3d-printed composites of phase separation materials

Abstract

This disclosure provides methods, systems, apparatus, and kits for producing composite materials from a single resin, the composite materials having multiple continuous phases. This disclosure includes a process for 3D printing objects having composite properties (e.g., orthodontic appliances). In some aspects, the composite properties are formed by a single formulation having components that have hard and soft continuous phases during processing. In some aspects, the composite properties are formed by separately treating the hard and soft phase components. In some aspects, the treated material is used to 3D print composite materials and apparatus.

Description

This application is a divisional application of the following invention patent application: filed on August 31, 2021, application number 202180073277.5, entitled 3D printing composite of phase-separated materials. Cross-references

[0001] This application claims the benefit of U.S. Provisional Application No. 63 / 072,804, filed August 31, 2020, which is incorporated herein by reference in its entirety for all purposes. Background Technology

[0002] Orthodontic surgery typically involves repositioning a patient's teeth into a desired arrangement to correct malocclusion and / or improve aesthetics. To achieve these goals, orthodontists and / or patients may apply orthodontic appliances such as braces, retainers, and shell aligners to the patient's teeth. These appliances are configured to apply force to one or more teeth to achieve the desired tooth movement. The application of force can be adjusted periodically (e.g., by changing the appliance or using different types of appliances) to gradually reposition the teeth into the desired arrangement. Polymer materials can be used to manufacture appliances for repositioning a patient's teeth. Summary of the Invention

[0003] Polymer materials possessing both stiffness and elasticity are desirable, such as 3D-printable resins that can be formed from these polymers. This disclosure provides methods, systems, and apparatus for generating composite materials from a single resin using phase separation.

[0004] This summary is provided to introduce some concepts in a simplified form, which will be further described in the detailed embodiments below. This summary is not intended to specify key features of the claimed subject matter, nor is it intended to help determine the scope of the claimed subject matter.

[0005] This document provides methods, systems, apparatus, and kits for producing composite materials from a single resin. In some embodiments, the resin comprises: a first continuous phase including a component having a first reactive property; and a second continuous phase including a component having a second reactive property, the first reactive property being greater than the second reactive property, and the resin is a 3D printable resin. This document also provides a method for producing composite materials using a resin comprising: a first continuous phase including a component having a first reactive property; and a second continuous phase including a component having a second reactive property, the first reactive property being greater than the second reactive property, the resin being a 3D printable resin, and initiating a polymerization reaction by curing the resin. This document also provides orthodontic appliances using the composite materials or compositions disclosed herein.

[0006] In various respects, this document provides a curable resin comprising: a first continuous phase comprising a first polymerizable component having a first polymerization rate; and a second continuous phase comprising a second polymerizable component having a second polymerization rate, wherein the first polymerization rate and the second polymerization rate are determined under conditions sufficient for 3D printing.

[0007] In various respects, this document provides a curable resin comprising: a first continuous phase comprising a first polymerizable component and a second polymerizable component, wherein the first polymerizable component is present at a higher concentration than the second polymerizable component; and a second continuous phase comprising the first polymerizable component and the second polymerizable component, wherein the first polymerizable component is present at a lower concentration than the second polymerizable component.

[0008] In various respects, this document provides a curable resin comprising: a first continuous phase comprising a first polymerizable component; a second continuous phase comprising a second polymerizable component; and a third continuous phase comprising a third polymerizable component.

[0009] In various respects, this document provides a curable resin comprising: a first continuous phase comprising a radically polymerizable component; and a second continuous phase comprising an ionicly polymerizable component, wherein the radically polymerizable component has a higher polymerization rate than the ionicly polymerizable component.

[0010] In some embodiments, the first continuous phase, upon curing, comprises a first polymer region having a first hardness of 60 Shore A to 85 Shore D; the second continuous phase, upon curing, comprises a second polymer region having a second hardness of 60 Shore A to 85 Shore D, wherein the first hardness, determined after 24 hours in an aqueous environment at 37°C, is less than the second hardness. In some aspects, the first polymerizable component comprises a methacrylate portion, and the second polymerizable component comprises an acrylate portion. In some aspects, the first polymerization rate has a minimum of 3.5 × 10⁻⁶. 3 s -1 and not greater than 5×10 3 s -1 The rate constant, the second polymerization rate has at least 1.8 × 10⁻⁶. 3 s -1 and not greater than 2.5 × 10 3 s -1The rate constant. In some aspects, the component having a first polymerization rate is an acrylate, and the component having a second polymerization rate is a methacrylate. In some aspects, the acrylate is bifunctional, and the methacrylate is monofunctional. In some aspects, the acrylate is bifunctional, the methacrylate is bifunctional, and the methacrylate is spatially larger than the acrylate. In some aspects, the component having a second polymerization rate is a vinyl ester. In some aspects, the component having a first polymerization rate is an acrylate or a methacrylate. In some aspects, the component having a first polymerization rate is radically polymerizable. In some aspects, the component having a first polymerization rate is a radically polymerizable monomer. In some aspects, the component having a first polymerization rate includes acrylates, methacrylate monomers, or combinations thereof. In some aspects, the component having a second polymerization rate is ionicly polymerizable. In some aspects, the component having a second polymerization rate is an ionicly polymerizable monomer. In some aspects, the component having a second polymerization rate includes an epoxide. In some aspects, the epoxide is a cationically curable epoxide. In some aspects, the resin described herein may also include a third phase, a fourth phase, or more than four phases. In some aspects, the third phase includes fillers. In some aspects, the third phase includes polymers. In some aspects, the polymer includes thermoplastics. In some aspects, the polymer is selected from polyolefins, polyesters, polyacrylates, polymethacrylates, polystyrene, polypropylene, polyethylene, polyethylene terephthalate, polylactic acid, polyurethane, epoxy polymers, polyethers, polyvinyl chloride, polysiloxanes, polycarbonates, polyaramids, polyacrylonitrile, polybutadiene, polycyclic olefins, and copolymers. In some aspects, the component having a first polymerization rate includes a polymer, and the component having a polymerization rate includes a polymerizable monomer; or the component having a first polymerization rate includes a polymerizable monomer, and the component having a second polymerization rate includes a polymer. In some aspects, the polymer is a thermoplastic. In some aspects, the polymer is miscible with the polymerizable monomer. In some aspects, the polymer is partially or completely immiscible with the polymerizable monomer. In some aspects, the polymer is partially or completely insoluble in the resin during the polymerization of the polymerizable monomer. In some aspects, the polymer is partially or completely insoluble in the resin. In some aspects, the polymer includes one or more reactive functional groups. In some aspects, the resin herein may also include a filler. In some aspects, the resin herein may also include a discontinuous phase comprising the filler. In some aspects, the resin herein may also include a continuous phase comprising the filler. In some aspects, the filler is functionalized, including fibers or combinations thereof. In some aspects, the resin herein may also include three, four, five, six, or more than six phases. In some aspects, the resin herein may also include multiple hard phases. In some aspects, the resin herein may also include multiple soft phases.

[0011] In various respects, this document provides a method for producing a composite polymer composition, the method comprising: providing a resin according to any one of claims 1 to 38; and initiating a polymerization reaction by curing the resin.

[0012] In various respects, this document provides a method comprising: curing a resin comprising a first continuous phase and a second continuous phase to produce a composite material comprising a soft region having a first hardness and a hard region having a second hardness, wherein the first hardness is less than the second hardness; manufacturing an orthodontic appliance using the composite material; and analyzing the orthodontic appliance to identify the soft and hard regions of the composite material. In some cases, the analysis includes the use of microscopy techniques.

[0013] In various respects, this document provides a method for generating a composite material, the method comprising: placing a curable resin comprising a first polymerizable component and a second polymerizable component under conditions sufficient to initiate polymerization; and polymerizing the first polymerizable component faster than the second polymerizable component to generate a composite material comprising: a soft polymer region having a first hardness and comprising the first polymerizable component in a polymerized form, and a hard polymer region having a second hardness and comprising the second polymerizable component in a polymerized form.

[0014] In various aspects, this document provides a method for generating a composite material, comprising: placing a first polymerizable component of a resin under a first set of conditions sufficient to initiate polymerization of the first polymerizable component; and placing a second polymerizable component of the resin under a second set of conditions sufficient to initiate polymerization of the second polymerizable component, wherein the first set of conditions and the second set of conditions differ, and wherein the first set of conditions includes one or more of a first light wavelength and a first temperature, and the second set of conditions includes one or more of a second light wavelength and a second temperature. In some aspects, the cured resin includes a photocurable resin, a thermocurable resin, or a combination thereof. In some aspects, the polymerization conditions include one or more photocuring steps, one or more thermocuring steps, or a combination thereof. In some aspects, photocuring includes two or more photocuring steps. In some aspects, thermocuring includes two or more thermocuring steps. In some aspects, this method may also include manufacturing an object using the cured polymer material. In some aspects, the manufacturing includes printing with a 3D printer. In some aspects, the object is an orthodontic appliance. In some aspects, the orthodontic appliance is an orthodontic appliance, an expander, or a spacer. In some aspects, an orthodontic appliance includes a plurality of tooth receiving cavities configured to reposition a tooth from a first configuration to a second configuration. In some aspects, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition a tooth from an initial configuration to a target configuration. In some aspects, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition a tooth from an initial configuration to a target configuration. In some aspects, the orthodontic appliance is an orthodontic appliance.

[0015] In various respects, this document also provides composite materials prepared by any one or more of the resins and / or methods described herein.

[0016] In various aspects, this document also provides a composite material comprising: a first continuous phase comprising a first polymeric region comprising a first polymerizable component in a polymerizable form and having a first hardness of 60 Shore A to 85 Shore D; and a second continuous phase comprising a second polymeric region comprising a second polymerizable component in a polymerizable form and having a second hardness of 60 Shore A to 85 Shore D, wherein the first polymerizable component polymerizes faster than the second polymerizable component, and wherein the first hardness, determined after 24 hours in an aqueous environment at 37°C, is less than the second hardness. In some aspects, the first polymerizable component comprises methacrylate. In some aspects, the second polymerizable component comprises acrylate. In some aspects, the first polymerizable component comprises methacrylate, and the second polymerizable component comprises acrylate. In some aspects, the first polymerizable component has a higher molecular weight than the second polymerizable component. In some aspects, the first polymerizable component comprises methacrylate or an acrylate portion, and the second polymerizable component comprises a vinyl ester. In some aspects, the composite material comprises an interpenetrating network. In some aspects, the second polymeric region comprises an epoxide. In some aspects, the epoxide is a cationicly cured epoxide. In some aspects, the first continuous phase comprises a vertical dimension of less than 100 nm, a lateral dimension of less than 100 nm, or a combination thereof. In some aspects, the second continuous phase comprises a vertical dimension of less than 100 nm, a lateral dimension of less than 100 nm, or a combination thereof (see, for example...). Figure 5In some aspects, the composite material described herein may further include a gradient between the first continuous phase and the second continuous phase. In some aspects, the composite material is characterized by one or more of the following: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; and residual stress greater than or equal to 0.01 MPa. In some aspects, the first continuous phase is characterized by one or more of the following: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; and residual stress greater than or equal to 0.01 MPa. In some aspects, the second continuous phase is characterized by one or more of the following: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; and residual stress greater than or equal to 0.01 MPa. In some aspects, the composite material, the first continuous phase, the second continuous phase, or a combination thereof, is characterized by a residual stress of 5% to 45% of the initial load, or a residual stress of 20% to 45% of the initial load. In some aspects, the composite material, the first continuous phase, the second continuous phase, or combinations thereof are characterized by a tensile modulus of 500 MPa to 2000 MPa, or a tensile modulus of 800 MPa to 2000 MPa. In some aspects, the composite material is characterized by: an elongation at break greater than or equal to 5%; a storage modulus greater than or equal to 500 MPa; a tensile modulus greater than or equal to 500 MPa; and a residual stress greater than or equal to 0.01 MPa. In some aspects, the composite material, the first continuous phase, the second continuous phase, or combinations thereof are characterized by an elongation at break greater than 10%, an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break between 40% and 250%. In some aspects, the composite material, the first continuous phase, the second continuous phase, or combinations thereof are characterized by a storage modulus of 0.1 MPa to 4000 MPa, a storage modulus of 300 MPa to 3000 MPa, or a storage modulus of 750 MPa to 3000 MPa. In some aspects, the composite material, the first continuous phase, the second continuous phase, or combinations thereof are characterized by a residual stress of 0.01 MPa to 15 MPa, or a residual stress of 2 MPa to 15 MPa. In some aspects, greater than 70% of visible light passes through the composite material, the first continuous phase, the second continuous phase, or combinations thereof. In some aspects, the composite material, the first continuous phase, the second continuous phase, or combinations thereof are biocompatible, bioinert, or combinations thereof.

[0017] This document also provides orthodontic appliances comprising one or more composite materials disclosed herein. In some aspects, the orthodontic appliance is an orthodontic appliance, an expander, or a spacer. In some aspects, the orthodontic appliance includes a plurality of tooth receiving cavities configured to reposition a tooth from a first configuration to a second configuration. In some aspects, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition a tooth from an initial configuration to a target configuration. In some aspects, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition a tooth from an initial configuration to a target configuration according to a treatment plan. In some aspects, the orthodontic appliance is an orthodontic appliance. By incorporating references

[0018] All publications, patents and patent applications mentioned in this specification are incorporated herein by reference, to the same extent as if each individual publication, patent or patent application were specifically and individually identified by reference. Attached Figure Description

[0019] The novel features of the invention are specifically set forth in the appended claims. A better understanding of the features and advantages of this disclosure will be obtained by referring to the following detailed description and accompanying drawings, which illustrate illustrative embodiments utilizing the principles of the invention, in which:

[0020] Figure 1A A tooth repositioning appliance according to an embodiment is shown.

[0021] Figure 1B A tooth repositioning system according to an embodiment is shown.

[0022] Figure 1C A method for orthodontic treatment using multiple appliances according to an embodiment is shown.

[0023] Figure 2 A method for designing orthodontic appliances according to an embodiment is shown.

[0024] Figure 3 A method for digitally planning orthodontic treatment is illustrated according to an embodiment.

[0025] Figure 4 The generation and application of treatment according to an embodiment of the invention are illustrated.

[0026] Figure 5 The horizontal and vertical dimensions are shown as used in this article.

[0027] Figure 6 A schematic configuration of a high-temperature additive manufacturing apparatus for curing the curable composition disclosed herein using a 3D printing process is shown. Detailed Implementation

[0028] This disclosure provides compositions, methods, systems, apparatuses, and kits for producing composite materials from a single resin. More specifically, in some aspects, this disclosure relates to methods, systems, apparatuses, and kits for forming composite materials having multiple continuous phases, wherein the multiple phases are generated from a single-formulated resin. In some aspects, this disclosure includes a process for three-dimensionally printing objects having composite properties (e.g., orthodontic appliances). In some aspects, the composite properties are formed by a single formulation having components having hard and soft continuous phases during processing. In some aspects, the composite properties are formed by separately processing the hard phase component and the soft phase component. In some aspects, a three-dimensional printing apparatus is used with treated materials. Complex components

[0029] This disclosure provides composite materials comprising at least two continuous phases formed from a single resin. In embodiments described herein, the composite material (also referred to herein as a polymeric composite) comprises a first continuous phase and a second continuous phase. In some embodiments, the first continuous phase comprises a soft polymer region (i.e., a soft phase). In some embodiments, the first continuous phase is a soft polymer region (i.e., a soft phase). In some embodiments, the second continuous phase comprises a hard polymer region (i.e., a hard phase). In some embodiments, the second continuous phase is a hard polymer region (i.e., a hard phase). In some embodiments described herein, the composite material is formed from a single polymerizable resin. In some embodiments, photopolymerization is used to polymerize the resin to form the composite material.

[0030] In some aspects, this disclosure provides resins capable of forming multiple composite materials. In some embodiments, this disclosure provides a resin comprising a first continuous phase and a second continuous phase, the first continuous phase comprising a component having a first reactivity (i.e., a first component), and the second continuous phase comprising a component having a second reactivity (i.e., a second component). In some embodiments, the first reactivity is greater than the second reactivity. In some embodiments, the resin is capable of 3D printing (i.e., is a 3D-printable resin).

[0031] In some embodiments, the soft phase is characterized by the presence of a more reactive component (e.g., including the first component when it is highly reactive). In some embodiments, the hard phase is characterized by the presence of a less reactive component (e.g., including the second component when it is less reactive). In some embodiments, the more reactive component of the resin described herein is polymerized to form the soft phase (i.e., soft regions) of the composite material. In some embodiments, the less reactive component of the resin described herein is polymerized to form the hard phase (i.e., hard regions) of the composite material. As a non-limiting example, a resin comprising a highly reactive component corresponding to the soft phase and a less reactive component corresponding to the hard phase forms a composite material comprising a hard phase and a soft phase upon polymerization. In some embodiments, it is preferred that the soft phase is treated (e.g., polymerized) prior to the hard phase. In some embodiments, it is preferred that the soft phase comprises a component more reactive than the components of the hard phase (e.g., causing the soft phase to be treated or polymerized first). In some embodiments, the soft phase is formed prior to the formation of the hard phase. In some embodiments, the soft phase is substantially polymerized (e.g., more than 90% polymerized, as determined, for example, by FTIR analysis of double-to-single bond conversion). In some embodiments, the soft phase is substantially polymerized (e.g., more than 90% polymerized) before the hard phase polymerizes at 5%, 10%, or 15%.

[0032] In some embodiments, the first continuous phase includes a first polymer region upon curing. As a non-limiting example, a first continuous phase comprising a first component having a first reactivity (also referred to herein as the first component, the first polymerizable component, and component 1) polymerizes upon curing and forms a first polymer (also referred to herein as polymer 1) in the first polymer region. In some embodiments, the first component is a polymerizable monomer (also referred to herein as the first polymerizable monomer and monomer 1). In some embodiments, the second continuous phase includes a second polymer region upon curing. As a non-limiting example, a second continuous phase comprising a second component having a second reactivity (also referred to herein as the second component, the second polymerizable component, and component 2) polymerizes upon curing and forms a second polymer (also referred to herein as polymer 2) in the second polymer region. In some embodiments, the second component is a polymerizable monomer (also referred to herein as the second polymerizable monomer and monomer 2).

[0033] As used herein, a monomer can refer to a reagent capable of polymerization under one or more specified conditions. A monomer reagent may include at least one monomer molecule, wherein the monomer molecule is a molecule capable of polymerization, thereby contributing to the structure of a polymer or oligomer or aggregate. In embodiments, a monomer reagent may be represented by an average or dominant chemical structure and may include a plurality of monomer molecules having that chemical structure, but may also contain components having other chemical structures. For example, a monomer reagent may include impurities having chemical structures other than the average or dominant structure of the reagent. Oligomers or oligomer reagents are also reagents capable of polymerization under suitable conditions. Oligomer reagents include oligomer molecules comprising a small number of units derived from molecules of lower relative molecular mass. In embodiments, hyperbranched crosslinking reagents suitable for use in the present invention may be considered oligomer reagents.

[0034] In some embodiments, it is advantageous that the curable resin comprises a combination of a polymeric component (e.g., oligomers and / or polymers) and a monomeric component (e.g., reactive monomers such as reactive diluents). In some embodiments, the first component and / or the second component is a polymer. In some embodiments, the polymer is a reactive polymer (i.e., capable of further reactions), such as a functionalized or telechelic polymer capable of further polymerization. In some embodiments, the first component is a polymer, and the second component is a polymerizable monomer. In other embodiments, the first component comprises a polymerizable monomer, and the second component comprises a polymer. In some embodiments, the first component is a polymerizable monomer, and the second component is a polymer.

[0035] In some embodiments, the polymer is a thermoplastic, plastic, and / or thermosetting plastic. In some embodiments, the polymer is a thermoplastic. In some embodiments, the polymer is a plastic as further described herein. In some embodiments, the polymer is miscible with a polymerizable monomer (e.g., where the first component is the polymer, the second component is the polymerizable monomer, and the polymer is miscible with the polymerizable monomer). In some embodiments, the polymer is partially immiscible with the polymerizable monomer. In some embodiments, the polymer is completely immiscible with the polymerizable monomer.

[0036] In some embodiments, differences in density and / or immiscibility cause the phase or polymerizable component to separate into multiple parts, wherein a local point in the resin may include a liquid ratio different from that of different local points within the resin. As a non-limiting example, polymerization-induced phase separation (PIPS) can facilitate the separation of a continuous phase by altering the miscibility of the polymeric component in the resin. PIPS can, for example, increase the molecular weight of the first component, decrease the miscibility of the component, and cause phase separation. In some embodiments, the second component is partially immiscible with the polymer (e.g., the first polymer) formed from the first component during polymerization. In some embodiments, the first component is partially immiscible with the polymer (e.g., the second polymer) formed from the second component during polymerization. In some embodiments, the second component is completely immiscible with the first polymer. In some embodiments, the first component is completely immiscible with the second polymer.

[0037] In some embodiments, the polymer formed is insoluble in the resin. In some embodiments, the polymer is partially insoluble in the resin when the polymerizable monomer is polymerized in the resin (e.g., the polymerization of a first polymerizable monomer and / or a second polymerizable monomer to form the corresponding polymer). In some embodiments, the polymer is completely insoluble in the resin when the polymerizable monomer is polymerized in the resin. In some embodiments, the polymer formed herein is partially insoluble in the resin. In some embodiments, the polymer formed herein is completely insoluble in the resin. In some embodiments, the polymer includes one or more reactive functional groups. Reactive functional groups are further described herein.

[0038] In the embodiments described herein, a first polymeric region (e.g., a first continuous phase) has different mechanical and / or polymeric properties than a second polymeric region (e.g., a second continuous phase). In some embodiments, the first polymeric region has different mechanical properties than the second polymeric region. In some embodiments, the first polymeric region has a hardness lower than that of the second polymeric region. In some embodiments, the first continuous phase is at least 5%, at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 75%, at least 100%, at least 200%, at least 300%, at least 400%, at least 500%, at least 600%, at least 700%, at least 800%, at least 900%, or at least 1000% softer than the second continuous phase. In some embodiments, the first polymer (e.g., formed during the polymerization of a first polymerizable monomer) has different mechanical properties than the second polymer (e.g., formed during the polymerization of a second polymerizable monomer). In some embodiments, the first polymer has a hardness lower than that of the second polymer.

[0039] When compared to homopolymers of similar monomer types and / or when compared to homogeneously formed materials (e.g., excluding the first and second continuous phases described herein), the polymer composites and composite materials described herein can have enhanced physical properties. For example, a composite of a first polymer with high strength (e.g., storage modulus) and a second polymer with high flexibility can enable the composite to have higher toughness than homopolymers of either monomer type.

[0040] In some embodiments, a polymer is a molecule composed of repeating structural units (e.g., monomers) linked by covalent chemical bonds and is characterized by a large number of repeating units. In some embodiments, the polymer comprises 10 or more repeating units. In some embodiments, the polymer comprises 50 or more repeating units. In some embodiments, the polymer comprises 100 or more repeating units. In some embodiments, the polymer has a high molecular weight (e.g., greater than or equal to 5,000 Da). The polymer is typically a polymerization product of one or more monomer precursors. In some embodiments, the polymer is a homopolymer composed of a single type of repeating monomer subunits. In some embodiments, the polymer is a copolymer comprising two or more different types of monomers linked in the same polymer. The copolymer may comprise two or more monomer subunits and includes random copolymers, block copolymers, alternating copolymers, segment copolymers, graft copolymers, cone copolymers, and other copolymers. The term polymer also includes dendritic polymers, branched polymers, and crosslinked polymers. The term polymer may refer to inorganic polymers, organic polymers, or hybrid polymers. Useful polymers include organic polymers or inorganic polymers. In some embodiments, the polymer includes homopolymers, linear copolymers, block copolymers, alternating copolymers, periodic copolymers, statistical copolymers, random copolymers, gradient copolymers, branched copolymers, brush copolymers, comb copolymers, dendritic polymers, or any combination thereof. In some embodiments, the polymers disclosed herein are crosslinked.

