Photopolymerizable compositions comprising urea / acrylamide functional components, articles, and methods

Abstract

The present disclosure provides a photopolymerizable composition comprising a polymerization reaction product of at least one (meth) acrylate reactive diluent and a component comprising a urea functional component or an acrylamide functional component. The disclosure also provides orthodontic articles and methods of making orthodontic articles. The method includes obtaining a photopolymerizable composition, and selectively curing the photopolymerizable composition to form an orthodontic article. Further, there is provided a method comprising the steps of: receiving, by a manufacturing apparatus having one or more processors, a digital object comprising data specifying an orthodontic article; and generating, using the manufacturing apparatus, the orthodontic article based on the digital object by an additive manufacturing process. Also provided is a dental restoration tool or mold comprising a polymerization reaction product of the photopolymerizable composition.

Description

Technical Field

[0001] This disclosure relates broadly to polymerizable compositions, articles, and methods for preparing such articles, such as additive manufacturing methods. Background Technology

[0002] Recent developments in 3D printing (also known as additive manufacturing, layered manufacturing, or rapid prototyping) are advantageous in producing complex objects without the use of any molds or special processing. In particular, 3D photopolymerization-based technologies (such as stereolithography) can fabricate systems based on multifunctional materials with controllable mechanical, optical, physical, and chemical properties. Stereolithography's ability to achieve high resolution and flexibility makes it more suitable for 3D printing than other tank polymerization processes (and other tank polymerization technologies such as digital light processing and continuous liquid interface production).

[0003] Stereolithography utilizes the photocuring or photocrosslinking of liquid resin in the presence of a photoinitiator. Stereolithographic 3D printing can be performed via a top-down or bottom-up process, employing a layer-by-layer approach and a repetitive two-step technique. The first step involves curing a layer of curable liquid composition corresponding to the desired cross-sectional area of ​​the 3D-printed article with appropriate radiation, and the second step involves covering the first cured layer with a second new layer of curable composition, repeating these steps until a desired green preform of the 3D article with a defined shape and size is obtained. The method also includes post-processing the green preform to achieve complete curing and strengthen the article.

[0004] Besides photo-based 3D printing, nozzle-based technologies such as inkjet printing can also be used to print a variety of three-dimensional artifacts. Inkjet printing uses a layer-by-layer deposition technique, ejecting ink / curable photopolymerizable liquid through a printhead, followed by curing. Inkjet printers can optionally be used in conjunction with support materials or adhesives. In some cases, inkjet printers use inks or build materials that are solid at ambient temperature and become liquid at elevated jet temperatures. In other cases, the build material is liquid at ambient temperature. Summary of the Invention

[0005] Successful 3D printing ultimately depends on using compatible polymerizable / printable compositions that exhibit the desired stiffness, minimal elongation, and high glass transition temperature. Available polymer resins are too brittle for dental appliances such as orthodontic appliances, dental prosthetic tools, or molds. Dental appliances made from existing polymeric resins may be prone to breakage, potentially causing injury during use in dental procedures. Furthermore, the poor tensile properties of these appliances can lead to tissue puncture, material abrasion, or breakage, posing a risk of ingestion. Additionally, it is important that the uncured polymerizable composition has appropriate viscosity and a suitable curing rate to facilitate 3D printing. Therefore, there is a pressing need to develop customizable curable liquid resin compositions suitable for manufacturing elastic articles via 3D printing methods such as additive manufacturing. Preferably, the curable liquid resin composition should have low viscosity, an optimal curing rate, and produce a final cured article with excellent mechanical properties. Conversely, compositions used in inkjet printing methods require even lower viscosity to be ejected through the nozzle, a characteristic not possessed by most tubular polymeric resins.

[0006] In a first aspect, a photopolymerizable composition is provided. This photopolymerizable composition comprises a) 30% to 60% by weight of at least one (meth)acrylate reactive diluent; b) a photoinitiator; and c) 30% to 60% by weight of a polymerization product comprising a urea-functionalized component or an acrylamide-functionalized component. When measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s, the photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP).

[0007] In a second aspect, an orthodontic article is provided. The orthodontic article comprises a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises, based on the total weight of the photopolymerizable composition, 45% to 60% of at least one (meth)acrylate reactive diluent; a photoinitiator; and based on the total weight of the photopolymerizable composition, 30% to 50% of a first polymerization product. The first polymerization product comprises a first polyether polyamine; and an olefinically unsaturated isocyanate functional monomer. The photopolymerizable composition optionally comprises up to 10% by weight of a component having a glass transition temperature (T0) of 50°C or higher. gThe photopolymerizable composition comprises a crosslinking agent; and optionally, at most 12% by weight of a second polymerization product based on the total weight of the photopolymerizable composition. The second polymerization product comprises a second polyether polyamine; and an olefinically unsaturated isocyanate functional monomer. The photopolymerizable composition comprises: A) when the first polymerization product of the component is present in an amount of 40% to 50% by weight, the composition comprises no more than 5% by weight of the second polymerization product of the component; and B) when the first polymerization product of the component is present in an amount of 30% to less than 40% by weight, the composition comprises at least one of the following: i) 55% to 60% by weight of a (meth)acrylate reactive diluent; ii) 5% to 12% by weight of the second polymerization product of the component; or iii) 5% to 10% by weight of a crosslinking agent; or iv) 1% to 10% by weight of methacrylic acid. The polymerization product has a Tg of 50°C or higher. g .

[0008] In a third aspect, an orthodontic article is provided. The orthodontic article comprises a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises 30% to 50% by weight of a (meth)acrylate reactive diluent; a photoinitiator; and 40% to 60% by weight of the polymerization product. The polymerization product comprises a polymeric glycol; and acrylonitrile. Typically, the polymerization product has a To of 50°C or higher. g .

[0009] In a fourth aspect, a method for manufacturing an orthodontic article is provided. The method includes (a) providing a photopolymerizable composition (e.g., the photopolymerizable composition according to the first aspect), and (b) selectively curing the photopolymerizable composition to form a layer of the orthodontic article. The method further includes (c) repeating steps (a) and (b) to form a plurality of layers and manufacture an orthodontic article having a three-dimensional structure. Optionally, the method includes curing any remaining unpolymerized photopolymerizable composition after step (c). The method also optionally includes removing at least a portion of the remaining unpolymerized photopolymerizable composition after step (c).

[0010] In a fifth aspect, a method is provided. The method includes receiving a digital object by a manufacturing apparatus having one or more processors, the digital object including data specifying multiple layers of an orthodontic article; and generating the orthodontic article based on the digital object using the manufacturing apparatus via an additive manufacturing process, the orthodontic article comprising a reaction product of a photopolymerizable composition (e.g., a photopolymerizable composition according to the first aspect).

[0011] In a sixth aspect, a dental restorative tool or mold is provided. The dental restorative tool or mold comprises a polymerization product of a photopolymerizable composition according to the first aspect.

[0012] In a seventh aspect, a system is provided. The system includes a) a display showing a 3D model of an orthodontic article; and b) one or more processors that, in response to a 3D model selected by a user, cause a 3D printer to produce a physical object of the orthodontic article. The orthodontic article comprises reaction products of a photopolymerizable composition (e.g., a photopolymerizable composition according to the first aspect).

[0013] Studies have found that transparent tray orthodontic appliances (e.g., orthodontic trays) and stretch bars prepared according to at least some embodiments of this disclosure exhibit low brittleness, good water resistance, and good toughness.

[0014] The foregoing overview of this disclosure is not intended to describe every embodiment or every specific implementation of this disclosure. The following description illustrates exemplary embodiments in more detail. Throughout the application, guidance is provided by a list of examples that may be used in various combinations. In each case, the drawn list is intended only as a representative group and should not be construed as an exclusive list. Attached Figure Description

[0015] Figure 1 This is a flowchart of a method for constructing articles using the photopolymerizable compositions disclosed herein.

[0016] Figure 2 This is a generalized schematic diagram of a stereolithography equipment.

[0017] Figure 3 This is an isometric view of a printed transparent tray orthodontic appliance according to one embodiment of the present disclosure.

[0018] Figure 4 This is a flowchart of a process for manufacturing printed orthodontic appliances according to this disclosure.

[0019] Figure 5 This is a generalized schematic diagram of a device in which radiation is guided through a container.

[0020] Figure 6 This is a block diagram of a generalized system 600 for additive manufacturing of products.

[0021] Figure 7 It is a block diagram used for the generalized manufacturing process of an article.

[0022] Figure 8 This is a high-level flowchart of an exemplary article manufacturing process.

[0023] Figure 9 This is a high-level flowchart of an exemplary additive manufacturing process for an article.

[0024] Figure 10This is a schematic front view of an exemplary computing device 1000.

[0025] While the foregoing figures illustrate several embodiments of this disclosure, other embodiments are contemplated as indicated in the description. The figures are not necessarily drawn to scale. In all instances, this disclosure is presented by way of example and not limitation. It should be understood that those skilled in the art can devise many other modifications and embodiments that fall within the scope and spirit of the principles of this invention. Detailed Implementation

[0026] Those skilled in the art will understand that various changes and modifications exist beyond the specific description herein. It should be understood that this disclosure includes all such changes and modifications. This disclosure also includes all such steps, features, compositions, and compounds individually or collectively mentioned or indicated in this specification, and any and all combinations of any or more such steps or features.

[0027] definition

[0028] For convenience, certain terms and examples used in this specification are described herein before further description of this disclosure. These definitions should be read in accordance with the remainder of this disclosure and as understood by those skilled in the art. The terms used herein have meanings recognized and known to those skilled in the art; however, for convenience and completeness, specific terms and their meanings are set forth below.

[0029] As used herein, the term "at least one" is used to mean one or more, and therefore includes individual components as well as mixtures / combinations.

[0030] As used herein, the term "aliphatic group" refers to a saturated or unsaturated straight-chain, branched, or cyclic hydrocarbon group. The term "alicyclic" refers to a cyclic hydrocarbon group. This term is used to encompass, for example, alkyl, alkenyl, and alkynyl groups.

[0031] As used herein, the term "alkyl" refers to a straight-chain or branched, cyclic or acyclic saturated monovalent hydrocarbon having one to thirty-two carbon atoms, such as methyl, ethyl, 1-propyl, 2-propyl, pentyl, etc.

[0032] As used herein, the term "alkenyl" refers to a monovalent straight-chain or branched unsaturated aliphatic group having one or more carbon-carbon double bonds, such as a vinyl group. Unless otherwise specified, alkenyl groups typically contain two to twenty carbon atoms.

