radical photoinitiator. In certain embodiments, the free radical photoinitiator comprises an α-hydroxy ketone moiety (e.g., 2-hydroxy-2-methylpropiophenone or 1-hydroxycyclohexyl phenyl ketone), an α-amino ketone (e.g., 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), 4-methylbenzophenone, an azo compound (e.g., 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile, azobisisobutyronitrile, 2,2'- azobis(2-methylpropionitrile) or 2,2'-azobis(2-methylpropionitrile)), inorganic peroxides, organic peroxides, or any combination thereof. In some embodiments, the composition comprises a photoinitiator comprising TPO-L (ethyl(2,4,6-trimethylbenzoyl)phenylphosphinate). In some embodiments, the photocurable resin comprises a mixture selected from benzophenone, benzophenone and a tertiary amine (containing a carbonyl group directly bonded to at least one aromatic ring), 2-methyl-1-[4-(methylthio)-phenyl]- In some embodiments, the photoinitiator includes an acetophenone photoinitiator (e.g., 4'-hydroxyacetophenone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone), benzoin, benzoin derivatives, benzil, benzil derivatives, benzophenone (e.g., 4-benzoylbiphenyl, 3,4-(dimethylamino)benzophenone, 2-methylbenzophenone), a cationic photoinitiator (e.g., diphenyliodonium nitrate, (4 -iodophenyl) diphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoromethanesulfonate), anthraquinone, quinone (e.g., camphorquinone), phosphine oxide, phosphinate, 9,10-phenanthrenequinone, thioxanthone, coumarin (e.g., 3-benzoyl-7-methoxycoumarin, 3-benzoyl-6,8-dichlorocoumarin, 7-diethylamino-3-thenoylcoumarin), benzoylformate (e.g., methyl benzoylformate), any combination thereof, or any derivative thereof.

[0194] In some embodiments, the maximum wavelength absorbance of the photoinitiator can be 200 to 300nm, 300 to 400nm, 400 to 500nm, 500 to 600nm, 600 to 700nm, 700 to 800nm, 800 to 900nm, 150 to 200nm, 200 to 250nm, 250 to 300nm, between 300 to 350nm, 350 to 400nm, 400 to 450nm, 450 to 500nm, 500 to 550nm, 550 to 600nm, 600 to 650nm, 650 to 700nm or 700 to 750nm. In some embodiments, the maximum wavelength absorbance of the photoinitiator is 300 to 500nm.

[0195] In some embodiments, the curable composition may include a phosphine oxide photoinitiator that can absorb light in the range of about 300 to about 600 nm. Examples of phosphine oxide photoinitiators include ethyl 2,4,6-trimethylbenzylphenylphosphinate (TPO), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO819), and bis(2,6-dimethoxybenzoyl)-(2,4,4-trimethylpentyl)phosphine oxide. In some embodiments, the curable composition includes a photoinitiator system that includes two or more phosphine oxide photoinitiators. In some embodiments, the photoinitiator system includes a mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1-one in a weight ratio of 25:75, a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropane-1-one in a weight ratio of 1:1, and a mixture of BAPO and oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone in a weight ratio of 25:75. In a specific embodiment, the photoinitiator system includes 1 wt% BAPO and 3 wt% oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone based on the total weight of the curable composition.

[0196] 7) Glass transition temperature modifier

[0197] In some embodiments, the curable composition herein comprises, in addition to the polymerizable compound described herein, a component that can change the glass transition temperature of the cured polymer material. In this case, based on the total weight of the composition, the glass transition temperature modifier (also referred to herein as T g The photocurable resin may contain a modifier or a glass transition modifier in an amount of about 0 to 50 wt %. gThe modifier may have a high glass transition temperature, which results in a high heat distortion temperature, which may be necessary for using the material at elevated temperatures. In some embodiments, the curable resin comprises 0 to 80 wt%, 0 to 75 wt%, 0 to 70 wt%, 0 to 65 wt%, 0 to 60 wt%, 0 to 55 wt%, 0 to 50 wt%, 1 to 50 wt%, 2 to 50 wt%, 3 to 50 wt%, 4 to 50 wt%, 5 to 50 wt%, 10 to 50 wt%, 15 to 50 wt%, 20 to 50 wt%, 25 to 50 wt%, 30 to 50 wt%, 35 to 50 wt%, 0 to 40 wt%, 1 to 40 wt%, 2 to 40 wt%, 3 to 40 wt%, 4 to 40 wt%, 5 to 40 wt%, 10 to 40 wt%, 15 to 40 wt% or 20 to 40 wt% of T g In certain embodiments, the curable resin comprises 0 to 50 wt % of a glass transition modifier. In some cases, T g The number average molecular weight of the modifier is 0.4 to 5 kDa. g The number average molecular weight of the modifier is 0.1 to 5 kDa, 0.2 to 5 kDa, 0.3 to 5 kDa, 0.4 to 5 kDa, 0.5 to 5 kDa, 0.6 to 5 kDa, 0.7 to 5 kDa, 0.8 to 5 kDa, 0.9 to 5 kDa, 1.0 to 5 kDa, 0.1 to 4 kDa, 0.2 to 4 kDa, 0.3 to 4 kDa, 0.4 to 4 kDa, 0.5 to 4 kDa, 0.6 to 4 kDa, 0.7 to 4 kDa, 0.8 to 4 kDa, 0.9 to 4 kDa, 1 to 4 kDa, 0.1 to 3 kDa, 0.2 to 3 kDa, 0.3 to 3 kDa, 0.4 to 3 kDa, 0.5 to 3 kDa, 0.6 to 3 kDa, 0.7 to 3 kDa, 0.8 to 3 kDa, 0.9 to 3 kDa or 1 to 3 kDa. The polymerizable compounds of the present disclosure (which, in some cases, can themselves serve as g modifier) ​​and T alone g The modifier compounds may be miscible and compatible in the methods described herein. When used in the subject compositions, T g Modifiers can provide high T g and strength values, sometimes at the expense of elongation at break. In some cases, toughness modifiers can provide high elongation at break and toughness through a reinforcing effect, and the polymerizable monomers described herein can improve the processability of formulations (particularly those containing large amounts of toughness modifiers), for example, by acting as a reactive diluent while maintaining high strength and T g value.

[0198] In some embodiments, T gThe modifier comprises multiple aliphatic rings. g The modifier comprises a plurality of aliphatic rings. In some embodiments, the aliphatic ring is a hydrocarbon ring. In some embodiments, the aliphatic ring is saturated. In some embodiments, the plurality of aliphatic rings comprises cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane or any combination thereof. In some embodiments, the plurality of aliphatic rings comprises a bridged ring structure. In some embodiments, the plurality of aliphatic rings comprises a fused ring structure. In certain embodiments, T g The middle portion of the modifier comprises cyclohexane-1,4-dicarboxylic acid, cyclohexanedimethanol, cyclohexane-1,4-diylbis(methylene)dicarbamate, or a combination thereof. g The center of the modifier structure contains cyclohexane-1,4-diylbis(methylene)dicarbamate (eg, TGM1, TGM2, and TGM3).

[0199] In some embodiments, T g The modifier comprises methacrylate. In some embodiments, T g The modifier comprises at least two methacrylates. g The modifier has a terminal portion comprising methacrylate. g The modifier has a structure capped with methacrylate at each end. g The modifier was bis(2-methacrylate).

[0200] In some embodiments, T g The modifier is selected from H1188 (bis((2-((methacryloyloxy)methyl)octahydro-1H-4,7-methaninden-5-yl)methyl)cyclohexane-1,4-dicarboxylate), TGM 1, TGM 2, TGM 3, TGM 4 or a combination thereof.

[0201] In some embodiments, T g The modifier is H1188:

[0202]

[0203] In some embodiments, T g The modifier is TGM1:

[0204]

[0205] In some embodiments, T g The modifier is TGM2:

[0206]

[0207] In some embodiments, T g The modifier is TGM3:

[0208]

[0209] In some embodiments, T g The modifier is TGM4:

[0210]

[0211] 8) UV blocker

[0212] In some embodiments, the curable composition includes a UV blocker. The UV blocker can absorb UV light to reduce or present the rapid degradation of the color of the orthodontic appliance when it is in use. As a result, the color stability of the orthodontic appliance is improved. In some embodiments, based on the gross weight of the composition, the curable composition herein includes 0.05 to 1wt%, 0.05 to 2wt%, 0.05 to 3wt%, 0.05 to 4wt%, 0.05 to 5wt%, 0.1 to 1wt%, 0.1 to 2wt%, 0.1 to 3wt%, 0.1 to 4wt%, 0.1 to 5wt%, or 0.1 to 6wt% of UV blocker. Examples of UV blockers include, but are not limited to, triazines, benzoxazinones, benzotriazoles, benzophenones, benzoates, formamidines, cinnamates / acrylates, aromatic acetones, benzimidazoles, alicyclic ketones, formanilides (including oxoamides), cyanoacrylates, benzopyrones, salicylates, vinillins, and mixtures thereof. In some more specific embodiments, the UV blocking agent includes 2-hydroxy-4-n-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenone, 2-(4-benzoyl-3-hydroxyphenoxy)-2-ethyl acrylate, 2,2'-dihydroxy-4-methoxybenzophenone, dioxybenzophenone, 2-hydroxy-4-(2-hydroxy-3-decyloxypropoxy)benzophenone, 2-hydroxy-4-(2-hydroxy-3-octyloxypropoxy)benzophenone; 2,4,4'-trihydroxybenzoyl-3-hydroxyphenoxy-2-ethyl acrylate. Benzophenone, 2-hydroxy-4-(isooctyloxy)benzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone, disodium salt; 2,4-dihydroxybenzophenone, 4-benzoylresorcinol, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4-(2-hydroxyethoxy)benzophenone, 2-hydroxy-4-benzyloxybenzophenone or mixtures thereof.

[0213] In some embodiments, the curable composition further comprises an optical brightener, which is used in combination with a UV absorber to absorb UV radiation and re-emit it in the form of fluorescence in the blue light region, thereby increasing the cut-off wavelength and increasing the blueness of the material. Examples of optical brighteners include, but are not limited to, stilbene, disulfonates, tetrasulfonates, and hexasulfonates. In some embodiments, the curable composition herein comprises 0.005 to 0.6 wt%, 0.001 to 0.8 wt%, 0.05 to 0.2 wt%, or 0.1 to 0.3 wt% of an optical brightener, based on the total weight of the composition.

[0214] In some embodiments, the curable composition further comprises a hindered amine light stabilizer (HALS) containing at least one secondary or tertiary amine group and used in combination with a UV absorber to improve light stability. Examples of HALS include, but are not limited to, oxopiperazinyl triazines, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, or bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) succinate. In some embodiments, the curable composition herein comprises 0.001 to 2 wt% or 0.05 to 1 wt% of HALS, based on the total weight of the composition.

[0215] 9) Solvent

[0216] In some embodiments, the curable composition comprises a solvent. In some embodiments, the solvent is non-polar. In certain embodiments, the non-polar solvent comprises pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, ether, dichloromethane, their derivatives or combinations thereof. In some embodiments, the solvent is polar and non-protic. In certain embodiments, the polar aprotic solvent comprises tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, their derivatives or combinations thereof. In some embodiments, the solvent comprises a polar protic solvent. In certain embodiments, the polar protic solvent comprises formic acid, n-butanol, isopropanol, n-propanol, tert-butanol, ethanol, methanol, acetic acid, water, their derivatives or combinations thereof. In some embodiments, the photocurable resin comprises less than 90%, less than 80%, less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 20%, less than 15%, less than 10%, less than 5%, less than 3%, less than 2%, or less than 1% solvent by weight. In some cases, the solvent is configured to evaporate or separate from the curable composition after curing.

[0217] 10) Curable resin properties

[0218] The curable compositions of the present disclosure can be 3D printed at temperatures above 25° C. In some cases, the printing temperature is at least about 30° C., 40° C., 50° C., 60° C., 80° C., or 100° C. As described herein, the polymerizable monomers of the present disclosure can be used as part of a curable composition and can have a low vapor pressure and / or low mass loss at the printing temperature, thereby providing improved printing conditions compared to conventional compositions for additive manufacturing.

[0219] In some embodiments, the melting temperature of the curable composition herein is higher than room temperature. In some embodiments, the melting temperature of the curable composition is higher than 20°C, higher than 25°C, higher than 30°C, higher than 35°C, higher than 40°C, higher than 45°C, higher than 50°C, higher than 55°C, higher than 60°C, higher than 65°C, higher than 70°C, higher than 75°C, or higher than 80°C. In some embodiments, the melting temperature of the curable composition is 20°C to 250°C, 30°C to 180°C, 40°C to 160°C or 50°C to 140°C. In some embodiments, the melting temperature of the curable composition is higher than 60°C. In other embodiments, the melting temperature of the curable composition is 80°C to 110°C. In some cases, the melting temperature of the curable composition before polymerization can be about 80°C, and after polymerization, the melting temperature of the resulting polymer material can be about 100°C.

[0220] In some cases, it may be advantageous for the curable composition to be in a liquid phase at high temperatures. For example, a conventional curable composition may include a polymerizable component that becomes viscous at a processing temperature, so it may be difficult to use when manufacturing an object (e.g., using 3D printing). As a solution to this technical problem, the present disclosure provides a curable composition comprising a photopolymerizable component, such as a monomer as described herein, which can be melted at a higher temperature, such as, at a temperature during the manufacturing process (e.g., during 3D printing), and at this higher temperature, viscosity can be reduced, which makes this type of curable composition more suitable for purposes such as 3D printing. Therefore, in some embodiments, provided herein is a curable composition that is liquid at a higher temperature. In some embodiments, this higher temperature is equal to or higher than the melting point (T ) of the curable composition. m). In certain embodiments, the higher temperature may be a temperature in the range of about 40°C to about 100°C, about 60°C to about 100°C, about 80°C to about 100°C, about 40°C to about 150°C, or about 150°C to about 350°C. In some embodiments, the higher temperature is a temperature above about 40°C, above about 60°C, above about 80°C, or above about 100°C. In some embodiments, the curable composition herein is liquid at the higher temperature, and its viscosity is less than about 50PaS, less than about 20PaS, less than about 10PaS, less than about 5PaS, or less than about 1PaS. In some embodiments, the curable composition herein is liquid at a temperature above about 40°C, and its viscosity is less than about 20PaS. In some other embodiments, the curable composition herein is liquid at a temperature above about 40°C, and its viscosity is less than about 1PaS.

[0221] In some embodiments, the melting temperature of at least a portion of the curable composition herein is about 100° C. or less, about 90° C. or less, about 80° C. or less, about 70° C. or less, or about 60° C. or less. In some embodiments, at least a portion of the curable composition herein melts at a higher temperature of about 100° C. to about 20° C., about 90° C. to about 20° C., about 80° C. to about 20° C., about 70° C. to about 20° C., about 60° C. to about 20° C., about 60° C. to about 10° C., or about 60° C. to about 0° C.

[0222] In various embodiments, the curable compositions and photopolymerizable components thereof herein can be biocompatible, bioinert or a combination thereof. In various cases, the photopolymerizable compounds in the compositions herein can produce biocompatible and / or bioinert metabolic (e.g., hydrolysis) products.

[0223] The curable compositions of the present disclosure may include less than about 20 wt% or less than about 10 wt% of hydrogen-bonded units. In some aspects, the curable compositions herein include less than about 15 wt%, less than about 10 wt%, less than about 9 wt%, less than about 8 wt%, less than about 7 wt%, less than about 6 wt%, less than about 5 wt%, less than about 4 wt%, less than about 3 wt%, less than about 2 wt% or less than about 1 wt% of hydrogen-bonded units.

[0224] 11) Exemplary curable compositions according to the present disclosure

[0225] In some cases, the curable composition comprises a plurality of cross-linking agents having different properties and chemical structures. In some cases, at least 70%, at least 80%, at least 85%, at least 90%, at least 95%, at least 97.5% or at least 99% of the polymerizable functional groups in the curable composition are disposed in a cross-linking agent, wherein the cross-linking agent comprises two cross-linking agents having different skeletons. In some embodiments, the first cross-linking agent has a rigid skeleton for imparting high strength to the orthodontic appliance, while the second cross-linking agent has a non-rigid (i.e., flexible) skeleton for imparting high toughness to the orthodontic appliance. In some embodiments, the second cross-linking agent can also act as a reactive diluent to improve the printability of the curable composition. The curable composition may comprise any number of the first cross-linking agent and the second cross-linking agent so that the dental attachment made from the curable composition has sufficient strength to transmit force to the attached teeth without causing deformation or breakage of the attachment.

[0226] In some embodiments, the first cross-linking agent has the following structure (I):

[0227] Y 1 —X 1 —L 1 -A—L 2 -X 2 -Y 2 ,

[0228] (I)

[0229] in:

[0230] A is cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylenealkylene, heterocycloalkylene, arylene, heteroarylene, alkylenearylene, or alkylenearylenealkylene;

[0231] L 1 and L 2 are independently amide, ether, ester, carbonate, carbamate or urea bonds;

[0232] X 1 and X 2 are independently an alkylene or heteroalkylene linking group; and

[0233] Y 1 and Y 2 are independently polymerizable functional groups.

[0234] In some embodiments, A has one of the following structures:

[0235]

[0236] Where R 1 , R 2and R 3 are independently H or alkyl.

[0237] In some embodiments, R 1 , R 2 and R 3 It is methyl.

[0238] In some embodiments, X 1 and X 2 Independently

[0239]

[0240] wherein n is an integer from 1 to 20.

[0241] In some embodiments, Y 1 and Y 2 Independently has one of the following structures:

[0242]

[0243] Where R 4 is H or alkyl.

[0244] In some embodiments, the first cross-linking agent is a di(meth)acrylate having aromatic or alicyclic functional groups. Examples of the first cross-linking agent include, but are not limited to, ethoxylated bisphenol A dimethacrylate (BisEMA6), bisphenol A diglycidyl dimethacrylate (BisGMA), or isophorone urethane dimethacrylate.

[0245] In some embodiments, the second cross-linking agent has the following structure (II):

[0246] Y 3 -X 3 -L 3 -B—L 4 —X 4 —Y 3 ,

[0247] (II)

[0248] in:

[0249] B is a straight or branched chain alkylene or heteroalkylene;

[0250] L 3 and L 4 are independently optional amide, ether, ester, carbonate, carbamate or urea bonds;

[0251] X 3 and X 4 is independently an optional alkylene or heteroalkylene linking group; and

[0252] Y 3 and Y 4 are independently polymerizable functional groups.

[0253] In some embodiments, B has one of the following structures:

[0254]

[0255] wherein m is an integer from 1 to 20.

[0256] In some embodiments, X 3 and X 4 Independently has one of the following structures:

[0257]

[0258] wherein n is an integer from 1 to 20.

[0259] In some embodiments, Y 3 and Y 4 Independently has one of the following structures:

[0260]

[0261] Where R 4 is H or alkyl.

[0262] In some embodiments, the second cross-linking agent is a di(meth)acrylate having a linear or branched aliphatic functional group. Examples of the second cross-linking agent include, but are not limited to, triethylene glycol dimethacrylate (TEGDMA), glycerol dimethacrylate (GDMA), ethylene glycol dimethacrylate, neopentyl glycol dimethacrylate (NPGDMA), polyethylene glycol di(meth)acrylate (PEGDMA), Ebecryl 8402 (aliphatic urethane diacrylate with a molecular weight of 1000), Ebecryl 8409 (aliphatic urethane diacrylate with a molecular weight of 100), and BRC-443D (aliphatic hydrophobic urethane diacrylate).

[0263] In some cases, at least 90% of the polymerizable functional groups of the curable composition are arranged in a crosslinker, wherein the crosslinker includes at least two crosslinkers with different skeletons. In some cases, the curable composition is photocurable, chemically curable, thermally curable, or any combination thereof. In some cases, the curable composition is photocurable. In some cases, the composition further comprises a filling material. In some cases, the filling material comprises silica, glass, radiopaque material, prepolymer filler, ceramic, metal, metal oxide, crystal, or any combination thereof. In some cases, the filling material comprises fumed silica, glass powder, radiopaque filler, prepolymer filler, or any combination thereof. In some cases, the curable composition further comprises a wetting agent. In some cases, the wetting agent comprises siloxane. In some cases, the curable composition further comprises a pigment. In some cases, the pigment is inorganic. In some cases, the composition further comprises a photoinitiator. In some cases, the photoinitiator comprises an oligomer or a polymer. In some cases, the curable composition includes about 50 wt % to about 100 wt %, about 70 to about 100 wt %, about 80 to about 100 wt %, about 90 to about 100 wt %, about 95 to 100 wt %, or about 60 to about 90 wt % of the polymerizable species.

[0264] In some cases, the curable composition has a color and transparency that allows it to be detected by a 3D scanner and has a neutral appearance when placed in the mouth. In some cases, the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured. In some cases, the curable composition is configured to exhibit a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured.

[0265] In a specific example, the curable composition includes a first cross-linking agent, which includes a first plurality of polymerizable functional groups and an aryl or heteroaryl group disposed between at least two polymerizable functional groups in the first plurality of polymerizable functional groups; and a second cross-linking agent, which includes a second plurality of polymerizable functional groups and a carbamate, diol, carbonate, urea, ester, amide, thioether, thioester, guanidine or a combination thereof disposed between at least two polymerizable functional groups in the second plurality of polymerizable functional groups. In some such cases, each of the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups is a plurality of ethylenically unsaturated functional groups. In some cases, each of the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups includes two polymerizable functional groups. In some cases, the first plurality of polymerizable functional groups includes two polymerizable functional groups, and the second plurality of polymerizable functional groups includes more than two polymerizable functional groups. In some cases, each of the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups includes more than two polymerizable functional groups. In some cases, the second cross-linking agent comprises a carbamate, a diol, or a combination thereof disposed between at least two of the second plurality of polymerizable functional groups. In some cases, the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups, or a combination thereof. In some cases, the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, or a combination thereof. In some cases, the molecular weights of the first cross-linking agent and the second cross-linking agent differ by at least 200 Daltons (Da).

[0266] In some cases, at least two of the first plurality of polymerizable functional groups are separated by at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, at least 22, or at least 30 atoms. In some cases, at least two of the first plurality of polymerizable functional groups are separated by at least 14 atoms. In some cases, at least two of the second plurality of polymerizable functional groups are separated by at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, at least 22, or at least 30 atoms. In some cases, at least two of the second plurality of polymerizable functional groups are separated by at least 14 atoms.