[0041] In some embodiments, a plurality of monomer units form an oligomer, and the oligomer consists of repeating structural units linked by covalent chemical bonds, characterized in that the number of repeating units is less than the number of repeating units in the polymer (e.g., equal to or less than 20, 10 repeating units) and / or the molecular weight is less than that of the polymer (e.g., less than or equal to 5,000 Da). In some embodiments, the oligomer is a polymerization product of one or more monomer precursors.

[0042] In some embodiments, the polymer is formed via a polymerization reaction of a polymer precursor. In some embodiments, the resin is a viscous substance comprising a polymer precursor. In some embodiments, the resin may comprise multiple components, such as monomeric components that can be selectively activated to form a polymer (e.g., they are polymerizable components, such as the first and second polymerizable monomers described herein). The monomeric components within the resin may undergo polymerization to form the polymer. In some embodiments, the resin comprises more than one type or variety of monomeric components. In some embodiments, the resin herein comprises a first monomeric component having a different reactivity than the second monomeric component. In some embodiments, the resin comprises a first monomeric component that is more reactive than the second monomeric component. As a non-limiting example, the difference in reactivity may be attributed to differences in reactivity at a given photopolymerization wavelength, differences in reactivity at a given temperature (e.g., during thermosetting), and / or differences in the chemical rate of reactivity. In some embodiments, the resin comprises a third monomeric component that can be polymerized. In some embodiments, the resin comprises more than three monomeric components, each of which can be polymerized.

[0043] In some embodiments, the difference in reactivity between the first polymerizable component and the second polymerizable component is due to a difference in chemical reaction rates. In some embodiments, the first reactive component is methacrylate, and the second reactive component is acrylate. In some embodiments, the methacrylate component is more reactive than the acrylate component. In embodiments where the first polymerizable component is methacrylate and the second polymerizable component is acrylate, the resin comprises a soft methacrylate phase and a hard, less reactive acrylate phase. In some embodiments, the component with the first reaction rate is acrylate, and the component with the second reaction rate is methacrylate. In embodiments where the first polymerizable component is acrylate and the second polymerizable component is methacrylate, the resin comprises a soft acrylate phase and a hard, less reactive methacrylate phase.

[0044] In some embodiments, the resin comprises at least two components with different reactivity (e.g., one polymerizes at a faster rate than the other). In some embodiments, it is preferred that the component corresponding to the soft phase (i.e., the soft continuous phase) polymerizes before the component corresponding to the hard phase (i.e., the hard continuous phase). In some embodiments, it is preferred that the soft phase of the resin cures before the hard phase. As a non-limiting example, a resin comprising a methacrylate component corresponding to the soft phase and an acrylate component corresponding to the hard phase is preferentially cured such that the soft phase (methacrylate component) polymerizes before (and / or faster than) the hard phase (acrylate component) cures. For example, such curing of the soft phase before the hard phase can improve material properties such as increased modulus and longer elongation. In some embodiments, when the composite material is compared with conventional materials, improved material properties are observed in the resulting material when the acrylate component is applied in the formation of the hard phase and the methacrylate component is applied in the formation of the soft phase (e.g., the methacrylate component (with a higher modulus) is applied in the hard phase and the acrylate component is applied in the soft phase).

[0045] In all cases, methacrylates have a higher glass transition temperature (T0) compared to their corresponding acrylates. g Therefore, it is generally preferred during the production of hard materials, such as during the production of the hard phase. In contrast, in some embodiments disclosed herein, acrylates are used for the production of the hard phase and methacrylates are used for the production of the soft phase. By forming the hard phase from the acrylate component, there may be a slight decrease in the glass transition temperature, but the phases are better separated, which can improve the overall toughness of the resulting composite material. Thus, in some embodiments, the resins disclosed herein comprise both acrylate and methacrylate components, wherein, upon polymerization, the resulting composite material comprises a hard phase containing the acrylate component and a soft phase containing the methacrylate component. In some embodiments, such a composite material has increased overall toughness when compared to a material having a hard phase containing the methacrylate component and a soft phase containing the acrylate component.

[0046] In some embodiments, the first or second component comprises a vinyl ester. In some embodiments, it is advantageous to use a component comprising a vinyl ester as a less reactive component. In some embodiments, the component having a second reactivity (e.g., a second component corresponding to hardness) is a vinyl ester. In some embodiments, the component having a first reaction rate (e.g., a first polymerizable monomer) is an acrylate. In some embodiments, the first polymerizable component is a methacrylate. In some embodiments, the first polymerizable component is an acrylate, and the second polymerizable component is a vinyl ester. In some embodiments, the first polymerizable component is a methacrylate, and the second polymerizable component is a vinyl ester. In some embodiments, the second polymerizable component (vinyl ester) forms a relatively hard polymer upon curing (i.e., having a higher hardness than the polymer formed from the first polymerizable component). In some embodiments, the second polymerizable component (vinyl ester) forms a hard continuous phase upon curing.

[0047] In some embodiments, the resin comprises 3, 4, 5, 6, or more than 6 phases. In some embodiments, the resin comprises 3, 4, 5, 6, or more than 6 continuous phases. In some embodiments, the resin comprises multiple hard phases. In some embodiments, the resin comprises multiple hard continuous phases. In some embodiments, the resin comprises multiple soft phases. In some embodiments, the resin comprises multiple soft continuous phases.

[0048] In some embodiments, the resin further includes a third phase, a fourth phase, or more than four phases. In some embodiments, the third phase includes a filler, a polymer, or a non-reactive component. In some embodiments, the third phase is a filler. In some embodiments, the third phase is a non-reactive component. In some embodiments, the third phase is a polymer. In some embodiments, the polymer is a thermoplastic. In some embodiments, the polymer includes polystyrene and / or copolymers containing polystyrene blocks.

[0049] In some embodiments, the thermoplastic, plastic, or thermosetting plastic is dissolved in the resin (e.g., as a third phase). In some embodiments, the added component (e.g., the thermoplastic, plastic, or thermosetting plastic) is uniformly mixed into the resin, and the added component precipitates out as its own phase during or after polymerization. In some embodiments, the added component precipitates out as its own continuous phase. In some embodiments, the added component (e.g., the thermoplastic, plastic, or thermosetting plastic) forms an emulsion in the resin (i.e., phase separation prior to polymerization), and after polymerization, the added component forms its own continuous phase. In some embodiments, it continuously interpenetrates into the polymer network of hard and soft phases.

[0050] In some embodiments, the third phase comprises plastics, thermosetting plastics, and / or thermoplastic plastics. Examples of plastics include, but are not limited to, plastics or mixtures of plastics selected from: polyolefins, polyesters, polyacrylates, polymethacrylates, polystyrene, polypropylene, polyethylene, polyethylene terephthalate, polylactic acid, polyurethane, epoxy polymers, polyethers, polyvinyl chloride, polysiloxanes, polycarbonates, polyaramids, polyacrylonitrile, polybutadiene, polycyclic olefins, and copolymers. In some embodiments, the plastic, thermosetting plastic, and / or thermoplastic plastic component has at least one reactive functionality. In some embodiments, the plastic, thermosetting plastic, and / or thermoplastic plastic component has more than one reactive functionality (e.g., a thermosetting plastic having more than one reactive functional group). In such embodiments, the added third phase may form its own phase as described herein, but may be chemically bonded to another phase (e.g., a soft phase and / or a hard phase). In some embodiments, the third phase includes styrene block copolymers, silicone rubber, elastomer alloys, thermoplastic elastomers, thermoplastic vulcanized rubber elastomers, polyurethane elastomers, block copolymer elastomers, polyolefin blend elastomers, thermoplastic copolyester elastomers, or thermoplastic polyamide elastomers.

[0051] In some embodiments, the resin further includes a thermal initiator, a polymerization catalyst, a polymerization inhibitor, a light blocker, a plasticizer, a solvent, a surface energy modifier (e.g., a release agent), a pigment, a dye, a filler, a seed crystal, a crystallization catalyst, a biologically meaningful chemical, or any combination thereof.

[0052] In some embodiments, the resin includes a filler. In some embodiments, the filler has a glass transition temperature (T0) corresponding to the resin formulation. gIn some embodiments, the resin comprises a discontinuous phase containing filler, as further described herein (e.g., as a third phase). In some embodiments, the resin comprises a continuous phase comprising filler (e.g., filler comprising fibers or functionalized filler). In some embodiments, the filler comprises fibers. In some embodiments, the filler is functionalized. In some embodiments, the filler is functionalized with reactive functional groups as described herein. In some embodiments, the filler comprises functionalized fibers. In some embodiments, the filler includes calcium carbonate (i.e., chalk), kaolin, metakaolin, kaolin derivatives, magnesium hydroxide (i.e., talc), calcium silicate (i.e., wollastonite), glass filler (e.g., glass beads, short glass fibers, or long glass fibers), nanofiller (e.g., nanoplates, nanofibers, or nanoparticles), silica filler (e.g., mica, silica gel, fumed silica, or precipitated silica), carbon black, dolomite, barium sulfate, ATH Al(OH)3, MDH Mg(OH)2, diatomaceous earth, magnetite, halloysite, zinc oxide, titanium dioxide, cellulose, lignin, carbon filler (e.g., chopped carbon fibers or carbon fibers), derivatives thereof, or combinations thereof.

[0053] In some embodiments, the resin includes a thermal initiator. In some embodiments, the thermal initiator includes an azo compound, an inorganic peroxide, an organic peroxide, or any combination thereof. In some embodiments, the thermal initiator is selected from tert-amyl peroxybenzoate, 4,4-azobis(4-cyanopentanoic acid), 1,1'-azobis(cyclohexanenitrile), 2,2'-azobisisobutyronitrile (AIBN), benzoyl peroxide, 2,2-bis(tert-butylperoxy)butane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,5-bis(tert-butyl-peroxy-2,5-dimethylhexane), 2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne, bis(1-(tert-butylperoxy)cyclohexane, etc. Butylperoxy)-3,3,5-trimethylcyclohexane, tert-butyl hydroxyperoxide, tert-butyl peracetate, tert-butyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, cumene hydroperoxide, cyclohexanone peroxide, dicumene peroxide, lauroyl peroxide, 2,4-pentanedione peroxide, peracetic acid, potassium persulfate, derivatives thereof, and combinations thereof. In some embodiments, the thermal initiator includes a thermal acid generator or a thermal alkali generator.

[0054] In some embodiments, the resin comprises a polymerization catalyst. In some embodiments, the polymerization catalyst comprises a tin catalyst, a platinum catalyst, a rhodium catalyst, a titanium catalyst, a silicon catalyst, a palladium catalyst, a metal trifluoromethanesulfonate catalyst, a boron catalyst, a bismuth catalyst, or any combination thereof. Non-limiting examples of titanium catalysts include di-n-butylbutoxychlorotin, di-n-butyldiacetoxytin, di-n-butyldilauryltin, dimethyldineodecanate, dioctyldilauryltin, tetramethyltin, and dioctylbis(2-ethylhexyl maleate)tin. Non-limiting examples of platinum catalysts include platinum-divinyltetramethyl-disiloxane complexes, platinum-cyclovinylmethyl-siloxane complexes, platinum-octanal complexes, and platinum carbonylcyclovinylmethylsiloxane complexes. Non-limiting examples of rhodium catalysts include tris(dibutyl sulfide)rhodium trichloride. Non-limiting examples of titanium catalysts include titanium isopropoxide, titanium 2-ethylhexanoate, titanium triisopropoxide chloride, titanium ethoxide, and titanium bis(ethyl acetoacetate)diisopropoxide. Non-limiting examples of silicon catalysts include tetramethylammonium siloxanolate and tetramethylsilylmethyl-trifluoromethanesulfonate. Non-limiting examples of palladium catalysts include tetra(triphenylphosphine)palladium(0). Non-limiting examples of metal trifluoromethanesulfonate catalysts include scandium trifluoromethanesulfonate, lanthanum trifluoromethanesulfonate, and ytterbium trifluoromethanesulfonate. Non-limiting examples of boron catalysts include tris(pentafluorophenyl)boron. Non-limiting examples of bismuth catalysts include zinc bismuth neodecanoate, bismuth 2-ethylhexanoate, metal carboxylates of bismuth and zinc, and metal carboxylates of bismuth and zirconium.

[0055] In some embodiments, the resin includes a polymerization inhibitor to stabilize the composition and prevent premature polymerization. In some embodiments, the polymerization inhibitor is a photopolymerization inhibitor (e.g., oxygen). In some embodiments, the polymerization inhibitor is a phenolic compound (e.g., BHT). In some embodiments, the polymerization inhibitor is a stable free radical (e.g., 2,2,4,4-tetramethylpiperidinyl-1-oxy radical, 2,2-diphenyl-1-picrylhydrazyl radical, galvinoxyl radical, or triphenylmethyl radical). In some embodiments, more than one polymerization inhibitor is present in the resin. In some embodiments, the polymerization inhibitor acts as a free radical scavenger. In some embodiments, the polymerization inhibitor is an antioxidant, a hindered amine light stabilizer (HAL), a hindered phenol, or an inactivating free radical (e.g., a peroxide compound). In some embodiments, the polymerization inhibitor is selected from 4-tert-butylcatechol, tert-butylhydroquinone, 1,4-benzoquinone, 6-tert-butyl-2,4-dicresol, 2-tert-butyl-1,4-benzoquinone, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 1,1-diphenyl-2-picrylhydrazyl radical, hydroquinone, 4-methoxyphenol, phenothiazine, any derivative thereof, and any combination thereof.

[0056] In some embodiments, the resin includes a light-blocking agent to dissipate UV radiation. In some embodiments, the light-blocking agent absorbs specific UV energy values ​​and / or ranges. In some embodiments, the light-blocking agent is a UV light absorber, a pigment, a color concentrate, or an IR light absorber. In some embodiments, the light-blocking agent includes benzotriazole (e.g., 2-(2'-hydroxy-phenylbenzotriazole), hydroxyphenyltriazine, oxaloyl aniline, benzophenone, or combinations thereof).

[0057] In some embodiments, the resin comprises pigments, dyes, or combinations thereof. The pigment may be a suspension of solids insoluble in the resin. The dye may be soluble in the resin. In some embodiments, the pigment comprises inorganic pigments. In some embodiments, inorganic pigments include iron oxide, barium sulfide, zinc oxide, antimony trioxide, yellow iron oxide, red iron oxide, ferric ammonium ferrocyanide, chrome yellow, carbon black, or aluminum flakes. In some embodiments, the pigment comprises organic pigments. In some embodiments, organic pigments include azo pigments, anthraquinone pigments, copper phthalocyanine (CPC) pigments (e.g., phthalocyanine blue or phthalocyanine green), or combinations thereof. In some embodiments, the dye comprises azo dyes (e.g., diaryl compounds or Sudan dyes), anthraquinones (e.g., Oil Blue A or Disperse Red 11), or combinations thereof.

[0058] In some embodiments, the resin includes a surface energy modifier. In some embodiments, the surface energy modifier can facilitate the process of releasing the polymer from the mold. In some embodiments, the surface energy modifier can act as a defoamer. In some embodiments, the surface energy modifier includes a defoamer, degassing agent, hydrophobic agent, leveling agent, wetting agent, emulsion stabilizer, emulsion destabilizer, or agent for adjusting the flow properties of the resin. In some embodiments, the surface energy modifier includes an alkoxylated surfactant, a silicone surfactant, a sulfosuccinate, a fluorinated polyacrylate, a fluoropolymer, a silicone resin, a star polymer, an organically modified silicone resin, or any combination thereof.

[0059] In some embodiments, the resin includes a plasticizer. The plasticizer may be a non-volatile material that reduces interactions between polymer chains, which can lower the glass transition temperature, melt viscosity, and elastic modulus. In some embodiments, the plasticizer includes dicarboxylic acid ester plasticizers, tricarboxylic acid ester plasticizers, trimellitic acid esters, adipate esters, sebacic acid esters, maleic acid esters, or bio-based plasticizers. In some embodiments, the plasticizer comprises a dicarboxylic acid ester or a tricarboxylic acid ester, including diesters, phthalates, bis(2-ethylhexyl) phthalate (DEHP), bis(2-propylheptyl) phthalate (DPHP), diisononyl phthalate (DINP), di-n-butyl phthalate (DBP), butyl benzyl phthalate (BBzP), diisodecyl phthalate (DIDP), dioctyl phthalate (DOP), diisooctyl phthalate (DIOP), diethyl phthalate (DEP), diisobutyl phthalate (DIBP), di-n-hexyl phthalate, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer comprises trimellitate, including trimethyl trimellitate (TMTM), tri(2-ethylhexyl) trimellitate (TEHTM), tri(n-octyl,n-decyl) trimellitate (ATM), tri(heptyl,nonyl)trimellitate (LTM), n-octyl trimellitate (OTM), trioctyl trimellitate, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer comprises adipate esters, including bis(2-ethylhexyl)adipate (DEHA), dimethyl adipate (DMAD), monomethyl adipate (MMAD), dioctyl adipate (DOA), bis[2-(2-butoxyethoxy)ethyl] adipate, dibutyl adipate, diisobutyl adipate, diisodecyl adipate, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer comprises sebacic acid esters, including dibutyl sebacic acid (DBS), bis(2-ethylhexyl) sebacic acid, diethyl sebacic acid, dimethyl sebacic acid, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer comprises maleic acid esters, including bis(2-ethylhexyl) maleate, dibutyl maleate, diisobutyl maleate, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer includes a bio-based plasticizer, comprising acetylated monoglycerides, alkyl citrates, methyl ricinoleate, or green plasticizers. In some embodiments, the alkyl citrate is selected from triethyl citrate, acetyl triethyl citrate, tributyl citrate, acetyl tributyl citrate, trioctyl citrate, acetyl trioctyl citrate, trihexyl citrate, acetyl trihexyl citrate, butyryl trihexyl citrate, trimethyl citrate, derivatives thereof, or combinations thereof.In some embodiments, the green plasticizer is selected from epoxidized soybean oil, epoxidized vegetable oil, epoxidized esters of soybean oil, derivatives thereof, or combinations thereof. In some embodiments, the plasticizer includes azelaic acid esters, benzoic acid esters (e.g., sucrose benzoate), terephthalic acid esters (e.g., dioctyl terephthalate), diisononyl 1,2-cyclohexanedicarboxylate, alkyl sulfonates, sulfonamides (e.g., N-ethyltoluenesulfonamide, N-(2-hydroxypropyl)benzenesulfonamide, N-(n-butyl)benzenesulfonamide), organophosphates (e.g., tricresyl phosphate or tributyl phosphate), glycols (e.g., triethylene glycol dihexanoate or tetraethylene glycol diheptanoate), polyethers, polymeric plasticizers, polybutene, derivatives thereof, or combinations thereof.

[0060] In some embodiments, the resin includes a solvent. In some embodiments, the solvent includes a nonpolar solvent. In some embodiments, the nonpolar solvent includes pentane, cyclopentane, hexane, cyclohexane, benzene, toluene, 1,4-dioxane, chloroform, diethyl ether, dichloromethane, derivatives thereof, or combinations thereof. In some embodiments, the solvent includes a polar aprotic solvent. In some embodiments, the polar aprotic solvent includes tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, DMSO, propylene carbonate, derivatives thereof, or combinations thereof. In some embodiments, the solvent includes a polar protic solvent. In some embodiments, the polar protic solvent includes formic acid, n-butanol, isopropanol, n-propanol, tert-butanol, ethanol, methanol, acetic acid, water, derivatives thereof, or combinations thereof.

[0061] In some embodiments, the resin includes biologically significant chemicals. In some embodiments, biologically significant chemicals include hormones, enzymes, active pharmaceutical ingredients, antibodies, proteins, pharmaceuticals, or any combination thereof. In some embodiments, biologically significant chemicals include pharmaceutical components, chemicals, genes, peptides, enzymes, biomarkers, dyes, compliance indicators, antibiotics, analgesics, medical-grade pharmaceuticals, chemical reagents, bioactive reagents, antibacterial agents, antibiotics, anti-inflammatory agents, immunosuppressive agents, immunostimulatory agents, dentin desensitizers, odor masking agents, immunomodulatory agents, anesthetics, nutritional agents, antioxidants, lipopolysaccharide complexing agents, or peroxides.

[0062] In some embodiments, the first component and / or the second component includes at least one reactive functional group. In some embodiments, the reactive functional group allows for further modification of the polymer material, such as additional polymerization. In some embodiments, the first polymerizable component and / or the second polymerizable component includes 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or more than 10 reactive functional groups. The reactive functional groups may be identical, or they may have different functionalities. In some embodiments, one or more functional groups are located at the ends of the first polymerizable component and / or the second polymerizable component (e.g., where the first polymerizable component and / or the second polymerizable component is a component of a first polymerizable oligomer and a second polymerizable oligomer). In some embodiments, multiple reactive functional groups are identical. In other embodiments, multiple reactive functional groups are different from each other. In some embodiments, multiple reactive functional groups include at least two identical functional groups.

[0063] Non-limiting examples of reactive functional groups include radical polymerizable functional groups, photoactive groups, groups that promote stepwise growth polymerization, thermally reactive groups, and / or groups that promote bond formation (e.g., covalent bond formation). In some embodiments, functional groups include acrylates, methacrylates, acrylamides, vinyl groups, vinyl ethers, thiols, allyl ethers, norbornene, vinyl acetate, maleates, fumarates, maleimides, epoxides, cyclic strained ethers, cyclic strained sulfides, cyclic esters, cyclic carbonates, cyclic silanes, cyclic siloxanes, hydroxyl groups, amines, isocyanates, blocked isocyanates, acyl chlorides, activated esters, Diels-Alder reactive groups, furans, cyclopentadiene, acid anhydrides, groups that promote photodimerization (e.g., anthracene, acenaphthene, and / or coumarin), groups that photodegrade into reactive substances (e.g., Norrish type 1 and 2 materials), azides, derivatives thereof, or combinations thereof.

[0064] In some embodiments, the first polymerizable component comprises more functional groups (also referred to herein as reactive functional groups) than the second polymerizable component. In some embodiments, the first component is bifunctional, trifunctional, or comprises more than three functional groups, and the second component comprises fewer functional groups. In some embodiments, the first component is bifunctional and the second component is monofunctional. In some embodiments, the first polymerizable component is a bifunctional acrylate, and the second polymerizable component is a monofunctional methacrylate.

[0065] In some embodiments, the resin forms a polymer interpenetrating network (IPN) during polymerization. In some embodiments, at least one phase of the resin includes a polymer interpenetrating network. In some embodiments, one phase of the resin includes a polymer interpenetrating network. In some embodiments, the resin includes a polymer interpenetrating network, and the IPN forms a first phase and a second phase upon curing (i.e., in some embodiments, the multiphase resin described herein comprises a single IPN formulation prior to polymerization and forms a multiphase composite material as described herein after polymerization). In some embodiments, the IPN phase of the resin includes a first phase (i.e., a first continuous phase) and a second phase (i.e., a second continuous phase), as further described herein. In some embodiments, a resin comprising an IPN formulation may form more than two phases, such as three phases, four phases, or more than four phases.

[0066] In some embodiments, the polymer interpenetrating network (IPN) forms multiple (e.g., two or more) interpenetrating networks. In some embodiments, the IPN forms multiple interpenetrating phases (e.g., a continuous phase) upon curing. In some embodiments, the IPN forms an interpenetrating network through differences in reaction mechanisms. For example, resins comprising radically polymerizable monomer systems and ionicly polymerizable monomer systems can be mixed together, and both systems can begin polymerization upon initiation, but the radical system reacts faster (e.g., kinetically faster) and cures faster than the ionicly polymerizable system. In some embodiments, the first polymerizable component is radically polymerizable (i.e., polymerizable by radical polymerization). In some embodiments, the second polymerizable component is ionicly polymerizable (i.e., polymerizable by ionic polymerization). In some embodiments, the second polymerizable component is an ionicly polymerizable monomer. In some embodiments, polymerization of the ionicly polymerizable system and the radically polymerizable system is initiated simultaneously or nearly simultaneously, and the radically polymerizable system is nearly completely cured (e.g., at least 80%, at least 90%, at least 95%, or at least 99% cured) before the ionicly polymerizable system is significantly cured (e.g., less than 10% cured, or less than 5% cured). Therefore, in such embodiments, activation of polymerization can be performed using two processes separated by a short time period (e.g., milliseconds), allowing multiple polymerization reactions to occur on different phases, but the more reactive phase (e.g., radical monomers) can be substantially cured before the less reactive phase (e.g., ionic monomers) is significantly cured. In some embodiments, a radically polymerizable monomer system of greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% is polymerized before the ionicly polymerizable system reaches 10% polymerization. In some embodiments, a radically polymerizable monomer system of greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% is polymerized before the ionicly polymerizable system reaches 5% polymerization. In some embodiments, polymerization of the two phases is initiated simultaneously. In some embodiments, the polymerization of the two phases is initiated almost simultaneously (e.g., within 10 milliseconds). In some embodiments, the initiation of polymerization of the two phases includes two distinct processing steps, as further described herein. In such embodiments, the radical polymer forms its own phase from the IPN resin, while the ionic system becomes its own phase as it continues to polymerize.