[0033] As used herein, the term "alkynyl" refers to a monovalent, straight-chain or branched, unsaturated aliphatic group having one or more carbon-carbon triple bonds. Unless otherwise specified, alkynyl groups typically contain two to twenty carbon atoms.

[0034] As used herein, the term "arylene" or "aryl" refers to a carbocyclic aromatic structure. This group has one to five linked, fused, or combined rings. The other rings can be aromatic, non-aromatic, or combinations thereof. In some embodiments, the arylene group has up to five rings, up to four rings, up to three rings, up to two rings, or one aromatic ring. For example, the arylene group can be phenylene.

[0035] As used herein, the term "cycloalkyl" refers to a fully saturated carbocyclic group. This group has one to five linked, fused, or combined rings. Other rings may be aromatic, non-aromatic, or combinations thereof. In some embodiments, the cycloalkyl group has up to five rings, up to four rings, up to three rings, up to two rings, or one saturated carbocyclic ring.

[0036] As used herein, the term "heterocyclic" refers to a carbocyclic group having at least one heteroatom. This group has one to five linked, fused, or combined rings. Other rings may be aromatic, non-aromatic, or combinations thereof. In some embodiments, the heterocyclic group has at most five rings, at most four rings, at most three rings, at most two rings, or one heterocycle. In some embodiments, the heterocyclic group has at least one, at least two, or at least three heteroatoms. Heteratoms include atoms other than carbon and hydrogen, preferably nitrogen, sulfur, oxygen, phosphorus, etc.

[0037] As used herein, in the context of a composition being substantially free of components, the term “substantially free” means that the composition contains less than 1 wt.%, 0.5 wt.% or less, 0.25 wt.% or less, 0.1 wt.% or less, 0.05 wt.% or less, 0.001 wt.% or less, or 0.0001 wt.% or less of a component based on the total weight of the composition.

[0038] As used herein, the term "glass transition temperature" (T) for polymers... g (T) refers to the temperature at which the glass transition occurs, that is, the temperature at which an uncrosslinked polymer changes from a glassy state to a rubbery state. g It can be determined by differential scanning calorimetry (DSC), such as by measuring at a heating rate of 10°C per minute in a nitrogen stream. The T of the monomer... g It also refers to the T of the homopolymer of this monomer. g Homopolymers must have a sufficiently high molecular weight so that T g Reaching the limit value, because it is generally understood that the T of homopolymers... g This increases to a limit with increasing molecular weight. Homopolymers are also understood to be essentially free of moisture, residual monomers, solvents, and other substances that may affect T. g Other contaminants. Suitable DSC methods and analytical modes are described in Matsumoto, A. et al. J. Polym.Sci.A., Polym. Chem. 1993, 31, 2531-2539 (Polymer Science: Series A, Polymer Chemistry, 1993, Vol. 31) (Pages 2531–2539) In an alternative method, the T of the crosslinked polymer... g This can be obtained by measuring the tanδ of the crosslinked polymer, which is determined by dynamic mechanical analysis, and T g It is defined as the peak value of tanδ.

[0039] As used herein, the term "Young's modulus" refers to the mechanical property of a polymer, which is a measure of the polymer's tensile strength or stiffness under the presence of an applied external force. Young's modulus is also known as the elastic modulus or tensile modulus, indicating the material's ability to be stretched or bent. A higher Young's modulus indicates that the polymer is harder, less brittle, and does not deform.

[0040] As used herein, the term "fracture tensile strain" refers to a measure of the maximum strain a material can withstand when stretched before it fractures. Tensile strain is a measure of the increase in length a material will reach before it fractures. Higher fracture tensile strain means that the polymer can withstand a significant amount of strain before it breaks.

[0041] As used herein, the terms "tensile stress at break" or "ultimate tensile strength" refer to the maximum stress a polymer can withstand when stretched before breaking. Tensile stress is a measure of polymer stiffness, and a higher tensile stress at break means that the polymer can withstand a significant amount of stress before fracture.

[0042] As used herein, the term "dynamic viscosity" refers to a measure of the flow resistance of a polymer when an external force is applied. As used herein, the term "dynamic viscosity" is the viscosity of a moving fluid (i.e., an uncured photopolymerizable composition). The dynamic viscosity of the uncured photopolymerizable compositions of this disclosure was measured using a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s.

[0043] As used herein, the term "hardenable" means that a material can be cured or solidified, for example, by heating to remove solvents, heating to induce polymerization, chemical crosslinking, radiation-induced polymerization or crosslinking, etc.

[0044] As used herein, the term “curing” refers to the process by which a composition is fully or partially hardened by any mechanism, such as heat, light, radiation, electron beams, microwaves, chemical reactions, or combinations thereof.

[0045] As used herein, the term "cured" means that a material or composition has been hardened or partially hardened by curing (e.g., polymerization or crosslinking).

[0046] As used in this article, "integrated" means manufactured simultaneously, or cannot be separated without damaging one or more (integrated) components.

[0047] As used herein, the term "(meth)acrylate" refers to acrylates, methacrylates, or combinations thereof. "(meth)acrylic acid" is an abbreviation for acrylic acid, methacrylic acid, or combinations thereof, and "(meth)acryloyl" is an abbreviation for acryloyl and methacryloyl groups. "Acryloyl" refers to derivatives of acrylic acid, such as acrylates, methacrylates, acrylamides, and methacrylamides. "(meth)acryloyl" refers to a monomer or oligomer having at least one acryloyl or methacryloyl group, and if containing two or more groups, they are linked by aliphatic segments.

[0048] As used herein, the term "photopolymerizable composition" refers to a curable composition capable of polymerization upon photoinitiation. Typically, prior to polymerization (e.g., curing), the photopolymerizable composition has viscosity characteristics consistent with the requirements and parameters of one or more 3D printing systems. In some embodiments, for example, curing involves irradiation with photochemical radiation of sufficient energy to initiate a polymerization or crosslinking reaction. It should be noted that the total amount of polymerizable components in the photopolymerizable composition will be up to 100% by weight. Therefore, additives that do not participate in polymerization (such as fillers) are not included in the weight percentage of the various components in the photopolymerizable composition.

[0049] As used herein, "polymerization product" refers to a product obtained by polymerization of one or more components in the presence of a suitable initiator and optionally a crosslinking agent. In some embodiments, the polymerization product includes the reaction product of a photopolymerizable composition as disclosed herein.

[0050] As used herein, "resin" contains all polymerizable components (monomers, oligomers, and / or polymers) present in a curable composition. A resin may contain only one polymerizable component compound or a mixture of different polymerizable compounds.

[0051] As used in this article, “occlusion” refers to the direction toward the outer tip of the patient’s teeth; “facial” refers to the direction toward the patient’s lips or cheeks; and “lingual” refers to the direction toward the patient’s tongue.

[0052] The terms "preferred" and "ideally" refer to embodiments of this disclosure that may provide certain benefits in certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are useless, nor is it intended to exclude other embodiments from the scope of this disclosure.

[0053] As used herein, terms such as “a,” “an,” and “the / described” are not intended to refer only to a singular entity, but rather to include general categories that may be illustrated by their specific examples. The terms “a,” “an,” and “the / described” are used interchangeably with the term “at least one / a kind.” The phrases “at least one of…” and “including at least one of…” followed by a list refer to any one of the items in the list and any combination of two or more items in the list.

[0054] As used herein, the term “or” is generally used in its usual sense, including “and / or”, unless otherwise expressly stated in the text.

[0055] As used herein, the term “and / or” means one or all of the listed elements or any combination of two or more of the listed elements.

[0056] As used herein, the terms “comprising” and “including” are used in an inclusive and open sense, meaning that additional elements may be included. The terms “comprising” and “including” are not intended to be construed as “consisting of only…”. Throughout this specification, unless the context requires otherwise, the word “comprising” and its variations (such as “including” and “containing”) will be understood to imply inclusion of the stated element or step or a group of elements or steps, but not to exclude any other element or step.

[0057] The term "including" is used to mean "including but not limited to", and "including" and "including but not limited to" are used interchangeably.

[0058] Similarly, in this document, it is assumed that all numbers are modified by the term “about,” and preferably by the term “precisely.” As used herein in conjunction with the quantity being measured, the term “about” refers to a variation in the quantity that would be expected by a technician performing the measurement and at a level of care commensurate with the purpose of the measurement and the precision of the measuring equipment used. Also in this document, numerical ranges expressed by endpoints include all numbers within that range as well as the endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0059] As used herein as modifiers of properties or attributes, unless otherwise specifically defined, the term "generally" means that the property or attribute will be easily recognized by a person skilled in the art but does not require absolute precision or perfect matching (e.g., within + / - 20% for quantifiable properties). Unless otherwise specifically defined, the term "substantially" means highly approximate (e.g., within + / - 10% for quantifiable properties), but also does not require absolute precision or perfect matching. Terms such as identical, equal, consistent, constant, and rigorous are understood to refer to tolerances or measurement errors applicable to a particular situation, without requiring absolute precision or perfect matching.

[0060] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. While any methods and materials similar to or equivalent to those described herein may be used in the practice or testing of this disclosure, preferred methods and materials are described hereafter. All publications mentioned herein are incorporated herein by reference.

[0061] The scope of this disclosure is not limited to the specific embodiments described herein, which are intended for illustrative purposes only. Functionally equivalent products, compositions, and methods are clearly within the scope of this disclosure, as described herein.

[0062] In a first aspect, this disclosure provides a photopolymerizable composition. The photopolymerizable composition comprises a) 30% to 60% by weight of at least one (meth)acrylate reactive diluent; b) a photoinitiator; and c) 30% to 60% by weight of a polymerization product comprising a urea-functionalized component or an acrylamide-functionalized component. When measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s, the photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP).

[0063] The photopolymerizable composition comprises a) at least one (meth)acrylate reactive diluent based on 45% to 60% by weight of the total weight of the photopolymerizable composition; b) a first polymerization product based on 30% to 50% by weight of components including: a first polyether polyamine; and an olefinically unsaturated isocyanate functional monomer; c) optionally up to 10% by weight of a product having a glass transition temperature (T0) of 50°C or higher. g The photopolymerizable composition comprises: d) a crosslinking agent; and d) optionally, at most 12% by weight of a second polymerization product based on the total weight of the photopolymerizable composition, including a second polyether polyamine; and an olefinically unsaturated isocyanate functional monomer. The photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product and no more than 5% by weight of a second polymerization product. The photopolymerizable composition comprises 30% to less than 40% by weight of a first polymerization product, and then comprises at least one of 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product, 5% to 10% by weight of a crosslinking agent, or 1% to 10% by weight of methacrylic acid.