[0267] In some cases, the composition further comprises a third cross-linking agent comprising a third plurality of polymerizable functional groups and an alkyl backbone connecting at least two of the third plurality of polymerizable functional groups. In some cases, the alkylene backbone is substituted with a functional group selected from halogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxyl, amine, thiol, cyano, aryl, heteroaryl, ester, amide, carbamate, carbonate, and combinations thereof. In some cases, the alkylene backbone is unsubstituted.

[0268] In some cases, the third plurality of polymerizable functional groups are multiple ethylenically unsaturated functional groups. In some cases, the third plurality of polymerizable functional groups are multiple acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups or combinations thereof. In some cases, the third plurality of polymerizable functional groups are multiple acrylate groups, methacrylate groups or combinations thereof. In some cases, the third plurality of polymerizable functional groups include two polymerizable functional groups. In some cases, the third plurality of polymerizable functional groups include more than two polymerizable functional groups.

[0269] In some cases, at least two polymerizable functional groups are separated by 5 to 20 carbon atoms of the alkylene backbone. In some cases, the alkylene backbone is unsubstituted. In some cases, at least two polymerizable functional groups are separated by 6 to 15 carbon atoms of the alkylene backbone. In some cases, at least two polymerizable functional groups are separated by 8 to 12 carbon atoms of the alkylene backbone.

[0270] In some cases, at least two polymerizable functional groups in the third plurality of polymerizable functional groups are separated by at least 4, at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, or at least 22 atoms. In some cases, at least two polymerizable functional groups in the first plurality of polymerizable functional groups are each separated by at least 6 atoms. In some cases, at least two polymerizable functional groups in the second plurality of polymerizable functional groups are separated by at least 6, at least 8, at least 10, at least 12, at least 14, at least 18, at least 22, or at least 30 atoms. In some cases, the third cross-linking agent differs in molecular weight from each of the first and second cross-linking agents by at least 100 Da, but differs by at least 150 Da, at least 200 Da, at least 250 Da, at least 300 Da, at least 400 Da, or at least 500 Da. In some cases, the third cross-linking agent differs in molecular weight from each of the first and second cross-linking agents by at least 200 Da.

[0271] In some cases, the composition further comprises a fourth cross-linking agent comprising a fourth plurality of polymerizable functional groups and an alkyl backbone linking at least two polymerizable functional groups in the fourth plurality of polymerizable functional groups.

[0272] In some cases, the cross-linking agent (for example, the first, second, third or fourth cross-linking agent) is an alkanediol diacrylate or dimethacrylate. In some cases, the alkanediol diacrylate or dimethacrylate is hexanediol, heptanediol, octanediol, nonanediol, decanediol, undecanediol, dodecanediol, tridecanediol or tetradecanediol diacrylate or dimethacrylate. In some cases, the alkanediol diacrylate or alkanediol dimethacrylate is octanediol, nonanediol, decanediol, undecanediol or dodecanediol diacrylate or dimethacrylate. In some cases, the alkanediol diacrylate or alkanediol dimethacrylate is decanediol diacrylate or dimethacrylate.

[0273] In some cases, the crosslinking agent is bisphenol diacrylate or bisphenol dimethacrylate. In some cases, the bisphenol acrylate or bisphenol dimethacrylate is bisphenol glycidyl diacrylate or bisphenol glycidyl dimethacrylate. In some cases, the bisphenol acrylate or dimethacrylate is bisphenol A-glycidyl acrylate or bisphenol A-glycidyl methacrylate. The bisphenol acrylate or bisphenol dimethacrylate is ethoxylated bisphenol A diacrylate or ethoxylated bisphenol A dimethacrylate. In some cases, two crosslinking agents (e.g., two of the first, second, third, and fourth crosslinking agents) of the curable composition are bisphenol A diacrylate or bisphenol A dimethacrylate. In some such cases, the first crosslinking agent is bisphenol A-glycidyl methacrylate and the second crosslinking agent is ethoxylated bisphenol A dimethacrylate.

[0274] In some cases, the crosslinker is a urethane diacrylate or a urethane dimethacrylate.

[0275] In some cases, the curable composition comprises a formulation as described in any of the following Tables 1-11:

[0276] Table 1 - Exemplary Curable Compositions

[0277] Element Weight percentage (wt%) First cross-linking agent 1-40 Second crosslinking agent 1-40 The third crosslinking agent 1-40 Photoinitiator 0.1-5

[0278] Table 2 - Exemplary Curable Compositions

[0279] Element Weight percentage (wt%) Alkanediol diacrylate or dimethacrylate 1-40 Bisphenol diacrylate or dimethacrylate 1-40 Urethane diacrylate or dimethacrylate 1-40 Photoinitiator 0.1-5

[0280] Table 3 - Exemplary Curable Compositions

[0281] Element Weight percentage (wt%) First cross-linking agent 5-40 Second crosslinking agent 5-40 The third crosslinking agent 5-40 Photoinitiator 0.1-5 pigment 0.005-2 Wetting Agents 0.1-1.5

[0282] Table 4 - Exemplary Curable Compositions

[0283] Element Weight percentage (wt%) Alkanediol diacrylate or dimethacrylate 5-40 Bisphenol diacrylate or dimethacrylate 5-40 Urethane diacrylate or dimethacrylate 5-40 Photoinitiator 0.1-5 pigment 0.005-2 Wetting Agents 0.1-1.5

[0284] Table 5 - Exemplary Curable Compositions

[0285] Element Weight percentage (wt%) First cross-linking agent 5-40 Second crosslinking agent 5-40 The third crosslinking agent 5-40 The fourth cross-linking agent 5-40 Photoinitiator 0.1-5 pigment 0.005-2 Wetting Agents 0.1-1.5

[0286] Table 6 - Exemplary Curable Compositions

[0287] Element Weight percentage (wt%) Alkanediol diacrylate or dimethacrylate 5-40 First bisphenol diacrylate or dimethacrylate 5-40 Second bisphenol diacrylate or dimethacrylate 5-40 Urethane diacrylate or dimethacrylate 5-40 Photoinitiator 0.1-5 pigment 0.005-2 Wetting Agents 0.1-1.5

[0288] Table 7 - Exemplary Curable Compositions

[0289]

[0290] Table 8 - Exemplary Curable Compositions

[0291]

[0292] Table 9 - Exemplary Curable Compositions

[0293] Element Weight percentage (wt%) First cross-linking agent 1-35 Second crosslinking agent 1-50 The third crosslinking agent 1-80 Filling material 10-60 Photoinitiator 0.1-5 pigment 0.005-3 Wetting Agents 0.005-3

[0294] Table 10 - Exemplary Curable Compositions

[0295] Element Weight percentage (wt%) First cross-linking agent 1-25 Second crosslinking agent 1-40 The third crosslinking agent 1-80 The fourth cross-linking agent 1-40 Filling material 10-60 Photoinitiator 0.1-5 pigment 0.005-3 Wetting Agents 0.005-3

[0296] Table 11 - Exemplary Curable Compositions

[0297]

[0298]

[0299] III. Printing Materials

[0300] Aspects of the present disclosure provide materials printed by curable compositions disclosed herein. The printed material may be composed of curable compositions disclosed herein (e.g., printed into an accessory placement device, the device being composed of greater than 90%, greater than 95%, or greater than 99% of the curable composition), or may be printed into a device or article comprising a plurality of materials (e.g., printed into a dental brace comprising a curable composition layer interspersed with a low viscosity curable adhesive layer). The printed material may have properties that are advantageous for medical devices, particularly orthodontic devices. In some cases, these printed materials are configured to be used as an accessory placement device.

[0301] In some cases, the printed material comprises a modulus of about 600 MPa to about 3200 MPa. In some cases, the printed material comprises a modulus of about 800 to about 2400 MPa. In some cases, the printed material comprises a modulus of about 1000 to about 2400 MPa. In some cases, the printed material comprises a modulus of at least about 600 MPa, at least about 800 MPa, at least about 1000 MPa, at least about 1200 MPa, at least about 1500 MPa, at least about 1800 MPa, or at least about 2400 MPa.

[0302] In some cases, the printed material comprises a maximum stress of about 25 to about 160 MPa. In some cases, the printed material comprises a strength of about 30 to about 140 MPa. In some cases, the printed material comprises a strength of about 40 to about 120 MPa. In some cases, the printed material comprises a strength of at least about 25 MPa, at least about 30 MPa, at least about 40 MPa, at least about 50 MPa, at least about 60 MPa, at least about 70 MPa, or at least about 80 MPa.

[0303] In some cases, the printed material comprises a strain at break of about 1.5% to about 9%. In some cases, the printed material comprises a strain at break of about 2.5% to about 7.5%. In some cases, the printed material comprises a strain at break of about 3% to about 7%. In some cases, the printed material comprises a strain at break of about 3.5% to about 6.5%. In some cases, the printed material comprises at least about 1.5%, at least about 2%, at least about 2.5%, at least about 3%, at least about 3.5%, at least about 4%, at least about 4.5%, or at least about 5%.

[0304] In some cases, the printed material comprises a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22. In some cases, the printed material comprises a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16. In some cases, the printed material has an average transmittance of at least about 50%, at least about 60%, at least about 70%, at least about 80%, at least about 85%, at least about 90%, or at least about 95% over the visible spectrum (about 380 to about 700 nanometers). In some cases, the printed material has an average transmittance of at most about 60%, at most about 50%, at most about 40%, at most about 30%, at most about 20%, at most about 10%, or at most about 5% over the visible spectrum (about 380 to about 700 nanometers).

[0305] In some cases, the printed material can be a medical device or a portion thereof. The medical device can be an orthodontic appliance. In some cases, the orthodontic appliance can be a dental attachment, a dental brace, one or more incremental palatal expanders, or a dental separator. In certain cases, the medical device is a dental attachment. In some cases, the dental attachment is configured for use with a dental brace.

[0306] IV. Printing Method

[0307] The present disclosure provides methods for synthesizing polymerizable compounds of the present disclosure, methods for using compositions (e.g., resins and polymer materials) containing such compounds (e.g., homogenizing or patterning compounds and substances in compositions), and methods for producing objects such as medical devices. The polymerizable compounds of the present disclosure (e.g., crosslinkers described herein) can be used as components of a range of materials suitable for use in a variety of different industries (e.g., transportation, hobbies, prototyping, medical, art and design, microfluidics and molding, etc.). As disclosed herein, printable medical devices can include orthodontic appliances.

[0308] 1) Manufacture and use of orthodontic appliances

[0309] Provided herein are methods of using polymerizable compounds, curable resins, and compositions comprising such compounds, and polymeric materials made from such resins and compositions, for making medical devices, e.g., orthodontic appliances (e.g., dental braces, one or more incremental palatal expanders, dental separators, and / or accessory placement devices). These methods may include homogenizing, dispersing, or patterning components of curable resins, thereby varying the properties of the curable resins or polymerizable materials produced therefrom.

[0310] Therefore, in some embodiments, the method herein also includes the step of using an additive manufacturing device to manufacture a device or object, wherein the additive manufacturing device assists in curing. In some embodiments, the curing of the polymerizable resin produces a cured polymer material. In certain embodiments, the polymerizable resin is cured using an additive manufacturing device to produce a cured polymer material. In some embodiments, the method also includes the step of cleaning the cured polymer material. In certain embodiments, the cleaning of the cured polymer material includes washing and / or rinsing the cured polymer material with a solvent, which can remove uncured resin and undesirable impurities from the cured polymer material. Cleaning can also include centrifuging the print to remove excess and / or uncured material therein.

[0311] In some embodiments, the polymerizable resins herein may be curable and have a melting point <100°C so as to be liquid and, therefore, processable at temperatures typically employed in currently available additive manufacturing techniques. As described herein, the polymerizable monomers of the present disclosure used as components in the curable resin may have a vapor pressure of about 0.01 mmHg at printing temperatures, compared to conventional reactive diluents or other polymerizable components used in curable resins. Such low vapor pressures of the monomers described herein are particularly advantageous for use in curable (e.g., photocurable) compositions and additive manufacturing, where higher temperatures (e.g., 60°C, 80°C, 90°C, or higher) may be used. In various cases, the vapor pressure of the polymerizable monomer at a temperature of 60°C may be up to about 12 Pa or less, as further described herein.

[0312] In some embodiments, the curable resin herein may contain at least one photopolymerization initiator (i.e., photoinitiator) and may be heated to a predetermined higher process temperature of about 50° C. to about 120° C., for example, about 90° C. to about 120° C., and then irradiated with light of a suitable wavelength to be absorbed by the photoinitiator, thereby causing activation of the photoinitiator, inducing polymerization of the curable resin, and obtaining a cured polymer material, which may be optionally cross-linked.

[0313] In some embodiments, the method for forming a polymer material disclosed herein is part of a photopolymerization process based on high temperature photolithography, in which a curable resin (e.g., a photocurable resin) containing at least one photopolymerization initiator is heated to a higher process temperature (e.g., about 50°C to about 120°C, for example, about 90°C to about 120°C). Therefore, the method for forming a polymer material according to the present disclosure can provide the possibility of quickly and easily producing devices (e.g., orthodontic appliances), for example, by additive manufacturing (e.g., 3D printing) using the curable resin disclosed herein. In various embodiments, such a curable resin is a photocurable resin, which contains two or more cross-linking agents and optionally contains a filling material as described herein, for example, a plurality of cross-linking agents and an inorganic filler.

[0314] Photopolymerization can occur when the photocurable resin of the present invention is exposed to radiation (e.g., UV or visible light) of a wavelength sufficient to initiate polymerization. The wavelength of the radiation that can be used to initiate polymerization may depend on the photoinitiator used. As used herein, "light" includes any wavelength and power capable of initiating polymerization. Some wavelengths of light include ultraviolet (UV) or visible light. UV light sources include UVA (wavelength of about 400 nanometers (nm) to about 320nm), UVB (about 320nm to about 290nm) or UVC (about 290nm to about 100nm). Any suitable source can be used, including a laser source. The source can be broadband or narrowband or a combination thereof. The light source can provide continuous or pulsed light during processing. The length of time the system is exposed to UV light and the intensity of the UV light can be changed to determine the ideal reaction conditions.

[0315] In some embodiments, the methods disclosed herein include using additive manufacturing to produce a device comprising a solidified polymer material. Such a device may be an orthodontic appliance. An orthodontic appliance may be a dental brace, one or more incremental palatal expanders, a dental separator, and / or an accessory placement device. In certain embodiments, the methods disclosed herein use additive manufacturing to produce a device comprising, consisting essentially of, or consisting of a solidified polymer material. Additive manufacturing includes various techniques for manufacturing three-dimensional objects directly from a digital model through an additive process. In some aspects, successive layers of material are deposited and "solidified in situ". A variety of techniques are known in the field of additive manufacturing, including selective laser sintering (SLS), fused deposition modeling (FDM), and injection or extrusion. In many embodiments, selective laser sintering involves using a laser beam to selectively melt and fuse layers of powdered material according to a desired cross-sectional shape in order to construct an object geometry. In many embodiments, fused deposition modeling involves melting and selectively depositing filaments of thermoplastic polymers in a layer-by-layer manner to form an object. In yet another example, 3D printing can be used to manufacture the orthodontic appliances of this article. In many embodiments, 3D printing involves spraying or extruding one or more materials (e.g., a crystallizable resin disclosed herein) onto a build surface to form continuous layers of the geometry of an object. In some embodiments, the photocurable resins described herein can be used for inkjet or coating applications. Cured polymer materials can also be made by a "vat" process, which uses light to selectively cure a curable resin in a tank or reservoir. Each layer of the curable resin can be selectively exposed to light in a single exposure or by scanning a light beam through the layer. Specific techniques that can be used herein may include stereolithography (SLA), digital light processing (DLP), and two-photon induced photopolymerization (TPIP).

[0316] In some embodiments, the method disclosed herein uses continuous direct manufacturing to produce a device comprising a cured polymer material. Such a device can be an orthodontic appliance described herein. In certain embodiments, the method disclosed herein can include using continuous direct manufacturing to produce a device (e.g., an orthodontic appliance) that contains a cured polymer material, is substantially composed of a cured polymer material, or is composed of a cured polymer material. A non-limiting exemplary direct manufacturing process can achieve continuous construction of the geometry of an object by continuously moving the building platform in the radiation phase (e.g., along the longitudinal or Z direction), so that the hardening depth of the irradiated photopolymer (e.g., irradiated photocurable resin, which hardens during the formation of the cured polymer material) is controlled by the movement speed. Therefore, continuous polymerization of materials can be achieved on the building surface (e.g., polymerizing the photocurable resin into a cured polymer material). Such methods are described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference as a whole. In another example, the continuous direct manufacturing method utilizes a "helical lithography" method, in which a liquid resin (e.g., a photocurable resin) is cured by focused radiation while the building platform is continuously rotated and lifted. Therefore, the object geometry can be continuously constructed along the spiral construction path. Such methods are described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety. The continuous liquid interface production of 3D objects is also reported in the literature (J. Tumbleston et al., Science, 2015, 347 (6228), pp1349-1352), which is incorporated herein by reference in its entirety to describe the process. Another example of a continuous direct manufacturing method can include extruding a material consisting of a curable liquid material or resin surrounding a solid strand. The material can be extruded along a continuous three-dimensional path to form an object. Such methods are described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0317] In some embodiments, the method disclosed herein may include using high temperature lithography to produce a device comprising a cured polymer material. Such a device may be an orthodontic appliance as described herein. In certain embodiments, the method disclosed herein uses high temperature lithography to produce a device comprising a cured polymer material, consisting essentially of a cured polymer material, or consisting of a cured polymer material. As used herein, "high temperature lithography" may refer to any lithography-based photopolymerization process involving heating a photopolymerizable material (e.g., a photocurable resin disclosed herein). Heating can reduce the viscosity of the photocurable resin before and / or during curing. Non-limiting examples of high temperature lithography processes include those described in WO 2015 / 075094, WO 2016 / 078838, and WO 2018 / 032022. In some embodiments, high temperature lithography may involve applying heat to a material to about 50°C to about 120°C, for example, about 90°C to about 120°C, about 100°C to about 120°C, about 105°C to about 115°C, about 108°C to about 110°C, etc. The material may be heated to a temperature above about 120° C. It should be noted that other temperature ranges may be used without departing from the scope and spirit of the inventive concepts described herein.

[0318] Since, in some cases, the polymerizable compounds of the present disclosure can be copolymerized as part of a photocurable resin during the polymerization process according to the method of the present disclosure, the result can be an optionally cross-linked polymer that contains one or more portions of the polymerizable compounds as repeating units. In some cases, such polymers are cross-linked polymers that are generally suitable for and useful in applications in orthodontic appliances. The polymerizable compounds of the present disclosure containing multiple reactive functional groups can provide a uniform and continuous polymer network with clear phase separation.

[0319] In many cases, the method herein may include polymerizing a curable resin, the curable resin comprising one or more crosslinking agents, which can provide a crosslinked polymer matrix when polymerized, and the crosslinked polymer matrix can include a portion derived from a polymerizable compound of the present disclosure as a repeating unit. In order to obtain a crosslinked polymer that can be particularly suitable as an orthodontic appliance, at least one polymerizable substance used in the method according to the present disclosure can be selected according to several thermomechanical properties of the resulting polymer. In some cases, the curable resin of the present disclosure may include one or more polymerizable compounds. In some cases, the polymerizable monomer of the present disclosure may also have a crosslinking functional group, and in the case where it contains multiple reactive functional groups (similar to the polymerizable compounds of the present invention), it not only acts as a reactive diluent with a low vapor pressure, but also acts as a crosslinking agent during the polymerization of the curable resin described herein. In other embodiments, the resin includes a polymerizable compound, a polymerizable monomer, and a crosslinking monomer as described herein, wherein the two monomers are different substances (i.e., chemical entities).

[0320] V. Orthodontic appliances and their uses

[0321] The polymerizable compounds according to the present disclosure can be used as components of curable compositions that can be additively manufactured into dental appliances, including but not limited to: one or more aligners comprising a plurality of tooth receiving cavities shaped to move a patient's dentition from a first arrangement toward a target arrangement; one or more incremental palatal expanders shaped to expand a patient's palate from a first configuration to a target configuration; one or more dental separators; and / or accessory placement devices.

[0322] The polymerizable compounds according to the present disclosure can be used as components of curable compositions, which, when additively manufactured, become aligners with tooth receiving cavities that are capable of moving a patient's teeth from a first arrangement toward a second arrangement, and / or have excellent mechanical properties (elongation at break, stiffness, stress, strain, etc.) required to achieve the same function. The aligner can perform one or more tooth repositioning methods disclosed herein, wherein the method includes: (i) generating a treatment plan for a patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; (ii) preparing a dental appliance comprising a polymer material described herein (e.g., a polymer material in a polymerized form distributed in a uniform, dispersed, or patterned manner); and moving at least one of the patient's teeth toward an intermediate tooth arrangement or a final tooth arrangement along a predetermined trajectory by the dental appliance.

[0323] The polymerizable compounds according to the present disclosure can be used as components of curable compositions that, when additively manufactured, can form one or more incremental palatal expanders that expand a patient's palate from a first alignment toward a target alignment. The incremental palatal expanders can be locked into the patient's palate, and one or more stages of a digital treatment plan can be implemented with or without an orthotic device.

[0324] In various embodiments, polymerizable compounds according to the present disclosure may be used as components of curable compositions that, when additively manufactured, may form one or more accessory placement devices for placing and / or attaching accessories to a patient's dentition. As used herein, an accessory placement device may include a dental appliance that can be coupled to a patient's dentition and, when coupled to a patient's dentition, can help place and / or attach accessories to portions of a patient's dentition. The accessory placement device may include a placement surface that includes mating surfaces that are sized and / or shaped to approximate the contour of one or more teeth and accurately assemble the accessory for one or more teeth in a specific position and / or orientation. In some embodiments, the accessory placement device may include one or more accessory supports extending from a placement element, wherein the accessory support is fragilely coupled to a disconnectable accessory at a specific position and / or orientation on the patient's teeth. The accessory placement device may also include one or more additively manufactured accessories that are detachably carried by the accessory support to a specific position and / or orientation on the patient's teeth. The attachment placement device may also include an adhesive (e.g., an adhesive material) for coupling the attachment to the tooth. The attachment placement device may include one or more grooves surrounding at least a portion of the attachment, wherein the grooves are configured to collect or shape excess adhesive material for removal. The attachment groove may include an edge configured to make surface contact with the tooth. The edge may define an edge of the attachment, separating the attachment from excess attachment material in the groove, thereby facilitating removal of the excess attachment material.