[0067] In some embodiments, the IPN system includes an acrylate component or a methacrylate component mixed with an ion-cured epoxide (e.g., a cationic curable epoxide). In some embodiments, the component having a first reaction rate includes an acrylate monomer. In some embodiments, the component having a first reaction rate includes a methacrylate monomer. In some embodiments, the component having a second reaction rate includes an epoxide. In some embodiments, the second polymerizable component is an epoxide. In some embodiments, the epoxide is a cationic curable epoxide. In some embodiments, the epoxide is a cationic curable epoxide.

[0068] In some embodiments, the polymer interpenetrating network (IPN) includes an additional system such that three or more phases are formed upon resin curing. As a non-limiting example, an inert filler (e.g., fumed silica or talc, or another filler as further described herein) may be added to the aforementioned IPN resin, and after curing, the resulting material may have a hard continuous phase, a soft continuous phase, and filler material islands (i.e., discontinuous phases). In some embodiments, the additional system is an additional monomer system. As a non-limiting example, an added polymer system (e.g., polystyrene) may be added to the IPN and formulated such that it is soluble in the IPN system at a resin stage, but after polymerization, the polystyrene precipitates out as its own separate phase, thus the material will include a hard continuous phase, a soft continuous phase, and a third continuous phase comprising polystyrene. In some embodiments, the additional monomer system interpenetrates into the IPN. As another non-limiting example, an IPN resin including an additional polymer system (e.g., polystyrene) and filler may include four phases (e.g., a hard continuous phase, a soft continuous phase, a polystyrene continuous phase, and a discontinuous filler phase) after polymerization. In some embodiments, the above-described IPN resin system further comprises a thermoplastic, plastic, or thermoformed material, as further described herein (e.g., polystyrene). In some embodiments, the IPN resin system further comprises fillers, as further described herein.

[0069] In some embodiments, the first polymerizable component and the second polymerizable component have the same number of functional groups, and the difference in reaction rate includes a difference in component size. In some embodiments, the first polymerizable component is smaller than the second polymerizable component.

[0070] In some embodiments, the resin comprises a methacrylate component that is less reactive than the acrylate component. As a non-limiting example, an acrylate component that is less readily and / or more readily functionalized (e.g., bifunctional) than the methacrylate component (e.g., larger and / or monofunctional) may tend to react faster than the methacrylate component (i.e., the acrylate is more reactive than the methacrylate). As further described herein, in some embodiments, it is advantageous that the soft phase polymerizes prior to the hard phase, so that in such embodiments as described above, the more reactive component corresponds to the soft phase and the less reactive component corresponds to the hard phase. As a non-limiting example, in some embodiments, such as when the acrylate component is more reactive than the methacrylate component, the soft phase of the resin corresponds to the acrylate component, and the hard phase of the resin corresponds to the methacrylate component, as described herein.

[0071] In some embodiments, the first polymerizable component is an acrylate, and the second polymerizable component is a methacrylate, wherein the methacrylate is larger than the acrylate (e.g., larger in space and / or with a larger calculated molecular surface area). In some embodiments, it is advantageous that the component comprising the acrylate polymerizes more preferentially than the component comprising the methacrylate. In some embodiments, the resin comprises a methacrylate component and an acrylate component, and the methacrylate component polymerizes preferentially than the acrylate (i.e., the methacrylate is more reactive than the acrylate in its polymerization). In some embodiments, the soft phase of the resin corresponds to the methacrylate component. In some embodiments, the soft phase of the resin is characterized by the presence of the methacrylate component. In some embodiments, the hard phase of the resin is characterized by the presence of the acrylate component. In some embodiments, the hard phase of the resin corresponds to the acrylate component. In some embodiments, the first polymerizable component is a difunctional acrylate, the second polymerizable component is a difunctional methacrylate, and the methacrylate is larger than the acrylate. In some embodiments, the acrylate component is larger than the methacrylate component. In some embodiments, the acrylate component is more functionalized than the methacrylate component (e.g., as a non-limiting example, the acrylate component is difunctionalized and the methacrylate component is monofunctionalized, or the acrylate component is trifunctionalized and the methacrylate component is monofunctionalized or difunctionalized).

[0072] In some embodiments, the resin is a photopolymerizable liquid composition. In some embodiments, the resin comprises a first polymerizable component (e.g., a first component), a second polymerizable component (e.g., a second component), and a photoinitiator. In some embodiments, the resin has a liquid ratio of the first polymerizable component to the second polymerizable component. In some embodiments, the liquid ratio is the same throughout the resin (e.g., a homogeneous resin). In some embodiments, the liquid ratio has local characteristics, wherein the ratio depends on the location within the resin that determines the ratio. As a non-limiting example, differences in density and / or immiscibility may cause phase separation or separation of the polymerizable component into multiple parts, wherein a local point in the resin may include a liquid ratio different from that of different local points within the resin.

[0073] In some embodiments, the resin is exposed to a light source that initiates the polymerization of a first polymer and / or a second polymer, thereby forming a first polymer region or a second polymer region, respectively. In some embodiments, the resin is exposed to a light source that initiates the polymerization of a first polymer or a second polymer, thereby forming a first polymer region or a second polymer region, respectively. In some embodiments, the resin is treated separately. In some embodiments, treating the resin separately includes polymerizing some, but not all, of the polymerizable components. For example, in some embodiments, exposure to a light source (e.g., for photopolymerization) causes the first polymerizable component to polymerize, but the second polymerizable component does not (e.g., to a measurable extent) polymerize or is substantially non-polymerized (e.g., less than 5% of the polymerizable component polymerizes). In some embodiments, exposure to a light source causes the second polymerizable component to polymerize, but the first polymerizable component does not polymerize or is substantially non-polymerized. In some embodiments, the first polymerizable component and the second polymerizable component have different polymerization rates when photopolymerization is performed at a specified wavelength of light. In some embodiments, the first polymerizable component and the second polymerizable component have different polymerization rates when polymerized at a specified temperature. In some embodiments, the first polymer region has a first ratio of the first polymerizable component to the second polymerizable component. In some embodiments, light exposure activates the polymerization of the first polymer. In some embodiments, a first polymerizable component can freely diffuse through a resin, a second polymerizable component can freely diffuse through a resin, both the first and second polymerizable components can freely diffuse through a resin, the first polymerizable component can freely diffuse through a first polymer, the second polymerizable component can freely diffuse through a first polymer, and / or both the first and second polymerizable components can freely diffuse through a first polymer.

[0074] In some embodiments, during the processing step, the polymerization rate of the first polymerizable component is greater than the polymerization rate of the second polymerizable component. In some embodiments, the processing step is exposure to light of a specified wavelength. In some embodiments, the processing step is exposure to a specified temperature. In some embodiments, the processing step includes exposure to light of a specified wavelength, exposure to a specified temperature, or a combination thereof. In some embodiments, the polymerization rate of the first polymerizable component is greater than 1, 2, 3, 4, 5, 10, 20, 30, 40, 50, or 100 times faster than the polymerization rate of the second polymerizable component. In some embodiments, the specified wavelength of light includes wavelengths of 10 nm to 200 nm, 200 nm to 350 nm, 350 nm to 450 nm, 450 nm to 550 nm, 550 nm to 650 nm, 650 nm to 750 nm, 750 nm to 850 nm, 850 nm to 1000 nm, or 1000 nm to 1500 nm. In some embodiments, the specified temperature is an operating temperature. As used herein, the operating temperature can be less than or equal to 20°C, 20°C to 40°C, or greater than or equal to 40°C. In a preferred embodiment, the operating temperature includes temperatures between 20°C and 40°C. In other preferred embodiments, the operating temperature is between 50°C and 100°C. In other embodiments, the operating temperature is between 100°C and 150°C. In other embodiments, the operating temperature is higher than 150°C.

[0075] In some embodiments, during the processing step, the polymerization rate of the second polymerizable component is greater than the polymerization rate of the first polymerizable component. In some embodiments, the processing step is exposure to light of a specified wavelength. In some embodiments, the processing step is exposure to a specified temperature. In some embodiments, the processing step includes exposure to light of a specified wavelength, exposure to a specified temperature, or a combination thereof. In some embodiments, the polymerization rate of the second polymerizable component is greater than or equal to 1, 2, 3, 4, 5, 10, 20, 30, 40, 50, or 100 times faster than the polymerization rate of the first polymerizable component. In some embodiments, the specified wavelength of light includes wavelengths of 10 nm to 200 nm, 200 nm to 350 nm, 350 nm to 450 nm, 450 nm to 550 nm, 550 nm to 650 nm, 650 nm to 750 nm, 750 nm to 850 nm, 850 nm to 1000 nm, or 1000 nm to 1500 nm. In some embodiments, the specified temperature is an operating temperature. In some embodiments, the operating temperature is -50°C to 500°C, -10°C to 300°C, -5°C to 200°C, 0°C to 100°C, 10°C to 90°C, or 20°C to 80°C. In some embodiments, the operating temperature is less than or equal to 20°C, 20°C to 40°C, or greater than or equal to 40°C. In a preferred embodiment, the operating temperature includes temperatures between 20°C and 40°C. In other preferred embodiments, the operating temperature is between 50°C and 100°C. In other embodiments, the operating temperature is between 100°C and 150°C. In other embodiments, the operating temperature is above 150°C.

[0076] Photopolymerization can occur when a suitable formulation (e.g., the resin disclosed herein) is exposed to radiation of a wavelength (e.g., UV or visible light) with sufficient power to initiate polymerization. The wavelength and / or power of the radiation that can be used to initiate polymerization can depend on the photoinitiator used. As used herein, “light” includes any wavelength and power capable of initiating polymerization. Some wavelengths of light (e.g., light of a specified wavelength) include ultraviolet (UV) or visible light. UV light sources include UVA (wavelengths from about 400 nanometers (nm) to about 320 nm), UVB (about 320 nm to about 290 nm), or UVC (about 290 nm to about 100 nm). Any suitable source can be used, including laser sources. The source can be broadband or narrowband or a combination thereof. The light source can provide continuous or pulsed light during the process. The duration and intensity of the UV light exposure can be varied to determine the ideal reaction conditions.

[0077] In some embodiments, the polymerization region is spatially controllable. In some embodiments, exposing the resin to light in a region (e.g., a first exposure region) can initiate polymerization and generate a first polymer region. In some embodiments, the size and / or shape of the first polymer region is controlled by selectively exposing it to light (e.g., by using a mask). In some embodiments, a polymerizable component can diffuse through the resin during polymerization in the first polymer region, thereby increasing or decreasing the amount of the polymerizable component in that region. As a non-limiting example, the combination of photoactivated polymerization of the first polymerizable component in the first polymer region into the first polymer and the diffusion of the component can result in migration of the first polymerizable component into the first polymer region, thereby increasing a first ratio of the first polymerizable component to the second polymerizable component in the first polymer region while decreasing the ratio of the first polymerizable component to the second polymerizable component in the second region (e.g., a second ratio). In some embodiments, the second region is adjacent to, contacts, or overlaps with the first exposure region, and the second region is different from the first region. In some embodiments, the resin ratio (liquid ratio) of the first polymerizable component to the second polymerizable component, the first region ratio, and the second region ratio are different.

[0078] In some embodiments, the polymerizable component is a monomer, polymer, and / or oligomer capable of entering polymerization via reactive groups. In some embodiments, the polymerizable component is a component of a solution or a molecule in a solution capable of polymerizing with itself or with other components or molecules in the solution. In some embodiments, a first monomer or monomer 1 is a first polymerizable component in the X, Y, Z volumes that preferentially polymerizes upon initial exposure to a radiation source (e.g., light of a specified wavelength). In some embodiments, a second monomer or monomer 2 is a polymerizable component that does not preferentially polymerize upon initial exposure to a radiation source. In some embodiments, the second monomer preferentially polymerizes upon initial exposure to a radiation source (e.g., light of a specified wavelength), and the first monomer does not preferentially polymerize upon exposure to the radiation source. In some embodiments, the first polymer or polymer 1 comprises at least a majority of monomer 1. In some embodiments, the first polymer or polymer 1 is composed of monomer 1. In some embodiments, the first polymer or polymer 1 is substantially composed of monomer 1. In some embodiments, the second polymer or polymer 2 comprises a majority of monomer 2. In some embodiments, the second polymer or polymer 2 is substantially composed of monomer 2. In some embodiments, the first monomer comprises a first polymerizable component. In some embodiments, the second monomer comprises a second polymerizable component.

[0079] In some embodiments, oligomer and polymer mixtures can be characterized and distinguished from other oligomer and polymer mixtures by measuring molecular weight and molecular weight distribution. The following definition of molecular weight can be applied to this characterization (see: LH Sperling, Introduction to Physical Polymer Science, 2nd ed., Wiley New York (1992)). The average molecular weight (M) is the average number of repeating units n (or dp.) × the molecular weight or molar mass (Mi) of the repeating units. Number-average molecular weight (M0) n The weight-average molecular weight (Mw) is the arithmetic mean, representing the total weight of the molecules present divided by the total number of molecules. Molecular weight can also be measured using weight-average molecular weight (Mw) and z-average molecular weight (Mz).

[0080] In some embodiments, this disclosure provides a method for generating a composite polymer composition using a single resin. In some embodiments, the single resin includes two types of monomer components, three types of monomer components, four types of monomer components, five types of monomer components, six types of monomer components, seven types of monomer components, eight types of monomer components, nine types of monomer components, ten types of monomer components, eleven types of monomer components, twelve types of monomer components, or more than twelve types of monomer components. In some embodiments, the resin includes two polymerizable components (also referred to herein as polymerizable monomers), three polymerizable components, four polymerizable components, five polymerizable components, six polymerizable components, seven polymerizable components, eight polymerizable components, nine polymerizable components, ten polymerizable components, eleven polymerizable components, twelve polymerizable components, thirteen polymerizable components, fourteen polymerizable components, fifteen polymerizable components, or more than fifteen polymerizable components.

[0081] Monomer components can be polymerized to form polymers (i.e., are polymerizable monomers). In some embodiments, monomer components react only with their own type to form homopolymers. In some embodiments, monomer components react with other types of monomer components to form copolymers, as described herein.

[0082] In some embodiments, the resin comprises a first component and a second component, wherein the two components have different reactivity. Reactivity is a defined value. The monomer reactivity ratio is a value comparing the reactivity of one monomer to that of the second monomer. The reactivity ratios of the components are available in the art (see, for example, G. Odian, Principles of Polymerization, 4th Edition, 2004, which is incorporated herein by reference). In some embodiments, the reactivity ratio, or the ratio of reactivity, refers to the ratio of the rate coefficient of a monomer reacting with itself to the rate coefficient of a monomer reacting with different monomers. In some embodiments, the reactivity ratio is defined by the following formula: Where, k 11 It is the rate coefficient corresponding to the reaction between monomer 1 (or the polymer of monomer 1 at the terminal position) and monomer 1, k 12 It is the rate constant coefficient for the reaction between monomer 1 (or the polymer of monomer 1 at the terminal position) and monomer 2. In some embodiments, the reactivity ratio depends on exposure to a specified temperature, concentration, functionality of the reactants, solubility parameters, exposure to light of a specified wavelength, and other physical conditions.

[0083] In some embodiments, the reactivity ratio between the first component (e.g., the first polymerizable monomer) and the second component (e.g., the second polymerizable monomer) is greater than or equal to one. In some embodiments, the reactivity ratio between the first component and the second component is greater than or equal to 10, greater than or equal to 20, greater than or equal to 30, greater than or equal to 50, greater than or equal to 100, greater than or equal to 500, greater than or equal to 1000, greater than or equal to 50000, or greater than or equal to 100000. In some embodiments, the reactivity ratio between the first component and the second component is 1 to 10, 1 to 20, 1 to 30, 1 to 50, 1 to 100, 1 to 500, 1 to 1000, 1 to 5000, 1 to 50000, 1 to 100000, 2 to 10, 2 to 20, 2 to 30, 2 to 50, 2 to 100, 2 to 500, 2 to 1000, 2 to 5000, 2 to 10000, 2 to 50000, or 2 to 100000.

[0084] In some embodiments, the resin includes a first component (e.g., a first polymerizable monomer) and a second component (e.g., a second polymerizable monomer), wherein one component is more reactive than the other. In some embodiments, during the polymerization reaction and under a given set of polymerization conditions, the first component is at least 1.1 times, 2 times, 3 times, 5 times, 10 times, 15 times, 25 times, 50 times, 100 times, 250 times, 50 times, 500 times, 750 times, 1000 times, 1250 times, 1500 times, 2000 times, 5000 times, 10000 times, 20000 times, 50000 times, or 50000 times more reactive than the second component. In some embodiments, polymerization conditions include exposure to a specified wavelength, exposure to a specified temperature, or any combination thereof. In some embodiments, under polymerization conditions, the first component is always more reactive than the second component.

[0085] In some embodiments, a resin comprising a first polymerizable component and a second polymerizable component undergoes polymerization to form a polymer. In some embodiments, the first polymerizable component is incorporated into a first polymer. In some embodiments, the second polymerizable component is incorporated into a second polymer. In some embodiments, a polymerization activator initiates the polymerization. In some embodiments, the polymerization activator includes a free radical initiator, a photoinitiator, a thermal initiator, a catalyst, a reactive nuclide, or any combination thereof.

[0086] In some embodiments, the free radical initiator is selected from halogens, chlorine, azo compounds, azobisisobutyronitrile (AIBN), 1,1'-azobis(cyclohexanecarboxynitrile) (ABCN), organic peroxides, di-tert-butyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, acetone peroxide, inorganic peroxides, peroxydisulfate, transition metal catalysts, or any combination thereof.

[0087] In some embodiments, the resin further includes a photoinitiator. Photoinitiators in this disclosure include those that can utilize photoactivation to initiate the polymerization of polymerizable components of the resin. In some embodiments, the photoinitiator can be used for various purposes, including for the curing of polymers, including those that can utilize photoactivation to initiate the polymerization of polymerizable components of the formulation. In some embodiments, the photoinitiator is a radical photoinitiator, a cationic photoinitiator, and / or anionic photoinitiator. In some embodiments, the photoinitiator is a type I photoinitiator that undergoes unimolecular bond cleavage to generate a free radical. In other embodiments, the photoinitiator is a type II photoinitiator that undergoes a bimolecular reaction to generate a free radical. Common type I photoinitiators include, but are not limited to, benzoin ethers, benzoyl ketals, α-dialkoxyacetophenone, α-hydroxyalkylphenyl ketone, and acylphosphine oxides. Common type II photoinitiators include benzophenone / amine and thioxanone / amine. Cationic initiators include aryl diazonium salts, diaryliodomonium salts, and triarylsulfonium salts. In some embodiments, the initiator includes a photobase generator.

[0088] In some embodiments, the photoinitiator includes acetophenone, 2-benzyl-2-(dimethylamino)-4'-morpholinobutyrophenone, 4'-tert-butyl-2',6'-dimethylacetophenone, 2,2-diethyoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 4'-ethoxyacetophenone, 3'-hydroxyacetophenone, 4'-hydroxyacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)- 2-Methylphenylacetone (2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropio-phenone), 2-hydroxy-2-methylpropiophenone, 2-methyl-4'-(methylthio)-2-morpholinopropiophenone, 4'-phenoxyacetophenone, benzyl, benzoin, benzoin ethyl ether, benzoin methyl ether, benzoin methyl ether, 4,4'-dimethoxybenzoin, 4,4'-dimethylbenzoin, benzophenone, benzophenone-3,3',4,4'-tetracarboxylic dianhydride dianhydride), 4-benzeneparaben, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis[2-(1-propenyl)phenoxy]-benzophenone, 4-(diethylamino)benzophenone, 4,4'-dihydroxybenzophenone, 4-(dimethylamino)-benzophenone, 3,4-Dimethylbenzophenone, 3-hydroxybenzophenone, 3-hydroxybenzophenone, 4-hydroxybenzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, methylbenzoylformate, Michler's ketone, cationic initiator, anionic initiator, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl)iodonium p-toluenesulfonate, bis(4-tert-butylphenyl)-iodonium trifluoromethanesulfonate triflate, boc-methoxyphenyldiphenylsulfonium triflate, (4-tert-butylphenyl)diphenylsulfonium triflate, diphenyliodonium hexafluorophosphate, diphenyliodonium nitrate, diphenyliodonium p-toluene-sulfonate, diphenyliodonium triflate, (4-fluorophenyl)diphenylsulfonium triflate, N-hydroxynaphthalimide trifluoromethanesulfonate triflate), N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butyrate (N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butyrate)3-Dicarboximide perfluoro-1-butanesulfonate, (4-iodophenyl)-diphenylsulfonium triflate, (4-methoxyphenyl)diphenylsulfonium triflate, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, (4-methylthiophenyl)methyl phenyl sulfonium triflate, 1-naphthyl diphenylsulfonium triflate, (4-phenoxyphenyl)diphenylsulfonium Triflate, (4-phenylthiophenyl)-diphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salt, triarylsulfonium hexafluorophosphate salt, triphenylsulfonium perfluoro-1-butanesulfonate, triphenylsulfonium triflate, tris(4-tetra-butylphenyl)-sulfonium perfluoro-1-butanesulfonate, tris(4-tert-butylphenyl)sulfonium triflate, anthraquinone-2-sulfonic acid sodium salt), 2-tert-butylanthraquinone, camphorquinone, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, phenyl-2,4,Lithium phenyl-2,4,6-trimethylbenzoylphosphinate, 9,10-phenanthrenequinone, and phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide), thioxanthone, 1-chloro-4-propoxy-9H-thioxanthen-9-one, 2-chloro-thioxanthen-9-one, 2,4-diethyl-9H-thioxanthen-9-one, isopropyl-9H-thioxanthen-9-one, 10-methyl-phenothiazine, thioxanthen-9-one, photoinitiator products, TPO-L, their derivatives, or combinations thereof.

[0089] In some embodiments, the photoinitiator uses light energy to initiate photopolymerization. In some embodiments, the photoinitiator initiates photopolymerization by exposure to light energy at wavelengths of 800 nm to 250 nm, 800 nm to 350 nm, 800 nm to 450 nm, 800 nm to 550 nm, 800 nm to 650 nm, 600 nm to 250 nm, 600 nm to 350 nm, 600 nm to 450 nm, or 400 nm to 250 nm. In some embodiments, the photoinitiator initiates photopolymerization after absorbing two photons (simultaneously or sequentially), and it can use light of a longer wavelength to initiate photopolymerization.

[0090] In some embodiments, the initiator is a thermal initiator. In some embodiments, the resin includes more than one initiator (e.g., two, three, four, five, or more than five initiators).

[0091] In some embodiments, the resin comprises an azo compound. In some embodiments, polymerization is initiated using an azo compound, such as 2,2'-azobis(2-methylpropionitrile), 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexanecarbonitrile), azobisisobutyronitrile, benzophenone, inorganic peroxides, ammonium persulfate, monosodium hydroxymethanesulfinate, potassium persulfate, sodium persulfate, organic peroxides, tert-butyl hydroperoxide, tert-butyl peracetate, and cumene. hydroxy-peroxide), 2,5-di(tert-butyl)peroxy-2,5-dimethyl-3-hexyne, dicumyl peroxide 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane, 2,4-pentanedioneperoxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, benzoyl peroxide, tert-butyl peroxide, tert-butyl benzoate, TBEC, tert-butyl hydroperoxide, derivatives thereof, or combinations thereof.