[0064] The photopolymerizable composition comprises 30% to 50% by weight of a (meth)acrylate reactive diluent; and 40% to 60% by weight of a polymerization product comprising: a polymeric diol; and acrylonitrile.

[0065] (Meth)acrylate reactive diluent

[0066] The photopolymerizable compositions disclosed herein comprise at least one (meth)acrylate reactive diluent. As used herein, a "reactive diluent" is a component containing at least one free radical reactive group capable of co-reacting with another component (e.g., a polymerizable urea-functionalized component or an acrylamide-functionalized component). In one embodiment, the photopolymerizable composition comprises a component having a glass transition temperature (T0). g (Meth)acrylate reactive diluents, i.e., whose cured homopolymers have a Tc of 30°C or higher. g In some embodiments, a monofunctional (meth)acrylate monomer is present, and the cured homopolymer has a T value of 40°C or higher, 50°C or higher, 60°C or higher, 70°C or higher, 80°C or higher, 90°C or higher, 100°C or higher, 110°C or higher, 120°C or higher, 125°C or higher, 130°C or higher, 135°C or higher, 140°C or higher, 145°C or higher, 150°C or higher, 155°C or higher, 160°C or higher, 165°C or higher, 170°C or higher, 175°C or higher, 180°C or higher, 185°C or higher, 190°C or higher, or even 195°C or higher. g In the selected embodiment, a monofunctional (meth)acrylate monomer is present, and the cured homopolymer has a Tc of 150°C or higher, 170°C or higher, or 180°C or higher. g Ti of homopolymers of monofunctional (meth)acrylate monomers g Typically, the temperature does not exceed approximately 260°C. In some embodiments, the To of the homopolymer of the monofunctional (meth)acrylate monomer... g Temperatures not exceeding 255℃, 250℃, 245℃, 240℃, 235℃, 230℃, 225℃, 220℃, 215℃, 210℃, 205℃, or 200℃.

[0067] The photopolymerizable composition contains one or more monofunctional (meth)acrylate monomers, and its cured homopolymer has a T0 of 50°C or higher. g This helps reduce the viscosity of the composition and also increases the relaxation modulus of the polymerization product, as measured after immersion in deionized water. Typically, the To of the monomer homopolymer... g This information can be found in the literature, such as in Table A below. Table A includes reports on homopolymers of many monofunctional (meth)acrylate monomers. g and report T g The sources of the literature.

[0068]

[0069] In some embodiments, the (meth)acrylate reactive diluent is present in amounts of 30 or more, 31 or more, 35 or more, 40 or more, 45 or more, 50 or more, or 55 or more per 100 parts by weight of the total photopolymerizable composition; and in amounts of 60 or less, 59 or less, 58 or less, 57 or less, 56 or less, or 55 or less per 100 parts by weight of the total photopolymerizable composition.

[0070] In some implementations, T g The (meth)acrylate reactive diluent for at least 30°C is present in an amount of at least 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, or 55 wt% based on the total weight of the organic components of the composition.

[0071] In some embodiments of this disclosure, the cured material will come into contact with an aqueous environment. In these cases, it is advantageous to use materials with low affinity for water. The affinity of certain (meth)acrylate monomers for water can be estimated by calculating the partition coefficient (P) between water and an immiscible solvent such as octanol. This can be used as a quantitative indicator of hydrophilicity or lipophilicity. The octanol / water partition coefficient can be calculated using a software program (such as ACD ChemSketch, Advanced Chemistry Development, Inc., Toronto, Canada) using the logarithm (log P) module of the octanol / water partition coefficient.

[0072] In embodiments of the invention, the calculated log P value is greater than 1, 1.5, 2, 2.5, 3, 3.5, or 4. The calculated log P value is typically no greater than 12.5. In some embodiments, the calculated log P value is no greater than 12, 11.5, 11, 10.5, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, or 5.5. Furthermore, in some embodiments, the photopolymerizable composition is free of significant amounts of hydrophilic (meth)acrylate monomers because it is substantially free of any (meth)acrylate reactive diluents having a log P value of less than 3, less than 2, or less than 1.

[0073] In some embodiments, the photopolymerizable composition comprises less than 30% by weight of a hydrophilic (meth)acrylate monomer, oligomer, or polymer (e.g., hydrophilic polyurethane (meth)acrylate) having a log P value of less than 3, less than 2, or less than 1, such as 29% or less, 28%, 27%, 26%, 25%, 24%, 23%, 22%, 21%, 20%, 19%, 18%, 17%, 16%, 15%, 14%, 13%, 12%, or 11% or less of a hydrophilic component based on the total weight of the photopolymerizable composition; and 1% or more, 2%, 3%, 4%, 5%, 7%, 9%, or 10% or more (e.g., 1% to 29% by weight) of a hydrophilic component based on the total weight of the photopolymerizable composition. In some embodiments, the hydrophilic component and the (meth)acrylate reactive diluent monomer (whose cured homopolymer has a T value of 150°C or higher) are present. g Combinations of these components can impart advantageous properties to the article; for example, when 1% to 29% by weight of a hydrophilic component is present, 20% by weight or more of high-T components can be included. g Monomers, 22% wt%, 25% wt%, 27% wt%, 30% wt%, 32% wt%, 35% wt%, 37% wt%, 40% wt%, 42% wt%, 45% wt%, 47% wt% or 50% wt% or more of monofunctional (meth)acrylate monomers (whose cured homopolymers have a Tc of 150°C). g Each is based on the total weight of the photopolymerizable composition.

[0074] In some embodiments, for photopolymerizable compositions containing very little or no low molecular weight bifunctional components (e.g., dimethacrylate), a deficiency of a relatively high Tg is added. g Monomers (e.g., above 125°C, 140°C, 150°C or above 160°C) may negatively affect the ability of the photopolymerizable composition to produce polymerization products (e.g., leading to increased brittleness).

[0075] In some embodiments, the (meth)acrylate reactive diluent includes, for example, but not limited to, at least one of isobornyl methacrylate, isobornyl acrylate, methyl methacrylate, tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tricyclodecanediethanol diacrylate, or combinations thereof. In one embodiment, the (meth)acrylate reactive diluent is isobornyl methacrylate. Suitable (meth)acrylate reactive diluents for the component include, for example, but not limited to those commercially available from Sartomer, Warrington, Pennsylvania, under the series SR423A, SR218, SR421, and SR506.

[0076] Urea functional components

[0077] In one embodiment, the photopolymerizable composition comprises 30% to 60% by weight of a polymerization product including a urea-functional component. In some embodiments, the urea-functional component is a reaction product including an amine and an isocyanate. In another embodiment, the urea-functional component is obtained as a reaction product of a polyether polyamine and an olefinically unsaturated isocyanate functional monomer. In other embodiments, the urea-functional component is obtained as a first polymerization product including a first polyether polyamine and an olefinically unsaturated isocyanate functional monomer. In other embodiments, the urea-functional component is obtained as a second polymerization product including a second polyether polyamine and an olefinically unsaturated isocyanate functional monomer.

[0078] In some embodiments, the photopolymerizable composition comprises about 30% to 60% by weight of a polymerization product including a urea-functional component. In various embodiments, the photopolymerizable composition comprises about 30% to 50% by weight of a polymerization product including a urea-functional component. In other embodiments, the photopolymerizable composition comprises about 40% to 50% by weight of a polymerization product including a urea-functional component. In some embodiments, the photopolymerizable composition comprises about 30% to 40% by weight of a polymerization product including a urea-functional component.

[0079] In other embodiments, the photopolymerizable composition comprises about 30% to 50% by weight of a first polymerization product comprising a urea-functional component. In other embodiments, the photopolymerizable composition optionally comprises up to 12% by weight of a second polymerization product comprising a urea-functional component.

[0080] In some embodiments, the polymerization product comprises 30 or more, 31 or more, 35 or more, 40 or more, 45 or more, 50 or more, or 55 or more urea functional component per 100 parts by weight of the total photopolymerizable composition; and 60 or less, 59 or less, 58 or less, 57 or less, 56 or less, or 55 or less urea functional component per 100 parts by weight of the total photopolymerizable composition.

[0081] In some embodiments, the polymerization product comprising the urea functional component is the first polymerization product of the component and is present in an amount of 30 or more, 31 or more, 35 or more, 40 or more, 45 or more, or 49 or more per 100 parts by weight of the total photopolymerizable composition; and in an amount of 50 or less, 49 or less, 48 ​​or less, 47 or less, 46 or less, or 45 or less per 100 parts by weight of the total photopolymerizable composition.

[0082] In some embodiments, the polymerization product including the urea functional component is a second polymerization product of the component and is present in an amount of 5 or more, 6 or more, 7 or more, 8 or more, 9 or more parts by weight per 100 parts of the total photopolymerizable composition; and in an amount of 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less parts by weight per 100 parts of the total photopolymerizable composition.

[0083] In some embodiments, the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product of the component, and the composition comprises no more than 5% by weight of a second polymerization product of the component. In other embodiments, the photopolymerizable composition comprises 30% to less than 40% by weight of a first polymerization product of the component, and the composition may comprise 5% to 12% by weight of a second polymerization product of the component.

[0084] Polyether polyamine

[0085] Polyethertriamine

[0086] In some embodiments, the polyether polyamine is a polyether triamine. In some embodiments, the polyether triamine has the structure of Formula II.

[0087] In this context, the subscript "n" is typically at least 1, 2, 3, 4, 5, or greater. The subscript "n" is no greater than 10, 9, 8, 7, or 6. The subscript "x" is typically at least 1, 2, 3, 4, 5, or greater; and the subscript "x" is no greater than 84, 80, 75, 70, 65, or 60. The subscript "y" is typically at least 1, 2, 3, 4, 5, or greater; and the subscript "y" is no greater than 84, 80, 75, 70, 65, or 60. The subscript "z" is typically at least 1, 2, 3, 4, 5, or greater; and the subscript "z" is no greater than 84, 80, 75, 70, 65, or 60.