[0325] A treatment method may include coupling an accessory placement device to one or more teeth of a patient so as to place an accessory on the accessory placement device in a desired position and / or orientation. A placement element on the accessory placement device may hold the accessory placement device on the patient's dentition so that the accessory may be properly placed. An accessory support may dock between the placement element and a prefabricated accessory placed on the patient's teeth. A practitioner may apply an adhesive to a prefabricated accessory on the accessory placement device, and / or release an existing adhesive from an accessory on the accessory placement device (e.g., by removing a sticker / backing). (Removal may but need not occur before placing the accessory placement device on the patient's dentition). A practitioner may further separate (e.g., break) the accessory support at an appropriate location so that the accessory can be frangibly released to an appropriate location and / or orientation on the patient's teeth. Once the accessories are on the patient's teeth, they may engage with other portions of the groove and / or tooth receiving cavity to achieve the desired displacement and / or force on the patient's dentition. This engagement may hold the dental appliance in a desired position or orientation, may facilitate the proper transfer of force from the dental appliance to the teeth, and may enhance treatment comfort.

[0326] As further described herein, such dental appliances can be produced using processes including additive manufacturing.

[0327] As used herein, the terms “rigidity” and “stiffness” may, but need not be, used interchangeably, as may the corresponding terms “rigid” and “stiff.” As used herein, “a plurality of teeth” includes two or more teeth.

[0328] In many embodiments, the one or more posterior teeth include one or more of molars, premolars, or canines, and the one or more anterior teeth include one or more of central incisors, lateral incisors, canines, first bicuspids, or second bicuspids.

[0329] In some embodiments, the compositions and methods described herein can be used to couple one or more sets of teeth to each other. One or more sets of teeth can include a first set of one or more anterior teeth and a second set of one or more posterior teeth. The first set of teeth can be coupled to the second set of teeth using a polymer shell appliance disclosed herein.

[0330] The embodiments disclosed herein are well suited for moving one or more teeth in a first group of one or more teeth, or moving one or more teeth in a second group of one or more teeth, and combinations thereof.

[0331] The embodiments disclosed herein are well suited for combination with one or more known commercially available tooth movement components (e.g., attachments and polymer shell appliances). In many embodiments, the appliance and one or more attachments are configured to move one or more teeth along a tooth motion vector comprising six degrees of freedom, three of which are rotational and three of which are translational.

[0332] The present disclosure provides orthodontic systems and related methods for designing and providing improved or more effective tooth movement systems for inducing desired tooth movement and / or repositioning teeth into a desired arrangement.

[0333] Although reference is made to appliances comprising polymer shell appliances, the embodiments disclosed herein are well suited for use with many appliances that receive teeth, for example, appliances that do not have one or more of a polymer or shell. The appliance can be made with one or more of many filling materials, for example, metal, glass, reinforcing fibers, carbon fibers, composite materials, reinforced composite materials, aluminum, biomaterials, and combinations thereof. In some cases, the reinforced composite material may include a polymer matrix reinforced with, for example, ceramic or metal particles. The appliance can be formed in many ways, for example, by thermoforming or direct manufacturing as described herein. Alternatively or in combination, the appliance can be manufactured by machining, for example, by computer numerical control machining of an appliance made from a block of material. In some cases, a polymerizable compound according to the present disclosure is used, for example, a monomer is used as a reactive diluent for a curable resin to manufacture the appliance.

[0334] 1) Accessory placement device

[0335] In some embodiments, the polymerizable compounds and / or polymer materials according to the present disclosure may be additively manufactured to form an accessory placement device. An accessory placement device additively manufactured using the polymerizable compounds and / or polymer materials according to the present disclosure may be coupled to the patient's dentition and may guide the placement of dental accessories (e.g., items placed and / or bonded to the teeth by bonding, which are used in conjunction with the braces to displace and / or apply forces to the teeth). The accessories may include items made of a bonding adhesive that are shaped to engage with grooves within the braces and are capable of displacing and / or applying forces to the teeth when engaged with the grooves within the braces. In some embodiments, the accessories include prefabricated (e.g., additively manufactured) items that are coupled to the teeth by an adhesive and have one or more shapes that engage with grooves within the braces and are capable of displacing and / or applying forces to the teeth when engaged with grooves within the braces. As described herein, the size and / or shape of the placement surface of the accessory placement device can be set to approximate the contour of the patient's dentition and fit the teeth in the dentition with accessories (e.g., accessories made of bonding material, prefabricated accessories, etc.) at specific positions and / or orientations. In some embodiments, the accessory placement device may include one or more accessory supports extending from the placement element, wherein the accessory supports are fragilely coupled to the detachable accessories at specific positions and / or orientations on the patient's teeth. The accessory placement device may also include one or more additively manufactured accessories that are detachably carried by the accessory supports to specific positions and / or orientations on the patient's teeth. The accessory placement device may also include an adhesive (e.g., bonding material) to enable the accessory to be coupled to the tooth. The accessory placement device may include one or more grooves surrounding at least a portion of the accessory, the grooves being configured to collect or shape excess adhesive material for removal thereof. The accessory groove may include an edge configured to make surface contact with the tooth. The edge may define an edge of the accessory, separating the accessory from excess accessory material in the groove to facilitate removal of excess accessory material.

[0336] In some aspects, the attachment placement device and / or attachment includes a body shaped to fit the contour of the patient's dentition and may also be configured to accommodate one or more attachments connected to the outer surface of the patient's dentition, and / or one or more light sources, for example, as described in U.S. patent application Ser. No. 14 / 939,246, entitled "Dental attachment formation structure," filed by Peter Webber on November 11, 2015, the contents of which are incorporated herein by reference in their entirety as if fully set forth herein.

[0337] In various aspects, a dental attachment device and / or attachment includes a body having a first surface that is shaped to conform to an outer surface of a tooth, and a recessed portion of the first surface that is shaped as an attachment to be attached to the outer surface of the tooth. A release layer is formed on the surface of the recess so that the attachment can be removed from the recess, and an attachment material for forming the attachment is placed in the recess, as described in U.S. Patent Application No. 14 / 939,252, filed by Webber et al. on November 11, 2015, entitled "Dental Attachment Forming Structure," the contents of which are incorporated herein by reference in their entirety as if fully set forth herein. Fig. 6A A front view of a dental attachment former 600 is shown according to various aspects. Figure 6B A top view of a dental attachment former 600 is shown according to various aspects. Fig. 6A and 6B In the example of , an appliance 600 (an appliance) includes a body 601 having a surface shaped to conform to the contour of at least one outer surface of a tooth (in this example, the body has surfaces that conform to the buccal, lingual, and occlusal surfaces of the teeth). The body 601 also includes recesses 602 formed in the appliance 600 that provide a template for the shape of the attachment and the location and orientation of the attachment on one or more teeth of the patient. The recesses can then be filled with an attachment forming material 604, which is cured to form the attachment. Figure 7 FIG. 8 shows a front view of an attachment former 700 according to some embodiments. Figure 7 In the example of the embodiment, the device 700 includes a body 710 having a plurality of grooves 714-1, 714-2, and 714-N formed on a surface to be applied to teeth. In this example, two grooves are formed in the rightmost section. In addition, one groove is formed in the second section from the left. Multiple grooves can be formed on the same section and / or multiple different sections of the dental placement device.

[0338] In various aspects, a dental accessory device and / or accessory includes a body having an accessory placement surface to be placed on the accessory fixing surface of a tooth, and wherein the accessory placement surface includes a portion formed to allow the accessory to be placed at a specific position on the tooth fixing surface, and a portion of the body has a contour formed to correspond to the contour of the tooth alignment surface, and when the body contour is aligned with the corresponding contour, the accessory is placed at a specific position and fixed to the tooth fixing surface, for example, as described in U.S. patent application No. 14 / 963,527, entitled "Dental Attachment Forming Structure," filed by Webber et al. on December 9, 2015, the contents of which are incorporated herein by reference in their entirety as if fully set forth herein. Fig. 8AFIG. 8 is a front view of a dental accessory placement structure 800 for placing an accessory according to various embodiments of the present disclosure. Fig. 8A In the example of , the device 800 includes a body 801 having at least one surface shaped to conform to one or more contours of an outer surface of a tooth. Fig. 8A In the example of FIG. 8 , the body has multiple surfaces (the inner surfaces of portions 802-1 and 802-2), each of which is shaped to fit multiple contours of the outer surface of the tooth, and the combination Figure 8B The body 801 may also include an accessory mounting structure 804 that includes an accessory 806, an opening 810 for placing the accessory 806 on a tooth surface, and a plurality of supports 808.

[0339] Figure 8B Shows Fig. 8A 806 and support 808, and two inner surfaces of portions 802-1 and 802-2 of body 801 are shown, each of which is shaped to fit multiple contours of the outer surface of a tooth. As used herein, a surface shaped to fit the contours of the outer surface of a tooth (i.e., an alignment surface) can be used to accurately place and / or orient the accessory on the tooth. For example, if a surface of the device is shaped to fit the contours of the front surface of a tooth (e.g., Fig. 8A If the attachment is in contact with the surface 802-1 shown, then when the device is pressed against the front surface of the tooth and the contours of the tooth and the device are aligned with each other, the attachment will be correctly oriented relative to the angle between the back of the attachment and the tooth surface. Figure 8C Shown is a diagram of a tooth placed on a patient's teeth. Fig. 8A and Figure 8B Front view of the dental attachment placement structure. Figure 8C , several teeth and gums of a patient are shown, including teeth 834-1, 834-2, 834-3 to 834-R. Device 800 has been placed on two teeth (834-2 and 834-3) so that the inner surfaces of portions 802-1 and 802-2 are placed in contact with tooth surfaces 836-1 and 836-2, respectively. Fig.8D Shows the use of Fig. 8A and 8B A front view of a dental attachment being attached to a patient's tooth by means of a dental attachment placement structure. The final placement is achieved by Fig. 8A and 8B The accessory installation structure shown is implemented.

[0340] Fig. 9FIG. 8 shows a front view of a dental accessory placement structure 900 according to some embodiments, on which a plurality of accessory placement components are provided. Fig. 9 In the example of the embodiment, the body 901 of the device 940 has an accessory mounting structure having an opening 932-1 in which the accessory 906-1 is placed. By using the device 940, the accessory is in a desired position and orientation so as to be secured to the surface 936-3 of the tooth 934-1. The accessories 906-2, 906-3, 906-4 and 906-S are also placed in the openings 932-2, 932-3, 932-4 and 932-V on the surface 936-1 of the tooth 934-2, the surface 936-2 of the tooth 934-3 and the surface 936-T of the tooth 934-R, respectively. In such an embodiment, multiple accessories can be secured to one or more teeth. To save manufacturing time and material costs, the device can include multiple attachment locations, but only some of them may be used at any given time. In such applications, for example, device 940 may be used at one point in time to secure accessory 906-2 and may be reused at a different time to attach accessory 906-S at opening 932-V or at one or more other locations on the device (e.g., openings 932-1, 932-2, and / or 932-3). Fig. 9 Another feature of the illustrated embodiment is that, in order to save manufacturing time and material costs, a device with less material can be used. In such embodiments, the device can be designed to use a reduced or minimized amount of material in order to correctly place the accessory in the desired position.

[0341] Fig. 10A and 10B Another embodiment of a device that can be used to place an attachment on a tooth surface is shown. Fig. 10A A front view of a dental attachment placement structure for etching teeth is shown in accordance with various embodiments of the present disclosure. Fig. 10B Shows Fig. 10A Rear view of the dental attachment placement structure. Fig. 10A In the example of , body 1001 includes an opening 1024 formed in portion 1002-1. Opening 1024 has a specific shape 1022 that will allow etching of the attachment area (i.e., the area where the attachment will be attached) without etching other areas of the tooth when device 1020 is properly placed on the tooth. Fig. 10A The illustrated configuration allows a treating professional to place the device 1020 on a patient's teeth to provide a mask for etching to more accurately position and orient the placement of the attachment. Fig. 10BThe illustrated example includes multiple surfaces that can be used to assist in aligning the etching mask with the intended surface of the tooth to which the attachment is to be affixed. For example, in various embodiments of the present disclosure, one or more of surfaces 1012-1, 1012-2, 1012-10, 1012-M, 1014, 1016-1, 1016-2, 1016-10, 1016-N, 1018, and / or the interior surfaces of portions 1002-1 and / or 1002-2 can be utilized. The surface of the tooth can be etched with an etching material, for example, which a treating professional can brush onto the tooth surface through opening 1024. Fig. 10A and 10B In some embodiments, the size and shape of the shape 1022 of the opening 1024 is designed to be as large as or slightly larger or smaller than the attachment to be placed on the tooth. However, in some embodiments, the size and / or shape of the opening may be different from the surface of the attachment to be placed on the tooth.

[0342] Fig. 10C shows a front view of an etched area on a patient's tooth that has been Fig. 10A and 10B The dental attachment placement structure is etched. The resulting etched area 1006 is achieved through the attachment mounting structure shown in Figures A and 3B. In this way, an area can be etched on the tooth surface that is large enough to secure the attachment but not too large. Likewise, in this way, the attachment can be properly placed on the surface of the tooth 1034-3 and oriented to provide the desired force to the patient's teeth (e.g., 1034-1, 1034-2, 1034-3, 1034-R and / or other teeth of the patient) when combined with the dental appliance to be attached to the attachment.

[0343] Fig.11 FIG. 1 is a front view of a dental accessory placement structure 1100 having a plurality of accessory placement components provided thereon in accordance with various embodiments of the present disclosure. Fig.11 In an embodiment, the body 1101 of the device 1100 has an accessory mounting structure that includes a plurality of openings 1132-1, 1132-2, 1132-3, 1132-4, and 1132-V that can be used to etch portions of teeth 1134-1, 1134-2, 1134-3, 1134-R on surfaces 1136-1, 1136-2, 1136-3, and 1136-T. To save manufacturing time and material costs, the device can include multiple etching locations, and only some of them may be used at any given time. In such applications, the device 11110 can, for example, be used to etch one location on a tooth at one point in time and reused to etch another location on the tooth at another point in time.

[0344] Figure 2 A shows a front view of another dental attachment placement structure for etching teeth according to the present disclosure. Fig. 12A In the example of FIG. 1 , the device 1220 includes a body 1201 having at least one surface shaped to conform to one or more contours of the outer surface of a tooth. The body has multiple surfaces, 1202-1 and 1202-2, each of which is shaped to conform to multiple contours of the outer surface of a tooth. Some embodiments may have one or more similar Fig. 10B Other surfaces are shown to aid in the alignment of the dental attachment placement structure with the tooth. Fig. 12A In the example of FIG. 1 , surface 1202 - 1 is located on tooth surface 12312 - 1 , and surface 1202 - 2 is located on tooth surface 12312 - 2 .

[0345] Fig. 12B Shows the use of Fig. 12A A front view of a dental attachment placement structure of a dental attachment attached to a patient's tooth. The figure includes a tooth surface 1235-1 of a first tooth and a tooth surface 1235-2 of a second tooth, and an attachment 1206 mounted on the surface 1235-1.

[0346] Fig.13A A front view of another dental attachment placement structure for etching teeth according to the present disclosure is shown. Fig.13A An example is shown where the body 1301 of a dental attachment placement structure has an opening that does not completely surround the area to be etched. The body can be used as a guide for which area to be etched (e.g., areas 1374-1 and 1374-2), as well as a guide for placing one or more attachments (e.g., 1306-1 and 1306-2), but also allows the body 1301 to be removed after the attachment has been secured to the tooth surface (e.g., 1335-1 and / or 1335-2). For example, Fig. 13B Shows the use of Fig.13A A front view of a plurality of dental attachments attached to a plurality of teeth of a patient using a dental attachment placement structure. The figure includes a tooth surface 1335-1 of a first tooth and a tooth surface 1335-2 of a second tooth, and attachments 13013-1 and 13013-2 mounted on the surfaces 1335-1 and 1335-2, respectively. Fig. 13BAs shown, the position and orientation of the attachments 13013-1 and 13013-2 on the tooth surfaces 1335-1 and 1335-2 are the same as the position and orientation of the etched areas 1374-1 and 1374-2, so that the attachments 13013-1 and 13013-2 are better adhered to the tooth surfaces 1335-1 and 1335-2. This is because the attachments are placed at the openings of the body while they are on the tooth surfaces 1335-1 and 1335-2, and then removed after the attachments 13013-1 and 13013-2 are adhered to the etched areas 1374-1 and 1374-2.

[0347] Fig.14A A front view of another dental attachment placement structure for etching a tooth according to the present disclosure is shown. Fig.14A Examples with Fig. 12A The example is similar to Fig.14A In the example of , the device 1420 includes a body 1401 having at least one surface shaped to conform to one or more contours of the outer surface of a tooth. The body has multiple surfaces, 1402-1 and 1402-2, each of which is shaped to conform to multiple contours of the outer surface of a tooth.

[0348] Fig. 14B Shows the use of Fig.14A A front view of a dental attachment placed on a patient's tooth. The figure includes a tooth surface 1435-1 of a first tooth and a tooth surface 1435-2 of a second tooth, and an attachment 1406 mounted on the surface 1435-1. As shown in the figure, the position and orientation of the attachment 1406 on the tooth surface 1435-1 are the same as the position and orientation of the etched area 14144, so that the attachment 1406 is better adhered to the tooth surface 1435-1. Fig. 12A As with the embodiment of FIG. 12 , this is because the attachments are placed in the openings of the body 1401 while they are positioned on the tooth surfaces 1435 - 1 and 1435 - 2 , and then removed after the attachments 1406 have been adhered to the etched areas 1434 .

[0349] In some aspects, an attachment placement device and / or an attachment includes a body configured to place one or more attachments on a tooth of a dental arch, the body including a plurality of openings, the body also including a contoured surface for cooperating with one or more teeth of the dental arch to align each opening with a specific corresponding position on the surface of the tooth, wherein each opening has an attachment, the attachment being attached to one or more supports extending from the body, the supports being arranged radially relative to the attachment to support the attachment within the opening and align the attachment with the specific corresponding position. Each attachment may include one or more engagement surfaces configured to engage with an orthodontic dental appliance to apply force to one or more teeth. The supports of the attachment may be configured to disconnect from the attachment at or near a location where at least two supports and the attachment are connected. Examples of such attachment placement devices include those described in U.S. Patent Application No. 15 / 623,263, filed by Webber et al. on June 14, 2017, entitled "Dental Attachment Placement Structure," the contents of which are incorporated herein by reference as if fully set forth herein.

[0350] Figures 15A-17C Several embodiments are provided, each including a different support structure that establishes a connection between the main body of the dental attachment placement structure and the attachment. Each of these embodiments may have advantages for certain applications, and these differences and their advantages are discussed below.

[0351] like Figures 15A-17C In the embodiment shown and described, the accessory is located in the opening, and the dental accessory placement structure includes at least one support for connecting the accessory to the body. Fig. 15C As can be seen in the embodiment of the present invention, the attachment 1506 can be connected to one or more supports 1508. As shown, the direct connection can be curved to reduce or eliminate contact between the support and the tooth surface.

[0352] Such an arcuate shape may be beneficial, for example, because the treating professional may not need to operate the removal tool as close to the tooth as in embodiments where the support or the connection between the support and the attachment contacts the tooth surface. In some such embodiments, the support may be connected to the attachment so that it can be released from the attachment.

[0353] For example, in some embodiments, the connection between the accessory and the support may include a feature that facilitates the removal of the accessory from the support. The feature may be located at or near the transition area between the support material and the accessory material.

[0354] The feature can be, for example, a physical feature provided at the connection, such as one or more perforations, a portion that is thinner than the rest of the support and / or attachment, or a different material than the attachment and / or support, as well as other attachment separation structures discussed herein. The feature can also be the use of a specific material at the connection so that a stimulus can be applied to the material, thereby making the attachment easier to remove. For example, these materials can make the material more brittle, making it more likely to break, or cause the material to dissolve or decompose. Examples of stimuli include wavelengths of light, such as UV, or chemical materials that cause the above effects based on interaction with the support material at the connection between the attachment and one or more supports.

[0355] Once the attachment 1506 is separated from the body 1501, the attachment will remain on the tooth during part or all of one or more treatments (e.g., the attachment is secured to the tooth surface by an adhesive), and the dental attachment placement structure body will be removed from the patient's tooth. For example, this can be achieved by lifting the body portion over the attachment or cutting / breaking the body into pieces and removing it in this manner.

[0356] Embodiments also include a dental attachment placement structure that is connected to the dental attachment to hold the attachment in a specific position. A portion of the body has a contour shaped to correspond to a tooth alignment surface contour so that when the contour of the body and the corresponding contour of the tooth are aligned, the opening is located above a specific position on the tooth surface.

[0357] Fig.15A An oblique front view of a dental attachment placement structure according to multiple embodiments of the present disclosure is shown, wherein the structure is provided with an attachment placement component, fits against the tooth surface, and has a top surface. Fig.15A In the view of FIG. 1 , an attachment placement structure is shown that fits against the top, side, and anterior surfaces of the bottom of a tooth (along the gum line of the tooth). The illustrated structure shows the situation of the lower jaw, but such embodiments are not limited to use in the lower jaw. Fig.15A The accessory placement structure 1500 includes a main body 1501 having a plurality of toothed portions, at least one of which has an accessory 1506 connected thereto via a plurality of supports 1508 separated by one or more openings 1510.

[0358] Fig.15A An accessory 1506 is shown attached to the body 1501 via three supports 15015. Fig.15A A feature of the supports shown in is that they are arcuate along the elongated direction. This feature allows the surface of the support closest to the tooth to be farther from the tooth than the surface of the attachment closest to the tooth (i.e. the surface of the attachment to be attached to the tooth) is farther from the tooth.