[0092] In some embodiments, a thermosetting temperature is used during polymerization. In some embodiments, the thermosetting temperature can be -50°C to 500°C, -10°C to 300°C, -5°C to 200°C, 0°C to 100°C, 10°C to 90°C, or 20°C to 80°C. In some embodiments, the amount of time the material spends at the thermosetting temperature is controlled. In some embodiments, the amount of time the material spends at the thermosetting temperature is between 1 minute and 2 weeks, between 1 minute and 1 week, between 1 minute and 6 days, between 1 minute and 5 days, between 1 minute and 4 days, between 1 minute and 3 days, between 1 minute and 2 days, between 1 minute and 24 hours, between 1 minute and 12 hours, between 1 minute and 6 hours, between 1 minute and 3 hours, between 1 minute and 2 hours, between 1 minute and 1 hour, between 5 minutes and 1 hour, between 10 minutes and 1 hour, between 15 minutes and 2 hours, or between 30 minutes and 2 hours.

[0093] In some embodiments, polymerization includes the use of a radiation source. In some embodiments, polymerization is activated by exposure to a radiation source (e.g., photopolymerization). In some embodiments, the radiation source includes ultraviolet light, visible light, infrared light, microwave radiation, laser exposure, holography, DLP projection, optical lithography, pulsed light, or combinations thereof. In some embodiments, polymerization includes the use of more than one radiation source (e.g., separately treating a first phase and a second phase of the resin).

[0094] In some embodiments, it is preferred that the initial exposure intensity be low in order to advantageously induce the polymerization of a component (e.g., a monomer component). As a non-limiting example, in some embodiments, it is preferred that the first exposure having a first specified wavelength has a relatively low exposure intensity in order to advantageously induce the polymerization of the polymerizable component. In some embodiments, the first exposure using light of a specified wavelength is used to form a first polymer. In some embodiments, the first exposure using light of a specified wavelength is used to form a second polymer. In some embodiments, the intensity of the first exposure (values ​​expressed in watts / cm²) is... 2 (Given) is between 10 watts / cm² 2 With 100 watts / cm 2 Between, between 50 watts / cm 2 With 80 watts / cm 2 Between, between 100 watts / cm 2 With 50 watts / cm 2 Between, between 100 watts / cm 2 With 10 watts / cm 2 Between, between 0.1 watts / cm 2 With 8 watts / cm 2 Between, between 0.1 watts / cm2 With 6 watts / cm 2 Between, between 0.1 watts / cm 2 With 4 watts / cm 2 Between, or between 0.1 watts / cm 2 With 2 watts / cm 2 In some embodiments, a second exposure using light of a specified wavelength is used to form the first polymer. In some embodiments, a second exposure using light of a specified wavelength is used to form the second polymer. In some embodiments, the intensity of the second exposure (values ​​expressed in watts / cm²) is... 2 (Given) is between 10 watts / cm² 2 With 100 watts / cm 2 Between, between 50 watts / cm 2 With 80 watts / cm 2 Between, between 100 watts / cm 2 With 50 watts / cm 2 Between, between 100 watts / cm 2 With 10 watts / cm 2 Between, between 0.1 watts / cm 2 With 8 watts / cm 2 Between, between 0.1 watts / cm 2 With 6 watts / cm 2 Between, between 0.1 watts / cm 2 With 4 watts / cm 2 Between, or between 0.1 watts / cm 2 With 2 watts / cm 2 between.

[0095] In some embodiments, preferably, the second exposure has a high exposure intensity to induce polymerization of any remaining monomers that did not undergo polymerization in the first exposure. In some embodiments, the second exposure comprises light of a specified wavelength. In some embodiments, the second exposure is used to form a second polymer. In some embodiments, the second exposure is used to form a first polymer. In some embodiments, the intensity of the second exposure (values ​​expressed in watts / cm²) is... 2 (Given) is between 1 watt / cm 2 With 1000 watts / cm 2 Between, between 5 watts / cm 2 With 500 watts / cm 2 Between, between 5 watts / cm 2 With 100 watts / cm 2 Between, or between 10 watts / cm 2 With 100 watts / cm 2Between. In some embodiments, the intensity of the first exposure is high. In systems using lasers as the light source, the light intensity can be greater than 1 W / cm². 2 Especially when considering the spot size, but the delivered dose can be low enough not to burn the resin.

[0096] In some embodiments, the polymerization reaction includes step-growth polymerization, chain-growth polymerization, free radical polymerization, living polymerization, cationic addition polymerization, anionic addition polymerization, emulsion polymerization, solution polymerization, precipitation polymerization, photopolymerization, or any combination thereof. In a preferred embodiment, the polymerization reaction includes photopolymerization.

[0097] In some embodiments, when spatially controlling the polymerization exposure, the diffusion of all components results in a higher concentration of more reactive components (e.g., polymerizable monomers) in the reactive region (e.g., a first region comprising a first phase) and a higher concentration of less reactive components in the non-reactive region (e.g., a second region comprising a second phase). In some embodiments, the reactive region (first region) is characterized by exposure to a radiation source during initial exposure. In some embodiments, the non-reactive region (second region) is not exposed to a radiation source during initial exposure.

[0098] In some embodiments, diffusion of the resin components occurs within the resin and / or forming polymer. In some embodiments, a first component (e.g., a first polymerizable monomer) and a second component (e.g., a second polymerizable monomer) diffuse through the first polymer during polymerization of the first polymer. In some embodiments, diffusion of the first component is slowed as it polymerizes into the first polymer. In some embodiments, only the second component undergoes diffusion through the first polymer. In some embodiments, diffusion creates regions with higher component concentrations. As further described herein, in some embodiments, for example, regional control of the polymerization reaction (i.e., control of the size, shape, and / or location of the phase reaction) is achieved by using a mask during photopolymerization. In some embodiments, regional control of polymerization is achieved by controlling the following: temperature, polymer size, solubility parameters, monomer size, curing rate, light intensity, light dose, presence and / or amount of catalyst, and any combination thereof.

[0099] For example, a region-specific polymerization reaction that polymerizes the first component but not the second component will produce the first polymer in a specific region, while the second component diffuses toward other regions. Therefore, regions of the composite material (e.g., the first continuous phase) may include, by weight, greater than 0.1%, greater than 5%, greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of the first component. The first component may undergo polymerization partially or completely, and thus regions of the composite material (e.g., the first continuous phase) may include, by weight, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of the first polymer.

[0100] In some embodiments, the diffusion of the second component out of the first region results in a reduction in the amount of the second component in the first region. In some embodiments, the region of the composite material may include less than 100% by weight of the second component, less than 95% by weight of the second component, less than 90% by weight of the second component, less than 80% by weight of the second component, less than 70% by weight of the second component, less than 60% by weight of the second component, less than 50% by weight of the second component, less than 40% by weight of the second component, less than 30% by weight of the second component, less than 20% by weight of the second component, less than 10% by weight of the second component, or less than 5% by weight of the second component. The non-reactive region may polymerize later. The second component may undergo polymerization partially or completely, and therefore the region of the composite material may include less than 50% by weight of the second polymer, less than 40% by weight of the second polymer, less than 30% by weight of the second polymer, less than 20% by weight of the second polymer, less than 10% by weight of the second polymer, or less than 5% by weight of the second polymer.

[0101] In some embodiments, the composite material may undergo copolymerization in selective regions. In some embodiments, the composite material undergoes copolymerization based on exposure to a radiation source. In some embodiments, diffusion of resin components occurs, wherein a first component and a second component diffuse through the resin during polymerization to form a copolymer comprising the first and second components. Thus, selective polymerization can provide regions comprising copolymers, while regions not exposed to the radiation source comprise less copolymer or even no copolymer. In some embodiments, diffusion produces regions with higher component or copolymer concentrations. For example, a region-specific polymerization reaction of the first and second components will produce copolymers in a specific region while other resin components diffuse toward other regions. The first and second components may undergo polymerization partially or completely, so regions of the composite material (e.g., the first continuous phase) may comprise more than 50%, more than 60%, more than 70%, more than 80%, more than 90%, or more than 95% of the first copolymer by weight.

[0102] In some embodiments, polymerization of the resin region provides a change in the percentage of monomers present, or a corresponding change in the presence of their corresponding polymers. In some embodiments, this enrichment of the polymerizable component or polymer can be provided using a radiation source including a specified wavelength. In some embodiments, the percentage of a component present in the region is higher than the percentage expected under bulk curing conditions. In a preferred embodiment, the percentage change relative to the initial resin value is greater than 10% (molar percentage). In some embodiments, the percentage change relative to the initial resin value is about 5% or greater than 5%. In some embodiments, the percentage change relative to the initial resin value is greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 98% (molar percentage). As a non-limiting example, a resin comprising an initial amount of 60% monomer A and 40% monomer B is polymerized to provide a bulk copolymer material having an average of 60% monomer A and 40% monomer B in the bulk-cured copolymer. In contrast, using the methods disclosed herein, preferential polymerization of the same resin at a specified wavelength and / or a specified temperature can produce copolymers with an average composition of 50% monomer A and 50% monomer B, which will reduce the concentration of monomer A in the region by 17% and increase the average regional copolymer composition of monomer B by 25%. This percentage can be based on the initial and final molar percentages of monomer concentrations in the starting monomer mixture and the initial and final molar percentages of monomer concentrations in the copolymer bound to the defined spatial region. In some embodiments, the concentrations or compositions of the starting monomer mixture and the final polymer composition are described as weight percentages.

[0103] In some embodiments, differences in reactivity include differences in polymerization rate coefficients, concentrations, functionality (such as monofunctional, difunctional, trifunctional, etc.), solubility, diffusivity of the first component, diffusivity of the second component, polymerization activity at a specified temperature, polymerization activity upon exposure to light of a specified wavelength, reactivity with a photoinitiator, or any combination thereof. In some embodiments, the composition of the first polymer can be altered using various techniques compared to the composition of the second polymer. In some embodiments, the composition of the first polymer is determined by differences in reactivity between the first and second components. In specific embodiments, differences in reactivity include differences in oxygen inhibition, light absorption, photoinitiator concentration, component concentration, temperature, component solubility, polymer solubility, or combinations thereof.

[0104] In some embodiments, the first continuous phase may have a first polymerization rate, and the second continuous phase may have a second polymerization rate. When the first continuous phase polymerizes via a radical-induced polymerization reaction and the second continuous phase polymerizes via an ion-induced polymerization reaction, the radical-induced polymerization rate may be higher than the ion-induced polymerization rate. In some cases, the first polymerization rate may be greater than about 1 × 10⁻⁶. 3 s -1 And not exceeding 1×10 5 s -1 Greater than approximately 2.5 × 10 3 s -1 And not exceeding 5×10 4 s -1 Greater than approximately 2.5 × 10 3 s -1 And not exceeding 7.5×10 3 s -1 or greater than approximately 3.5 × 10 3 s -1 And not exceeding 5×10 3 s -1 In some cases, the second polymerization rate can be greater than about 1 × 10⁻⁶. 2 s -1 And not exceeding 1×10 4 s -1 Greater than approximately 2.5 × 10 2 s -1 And not exceeding 7.5×10 3 s -1 Greater than approximately 1×10 3 s -1 And not exceeding 5×10 3 s -1 or greater than approximately 1.5 × 10 3 s-1 And not exceeding 2.5×10 3 s -1 In some embodiments, such a first polymerization rate corresponds to a first continuous phase comprising an acrylate moiety, and such a second polymerization rate corresponds to a second continuous phase comprising a methacrylate moiety. In some cases, the polymerization rate herein may be per mole of monomer, and thus in M -1 s -1 express.

[0105] In some embodiments, photopolymerization is used, and the region is generated by a mask, photomask, laser path, digital light processor projector, digital mirror device, liquid crystal display, or overlay protecting non-reactive areas from the light source. In some embodiments, the mask or overlay includes a pattern to form a patterned polymerized region on a layer. In some embodiments, the mask includes multiple lines, multiple parallel lines, multiple brick shapes, multiple circular holes, multiple vertical lines forming a shadow pattern, or combinations thereof.In some embodiments, the mask includes a region that allows unobstructed radiation, wherein the minimum axis dimension of the region is 5 nm to 100 micrometers, 5 nm to 100 nm, 5 nm to 200 nm, 5 nm to 300 nm, 5 nm to 400 nm, 5 nm to 500 nm, 10 nm to 200 nm, 10 nm to 300 nm, 10 nm to 400 nm, 10 nm to 500 nm, 10 nm to 1 micrometer, 10 nm to 100 micrometers, 20 nm to 100 micrometers, 20 nm to 10 micrometers, 20 nm to 1 micrometer, 20 nm to 500 nm, etc. 0nm, dimensions from 20nm to 300nm, dimensions from 40nm to 200nm, dimensions from 40nm to 300nm, dimensions from 40nm to 400nm, dimensions from 40nm to 500nm, dimensions from 40nm to 1 micrometer, dimensions from 40nm to 100 micrometers, dimensions from 60nm to 200nm, dimensions from 60nm to 300nm, dimensions from 60nm to 400nm, dimensions from 60nm to 500nm, dimensions from 60nm to 1 micrometer, dimensions from 60nm to 100 micrometers, dimensions from 80nm to 200nm, dimensions from 80nm to 300nm, dimensions from 80nm to 400nm, dimensions from 80nm to 500nm, dimensions from 80nm Sizes ranging from 1 micrometer to 80 nm to 100 micrometers, sizes ranging from 100 nm to 100 micrometers, sizes ranging from 100 nm to 10 micrometers, sizes ranging from 100 nm to 1 micrometer, sizes ranging from 100 nm to 500 nm, sizes ranging from 200 nm to 100 micrometers, sizes ranging from 200 nm to 50 micrometers, sizes ranging from 200 nm to 25 micrometers, sizes ranging from 200 nm to 5 micrometers, sizes ranging from 200 nm to 1 micrometer, sizes ranging from 500 nm to 100 micrometers, sizes ranging from 500 nm to 5 micrometers, sizes ranging from 500 nm to 1 micrometer, sizes ranging from 1 micrometer to 100 micrometers, sizes Sizes range from 1 micrometer to 50 micrometers, 1 micrometer to 40 micrometers, 1 micrometer to 30 micrometers, 1 micrometer to 20 micrometers, 1 micrometer to 10 micrometers, 2 micrometers to 100 micrometers, 2 micrometers to 50 micrometers, 2 micrometers to 25 micrometers, 2 micrometers to 10 micrometers, 4 micrometers to 100 micrometers, 4 micrometers to 50 micrometers, 4 micrometers to 40 micrometers, 4 micrometers to 20 micrometers, 4 micrometers to 10 micrometers, 6 micrometers to 100 micrometers, 6 micrometers to 50 micrometers, 6 micrometers to 25 micrometers, 6 micrometers to 20 micrometers, 10 micrometers to 100 micrometers, or 10 micrometers to 50 micrometers.

[0106] In some embodiments, photopolymers are manufactured using a "vat" process, in which segments or portions of resin in a vat or reservoir are selectively cured using light. Each layer of the object being manufactured can be selectively exposed to light in a single exposure or by scanning a beam of light through the layer. Specific techniques include stereolithography (SLA), digital light processing (DLP), holographic projection, and two-photon induced photopolymerization (TPIP).

[0107] In some embodiments, the resin is in a liquid phase at the use temperature (e.g., manufacturing temperature) and / or at elevated temperatures. High-viscosity resins can pose challenges during object fabrication (e.g., using 3D printing). In some embodiments, the resin is liquid at the manufacturing temperature. In some embodiments, the resin is liquid at an elevated temperature. In some embodiments, the manufacturing temperature is an elevated temperature. In some embodiments, the elevated temperature is equal to or higher than the melting temperature (T0) of the resin components (e.g., the first component and the second component). m In some embodiments, the elevated temperature is within the range of 40°C to 100°C, 60°C to 100°C, 80°C to 100°C, 40°C to 150°C, or 150°C to 350°C. In some embodiments, the elevated temperature is above 40°C, above 60°C, above 80°C, or above 100°C. In some embodiments, the resin at the elevated temperature is a liquid with a viscosity of less than 50 PaS, less than 20 PaS, less than 10 PaS, less than 5 PaS, or less than 1 PaS. In a preferred embodiment, the resin at the elevated temperature is a liquid with a viscosity of less than 20 PaS. In a more preferred embodiment, the resin at the elevated temperature is a liquid with a viscosity of less than 1 PaS.

[0108] In some embodiments, the resin has a viscosity of less than 60 PaS, less than 50 PaS, less than 40 PaS, less than 30 PaS, less than 20 PaS, less than 10 PaS, less than 9 PaS, less than 8 PaS, less than 7 PaS, less than 6 PaS, less than 5 PaS, less than 4 PaS, less than 3 PaS, less than 2 PaS, less than 1 PaS, or less than 0.1 PaS at the elevated temperature. In some embodiments, the elevated temperature is the printing temperature. In some embodiments, the elevated temperature is equal to, higher than, or lower than room temperature. In some embodiments, the elevated temperature is 0°C to 25°C, 25°C to 40°C, 40°C to 150°C, or 10°C to 40°C. In a preferred embodiment, the resin has a viscosity of 0.05 PaS to 10 PaS at the printing temperature (i.e., the manufacturing temperature). In some embodiments, the resin has a viscosity of 1 PaS to 10 PaS at the printing temperature. In some embodiments, the printing temperature may include one or more temperatures between 20 and 120°C. The dynamic viscosity of a fluid represents its resistance to shear flow. The SI unit of dynamic viscosity is poise (Pa). Dynamic viscosity is usually given in centipoise, where 1 centipoise (cP) equals 1 mPa. Kinematic viscosity is the ratio of a fluid's dynamic viscosity to its density; the SI unit is m³. 2 / s. Apparatus used for measuring viscosity includes viscometers and rheometers. The viscosity of the composition described herein can be measured using a rheometer at 110°C. For example, the MCR 301 rheometer from Anton Paar can be used for rheological measurements in rotational mode (PP-25, 50 s⁻¹, 50-115°C, 3°C / min).

[0109] In some embodiments, the resins disclosed herein can be used in 3D printing processes to form objects. The resins are capable of 3D printing and provide polymeric materials with the beneficial properties further disclosed herein.

[0110] In some embodiments, the resin comprises a ratio (volume / volume) of a first component (e.g., a first polymerizable monomer) to a second component (e.g., a second polymerizable monomer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the resin comprises a first component (e.g., a first polymerizable monomer) to a second component (e.g., a second polymerizable monomer) in a ratio (volume / volume) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the resin comprises a ratio (volume / volume) of a first component (e.g., a first polymerizable monomer) to a second component (e.g., a second polymerizable monomer) between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1.

[0111] In some embodiments, the resin includes a ratio (volume / volume) of a second component (e.g., a second polymerizable monomer) to a first component (e.g., a first polymerizable monomer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the resin comprises a ratio (volume / volume) of a second component (e.g., a second polymerizable monomer) to a first component (e.g., a first polymerizable monomer) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the resin comprises a ratio (volume / volume) of a second component (e.g., a second polymerizable monomer) to a first component (e.g., a first polymerizable monomer) between a ratio between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1. Composite materials

[0112] In some embodiments, the polymer composites described herein possess enhanced physical properties compared to homopolymers of similar monomer types. For example, composites comprising a first polymer having high strength (e.g., high storage modulus) and a second polymer having high flexibility can form composites with higher strength and flexibility than homopolymers of either monomer type. Composites can provide two or more relative properties. For example, some embodiments of the composites disclosed herein have the relative properties of a high-modulus, low-elasticity material to generate forces for moving teeth, and are also a low-modulus, high-elasticity material to provide a good feel for patient comfort and less breakage.

[0113] In some embodiments, the composite material has enhanced properties relative to a simple mixture of corresponding monomers of a resin that forms a homogeneous mixture. For example, compared to a corresponding material that does not have multiple continuous phases (e.g., is homogeneous), the composite material herein may include increased modulus, increased elongation at break, increased yield stress, increased heat distortion temperature, and reduced stress relaxation (e.g., less creep).

[0114] In some embodiments, the composite material comprises a hard phase and a soft phase, the hard phase comprising an acrylate component (e.g., a polymerizable monomer of acrylate polymerized to form a polymer), and the soft phase comprising a methacrylate component (e.g., a polymerizable monomer of methacrylate polymerized to form a polymer). Advantageously, when the composite material is compared to conventional materials (e.g., with the methacrylate component applied in the hard phase and the acrylate component applied in the soft phase), an increased modulus is observed in embodiments where the acrylate component is applied in the hard phase formation and the methacrylate component is applied in the soft phase formation. This improvement in modulus endows the composite material and apparatus described herein with beneficial properties.

[0115] In some embodiments, this disclosure provides polymeric materials (also referred to herein as "polymeric materials" and "cured polymeric materials") generated from resins further described herein. Cured polymeric materials include a first continuous phase (also referred to herein as "first domain") and a second continuous phase (also referred to herein as "second domain"), the first continuous phase being a phase of polymeric material in which a first component of the resin described herein (e.g., incorporated into a first polymerizable monomer in a first polymer) is present, and the second continuous phase being a phase of polymeric material in which a second component (e.g., incorporated into a second polymerizable monomer in a second polymer) is present. A continuous phase is a phase that can be traced or connected from one side of a material to the other; for example, a closed-cell foam has a material comprising foam that can be traced on a sample, while closed-cell (bubbles) represent a discontinuous phase of cavitation. A discontinuous phase does not have a connected single phase (e.g., has material islands, such as glass fillers in a resin).

[0116] In some aspects, this disclosure provides composite materials comprising a first continuous phase and a second continuous phase. In some embodiments, the first continuous phase comprises a first polymer region (e.g., a polymer region comprising a first polymer, such as a first polymer formed from a first component of a resin). In some embodiments, the first polymer region is a soft polymer region. In some embodiments, the second continuous phase comprises a second polymer region (e.g., a polymer region comprising a second polymer, such as a second polymer formed from a second component of a resin). In some embodiments, the second polymer region is a hard polymer region. A soft polymer region is a region comprising a polymer with a hardness of about 60 Å to about 85 D. Thus, in some cases, the soft polymer region may have a hardness of about 60 Å to about 70 Å, about 70 Å to about 80 Å, about 80 Å to about 90 Å, or about 90 Å to about 100 Å. In other embodiments, the soft polymer region may have a hardness of about 60 D to about 70 D, about 70 D to about 80 D, or about 75 D to about 85 D. A hard polymer region is a region comprising a polymer with a hardness of about 60 Å to about 85 D. Therefore, in some cases, the hard polymer region may have a hardness of about 60 Å to about 70 Å, about 70 Å to about 80 Å, about 80 Å to about 90 Å, or about 90 Å to about 100 Å. In other embodiments, the hard polymer region may have a hardness of about 60 D to about 70 D, about 70 D to about 80 D, or about 75 D to about 85 D. The soft polymer region includes regions of polymers that may have a tensile modulus of about 1 MPa to about 600 MPa, about 300 MPa to about 600 MPa, or about 450 MPa to about 600 MPa. The hard polymer region includes regions of polymers that may have a tensile modulus of about 600 MPa to about 5000 MPa, about 700 MPa to about 2000 MPa, or about 800 MPa to about 1500 MPa.

[0117] The soft polymer region (e.g., a first continuous phase formed from a first component of the resin) is softer than the hard polymer region (e.g., a second continuous phase formed from a second component of the resin). In some embodiments, the hard polymer region is harder than the soft polymer region. In some embodiments, the hard polymer region (e.g., the second continuous phase) is 1.1 times, 1.5 times, 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 20 times, 30 times, 40 times, 50 times, 100 times, or more than 100 times harder than the soft polymer region (e.g., the first continuous phase). In some embodiments, the composite material includes a ratio of the hardness of a hard polymer region (e.g., a second continuous phase) to the hardness of a soft polymer region (e.g., a first continuous phase) greater than or equal to 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 100:1. In some embodiments, the composite material herein includes a hard polymer region having a first flexural modulus and a soft polymer region having a second flexural modulus, wherein the ratio between the first flexural modulus and the second flexural modulus may be greater than or equal to 1:1, greater than or equal to 1.1:1, greater than or equal to 1.2:1, greater than or equal to 1.3:1, greater than or equal to 1.4:1, greater than or equal to 1.5:1, greater than or equal to 1.6:1, greater than or equal to 1.7:1, greater than or equal to 1.8:1, greater than or equal to 1.9:1, greater than or equal to 2:1, greater than or equal to 3:1, greater than or equal to 4:1, greater than or equal to 5:1, greater than or equal to 6:1, greater than or equal to 7:1, greater than or equal to 8:1, greater than or equal to 9:1, greater than or equal to 10:1, greater than or equal to 20:1, greater than or equal to 30:1, greater than or equal to 40:1, greater than or equal to 50:1, or greater than or equal to 100:1.