[0088] In some embodiments, the polyether triamine has a weight-average molecular weight (Mi) of 300 g / mol to 6,500 g / mol.w ), where M w The determination was performed by gel permeation chromatography. In some embodiments, the present polyether triamine has an M value of 300 g / mol or greater, 350 g / mol or greater, 400 g / mol or greater, 450 g / mol or greater, 500 g / mol or greater, 550 g / mol or greater, 600 g / mol or greater, 650 g / mol or greater, 700 g / mol or greater, 750 g / mol or greater, 800 g / mol or greater, 850 g / mol or greater, 900 g / mol or greater, 950 g / mol or greater, 1,000 g / mol or greater, 2,000 g / mol or greater, or 3,000 g / mol or greater. n ; and M of 6,500 g / mol or less, 6,000 g / mol or less, 5,500 g / mol or less, 5,000 g / mol or less, 4,500 g / mol or less, 4,000 g / mol or less, 3,900 g / mol or less, 3,800 g / mol or less, 3,700 g / mol or less, 3,600 g / mol or less, 3,500 g / mol or less, 3,400 g / mol or less, 3,300 g / mol or less, 3,200 g / mol or less, 3,100 g / mol or less, 3,000 g / mol or less, 2,900 g / mol or less, 2,800 g / mol or less, or 2,700 g / mol or less. n In other words, polyether triamine can have M values ​​of 300 g / mol to 6,500 g / mol, 800 g / mol to 6,500 g / mol, 1,000 g / mol to 5,500 g / mol, 1,500 g / mol to 5,000 g / mol, 1,800 g / mol to 5,000 g / mol, 450 g / mol to 4,500 g / mol, 800 g / mol to 4,500 g / mol, 1,000 g / mol to 4,500 g / mol, 1,500 g / mol to 4,500 g / mol, or 1,800 g / mol to 4,500 g / mol. w .

[0089] Suitable polyether triamines for use in the components include, for example, but not limited to those commercially available under the trade name "Jeffamine" from Huntsman, The Woodlands, Texas, such as Jeffamine T-3000 and Jeffamine T-5000. These polyether triamines are also available from BASF Corporation under the trade name Baxxodur, specifically Baxxodur EC 310 from BASF Corporation, Florham Park, New Jersey.

[0090] polyether diamine

[0091] In some embodiments, the polyether polyamine is a polyether diamine. In some embodiments, the polyether diamine has the structure of Formula I.

[0092] The subscript "x" is usually at least 4, 5, 6, 7, 8 or greater. The subscript "x" is not greater than 90, 89, 88, 87 or 86.

[0093] In some embodiments, the polyether diamine has a weight-average molecular weight (Mi) of 100 g / mol to 4,000 g / mol. w ), where M w The determination was performed by gel permeation chromatography. In some embodiments, the present polyether diamine has an M value of 100 g / mol or greater, 150 g / mol or greater, 200 g / mol or greater, 250 g / mol or greater, 300 g / mol or greater, 350 g / mol or greater, 400 g / mol or greater, 550 g / mol or greater, 600 g / mol or greater, 650 g / mol or greater, 700 g / mol or greater, 750 g / mol or greater, 800 g / mol or greater, 850 g / mol or greater, 900 g / mol or greater, 950 g / mol or greater, 1,000 g / mol or greater, 2,000 g / mol or greater, or 3,000 g / mol or greater. w; and M of 5,000 g / mol or less, 4,500 g / mol or less, 4,000 g / mol or less, 3,500 g / mol or less, 3,000 g / mol or less, 2,900 g / mol or less, 2,800 g / mol or less, 2,700 g / mol or less, 2,600 g / mol or less, 2,500 g / mol or less, 2,400 g / mol or less, 2,300 g / mol or less, 2,200 g / mol or less, 2,100 g / mol or less, 2,000 g / mol or less, 1,900 g / mol or less, 1,800 g / mol or less, or 1,700 g / mol or less. w In other words, polyether diamines can have M values ​​of 100 g / mol to 5,000 g / mol, 200 g / mol to 4,000 g / mol, 500 g / mol to 5,000 g / mol, 1,500 g / mol to 4,000 g / mol, 1,800 g / mol to 4,000 g / mol, 250 g / mol to 3,500 g / mol, 800 g / mol to 3,500 g / mol, 1,000 g / mol to 3,500 g / mol, 1,500 g / mol to 3,500 g / mol, or 1,800 g / mol to 3,500 g / mol. w .

[0094] Suitable polyether diamines for use in the composition include, for example, but not limited to those commercially available under the trade name "Jeffamine" from Huntsman Corporation of Woodlands, Texas, such as Jeffamine D-400, Jeffamine D-2000, and Jeffamine D-4000, and those commercially available under the trade name Baxxodur from BASF Corporation, as Baxxodur EC 301 from BASF Corporation of Wyandotte, Michigan.

[0095] Alkene unsaturated isocyanate functional monomers

[0096] In some embodiments, the olefinically unsaturated isocyanate functional monomer comprises monomers and oligomers of esters having olefin saturation and one or more acid groups. The acid functional group typically comprises an oxyacid group of carbon, sulfur, or phosphorus, such as a carboxylic acid functional group, a phosphate functional group, a phosphonic acid functional group, a phosphonophosphonate functional group, a sulfonic acid functional group, a sulfinic acid functional group, or a combination thereof. In some embodiments, the olefinically unsaturated group is a (meth)acryloyl group, such as in (meth)acrylates. Alternatively, for example, in the cases of acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, citraconic acid, maleic acid, and oleic acid; the acid has an unsaturated carbon bond (i.e., an alkenyl group). In some embodiments, the olefinically unsaturated component having the acid functional group has a low affinity for water, such as in the case of oleic acid.

[0097] In some embodiments, the olefinically unsaturated isocyanate functional monomer comprises an ester of olefinically unsaturated (meth)acrylic acid. In some embodiments, the olefinically unsaturated isocyanate functional monomer comprises an isocyanoalkyl ester of olefinically unsaturated (meth)acrylic acid. Examples of isocyanoalkyl esters include, but are not limited to, 2-isocyanoethyl methacrylate and 2-isocyanoethyl acrylate. In some embodiments, the olefinically unsaturated isocyanate functional monomer comprises an acryloyl isocyanate. Examples of acryloyl isocyanates include, but are not limited to, methacryloyl isocyanate.

[0098] Suitable olefinic unsaturated isocyanate functional monomers for use in the components include, for example, but not limited to those commercially available from Resonac Corporation, Tokyo, Japan, such as 2-isocyanoethyl methacrylate (IEM) and 2-isocyanoethyl acrylate (IEA).

[0099] Acrylamide functional components

[0100] In one embodiment, the photopolymerizable composition comprises 30% to 60% by weight of a polymerization product comprising an acrylamide functional component. In some embodiments, the acrylamide functional component is a reaction product comprising a diol and a lactone. In some embodiments, the acrylamide functional component is obtained as a reaction product of a polymeric diol and an acrylamide. In other embodiments, the acrylamide functional component is obtained as a polymerization product of a polymeric diol and an acrylamide comprising 2-vinyl-4,4-dimethylacyllactone. In other embodiments, the polymeric diol comprises polyester diol, polycarbonate diol, polyether diol, polyolefin diol, or combinations thereof. In other embodiments, the acrylamide functional component is obtained as a polymerization product of a polycarbonate diol and an acrylamide. In other embodiments, the acrylamide functional component is obtained as a polymerization product of a polyester diol and an acrylamide. In other embodiments, the acrylamide functional component is obtained as a polymerization product of a polyether diol and an acrylamide. In other embodiments, the acrylamide functional component is obtained as a polymerization product of polyolefin diol and acrylonitrile.

[0101] In some embodiments, the photopolymerizable composition comprises about 40% to 60% by weight of the polymerization product of a component including an acrylamide functional group. In other embodiments, the photopolymerizable composition comprises about 42% to 57% by weight of the polymerization product of a component including an acrylamide functional group.

[0102] In some embodiments, the acrylamide functional component is present in amounts of 40 or more, 41 or more, 45 or more, 50 or more, or 55 or more per 100 parts by weight of the total photopolymerizable composition, and in amounts of 60 or less, 59 or less, 58 or less, 57 or less, 56 or less, or 55 or less per 100 parts by weight of the total photopolymerizable composition.

[0103] polycarbonate diol

[0104] In some embodiments, polycarbonate diol has formula III:

[0105] Each of R1 and R2 in each (O-R1-OC(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and the average number of carbon atoms in all combinations of R1 and R2 groups is 4 to 10, and m is an integer from 2 to 23. In other words, while some repeating units of R1 and / or R2 may have less than 4 carbon atoms (e.g., 2 or 3), sufficient repeating units have a sufficiently high number of carbon atoms such that when the average number of carbon atoms of all repeating units of R1 and R2 in the polycarbonate diol of Formula III is taken, the average falls within the range of 4 to 10, or within any of the ranges of 4 to 6, 4 to 7, 4 to 8, 4 to 9, 5 to 7, 5 to 8, 5 to 9, 5 to 10, 6 to 8, 6 to 9, 6 to 10, 7 to 9, 7 to 10, or 8 to 10. Conversely, polycarbonate diols with a molecular weight of about 1,500 g / mol, prepared from CO2 and propylene oxide, can be obtained from Saudi Aramco, Dhahran, Saudi Arabia as “CONVERGE POLYOL 212-20”, and have an average carbon number of only 3 for all combinations of R1 and R2 groups. In selected embodiments, at least one of R1 or R2 is -CH2CH2CH(CH3)CH2CH2-, -(CH2)6-, or -(CH2)4-, and preferably a combination of -CH2CH2CH(CH3)CH2CH2- and -(CH2)6-.

[0106] In some embodiments, the polycarbonate diol has a number-average molecular weight (M0.05) greater than 1,000 g / mol. n ), or the weighted average of all polycarbonate diols present in the component has an M greater than 1,000 g / mol. n M n Determined by the OH value. In other words, when the component contains a single polycarbonate diol of formula III, the polycarbonate diol has an M value higher than 1,000 g / mol. n .

[0107] When a component contains two or more polycarbonate diols (e.g., one or more having formula III), the M of at least one polycarbonate diol n It can be 1,000 g / mol or less, provided that all M of two or more polycarbonate diols are present. n The weighted average value is higher than 1,000 g / mol. For example, a component containing two polycarbonate diols may include M with a molar ratio of 1:2 and approximately 500 g / mol. n The first polycarbonate diol with M having approximately 1,500 g / mol n The second polycarbonate diol makes the weighted average Mn The number average molecular weight is 1,167 g / mol. In some embodiments, the polycarbonate diol (or the weighted average of all polycarbonate diols present in the composition) has a number average molecular weight of 1,500 g / mol or higher. In some embodiments, the polycarbonate diol (or the weighted average of all polycarbonate diols present in the composition) has a number average molecular weight of 2,000 g / mol or higher.