[0359] In addition, if Fig.15A As shown in the embodiment of the present invention, the support can be tapered from a first thickness where it connects to the body 1501 to a second, thinner thickness where it connects to the attachment 1506. This is beneficial in many ways. For example, the thinning connection of the support at the attachment end provides more space for the placement of the removal tool, while the thicker end provides a more stable and solid support component during placement and separation.

[0360] Fig.15A The illustration of the embodiment in also shows that the body may not cover the entire front surface of the tooth adjacent to the tooth to which the attachment 1506 will be fixed. For example, an opening 1509 can be formed in a portion of the body, and the body portion covers a portion of the adjacent tooth.

[0361] Fig. 15B Shows Fig.15A An oblique rear view of a dental attachment placement structure 1500. In this view, the body 1501 of the structure 1500 has a plurality of tooth cavities for placing teeth therein. Fig. 15B In the example of FIG. 4 , four tooth cavities are shown, but the implementation is not limited to four teeth, and in different implementations, more or fewer tooth cavities may be provided.

[0362] Each cavity is formed by multiple surfaces of a structure that are adapted to contact corresponding surfaces of the tooth on which the cavity is to be placed. Fig.15A As shown, these surfaces may represent complete surfaces or partial surfaces of a tooth (eg, opening 1509).

[0363] The device includes a body 1501 having a toothed surface that is shaped to fit the front surface of the tooth and to be placed against the front surface of the tooth. The toothed surface of the body may include an opening (e.g., opening 1510) to allow an attachment to be placed at a specific location on the tooth surface. It should be understood that in some embodiments, the opening may not be completely closed around its edges. Such designs should be considered within the scope of embodiments of the present disclosure.

[0364] like Fig.15A As shown, Fig. 15B Also shown are openings 1510 that provide spaces between supports 15015. Fig. 15B In the embodiment of the present invention, the structure further comprises a first back portion 1514 which is attached to the back of the first tooth and a second back portion 15115 which is attached to the back of the second tooth. Fig. 15C As discussed, the surface of the structure may also be used in conjunction with the occlusal surface of the tooth to improve the alignment of the attachment prior to securing it to the tooth.

[0365] In addition, the reader should note that the surface on which the line of element number 1506 is placed is the surface of the attachment to be attached to the tooth. It is on this surface that the adhesive material will be placed (adhesive not shown). The adhesive can be applied to the entire surface or a portion thereof. The adhesive can be an ultraviolet (UV) curable adhesive or any other suitable type of adhesive that can be used to secure the attachment to the tooth surface.

[0366] In some embodiments, the attachment may, for example, include an adhesive layer that is positioned to secure the attachment to the attachment surface of the tooth. In some embodiments, the adhesive is only located on the portion of the attachment that will contact the tooth. In this way, the adhesive is less likely to secure other portions of the device to the tooth or create excess dried adhesive that may need to be removed from the tooth.

[0367] In some embodiments, the surface of the attachment that contacts the tooth may contain a recessed groove or pocket into which the adhesive may be applied. This controls where the adhesive is applied and avoids problems caused by excess adhesive, such as unwanted flash, unwanted adhesion of the placement structure support to the tooth.

[0368] In some embodiments, a release layer is provided over the adhesive. The release layer can be a plastic film, wax paper, or other suitable covering that can be removed by the treating professional when the attachment is placed on the patient's tooth. This can be beneficial, for example, to allow the adhesive to be applied at or shortly after the device is manufactured without exposing the adhesive to contaminants (e.g., dust) that could harden the adhesive or reduce its effectiveness.

[0369] Surface (e.g. Fig. 15C The use of 1514, 1518 and / or 1512) in combination with other surfaces can also allow the corners of one or more teeth to be used to assist in the placement and / or orientation of the attachment. The benefit of using corners is that they can be used to control the placement of attachments in more axes of motion than using the edge surfaces of the teeth.

[0370] Fig. 15C Shows Fig.15A Cross-sectional side view of a dental accessory placement structure. Fig. 15C Views of the above cavity shapes are also provided, as well as more details regarding the support 15015 and attachment 1506 and their connections.

[0371] As mentioned above about Fig. 15B As discussed, the cavity for placing the tooth is formed by multiple surfaces of the body 1501. For example, in Figures 15A-15CIn an embodiment of the present invention, the cavity is formed by an inner surface that fits against the front side of the tooth (e.g., buccal side), a surface 1512 that contacts and wraps around the incisal edge of the tooth (in this embodiment, the top surface of the tooth, but if the structure is designed for the upper jaw, it can be the bottom surface), and a surface 1514 that fits against the back side of the tooth (e.g., lingual side). In this way, when these three surfaces are in contact with the tooth, the attachment can be more accurately positioned for placement on the tooth.

[0372] Fig.16A An oblique front view of a dental accessory placement structure structurally provided with an accessory placement assembly according to various embodiments of the present disclosure is shown. Fig. 16B Shows Fig.16A Oblique posterior view of the dental accessory placement structure.

[0373] exist Fig.16A and 16B In the embodiment, structure 1600 includes an attachment 1606 connected by a single connecting member 1605 to four supports 1608, which are connected to the body 1601. In this type of embodiment, severing the connection to remove the appliance from the rest of the dental attachment placement structure provides several benefits.

[0374] For example, the connection is a single connection, which allows disassembly by simply disconnecting the attachment. In addition, by using a single connection, any residual material from the single connection member is located in one area of ​​the attachment, making it easier to remove excess material.

[0375] In addition, Figures 16A-16C In the embodiment shown, the connection is located at the top of the attachment, which makes disassembly and removal of any excess material easier, as the connection area is away from the tooth surface and more easily accessible. In addition, the presence of these supports only affects one surface of the attachment, thus preserving the integrity of all other attachment surfaces. This is important because these surfaces play a key role in orthodontic treatment and require a high degree of dimensional accuracy.

[0376] Any suitable number of supports may be used. Figures 16A-16C Four supports 1608 are used, but in other embodiments, for example, Figures 15A-15C and Figures 17A-17C In the illustrated embodiments, other numbers of supports are provided.

[0377] In some embodiments, the support function may be provided by a material that spans at least a portion of the area covering the front surface of the tooth. In such embodiments, an attachment may be attached to the material or one or more connecting members, e.g. Fig.16A A connecting member of the type shown at 1605.

[0378] In such embodiments, for example, material can be cut away to allow access to the connection between the connecting member and the accessory, thereby removing the accessory. In some embodiments, an irritant can be applied as described above. In such embodiments, for example, an irritant can be used to embrittle the material (or a portion thereof) and / or the connecting member or to dissolve the material and / or the connection, thereby removing the accessory therefrom.

[0379] Fig. 16C Shows Fig.16A Cross-sectional side view of a dental accessory placement structure. Fig. 16C The single connecting member 1605 connecting the attachment 1606 and the support 1608 is more clearly shown. Figures 16A to 16C As shown, in some embodiments, there is only one connection area between the accessory and the accessory placement structure. As mentioned above, this makes it easier to separate the accessory from the rest of the device, and / or there is less possibility of damaging the tooth or accessory during the separation process.

[0380] Fig.17A An oblique front view of a dental accessory placement structure structurally provided with an accessory placement assembly according to various embodiments of the present disclosure is shown. Fig. 17B Shows Fig.17A Oblique posterior view of the dental attachment placement structure.

[0381] like Fig.17A and 17B In the illustrated embodiment, at least one accessory mounting structure may have a support connected between the main body and the dental attachment. In this way, the support may be cut rather than a whole layer of material, thereby making it easier to release the attachment from the rest of the device.

[0382] For example, in Fig.17A and Fig. 17B In the embodiment of the present invention, the support for connecting the attachment 1706 to the main body 1701 of the structure 1700 can be formed separately, or can be formed as a sheet and then the openings, such as the openings 1710, are formed in the sheet. The sheet can be formed with the main body 1701 or attached to the main body after manufacture. The support structure can be as shown in FIG. Fig.17A and Fig. 17B As shown, or can be manufactured to fill the entire interior area of ​​the tooth interior shape of the body 1701, and then remove a portion of the support to form the opening 1707.

[0383] The body may also include additional attachment mounting structures (e.g., a second attachment mounting structure) for attaching one or more dental attachments to the outer surface of another tooth. This allows for further confirmation of the position of the appliance using more elements of the patient's mouth. For example, this is because the surfaces and edges of the device, when contacting the patient's mouth, may contact the surfaces and edges of one or more teeth at the surfaces and edges of the device.

[0384] For example, Fig.17A and 17B As shown, more than one attachment may be provided on the structure to be attached to the user's teeth. In such an embodiment, the support may be of the same type of configuration, such as Fig.17A The support 1708 in FIG. 1 may also be a different type of configuration (for example, a configuration from Figures 15A-15C of the support, and / or of the type in other embodiments described herein).

[0385] In some embodiments, there is more support material (e.g., Figures 15A-15C Compared with the thinner support, Figures 17A-17C A support structure of the device may provide benefits in certain embodiments. For example, a more stable structure may help better position the accessory due to its rigidity or other properties.

[0386] Fig. 17C Shows Fig.17A Cross-sectional side view of the dental attachment placement structure. Fig. 17C The arrangement of the support structure 1708 and the opening 1707 formed relative to the attachment 1706 and the body 1701 is better shown. In this embodiment, the support structure is not curved, which may be easier to manufacture and have other advantages, and its connection with the attachment 1706 is away from the surface that will contact the patient's teeth. As described elsewhere, this can facilitate easier removal of the attachment 1706 from the support structure 1708 and reduce the possibility of damage to the teeth during removal, among other benefits.

[0387] In some aspects, the accessory placement device and / or the accessory can include a minimal framework for accommodating one or more dental accessories. The minimal framework can include features for registering and accurately aligning and orienting the dental accessories relative to the tooth surface, as well as features for securing the dental accessories to the teeth. The attachment position on the teeth can be determined based on an orthodontic treatment plan using a virtual model of the patient's dental arch. Examples of such accessory placement devices include those described in U.S. patent application Ser. No. 16 / 366,686, filed on March 27, 2019, entitled "Dental Attachment Placement Structure," the contents of which are hereby incorporated by reference as if fully set forth herein.

[0388] As discussed herein, dental attachments are structures of a specific shape that are intended to provide a specific force to move one or more teeth of a patient. They can be used to move teeth directly (e.g., to move the teeth to which they are attached), or to move teeth indirectly (e.g., to act as an anchor and direct force elsewhere to move the teeth to another location in the patient's mouth). As described herein, the attachment can be used to apply force to one or more teeth when used in conjunction with, for example, a cavity formed in an orthodontic appliance. The cavity can be shaped to have at least one surface that contacts a surface of the attachment, and the orthodontic appliance provides a force to the attachment, which is then used to move one or more teeth. In order to accurately apply the force, the attachment should be placed in an accurate location on the tooth surface and oriented toward the tooth in a specific direction so that when the orthodontic appliance is placed on the tooth, the dedicated cavity with an inner surface will contact the desired surface of the attachment in a manner that allows the desired force to be accurately applied with the desired force vector.

[0389] In some cases, attachments are configured to be used with an aligner to replace or supplement an appliance. For example, an attachment may be designed to engage with an elastic band or brace to provide more leverage and greater force on the teeth. In one specific example, the attachment includes a hook or slot into which the elastic band can hook. Such attachment features are sometimes referred to as power arms or buttons. The elastic band can hook onto two attachments to apply a pulling force to pull the two attachments together. Accurate positioning and orientation of such attachment features on the tooth surface may be important in order to apply the force in the desired direction.

[0390] The accurate positioning of the attachment is referred to herein as registration, which describes the condition of correct alignment or proper relative position and orientation relative to the tooth surface. The term can be used to describe the proper positioning of the attachment, and can also be used to describe the proper fit between the attachment placement structure and the tooth surface or edge used to ensure the correct positioning and orientation of the attachment placement structure. As described herein, this can involve the use of a contour surface with unique undulations or grooves on the attachment placement structure, which matches the unique undulations or grooves of the patient's specific tooth surface, wherein registration refers to the alignment of the undulations or grooves of the attachment placement structure surface with the undulations or grooves of the tooth surface, which, when aligned, indicates that the attachment placement structure is in the correct position and orientation for placing one or more attachments. The contour surface can be formed based on a computer model (e.g., 3D or 2D) of at least a portion of the patient's dentition. In some cases, the more features (e.g., the number of undulations, grooves, tooth surfaces, tooth edges, surfaces or edges of other teeth), the more accurate the positioning and orientation of the attachment.

[0391] In some embodiments, the accessory placement structure is formed together with one or more accessories attached thereto. This technique is particularly useful in some such embodiments because both can be manufactured in the same process. For example, the accessory placement structure and the accessories can be formed together using one or more of an additive manufacturing (3D printing) process, a subtractive manufacturing process (e.g., machining, cutting, milling, drilling, or etching), and a molding process.

[0392] In some embodiments, the body of the accessory placement structure can be in the form of a frame, with one or more accessories extending from the frame. In addition to the accessories, the frame can also support other features for placing and aligning the accessory placement device on the dental arch. For example, one or more registration anchors for registering the position of the accessory can also extend from the frame. In some embodiments, one or more retention supports for supporting the position of the accessory placement device extend from the frame.

[0393] One advantage of such a framework structure is that the accessory placement device can be made with a minimal amount of material and may be easier to manufacture. In some cases, the accessory placement device can be 3D printed without the use of supports used in traditional 3D printing processes. This can eliminate the need to remove such supports after the printing process, thereby reducing manufacturing time and costs. Thus, a portion of the accessory placement device can have a surface with a shape corresponding to the build plate used in the 3D printing process. In some cases, the surface is (e.g., substantially) flat. The framework structure can also make it easier to access portions of the dental arch when placing accessories because the framework takes up less space around the teeth than an accessory placement structure that covers and obscures more of the dental arch. Thus, a treating professional can access portions of the teeth and / or gums that cannot be accessed using a placement device with higher coverage.

[0394] Fig.18AA front view of a dental attachment placement structure according to various embodiments of the present disclosure is shown. The illustrated structure includes a plurality of components that, when used together, facilitate accurate positioning and orientation of one or more attachments on one or more buccal tooth surfaces of a dental arch 1840. The feature shown in the figure is a frame 1810 that is configured to extend over at least a portion of the dental arch. The frame can be a solid structure that follows the shape of a patient's dental arch or a portion of the dental arch. The frame can support one or more extension structures that cooperate with the frame to position one or more dental attachments (examples of which are identified as 1802-1, 1802-2, 1802-3, and 1802-4) to a predetermined tooth surface location. The dental attachment can be connected to the frame by one or more attachment supports (examples of which are identified as 1803-1 and 1803-4). This can allow the dental attachment to extend a certain distance from the frame and reach a predetermined position on the corresponding tooth surface. If multiple attachments are used, the attachment supports can extend in the same direction relative to the frame. For example, the attachment support can extend downward (or upward) from the frame to position the support below (or above) the frame.

[0395] A dental attachment is removably connected to an attachment support so that the attachment can be removed from the dental attachment placement structure, for example, after the attachment is secured to the tooth surface. The attachment can be attached to the attachment support at an interface area between the attachment and the attachment support. The interface area can be configured to facilitate disassembly. For example, the attachment support can have a thicker end near the frame and gradually become thinner in the interface area to make it easier to disassemble. In some embodiments, disassembly is accomplished using a disassembly tool, as described herein. In many embodiments, the interface area is sufficiently brittle that the attachment can be broken from the attachment support without the use of a disassembly tool. In some cases, a user can disassemble the attachment by applying compression, tension, or pressing force to the attachment (e.g., by hand).

[0396] The framework may also include one or more alignment anchors (examples of which are identified as 1801-2, 1801-3, and 1801-4) that extend from the framework and include contact surfaces that align with the corresponding one or more teeth. When the contact surface of the alignment anchor is aligned with the corresponding tooth, the dental attachment may also align with the corresponding tooth surface. In some cases, the alignment anchor contact surface is designed to fit the undulations and / or grooves of the corresponding surface of the one or more teeth. The contoured surface can be adapted to fit the surface of one or more teeth of any type, for example, one or more incisors, canines, premolars, and molars. The contoured surface can be adapted to fit any side of the tooth, for example, one or more of the lingual, occlusal, buccal, and distal surfaces. In some embodiments, the alignment anchor may at least partially wrap around the incisal edge of the tooth. The alignment anchor may and extend to cover multiple sides of the tooth, for example, portions of the top (e.g., crown), buccal, and / or lingual sides of the corresponding tooth. In Fig.18A In the example shown, the registration anchors extend over the apical and buccal sides of the corresponding teeth.

[0397] In some cases, the dental attachment is configured to be attached to the same tooth that the registration anchor is configured to contact. For example, attachment 1802-4 is aligned with the surface of tooth 1811-4, and tooth 1811-4 is the same tooth that registration anchor 1801-4 is aligned with. In some cases, the registration anchor is configured to be aligned with a tooth different from the tooth to which the dental attachment is configured to be attached. For example, attachment 1802-1 is aligned with the surface of tooth 1811-1, which is different from tooth 1811-2 that registration anchor 1801-3 is aligned with. The registration anchor can be configured to be aligned with multiple teeth. For example, registration anchor 1801-3 can be adapted to be aligned with the surfaces of tooth 1811-2 and tooth 1811-3. When one or more registration anchors are properly placed and aligned to the corresponding tooth surfaces, the dental attachment placement structure can be properly aligned with the dental arch, and the attachment can be accurately positioned relative to the tooth surface.

[0398] Fig.18B Shows Fig.18A1802 is a close-up view of an accessory portion of a dental accessory placement structure. In this example, the accessory support 1803 extends indirectly from the frame 1810 via the registration anchor 1801. This configuration allows the accessory 1802 to be connected to the same tooth as the registration anchor 1801 is registered. In the example shown, the registration anchor 1801 includes a clearance 1815 to provide proper positioning of the accessory 1802 without interference from the registration anchor 1801 and / or the accessory support 1803. The shape and depth of the clearance 1814 can vary depending on the desired tooth position of the accessory 1802. The thickness and height 1814 of the registration anchor 1801, as well as its offset from the tooth, can also vary depending on the desired placement location of the accessory 1802. In some cases, the clearance 1815 provides a treating professional with room to maneuver around the accessory 1802 during, for example, securing the accessory 1802 to the tooth.

[0399] In addition to extending the accessory downward or upward in a direction away from the frame and toward the tooth, the accessory support can also align the attachment surface (e.g., 1830) of the accessory with the tooth surface. In some cases, the accessory support directs the attachment surface (e.g., 1830) in the direction of the midline of the frame. For example, the accessory support can have an arcuate shape that orients the accessory so that the attachment surface is approximately parallel to the target tooth surface. In other embodiments, the accessory support has an inclined shape. Such an arcuate or inclined shape can also provide space for a user's hand or a removal tool to access the accessory for removal because the arcuate shape can bend outward. The shape and size of the dental attachment 1802 can vary depending on the desired force characteristics and the shape and type of the corresponding dental appliance (e.g., braces), as described herein.

[0400] In some embodiments, the dental accessory placement structure includes one or more retention supports extending from the frame and configured to hold the dental accessory in a predetermined position. Fig. 18C and 18D Shown on the dental arch Fig.18A1806-1, 1806-2, and 1806-3. The retention support may include a contact portion 1812 configured to contact one or more teeth and / or gums of a dental arch. In the example shown, the shape and size of the contact portion 1812 are designed to contact the interproximal area between the teeth. The contact portion may have any shape. In some cases, the contact portion has a generally spherical shape, as shown. Other non-limiting examples of shapes may include polyhedrons (e.g., tetrahedrons or cubes), cones, cylinders, and ovals. The retention support may include an arcuate or inclined portion that extends the tooth contact portion a distance from the frame. For example, the retention support may include a horizontal portion 1809 extending in a horizontal direction relative to the frame 1810, and a vertical portion 1807 extending in a vertical direction relative to the frame 1810, which positions the tooth contact portion 1812 on a surface (e.g., lingual side) of the dental arch.

[0401] In some cases, the retention support extends from a different side of the frame than the accessory support. For example, the retention support may extend from a first side of the frame, while the accessory support may extend from a second side of the frame. Fig. 18C and Fig.18D In the example shown, the retention support extends from the lingual side of the framework so that the retention support can contact the lingual portion of the dental arch, and the accessory support (e.g., 1803) extends from the buccal side of the framework so that the accessory (e.g., 1802) can be positioned on the buccal surface of the tooth. The retention support can support the lingual side of the framework to stabilize the position of the dental accessory placement structure on the dental arch in three-dimensional space.

[0402] The shape and size of the frame (e.g., 1810) can be designed to fit at least a portion of the dental arch. In some cases, the frame is in an arcuate shape (e.g., U-shaped) that matches the dental arch. In other embodiments, the frame covers only a portion of the dental arch. The frame can be a continuous portion or include multiple portions connected together. The portions can have a curved (e.g., arcuate) shape, or can be linear and connected together to form a generally curved (e.g., arcuate) shape. Although the illustrated example shows that the frame 1810 is adapted to match along the occlusal surface of the tooth (e.g., the top of the dental arch), other variations are also covered by the present disclosure. For example, the frame can be designed to match along the lingual and / or buccal sides of the tooth (e.g., the inner and / or outer sides of the dental arch). In some embodiments, the frame is designed to match along multiple sides of the tooth (e.g., two or more of the occlusal, lingual, and buccal sides). In some cases, the dental attachment placement structure includes more than one frame. For example, two or more frameworks can be designed to mate along one or more of the occlusal, lingual, and buccal sides of the teeth.Such variations can be included in any of the dental attachment placement structures described herein.

[0403] In some embodiments, the registration anchor is only registered with a portion of the teeth in the dental arch. In some examples, two or more registration anchors are used to make the framework span one or more teeth. For example, the registration anchors 1801-4 and 1801-5 extend from the framework 1810 so that they are separated by a gap portion 1810-1 of the framework. The registration anchors 1801-4 and 1801-5 are configured to be registered with non-adjacent teeth so that the gap portion 1810-1 of the framework spans teeth 1811-5 and 1811-6. This can make the gap portion 1810-1 of the framework suspend above the dental arch and position the dental attachments 1802-5, 1802-6 and the retention supports 1806-2, 1806-3, 1806-4 on their respective target teeth. This allows the dental attachment placement structure to block the dental arch less than a dental attachment placement structure that covers more tooth surfaces. For example, the treating professional may more easily access areas around intervening teeth 1811-5 and 1811-6 in order to attach accessories 1802-5 and 1802-6.