[0118] In some embodiments, the first continuous phase includes a vertical dimension of less than 100 nm. In some embodiments, the first continuous phase includes a lateral dimension of less than 100 nm. In some embodiments, the second continuous phase includes a vertical dimension of less than 100 nm. In some embodiments, the second continuous phase includes a lateral dimension of less than 100 nm.In some embodiments, the lateral and / or vertical dimensions of the first phase and / or the second phase are 5 nm to 100 micrometers, 5 nm to 100 nm, 5 nm to 200 nm, 5 nm to 300 nm, 5 nm to 400 nm, 5 nm to 500 nm, 10 nm to 200 nm, 10 nm to 300 nm, 10 nm to 400 nm, 10 nm to 500 nm, 10 nm to 1 micrometer, 10 nm to 100 micrometers, 20 nm to 100 micrometers, 20 nm to 10 micrometers, 20 nm to 1 micrometer, 20 nm to 500 nm, and 2... 0nm to 300nm, dimensions of 40nm to 200nm, dimensions of 40nm to 300nm, dimensions of 40nm to 400nm, dimensions of 40nm to 500nm, dimensions of 40nm to 1 micrometer, dimensions of 40nm to 100 micrometers, dimensions of 60nm to 200nm, dimensions of 60nm to 300nm, dimensions of 60nm to 400nm, dimensions of 60nm to 500nm, dimensions of 60nm to 1 micrometer, dimensions of 60nm to 100 micrometers, dimensions of 80nm to 200nm, dimensions of 80nm to 300nm, dimensions of 80nm to 400nm, dimensions of 80nm to 500nm, dimensions of 80nm to 1 micrometer. Sizes ranging from 80nm to 100μm, 100nm to 100μm, 100nm to 10μm, 100nm to 1μm, 100nm to 500nm, 200nm to 100μm, 200nm to 50μm, 200nm to 25μm, 200nm to 5μm, 200nm to 1μm, 500nm to 100μm, 500nm to 50μm, 500nm to 25μm, 500nm to 100μm, 500nm to 5μm, 500nm to 1μm, 1μm to 100μm, 1μm Sizes ranging from 1 to 50 micrometers, 1 to 40 micrometers, 1 to 30 micrometers, 1 to 20 micrometers, 1 to 10 micrometers, 2 to 100 micrometers, 2 to 50 micrometers, 2 to 25 micrometers, 2 to 10 micrometers, 4 to 100 micrometers, 4 to 50 micrometers, 4 to 40 micrometers, 4 to 20 micrometers, 4 to 10 micrometers, 6 to 100 micrometers, 6 to 50 micrometers, 6 to 25 micrometers, 6 to 20 micrometers, 10 to 100 micrometers, or 10 to 50 micrometers.

[0119] In some embodiments, the composite material includes a first continuous phase and a second continuous phase, the first continuous phase comprising soft polymer regions and the second continuous phase comprising hard polymer regions, wherein the composite material includes a gradient between the first and second continuous phases. In some embodiments, the first continuous phase corresponds to a polymer formed during the polymerization of a first component of the resin, and the second continuous phase corresponds to a polymer formed during the polymerization of a second component of the resin. The gradient between the first and second continuous phases is a region in which the boundary between the first and second continuous phases is not defined. As a non-limiting example, the composite material including the first and second phases forms phases under controlled exposure (e.g., by using a patterned mask), which has defined boundaries between the phases (e.g., initially exposed regions and initially unexposed regions). In contrast, in some embodiments described herein, such defined boundaries do not exist between the phases.

[0120] In some embodiments, the composite material described herein has a continuous phase formed in a more randomized manner compared to mask exposure, such that gradients exist between the phases. In some embodiments, the shape and / or size and / or location of at least one continuous phase is not controlled, thereby facilitating gradient formation. In some embodiments, the shape and / or size and / or location of a first continuous phase is not controlled. In some embodiments, the shape and / or size and / or location of a second continuous phase is not controlled. In some embodiments, the gradient and / or presence of the continuous phase is determined by atomic force microscopy (AFM). As phase demand decreases, atomic force microscopy can identify the presence of the first and second continuous phases in the composite material described herein. In some embodiments, AFM uses a tapping mode. In some embodiments, scanning electron microscopy (SEC) is used instead of AFM. In some embodiments, where phase demand is greater, differential scanning calorimetry (DSC) and / or dynamic mechanical analysis (DMA) can be used to observe the gradient and / or continuous phase.

[0121] In some embodiments, factors such as temperature, polymer size, solubility parameters, curing rate, light intensity, the presence and / or amount of catalyst or combinations thereof can affect the presence and extent of gradient formation between continuous phases.

[0122] Polymer materials can be formed by curing resins further disclosed herein. In some embodiments, curing includes a single curing step. In some embodiments, curing includes multiple curing steps. In a preferred embodiment, curing includes at least one curing step of exposing the resin to light. Exposing the resin to light can initiate and / or promote polymerization of at least one of the first or second components (e.g., photopolymerization), particularly in the presence of a photoinitiator in the resin. In some embodiments, the resin is exposed to UV (ultraviolet) light, visible light, IR (infrared) light, or any combination thereof. In some embodiments, the cured polymer material is formed from the resin using at least one step including exposure to a light source, wherein the light source includes UV light, visible light, and / or IR light. In some embodiments, the light source includes wavelengths of 10 nm to 200 nm, 200 nm to 350 nm, 350 nm to 450 nm, 450 nm to 550 nm, 550 nm to 650 nm, 650 nm to 750 nm, 750 nm to 850 nm, 850 nm to 1000 nm, or 1000 nm to 1500 nm. In some embodiments, the cured polymer material is formed from resin and is exposed to a light source at least a second time, wherein the light source includes UV light, visible light, and / or IR light. In some embodiments, the second exposure includes wavelengths of 10 nm to 200 nm, 200 nm to 350 nm, 350 nm to 450 nm, 450 nm to 550 nm, 550 nm to 650 nm, 650 nm to 750 nm, 750 nm to 850 nm, 850 nm to 1000 nm, or 1000 nm to 1500 nm.

[0123] The discussion of the properties of polymeric materials in this article refers to materials that are ready for use (e.g., cured and cooled materials for their intended purpose, such as cured and cooled orthodontic appliances designed to provide treatment to patients).

[0124] In some embodiments, the polymer material includes a ratio (by weight) of a first continuous phase (e.g., comprising a first component incorporated into a first polymer) to a second continuous phase (e.g., comprising a second component incorporated into a second polymer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the polymer material comprises a ratio (by weight) of a first continuous phase (e.g., comprising a first component incorporated into a first polymer) to a second continuous phase (e.g., comprising a second component incorporated into a second polymer) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the polymeric material comprises a ratio (by weight) of a first continuous phase (e.g., comprising a first component incorporated into a first polymer) to a second continuous phase (e.g., comprising a second component incorporated into a second polymer) between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1.

[0125] In some embodiments, the polymer material includes a ratio (by weight) of a second continuous phase (e.g., comprising a second component incorporated into a second polymer) to a first continuous phase (e.g., comprising a first component incorporated into a first polymer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the polymer material comprises a ratio (by weight) of a second continuous phase (e.g., including a second component incorporated into a second polymer) to a first continuous phase (e.g., including a first component incorporated into a first polymer) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the polymeric material includes a ratio (by weight) of a second continuous phase (e.g., comprising a second component incorporated into a second polymer) to a first continuous phase (e.g., comprising a first component incorporated into a first polymer) between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1.

[0126] In some embodiments, the polymer material includes a ratio (volume / volume) of a first continuous phase (e.g., comprising a first component incorporated into a first polymer) to a second continuous phase (e.g., comprising a second component incorporated into a second polymer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the polymer material comprises a first continuous phase (e.g., comprising a first component incorporated into a first polymer) to a second continuous phase (e.g., comprising a second component incorporated into a second polymer) at a ratio (volume / volume) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the polymer material includes a ratio (volume / volume) of a first continuous phase (e.g., including a first component incorporated into a first polymer) to a second continuous phase (e.g., including a second component incorporated into a second polymer) between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1.

[0127] In some embodiments, the polymer material includes a ratio (volume / volume) of a second continuous phase (e.g., comprising a second component incorporated into a second polymer) to a first continuous phase (e.g., comprising a first component incorporated into a first polymer) greater than 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 20:1, 30:1, 40:1, 50:1, or 99:1. In some embodiments, the polymer material comprises a second continuous phase (e.g., including a second component incorporated into a second polymer) to a first continuous phase (e.g., including a first component incorporated into a first polymer) at a ratio (volume / volume) of at least 1:10, at least 1:9, at least 1:8, at least 1:7, at least 1:6, at least 1:5, at least 1:4, at least 1:3, at least 1:2, at least 1:1, at least 2:1, at least 3:1, at least 4:1, at least 5:1, at least 6:1, at least 7:1, at least 8:1, at least 9:1, at least 10:1, at least 20:1, at least 30:1, at least 40:1, at least 50:1, or at least 99:1. In some embodiments, the polymer material includes a ratio (volume / volume) of a second continuous phase (e.g., including a second component incorporated into a second polymer) to a first continuous phase (e.g., including a first component incorporated into a first polymer) between 1:9 and 99:1, between 1:9 and 9:1, between 1:4 and 4:1, between 1:4 and 1:1, between 3:5 and 1:1, between 1:1 and 5:3, or between 1:1 and 4:1.

[0128] In some embodiments, the polymer material is biocompatible. Biocompatible can refer to a material that, when placed in a biological environment within an organism, does not elicit immune rejection or adverse effects (referred to herein as an adverse immune response). For example, in embodiments, when a human or other animal is exposed to or comes into contact with the biocompatible material, the change in biomarkers indicative of an immune response from baseline 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 at the tissue structure level, wherein a local immune response is assessed by visually evaluating markers in and adjacent to the material, including immune cells or markers involved in immune response pathways. In one aspect, as determined at the tissue structure level, the biocompatible material or device does not observably alter the immune response. In some embodiments, this disclosure provides biocompatible devices configured for long-term use (e.g., approximately several weeks to several months) without evoking an adverse immune response. Biological effects 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 supplemental assessment include chronic toxicity testing. In some embodiments, the polymeric material is bioinert. Bioinertness means that a material does not elicit an immune response from a human or animal when placed in an in vivo biological environment. For example, when a human or animal is exposed to or comes into contact with a bioinert material, biomarkers indicating an immune response remain substantially constant (plus or minus 5% of baseline values). In some embodiments, this disclosure provides bioinert devices. Evaluation of polymer materials

[0129] In some embodiments, this disclosure provides polymeric materials formed from the resins described herein using the methods and / or systems described herein. The polymeric materials disclosed herein possess properties beneficial to the production of many applications and various devices. As a non-limiting example, the polymeric materials described herein are used to produce orthodontic appliances, such as braces. Orthodontic appliances require toughness and flexibility to move a patient's teeth while maintaining durability for use. In some embodiments, the polymeric materials have a high glass transition temperature, low creep, and low stress relaxation.

[0130] In some embodiments described herein, the polymeric material has properties measured after being placed in an aqueous environment at 37°C for 24 hours. The property values ​​of the polymeric material can be determined, for example, by using the following methods: stress relaxation properties can be evaluated using an RSA-G2 instrument from TA Instruments, according to ASTM D790, with a 3-point bending test; stress relaxation can be measured at 30°C and immersed in water, and reported as the residual load after 24 hours, or as a percentage (%) of the initial load; storage modulus can be measured at 37°C and reported in MPa; the Tc of the cured polymeric material... g Dynamic mechanical analysis (DMA) can be used for evaluation, and is provided herein as the peak tan δ when running at a temperature ramp of 2 °C / min at 1 Hz; tensile modulus, tensile strength, yield elongation, and elongation at break can be evaluated according to ISO 527-2 5B; yield tensile strength, elongation at break, tensile strength, and Young's modulus can be evaluated according to ASTM D1708; and the residual bending stress relaxation (“residual bending stress”) after 24 hours in a humid environment at 37 °C can be evaluated according to ASTM E328. In some embodiments, sample measurements are performed using a 1 mm thick sample. Other methods can be used to characterize the material described herein, and the methods described above provide exemplary methods.

[0131] As further described herein, in some embodiments, the polymer material formed using the methods and systems described herein is a multiphase material comprising at least a first continuous phase and a second continuous phase (e.g., formed correspondingly by a first component that generates a first polymer and a second component that forms a second polymer). In some embodiments, such a material has more than one continuous phase, each continuous phase having distinct and identifiable characteristics. In such embodiments, the polymer material may have more than one (e.g., two, three, four, five, or more) of the following polymer material characteristics. For example, in some embodiments, a polymer material having two continuous phases is a material in which the first phase is characterized by a first tensile stress-strain curve, the second phase by a second tensile stress-strain curve, and the aggregate material (i.e., the polymer material as a combination of phases) is characterized by a third tensile stress-strain curve. In some embodiments, the first stress-strain curve, the second stress-strain curve, and the third stress-strain curve are not identical. As further described herein, in some embodiments, the material properties of the cured polymer material refer to the material properties of a multiphase (e.g., a combination of all phases of the cured material) aggregate material, and these properties are identifiable and as described below. In some embodiments, the material properties of the cured polymer material refer to the properties of the individual phases of the cured material (e.g., the first continuous phase and / or the second continuous phase), and these properties are defined and as described herein.

[0132] In some embodiments, the physical properties of regions (e.g., continuous phases) of a polymeric material are determined by forming a similar material comprising or composed of that phase and thereby determining its physical properties. As a non-limiting example, a photopolymerizable resin having multiple continuous regions can be formed, and the material properties of the aggregate (i.e., a polymeric material comprising all phases) can be determined directly from the formed material, while a sample of the polymeric material formed comprising only a first or second phase can be used to determine the properties of each corresponding phase. In some embodiments, the properties of the polymeric material and the properties of at least one or at least two regions of the polymeric material can be determined directly from the polymeric material (e.g., directly measured without forming separate samples representing each region).

[0133] In some embodiments, the cured polymer material (e.g., any of the first continuous phase, the second continuous phase, and all phases of aggregate polymer materials) is characterized by a tensile stress-strain curve showing the yield point after which the specimen continues to elongate without an increase in load. Such yield point behavior can “approach” the glass transition temperature, where the material is between a glassy and rubbery state and can be characterized as having viscoelastic behavior. In embodiments, viscoelastic behavior is observed in a temperature range of 20°C to 40°C. The yield stress is determined at the yield point. In some embodiments, the yield point is along an elastic region where the slope of the stress-strain curve is constant or nearly constant. In some embodiments, the modulus is determined based on the initial slope of the stress-strain curve or the modulus is determined as the secant modulus at 1% strain (e.g., when there is no linear portion of the stress-strain curve). The yield elongation is determined by the strain at the yield point. When the yield point occurs at the maximum stress, the ultimate tensile strength is less than the yield strength. For tensile specimens, strain is defined by ln(l / l0), which can be approximated as (l-l0) / l0 at smaller strains (e.g., less than about 10%), and elongation is l / l0, where l is the gauge length after some deformation and l0 is the initial gauge length. Mechanical properties can depend on the temperature at which they are measured. Test temperatures can be lower than the intended operating temperature for dental instruments, such as 35°C to 40°C. In some embodiments, the test temperature is 23 ± 2°C.

[0134] In some embodiments, the hardness of the cured polymer material (e.g., any one of the first continuous phase, the second continuous phase, and all phases of aggregate polymer material) is 60 Shore A to 85 Shore D. In some embodiments, the hardness of the cured polymer material is 60-70 Shore A, 70-80 Shore A, 80-90 Shore A, 90-100 Shore A, 0-10 Shore D, 10-20 Shore D, 20-30 Shore D, 30-40 Shore D, 40-50 Shore D, 50-60 Shore D, 60-70 Shore D, 70-80 Shore D, or 80-85 Shore D. In some embodiments, the hardness of the first continuous phase is 60-70 Shore A, 70-80 Shore A, 80-90 Shore A, 90-100 Shore A, 0-10 Shore D, 10-20 Shore D, 20-30 Shore D, 30-40 Shore D, 40-50 Shore D, 50-60 Shore D, 60-70 Shore D, 70-80 Shore D, or 80-85 Shore D. In some embodiments, the hardness of the second continuous phase is 60-70 Shore A, 70-80 Shore A, 80-90 Shore A, 90-100 Shore A, 0-10 Shore D, 10-20 Shore D, 20-30 Shore D, 30-40 Shore D, 40-50 Shore D, 50-60 Shore D, 60-70 Shore D, 70-80 Shore D, or 80-85 Shore D.

[0135] In some embodiments, the polymer material, the first region of the polymer material (e.g., a first continuous region), and / or the second region of the polymer material (e.g., a second continuous region) is characterized by one or more of the following: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; residual stress greater than or equal to 0.01 MPa; and flexural modulus greater than or equal to 60 MPa after immersion in water for 24 hours at ambient temperature (e.g., at 37°C). In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by an elongation at break greater than or equal to 5%. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a storage modulus greater than or equal to 500 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a tensile modulus greater than or equal to 500 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a residual stress greater than or equal to 0.01 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a flexural modulus greater than or equal to 60 MPa after immersion in water for 24 hours at ambient temperature (e.g., at 37°C). In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by two or more of the following: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; residual stress greater than or equal to 0.01 MPa; and a flexural modulus greater than or equal to 60 MPa after immersion in water for 24 hours at ambient temperature (e.g., at 37°C). In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by: elongation at break greater than or equal to 5%; storage modulus greater than or equal to 500 MPa; tensile modulus greater than or equal to 500 MPa; residual stress greater than or equal to 0.01 MPa; and a flexural modulus greater than or equal to 60 MPa after immersion in water for 24 hours at ambient temperature (e.g., at 37°C).

[0136] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by one or more of the following: a tensile modulus greater than or equal to 100 MPa after being placed in an aqueous environment at 37°C for 24 hours; a yield tensile strength greater than or equal to 5 MPa after being placed in an aqueous environment at 37°C for 24 hours; a storage modulus greater than or equal to 500 MPa after being placed in an aqueous environment at 37°C for 24 hours; a residual flexural stress (“residual stress”) greater than or equal to 1.5 MPa after being placed in an aqueous environment at 37°C for 24 hours; a hardness of 60 Shore A to 85 Shore D after being placed in an aqueous environment at 37°C for 24 hours; and an elongation at break greater than or equal to 15% before and / or after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a tensile modulus greater than or equal to 100 MPa after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a yield tensile strength greater than or equal to 5 MPa after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a storage modulus greater than or equal to 500 MPa after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a residual flexural stress (“residual stress”) greater than or equal to 1.5 MPa after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a hardness of 60 Shore A to 85 Shore D after being placed in an aqueous environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by an elongation at break greater than or equal to 15% before and / or after being placed in an aqueous environment at 37°C for 24 hours.In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by: a tensile modulus greater than or equal to 100 MPa after being placed in an aqueous environment at 37°C for 24 hours; a yield tensile strength greater than or equal to 5 MPa after being placed in an aqueous environment at 37°C for 24 hours; a storage modulus greater than or equal to 500 MPa after being placed in an aqueous environment at 37°C for 24 hours; a residual flexural stress (“residual stress”) greater than or equal to 1.5 MPa after being placed in an aqueous environment at 37°C for 24 hours; a hardness of 60 Shore A to 85 Shore D after being placed in an aqueous environment at 37°C for 24 hours; and an elongation at break greater than or equal to 15% before and / or after being placed in an aqueous environment at 37°C for 24 hours.

[0137] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a tensile modulus of 100 MPa to 3000 MPa, 100 MPa to 2500 MPa, 100 MPa to 2000 MPa, 500 MPa to 3000 MPa, 500 MPa to 2500 MPa, 500 MPa to 2000 MPa, 750 MPa to 3000 MPa, 750 MPa to 2500 MPa, 750 MPa to 2000 MPa, or 800 MPa to 2000 MPa after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the tensile modulus of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than or equal to 500 MPa after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a tensile modulus greater than or equal to 800 MPa after 24 hours in a humid environment at 37°C. In some embodiments, the tensile modulus is evaluated according to ISO-527-2 5B.

[0138] In some embodiments, the yield tensile strength of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 1 MPa to 100 MPa, 5 MPa to 85 MPa, 10 MPa to 75 MPa, 15 MPa to 65 MPa, 20 MPa to 55 MPa, or 25 MPa to 45 MPa. In some embodiments, the yield tensile strength of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 30 MPa to 60 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a yield tensile strength greater than or equal to 0.1 MPa, greater than or equal to 0.5 MPa, greater than or equal to 1 MPa, greater than or equal to 10 MPa, greater than or equal to 30 MPa, greater than or equal to 40 MPa, greater than or equal to 50 MPa, greater than or equal to 60 MPa, greater than or equal to 70 MPa, greater than or equal to 80 MPa, greater than or equal to 90 MPa, or greater than or equal to 100 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a yield tensile strength greater than or equal to 30 MPa. In some embodiments, the tensile strength is evaluated according to ISO-527-2 5B.

[0139] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a storage modulus of 0.1 MPa to 4000 MPa, 50 MPa to 2750 MPa, 100 MPa to 2500 MPa, 200 MPa to 2250 MPa, 300 MPa to 3000 MPa, 500 MPa to 3000 MPa, 750 MPa to 3000 MPa, or 1000 MPa to 3000 MPa after 24 hours of testing in a humid environment at 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a storage modulus of 0.1 MPa to 4000 MPa, a storage modulus of 300 MPa to 3000 MPa, or a storage modulus of 750 MPa to 3000 MPa after 24 hours of testing in a humid environment at 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a storage modulus greater than or equal to 300 MPa, 400 MPa, 500 MPa, 600 MPa, 700 MPa, 800 MPa, 900 MPa, or 1000 MPa. In some embodiments, the storage modulus is evaluated according to ASTM D790, DMA, or both. In some cases, the storage modulus is evaluated according to ASTM D790. In other cases, the storage modulus is evaluated according to DMA. In other embodiments, the storage modulus is evaluated according to ASTM D7028.

[0140] It may be advantageous that the residual flexural stress of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 5% or greater after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the residual flexural stress is 5% or greater, 10% or greater, 15% or greater, 20% or greater, 25% or greater, 30% or greater, 35% or greater, 40% or greater, 50% or greater, 60% or greater, or 70% or greater. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a residual flexural stress greater than 10% after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a residual flexural stress greater than 20% after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a residual flexural stress greater than 25% after being tested at 37°C in a humid environment for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is 5% to 50%, 10% to 50%, 15% to 50%, 20% to 50%, 25% to 50%, or 30% to 50% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is 5% to 100%, 10% to 100%, 15% to 100%, 20% to 100%, 25% to 100%, 30% to 100%, 40% to 100%, 50% to 100%, 60% to 100%, 70% to 100%, 80% to 100%, or 90% to 100% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is 20% to 45% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is greater than 50% of the initial load. In some embodiments, the residual flexural stress is measured using a 1 mm thick sample. In some embodiments, the residual flexural stress is evaluated according to ASTM E328.