[0108] In some embodiments, one or more polycarbonate diols are present, having an M of 450 g / mol or greater, 500 g / mol or greater, 550 g / mol or greater, 600 g / mol or greater, 650 g / mol or greater, 700 g / mol or greater, 750 g / mol or greater, 800 g / mol or greater, 850 g / mol or greater, 900 g / mol or greater, 950 g / mol or greater, or 1,000 g / mol or greater. n ; and M of 3,200 g / mol or less, 3,100 g / mol or less, 3,000 g / mol or less, 2,900 g / mol or less, 2,800 g / mol or less, 2,700 g / mol or less, 2,600 g / mol or less, 2,500 g / mol or less, 2,400 g / mol or less, 2,300 g / mol or less, 2,200 g / mol or less, 2,100 g / mol or less, 2,000 g / mol or less, 1,900 g / mol or less, 1,800 g / mol or less, or 1,700 g / mol or less. n In other words, polycarbonate diols can have M values ​​of 450 g / mol to 3,200 g / mol, 800 g / mol to 3,200 g / mol, 1,000 g / mol to 3,200 g / mol, 1,500 g / mol to 3,200 g / mol, 1,800 g / mol to 3,200 g / mol, 450 g / mol to 2,200 g / mol, 800 g / mol to 2,200 g / mol, 1,000 g / mol to 2,200 g / mol, 1,500 g / mol to 2,200 g / mol, or 1,800 g / mol to 2,200 g / mol. n On the other hand, adding M with a concentration greater than 3,200 g / mol... n Polycarbonate diols may negatively affect the stiffness of the polymer composition by increasing the elastomeric properties of the polymerization product.

[0109] In the selected embodiment, the photopolymerizable composition is substantially free of such diols, whose M nM less than that of one or more polycarbonate diols present in the component n In a mixture containing relatively low T g In embodiments of photopolymerizable compositions of monomers (e.g., below 90°C, 80°C, or below 60°C), an M having a concentration greater than 1,500 g / mol is added. n Polycarbonate diols may negatively affect the ability of the polymerization composition to produce polymerization products (e.g., leading to increased brittleness). Similarly, in compositions containing M with a concentration greater than 1,500 g / mol... n In embodiments of the photopolymerizable composition of polycarbonate diol, a deficiency of a certain amount of a relatively high T is added. g Monomers (e.g., above 90°C, 100°C, 125°C or above 150°C) may negatively affect the ability of the photopolymerizable composition to produce polymerization products (e.g., leading to increased brittleness).

[0110] Suitable polycarbonate diols for use in the composition include, for example, but not limited to those available under the trade name “KURARAYPOLYOL” from Kuraray Co. Ltd., Tokyo, JP, Japan, specifically, each of the KURARAY POLYOL C series: C-590, C-1090, C-2050, C-2090, and C-3090; and products from Covestro LLC, Pittsburgh, PA, under the trade name “DESMOPHEN”, specifically, each of the DESMOPHEN C series: C-2100, C-2200, and C XP-2613.

[0111] Polyester glycol

[0112] In some embodiments, the polyester diol has the following formula IV:

[0113] R5 and R6 are independently straight-chain, branched, or cyclic alkylene groups, which optionally contain heteroatoms such as oxygen. R5 and R6 independently contain 2 to 40 carbon atoms. The subscript "i" is typically at least 2, 3, 4, 5, 6, or 7. The subscript "i" is typically no greater than 50, 45, 40, 35, 30, 25, 20, or 15. In some embodiments, R5 and R6 are alkylene groups.

[0114] Representative polyester diols include, for example, neopentyl glycol adipate diol, butylene glycol adipate diol, 3-methyl-1,5-pentylene glycol adipate diol and 3-methyl-1,5-pentylene glycol sebacate diol, as well as diols based on dimer acids, which are derived from the dimerization reaction of, for example, two 18-carbon dicits (such as linoleic acid).

[0115] In some embodiments, such as the diol just described, the polyester diol contains a single R5 group (e.g., neopentyl or 3-methyl-1,5-pentyl) and a single R6 group (e.g., adipate ester).

[0116] In other embodiments, the polyester diol may be prepared from more than one diol and more than one acid. In this embodiment, the diol may contain two or more different R5 groups, such as in the case of ethylene glycol-hexanediol / adipate-azelate copolyester diol.

[0117] In other embodiments, the polyester diol has the following formula V:

[0118] R7 and R8 are independently straight-chain, branched, or cyclic alkylene groups, which optionally contain heteroatoms (such as oxygen), and independently contain 2 to 40 carbon atoms. The subscripts "j" and "k" are usually independently at least 4, 5, or 6. The subscripts "j" and "k" are usually independently no greater than 25, 20, or 15.

[0119] A representative polyester glycol of this type is polycaprolactone diol, such as that available from Perstorp. In this embodiment, R8 is a C-alkylene group and R7 is an alcohol residue, such as ethylene glycol, butanediol, diethylene glycol, etc.

[0120] In some embodiments, at least one of R5 or R6 of Formula IV and at least one of R7 and R8 of Formula V are straight-chain or branched or cyclic alkylene groups that independently contain at least 4, 5 or 6 carbon atoms.

[0121] In some embodiments, each of R5 or R6 of Formula IV is an alkylene group that independently comprises at least 4, 5, or 6 carbon atoms. In some embodiments, each of R7 and R8 of Formula V is an alkylene group that independently comprises at least 4, 5, or 6 carbon atoms.

[0122] Choose the values ​​of i, j, and k such that the molecular weight (M) of the diol is such that... nThe concentration of the diol is at least 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, or 1000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, or 1500 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, or 2000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The values ​​of i, j, and k can vary widely depending on the range of carbon atoms in the R5, R6, R7, and R8 groups.

[0123] Polyether diol

[0124] In some implementations, the polyether diol typically has the following formula VI:

[0125] Each R9 is independently selected from a straight-chain, branched, or cyclic alkylene group of 2 to 6 carbon atoms, more preferably 3 to 4 carbon atoms, and h is typically at least 7 but not higher than 80. The value of h is chosen such that the molecular weight (M...) of the diol... n The concentration of the diol is at least 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, or 1000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, or 1500 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, or 2000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight is not greater than 10,000 g / mol; 9,000 g / mol; 8,000 g / mol; 7,000 g / mol; 6,000 g / mol; 5,000 g / mol; 4,000 g / mol; or 3,000 g / mol. When the molecular weight is too low, the elongation may be insufficient (i.e., less than 15% to 20%).

[0126] Polyolefin diol

[0127] In some implementations, the polyolefin diol typically has the following formula VII:

[0128] Each R 10 The diol is independently selected from straight-chain, branched, or cyclic alkenyl groups having 2 to 12 carbon atoms, more preferably 3 to 4 carbon atoms, and l is typically at least 7, but not higher than 80. The value of l is chosen such that the molecular weight (M...) of the diol... n The concentration of the diol is at least 500 g / mol, 600 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, or 1000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1100 g / mol, 1200 g / mol, 1300 g / mol, 1400 g / mol, or 1500 g / mol. In some embodiments, the molecular weight (M) of the diol is... n The molecular weight (M) of the diol is at least 1600 g / mol, 1700 g / mol, 1800 g / mol, 1900 g / mol, or 2000 g / mol. In some embodiments, the molecular weight (M) of the diol is... n Not greater than 10,000 g / mol; 9,000 g / mol; 8,000 g / mol; 7,000 g / mol; 6,000 g / mol; 5,000 g / mol; 4,000 g / mol; or 3,000 g / mol.

[0129] Acetyl lactone

[0130] In some implementations, acrylonitrile typically has the following formula VIII:

[0131] Where R a and R b Each group is independently selected from H, nitrile groups, alkyl groups, alkenyl groups, cycloalkyl groups, heterocyclic groups, and aryl groups, or R. a and R 2 Together with the carbon atoms they are attached to, they form carbon rings; R c and R d Each is independently selected from alkyl groups, cycloalkyl groups, aryl groups, or R c and R d Together with the carbon atoms they are attached to, they form a carbocyclic ring; Q is selected from covalent bonds, aryl groups, and (-CH2-). o -CO-O-(CH2) o-、-CO-O-(CH2CH2O) o -、-CO-NR e -(CH2) o -CO-S-(CH2) o - linking groups, where o is 1 to 12, and R e It can be H, alkyl group, cycloalkyl group, heterocyclic group or aryl group; and n is 0 or 1.

[0132] Examples of acrylonitriles include, but are not limited to, vinylalkyl acrylonitriles, such as 2-vinyl-4,4-dimethyl acrylonitrile (also known as 2-vinyl-4,4-dimethyl-2-oxazoline-5-one), 2-(4-vinylphenyl)-4,4-dimethyl acrylonitrile, 2-isopropenyl-4,4-dimethyl acrylonitrile, 2-vinyl-4-ethyl-4-methyl-2-oxazoline-5-one, and 2-vinyl-4,4-dimethyl-1,3-oxazin-6-one.

[0133] Crosslinking agent

[0134] The photopolymerizable compositions disclosed herein optionally include a crosslinking agent. The crosslinking agent can be used to increase the cohesive strength and tensile strength of the polymerizable material. Suitable crosslinking additives used herein may have a plurality of alkoxylated (meth)acrylate groups. In some embodiments, the crosslinking agent is selected from those with a glass transition temperature (T0). g The crosslinker is a polyfunctional methacrylate compound that can form highly crosslinked substituents at 50°C or higher, and can provide a matrix with improved gas and water vapor barrier properties. Suitable examples include, but are not limited to, those under the following trade names: SR 348 (ethoxylated (2)bisphenol A di(meth)acrylate), SR540 (ethoxylated (4)bisphenol A di(meth)acrylate), SR444 (pentaerythritol triacrylate), SR351 (trimethacryloylpropane triacrylate), SR368 (tris(2-hydroxyethyl)isocyanurate triacrylate), SR833s (tricyclodecanediethanol diacrylate), and SR239 (1,6-hexanediol di(meth)acrylate), which are available from Sartomer USA, LLC, Exton, Pennsylvania.

[0135] In some embodiments, the crosslinking agent includes a photocrosslinking agent (e.g., a UV photocrosslinking agent). These photocrosslinking agents can be copolymerized with various monomers used to form the elastomeric material (e.g., copolymerizable benzophenone), or can be added after polymerization. Suitable photocrosslinking agents added after polymerization include, for example, multifunctional benzophenone, triazines (such as XL-330, i.e., 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-triazine from 3M Company, Saint Paul, MN), acetophenone, etc.