[0404] As described herein, a dental accessory placement structure can be formed using additive manufacturing technology. In some cases, this involves printing portions of the dental accessory placement structure on a build plate (sometimes referred to as a build platform or base plate) of an additive manufacturing machine without the use of a support. As is well known, manufacturing supports are often used in 3D printing to support 3D objects on the build plate during the printing process. Such manufacturing supports are typically used to support portions of 3D objects, such as overhangs, which are susceptible to deformation during the printing process and are generally removed from the 3D object after printing is completed. Such manufacturing supports require additional material to be added and increase the manufacturing time and cost of removing the support. In some embodiments, the dental accessory placement structure does not use a manufacturing support when printing, thereby saving materials, time and costs. Fig. 18C In the example shown, the framework 1810 can have a surface 1850 (e.g., a top or bottom surface) that can be formed on a build plate without the use of a manufacturing support to provide the above advantages. Surface 1850 can be a substantially flat surface that is consistent with a flat build plate surface. Flat surface 1850 can correspond to a top (or bottom) surface of a dental accessory placement structure, wherein an accessory support (e.g., 1803) and / or a retention support (e.g., 1806-1, 1806-2, 1806-3, 1806-4) extends relative to the bottom (or top) surface of the framework. In some cases, portions of the accessory support and / or retention support can also be constructed on the build plate and have corresponding flat surfaces.

[0405] To use the dental attachment placement device, the treating professional may position one or more registration anchors on the corresponding tooth surfaces. Figures 18A-18D In the illustrated embodiment, the registration anchor begins at the frame and extends until the anchor covers at least a portion of the incisal edge and extends over one or more sides of the corresponding tooth. This positions one or more dental attachments against the corresponding tooth surface at a predetermined position. One or more retention supports may also be positioned (in some cases, registered) on the surface of one or more teeth (e.g., on the lingual side of the dental arch) to maintain the position of the dental attachment. The dental attachment may be secured to the predetermined position on the tooth surface using one or more adhesives, such as those described herein. The dental attachment may be removed from the dental support so that only the dental attachment in the structure remains coupled to the patient's dental arch.

[0406] Fig.18E Shows Fig.18A A perspective view of a dental accessory placement structure in a toothless state, showing multiple aspects of the various contact portions (e.g., 1812-1 and 1812-2) of the retention support. Fig.18FA close-up view of the contact portion 1812-3 is shown. The contact portion can be configured to be placed in an interproximal region 1855 between adjacent teeth. The contact portion can include one or more fitting surfaces (e.g., 1856-1 and 1856-2) that are configured to fit the shape of the teeth and / or gums. The fitting shape enables the contact portion to grip the surface of the dental arch (e.g., on the lingual side). The shape of the contact portion 1812 can be determined based on a virtual model. For example, a virtual sphere (or cone, tetrahedron, etc.) can be placed in a virtual model of the interproximal region (based on a scan of the patient's dentition) and the area where the teeth are located is subtracted from the virtual sphere. In this process, in some embodiments, the gums are also taken into account. In some cases, the virtual model of the gums can be enlarged by a scaling factor (e.g., making the gums 10% larger), so that any portion of the virtual sphere that contacts the enlarged gums is subtracted from the sphere. In this way, the contact portion of the retention feature can be shaped so that its surface matches the surface of the tooth to be contacted and does not interfere with (e.g., contact) the gums, which may cause discomfort to the patient. In some embodiments, the contact portion of the retention feature includes one or more chamfered surfaces (e.g., 1857), for example, to reduce the amount of protrusion of the contact portion from the dental arch, which can also increase patient comfort.

[0407] Figure 18G and 18H Shows Fig.18A An alternative view of a dental attachment placement structure in which the dental attachment and retention support are removed in order to more closely examine and discuss certain features and to aid the reader's understanding. One or more registration anchors (e.g., 1801-1, 1801-2, 1801-3, 1801-4, and 1801-5) can be configured to align with one or more corresponding anchor teeth (e.g., 1815-1, 1815-2, 1815-3, 1815-4, 1815-5, and 1815-6). According to some embodiments, the buccal side 1813 (i.e., the highest point on the buccal surface of the tooth) of one or more anchor teeth can be used as the outermost limit of the dental attachment placement structure. The thickness (e.g., 1880) and width (e.g., 1882) of the framework (or portion of the framework) can be varied so that the distance between the framework and the buccal side 1813 is as small as possible, thereby minimizing the distance between the framework and the dental arch.

[0408] In some embodiments, one or more portions of the dental attachment placement structure are flexible to reduce stress concentrations in portions of the structure. Since the dental attachment placement structure can be made of brittle materials (e.g., certain composite materials), this flexible feature can make the structure more resilient and less prone to breaking while still being made of a material with desired properties (such as stiffness). The flexible feature can reduce the amount of breakage that occurs to the structure during handling (e.g., during manufacturing and transportation). Having a flexible feature can allow more structures to be printed in each 3D printing run (e.g., on a build plate). The flexible feature can also allow the structure to bend in a way that reduces the size of the structure, allowing for more efficient packaging. The flexible feature can also provide a certain tolerance, making it easier for the structure to fit the patient's dental arch. Figure 18G-18K Variations of dental attachment placement structures 18A with various flexibility features according to some embodiments are shown. For simplicity, Figure 18G-18K Certain features are not shown, such as dental attachments and retention supports; however, these features may be included.

[0409] Figure 18G A top view of a dental attachment placement structure is shown, wherein a portion 1810-1 of the frame is modified to have a sawtooth or "Z" shape as an alternative to an arc. In other variations, the flexible portion may have a sinusoidal or "S" shaped pattern. This geometry may allow the flexible portion 1810-1 to bend or twist under a force (e.g., push, pull, twist) applied to the frame, thereby dispersing stress and reducing stress concentration. Depending on specific needs, one or more portions 1810-1, 1810-2, 1810-3, and 1810-4 of the frame may include such a modified curved geometry. These types of changes in frame geometry allow the frame (or portions thereof) to be flexible without changing the frame material. That is, the flexible portion 1810-1 may be made of the same material as one or more portions 1810-2, 1810-3, and 1810-4 of the frame, the attachment support, the attachment support, and the retention anchor. This solution may be more cost-effective than manufacturing structures using different materials with different degrees of flexibility.

[0410] Fig.18J and 18K Shows an alternative Fig.18A The connecting joint of the middle arc-shaped frame part. The connecting joint may include mutually meshing connecting parts, for example, Figure 18K1870 and the second connector 1872 are marked in the figure. The connecting joint can include any number of intermeshing connectors (e.g., 2, 3, 4, 5, 6, 10, 20). The intermeshing characteristics of the connecting joint can allow the individual connectors to move relative to each other while still remaining connected to each other. As with the sawtooth or sine wave geometry, the connecting joint geometry can provide flexibility to the frame portion 1810-3 to resist breaking when force (e.g., pushing, pulling, twisting) is applied to the frame. The connecting joint can be placed anywhere along the frame as desired, including one or more portions 1810-1, 1810-2, 1810-3 and 1810-4 of the frame. It should be noted that the connected connecting joint geometry can be efficiently formed by a 3D printing process, so that the intermeshing connectors (i.e., connected) can be fully formed.

[0411] The dental attachment placement structure may have a flexible portion in addition to the frame. Figure 18L The device is shown with flexible attachment supports 1803-4, 1803-5 and 1803-6. Fig.18A An alternative variation of the structure. Unlike the accessory support (e.g., 1803-3) that tapers from a thicker diameter near the framework to a thinner diameter near the attachment, the flexible accessory support can have a thinner diameter and have a sinusoidal waveform or sawtooth shape, which can provide greater flexibility and resilience when subjected to external forces (e.g., pushing, pulling, twisting). The accessory support with greater flexibility can also allow the therapist to have more maneuverability with the attachment (e.g., 1803-4) during placement and fixation of the attachment, and can reduce the risk of the accessory support accidentally adhering to the tooth surface. The flexible accessory support can have any shape and is not limited to Figure 18K , or a sine wave or sawtooth shape as shown in . For example, a spring (e.g., a spiral), an arc, a bow, or a hook shape can also provide the desired amount of flexibility. The dental accessory placement structure can have any number of flexible accessory supports (e.g., 1, 2, 3, 4, 5, 8, 10). In some cases, one or more retention supports (e.g., 1806-1) can have a flexible geometry (e.g., a sine wave or sawtooth shape -

[0256] ).

[0412] According to some embodiments, the material forming one or more features of the dental attachment placement structure provides flexibility. Fig.24A perspective view of an example of a mesh structure is shown that can be incorporated into one or more parts of any dental attachment placement structure described herein. The mesh structure can contain cavities that can increase flexibility and / or reduce material consumption and weight of the structure. The mesh structure is incorporated into one or more parts of a dental attachment placement structure, such as a frame, registration anchors, attachments, attachment supports, retention supports, or other parts. Therefore, the rigidity or flexibility of these elements can be adjusted according to the desired implementation.

[0413] Dental attachment placement structures may include Figure 18G-18L and any combination of the flexible features of FIG. 18. For example, the structure may include one or more flexible frame portions 1819 (e.g., Fig.18I ), one or more flexible attachment supports 1821 (e.g., Figure 18L ) and / or one or more flexible retention supports. The number of flexible features can vary depending on specific needs. Generally, the structure can have a certain flexibility to resist breakage when placed on the patient's dental arch, and have sufficient rigidity to support and hold the attachment. In some embodiments, the flexible feature is made of the same material as the rest of the structure, as described above. The increase in flexibility can be at least partially due to the shape; for example, shapes such as sine waves, sawtooths, etc. can be used. In some embodiments, the flexible feature is made of a different material (e.g., more flexible) than the rest of the structure.

[0414] As described herein, a dental attachment placement structure can be formed based on a virtual model. According to some embodiments, the position and orientation of the frame and other structural features are determined based on the position of the dental attachment in the virtual model. Figure 18M and 18N shows how to form a virtual model Fig.18A An example of the features of a dental attachment placement structure. Figure 18M A side perspective view of the structure is shown, showing how the accessory support 1804-5 supporting the accessory 1802-05 includes a base portion 1809-5 and a bridge portion 1809-5. Although not required in all embodiments, the base portion 1809-5 can be a solid, extruded circular structure. The diameter and thickness of the accessory support can vary. The base portion 1809-5 can be thicker (e.g., diameter) than the bridge portion 1808-5.

[0415] To determine the position and orientation of the framework 1810, the center of the attachment 1802-3 can be located and projected vertically until it intersects the plane of the framework 1810. This point can be used as a reference (e.g., corresponding to the center of a circle) for creating the base portion 1809-5, thereby informing the position and orientation of the framework 1810. The bridge portion 1809-5 can be shaped to connect the base portion 1809-5 to the framework or alignment anchor. Similarly, the dental attachments 1802-4 and 1802-5 can also be used to create corresponding base portions and bridge portions to connect the attachment supports 1804-4 and 1804-5 to the framework or alignment anchor, as well as the remaining dental attachments and attachment supports until the position and orientation of the entire framework 2101 is determined. During, for example, a 3D printing process, the attachment support can be located directly below the dental attachment. Fig.18N Different perspectives of the base portion 1809 (without the bridging portion) of the accessory holder relative to the corresponding accessory 1802 are shown.

[0416] Fig.19A showing a buccal view of an alternative dental attachment placement structure according to various embodiments, Fig.19B A lingual view of the structure is shown. A dental attachment placement structure may have a structure similar to Fig. 12A -12N dental accessory placement structure features, for example, a frame 1910, one or more accessories (e.g., 1902-1 and 1902-2), one or more accessory supports (e.g., 1903-1 and 1903-2), one or more alignment anchors (e.g., 1901-1, 1902-2, and 1901-3), and one or more retention supports (e.g., 1906-1 and 1906-2). The one or more retention supports may include a contact portion (e.g., 1912-3), a horizontal portion 1909-3 extending in a horizontal direction relative to the frame 1910, and a vertical portion 1907-3 extending in a vertical direction relative to the frame 1910.

[0417] like Fig.19AAs shown, the accessory can be supported by an accessory frame (e.g., 1920) that is attached to an accessory support (e.g., 1903-1) and can at least partially surround the periphery of the accessory (e.g., 1902-1). The accessory can be connected to the accessory frame via one or more struts (e.g., 1925), which can correspond to fragile portions of the accessory frame. For example, the interface area between the strut and the accessory can be sufficiently fragile so that the accessory can be removed from the accessory frame without using a removal tool (e.g., the user's hands). In some cases, the strut has a tapered geometry, with its thickness gradually tapering from the accessory frame to the accessory. The accessory frame can include any number of struts (e.g., 1, 2, 3, 4, 5, 10, 20). In some cases, the strut at least partially surrounds the periphery of the accessory to keep the accessory in place within the accessory frame. The accessory frame can be configured to protect the accessory and / or the strut from being removed and / or damaged during manufacturing, handling, and transportation.

[0418] like Fig.19B As shown, one or more retention supports (e.g., 1906-1 and 1906-2) may be configured to contact a tooth surface (e.g., a single tooth) between interproximal regions. In some cases, one or more retention supports are configured to contact a crown surface of one or more teeth. This non-interproximal region contact configuration can provide greater retention by increasing surface contact with one or more teeth. In addition, this can provide a more accurate registration surface for the contact portion (e.g., 1912-3) because, in some cases, a digital scan of the interproximal region may not be as accurate as a scan of the tooth surface between the interproximal regions. In some embodiments, the dental accessory placement structure includes a combination of the following parts: one or more retention supports configured to contact one or more interproximal regions and one or more retention supports configured to contact a tooth surface between one or more interproximal regions.

[0419] Fig.19C Shows Fig.19A A top view of a dental accessory placement structure showing an identifier 1940 according to some embodiments. The identifier can be a device identifier 1940 that uniquely identifies a model, batch number, specific device, patient, or other identifying feature of a dental accessory placement structure. The identification can include one or more numbers, letters, and symbols. In some cases, the identifier is integrated into the device during the manufacturing process. For example, the identifier can be added in a virtual model of the dental accessory placement structure so that the identifier is integrated into the structure when 3D printed. In some cases, the identifier is added after the dental accessory placement structure is formed.

[0420] Fig.19D Shows Fig.19A1 , which shows an exemplary attachment surface 1950 of an attachment 1902-2 according to some embodiments. The attachment surface can be a textured surface to provide more surface area and increase the shear bond strength between the attachment and the surface of the target tooth. In some embodiments, the textured surface is a grid pattern, such as Fig.19D . Other variations of the textured surface can include one or more lines or strips (e.g., horizontal, vertical, diagonal and / or radial), cross-hatching, circles, zigzags, sinusoidal waves, and polygonal (e.g., squares, rectangles, triangles, hexagons) patterns. In some cases, the textured surface is added to a virtual model of the dental attachment placement structure and integrated into the structure during the manufacturing (e.g., 3D printing) process. In some cases, the textured surface is added after the dental attachment placement structure is formed.

[0421] In some embodiments, one or more of the dental attachments include auxiliary features to provide specific functions according to the treatment plan. The one or more auxiliary features can be used in conjunction with one or more orthodontic appliances (such as aligners, elastic bands, braces and / or brackets) to apply prescribed forces to the patient's teeth. According to some embodiments, the dental attachment placement structure includes an attachment with integrated auxiliary features to make it easier and more accurate to place the auxiliary features on the dental arch. Examples of auxiliary features may include one or more of power arms, hooks, buttons, springs, braces, brackets, wires, rods, bands, blades, coils, elastics, rings, tracks, connectors, and chains.

[0422] Fig. 20A and Fig. 20B A side view of an exemplary dental attachment with a powered arm assist feature attached to a dental arch using a dental attachment placement structure 2000 is shown. The dental attachment placement structure 2000 may include Fig. 12A -12N and 13A-13D have similar features to the structures, for example, one or more frames (e.g., 2010), one or more dental attachments (e.g., 2022 or 2024), one or more alignment anchors (e.g., 2042 or 2044), and one or more retention supports. One or more attachments may include auxiliary features (e.g., 2052 or 2054) extending from the attachment. In the example shown, the auxiliary features are elongated hooks, also referred to as power arms. In some cases, the auxiliary features are added to a virtual model of the dental attachment placement structure and are formed integrally with the structure (e.g., using 3D printing). The placement, size, angles, and other aspects of the auxiliary features can be determined (e.g., calculated) according to the desired movement of the teeth based on the treatment plan.

[0423] Once the dental attachment placement structure is formed, it can be positioned on the patient's dental arch, e.g. Fig. 20A As shown. For example, the alignment anchors 2042 and 2044 can be placed on corresponding teeth 2070 and 2072, respectively, and adjusted to align therewith. A retention support (if any) can also be positioned on the opposite side of the dental arch (e.g., the lingual side) to provide support. Once aligned in the predetermined position of the tooth, the accessory can be secured to the tooth using the methods described herein (e.g., using an adhesive). At the interface area (e.g., 2062 or 2064) between the accessory and the accessory support (e.g., 2065 or 2066), the accessory and auxiliary features can be removed from the dental accessory placement structure. In some embodiments, the interface area can be fragile so that the accessory can be removed without a removal tool. In some embodiments, the accessory is configured to be removed using a removal tool.

[0424] Fig. 20B A dental attachment with an auxiliary feature on a corresponding tooth is shown after the dental attachment placement structure is removed and the elastic band 2090 is hooked onto the auxiliary feature. In some embodiments, the auxiliary feature is configured to extend above (or below) the gum line so that a portion of the auxiliary feature extends in the direction of the gums 2074 and the root of the tooth. This can allow the auxiliary feature to increase the moment arm of the auxiliary feature, which is desirable in certain power arm applications. For example, the longer the auxiliary features 2052 and 2054, and the higher the position of the band 2090 on the auxiliary features 2052 and 2054, the greater the pulling force that pulls the teeth 2070 and 2072 closer to each other. In some embodiments, the attachment (e.g., 2022 or 2024) and / or the auxiliary feature (e.g., 2052 or 2054) are also used in conjunction with one or more additional orthodontic devices (e.g., braces) to move the teeth in the dental arch according to the treatment plan.

[0425] Fig.21 Another example of an application of a dental attachment with auxiliary features is shown. A first auxiliary feature 2152 can be attached to a first dental attachment 2122 on a tooth of a patient's first dental arch 2103. A second auxiliary feature 2154 can be attached to a second dental attachment 2124 on a tooth of a patient's second dental arch 2101. An elastic band 2190 can be hooked onto the first and second auxiliary features to provide a pulling force to pull the corresponding teeth toward each other. The angle of the first auxiliary feature and the second auxiliary feature can be varied depending on the direction of the desired force. In some embodiments, the attachments and / or auxiliary features are also used in conjunction with one or more additional orthodontic devices (e.g., one or more braces) to move teeth in the first and / or second dental arches according to a treatment plan.

[0426] Fig.22AAnother example of a dental attachment with an assist feature is shown.A dental attachment (eg, 2222 or 2224) can include an assist feature (eg, 2252 or 2254) in the form of a button. Fig. 22B An exemplary cross-sectional view of a button assist feature 2254 is shown, showing a groove 2280 into which an elastic band 1590 can be hooked. The elastic band 1590 can be hooked onto the button assist features 2252 and 2254 to apply tension to corresponding teeth on opposing dental arches 2201 and 2203. In some embodiments, the attachments and / or assist features are also used in conjunction with one or more additional orthodontic devices (e.g., one or more aligners) to move teeth in the first and / or second dental arches according to a treatment plan.

[0427] In some embodiments, auxiliary features and accessories are supported by an accessory frame, e.g. Fig.23 As shown in the example of . A dental accessory (e.g., 2320) with an auxiliary feature (e.g., 2350) attached thereto can be supported by an accessory frame (e.g., 2355) that is directly or indirectly connected to the frame. In some cases, the accessory frame is directly or indirectly connected to the frame via an accessory support (e.g., 2365) extending from the frame. The accessory frame can surround at least a portion of the accessory and / or auxiliary feature and be connected to the accessory and / or auxiliary feature via one or more struts (e.g., 2358). In some embodiments, one or more struts are frangibly connected to the accessory and / or auxiliary feature to facilitate removal (e.g., with or without a removal tool). One or more struts can have a tapered geometry.

[0428] As described herein, the dental attachment placement structure described herein can be made of one material or a combination of multiple materials. In some cases, the dental attachment placement structure can be formed by one or more polymers (e.g., polyester, copolyester, polycarbonate, thermoplastic polyurethane, polypropylene, polyethylene, polypropylene and polyethylene copolymers, acrylic acid, cyclic block copolymers, polyetheretherketone, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polyethersulfone, polytrimethylene terephthalate, or a combination thereof). In some embodiments, the dental attachment placement structure can be made of a second material different from the attachment material. For example, the attachment can be made of a composite material, and the dental attachment placement structure can be made of a polymer (e.g., those discussed above). In some embodiments, the attachment and the dental attachment placement structure can be constructed to be connected to each other. As discussed herein, this connection can be designed to be cut, broken, or otherwise released so that the dental attachment placement structure can be removed while the attachment is positioned on the tooth.

[0429] Fig.25AAn exemplary dental attachment 2501 is shown coupled to a plurality of teeth of a dental arch 2500. The dental attachment 2501 may be designed to engage with a portion of a dental brace to apply forces to the teeth in accordance with a dental treatment plan. The dental brace may be a polymer shell brace configured to interact with the dental attachment 2501 to reposition (e.g., straighten) the teeth. The dental attachment 2501 may be placed at a predetermined location on the teeth in accordance with a portion of the dental treatment plan to apply an appropriate force (e.g., in magnitude and / or direction). In some cases, the dental treatment plan includes replacing the dental attachment 2501 with a different set or sets of dental attachments during the treatment planning process. For example, a subsequent set of dental attachments may have a different shape and / or be positioned at a different location on the teeth and / or on different teeth than a current set of dental attachments 2501. In other cases, the same set of dental attachments 2501 is used throughout the treatment plan.