[0141] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a residual flexural stress of 0.01 MPa to 15 MPa, 0.05 MPa to 15 MPa, 0.1 MPa to 15 MPa, 0.5 MPa to 15 MPa, 1 MPa to 15 MPa, 2 MPa to 15 MPa, 3 MPa to 15 MPa, 4 MPa to 15 MPa, 5 MPa to 15 MPa, or 10 MPa to 15 MPa after 24 hours in a humid environment at 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a residual flexural stress of 2 MPa to 15 MPa after 24 hours in a humid environment at 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is greater than or equal to 0.1 MPa, greater than or equal to 0.5 MPa, greater than or equal to 1 MPa, greater than or equal to 1.5 MPa, greater than or equal to 2 MPa, greater than or equal to 2.5 MPa, greater than or equal to 3 MPa, greater than or equal to 4 MPa, greater than or equal to 5 MPa, greater than or equal to 6 MPa, greater than or equal to 7 MPa, greater than or equal to 8 MPa, greater than or equal to 9 MPa, greater than or equal to 10 MPa, or greater than or equal to 15 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual flexural stress after 24 hours in a humid environment at 37°C is greater than or equal to 1.5 MPa. In some embodiments, the flexural stress is evaluated according to ASTM E328.

[0142] In some embodiments, the polymer material, a first region of the polymer material, and / or a second region of the polymer material have stress relaxation measurements of 5% deflection on a 3-point bending test as defined by ASTM D790. In some embodiments, stress relaxation can be measured by monitoring time-dependent stress generated by steady-state strain. The degree of stress relaxation may also depend on temperature, relative humidity, and other applicable conditions (e.g., the presence of water). In some embodiments, stress relaxation is tested at 37 ± 2°C at 100% relative humidity or at 37 ± 2°C in water. Stress relaxation properties can be assessed using an RSA-G2 instrument from TA Instruments, employing a 3-point bending, 5% strain method. Stress relaxation is typically measured at 37°C and 100% relative humidity and reported as the residual load after 24 hours, reported as a percentage (%) of the initial load or in MPa. In some embodiments, the residual stress of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than or equal to 5% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by residual stress ranging from 5% to 45% of the initial load. In some aspects, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual stress is 20% to 45% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual stress is greater than or equal to 20% of the initial load or greater than or equal to 35% of the initial load. In some embodiments, the stress relaxation measurement of the polymer material in water at 30°C for 24 hours is greater than 10% of the initial stress. In some embodiments, the stress relaxation measurement of the polymer material, the first region of the polymer material, and / or the second region of the polymer material in water at 30°C for 24 hours is greater than 15%, greater than 20%, greater than 25%, greater than 30%, greater than 35%, greater than 40%, greater than 45%, or greater than 50% of the initial stress. In some embodiments, the residual stress of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than or equal to 0.01 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a residual stress of 0.01 MPa to 15 MPa. In other aspects, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by a residual stress of 2 MPa to 15 MPa.

[0143] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual stress is 5% to 85% of the initial load, for example, 5% to 45%, 15% to 85%, or 20% to 45% of the initial load. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual stress is 0.01 MPa to 15 MPa, such as 2 MPa to 15 MPa. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized in that the residual stress is greater than or equal to 20% of the initial load. In some embodiments, the residual stress is evaluated according to ASTM E328.

[0144] In some embodiments, it is advantageous that the polymer material, the first region of the polymer material, and / or the second region of the polymer material have a high flexural modulus, thereby forming a relatively rigid material. In some embodiments, the residual flexural modulus of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 50 MPa or greater, 60 MPa or greater, 70 MPa or greater, 80 MPa or greater, 90 MPa or greater, 100 MPa or greater, 125 MPa or greater, or 150 MPa or greater. In some embodiments, the residual flexural modulus is measured after 24 hours in a humid environment at the operating temperature. In some embodiments, the operating temperature is 37°C. In some embodiments, the flexural modulus is evaluated according to ASTM D790.

[0145] In some other embodiments, it is advantageous that the polymer material, the first region of the polymer material, and / or the second region of the polymer material have relatively low residual flexural stress, thereby forming a material that is not excessively rigid. In some embodiments, the residual flexural stress of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 80 MPa or less, 70 MPa or less, 60 MPa or less, 55 MPa or less, 50 MPa or less, or 45 MPa or less. In some embodiments, the residual flexural stress is measured after 24 hours in a humid environment at the operating temperature. In some embodiments, the operating temperature is 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material is characterized by a residual stress of 0.01 MPa to 15 MPa, or a residual stress of 2 MPa to 15 MPa, after 24 hours of testing in a humid environment at 37°C. In some embodiments, the residual stress is evaluated according to ASTM E328.

[0146] In some embodiments, the polymer material, a first region of the polymer material, and / or a second region of the polymer material may have residual flexural stress after a certain period of use. As a non-limiting example, orthodontic appliances (e.g., braces) may be formed of polymer materials with high flexural stress, but the flexural stress may decrease significantly and rapidly (e.g., within minutes) after the appliance is applied to a patient's teeth. This reduction in flexural stress may follow an exponential curve decreasing towards an asymptote during the expected lifespan of the appliance (e.g., within weeks for orthodontic appliances such as braces). In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material have residual flexural stress of 90 MPa or less, 85 MPa or less, 80 MPa or less, 75 MPa or less, 70 MPa or less, 65 MPa or less, 60 MPa or less, 55 MPa or less, or 50 MPa or less after a certain period of use. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material have residual flexural stress of 80 MPa or less after a certain period of use. In some embodiments, the usage period is 1 minute, 5 minutes, 10 minutes, 30 minutes, 1 hour, 24 hours, 48 ​​hours, 1 week, 2 weeks, 1 month, 2 months, 6 months, 1 year, 2 years, or more than 2 years. As a non-limiting example, an orthodontic appliance made of the polymer material described herein and placed on a patient's teeth is removed after 10 minutes with a bending stress of 70 MPa, characterized in that a residual bending stress of 70 MPa remains after a certain usage period, wherein the time period is 10 minutes. In some embodiments, the residual stress is evaluated according to ASTM E328.

[0147] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by an elongation at break greater than 10%, greater than 20%, greater than 30%, an elongation at break of 5% to 250%, an elongation at break of 20% to 250%, or an elongation at break value between 40% and 250%. In some embodiments, the elongation at break is measured under dry conditions (e.g., a dry environment). In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by an elongation at break greater than 10%, greater than 20%, greater than 30%, 5% to 250%, 20% to 250%, or an elongation at break value between 40% and 250% after being tested for 24 hours in a humid environment at 37°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by an elongation at break greater than 10% in a dry environment and an elongation at break greater than 20%, an elongation at break greater than 30%, an elongation at break between 5% and 250%, or an elongation at break between 20% and 250%, or an elongation at break between 40% and 250%, after testing in a humid environment at 37°C for 24 hours. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are characterized by an elongation at break greater than or equal to 5%, greater than or equal to 10%, greater than or equal to 20%, greater than or equal to 30%, greater than or equal to 40%, or greater than or equal to 50%. In some embodiments, the elongation at break is evaluated according to ASTM D1708-2 5B.

[0148] In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 11%, greater than 12%, greater than 13%, greater than 14%, or greater than 15%. In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 4% to 10% or 5% to 15%. In some embodiments, the yield elongation is measured under dry conditions (e.g., a dry environment). In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material after being tested at 37°C in a humid environment for 24 hours is greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 11%, greater than 12%, greater than 13%, greater than 14%, or greater than 15%. In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material after being tested at 37°C in a humid environment for 24 hours is 4% to 10% or 5% to 15%. In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material in a dry environment and the yield elongation after testing in a humid environment at 37°C for 24 hours are greater than 4%, greater than 5%, greater than 6%, greater than 7%, greater than 8%, greater than 9%, greater than 10%, greater than 11%, greater than 12%, greater than 13%, greater than 14%, or greater than 15%. In some embodiments, the yield elongation of the polymer material, the first region of the polymer material, and / or the second region of the polymer material in a dry environment and the yield elongation after testing in a humid environment at 37°C for 24 hours are 4% to 10% or 5% to 15%. In some embodiments, the yield elongation is evaluated according to ISO 527-2 5B.

[0149] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material have at least one glass transition temperature (T0) ranging from 0°C to 150°C. gIn some embodiments, at least one glass transition temperature of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than 60°C. In some embodiments, at least one glass transition temperature of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is greater than 75°C. In some embodiments, the at least one glass transition temperature is 0°C to 200°C, 0°C to 140°C, 0°C to 20°C, 20°C to 40°C, 40°C to 60°C, 60°C to 80°C, 80°C to 100°C, 100°C to 120°C, 120°C to 140°C, 140°C to 160°C, 160°C to 180°C, 180°C to 200°C, 0°C to 35°C, 35°C to 65°C, 65°C to 100°C, 0°C to 50°C, or 50°C to 100°C. In some embodiments, at least one glass transition temperature of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is 0°C to 10°C, 10°C to 20°C, 20°C to 30°C, 30°C to 40°C, 40°C to 50°C, 50°C to 60°C, 60°C to 70°C, 70°C to 80°C, or 80°C to 90°C. In some embodiments, at least one glass transition temperature of the polymer material, the first region of the polymer material, and / or the second region of the polymer material is -100°C to 40°C, -80°C to 10°C, -70°C to 0°C, -70°C to -10°C, -70°C to -20°C, -70°C to -30°C, -70°C to -40°C, -70°C to -50°C, or -80°C to -40°C. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material has at least two glass transition temperatures. In some embodiments, the first T of the polymer material, the first region of the polymer material and / or the second region of the polymer material g Less than 40℃ and the second T g Greater than 60℃, first T g Less than 0℃ and the second T g Greater than 60℃, first T g Less than 0℃ and the second T g Greater than 75℃, or the first T g Less than -20℃ and the second T g Greater than 80°C. In some embodiments, when running at a temperature ramp of 2°C / min at 1 Hz, the glass transition temperature is assessed as the peak value of tan δ using dynamic mechanical analysis. In some embodiments, T is measured immediately after immersion in water at 37°C for 24 hours. g .

[0150] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are transparent, substantially transparent, largely transparent, or opaque. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are transparent. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are substantially transparent. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are largely transparent. In some embodiments, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of visible light passes through the polymer material, the first region of the polymer material, and / or the second region of the polymer material. Transparency can be measured using a UV-Vis spectrophotometer. In some embodiments, transparency is measured by measuring the transparent wavelengths that pass through. In some embodiments, greater than 70%, greater than 80%, greater than 90%, greater than 95%, or greater than 99% of transparent wavelengths can pass through the polymer material, the first region of the polymer material, and / or the second region of the polymer material. In some embodiments, the transparent wavelengths are in the visible light range (i.e., 400 nm to 800 nm), in the infrared range, or in the ultraviolet range. In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are colorless. In other embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are white, off-white, or mostly transparent, and have a white tint detectable by the human eye.

[0151] In some embodiments, after 24 hours in a humid environment at 37°C, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, or greater than 95% of visible light penetrates the polymer material, the first region of the polymer material, and / or the second region of the polymer material. In some embodiments, after 24 hours in a humid environment at 37°C, greater than 70% of visible light penetrates the polymer material, the first region of the polymer material, and / or the second region of the polymer material.

[0152] In some embodiments, the polymer material, the first region of the polymer material, and / or the second region of the polymer material are biocompatible, bioinert, or a combination thereof. In some embodiments, 3D printing utilizing photopolymerization (i.e., additive manufacturing) is used. Figure 6The polymer material is formed. In some embodiments, the polymer material may be used in coatings, molds, injection molding machines, or other manufacturing methods that use light during the curing process. In some embodiments, the polymer material, a first region of the polymer material, and / or a second region of the polymer material are well-suited for applications requiring, for example, solvent resistance, moisture resistance, water resistance, creep resistance, or heat deformation resistance. Methods for preparing polymer materials

[0153] In some aspects, this disclosure provides a method for forming a cured polymeric material, the method comprising: providing a resin as described herein; and curing the resin to form a cured polymeric material.

[0154] In some embodiments, this disclosure provides a method for producing the polymeric material described herein from a printable resin as further described herein. In some embodiments, the method includes the steps of: providing a resin as further disclosed herein; and initiating a polymerization reaction by curing the resin to form a cured polymeric material.

[0155] In some embodiments, the method further includes the step of manufacturing an apparatus using an additive manufacturing apparatus, wherein the additive manufacturing apparatus facilitates curing. In some embodiments, the curing of the resin produces a polymer material. In some embodiments, an additive manufacturing apparatus is used to cure the resin to produce a polymer material. In some embodiments, the method further includes the step of cleaning the polymer material. In some embodiments, cleaning the polymer material includes washing and / or rinsing the polymer material with a solvent, which can remove monomers and unwanted impurities from the polymer material. In other embodiments, cleaning the polymer material includes using a centrifuge. One or more cleaning methods can be used to clean the polymer materials disclosed herein.

[0156] In some embodiments, this disclosure provides a method for forming a cured polymer material, the method comprising: providing a resin comprising a first continuous phase and a second continuous phase, the first continuous phase comprising a component having a first reactivity (i.e., a first component), and the second continuous phase comprising a component having a second reactivity (i.e., a second component); and polymerizing the resin to form a cured polymer material. In some embodiments, the first reactivity is greater than the second reactivity (i.e., the first component is more reactive than the second component). In some embodiments, the resin is a 3D printable resin.

[0157] In some embodiments, the resin polymerization is unpatterned. For example, exposing the resin to a light source without using a mask to induce polymerization is unpatterned. In some embodiments, the resin polymerization is performed using maskless polymerization. In some embodiments, the material formed by unpatterned polymerization includes smaller features compared to the material formed by patterned polymerization (e.g., by applying a mask).

[0158] In some embodiments, polymerizing a resin includes treating multiple phases using different steps. In some embodiments, polymerizing a resin includes a first processing step and separate, different second processing steps. In some embodiments, the first processing step treats (e.g., polymerizes) a first component, and the second processing step treats (e.g., polymerizes) a second component. In some embodiments, the first processing step polymerizes the first component to form a first polymer. In some embodiments, the second processing step polymerizes the second component to form a second polymer. In some embodiments, the first processing step includes exposure to light (e.g., for photopolymerization). In some embodiments, the first processing step includes exposure to temperature (e.g., for thermal polymerization). In some embodiments, the second processing step includes exposure to light (e.g., for photopolymerization). In some embodiments, the second processing step includes exposure to temperature (e.g., for thermal polymerization).

[0159] Separate processing steps can be advantageous in controlling the polymerization rate and sequence of components present in the resin. As a non-limiting example, in some embodiments, the first and second continuous phases are polymerized separately by controlling the exposure wavelength (e.g., in photopolymerization) or exposure temperature (e.g., in thermal polymerization). In some embodiments, separate processing includes processing the same region. In some embodiments, separate processing includes processing the same region at different times. As a non-limiting example, the first processing step may be performed 1 millisecond before the second processing step. As a non-limiting example, the resin may be exposed to light of a first wavelength to induce polymerization of the first component, and subsequently exposed to light of a second wavelength to induce polymerization of the second component.

[0160] In some embodiments, the time difference between the first processing step and the second processing step is less than 1 millisecond, less than 10 milliseconds, less than 100 milliseconds, less than 200 milliseconds, less than 300 milliseconds, less than 400 milliseconds, less than 500 milliseconds, less than 1 second, or less than or equal to 5 seconds. In some embodiments, the time difference between the first processing step and the second processing step is greater than 5 seconds. In some embodiments, the time difference between the first processing step and the second processing step is less than 1 millisecond to 10 milliseconds, less than 1 millisecond to 100 milliseconds, less than 1 millisecond to 200 milliseconds, less than 1 millisecond to 300 milliseconds, less than 1 millisecond to 400 milliseconds, less than 1 millisecond to 500 milliseconds, or less than 1 millisecond to 1 second. In some embodiments, the first processing step is processed first, followed by the second processing step. In some embodiments, an alternative processing order is advantageous. In some embodiments, the second processing step is processed first, followed by the first processing step. This variation in the process step order is particularly useful during printing to obtain very different properties at different layer heights and / or different spatial locations.

[0161] In some embodiments, the hard phase and soft phase of the resin are treated separately. In some embodiments, the first continuous phase is a soft phase and the second continuous phase is a hard phase. In some embodiments, this disclosure provides methods for separately treating the hard and soft phases of the resin described herein. In some embodiments, it is preferred that the soft phase is treated (e.g., polymerized) prior to the hard phase. In some embodiments, it is preferred that the soft phase includes components having a higher reactivity than the components of the hard phase (e.g., such that the soft phase is treated or polymerized first). In some embodiments, the soft phase is characterized by having components having a higher reactivity than the components of the hard phase.

[0162] In some embodiments, the curing resin includes a photocurable resin. In some embodiments, the curing resin includes a thermocurable resin. In some embodiments, the curing resin includes both photocurable and thermocurable resins. As further described herein, in some embodiments, the soft phase is characterized by including components that are more reactive than the components of the hard phase.

[0163] In some embodiments, the resin phases are processed separately. In some embodiments, a first portion of the resin is cured, and a second portion of the resin is cured in a different step. As a non-limiting example, a resin comprising two phases may be selectively cured such that the first phase is cured before the second phase is cured. In some embodiments, the curing of the phases overlaps spatially but differs temporally (e.g., milliseconds). In some embodiments, curing the resin includes at least two light-curing steps. In some embodiments, curing the resin includes two light-curing steps. In some embodiments, curing the resin includes two or more light-curing steps. In some embodiments, curing the resin includes at least two thermal curing steps. In some embodiments, curing the resin includes two thermal curing steps. In some embodiments, curing the resin includes two or more thermal curing steps. In some embodiments, curing the resin includes at least one light-curing step and at least one thermal curing step. In some embodiments, curing the resin includes one light-curing step and one thermal curing step.

[0164] In some embodiments, the method further includes manufacturing an object using the cured polymer material. In some embodiments, manufacturing includes additive manufacturing, as further described herein. In some embodiments, manufacturing includes printing resin using a 3D printer. In some embodiments, manufacturing includes stereolithography, digital light processing, two-photon induced photopolymerization, inkjet printing, multi-jet printing, fused deposition modeling, or any combination thereof. In some embodiments, the object is manufactured after the polymerization step. In some embodiments, the object is manufactured after a first processing step and / or a second processing step. In some embodiments, 3D printing provides enhanced thickness control when forming an object as further described herein, and therefore has improved properties superior to thermoforming.

[0165] In some embodiments, during the curing step, multiple components as further described herein (e.g., a first component and a second component and / or a first monomer and a second monomer) are combined into a cured polymer material. In some embodiments, after the curing step, multiple monomers are combined into a cured polymer material. In some embodiments, curing the resin involves exposure to a light source. In some embodiments, curing the resin includes free radical curing, ion curing, or a combination thereof.

[0166] In some embodiments, the cured resin forms a polymeric material comprising an interpenetrating network comprising a polymer formed from the components described herein. In some embodiments, the method further includes synthesizing and purifying multiple components (e.g., polymerizable monomers).

[0167] In some embodiments, the methods disclosed herein are part of a photopolymerization process based on high-temperature photolithography, wherein the curable component (i.e., the resin) includes at least one photopolymerization initiator and is heated, which makes the high-temperature photopolymerization process more preferably an additive manufacturing process, and most preferably a 3D printing process. The methods according to this disclosure provide the possibility of rapidly and easily producing devices such as orthodontic appliances using the resins disclosed herein via additive manufacturing such as 3D printing.

[0168] Photopolymerization occurs when a suitable formulation (e.g., the resin disclosed herein) is exposed to radiation of sufficient power and wavelength capable of initiating polymerization (e.g., UV or visible light). The wavelength and / or power of the radiation used to initiate polymerization can 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 (wavelengths from about 400 nanometers (nm) to about 320 nm), UVB (wavelengths from about 320 nm to about 290 nm), or UVC (wavelengths from about 290 nm to about 100 nm). Any suitable source can be used, including laser sources. The source can be broadband or narrowband or a combination thereof. The light source can provide continuous or pulsed light during the process. The duration and intensity of the UV light exposure can be varied to determine the ideal reaction conditions.

[0169] In some embodiments, the methods disclosed herein use additive manufacturing to produce devices comprising or composed of cured polymeric materials. In some embodiments, the methods disclosed herein use additive manufacturing to produce devices substantially composed of cured polymeric materials. Additive manufacturing includes various techniques for manufacturing three-dimensional objects directly from digital models via additive processes. In some aspects, continuous layers of material are deposited and “cured in situ.” Various techniques for additive manufacturing are known in the art, including selective laser sintering (SLS), fused deposition modeling (FDM), and jetting or extrusion. In many embodiments, selective laser sintering involves selectively melting and fusing layers of powdered material using a laser beam 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 apparatuses described herein. In many embodiments, 3D printing involves jetting or extruding one or more materials (e.g., the resins disclosed herein) onto a build surface to form continuous layers of an object geometry. In some embodiments, the resins described herein can be used in inkjet or coating applications. Cured polymer materials can also be manufactured using a "bucket" process, in which light is used to selectively cure a curable resin (e.g., the resin disclosed herein) in a bucket or reservoir. Each layer of the curable resin can be selectively exposed to light in a single exposure or by scanning a beam of light across the layer. Specific techniques include stereolithography (SLA), digital light processing (DLP), and two-photon induced photopolymerization (TPIP).

[0170] In some embodiments, the methods disclosed herein use continuous direct manufacturing to produce apparatus comprising cured polymeric materials. In some embodiments, the methods disclosed herein use continuous direct manufacturing to produce apparatus consisting substantially of cured polymeric materials. Non-limiting example direct manufacturing processes can achieve continuous construction of object geometry by continuously moving a build platform (e.g., along a vertical or Z-direction) during an irradiation phase, such that the curing depth of the irradiated photopolymer (e.g., irradiated resin, curing during the formation of the cured polymeric material) is controlled by the movement speed. Thus, continuous polymerization of materials on the build surface (e.g., resin polymerizing into cured polymeric material) can be achieved. 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. In yet another example, the continuous direct manufacturing method utilizes a "heliolithography" method, in which a liquid resin (e.g., resin) is cured using focused radiation while the build platform is continuously rotated and raised. Thus, object geometry can be continuously constructed along a helical build path. Such a method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety. Continuous liquid interface production of 3D objects is also reported (J. Tumbleston et al., Science, 2015, 347(6228), pp. 1349-1352), the entire contents of which are incorporated herein by reference for the purpose of describing the process. Another example of a continuous direct manufacturing method may involve extruding a material consisting of a curable liquid material surrounding a solid strand. The material can be extruded along a continuous three-dimensional path to form an object. Such a method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0171] In some embodiments, the methods disclosed herein use high-temperature lithography to produce apparatus comprising a cured polymeric material. In some embodiments, the methods disclosed herein use high-temperature lithography to produce apparatus consisting substantially of a cured polymeric material. As used herein, “high-temperature lithography” can refer to any lithography-based photopolymerization process involving heating a photopolymerizable material (e.g., the curable resin disclosed herein). Heating can reduce the viscosity of the photopolymerizable material 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 can involve applying heat to the material to bring the temperature between 50°C and 120°C, such as between 90°C and 120°C, between 100°C and 120°C, between 105°C and 115°C, between 108°C and 110°C, etc. The material can be heated to temperatures greater than 120°C. It should be noted that other scopes may be used without departing from the scope and spirit of the inventive concept described herein.

[0172] In another embodiment, the method disclosed herein includes a series of direct manufacturing steps. These steps may include extruding a material consisting of a curable liquid material (e.g., resin) surrounding a solid strand. The liquid material may be extruded along a continuous three-dimensional path to form an object or device. Such a method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety. Other relevant 3D printing techniques that can be used for continuous direct manufacturing include volumetric printing techniques such as xolography and tomographing.

[0173] In some embodiments, the methods disclosed herein further include manufacturing objects using polymer materials. In some embodiments, manufacturing objects includes additive manufacturing. In some embodiments, manufacturing objects using polymer materials includes printing using a 3D printer. In some embodiments, manufacturing objects using polymer materials includes digital light projection. In some embodiments, manufacturing objects using polymer materials includes using thermolithography.