[0136] In some embodiments, a thermal crosslinking agent may be used, optionally in combination with suitable accelerators and retarders. Suitable thermal crosslinking agents used herein include, but are not limited to, isocyanates (more specifically, trimisocyanates and / or sterically hindered isocyanates without blocking agents), or epoxide compounds, such as epoxide-amine crosslinking agent systems. Advantageous crosslinking agent systems and methods are described, for example, in specifications such as DE202009013255 U1, EP 2 305 389 A, EP 2 414 143 A, EP 2 192148 A, EP 2 186 869, EP 0 752 435 A, EP 1 802 722 A, EP 1 791 921 A, EP 1 791 922 A, EP 1 978 069 A and DE 10 2008 059 050 A. Suitable accelerator and retarder systems used herein are described, for example, in specifications such as US-A1-2011 / 0281964. Suitable thermal crosslinking agents used herein include epoxycyclohexyl derivatives, particularly epoxycyclohexyl carboxylic acid ester derivatives, especially (3,4-epoxycyclohexane)methyl 3,4-epoxycyclohexyl carboxylic acid ester, which is commercially available under the trade name UVACURE 1500 from Cytec Industries Inc.

[0137] In some embodiments, the crosslinking agent used herein is activated / can be activated by photochemical radiation (more preferably by electron beam irradiation).

[0138] In some embodiments, the crosslinking agent comprises the polymerization product of a polyamine and an acrylonitrile. The crosslinking agent can be obtained as the polymerization product of a polyether polyamine and an acrylonitrile. According to embodiments herein, the polyether polyamine may be selected from polyether diamine or polyether triamine. The acrylonitrile includes, but is not limited to, 2-vinyl-4,4-dimethyl acrylonitrile, 2-(4-vinylphenyl)-4,4-dimethyl acrylonitrile, 2-isopropenyl-4,4-dimethyl acrylonitrile, 2-vinyl-4-ethyl-4-methyl-2-oxazoline-5-one, and 2-vinyl-4,4-dimethyl-1,3-oxazin-6-one. In some embodiments, the crosslinking agent can be obtained as the polymerization product of a polyether diamine and 2-vinyl-4,4-dimethyl acrylonitrile.

[0139] If a crosslinking agent is present, it may be used in an amount, for example, up to 10% by weight, based on the total weight of the photopolymerizable composition. In some embodiments, the crosslinking agent may be used in an amount of up to 10%, up to 5%, up to 3%, or up to 1% by weight, based on the weight of the photopolymerizable composition. In some embodiments, the crosslinking agent may be used in an amount of 5% to 10% by weight, based on the weight of the photopolymerizable composition.

[0140] catalyst

[0141] The photopolymerizable compositions disclosed herein optionally include a catalyst. Typically, the catalyst content is from 0.001% to 5% by weight based on the total weight of the polymerizable components.

[0142] Examples of suitable catalysts include, but are not limited to: 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), dioctyl dilaurate (DOTDL), stannous octanoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin thiolate, dibutyltin thiocarboxylic acid, dibutyltin dimaleate, dioctyltin thiolate, dioctyltin thiocarboxylic acid, lead 2-ethylhexanoate, tetraalkyl titanate (such as tetrabutyl titanate (TBT)), triethylamine, N,N-dimethyl... β-Cyclohexylamine, N-methylmorpholine, N-ethylmorpholine, N,N-dimethyl-p-toluidine, β-(dimethylamino)propionitrile, N-methylpyrrolidone, N,N-dicyclohexylmethylamine, dimethylaminoethanol, dimethylamino-ethoxyethanol, triethylenediamine, N,N,N'-trimethylaminoethylethanolamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethyl-1,3-diamine, N,N,N',N'-tetramethyl-1,6-hexyl Diol-diamine, bis(N,N-dimethylaminoethyl) ether, N'-cyclohexyl-N,N-dimethylformamidinium, N,N'-dimethylpiperazine, trimethylpiperazine, bis(aminopropyl)piperazine, N-(N,N'-dimethylaminoethyl)morpholine, bis(morpholine ethyl) ether, 1,2-dimethylimidazolium, N-methylimidazolium, 1,4-diamidinium, diazabicyclo-[2.2.2]-octane (DABCO), 1,4-diazabicyclo-[3.3.0]-oct-4-ene (DBN), 1,8-diazabicyclo-[4.3.0]-non-5-ene (DBN) and its phenolic salts, salts (such as octanoate), N,N,N',N"-pentamethyldiethylenetriamine, N,N,N',N"-pentamethyldipropylenetriamine, tetramethylguanidine, N-cyclohexyl-N',N',N",N"-tetramethylguanidine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, 1,3,5-tris(N,N-dimethyl-propyl)hexahydro-1,3,5-triazine.

[0143] In one embodiment, the catalyst comprises zinc, amine, tin, zirconium, or bismuth. The catalyst may contain tin, such as dibutyltin diacrylate. Preferably, the catalyst is tin-free, as it may not be desirable to add a tin catalyst to orthodontic products that will come into contact with the patient's mouth.

[0144] The catalyst may comprise an organometallic zinc complex that does not contain 2-ethylhexyl carboxylate and 2-ethylhexanoic acid, such as a zinc catalyst commercially available under the trade name K-KAT XK-672 from King Industries, Inc., Norwalk, CT, Connecticut, and / or other zinc catalysts available from King Industries, such as K-KAT XK-661 and K-KAT XK-635. Another suitable catalyst is bismuth neodecanoate, such as Sigma-Aldrich, St. Louis, MO, Missouri, and bismuth catalysts commercially available under the trade names K-KAT XK-651 and K-KAT 348 from King Industries. Available aluminum-based catalysts include K-KAT 5218 from King Industries. Additionally, zirconium-based catalysts include K-KAT 4205 and K-KAT 6212, available from King Industries.

[0145] In some embodiments, the catalyst is present in amounts of 0.001 wt% or more, 0.002 wt% or more, 0.003 wt% or more, 0.005 wt% or more, 0.01 wt% or more, 0.1 wt% or more, 0.2 wt% or more, 0.5 wt% or more, 1 wt% or more, 2.0 wt% or more, 3.0 wt% or more, or 4.0 wt% or more; and in amounts of 5 wt% or less, 4.8 wt% or less. The catalyst may be present in amounts of 4.6 wt% or less, 4.4 wt% or less, 4.2 wt% or less, 4.0 wt% or less, 3.8 wt% or less, 3.6 wt% or less, 3.4 wt% or less, 3.2 wt% or less, 3.0 wt% or less, 2.8 wt% or less, 2.6 wt% or less, 2.4 wt% or less, 2.2 wt% or less, 2.0 wt% or less, 1.8 wt% or less, or 1.6 wt% or less. In other words, the catalyst may be present in amounts of about 0.001 wt% to 5 wt%, 0.002 wt% to 1 wt%, or 0.003 wt% to 0.5 wt% based on the total weight of the photopolymerizable composition.

[0146] Photoinitiator

[0147] The photopolymerizable compositions disclosed herein typically contain at least one photoinitiator.

[0148] Suitable exemplary photoinitiators are those available under the trade names IRGACURE and DAROCUR from BASF, Ludwigshafen, Germany, and include: 1-hydroxycyclohexylphenyl ketone (IRGACURE 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (IRGACURE 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (IRGACURE 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one (IRGACURE 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butanone (IRGACURE 369), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (IRGACURE 2959). 907), oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] (ESACURE ONE) (Lamberti SpA, Gallarate, Italy), 2-hydroxy-2-methyl-1-phenylpropane-1-one (DAROCUR1173), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (IRGACURE TPO) and 2,4,6-trimethylbenzoyl phenylphosphinate (IRGACURE TPO-L).

[0149] Other exemplary photoinitiators are those available under the trade name OMNIRAD from IGM Resins, Waalwijk, The Netherlands, and include: 1-hydroxycyclohexylphenyl ketone (OMNIRAD 184), 2,2-dimethoxy-1,2-diphenylethane-1-one (OMNIRAD 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (OMNIRAD 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propane-1-one (OMNIRAD 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (OMNIRAD 369), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholino-4-yl-phenyl)-butane-1-one (OMNIRAD 184 ... 379), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one (OMNIRAD 907), oligomeric [2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]acetone] (ESACURE ONE) (Nymbaldi, Galaratta, Italy), 2-hydroxy-2-methyl-1-phenylpropane-1-one (DAROCUR 1173), 2,4,6-trimethylbenzoyl diphenylphosphine oxide (OMNIRAD TPO) and 2,4,6-trimethylbenzoyl phenylphosphinate (OMNIRAD TPO-L). Other suitable photoinitiators include, for example, but not limited to, benzyl dimethyl ketal, 2-methyl-2-hydroxyphenylacetone, benzoin methyl ether, benzoin isopropyl ether, anisolein methyl ether, aromatic sulfonyl chlorides, optically active oximes, and combinations thereof.

[0150] In some embodiments, the photoinitiator is present in the photopolymerizable composition in an amount of up to about 5% by weight based on the total weight of the polymerizable components in the photopolymerizable composition. In some cases, the photoinitiator is present in amounts of 0.1 wt% or more, 0.2 wt% or more, 0.3 wt% or more, 0.4 wt% or more, 0.5 wt% or more, 0.6 wt% or more, 0.7 wt% or more, 0.8 wt% or more, 0.9 wt% or more, 1.0 wt% or more, 1.25 wt% or more, or 1.5 wt% or more; and in amounts of 5 wt% or less, 4.8 wt% or less, 4.6 wt% or less, 4.4 wt% or less, 4.2 wt% or less, 4.0 wt% or less, 3.8 wt% or less, 3.6 wt% or less, 3.4 wt% or less, 3.2 wt% or less, 3.0 wt% or less, 2.8 wt% or less, 2.6 wt% or less, 2.4 wt% or less, 2.2 wt% or less, 2.0 wt% or less, 1.8 wt% or less, or 1.6 wt% or less. In other words, the photoinitiator may be present in an amount of about 0.1% to 5% by weight, 0.2% to 5% by weight, 0.5% to 5% by weight, or 0.5% to 3% by weight, based on the total weight of the photopolymerizable composition.

[0151] In some embodiments, the initiator comprises a polymer having a free radical photoinitiator group, such as a polymer backbone and side-chain or terminal photoinitiator groups linked by the polymer chain. In some embodiments, the initiator comprises a macromolecule containing a photoinitiator group, wherein the macromolecule typically has a molecular weight of at least 500 g / mol. Such initiators are described in detail in International Publication No. 2019 / 104072 (Chakraborty et al.).