[0430] Fig.25B An exemplary dental attachment placement device 2502 is shown that can be used to properly place dental attachments 2501 so that they can cooperate with dental braces to apply the correct force on the teeth. The dental attachment placement device 2502 can include a body 2503 (also called a locator), which can be configured to be placed against the tooth surface of the dental arch. In some cases, the body 2503 is configured to contact the occlusal surface of the tooth and extend beyond the occlusal surface to contact the buccal and / or labial side of the tooth. In some cases, the body 2503 is configured to contact all teeth of the dental arch. In other cases, the body 2503 is configured to contact only a subset of the teeth of the dental arch (e.g., 1, 2, 3, 4, 5, etc.). The body can include a surface that aligns with the tooth surface of the dental arch to maintain the relative position of the dental attachment placement device 2502 relative to the dental arch when placed against the tooth surface. In some cases, the body can include one or more cavities shaped to receive a corresponding tooth or teeth to maintain a relative position of the dental attachment placement device with respect to the dental arch when placed against a tooth surface.

[0431] The body 2503 may include one or more accessory supports (e.g., accessory support structures) 2504 coupled to the body 2503 and configured to position one or more accessories 2501 adjacent to a corresponding tooth or teeth. The dental accessory 2501 may be formed with a body 2503 and an accessory support 2504 (prefabricated) so that when the body 2503 is placed on the dental arch, the dental accessory 2501 is in a predetermined position relative to the teeth. That is, when the body 2503 is correctly positioned on the teeth, the accessory support 2504 can align the accessory 2501 relative to the tooth surface for bonding. This helps the dentist ensure that the accessory 2501 is properly aligned when bonding with the teeth. In the example shown, the accessory support 2504 extends from one side of the body 2503 so that the accessory 2501 is positioned at a predetermined position on the buccal side of the tooth for bonding.

[0432] The dental attachment placement device 2502 can be formed using any manufacturing method, including one or more of additive manufacturing (e.g., 3D printing), molding, joining, casting, and / or other manufacturing techniques. In some cases, the dental attachment placement device 2502 is formed based on a computer model. Fig.25C An exemplary dental attachment placement device computer model 2502' that can be used to form a dental attachment placement device 2502 is shown. As shown, the computer model 2502' can include a body 2503' (corresponding to the body 2503), one or more attachment supports 2504' (corresponding to the attachment support 2504), one or more supports 2505' (corresponding to the supports 2505), and one or more dental attachments 2501' (corresponding to the dental attachments 2501). The computer model 2502' can be adjusted based on changes in the forces required to apply the appropriate forces to the teeth at different stages of the treatment plan. For example, the placement and number of dental attachments 2501 can be modified.

[0433] The dental attachment placement device may include a dental attachment replacement system to provide one or more replacement dental attachments for replacing the dental attachment 2501 (referred to herein as a first or primary attachment). This may be useful, for example, if one or more first or primary dental attachments 2501 are lost or damaged, for example, during transport or handling of the dental attachment placement device 2502. For example, if a dental attachment falls off during treatment or a dental attachment fails to engage, the dental professional may use a replacement system to replace it. The replacement system may be configured to ensure that the replacement dental attachment is properly placed relative to one or more teeth of the dental arch. The replacement system has little effect on the overall usability and accuracy of the dental attachment placement device and does not impose an additional burden on the manufacture of the device and / or the dental professional using the device. In some cases, the replacement system may be considered part of the attachment support 2504.

[0434] Figure 26A-32 C shows a dental attachment replacement system that can be integrated into any of the dental attachment placement devices described herein, for example, dental attachment placement device 1902 ( Fig.19A and 19B ) or the above reference Figure 1A - Any dental attachment placement device described in 18.

[0435] Figures 26A-26E An exemplary dental attachment replacement system 2620 configured to replace a first dental attachment 2601 with a second dental attachment 2621 is shown. As shown, the replacement system 2620 can be coupled to a body 2603 of a dental attachment placement device. The replacement system 2620 is configured to move the second dental attachment 2621 relative to the body 2603 to position the second dental attachment 2621 at a predetermined position adjacent to the tooth for engagement with the tooth. In this example, the replacement system 2620 includes a hinge 2606 configured to rotate the second dental attachment 2621 relative to the body 2603. The hinge 2606 can be configured to rotate the second dental attachment 2621 in a direction perpendicular to the tooth and toward the tooth.

[0436] like Figures 26A-26C As shown, the replacement system 2620 can include a first accessory support 2604 for supporting a first dental accessory 2601 in a position adjacent to a tooth. The first accessory support 2604 can have a frame shape that surrounds the first dental accessory 2601 in a plane. The first accessory support 2604 can include a support 2605 that connects the first dental accessory 2601 to the first accessory support 2604. In some cases, the support 2605 is frangible so that the first dental accessory 2601 can be easily removed from the first accessory support 2604. The second accessory support 2624 can similarly have a frame shape for supporting a second dental accessory 2621 therein. The second accessory support 2624 can include a support 2625 that connects the second dental accessory 2621 to the second accessory support 2624 and can also be frangible.

[0437] At least a portion of the first attachment support 2604 can be removed from the body 2603. For example, a breakable region 2607 at the base of the first attachment support 2604 can be configured to disconnect the first attachment support 2604 from the body 2603. Once the first attachment support 2604 is removed from the body 2603, the second attachment support 2624 supporting the second dental attachment 2621 can be rotated via the hinge 2606 to position the second dental attachment 2621 adjacent to the tooth, such as Fig.26D and 26EHinge 2606 may include a ring segment 2630 located on one side of body 2603 and forming an opening for receiving a rod 2632 of second accessory holder 2624. Ring segment 2630 may be configured to allow rod 2632 to rotate therein, thereby allowing second accessory holder 2624 and second dental attachment 2621 to rotate relative to body 2603. In some cases, hinge 2606 may include a guide or lock 2634 configured to ensure proper positioning of second accessory holder 2624 and / or to lock second accessory holder 2624 in place after second dental attachment 2621 is positioned near a tooth for engagement.

[0438] It is worth noting that Figures 26A-26E An example of a dental accessory replacement system 2620 for attaching a replacement accessory 2621 to a tooth is shown, which can be incorporated into a dental accessory placement device (e.g., 1902). However, the dental accessory placement device described herein can include any number of dental accessory replacement systems (e.g., 1, 2, 3, 4, 5, 6, 7, 8, 10, 12, or 26) for connecting any number of replacement accessories to any number of teeth.

[0439] In any of the dental attachment placement devices described herein, the replacement dental attachment can have the same shape and / or size as the corresponding primary attachment, or can have a different shape and / or size than the corresponding primary attachment. In addition, the dental attachment replacement system can be arranged to position the replacement dental attachment at the same position relative to the teeth as the corresponding dental attachment, or at a different position relative to the teeth than the corresponding dental attachment. For example, with reference to Figures 26A-26E, the second dental attachment 2621 can have the same size and shape as the first dental attachment 2601, for example, to provide a replica of the first dental attachment 2601 in the event that the first dental attachment 2601 is lost or damaged. In some cases, the second dental attachment 2621 can have a different shape and / or size than the first dental attachment 2601. Additionally or alternatively, the second attachment support 2624 can be configured to position the second dental attachment 2621 at the same position relative to the teeth as the first attachment support 2604 places the first dental attachment 2601, or at a different position relative to the teeth than the first attachment support 2604. For example, if the second dental attachment 2621 is used to apply a different force to the teeth (along the dental braces), this flexibility may be useful. For example, the second dental attachment 2621 can be used to apply a force to the teeth (along the dental braces) according to another step of the dental alignment plan. The second dental attachment 2621 can be made of the same material as the first dental attachment 2601 or a different material than the first dental attachment 2601. For example, if the second dental attachment 2621 is configured to withstand different forces than the first dental attachment 2601 , it may be useful to make the second dental attachment 2621 from a different material.

[0440] Fig. 27 Another exemplary dental attachment replacement system 2720 is shown, which is an example of a hinge-based attachment replacement system 2020, in which a second attachment support 2724 includes a post 2728 (rather than a frame) for supporting a second dental attachment 2727. The post 2728 can have a curved shape that bends toward the tooth to facilitate placement of the second dental attachment 2727. In this example, once the first dental attachment 2701 is removed from the first attachment support 2704, the first attachment support 2704 (e.g., a frame) can remain attached to the body 2703 while the second dental attachment 2727 is rotated adjacent to the tooth. In some cases, the shape and size of the first attachment support 2704 (e.g., a frame) can be designed to align the second dental attachment 2727 relative to the tooth. For example, the first attachment support 2704 (e.g., a frame) can include one or more inner surfaces 2710 that contact and align with the second dental attachment 2727.

[0441] Fig.28Another exemplary dental attachment replacement system 2820 is shown, which is another example of a hinge-based attachment replacement system 2020, wherein the dental attachment replacement system 2820 includes a sacrificial support 2836 coupling a second attachment support 2824 to the body 2803. The sacrificial support 436 can be configured to be cut / disconnected, for example, by a dental professional to release the second attachment support 2824 so that the second attachment support 2824 can be rotated to a position adjacent to the teeth. In some cases, the sacrificial support 2836 can act as a handle for the dental professional when positioning the dental attachment placement device on the patient's dental arch. Alternatively, the sacrificial support 2836 can be removed before being shipped to the dental professional. In this example, the rod 2832 of the second attachment support 2824 has a curved shape to extend the second attachment support 2824. Note that in the case where the dental attachment placement device is printed (e.g., using 3D printing), the sacrificial support 2836 can be oriented at the bottom so that the dental attachment placement device can be printed without an additional printing support.

[0442] Fig.29A and 29B Another exemplary dental accessory replacement system 2920 is shown, which is another example of a hinge-based accessory replacement system 2020, wherein the hinge 2906 is configured to rotate the second accessory holder 2924 to either side of the body 2903. In addition, the body 2903 can include an internal cutout 2935 that allows the hinge 2906 to move laterally within the body so that the second accessory holder 2924 (having the second dental accessory 2921 attached thereto) can be stored on a side 2936 of the body 2903 opposite the first accessory holder 2904 (e.g., supporting the first dental accessory 2901). This configuration can allow the second accessory holder 2924 and the second dental accessory 2921 to be positioned out of the way until needed.

[0443] Fig. 30A and 30B Another example of a dental accessory replacement system 3020 is shown, which is another example of a hinge-based accessory replacement system 2020, wherein a first accessory holder 3004 has a first frame 3040 that is configured to align with a second frame 3044 of a second accessory holder 3030. Fig. 30A A front view of the first frame 3040 and the second frame 3044 is shown viewed from the perspective of the teeth. The first frame 3040 can have a shape that accommodates the smaller second frame 3044 so that the second dental attachment 3021 can be positioned adjacent to the teeth. Thus, when rotated toward the teeth, the second frame 3044 can self-position into the first frame 3040 for proper alignment of the second dental attachment 3021. Fig. 30BA side view of the dental attachment replacement system 3020 is shown illustrating how the second attachment holder 3030 can be rotated relative to the body 3003 to replace the first dental attachment 3001 with the second dental attachment 3021 . Fig. 30C Another example is shown where the body 3003 includes an internal cutout 3046 that allows the second accessory holder 3030 to be further rotated to move the second accessory holder 3030 out of the way until needed.

[0444] Fig.31A and 31B An exemplary dental attachment replacement system 3120 is shown that includes a dial assembly in which a second attachment holder 3124 can be rotated about a post 3131. Once the first dental attachment is removed from the dental attachment placement device, the second attachment holder 3124 can be rotated so that the second dental attachment 3121 attached to the second attachment holder 3124 can be rotated from a storage position 3151 to a desired position 3152 adjacent to the tooth. The stopper 3150 can prevent the second attachment holder 3124 from rotating beyond the desired position 3152 so that the second dental attachment 3121 is properly positioned adjacent to the tooth.

[0445] Fig.32 An exemplary dental attachment replacement system 3220 is shown that includes a gear assembly. The teeth of the gear 3255 can engage with the teeth on the second support structure 3224 so that the rotational movement of the gear 3255 causes a linear translation of the second support structure 3224. For example, the gear 3255 can be rotated in a first direction to extend the second dental attachment 3221 above (or below) the body 3203 to a desired position adjacent to the tooth. Similarly, the gear 3255 can be rotated in a second (opposite) direction to retract the second dental attachment 3221, for example, away from the first dental attachment. In some cases, the guides 3257a, 3257b guide the second support structure 3224 so that the second dental attachment 3221 is appropriately positioned adjacent to the tooth.

[0446] Figures 33A-33CAn exemplary dental attachment replacement system 3320 is shown that includes a dowel joint assembly. In this example, a second support structure 3324 is connected to the body 3303 by a breakable support 3361. The breakable support 3361 can be broken, thereby releasing the second support structure 3324 from the body 3303. For example, if the first support structure 3304 is damaged or has a missing first dental attachment, the first support structure 3304 can be removed from the body 3303. The second support structure 3324 includes one or more alignment structures 3359 (e.g., dowel-shaped or cone-shaped) that are configured to fit within one or more correspondingly shaped openings 3360 of the body 3303, which aligns the second support structure 3324 with the second dental attachment 3321 to the appropriate position for coupling the second dental attachment 3321 to the tooth. In this example, the second support structure 3324 includes three alignment structures 3359 to maximize stability and ensure consistent placement of the second dental attachment 3321. However, the dental attachment replacement system 3320 may include more alignment structures 3359 (e.g., 4, 5, 6, 7, 10) or fewer alignment structures 3359 (e.g., 1 or 2) with corresponding openings 3360. In some cases, the second support structure 3324 includes a label 3357 (e.g., left upper and lower jaw "ULM") to track the second support structure 3324 when it is separated from the body 3303, thereby reducing the chance that the second support structure 3324 is incorrectly placed. In some cases, the second support structure 3324 is of a sufficiently large size that it can be handled by a dental professional without risk of damaging the second dental attachment 3321. In the case of a 3D printed part, the second support structure 3324 can be printed together with the rest of the dental attachment placement device, thereby eliminating tolerance accumulation and traceability issues associated with a large number of small independent spare parts. In addition, the dental attachment placement device. The second support structure 3324 can be removed from the body 3303 during manufacturing and placed in the kit, or can be removed by a dental professional.

[0447] Fig.34A and 34BAnother example of a dental attachment replacement system 3420 is shown having a dowel joint assembly. In this case, the body 3403 includes one or more alignment structures 3459 configured to fit within one or more correspondingly shaped openings 3460 of the second support structure 3424. The breakable support 3461 can be broken to release the second support structure 3424 from the body 3403 and then properly positioned adjacent to a tooth once the first dental attachment 3401 (and in some cases the first support structure 3404) is removed from the body 3403 by the one or more alignment structures 3459 being guided within the one or more correspondingly shaped openings 3460.

[0448] Figures 35A-35C Exemplary dental accessory replacement systems 3520, 3580, and 3590 are shown having a dispenser-type assembly. Fig.35A , the dental attachment replacement system 3520 includes a plurality of dental attachments 3501, 3521, and 3541 stored in a reservoir 3585 until they are needed. A push rod 3586 can be used to push a desired one of the plurality of dental attachments 3501, 3521, and 3541 into position adjacent to a tooth. For example, if a first dental attachment 3501 fails to engage, the first dental attachment 3501 can be removed, and a second dental attachment 3521 can be moved into position by pushing the push rod 3586. Fig.35B An example of a dental attachment replacement system 3550 is shown that is similar to the dental attachment replacement system 3520, except that the body 3533 (compared to the body 3503) extends partially around the reservoir 3585 and has a contoured shape. Fig.35C Another example of a dental attachment replacement system 3570 is shown that is similar to the dental attachment replacement system 3520, except that the dental attachments 3501, 3521, and 3541 are frangibly connected to the body 3503 by a breakable feature 3571 that can maintain the position of the dental attachments 3501, 3521, and 3541 within the reservoir 3585. Figures 35A-35C In the example of , the dental attachments 3501 , 3521 , and 3541 can be manufactured separately from or together with the manufacture of the dental attachment replacement systems 3520 , 3580 , and 3590 .

[0449] Figures 36A-36DAn example of a portion of a dental attachment placement device 3602 is shown, the device including anchors (e.g., 3690a, 3690b, 3690c, 3690d, 3690e, and 3690f) configured to be removably connected to a plurality of corresponding dental attachment replacement systems (e.g., 3620a, 3620b, 3620d, and 3620e). In this example, the anchor 3690 includes a locking hole 3691 configured to receive a protruding key 3692 of the anchor 3620. In some cases, the key 3692 is attached to the locking hole 3691 by a press fit. Allowing the dental attachment replacement system 3620 to be removably attached to the body 3603 adds a degree of flexibility to the device 3602. For example, a manufacturer or specialist can choose which dental attachment placement device 3602 to attach to the body 3603. The dental attachment replacement system 3620 can be manufactured together with the body 3603 or separately. This modular assembly may also allow any one replacement dental attachment to be replaced with a different type (e.g., shape or size) during treatment without having to manufacture the entire dental attachment placement device. Additional orders for aligners can utilize the same body—just order new anchors. In some cases, additional anchors can be stored in the specialist's office. Manufacturing the anchor and dental attachment as a single unit ensures accurate attachment placement every time, as it relies on the stability of the anchor for reliable placement. The anchor can be large enough so that it can be easily manufactured as a separate part and easily tracked, for example, by marking each replacement attachment.

[0450] Figures 37A-37C Other examples of dental accessory placement devices having removable dental accessory replacement systems are shown. Fig.37A An example is shown where the anchor is removably coupled (press-fitted) to a square or rectangular hole on the body. Fig.37B An example is shown where the anchor is removably coupled (press-fitted) to a circular hole on the body. Fig.37C An example is shown where the anchor is removably coupled (press-fitted) to the flexible body.

[0451] Figures 38A-38C Other examples of removable dental attachment replacement systems are shown. Fig.38A and 38C An example is shown in which a gap is provided between the anchor and the body so that the anchor and the body can be printed as separate parts (e.g., during a single 3D print). The anchor can fit tightly into the body (e.g., press fit, screw, slide, etc.). Additional anchors can be manufactured separately and provided in advance as spare parts, or provided as needed for individual teeth. Fig.38CAn example is shown in which a detachable support is provided between the body and the anchor so that the body and the anchor can remain connected during post-processing, packaging, transportation, etc. The user can press the anchor to break the detachable support to release the anchor from the body.

[0452] Certain aspects of the present disclosure provide dental attachments printed with the compositions and / or methods of the present disclosure. The dental attachment can be a solid object that is configured to be directly coupled to a tooth. In many cases, the dental attachment is coupled to the tooth surface by an adhesive such as an epoxy resin.

[0453] Dental attachments can be configured to be coupled to additional orthodontic appliances (e.g., one or more incremental palatal expanders or braces) to achieve, enhance, or improve treatment outcomes with these devices. For example, a tooth whose shape is difficult to couple to a dental brace (such as the dental brace shown in FIG1 ) can be coupled to a dental attachment coupled to the tooth, and force is transmitted through the dental attachment to affect the movement of the tooth. Dental attachments can include grooves, hooks, buttons, or other structures to facilitate coupling to orthodontic appliances. During certain treatment processes, each of the patient's teeth is coupled to a dental attachment. In other cases, dental attachments are only provided to a portion of the patient's teeth.

[0454] In some cases, the dental attachment is configured to be detected by a scanner or imaging system. Detecting the dental attachment can aid in the design of an orthodontic device (e.g., for designing a new dental brace during treatment). In some cases, the dental attachment is used as a reference point for tooth movement and treatment progression.

[0455] 2) Directly manufactured dental appliances

[0456] Figure 1AAn exemplary tooth repositioning appliance or aligner 100 is shown that can be worn by a patient to achieve incremental repositioning of individual teeth 102 within the jaw. In some cases, the repositioning appliance or aligner can be configured to be coupled to a dental attachment coupled to one or more teeth 102. The appliance can include a shell (e.g., a continuous polymer shell or a segmented shell) having tooth receiving cavities that receive and elastically reposition the teeth. The appliance or a portion thereof can be indirectly manufactured using a physical model of the teeth. For example, a physical model of the teeth and a layer of a suitable polymer material can be used to form the appliance (e.g., a polymer appliance). In some embodiments, the physical appliance is directly manufactured from a digital model of the appliance, for example, using rapid prototyping techniques. The appliance can cover all teeth present in the upper or lower jaw, or less than all teeth. The appliance can be specifically designed to accommodate the patient's teeth (e.g., the topography of the tooth receiving cavity matches the topography of the patient's teeth), and can be manufactured based on a positive or negative mold of the patient's teeth generated by an impression, a scan, or the like. Alternatively, the appliance may be a general purpose appliance that is configured to receive a tooth but is not necessarily shaped to match the topography of the patient's teeth. In some cases, only the specific tooth that the appliance is received by is repositioned by the appliance, while other teeth may provide a base or anchor area to hold the appliance in place while the appliance applies force to the target tooth to be repositioned. In some cases, at certain points during treatment, some, most, or even all of the teeth are repositioned. The teeth being moved may also serve as a base or anchor to secure the appliance while it is worn by the patient. Typically, no wire or other means is provided to secure the appliance in place over the tooth. However, in some cases, it may be desirable or necessary to provide a separate attachment or other anchoring element 104 on the tooth 102 and to provide a corresponding receptacle or opening 106 on the appliance 100 so that the appliance can apply a selected force to the tooth. Exemplary appliances, including Those used in the system are described in numerous patents and patent applications belonging to Align Technology, Inc., including, for example, U.S. Patent Nos. 6,450,807 and 5,975,893, and on the company's website, which is accessible on the World Wide Web (see, for example, the URL "invisalign.com"). Examples of tooth-mounted attachments suitable for use with orthodontic appliances are also described in patents and patent applications belonging to Align Technology, Inc., for example, U.S. Patent Nos. 6,309,215 and 6,830,450.