[0174] In some embodiments, the object is an orthodontic appliance. In some embodiments, the orthodontic appliance is an orthodontic appliance, an expander (e.g., a rapid palatal expander), or a spacer. In some embodiments, the orthodontic appliance is an orthodontic appliance. In some embodiments, the orthodontic appliance includes at least one mandibular advancement component. In some embodiments, the orthodontic appliance includes at least one accessory forming template. In some embodiments, the orthodontic appliance includes a plurality of tooth receiving cavities configured to reposition teeth from a first configuration to a second configuration. In some embodiments, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition teeth from an initial configuration to a target configuration. In some embodiments, the orthodontic appliance is one of a plurality of orthodontic appliances configured to reposition teeth from an initial configuration to a target configuration according to a treatment plan. In some embodiments, the orthodontic appliance is an orthodontic appliance. Devices including the polymer materials disclosed herein

[0175] As further described herein, the polymeric materials described herein can provide contrasting properties. Non-limiting examples of such contrasting properties include materials providing a high-modulus, low-elasticity phase to generate the force required, for example, to move teeth, and materials providing a low-modulus, high-elasticity phase to provide patient comfort, a good mouthfeel, and low fracture. Such contrasting properties are advantageous in the design of some devices, such as those described herein that include a first continuous phase and a second continuous phase. Non-limiting examples of devices benefiting from this contrasting property include a rapid palatal expander comprising a relatively rigid central portion that applies expansion forces, and relatively flexible lateral portions that facilitate insertion and removal of the device from the patient's teeth. Another non-limiting example of a device benefiting from this contrasting property includes an orthodontic appliance with a mandibular advancement feature, wherein the mandibular advancement feature is denser and / or more rigid than the portion of the appliance that moves the patient's teeth. Another non-limiting example of a device benefiting from this contrasting property includes a prefabricated appendage-forming template, in some embodiments of which requires a region or area to be more rigid while other regions or areas are less rigid.

[0176] In some embodiments, this disclosure provides devices comprising polymeric materials derived from resins, as further described herein. In some embodiments, this disclosure provides devices formed by processes and systems further described herein. In some embodiments, this disclosure is used to create devices intended to be placed in a person's oral cavity. Such devices may be, for example, orthodontic appliances that help move teeth to new positions. In some embodiments, the device may be a retainer that helps prevent teeth from moving to new positions. In some embodiments, the device may be used to expand the palate, move the position of the jaw, or prevent a person from snoring.

[0177] In some embodiments, this disclosure provides a method for producing the apparatus described herein, the apparatus comprising a polymer material. In some embodiments, the method includes a step of shaping a resin into a desired shape prior to a step of curing the resin, thereby producing a polymer material having said desired shape. In some embodiments, the method includes a step of shaping a resin into a desired shape during a step of curing the resin, thereby producing a polymer material having the desired shape. In some embodiments, the method includes a step of curing a resin to form a polymer material, and then shaping the polymer material into a desired shape. In some embodiments, the desired shape is an orthodontic appliance. In some embodiments, the desired shape is an apparatus and / or object as disclosed herein. In some embodiments, the shaping steps include extrusion, sheet production, film production, melt spinning, coating, injection molding, compression and transfer molding, blow molding, rotational blow molding, thermoforming, casting, or combinations thereof. In some embodiments, the polymer material described herein is thermoplastic or thermoset. In some embodiments, although the properties of the materials disclosed herein allow thermoset plastics to be molded, thermoplastic plastics tend to perform better based on molding techniques. In some embodiments, the materials disclosed herein are shape memory materials.

[0178] Exemplary embodiments of devices that can be cured using the materials disclosed herein include dental appliances for use in the human body. In some embodiments, such devices can be used as treatment systems for providing orthodontic treatment.

[0179] In some aspects, this disclosure provides a method for manufacturing orthodontic appliances comprising polymeric materials as described herein, wherein, as further described herein, the method includes providing a resin; and manufacturing the polymeric material by a direct or additive manufacturing process. The resin may be exposed to light during the direct or additive manufacturing process. The process may also include an additional curing step following the manufacture of the polymeric material.

[0180] In some respects, as further described herein, this disclosure provides orthodontic appliances comprising polymeric materials. Orthodontic appliances may be braces, expanders, or spacers. In some embodiments, an orthodontic appliance includes a plurality of tooth receiving cavities configured to reposition teeth from a first configuration to a second configuration. In some embodiments, the orthodontic appliance is one of a plurality of orthodontic appliances configured to optionally reposition teeth from an initial configuration to a target configuration according to a treatment plan. As used herein, "a plurality of teeth" includes two or more teeth.

[0181] In many embodiments, one or more posterior teeth include one or more of molars, premolars, or canines, and one or more anterior teeth include one or more of central incisors, lateral incisors, canines, first premolars, or second premolars.

[0182] The curable resins and cured polymer materials disclosed herein exhibit advantageous thermomechanical properties for use as orthodontic appliances, for example, for moving one or more teeth.

[0183] The embodiments disclosed herein can be used to connect one or more groups of teeth to each other. A group of one or more teeth may include a first group of one or more anterior teeth and a second group of one or more posterior teeth. The first group of teeth can be coupled to the second group of teeth using a polymer housing appliance as disclosed herein.

[0184] 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, or combinations thereof.

[0185] The embodiments disclosed herein are well-suited for combination with one or more known commercially available tooth movement components, such as attachments and polymer housing appliances. In several embodiments, the appliance and one or more attachments are configured to move one or more teeth along a tooth movement vector comprising six degrees of freedom, wherein three degrees of freedom are rotational and three degrees of freedom are translational.

[0186] This disclosure provides orthodontic systems and related methods for designing and providing improved or more efficient tooth movement systems for inducing desired tooth movement and / or repositioning teeth to a desired arrangement.

[0187] While references have been made to appliances including polymer-shelled devices, the embodiments disclosed herein are well-suited for use with a wide range of dental appliances, such as those without one or more polymers or shells. For example, the appliance may be manufactured using one or more of a variety of materials, including metals, glass, reinforcing fibers, carbon fibers, composites, reinforcing composites, aluminum, biomaterials, and combinations thereof. In some cases, the reinforcing composite may comprise a polymer matrix reinforced, for example, with ceramic or metal particles. For example, the appliance may be shaped in a variety of ways, such as thermoforming or direct manufacturing as described herein. Alternatively or in combination, the appliance may be manufactured by machining, such as by computer numerical control machining of appliances made from blocks of material. Preferably, the appliance is manufactured using a curable resin according to this disclosure.

[0188] Now turn to the accompanying drawings, in which the same reference numerals denote the same elements in each figure. Figure 1AAn exemplary tooth repositioning appliance or orthodontic appliance (100) is illustrated, which can be worn by a patient to achieve incremental repositioning of individual teeth (102) in the jaw, and the appliance comprises a cured polymer material disclosed herein. The appliance may include a housing (e.g., a continuous polymer housing or a segmented housing) having a tooth receiving cavity that receives and resiliently repositions the teeth. The appliance or portions thereof may be manufactured indirectly using a physical model of the teeth. For example, a sheet of suitable layers of polymer material may be used to form the appliance (e.g., a polymer appliance). In some embodiments, the physical appliance may be manufactured directly from a digital model of the appliance, for example using rapid prototyping techniques. The appliance may be fitted to all teeth present in the maxilla or mandible, or to fewer than all teeth. The appliance may be specifically designed to accommodate the patient's teeth (e.g., the morphology of the tooth receiving cavity matches the morphology of the patient's teeth) and may be manufactured based on a positive or negative model of the patient's teeth generated by impressions, scanning, etc. Alternatively, the appliance may be a general-purpose appliance configured to receive teeth, but not necessarily shaped to match the morphology of the patient's teeth. In some cases, only specific teeth received by the appliance will be repositioned by the appliance, while other teeth can provide a base or anchorage area to hold the appliance in place when the appliance applies force to one or more teeth that are the target of repositioning. In some cases, some, most, or even all teeth will be repositioned at a point during treatment. The moved teeth can also be used as a base or anchorage for holding the appliance in place while the patient wears it. Typically, no wire or other means will be provided to hold the appliance in place on the teeth. However, in some cases, it may be desirable or necessary to provide separate attachments or other anchorage elements (104) on the teeth (102), wherein the appliance (100) has a corresponding receiving portion or hole (106) that allows the appliance to apply selected forces on the teeth. Exemplary appliances, including those used in the Invisalign® system, are described in numerous patents and patent applications assigned to Alain Technologies, Inc., including, for example, those in U.S. Patent Nos. 6,450,807 and 5,975,893, and on the company’s website accessible on the World Wide Web (see, for example, the URL “invisalign.com”). Examples of tooth mounting attachments suitable for orthodontic appliances are also described in patents and patent applications assigned to Alain Technologies, Inc., including, for example, U.S. Patent Nos. 6,309,215 and 6,830,450.

[0189] Figure 1BA tooth repositioning system (110) comprising multiple appliances (112), (114), and (116) is illustrated. Any appliance described herein may be designed and / or provided as part of a set of multiple appliances for use in a tooth repositioning system. Each appliance may be configured such that the tooth receiving cavity has a geometry corresponding to an intermediate or final tooth arrangement intended for use with the appliance. By placing a series of incremental positional adjustment appliances on the patient's teeth, it is possible to progressively reposition the patient's teeth from an initial tooth arrangement to a target tooth arrangement. For example, the tooth repositioning system (110) may include a first appliance (112) corresponding to the initial tooth arrangement, one or more intermediate appliances (114) corresponding to one or more intermediate arrangements, and a final appliance (116) corresponding to the target arrangement. The target tooth arrangement may be the planned final tooth arrangement selected for the patient's teeth at the end of all planned orthodontic treatment. Alternatively, the target tooth arrangement can be one of several intermediate arrangements used for the patient's teeth during orthodontic treatment, which can include a variety of different treatment scenarios, including but not limited to: cases where surgery is recommended, cases where interproximal repositioning (IPR) is appropriate, cases where progress checks are scheduled, cases where anchor placement is optimal, cases where palatal expansion is satisfactory, and cases involving restorative dentistry (e.g., inlays, high-mounted inlays, crowns, bridges, implants, veneers, etc.). Therefore, it should be understood that the target tooth arrangement can be any planned arrangement for the patient's teeth following one or more incremental repositioning phases. Similarly, the initial tooth arrangement can be any initial arrangement for the patient's teeth prior to one or more incremental repositioning phases.

[0190] Figure 1CA method (150) for orthodontic treatment using multiple appliances according to an embodiment is illustrated. The method (150) can be practiced 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 dental arrangement to a second dental arrangement. In step (170), a second orthodontic appliance is applied to the patient's teeth to reposition the teeth from the second dental arrangement to a third dental arrangement. If necessary, the method (150) can be repeated using any suitable number and combination of sequential appliances to incrementally reposition the patient's teeth from the initial arrangement to the target arrangement. Appliances can be generated all at the same stage or in groups or batches (e.g., at the start of a treatment stage), or appliances can be manufactured one at a time, and the patient can wear each appliance until each appliance no longer leaves pressure on the teeth or until the maximum amount of compressed tooth movement for that given stage has been achieved. Multiple different appliances (e.g., a set) can be designed or even manufactured before the patient wears any of the appliances in the multiple appliances. After wearing an appliance for an appropriate period of time, the patient can replace the current appliance with the next appliance in the series until no appliances remain. Appliances are typically not attached to the teeth, and patients can place and change appliances at any time during treatment (e.g., patient-removable appliances). The final appliance or multiple appliances in the series may have one or more geometries selected for overcorrection of the tooth arrangement. For example, one or more appliances may have geometries that would (if fully achieved) move individual teeth beyond the tooth arrangement that has been selected as "final." This overcorrection may be desired to counteract potential repositioning after the repositioning method has been terminated (e.g., allowing individual teeth to move back toward their pre-corrected positions). Overcorrection can also be beneficial in accelerating the rate of correction (e.g., appliances with geometries positioned beyond desired intermediate or final positions can move individual teeth toward that position at a greater rate). In this case, appliance use can be terminated before the teeth reach the position defined by the appliance. Furthermore, overcorrection may be intentionally applied to compensate for any inaccuracies or limitations of the appliance.

[0191] The various embodiments of orthodontic appliances presented herein can be manufactured in a wide variety of ways. In some embodiments, the orthodontic appliances (or portions thereof) herein can be produced using direct manufacturing techniques, such as additive manufacturing (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 physical templates (e.g., molds, masks, etc.) to define the geometry of the object. Additive manufacturing technologies can be categorized as follows: (1) barrel photopolymerization (e.g., stereolithography), in which an object is constructed layer by layer from a barrel of liquid photopolymer resin; (2) material jetting, in which material is jetted onto a build platform using a continuous or on-demand dripping (DOD) method; (3) binder jetting, in which alternating layers of build material (e.g., powder-based materials) and binder material (e.g., liquid binder) are deposited via a printhead; (4) fused deposition modeling (FDM), in which material is ejected through a nozzle, heated, and deposited layer by layer; (5) powder bed melting, including but not limited to direct metal laser sintering (DMLS), electron beam melting (EBM), selective thermal sintering (SHS), selective laser melting (SLM), and selective laser sintering (SLS); (6) sheet lamination, including but not limited to laminated object manufacturing (LOM) and ultrasonic additive manufacturing (UAM); and (7) directional energy deposition, including but not limited to laser engineered net-shape forming, directional light manufacturing, direct metal deposition, and 3D laser cladding. For example, stereolithography can be used to directly manufacture one or more of the devices described herein. In some embodiments, stereolithography involves selectively polymerizing a photosensitive resin (e.g., a photopolymer) using light (e.g., ultraviolet light) according to a desired cross-sectional shape. By sequentially polymerizing multiple object cross-sections, an object geometry can be constructed in a layer-by-layer manner. As another example, the apparatus of this invention can be directly manufactured using selective laser sintering. In some embodiments, selective laser sintering involves selectively melting and fusing layers of powder material using a laser beam according to a desired cross-sectional shape to construct an object geometry. As yet another example, the apparatus of this invention can be directly manufactured by fused deposition modeling. In some embodiments, fused deposition modeling involves melting and selectively depositing filaments of a thermoplastic polymer in a layer-by-layer manner to form an object. In yet another example, material jetting can be used to directly manufacture the apparatus of this invention. In some embodiments, material jetting involves jetting or extruding one or more materials onto a build surface to form a continuous layer of an object geometry.

[0192] Alternatively or in combination, some embodiments of the appliances (or portions thereof) described herein may be manufactured using indirect manufacturing techniques, such as by thermoforming on a male or female mold. Indirect manufacturing of orthodontic appliances may involve producing a male or female mold according to the target arrangement of the patient's dentition (e.g., by rapid prototyping, milling, etc.) and thermoforming one or more sheets of material on a mold to generate the appliance housing.

[0193] In some embodiments, the direct manufacturing methods provided herein construct object geometry in a layer-by-layer manner, wherein continuous layers are formed in discrete construction steps. Alternatively or in combination, direct manufacturing methods that allow for the continuous construction of object geometry may be used, referred to herein as “continuous direct manufacturing.” Various types of continuous direct manufacturing methods can be used. As an example, in some embodiments, the apparatus of this document is manufactured using “continuous liquid-interphase printing,” wherein the object is continuously constructed from a reservoir of photopolymerizable resin by forming a gradient of partially cured resin between the construction surface of the object and a “dead zone” of polymerization inhibition. In some embodiments, a semi-permeable membrane is used to control the delivery of photopolymerization inhibitors (e.g., oxygen) into the dead zone to form the polymerization gradient. Continuous liquid-interphase printing can achieve manufacturing speeds approximately 25 to approximately 100 times faster than other direct manufacturing methods, and can be achieved approximately 1000 times faster by incorporating a cooling system. Continuous liquid phase printing is described in U.S. Patent Publications Nos. 2015 / 0097315, 2015 / 0097316 and 2015 / 0102532, the contents of which are incorporated herein by reference in their entirety.

[0194] As another example, a continuous direct manufacturing method can achieve continuous construction of an object geometry by continuously moving a build platform (e.g., along the vertical or Z-direction) during the irradiation phase, such that the hardening depth of the irradiated photopolymer is controlled by the movement speed. Thus, continuous polymerization of the material on the build surface can be achieved. 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.

[0195] In another example, a continuous direct manufacturing method may involve extruding a composite material consisting of a curable liquid material surrounding a solid strand. The composite material may be extruded along a continuous three-dimensional path to form an object. Such a method is described in U.S. Patent Publication No. 2014 / 0061974, the disclosure of which is incorporated herein by reference in its entirety.

[0196] In yet another example, the continuous direct manufacturing method utilizes a "spiral lithography" approach, in which a liquid photopolymer is cured using focused radiation while the build platform is continuously rotated and raised. Thus, the geometry of an object can be continuously built along a spiral build path. Such a method is described in U.S. Patent Publication No. 2014 / 0265034, the disclosure of which is incorporated herein by reference in its entirety.

[0197] Machine parameters may include curing parameters. For digital light processing (DLP) based curing systems, curing parameters may include power, curing time, and / or the grayscale of the complete image. For laser-based curing systems, curing parameters may include power, speed, beam size, beam shape, and / or beam power distribution. For printing systems, curing parameters may include material droplet size, viscosity, and / or curing power. These machine parameters may be periodically monitored and adjusted as part of process control on the manufacturing machine (e.g., some parameters at each 1-x layer and some parameters after each build). Process control can 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 using feedback loops. For DLP machines, depending on system stability, 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 nth build, once per hour, once per day, once per week, etc.). Furthermore, material properties and / or optical characteristics may be provided to the manufacturing machine, and the machine process control module may use these parameters to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variability in material properties. By implementing process control on manufacturing machines, the variability in tool accuracy and residual stress can be reduced.

[0198] Optionally, the direct manufacturing methods described herein allow for the manufacture of appliances comprising multiple materials, referred to herein as "multimaterial direct manufacturing." In some embodiments, the multimaterial direct manufacturing method involves simultaneously forming an object from multiple materials in a single manufacturing step. For example, a multi-tip extrusion apparatus can be used to selectively dispense multiple types of materials from different material supply sources 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 multimaterial direct manufacturing method may involve forming an object from multiple materials in multiple sequential manufacturing steps. For example, a first portion of the object may be formed from a first material according to any direct manufacturing method herein, then a second portion of the object may be formed from a second material according to the method herein, and so on, until the entire object is formed.

[0199] Direct manufacturing offers various advantages over other manufacturing methods. For example, compared to indirect manufacturing, direct manufacturing allows the production of orthodontic appliances without utilizing any molds or templates to shape the appliance, thereby reducing the number of manufacturing steps involved and improving the resolution and accuracy of the final appliance geometry. Additionally, direct manufacturing allows for precise control of the appliance's three-dimensional geometry, such as appliance thickness. Complex structures and / or auxiliary components can be integrally formed as a single piece with the appliance housing in a single manufacturing step, rather than being added to the housing in separate manufacturing steps. In some embodiments, direct manufacturing is used to produce appliance geometries that are difficult to produce using alternative manufacturing techniques, such as those with very small or fine features, complex geometries, undercuts, adjacent structures, housings with variable thicknesses, and / or internal structures (e.g., for increasing strength by reducing weight and material usage). For example, in some embodiments, the direct manufacturing method described herein allows the manufacture of orthodontic appliances with feature dimensions less than or equal to about 5 micrometers, or in the range of about 5 micrometers to about 50 micrometers, or in the range of about 20 micrometers to about 50 micrometers.

[0200] The direct manufacturing techniques described herein can be used to produce orthodontic appliances having substantially isotropic material properties, such as substantially the same or similar strength along all directions. In some embodiments, the direct manufacturing method described herein allows the production of orthodontic appliances with strength varying by no more than about 25%, about 20%, about 15%, about 10%, about 5%, about 1%, or about 0.5% along all directions. In some embodiments, the direct manufacturing techniques described herein can be used to produce appliances having substantially anisotropic material properties (e.g., substantially different strengths along all directions). In some embodiments, the direct manufacturing techniques described herein can produce orthodontic appliances with strength varying in a controlled manner along all directions by more than 10%, more than 15%, more than 20%, or more than 25%. Furthermore, compared to other manufacturing techniques, the direct manufacturing method described herein can be used to produce orthodontic appliances at a faster rate. In some embodiments, the direct manufacturing method described herein allows for the production of orthodontic appliances within time intervals 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 the rapid production of customized appliances as a “chair-side,” for example, during regular appointments or checkups.

[0201] In some embodiments, the direct manufacturing method described herein implements process control over various machine parameters of the direct manufacturing system or apparatus to ensure the manufacture of the resulting appliance with high precision. Such precision is beneficial in ensuring that the desired force system is accurately transmitted to the teeth to effectively induce tooth movement. Process control can be implemented to account for process variability caused by multiple sources, such as material properties, machine parameters, environmental variables, and / or post-processing parameters.

[0202] Material properties can vary depending on the properties of the raw materials, their purity, and / or process variables during mixing. In many embodiments, the resins or other materials used for direct manufacturing should be manufactured under strict process control to ensure minimal variation 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). Process control of the material manufacturing process can be achieved by screening the physical properties of the raw materials and / or controlling temperature, humidity, and / or other process parameters during the mixing process. By implementing process control over the material manufacturing process, the variability of process parameters for each batch of material can be reduced, resulting in more uniform material properties. Residual variability in material properties can be compensated for by process control of the machinery, as discussed further herein.

[0203] Machine parameters may include curing parameters. For digital light processing (DLP) based curing systems, curing parameters may include power, curing time, and / or the grayscale of the complete image. For laser-based curing systems, curing parameters may include power, speed, beam size, beam shape, and / or beam power distribution. For printing systems, curing parameters may include material droplet size, viscosity, and / or curing power. These machine parameters can be monitored and adjusted periodically as part of process control on the manufacturing machine (e.g., some parameters at each 1-x layer and some parameters after each build). Process control can 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 using feedback loops. For DLP machines, grayscale can be measured and calibrated at the end of each build. Furthermore, material properties and / or optical characteristics can be provided to the manufacturing machine, and the machine process control module can use these parameters to adjust machine parameters (e.g., power, time, grayscale, etc.) to compensate for variability in material properties. By implementing process control on the manufacturing machine, variability in instrument accuracy and residual stress can be reduced.

[0204] In many embodiments, environmental variables (e.g., temperature, humidity, sunlight, or exposure to other energy / curing sources) are kept within strict limits to reduce variability in appliance thickness and / or other properties. Optionally, machine parameters may be adjusted to compensate for environmental variables.

[0205] In many embodiments, post-treatment of the appliance includes cleaning, post-curing, and / or support removal processes. Relevant post-treatment parameters may include the purity of the cleaning agent, cleaning pressure and / or temperature, cleaning time, post-curing energy and / or time, and / or the consistency of the support removal process. These parameters can be measured and adjusted as part of a process control scheme. Furthermore, the physical properties of the appliance can be altered by modifying post-treatment parameters. Adjusting post-treatment machine parameters can provide another way to compensate for variability in material properties and / or machine properties.

[0206] The configuration of orthodontic appliances described herein can be determined based on a patient-specific treatment plan, such as a plan involving the sequential application of multiple appliances for incremental tooth repositioning. Computer-based treatment planning and / or appliance manufacturing methods can be used to facilitate appliance design and manufacturing. For example, one or more appliance components described herein can be digitally designed and manufactured using computer-controlled manufacturing equipment, such as computer numerical control (CNC) milling, computer-controlled rapid prototyping such as 3D printing, etc. The computer-based methods presented herein improve the accuracy, flexibility, and convenience of appliance manufacturing.

[0207] Figure 2 A method (200) for designing orthodontic appliances manufactured by direct manufacturing, according to an embodiment, is shown. The method (200) can be applied to any embodiment of the orthodontic appliances described herein. Some or all steps of the method (200) can be performed by any suitable data processing system or apparatus, such as one or more processors configured with suitable instructions.

[0208] 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, for example, by using wax bite, direct contact scanning, X-ray imaging, tomography, ultrasound imaging, and other techniques for obtaining information about the location and structure of teeth, jaws, gingiva, and other orthodontic-related tissues, from a mold or scan of the patient's teeth or oral tissues. Based on the obtained data, a set of digital data representing the initial (e.g., pre-processed) arrangement of the patient's teeth and other tissues can be derived. Optionally, the initial digital data set is processed to segment the tissue components. For example, a data structure digitally representing a single crown can be generated. Advantageously, a digital model of the entire tooth can be generated, including measured or inferred hidden surfaces and root structures, as well as surrounding bone and soft tissue.