[0152] In some respects, using more than one initiator helps to increase the percentage of monomers incorporated into the reaction product of the polymerizable component, and thus reduces the percentage of monomers that remain uncured. In some embodiments, at least one initiator comprises a first radical photoinitiator having sufficient absorbance in a first wavelength range; and a second radical initiator selected from: a second photoinitiator having sufficient absorbance in a second wavelength range (wherein the second wavelength range differs from the first wavelength range), or a thermal radical initiator. Such initiator systems are described in detail in International Publication No. WO 2019 / 104079 (Chakraborty et al.).

[0153] polyurethane components

[0154] The photopolymerizable compositions disclosed herein may contain no more than a small amount of polyurethane component. In some embodiments, the photopolymerizable compositions further contain a reaction product comprising the polyurethane component. The polyurethane is obtained as a reaction product of an isocyanate and an alcohol forming a urethane bond. In some embodiments, the photopolymerizable compositions contain 5% by weight or less of the polyurethane component. In some embodiments, the polyurethane component is present in amounts of 5% by weight or less, 4% by weight or less, 3% by weight or less, 2% by weight or less, or 1% by weight or less. Studies have found that suitable photopolymerizable compositions with advantageous low viscosity can be prepared using urea or acrylamide components without the need for a polyurethane component. Therefore, in some cases, the photopolymerizable compositions do not contain a polyurethane component.

[0155] additive

[0156] The photopolymerizable compositions disclosed herein may optionally also include at least one additive selected from inhibitors, stabilizers, sensitizers, absorption modifiers / UV absorbers, fillers, and combinations thereof.

[0157] Furthermore, the polymerizable material compositions described herein may also contain one or more sensitizers to increase the effectiveness of one or more photoinitiators that may be present simultaneously. In some embodiments, the sensitizers include isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX). Other sensitizers may also be used. If used in a photopolymerizable composition, the sensitizer may be present in an amount ranging from about 0.01% by weight or about 1% by weight based on the total weight of the photopolymerizable composition.

[0158] The photopolymerizable compositions described herein optionally include one or more polymerization inhibitors or stabilizers. Polymerization inhibitors are typically included in photopolymerizable compositions to provide additional thermal stability to the composition. In some cases, stabilizers comprise one or more antioxidants. Any antioxidant that does not conflict with the purposes of this disclosure may be used. In some embodiments, suitable antioxidants include, for example, various aryl compounds, including butylated hydroxytoluene (BHT), which may also be used as polymerization inhibitors in the embodiments described herein. Alternatively or as an alternative, polymerization inhibitors include methoxyhydroquinone (MEHQ).

[0159] In some embodiments, if a polymerization inhibitor is used, the polymerization inhibitor is present in an amount of about 0.001 wt% to 2 wt%, 0.001 wt% to 1.5 wt%, or 0.001 wt% to 1 wt% based on the total weight of the photopolymerizable composition. Furthermore, if a stabilizer is used, the stabilizer is present in the photopolymerizable composition described herein in an amount of about 0.001 wt% to 5 wt%, about 0.001 wt% to 4 wt%, or about 0.001 wt% to 3 wt% based on the total weight of the photopolymerizable composition.

[0160] The photopolymerizable compositions described herein may also contain one or more UV absorbers (including dyes, optical brighteners, pigments, particulate fillers, etc.) to control the penetration depth of photochemical radiation. A particularly suitable UV absorber is Tinuvin 326 ((2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol), available from BASF Corporation, Florem Park, New Jersey. Another particularly suitable UV absorber is an optical brightener, Tinopal OB (a benzoxazole, 2,2'-(2,5-thiophenediyl)bis[5-(1,1-dimethylethyl)]), also available from BASF Corporation.

[0161] If a UV absorber is used, the UV absorber may be present in an amount of about 0.001% to 5% by weight, about 0.001% to 1% by weight, about 0.001% to 3% by weight, or about 0.001% to 1% by weight, based on the total weight of the photopolymerizable composition.

[0162] In some embodiments, the photopolymerizable composition disclosed herein may contain at least one methacrylic acid. If methacrylic acid is used, it may be present in an amount of about 0.001% to 10% by weight or about 0.001% to 9.5% by weight based on the total weight of the photopolymerizable composition.

[0163] The polymerizable compositions disclosed herein may contain fillers, including nanoscale fillers. Examples of suitable fillers are naturally occurring or synthetic materials, including but not limited to: silica (SiO2 (e.g., quartz)); alumina (Al2O3), zirconium oxide, nitrides (e.g., silicon nitride); glasses and fillers derived from, for example, Zr, Sr, Ce, Sb, Sn, Ba, Zn, and Al; feldspar; borosilicate glass; kaolin (ceramic clay); talc; zirconium oxide; titanium dioxide; and submicron silica particles (e.g., pyrolytic silica, such as those available under the trade name AEROSIL, including “OX 50,” “130,” “150,” and “200” silica from Degussa Corp., Akron, OH, and CAB-O-SIL M5 and TS-720 silica from Cabot Corp., Tuscola, IL). Organic fillers made of polymeric materials are also feasible, such as those disclosed in International Publication No. WO09 / 045752 (Kalgutkar et al.).

[0164] The composition may also include fiber reinforcing materials and colorants, such as dyes, pigments, and pigment dyes. Examples of suitable fiber reinforcing materials include poly(glycolic acid) (PGA) microfibers, collagen microfibers, etc., as described in U.S. Patent No. 6,183,593 (Narang et al.). Examples of suitable colorants, as described in U.S. Patent No. 5,981,621 (Clark et al.), include 1-hydroxy-4-[4-methylphenylamino]-9,10-anthradinone (FD&C Purple No. 2); disodium salt of 6-hydroxy-5-[(4-sulfophenyl)oxo]-2-naphthalenesulfonic acid (FD&C Yellow No. 6); disodium salt of 9-(o-carboxyphenyl)-6-hydroxy-2,4,5,7-tetraiodo-3H-oxanthracene-3-one, monohydrate (FD&C Red No. 3); etc.

[0165] Discontinuous fibers are also suitable fillers, such as fibers containing carbon, ceramics, glass, or combinations thereof. Suitable discontinuous fibers can have a variety of compositions, such as ceramic fibers. Ceramic fibers can be produced in continuous lengths, or discontinuous ceramic fibers can be obtained by chopping or shearing. Ceramic fibers can be made from a variety of commercially available ceramic filaments. Examples of filaments that can be used to form ceramic fibers include ceramic oxide fibers sold under the trademark NEXTEL (3M Corporation of St. Paul, Minnesota). NEXTEL is a continuous filament ceramic oxide fiber with low elongation and shrinkage at operating temperatures, and provides good chemical resistance, low thermal conductivity, thermal shock resistance, and low porosity. Specific examples of NEXTEL fibers include NEXTEL 312, NEXTEL 440, NEXTEL 550, NEXTEL 610, and NEXTEL 720. NEXTEL 312 and NEXTEL 440 are refractory aluminoborosilicates containing Al2O3, SiO2, and B2O3. NEXTEL 550 and NEXTEL 720 are aluminum silicate, while NEXTEL 610 is aluminum oxide. During manufacturing, NEXTEL filaments are coated with organic sizing agents or surface treatment agents used as auxiliaries in textile processing. Sizing may involve applying starch, oil, wax, or other organic components to the filament bundle for protection and to aid in the treatment. Sizing agents can be removed from ceramic filaments by heat cleaning the filaments or ceramic fibers at 700°C for one to four hours.

[0166] Ceramic fibers can be cut, ground, or chopped to provide relatively uniform lengths, which can be achieved by cutting continuous filaments of ceramic material in mechanical shearing, laser cutting, or other cutting operations. Because some cutting operations are highly controllable, the particle size distribution of ceramic fibers is very narrow, allowing for control over the properties of the composite material. The length of ceramic fibers can be determined, for example, using an optical microscope (Olympus MX61, Olympus, Tokyo, Japan) equipped with a CCD camera (Olympus DP72, Tokyo, Japan) and analytical software (Olympus Stream Essentials, Tokyo, Japan). Samples can be prepared by spreading a representative sample of ceramic fibers onto a glass slide and measuring the length of at least 200 ceramic fibers at 10x magnification.

[0167] Suitable fibers include, for example, ceramic fibers available under the trade name NEXTEL (from 3M Corporation, St. Paul, Minnesota), such as NEXTEL 312, 440, 610, and 720. A currently preferred ceramic fiber comprises polycrystalline α-Al₂O₃. Suitable alumina fibers are described, for example, in U.S. Patent Nos. 4,954,462 (Wood et al.) and 5,185,299 (Wood et al.). Exemplary α-alumina fibers are marketed under the trade name NEXTEL 610 (3M Corporation, St. Paul, Minnesota). In some embodiments, the alumina fiber is a polycrystalline α-alumina fiber and, on a theoretical oxide basis, comprises more than 99 wt% Al₂O₃ and 0.2 wt% to 0.5 wt% SiO₂ based on the total weight of the alumina fiber. In other embodiments, some desirable polycrystalline α-alumina fibers comprise α-alumina with an average particle size of less than 1 micrometer (or even less than 0.5 micrometers in some embodiments). In some embodiments, the polycrystalline α-alumina fibers have an average tensile strength of at least 1.6 GPa (in some embodiments, at least 2.1 GPa, or even at least 2.8 GPa). Suitable aluminosilicate fibers are described, for example, in U.S. Patent No. 4,047,965 (Karst et al.). Exemplary aluminosilicate fibers are sold by 3M Corporation of St. Paul, Minnesota, under the trade names NEXTEL 440 and NEXTEL 720. Aluminoborosilicate fibers are described, for example, in U.S. Patent No. 3,795,524 (Sowman). Exemplary aluminoborosilicate fibers are sold by 3M Corporation under the trade name NEXTEL 312. Boron nitride fibers can be prepared, for example, as described in U.S. Patent No. 3,429,722 (Economy) and U.S. Patent No. 5,780,154 (Okano et al.).

[0168] Ceramic fibers can also be formed from other suitable ceramic oxide filaments. Examples of such ceramic oxide filaments include those available from Central Glass Fiber Co., Ltd. (e.g., EFH75-01, EFH150-31). Alumina borosilicate glass fibers containing less than about 2% alkali or substantially alkali-free (i.e., "E-glass" fibers) are also preferred. E-glass fibers are available from many commercial suppliers.