[0457] Figure 1BA tooth repositioning system 110 is shown that includes a plurality of appliances 112, 114, 116. Any appliance described herein may be designed and / or provided as part of a set of a plurality of appliances for use with the tooth repositioning system. Each appliance may be configured to provide a tooth receiving cavity with a geometry corresponding to an intermediate or final tooth arrangement intended for the appliance. The patient's teeth may be incrementally repositioned from an initial tooth arrangement to a target tooth arrangement by placing a series of incrementally position-adjusted appliances on the patient's teeth. For example, the tooth repositioning system 110 may include a first appliance 112 corresponding to an initial tooth arrangement, one or more intermediate appliances 114 corresponding to one or more intermediate arrangements, and a final appliance 116 corresponding to a target arrangement. The target tooth arrangement may be a planned final tooth arrangement selected for the patient's teeth at the end of all planned orthodontic treatment. Alternatively, the target arrangement can be one of certain intermediate arrangements of the patient's teeth during the course of orthodontic treatment, which can include a variety of different treatment scenarios, including but not limited to the following: surgery is recommended, interproximal enamel removal (IPR) is appropriate, a progress check is scheduled, optimal anchor placement, palate expansion is required, restorative dentistry (e.g., inlays, onlays, crowns, bridges, implants, veneers, etc.) is involved, etc. Therefore, it is understood that the target tooth arrangement can be any planned final arrangement of the patient's teeth after one or more incremental repositioning stages. Similarly, the initial tooth arrangement can be any initial arrangement of the patient's teeth before one or more incremental repositioning stages.

[0458] Figure 1CA method 150 for orthodontic treatment using multiple appliances according to an embodiment is shown. The method 150 can be implemented using any appliance or set of appliances described herein. In step 160, a first orthodontic appliance is applied to the patient's teeth to reposition the teeth from a first tooth arrangement to a second tooth arrangement. In step 170, a second orthodontic appliance is applied to the patient's teeth to reposition the teeth from the second tooth arrangement to a third tooth arrangement. The method 150 can be repeated as needed using any suitable number and combination of consecutive appliances to incrementally reposition the patient's teeth from an initial arrangement to a target arrangement. The appliances can be generated all at once in the same phase, or in groups or batches (e.g., at the beginning of a phase of treatment), or the appliances can be made one at a time and the patient can wear each appliance until the pressure of each appliance on the teeth is no longer felt, or until the maximum amount of tooth movement expressed in a given phase has been achieved. Multiple different appliances (e.g., a set) can be designed and even manufactured before the patient wears any of the multiple appliances. After wearing an appliance for an appropriate period of time, the patient may replace the current appliance with the next appliance in the series until there are no appliances remaining. Appliances are typically not fixed to the teeth, and the patient may place and replace appliances at any time during treatment (e.g., patient-removable appliances). The last appliance or appliances in the series may have a geometry selected to overcorrect the tooth arrangement. For example, one or more appliances may have a geometry that, if fully implemented, would move individual teeth to a position beyond the selected "final" arrangement. Such overcorrection may be desirable in order to offset potential relapse after termination of the repositioning method (e.g., allowing individual teeth to move back to their pre-correction position). Overcorrection may also help to speed up the rate of correction (e.g., an appliance with a geometry that exceeds the intended intermediate or final position may move individual teeth toward that position at a faster rate). In this case, use of the appliance may be discontinued before the teeth reach the position defined by the appliance. In addition, overcorrection may be intentionally performed to compensate for any inaccuracies or limitations of the appliance.

[0459] Various embodiments of orthodontic appliances presented herein can be manufactured in a variety of ways. In some embodiments, the orthodontic appliances herein (or portions thereof) can be produced using direct manufacturing, e.g., additive manufacturing techniques (also referred to herein as "3D printing") or subtractive manufacturing techniques (e.g., milling). In some embodiments, direct manufacturing involves forming an object (e.g., an orthodontic appliance or a portion thereof) without using a physical template (e.g., a mold, a mask, etc.) to define the geometry of the object. Additive manufacturing techniques may include: (1) vat photopolymerization (e.g., stereolithography), in which an object is constructed layer by layer from a vat of liquid photopolymer resin; (2) material jetting, in which material is jetted onto a build platform using a continuous or drop-on-demand (DOD) process; (3) binder jetting, in which alternating layers of a build material (e.g., a powder-based material) and a binding material (e.g., a liquid binder) are deposited by a print head; (4) fused deposition modeling (FDM), in which material is drawn through a nozzle, heated, and deposited layer by layer; (5) powder bed fusion, including but not limited to direct metal laser sintering (DMLS), electron beam melting (EBM), selective heat sintering (SHS), selective laser melting (SLM), and selective laser sintering (SLS); (6) sheet lamination, including but not limited to layered object manufacturing (LOM) and ultrasonic additive manufacturing (UAM); and (7) directed energy deposition, including but not limited to laser engineered net shaping, directed light manufacturing, direct metal deposition, and 3D laser cladding. For example, stereolithography may be used to directly manufacture one or more of the devices described herein. In some embodiments, stereolithography involves the use of light (e.g., ultraviolet light) to selectively polymerize a photosensitive resin (e.g., a photopolymer) according to a desired cross-sectional shape. By sequentially polymerizing multiple object cross sections, the object geometry can be built layer by layer. As another example, selective laser sintering can be used to directly manufacture the apparatus herein. In some embodiments, selective laser sintering involves the use of a laser beam to selectively melt and fuse layers of powdered material according to a desired cross-sectional shape to establish the object geometry. As yet another example, the apparatus herein can be directly manufactured by fused deposition molding. In some embodiments, fused deposition molding involves melting and selectively depositing filaments of thermoplastic polymers in a layer-by-layer manner to form an object. In yet another example, material jetting can be used to directly manufacture the apparatus herein. In some embodiments, material jetting involves spraying or extruding one or more materials onto a build surface to form continuous layers of the object geometry.

[0460] Alternatively or in combination, some embodiments of the appliances (or portions thereof) herein can be produced using indirect manufacturing techniques, e.g., by thermoforming on a male or female mold. Indirect manufacturing of an orthodontic appliance can involve producing a male or female mold of the patient's dentition with a target arrangement (e.g., by rapid prototyping, milling, etc.), and thermoforming one or more sheets of material on the mold to produce the appliance shell.

[0461] In some embodiments, the direct manufacturing method provided herein builds object geometries in a layer-by-layer manner, wherein continuous layers are formed in discrete building steps. Alternatively or in combination, a direct manufacturing method that allows continuous construction of object geometries can be used, referred to herein as "continuous direct manufacturing". Various types of continuous direct manufacturing can be used. As an example, in some embodiments, the apparatus of this article is manufactured using "continuous liquid interphase printing", wherein objects are continuously built from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the building surface of the object and the polymerization inhibition "dead zone". In some embodiments, a semipermeable membrane is used to control the transport of photopolymerization inhibitors (e.g., oxygen) into the dead zone to form a polymerization gradient. Continuous liquid interphase printing can achieve a manufacturing speed that is about 25 times to about 100 times faster than other direct manufacturing methods, and a speed that is about 1000 times faster can be achieved by combining a cooling system. Continuous liquid interphase printing is described in U.S. Patent Publication Nos. 2015 / 0097315, 2015 / 0097316, and 2015 / 0102532, the disclosures of each of which are incorporated herein by reference in their entirety.

[0462] As another example, a continuous direct manufacturing method can achieve continuous construction of object geometry by continuous movement of the building platform during the irradiation phase (e.g., along the longitudinal or Z direction), so that the hardening depth of the irradiated photopolymer is controlled by the movement speed. Thus, continuous polymerization of material can be achieved on the building surface. Such a method is described in U.S. Patent No. 7,892,474, the disclosure of which is incorporated herein by reference in its entirety.

[0463] In another example, a continuous direct manufacturing method can include extruding a composite material consisting of a curable liquid material surrounding a solid strand. The composite material can be extruded along a continuous three-dimensional path to form an object. This method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0464] In yet another example, a continuous direct manufacturing method utilizes a "heliolithography" method, in which a liquid photopolymer is cured using focused radiation while the build platform is continuously rotated and raised. Thus, object geometries can be continuously built along a spiral build path. This method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0465] Direct manufacturing method provided herein is compatible with multiple materials, including but not limited to one or more of the following materials: polyester, copolyester, polycarbonate, thermoplastic polyurethane, polypropylene, polyethylene, polypropylene and polyethylene copolymer, acrylic acid, cyclic block copolymer, polyetheretherketone, polyamide, polyethylene terephthalate, polybutylene terephthalate, polyetherimide, polyethersulfone, polytrimethylene terephthalate, styrene block copolymer (SBC), silicone rubber, elastomeric alloy, thermoplastic elastomer (TPE), thermoplastic vulcanizate (TPV) elastomer, polyurethane elastomer, block copolymer elastomer, polyolefin blended elastomer, thermoplastic copolyester elastomer, thermoplastic polyamide elastomer, thermosetting material or its combination. Material for direct manufacturing can be provided in uncured form (e.g., liquid, resin, powder, etc.), and can be cured (e.g., by photopolymerization, light curing, gas curing, laser curing, crosslinking, etc.) to form orthodontic appliance or a part thereof. The property of the material before curing can be different from the property of the material after curing. Once cured, the materials herein can exhibit sufficient strength, stiffness, durability, biocompatibility, etc., to be used in orthodontic appliances. The post-curing properties of the materials used can be selected according to the desired properties of the corresponding part of the appliance.

[0466] In some embodiments, relatively rigid portions of an orthodontic appliance can be formed by direct manufacturing using one or more of the following materials: polyesters, copolyesters, polycarbonates, thermoplastic polyurethanes, polypropylene, polyethylene, copolymers of polypropylene and polyethylene, acrylics, cyclic block copolymers, polyetheretherketones, polyamides, polyethylene terephthalate, polybutylene terephthalate, polyetherimides, polyethersulfones, and / or polytrimethylene terephthalate.

[0467] In some embodiments, the relatively elastic portion of the orthodontic appliance can be formed by direct manufacturing using one or more of the following materials: styrene block copolymers (SBC), silicone rubber, elastomeric alloys, thermoplastic elastomers (TPE), thermoplastic vulcanizate (TPV) elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers and / or thermoplastic polyamide elastomers.

[0468] The machine parameters may include curing parameters. For curing systems based on digital light processing (DLP), the curing parameters may include power, curing time, and / or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and / or power distribution of the beam. For printing systems, the curing parameters may include material droplet size, viscosity, and / or curing power. These machine parameters may be monitored and adjusted regularly (e.g., some parameters every 1-x layers and some parameters after each build) as part of process control on the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters every layer or every few seconds and automatically adjust them through a feedback loop. For DLP machines, depending on the stability of the system, the grayscale may be measured and calibrated before, during, and / or at the end of each build and / or at predetermined time intervals (e.g., every n builds, once an hour, once a day, once a week, etc.). In addition, material properties and / or light characteristics may be provided to the manufacturing machine, which the machine process control module may use to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for changes in material properties. By implementing process control on the manufacturing machines, reduced variation in tooling accuracy and residual stresses can be achieved.

[0469] Optionally, the direct manufacturing methods described herein allow for the manufacture of devices comprising multiple materials, referred to herein as "multi-material direct manufacturing". In some embodiments, the multi-material direct manufacturing method involves the simultaneous formation of an object from multiple materials in a single manufacturing step. For example, a multi-tip extrusion device can be used to selectively dispense multiple types of materials from different material supply sources in order to manufacture an object from multiple different materials. Such a method is described in U.S. Patent No. 6,749,414, the disclosure of which is incorporated herein by reference in its entirety. Alternatively or in combination, the multi-material direct manufacturing method can involve the formation of an object from multiple materials in multiple consecutive manufacturing steps. For example, according to any direct manufacturing method herein, a first portion of an object can be formed from a first material, and then according to the methods herein, a second portion of the object can be formed from a second material, and so on, until the entirety of the object has been formed.

[0470] Direct manufacturing can provide various advantages over other manufacturing methods. For example, compared with indirect manufacturing, direct manufacturing allows orthodontic appliances to be produced without using any molds or templates to shape the appliances, thereby reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry. In addition, direct manufacturing allows precise control of the three-dimensional geometry of the appliance, for example, the thickness of the appliance. Complex structures and / or auxiliary components can be integrally formed with the appliance shell in a single manufacturing step, rather than added to the shell in a separate manufacturing step. In some embodiments, direct manufacturing is used to produce appliance geometries that are difficult to create using alternative manufacturing techniques, for example, appliances with very small or fine features, complex geometries, undercuts, adjacent structures, shells with variable thickness, and / or internal structures (e.g., appliances with reduced weight and material usage to improve strength). For example, in some embodiments, the direct manufacturing method herein allows the manufacture of orthodontic appliances with feature sizes less than or equal to about 5 μm or in the range of about 5 μm to about 50 μm or in the range of about 20 μm to about 50 μm.

[0471] The direct manufacturing techniques described herein can be used to produce appliances with substantially isotropic material properties, for example, substantially the same or similar strengths in all directions. In some embodiments, the direct manufacturing methods herein allow the production of orthodontic appliances with strengths that vary no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% in all directions. In addition, compared with other manufacturing techniques, the direct manufacturing methods herein can be used to produce orthodontic appliances at a faster rate. In some embodiments, the direct manufacturing methods herein allow the production of orthodontic appliances in a time interval of less than or equal to about 1 hour, about 30 minutes, about 25 minutes, about 20 minutes, about 15 minutes, about 10 minutes, about 5 minutes, about 4 minutes, about 3 minutes, about 2 minutes, about 1 minute, or about 30 seconds. This manufacturing speed allows for rapid "chair-side" production of custom appliances, for example, during routine appointments or examinations.

[0472] In some embodiments, the direct manufacturing methods described herein implement process controls on various machine parameters of the direct manufacturing system or device to ensure that the resulting appliance is manufactured with high precision. Such precision can be beneficial in ensuring that the desired force system is accurately transmitted to the teeth, thereby effectively causing tooth movement. Process controls can be implemented to account for process variability caused by a variety of sources, such as material properties, machine parameters, environmental variables, and / or post-processing parameters.

[0473] Material properties can be different depending on the properties of the raw materials, the purity of the raw materials, and / or the process variables in the raw material mixing process. In many embodiments, the resin or other materials used for direct manufacturing should be manufactured under strict process control to ensure that the changes in optical properties, material properties (e.g., viscosity, surface tension), physical properties (e.g., modulus, strength, elongation), and / or thermal properties (e.g., glass transition temperature, heat distortion temperature) are small. Process control of the material manufacturing process can be achieved by screening the raw materials for physical properties and / or controlling temperature, humidity, and / or other process parameters during the mixing process. By implementing process control on the material manufacturing procedure, it is possible to achieve a reduction in the variability of process parameters and make the material properties of each batch of materials more uniform. As further discussed herein, residual changes in material properties can be compensated by process control on the machine.

[0474] The machine parameters may include curing parameters. For curing systems based on digital light processing (DLP), the curing parameters may include power, curing time, and / or grayscale of the complete image. For laser-based curing systems, the curing parameters may include power, speed, beam size, beam shape, and / or power distribution of the beam. For printing systems, the curing parameters may include material droplet size, viscosity, and / or curing power. These machine parameters may be monitored and adjusted regularly (e.g., some parameters per 1-x layers and some parameters after each build) as part of process control on the manufacturing machine. Process control may be achieved by including sensors on the machine that measure power and other beam parameters per layer or every few seconds and automatically adjust them through a feedback loop. For DLP machines, grayscale may be measured and calibrated at the end of each build. In addition, material properties and / or light characteristics may be provided to the manufacturing machine, which the machine process control module may use to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for changes in material properties. By implementing process control on the manufacturing machine, reduced variation in tool accuracy and residual stress may be achieved.

[0475] In many embodiments, environmental variables (e.g., temperature, humidity, sunlight, or exposure to other energy / curing sources) are maintained within narrow ranges to reduce variability in tool thickness and / or other properties. Optionally, machine parameters can be adjusted to compensate for environmental variables.

[0476] In many embodiments, the post-processing of the utensil comprises cleaning, post-curing and / or support removal process.Related post-processing parameters can comprise the purity of detergent, cleaning pressure and / or temperature, cleaning time, post-curing energy and / or time and / or consistency of support removal process.These parameters can be measured and adjusted as a part of process control scheme.In addition, the physical property of the utensil can be changed by revising the post-processing parameters.Adjusting the post-processing machine parameters can provide another way to compensate for the variability of material properties and / or machine properties.

[0477] The configuration of the orthodontic appliance herein can be determined according to a treatment plan for the patient, for example, a treatment plan involving the sequential application of multiple appliances to incrementally reposition the teeth. Computer-based treatment plans and / or appliance manufacturing methods can be used to facilitate the design and manufacture of appliances. For example, one or more appliance assemblies described herein can be digitally designed and manufactured with the aid of a computer-controlled manufacturing device (e.g., computer numerical control (CNC) milling, computer-controlled rapid prototyping, e.g., 3D printing, etc.). The computer-based methods presented herein can improve the accuracy, flexibility, and convenience of appliance manufacturing.

[0478] Figure 2 A method 200 for designing an orthodontic appliance produced by direct manufacturing according to an embodiment is shown. The method 200 can be applied to any embodiment of the orthodontic appliance described herein. Some or all of the steps of the method 200 can be performed by any suitable data processing system or device, for example, one or more processors configured with appropriate instructions.

[0479] In step 210, a movement path for moving one or more teeth from an initial arrangement to a target arrangement is determined. The initial arrangement can be determined by a mold or scan of the patient's teeth or oral tissue, for example, using a wax articulation, direct contact scanning, x-ray imaging, tomography, ultrasound imaging, and other techniques for obtaining information about the position and structure of teeth, jaws, gums, and other orthodontically relevant tissues. From the acquired data, a digital data set can be derived that represents the initial (e.g., before treatment) arrangement of the patient's teeth and other tissues. Optionally, the initial digital data set is processed to segment tissue components from each other. For example, a data structure that digitally represents a single crown can be generated. Advantageously, a digital model of the entire tooth can be generated, including measured or extrapolated hidden surface and root structures, as well as surrounding bone and soft tissue.

[0480] The target arrangement of teeth (e.g., the desired and expected end result of orthodontic treatment) can be received from a clinician in the form of a prescription, can be calculated based on basic orthodontic principles, and / or can be computationally inferred from the clinical prescription. With a description of the desired final position of the teeth and a digital representation of the teeth themselves, the final position and surface geometry of each tooth can be specified to form a complete model of the expected dental arrangement at the end of treatment.

[0481] After obtaining an initial position and a target position for each tooth, a movement path can be defined for the movement of each tooth. In some embodiments, the movement path is configured to move the tooth in the fastest manner with the least number of round trips to move the tooth from its initial position to its desired target position. The tooth path can optionally be segmented, and the segments can be calculated so that the movement of each tooth within a segment remains within threshold limits for linear and rotational translation. In this way, the endpoints of each path segment can constitute a clinically feasible repositioning, and the collection of segment endpoints can constitute a clinically feasible sequence of tooth positions such that moving from one point to the next in the sequence does not result in tooth collision.

[0482] In step 220, a force system is determined to produce movement of one or more teeth along the movement path. It should be noted that in various embodiments, it is not necessary to determine a force system, and the exemplary method can determine the movement path without explicitly determining / defining a force system for a given patient. (For example, in some embodiments, a set of displacements can be determined for a given patient without determining the force system required to produce these displacements for the given patient). The force system may include one or more translational forces and / or one or more torques. Different force systems will result in different types of tooth movement, such as tilting, translation, rotation, extrusion, intrusion, root movement, etc. Biomechanical principles, modeling techniques, force calculation / measurement techniques, etc., including knowledge and methods commonly used in orthodontics, can be used to determine the appropriate force system to be applied to the teeth to achieve tooth movement. When determining the force system to be applied, sources that can be considered include literature, force systems determined by experiments or virtual modeling, computer-based modeling, clinical experience, minimizing unwanted forces, etc.

[0483] Determination of the force system may include constraints on the permissible forces, eg, permissible directions and magnitudes, and the desired motion resulting from the applied forces.

[0484] Determination of the force system can also include modeling of the patient's facial structure, such as the dentition and / or the skeletal structure of the jaw and palate. For example, scanned data of the dentition (e.g., X-ray data or 3D optical scan data) can be used to determine the parameters of the patient's oral cavity, thereby determining the force sufficient to provide the desired expansion of the patient's dentition and / or palate and / or dental arch. In some embodiments, various parameters of the patient's dentition can be measured or input by a treating professional. In other embodiments, the treating professional can select an appropriate treatment based on the patient's physiological characteristics. For example, the dentition characteristics can also be estimated based on factors such as the patient's age and other characteristics.

[0485] In step 230, a design of an orthodontic appliance configured to generate a force system is determined. Determination of the design, appliance geometry, material composition, and / or properties can be performed using a treatment or force application simulation environment. The simulation environment can include, for example, a computer modeling system, a biomechanical system or device, etc. Optionally, a digital model of the appliance and / or teeth, such as a finite element model, can be generated. The finite element model can be created using computer program application software available from a variety of suppliers. To create a solid geometric model, a computer-aided engineering (CAE) or computer-aided design (CAD) program can be used, such as provided by Autodesk, Inc. of San Rafael, California. Software Products. To create finite element models and analyze them, program products from several vendors may be used, including finite element analysis packages from ANSYS, Inc. of Canonsburg, Pennsylvania, and SIMULIA (Abaqus) software products from Dassault Systèmes of Waltham, Massachusetts.

[0486] Optionally, one or more designs can be selected for testing or force modeling. As described above, desired tooth movement can be identified, as well as the force system required or desired to cause the desired tooth movement. Using the simulation environment, the candidate designs can be analyzed or modeled to determine the actual force system produced using the candidate appliance. Optionally, one or more modifications can be made to the candidate appliance, and the force modeling can be further analyzed as described, for example, to iteratively determine the appliance design that produces the desired force system.

[0487] In step 240, manufacturing instructions for an orthodontic appliance incorporating the appliance design are generated. The instructions may be configured to control a manufacturing system or device to produce an orthodontic appliance having a specified dental arch or palatal expander design. In some embodiments, the instructions are configured to manufacture the orthodontic appliance using direct manufacturing (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct manufacturing, multi-material direct manufacturing, etc.) according to the various methods provided herein. In alternative embodiments, the instructions may be configured to manufacture the appliance indirectly, for example, by thermoforming.

[0488] Method 200 may include the additional steps of 1) performing an intraoral scan of the patient's dentition to generate three-dimensional data of the dentition; and 2) determining a three-dimensional shape contour of an appliance to provide a plurality of tooth receiving cavities to move the patient's dentition from an initial arrangement to a target arrangement as described herein.

[0489] Although the above steps illustrate a method 200 for designing an orthodontic appliance according to some embodiments, a person of ordinary skill in the art will recognize some variations based on the teachings described herein. Some steps may include sub-steps. Some of these steps may be repeated as needed. One or more steps of method 200 may be performed using any suitable manufacturing system or device (e.g., the embodiments described herein). Some steps may be optional, and the order of the steps may be changed as needed.