[0209] The target arrangement of teeth (e.g., the expectation and anticipated end result of orthodontic treatment) can be received from the clinician in the form of a prescription, calculated from basic orthodontic principles, and / or inferred from a clinical prescription. By specifying the expected 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 tooth arrangement at the expected end of treatment.

[0210] Given the initial and target positions of 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 from its initial position to its desired target position in the fastest manner with the fewest round trips. The tooth path can optionally be segmented, and the segments can be computed such that the movement of each tooth within a segment remains within threshold limits for linear translation and rotational translation. In this way, the endpoints of each path segment can constitute a clinically feasible repositioning, and the set of segment endpoints can constitute a clinically feasible sequence of tooth positions such that moving from one point in the sequence to the next does not result in tooth collision.

[0211] In step (220), a force system is determined that produces the movement of one or more teeth along the movement path. The force system may include one or more forces and / or one or more torques. Different force systems can 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. In determining the force system to be applied, sources can be considered, including literature, force systems determined through experimental or virtual modeling, computer-based modeling, clinical experience, minimization of unwanted forces, etc.

[0212] Determining the force system can include constraints on permissible forces, such as permissible direction and magnitude, and the desired movement resulting from the applied force. For example, different patients may require different movement strategies when fabricating a palatal expander. For instance, the magnitude of the force required to dissect the palate can depend on the patient's age, as very young patients may not have fully formed sutures. Therefore, in adolescent patients and other patients without fully closed palatal sutures, smaller forces can be used to achieve palatal expansion. Slower palatal movement can also aid bone growth to fill the expanded sutures. For other patients, faster expansion may be desired, which can be achieved by applying greater forces. These requirements can be combined as needed to select the structure and materials of the appliance; for example, by selecting a palatal expander capable of applying greater forces to break palatal sutures and / or induce rapid expansion of the palate. Subsequent appliance stages can be designed to apply forces of varying magnitudes, such as initially applying larger forces to break the sutures, followed by smaller forces to maintain suture separation or gradually expand the palate and / or dental arch.

[0213] Determining the force system may also include modeling the patient's facial structures, such as the skeletal structure of the jaw and palate. For example, scan data of the palate and dental arch (such as X-ray data or 3D optical scan data) can be used to determine parameters of the skeletal and muscular systems of the patient's oral cavity in order to determine the force sufficient to provide the desired expansion of the palate and / or dental arch. In some embodiments, the thickness and / or density of sutures in the palate may be measured or entered by a treatment professional. In other embodiments, the treatment professional may select appropriate treatment based on the patient's physiological characteristics. For example, the nature of the palate may also be estimated based on factors such as the patient's age; for instance, younger adolescent patients typically require less force to expand the sutures than older patients because the sutures have not yet fully formed.

[0214] In step (230), the design of the dental arch or palatal expander for the orthodontic appliance configured to generate a force system is determined. The determination of the dental arch or palatal expander design, appliance geometry, material composition, and / or properties can be performed using a treatment or force simulation environment. The simulation environment may include, for example, a computer modeling system, a biomechanical system, or a device. 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 multiple vendors. To create the solid geometry model, computer-aided engineering (CAE) or computer-aided design (CAD) programs can be used, such as AutoCAD® software products available from Autodesk, Inc., San Rafael, California. To create and analyze the finite element model, program products from multiple vendors can be used, including the finite element analysis package from ANSYS, Inc., Fort Cannos, Pennsylvania, and the SIMULIA (Abaqus) software product from Dassault Systèmes, Waltham, Massachusetts.

[0215] Optionally, one or more dental arch or palatal expander designs can be selected for testing or force modeling. As described above, the desired tooth movement and the required or desired force system to induce the desired tooth movement can be identified. Using a simulation environment, candidate dental arch or palatal expander designs can be analyzed or modeled to determine the actual force system generated by using the candidate appliances. Optionally, one or more modifications can be made to the candidate appliances, and force modeling can be further analyzed as described, for example, to iteratively determine the appliance design that produces the desired force system.

[0216] In step (240), instructions are generated for manufacturing orthodontic appliances incorporating a dental arch or palatal expander design. The instructions may be configured to control a manufacturing system or apparatus to produce orthodontic appliances having a specified dental arch or palatal expander design. In some embodiments, the instructions are configured to manufacture the orthodontic appliance using direct manufacturing methods (e.g., stereolithography, selective laser sintering, fused deposition modeling, 3D printing, continuous direct manufacturing, multimaterial direct manufacturing, etc.) according to the various methods presented herein. In alternative embodiments, the instructions may be configured to indirectly manufacture the appliance, for example, by thermoforming.

[0217] Method (200) may include additional steps: 1) intraorally scanning the patient’s maxillary arch and palate to generate three-dimensional data of the palate and maxillary arch; 2) determining the three-dimensional shape profile of the appliance to provide the gap and tooth engagement structure as described herein.

[0218] While the steps described above illustrate a method (200) for designing orthodontic appliances according to some embodiments, those skilled in the art will recognize some variations based on the teachings described herein. Some steps may include sub-steps. Some steps may be repeated as needed. One or more steps of the method (200) may be performed using any suitable manufacturing system or apparatus, such as the embodiments described herein. Some steps may be optional, and the order of the steps may vary as needed.

[0219] Figure 3 A method (300) for digitally planning or designing or manufacturing orthodontic treatment and / or appliances according to an embodiment is shown. The method (300) can be applied to any treatment procedure described herein and can be performed by any suitable data processing system.

[0220] 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, gingival tissue, etc.). The surface topography data can be generated by directly scanning the oral cavity, a physical model (positive or negative mold) 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.).

[0221] In step (320), one or more treatment phases are generated based on the digital representation of the teeth. A treatment phase can be an incremental repositioning phase of an orthodontic treatment process designed to move one or more of the patient's teeth from an initial tooth arrangement to a target arrangement. For example, a treatment phase can be generated by determining an initial tooth arrangement indicated by the digital representation, by determining a target tooth arrangement, and by determining the movement paths of one or more teeth in the initial arrangement required to achieve the target tooth arrangement. The movement paths can be optimized based on minimizing the total distance of movement, preventing collisions between teeth, avoiding more difficult tooth movements, or any other suitable criteria.

[0222] In step (330), at least one orthodontic appliance is manufactured based on the generated treatment phase. For example, a set of appliances may be manufactured, each appliance shaped according to a tooth arrangement specified by one of the treatment phases, such that the appliances can be worn sequentially by the patient to incrementally reposition the teeth from the initial arrangement to the target arrangement. The set of appliances may include one or more of the orthodontic appliances described herein. The manufacture of the appliances may involve creating a digital model of the appliance for use as input to a computer-controlled manufacturing system. Direct manufacturing methods, indirect manufacturing methods, or a combination thereof may be used to form the appliances, as needed.

[0223] In some cases, the segmentation of various arrangements or treatment phases may not be necessary for the design and / or manufacture of the appliance. For example... Figure 3As shown by the dashed line, the design and / or manufacture of orthodontic appliances and possible specific orthodontic treatments may include using a representation of the patient’s teeth (e.g., receiving a digital representation of the patient’s teeth (310)) and then designing / or manufacturing orthodontic appliances based on the representation of the patient’s teeth in the arrangement represented by the received representation. On-Track Treatment

[0224] In some embodiments, this disclosure provides a method for repositioning a patient's teeth, the method comprising applying an orthodontic appliance disclosed herein to at least one of the patient's teeth and moving at least one of the patient's teeth toward an intermediate or final tooth arrangement.

[0225] In some embodiments, this disclosure provides a method for repositioning a patient's teeth, the method comprising: generating a treatment plan for the patient, the plan including a plurality of intermediate tooth arrangements for moving the teeth along a treatment path from an initial arrangement toward a final arrangement; producing a 3D-printed orthodontic appliance comprising materials as further described herein; and using the orthodontic appliance to steadily move at least one of the patient's teeth toward an intermediate arrangement or a final tooth arrangement.

[0226] refer to Figure 4 The method according to this disclosure is illustrated (400). Various aspects of the method are discussed in further detail below. The method includes receiving information about the patient's orthodontic status and / or treatment information (402), generating a case assessment (404), and generating a treatment plan for repositioning the patient's teeth (406). In short, the patient / treatment information will include obtaining data including the initial arrangement of the patient's teeth, which typically includes obtaining impressions or scans of the patient's teeth prior to the start of treatment, and may also include identifying one or more treatment goals selected by the physician and / or the patient. The case assessment (404) can be generated to evaluate the complexity or difficulty of moving a specific patient tooth, generally or specifically, corresponding to the identified treatment goal, and may also include the physician's experience and / or comfort during the application of the desired orthodontic treatment. However, in some cases, the assessment may include simply identifying specific treatment options of interest to the patient and / or physician (e.g., appointment scheduling, progress tracking, etc.). The information and / or corresponding treatment plan will include identifying the desired final or target arrangement of the patient's teeth, and successive or intermediate tooth arrangements of multiple plans for moving the teeth along the treatment path from the initial arrangement toward the selected final or target arrangement.

[0227] The method also includes generating customized treatment guidelines (408). Treatment protocols typically comprise multiple treatment phases, wherein a customized set of treatment guidelines corresponding to the phases of the treatment protocol is generated. The guidelines will include detailed information about the timing and / or content (e.g., specific tasks) to be completed during a given treatment phase and will be detailed enough to guide physicians throughout the treatment phase, including less experienced physicians or those with relatively little experience with a particular orthodontic treatment procedure. Because the guidelines are designed to specifically correspond to the treatment protocol and provide guidance on activities specifically identified in the treatment information and / or generated treatment protocol, the guidelines are referred to as customized. The customized treatment guidelines are then provided to the physician to help guide them on how to perform the given treatment phases. As described above, appliances can be generated based on a planned arrangement, and the appliances will be provided to the physician and ultimately administered to the patient (410). Appliances are typically provided and / or managed as a set or batch of appliances, such as 2, 3, 4, 5, 6, 7, 8, 9, or more appliances, but are not limited to any particular administration protocol. The instrument can be provided to the physician along with a given set of guidelines, or the instrument and guidelines can be provided separately.

[0228] After treatment begins according to the plan and after appliances are applied to the patient, treatment progress is tracked, for example by tooth matching, to assess the current and actual arrangement of the patient's teeth compared to the planned arrangement (412). If the patient's teeth are determined to be "steady" and progressing according to the treatment protocol, treatment proceeds as planned and moves to the next treatment phase (414). If the patient's teeth have substantially achieved the final arrangement initially planned, treatment moves to the final stage of treatment (414). If it is determined that the patient's teeth are being tracked according to the treatment protocol but have not yet achieved the final arrangement, the next set of appliances may be applied to the patient.

[0229] Table 1 below provides threshold differences between the planned and actual positions of teeth selected as indicators of steady progress in a patient's teeth. Progress is considered steady if a patient's teeth have progressed to or within the threshold. Progress is considered off track if a patient's teeth have progressed beyond the threshold.

[0230] A patient's dental treatment is determined to be progressing steadily by comparing the teeth in their current position to those in their expected or planned position, and by confirming that the teeth are within the variance of the parameters disclosed in Table 1. If a patient's dental treatment is determined to be progressing steadily, treatment can proceed according to the existing or original treatment plan. For example, one or more follow-up appliances, such as the next set of appliances, may be administered to a patient determined to be progressing steadily, according to the treatment plan. Treatment may progress to a final stage and / or reach a point in the treatment plan where repeated occlusal matching is performed to determine whether the patient's teeth are progressing as planned or whether the teeth are off track.

[0231] In some embodiments, as further disclosed herein, this disclosure provides a method of treating a patient using a 3D-printed orthodontic appliance. In some embodiments, the method of repositioning a patient's teeth (or, in some embodiments, a single tooth) includes: generating a treatment plan for the patient, the plan including a tooth arrangement for moving the teeth along a treatment path from an initial arrangement toward a final arrangement; producing a 3D-printed orthodontic appliance; and using the orthodontic appliance to steadily move at least one of the patient's teeth toward an intermediate or final tooth arrangement. In some embodiments, the 3D-printed orthodontic appliance is produced using resins further disclosed herein. Steady performance can be determined, for example, from Table 1 above.

[0232] In some embodiments, the method further includes tracking the progress of the patient's teeth along the treatment path after the application of an orthodontic appliance. In some embodiments, tracking includes comparing the current arrangement of the patient's teeth with the planned arrangement of the teeth. As a non-limiting example, after the initial application of the orthodontic appliance, the current arrangement of the patient's teeth (i.e., two weeks of treatment) can be compared with the planned arrangement of the teeth after a period of time (e.g., two weeks of treatment). In some embodiments, progress can also be tracked by comparing the current arrangement of the patient's teeth with the initial configuration of the patient's teeth. For example, this time period can be greater than 3 days, greater than 4 days, greater than 5 days, greater than 6 days, greater than 7 days, greater than 8 days, greater than 9 days, greater than 10 days, greater than 11 days, greater than 12 days, greater than 13 days, greater than 2 weeks, greater than 3 weeks, greater than 4 weeks, or greater than 2 months. In some embodiments, this time period can be at least 3 days to at most 4 weeks, at least 3 days to at most 3 weeks, at least 3 days to at most 2 weeks, at least 4 days to at most 4 weeks, at least 4 days to at most 3 weeks, or at least 4 days to at most 2 weeks. In some embodiments, this time period can be restarted after the application of a new orthodontic appliance.

[0233] In some embodiments, after a period of use with orthodontic appliances as further disclosed herein, greater than 50%, greater than 55%, greater than 60%, greater than 65%, greater than 70%, greater than 75%, greater than 80%, greater than 85%, greater than 90%, greater than 91%, greater than 92%, greater than 93%, greater than 94%, greater than 95%, greater than 96%, greater than 97%, greater than 98%, or greater than 99% of patients' teeth are consistent with the treatment plan. In some embodiments, this time period is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or greater than 4 weeks. Device properties

[0234] In some embodiments of the methods disclosed above, the 3D-printed orthodontic appliance has a retaining repositioning force (i.e., a repositioning force after the orthodontic appliance has been applied to or worn by the patient for a period of time), and the retaining repositioning force on at least one of the patient's teeth after that period of time is at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 55%, at least 60%, at least 65%, at least 70%, at least 75%, at least 80%, at least 85%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, or at least 99% of the initial repositioning force applied to at least one of the patient's teeth (i.e., in the case of initial application of the orthodontic appliance). In some embodiments, this time period is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 2 weeks, 3 weeks, 4 weeks, or more than 4 weeks.

[0235] In some embodiments, the orthodontic appliances disclosed herein are capable of providing steady movement of at least one of a patient's teeth. Steady movement has been further described herein, for example, in Table 1. In some embodiments, the orthodontic appliances disclosed herein are capable of achieving steady movement of at least one of a patient's teeth to an intermediate tooth arrangement. In some embodiments, the orthodontic appliances disclosed herein are capable of achieving steady movement of at least one of a patient's teeth to a final tooth arrangement.

[0236] In some embodiments, the orthodontic appliance includes a first bending stress before steadily moving at least one of the patient's teeth toward an intermediate or final tooth arrangement; and after achieving steady movement of at least one of the patient's teeth toward an intermediate or final tooth arrangement, the orthodontic appliance includes a second bending stress. In some embodiments, the second bending stress is 80 MPa to 0.5 MPa, 70 MPa to 0.5 MPa, 60 MPa to 1 MPa, 50 MPa to 1 MPa, 40 MPa to 1 MPa, 30 MPa to 2 MPa, 25 MPa to 2 MPa, 20 MPa to 2 MPa, 15 MPa to 2 MPa, or 15 MPa to 0.01 MPa. In some embodiments, the bending stress is evaluated according to ASTM E328. In some embodiments, the time period between the initial placement of the orthodontic appliance on the patient's teeth and the achievement of steady movement is 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, two weeks, or less than two weeks.

[0237] In some embodiments, the orthodontic appliance is characterized by retention after use of the orthodontic appliance before moving at least one of the patient's teeth toward intermediate or final tooth arrangement using the orthodontic appliance.

[0238] As provided herein, the disclosed methods can be used with orthodontic appliances further disclosed herein. These orthodontic appliances can be directly manufactured using resins, such as those disclosed herein. In some embodiments, direct manufacturing includes crosslinking the resin.

[0239] Appliances formed from the resins disclosed herein offer improved durability, strength, and flexibility, which in turn further improves the rate of steady progress in treatment regimens. In some embodiments, patients treated with greater than 60%, 70%, 80%, 90%, or 95% of the orthodontic appliances (e.g., braces) disclosed herein are classified as steady at a given treatment stage. In some embodiments, patients treated with greater than 60%, 70%, 80%, 90%, or 95% of the orthodontic appliances (e.g., braces) disclosed herein are classified as steady when their tooth movement is greater than 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, or 95%.

[0240] As further disclosed herein, the cured polymer materials contain advantageous features that derive at least in part from the presence of a first continuous phase and a second continuous phase. These cured polymer materials can exhibit enhanced damage resistance and resilience compared to similar polymer materials. The cured polymer materials can be used in devices both within and outside the orthodontic field. Example

[0241] The specific composition, synthesis, formulation, and description of any materials, apparatus, systems, and components thereof disclosed herein may readily vary depending on the intended application, as will be apparent to those skilled in the art given the content of this disclosure. Furthermore, it should be understood that the examples and aspects described herein are for illustrative purposes only, and those skilled in the art may be advised to make various modifications or alterations thereto, which are included within the spirit and scope of this application and within the scope of the appended claims. Many different combinations of the aspects described herein are possible, and such combinations are considered part of this disclosure. Additionally, all features discussed in conjunction with any aspect herein are readily applicable to other aspects herein. The use of different terms or reference numerals for similar features in different aspects does not necessarily imply differences other than those expressly set forth. Therefore, this disclosure is intended to be described solely by reference to the appended claims and is not intended to be limited to the aspects disclosed herein. Example 1 Comparative properties of the formulation

[0242] This example describes the formation of a material using a formulation that includes methacrylate as the hard phase and compares it with a formulation that includes acrylate as the hard phase. The example also compares the properties of the material formed for each method.

[0243] A methacrylate hard-phase resin (resin 1) was prepared by combining 15 wt% TGM1-RD1 (TGM1 and RD1), 35 wt% tetramethylxylene diisocyanate methacrylate (TMX)-methacrylate, and 50 wt% 2-isopropyl-5-methylcyclohexyl 2-(methacryloxy)benzoate (menthylsalicylate methacrylate or MSMA). TMX-methacrylate served as the soft continuous phase, MSMA as the hard (methacrylate) phase, and TGM1-RD1 as the crosslinking agent. 1 wt% TPO-L (photoinitiator) was added to the resulting resin.

[0244] An acrylate hard-phase resin (resin 2) was prepared by combining 15 wt% TGM1-RD1 (TGM1 and RD1), 35 wt% (TMX)-methacrylate, and 50 wt% 2-isopropyl-5-methylcyclohexyl2-(acryloxy)benzoate (MSA). TMX-methacrylate served as the soft continuous phase, MSA as the hard (acrylate) phase, and TGM1-RD1 as the crosslinking agent. 1 wt% TPO-L (photoinitiator) was added to the resulting resin.

[0245] Each resin was cured. Resin 1 was cured to form material 1, and resin 2 was cured to form material 2. The material properties of material 1 and material 2 were tested, as shown in Table 2 below: Table 2 Wherein, "c" corresponds to the water absorption rate, expressed as a percentage, of the material sample with dimensions of 50 mm × 21 mm × 0.78 mm over 24 hours at 37°C. The data shows that Material 2 (including the acrylate hard phase) exhibits superior overall material properties compared to Material 1 (including the methacrylate hard phase). This indicates that relatively soft materials (e.g., acrylates) can provide advantageous properties, including increased overall hardness due to the formation of hard and soft phases within the polymer network and their interconnection. Therefore, acrylate materials exhibit increased hardness alongside increased elongation properties. Example 2 Treatment using orthodontic appliances

[0246] This example describes the use of directly 3D-printed orthodontic appliances to move a patient's teeth according to a treatment plan. The example also describes the characteristics that the orthodontic appliance may have after use, compared to its characteristics before use.

[0247] For patients who require or wish to undergo therapeutic treatment to realign at least one tooth, their dental arrangement is evaluated. An orthodontic treatment plan is generated for the patient. The orthodontic treatment plan includes multiple intermediate dental arrangements for moving teeth along a treatment path from an initial arrangement (e.g., the arrangement initially evaluated) toward a final arrangement. The treatment plan includes orthodontic appliances manufactured using resins and methods further disclosed herein to provide orthodontic appliances having multiple polymer phases. In some embodiments, multiple orthodontic appliances are used, each of which may be manufactured using resins and methods further disclosed herein.

[0248] Orthodontic appliances are provided and iteratively applied to the patient's teeth to move the teeth toward the final arrangement through each intermediate tooth placement. The patient's tooth movement is tracked. A comparison is made between the patient's actual tooth placement and the planned intermediate placement. If, according to the treatment plan, it is determined that the patient's teeth are being tracked but have not yet reached the final placement, the next set of appliances may be applied to the patient. The threshold differences between the planned and actual positions of teeth selected as indicators of steady progress in the patient's teeth are provided above in Table 1. Progress is considered steady if the patient's teeth have progressed to or within the threshold. Advantageously, the use of the appliances disclosed herein increases the likelihood of steady tooth movement.

[0249] For example, treatment can be assessed and determined one week (7 days) after the initial application of the orthodontic appliance to determine whether the treatment is progressing steadily. Following this application period, additional parameters related to the durability of the orthodontic appliance can also be assessed. For example, relative repositioning force (compared to the initial force provided by the appliance), polymer chain integrity (e.g., the percentage of unbroken polymer chains), relative flexural modulus, and relative elongation at break can be determined.

Claims

1. A curable resin, comprising: A first continuous phase, comprising a first polymerizable component having a first polymerization rate; as well as The second continuous phase includes a second polymerizable component having a second polymerization rate. The first polymerization rate and the second polymerization rate are determined under conditions sufficient for 3D printing.

2. A curable resin, comprising: A first continuous phase comprising a first polymerizable component and a second polymerizable component, wherein the first polymerizable component is present at a higher concentration than the second polymerizable component; and The second continuous phase includes the first polymerizable component and the second polymerizable component, wherein the first polymerizable component is present at a lower concentration than the second polymerizable component.

3. A curable resin, comprising: A first continuous phase, comprising a first polymerizable component; The second continuous phase includes a second polymerizable component; as well as The third continuous phase includes a third polymerizable component.

4. A curable resin, comprising: The first continuous phase comprises a radical polymerizable component; as well as The second continuous phase comprises ionicly polymerizable components. The free radical polymerizable component has a higher polymerization rate than the ionic polymerizable component.

5. A method for producing a composite polymer composition, the method comprising: Provide the resin as described in any one of claims 1 to 4; as well as The polymerization reaction is initiated by curing the resin.

6. A method comprising: Curing a resin comprising a first continuous phase and a second continuous phase to produce a composite material comprising a soft region having a first hardness and a hard region having a second hardness, wherein the first hardness is less than the second hardness; Orthodontic appliances are manufactured using the composite material; and The orthodontic appliance is analyzed to identify the soft and hard regions of the composite material.

7. A method for generating a composite material, comprising: The curable resin comprising a first polymerizable component and a second polymerizable component is placed under conditions sufficient to initiate polymerization; The first polymerizable component is polymerized faster than the second polymerizable component to generate a composite material, the composite material comprising: A soft polymer region having a first hardness and comprising the first polymerizable component in a polymerized form, and A hard polymer region having a second hardness and comprising the second polymerizable component in a polymerized form.

8. A method for generating a composite material, comprising: The first polymerizable component of the resin is placed under a first set of conditions sufficient to initiate polymerization of the first polymerizable component; as well as The second polymerizable component of the resin is placed under a second set of conditions sufficient to initiate polymerization of the second polymerizable component. Wherein, the first set of conditions differs from the second set of conditions, and The first set of conditions includes one or more of a first light wavelength and a first temperature, and the second set of conditions includes one or more of a second light wavelength and a second temperature.

9. A composite material prepared by the method of claim 7 or 8.

10. An orthodontic appliance comprising the composite material as described in claim 9.

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