[0490] Figure 3 A method 300 for digitally planning orthodontic treatment and / or designing or manufacturing appliances according to an embodiment is shown. The method 300 may be applied to any treatment procedure described herein and may be performed by any suitable data processing system.

[0491] In step 310, a digital representation of the patient's teeth is received. The digital representation may include surface topography data of the patient's oral cavity (including teeth, gum tissue, etc.). The surface topography data may be generated by directly scanning the oral cavity, a physical model (positive or negative) of the oral cavity, or an impression of the oral cavity using a suitable scanning device (e.g., a handheld scanner, a desktop scanner, etc.).

[0492] In step 320, one or more treatment phases are generated based on the digital representation of the teeth. The treatment phases may be incremental repositioning phases of an orthodontic treatment procedure designed to move one or more teeth of a patient from an initial tooth arrangement to a target tooth arrangement. For example, the treatment phases may be generated by determining an initial tooth arrangement indicated by the digital representation, determining a target tooth arrangement, and determining a movement path of one or more teeth in the initial arrangement required to achieve the target tooth arrangement. The movement path may be optimized based on minimizing the total distance moved, preventing inter-tooth collisions, avoiding more difficult to achieve tooth movement, or any other suitable criteria.

[0493] In step 330, at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances can be manufactured, each appliance is formed according to the tooth arrangement specified by a treatment phase, so that the patient can wear the appliances in sequence to incrementally reposition the teeth from the initial arrangement to the target arrangement. The appliance set can include one or more orthodontic appliances described herein. The manufacture of the appliance can involve creating a digital model of the appliance for use as an input to a computer-controlled manufacturing system. The appliance can be formed using direct manufacturing methods, indirect manufacturing methods, or a combination thereof as desired.

[0494] In some cases, various arrangements or staging of treatment phases may not be necessary for the design and / or manufacture of the device. Figure 3 As shown by the dashed lines in , the design and / or manufacture of orthodontic appliances and possible specific orthodontic treatments may include using a representation of a patient's teeth (e.g., receiving a digital representation of the patient's teeth 310), and then designing and / or manufacturing the orthodontic appliance based on the representation of the patient's teeth in the arrangement represented by the received representation.

[0495] 2) Treatment by track

[0496] refer to Figure 4 , showing a method 400 according to the present disclosure. Various aspects of the method will be discussed in further detail below. The method includes receiving information about a patient's orthodontic condition and / or treatment information (402), generating a case assessment (404), and generating a treatment plan (406) for repositioning the patient's teeth. In short, the patient / treatment information includes data containing an initial arrangement of the patient's teeth, which includes obtaining an impression or scan of the patient's teeth before starting treatment, and may also include identification of one or more treatment goals selected by the practitioner and / or the patient. A case assessment (404) can be generated to assess the complexity or difficulty of moving the patient's specific teeth in general or specifically corresponding to the identified treatment goals, and may also include the practitioner's experience and / or comfort in implementing the desired orthodontic treatment. However, in some cases, the assessment may include simply identifying specific treatment options (e.g., appointment scheduling, progress tracking, etc.) that the patient and / or practitioner are interested in. The information and / or corresponding treatment plan includes identifying a desired final or target arrangement of the patient's teeth, as well as a plurality of planned continuous or intermediate tooth arrangements for moving the teeth from the initial arrangement to the selected final or target arrangement along the treatment path.

[0497] The method also includes generating a customized treatment guide (408). The treatment plan may include multiple treatment phases, and a set of customized treatment guide groups corresponding to the phases of the treatment plan are generated. The guide may include detailed information about the time and / or content (e.g., specific tasks) to be completed in a given treatment phase, and may be detailed enough to guide practitioners throughout the treatment phase, including less experienced practitioners or practitioners who are relatively unfamiliar with a particular orthodontic treatment process. Because the guide is designed to correspond specifically to the treatment plan and provide guidance on activities clearly identified in the treatment information and / or generated treatment plan, the guide is referred to as customized. The customized treatment guide is then provided to the practitioner to help guide the practitioner on how to provide a given treatment phase. As described above, appliances can be generated based on the planned arrangement, and can be provided to the practitioner and ultimately applied to the patient (410). Appliances can be provided and / or applied in sets or batches, for example, 2, 3, 4, 5, 6, 7, 8, 9 or more appliances, but are not limited to any specific application scheme. The appliance may be provided to the practitioner simultaneously with a given set of guidelines, or the appliance and guidelines may be provided separately.

[0498] After treatment has been initiated as planned, and after appliances have been administered to the patient, treatment progress tracking is performed, for example, by tooth matching, to assess the current and actual alignment of the patient's teeth as compared to the planned alignment (412). If it is determined that the patient's teeth are "on track" and progressing as per the treatment plan, then treatment will progress as planned and the treatment proceeds to the next treatment phase (414). If the patient's teeth have substantially achieved the final alignment originally planned, then treatment proceeds to the final treatment phase (414). If it is determined that the patient's teeth are moving as per the treatment plan, but have not yet achieved the final alignment, the next set of appliances may be administered to the patient.

[0499] Table 12 below gives the threshold differences between the planned and actual positions of teeth that are selected as an indication that the patient's teeth have progressed on track. If the patient's teeth progress at or within the threshold, then the progress is considered to be on track. If the patient's teeth progress exceeds the threshold, then the progress is considered to be off track.

[0500] Table 12

[0501]

[0502]

[0503] 3) Experimental methods

[0504] Unless otherwise stated, all chemicals were purchased from commercial sources and used without further purification.

[0505] In some embodiments, stress relaxation of a material or device can be measured by monitoring the time-dependent stress caused by the stable strain. The degree of stress relaxation can also depend on temperature, relative humidity and other applicable conditions (e.g., the presence of water). In various embodiments, the test conditions for stress relaxation are a temperature of 37±2° C. at 100% relative humidity or a temperature of 37±2° C. in water.

[0506] The dynamic viscosity of a fluid indicates its resistance to shear flow. The SI unit for dynamic viscosity is Poiseuille (Pa·s). Dynamic viscosity is usually given in centipoise, where 1 centipoise (cP) is equal to 1 mPa·s. Kinematic viscosity is the ratio of dynamic viscosity to the density of the fluid; the SI unit is m 2 / s. Devices for measuring viscosity include viscometers and rheometers. For example, the MCR 301 rheometer from Anton Paar can be used for rheological measurements in rotational mode (PP-25, 50s-1, 50-115°C, 3°C / min).

[0507] Determining the moisture content at full saturation at the use temperature may include exposing the polymeric material to 100% humidity at the use temperature (eg, 40° C.) for a period of 24 hours and then determining the moisture content by methods known in the art, eg, by weight.

[0508] In some embodiments, the presence of a crystalline phase and an amorphous phase provides advantageous material properties for the polymer material. For example, the property values ​​of the cured polymer material can be determined by using the following method:

[0509] Storage modulus can be measured at 37°C and reported in MPa;

[0510] T of cured polymer materials g It can be evaluated using dynamic mechanical analysis (DMA) and is provided herein as tan delta peak;

[0511] Tensile modulus, tensile strength, elongation at yield, and elongation at break may be evaluated according to ISO 527-25B; and tensile strength at yield, elongation at break, tensile strength, and Young's modulus may be evaluated according to ASTM D1708.

[0512] As a non-limiting example, additive manufacturing or 3D printing methods for producing devices (e.g., orthodontic appliances) herein may be performed using a prototype thermolithography device from Cubicure (Vienna, Austria), which may be substantially as described herein. Figure 5 In this case, the photocurable resin (e.g., resin) according to the present disclosure may be filled into Figure 5The device shown is in a transparent material vat, which can be heated to 90-110° C. The building platform can also be heated to 90-110° C. and lowered to establish full contact with the upper surface of the curable composition. By irradiating the composition with 375 nm UV radiation using a diode laser from Soliton, which can have an output power of 70 mW, which can be controlled to track a predetermined prototype design, and alt...

Claims

1. A curable composition for additive manufacturing, the curable composition comprising: a plurality of polymerizable monomers, the polymerizable monomers comprising at least 80 wt % of a crosslinking agent; At least 10 wt% filler material.

2. A curable composition comprising: a plurality of polymerizable monomers, the polymerizable monomers comprising at least 80 wt % of a crosslinking agent; and At least 0.5 wt% of a wetting agent.

3. A curable composition comprising: a plurality of polymerizable monomers, the polymerizable monomers comprising at least 80 wt % of a crosslinking agent; wherein the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 upon curing.

4. The curable composition of any one of claims 1 to 3, wherein the crosslinking agent comprises at least 90 wt% of the polymerizable monomers.

5. The curable composition of any one of claims 1 to 4, wherein the crosslinking agent comprises at least 95 wt% of the polymerizable monomers.

6. The curable composition according to any one of claims 1 to 5, wherein the crosslinking agent comprises a plurality of crosslinking agents having different molecular weights.

7. The curable composition of any one of claims 1 to 6, wherein 50 to 100 wt% of the crosslinking agent comprises two polymerizable functional groups.

8. The curable composition of any one of claims 1 to 7, wherein 50 to 100 wt% of the crosslinker comprises at least 14 atoms between polymerizable functional groups.

9. The curable composition of any one of claims 1 to 8, wherein the curable composition is photocurable, chemically curable, thermally curable, or any combination thereof.

10. The curable composition according to any one of claims 1 to 9, wherein the curable composition is photocurable.

11. The curable composition of any one of claims 1 to 10, wherein 50 to 100 mole percent of the functional groups of the plurality of polymerizable monomers are ethylenically unsaturated functional groups.

12. The curable composition of any one of claims 1 to 11, wherein 50 to 100 mole percent of the functional groups of the plurality of polymerizable monomers are acrylates, methacrylates, or combinations thereof.

13. The curable composition of any one of claims 1-12, wherein 50 to 100 wt% of the polymerizable monomer has a molecular weight of at least 250 Da.

14. The curable composition according to any one of claims 1 to 13, wherein the crosslinking agent comprises an alkane backbone, an alkane diol backbone, an oligoethylene glycol backbone, a diphenyl backbone, a glycidyl backbone, a urethane backbone, or a combination thereof.

15. The curable composition according to any one of claims 2 to 14, further comprising a filler material.

16. The curable composition of any one of claims 1-15, wherein the filler material comprises silica, glass, a radiopaque material, a ceramic, a metal, a metal oxide, a crystal, a prepolymerized substance, or any combination thereof.

17. The curable composition according to claim 15 or 16, wherein the curable composition comprises 0.05 to 60 wt% of a filler material.

18. The curable composition according to claim 15 or 16, wherein the curable composition comprises 1 to 20 wt% of a filler material.

19. The curable composition of any one of claims 1-18, wherein the curable composition comprises from about 60 wt% to about 90 wt% of the polymerizable monomer.

20. The curable composition of any one of claims 1 or 3-19, further comprising a wetting agent.

21. The curable composition of any one of claims 1-20, wherein the wetting agent comprises a siloxane.

22. The curable composition of any one of claims 1 to 21 further comprising a pigment.

23. The curable composition of claim 22, wherein the pigment is inorganic or organometallic.

24. The curable composition of any one of claims 1 to 23, further comprising a photoinitiator.

25. The curable composition of claim 24, wherein the photoinitiator comprises an oligomer or a polymer.

26. The curable composition of any one of claims 1-2 or 4-25, wherein the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured.

27. The curable composition of any one of claims 1-26, wherein the curable composition is configured to exhibit a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured.

28. A curable composition for additive manufacturing, the curable composition comprising: an initiator that initiates the reaction; A first cross-linking agent comprising: a first plurality of polymerizable functional groups, and an arylene group or a heteroarylene group disposed between at least two polymerizable functional groups in the first plurality of polymerizable functional groups; and A second cross-linking agent comprising: a second plurality of polymerizable functional groups, and An alkylene or heteroalkylene group is disposed between at least two polymerizable functional groups in the second plurality of polymerizable functional groups.

29. The curable composition of claim 28, wherein the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups are each a plurality of ethylenically unsaturated functional groups.

30. The curable composition of claim 28 or 29, wherein the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups each comprise two polymerizable functional groups.

31. The curable composition of any one of claims 28-30, wherein the second crosslinker comprises a carbamate, a diol, or a combination thereof disposed between at least two polymerizable functional groups in the second plurality of polymerizable functional groups.

32. The curable composition of any one of claims 28-31, wherein the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups, or combinations thereof.

33. The curable composition of any one of claims 28-32, wherein the first plurality of polymerizable functional groups and the second plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, or a combination thereof.

34. The curable composition of any one of claims 28-33, wherein at least two polymerizable functional groups in the first plurality of polymerizable functional groups are separated by at least 14 atoms.

35. The curable composition of any one of claims 28-34, wherein at least two polymerizable functional groups in the second plurality of polymerizable functional groups are separated by at least 14 atoms.

36. The curable composition of any one of claims 28-35, wherein the molecular weights of the first crosslinking agent and the second crosslinking agent differ by at least 200 Daltons (Da).

37. The curable composition according to any one of claims 28 to 36, further comprising a third crosslinking agent, the third crosslinking agent comprising: a third plurality of polymerizable functional groups, and An alkylene backbone connecting at least two polymerizable functional groups of the third plurality of polymerizable functional groups.

38. The curable composition of any one of claims 28-37, wherein the alkylene backbone is substituted with a functional group selected from the group consisting of halogen, alkyl, alkenyl, alkynyl, alkoxy, hydroxyl, amine, thiol, cyano, aryl, heteroaryl, ester, amide, carbamate, carbonate, and combinations thereof.

39. The curable composition of any one of claims 28-37, wherein the alkylene backbone is unsubstituted.

40. The curable composition of any one of claims 37-39, wherein at least two polymerizable functional groups in the third plurality of functional groups are separated by 6 to 15 carbons of the alkylene backbone.

41. The curable composition of any one of claims 37-40, wherein the third plurality of polymerizable functional groups comprises two polymerizable functional groups.

42. The curable composition of any one of claims 37-41, wherein the third plurality of polymerizable functional groups is a plurality of ethylenically unsaturated functional groups.

43. The curable composition of any one of claims 37-42, wherein the third plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, acrylamide groups, methacrylamide groups, vinyl ether groups, styryl groups, epoxy groups, or combinations thereof.

44. The curable composition of any one of claims 37-43, wherein the third plurality of polymerizable functional groups are a plurality of acrylate groups, methacrylate groups, or combinations thereof.

45. The curable composition of any one of claims 37-44, wherein at least two polymerizable functional groups in the third plurality of polymerizable functional groups are separated by at least 6 atoms.

46. ​​The curable composition of any one of claims 28-45, wherein the molecular weights of the first crosslinker, the second crosslinker, and the third crosslinker differ by at least 200 Daltons (Da).

47. The curable composition of any one of claims 28-46, wherein at least 90% of the polymerizable functional groups of the curable composition are disposed within a crosslinker.

48. The curable composition of any one of claims 28-47, wherein the curable composition is photocurable, chemically curable, thermally curable, or any combination thereof.

49. The curable composition of any one of claims 28-48, wherein the curable composition is photocurable.

50. The curable composition of any one of claims 28-49, further comprising a filler material.

51. The curable composition of claim 50, wherein the filler material comprises silica, glass, a radiopaque material, a ceramic, a metal, a metal oxide, a crystal, or any combination thereof.

52. The curable composition of claim 50 or 51, wherein the curable composition comprises 0.05 to 60 wt% of filler material.

53. The curable composition of claim 50 or 51, wherein the curable composition comprises 1 to 20 wt% of a filler material.

54. The curable composition of any one of claims 28-53, wherein the curable composition comprises 60 wt% to 90 wt% of the polymerizable species.

55. The curable composition of any one of claims 28-54, further comprising a wetting agent.

56. The curable composition of claim 55, wherein the wetting agent comprises a siloxane.

57. The curable composition of any one of claims 28-56, further comprising a pigment.

58. The curable composition of claim 57, wherein the pigment is inorganic or organometallic.

59. The curable composition of any one of claims 28-58, wherein the initiator comprises a photoinitiator.

60. The curable composition of claim 59, wherein the photoinitiator comprises an oligomer or a polymer.

61. The curable composition of any one of claims 28-60, wherein the curable composition is configured to exhibit a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured.

62. The curable composition of any one of claims 28-61, wherein the curable composition is configured to exhibit a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured.

63. A printed device produced from the curable composition of any one of claims 1-62.

64. The printed device according to claim 63, wherein the printed device has a strength of 30 MPa to 120 MPa.

65. The printed device according to claim 63 or 64, wherein the printed device has a modulus of 800 MPa to 2000 MPa.

66. The printed device according to any one of claims 63-65, wherein the printed device has a fracture strain of 2.5% to 6.5%.

67. The printed device of any one of claims 63-66, wherein the printed device has a color defined by an L* value of 70 to 95, an a* value of -11 to 1, and a b* value of 2 to 22 when cured.

68. The printed device of any one of claims 63-67, wherein the printed device has a color defined by an L* value of 78 to 87, an a* value of -7 to -3, and a b* value of 8 to 16 when cured.

69. The printed device according to any one of claims 63-68, wherein the printed device is configured for use as a medical device.

70. The printed device of claim 69, wherein the medical device is an orthodontic appliance.

71. The printed device of claim 70, wherein the orthodontic appliance comprises an incremental palatal expander, a separator, an appliance, a prefabricated attachment template, or a dental attachment placement device.

72. A printed device according to claim 70 or 71, wherein the orthodontic appliance comprises one or more dental attachments shaped to attach to a person's dentition.

73. The printed device of claim 72, wherein the dental attachment is shaped to engage with corresponding one or more attachment grooves of an orthodontic appliance and, when engaged with the one or more attachment grooves, apply one or more forces to a person's dentition.

74. A method of treating a subject in need thereof, the method comprising applying the medical device of any one of claims 69-73 to the subject, thereby treating the subject.

75. The method of claim 74, wherein the medical device is a dental attachment, and wherein the applying comprises adhering the dental attachment to a tooth of the subject.

76. The method of claim 75, further comprising coupling a dental brace to the dental attachment.

77. A method of repositioning a patient's teeth, the method comprising: generating a treatment plan for the patient, the plan comprising a plurality of intermediate tooth arrangements for moving teeth along a treatment path from an initial tooth arrangement toward a final tooth arrangement; Providing a dental attachment, the dental attachment comprising a printed device according to any one of claims 63-73; and adhering the dental attachment to the patient's tooth; as well as A dental appliance is coupled to the dental attachment, wherein the dental appliance is configured to move at least one of the patient's teeth toward an intermediate dental arrangement or the final dental arrangement.

78. The method of claim 77, further comprising producing the dental attachment by 3D printing the dental attachment.

79. The method of claim 77 or 78, further comprising tracking the progress of the patient's teeth along the treatment path after applying the dental attachment to the patient, the tracking comprising comparing the current arrangement of the patient's teeth with the planned arrangement of the patient's teeth.

80. The method of any one of claims 77-79, wherein after 2 weeks of treatment, greater than 60% of the patient's teeth comply with the treatment plan.

81. A method of manufacturing an accessory placement device, the method comprising: Obtaining a curable composition according to any one of claims 1 to 62; and The curable composition is used to additively manufacture a printed article including the accessory placement device.

82. A dental attachment placement device produced by an additive manufacturing process from a curable composition, the curable composition comprising: at least one first cross-linking agent having a rigid backbone between the plurality of first polymerizable functional groups; at least one second cross-linking agent having a flexible backbone between the plurality of second polymerizable functional groups; Photoinitiator, in, The polymer material formed from the curable composition has a tensile strength of about 50 MPa or more, a modulus strength of 1200 MPa or more, and a strain at break of about 4% or more.

83. The dental attachment placement device of claim 82, wherein the at least one first cross-linking agent has the following structure (I): Y 1 —X 1 -L 1 —A——L 2 —X 2 —Y 2 , (I) in: A is cycloalkylene, alkylenecycloalkylene, alkylenecycloalkylenealkylene, heterocycloalkylene, arylene, heteroarylene, alkylenearylene, or alkylenearylenealkylene; L 1 and L 2 are independently amide, ether, ester, carbonate, carbamate or urea bonds; X 1 and X 2 are independently an alkylene or heteroalkylene linking group; and Y 1 and Y 2 are independently polymerizable functional groups.

84. The dental attachment placement device of claim 83, wherein A has one of the following structures: Where R 1 , R 2 and R 3 are independently H or alkyl.

85. The dental attachment placement device of claim 83, wherein X 1 and X 2 Independently has one of the following structures: wherein n is an integer from 1 to 20.

86. The dental attachment placement device of claim 83, wherein Y 1 and Y 2 Independently has one of the following structures: Where R 4 is H or alkyl.

87. The dental attachment placement device of any one of claims 82-86, wherein the at least one second cross-linking agent has the following structure (II): Y 3 —X 3 —L 3 —B—L 4 —X 4 —Y 3 , (II) in: B is a linear or branched alkylene or heteroalkylene group; L 3 and L 4 are independently an optional amide bond, ether bond, ester bond, carbonate bond, urethane bond or urea bond; X 3 and X 4 is independently an optional alkylene or heteroalkylene linking group; and Y 3 and Y 4 are independently polymerizable functional groups.

88. The dental attachment placement device according to claim 87, wherein B has one of the following structures: wherein m is an integer from 1 to 20.

89. The dental attachment placement device of claim 87, wherein X 3 and X 4 Independently has one of the following structures: wherein n is an integer from 1 to 20.

90. The dental attachment placement device of claim 87, wherein Y 3 and Y 4 Independently has one of the following structures: Where R 4 is H or alkyl.

91. The dental attachment placement device of any one of claims 82-90, wherein the photoinitiator comprises a mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (BAPO) and oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl].

92. A dental attachment placement device produced by an additive manufacturing process from a curable composition as described in any one of claims 1 to 62, Wherein the dental attachment placement device comprises: main body; one or more additively manufactured dental attachments shaped to attach to a person's dentition at corresponding locations, wherein the one or more additively manufactured dental attachments are shaped to engage with corresponding one or more attachment recesses of an orthodontic appliance and, when engaged with the one or more attachment recesses, apply one or more forces to the person's dentition; as well as One or more additively manufactured supports for removably coupling the one or more additively manufactured accessories to the body.

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