[0169] Examples of useful pigments include, but are not limited to: white pigments such as titanium dioxide, zinc phosphate, zinc sulfide, zinc oxide, and zinc barium white; red and orange-red pigments such as iron oxide (maroon, red, light red), iron oxide / chromium oxide, cadmium sulfide selenide, and cadmium mercury (maroon, red, orange); ultramarine (blue, pink, and purple), chromium-tin (pink), manganese (purple), and cobalt (purple); orange, yellow, and light yellow pigments such as barium titanate, cadmium sulfide (yellow), chromium (orange, yellow), molybdate (orange), zinc chromate (yellow), nickel titanate (yellow), iron oxide (yellow), nickel tungsten titanium, zinc ferrite, and chromium titanate; brown pigments such as iron oxide (light yellow, brown), manganese / antimony / titanium oxide, manganese titanate, natural ochre (ochre), and titanium tungsten manganese; blue-green pigments such as chromium aluminate (blue), chromium cobalt-alumina (cyan), iron blue (blue), manganese (blue), chromium and chromium oxide (green), and titanium green; and black pigments such as iron oxide black and carbon black. A combination of pigments is typically used to achieve the desired hue in the cured composition.

[0170] The use of fluorescent dyes and pigments also helps to make the printed composition visible under black light. A particularly useful hydrocarbon-soluble fluorescent dye is 2,5-bis(5- / -butyl-2-benzoxazolyl)1-thiophene. Fluorescent dyes (such as rhodamine) can also be incorporated into cationic polymers and as part of the resin.

[0171] If desired, the compositions disclosed herein may contain other additives, such as indicators, accelerators, surfactants, wetting agents, tartaric acid, chelating agents, buffers, and other similar ingredients that are readily apparent to those skilled in the art. Additionally, pharmaceutical or other therapeutic substances may optionally be added to the photopolymerizable compositions. Examples include, but are not limited to, fluoride sources, whitening agents, caries remedies (e.g., xylitol), remineralizing agents (e.g., calcium phosphate compounds and other calcium and phosphate sources), enzymes, breath fresheners, anesthetics, coagulants, acid neutralizers, chemotherapeutic agents, immunomodulators, thixotropic agents, polyols, anti-inflammatory agents, antimicrobial agents, antifungal agents, agents for treating dry mouth, desensitizing agents, etc., types commonly used in dental compositions.

[0172] Any combination of the above-mentioned additives may also be used. The selection and amount of any such additive can be chosen by those skilled in the art to achieve the desired results without excessive experimentation.

[0173] The photopolymerizable compositions described herein also exhibit a variety of desired properties in their uncured, cured, and cured article states. The uncured photopolymerizable compositions have viscosity characteristics consistent with the requirements and parameters of one or more additive manufacturing apparatuses (e.g., 3D printing systems). Advantageously, in many embodiments, the photopolymerizable compositions contain a minimal amount of solvent. For example, the composition may contain 95% to 100% solids, preferably 100%. In some cases, the photopolymerizable compositions described herein exhibit a viscosity of less than 5000 centipoise (cP) in their uncured state when measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s. In some cases, the photopolymerizable compositions described herein exhibit viscosities of 4800 cP or less, 4700 cP or less, 4500 cP or less, 4300 cP or less, 4100 cP or less, 3900 cP or less, 3500 cP or less, 3000 cP or less, 2500 cP or less, or 2000 cP or less when uncured; and viscosities of 300 cP or more, 350 cP or more, 400 cP or more, 500 cP or more, 600 cP or more, 700 cP or more, 800 cP or more, 900 cP or more, 1000 cP or more, 1100 cP or more, or 1500 cP or more when uncured. In some cases, the photopolymerizable compositions described herein exhibit, when uncured, dynamic viscosities of less than 2000 cP, 1900 cP or less, 1800 cP or less, 1500 cP or less, 1300 cP or less, or 1100 cP or less at 40°C; and dynamic viscosities of 800 cP or more, 900 cP or more, or 1000 cP or more. In some cases, the photopolymerizable compositions described herein exhibit, when uncured, dynamic viscosities of less than 400 cP, or 380 cP or less, 360 cP or less, 330 cP or less, or 300 cP or less at 60°C; and dynamic viscosities of 200 cP or more, 230 cP or more, 250 cP or more, or 280 cP or more.

[0174] Orthodontic products

[0175] In a second aspect, this disclosure provides an orthodontic article. The orthodontic article comprises a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises a) at least one (meth)acrylate reactive diluent based on 45% to 60% by weight of the total weight of the photopolymerizable composition; b) a photoinitiator; c) a first polymerization product based on 30% to 50% by weight of components including: a first polyether polyamine; and an olefinically unsaturated isocyanate functional monomer; d) optionally up to 10% by weight of a component having a glass transition temperature (T0) of 50°C or higher.g The photopolymerizable composition comprises, e) a crosslinking agent; and e) optionally, at most 12% by weight of a second polymerization product based on the total weight of the photopolymerizable composition, including a second polyether polyamine; and an olefinically unsaturated isocyanate functional monomer. The photopolymerizable composition comprises 40% to 50% by weight of the first polymerization product and no more than 5% by weight of the second polymerization product. The photopolymerizable composition comprises 30% to less than 40% by weight of the first polymerization product, and then the composition comprises 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of the second polymerization product, 5% to 10% by weight of a crosslinking agent, or at least 1% to 10% by weight of methacrylic acid. The polymerization product has a Tg of 50°C or higher. g .

[0176] In a third aspect, an orthodontic article is provided. The orthodontic article comprises a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises 30% to 50% by weight of a (meth)acrylate reactive diluent; and 40% to 60% by weight of a polymerization product comprising: a polymeric glycol; and acrylonitrile. The polymerization product has a Tg of 50°C or higher. g .

[0177] The polymerization product of the photopolymerizable composition disclosed above has the shape of an orthodontic article. The conformability and durability of the cured orthodontic article made from the photopolymerizable composition of this disclosure can be determined in part by standard tensile, modulus and / or elongation tests. The photopolymerizable composition, after curing, can generally be characterized by at least one of the following parameters.

[0178] Because orthodontic products are used in the moist environment of a patient's mouth, their absorbency is related to their composition. When selected products are soaked in deionized water at 20°C to 25°C for 72 hours, their absorbency is less than 1%, less than 0.5%, less than 0.2%, or even less than 0.1%.

[0179] Orthodontic articles preferably exhibit at least one desired physical property. These physical properties include the following: initial relaxation modulus, Young's modulus, tensile stress at break, tensile strain at break, loss modulus exhibiting a large temperature range, peak tanδ, and water absorption by weight percentage. Preferably, the orthodontic article exhibits at least two different desired physical properties, more preferably at least three different desired physical properties, and most preferably Young's modulus, tensile stress at break, and tensile strain at break. The values ​​of these different physical properties are described below.

[0180] Orthodontic products optionally exhibit a fracture (or maximum) tensile stress or tensile strength of 15 MPa or greater as determined by ASTM-D638-14. Yield strength is defined as the maximum tensile stress a material can withstand before permanent deformation. Fracture tensile stress is the point on the stress-strain curve where the material breaks. A yielded sample can undergo strain hardening through deformation before fracture. However, brittle materials do not have a yield point on their stress-strain curves, typically exhibiting a linear relationship across the entire strain range, eventually fractured at maximum tensile strength without significant plastic flow.

[0181] In some embodiments, the polymerized composition (e.g., orthodontic articles) exhibits a Young's modulus of 175 MPa or greater, a tensile strain at break of 65% or greater, and a tensile stress at break of 15 MPa or greater, as determined according to ASTM D638-14. In selected embodiments, the orthodontic article exhibits a Young's modulus of 175 MPa, a tensile strain at break of 65%, and a tensile stress at break of 15 MPa. In some embodiments, the polymerized composition (e.g., orthodontic articles) exhibits a Young's modulus of 300 MPa or greater, a tensile strain at break of 65% or greater, and a tensile stress at break of 15 MPa or greater, as determined according to ASTM D638-14. In selected embodiments, the orthodontic article exhibits a Young's modulus of 300 MPa, a tensile strain at break of 65%, and a tensile stress at break of 15 MPa. Similarly, the article may exhibit any combination of the above-mentioned preferred values ​​for each of the Young's modulus, tensile stress at break, and tensile strain at break. Surprisingly, it has been found that photopolymerizable compositions according to at least some embodiments are capable of forming articles possessing all three of these physical properties simultaneously.

[0182] In some embodiments, the polymerized composition (e.g., dental prosthetic tools or molds) exhibits a Young's modulus of 500 MPa or greater, a tensile strain at break of 4% or greater, and a tensile stress at break of 25 MPa or greater, as determined by ASTM D638-14.

[0183] In selected embodiments, based on dynamic mechanical analysis of the articles of this disclosure, a peak loss modulus is exhibited below 20°C, more preferably below 15°C, and most preferably below 10°C. In some embodiments, the peak loss modulus temperature is at least -70°C, -60°C, or -50°C. The term "peak" does not necessarily refer to the global maximum on the loss modulus curve, but may also refer to a local maximum, or a shoulder peak on a larger peak. These articles tend to exhibit high levels of elongation at break. In other embodiments, the articles may exhibit a tanδ peak >70°C, >75°C, more preferably >78°C, and most preferably >80°C. In some embodiments, the peak tanδ temperature is not higher than 150°C, 140°C, 135°C, 130°C, 120°C, or 110°C. Articles exhibiting a Young's modulus of 175 MPa or greater and a tensile stress at break of 15 MPa or greater have a peak loss modulus at below 20°C and a tanδ peak above 70°C. Articles exhibiting a Young's modulus of 300 MPa or greater and a tensile stress at break of 15 MPa or greater have a loss modulus that peaks below 20°C and a tanδ peak above 70°C. In some embodiments, the article has a first phase and a second phase, the first phase having a peak loss modulus temperature below 0°C, -5°C, or -10°C, and the second phase having a peak tanδ temperature above 30°C, 40°C, 50°C, 60°C, 70°C, or 80°C, determined according to dynamic mechanical analysis after conditioning in deionized water at 37°C for 24 hours. Loss modulus and tanδ are described, for example, in Sepe, MP (1998 Dynamic Mechanical Analysis for Plastics Engineering. William Andrew Publishing / Plastics Design Library).

[0184] In selected embodiments, orthodontic articles according to this disclosure optionally exhibit an initial relaxation modulus of 2 MPa or greater, measured at 37°C, 95% humidity, and 1% strain, as determined by dynamic mechanical analysis (DMA) after a material sample of the orthodontic article has been conditioned (i.e., immersed) in deionized water at room temperature (i.e., 22°C to 25°C) for 48 hours. The DMA procedure is described in detail in the following examples. Preferably, the orthodontic article exhibits an initial relaxation modulus of 2 MPa or greater, 3 MPa or greater, 4 MPa or greater, 5 MPa or greater, 6 MPa or greater, 7 MPa or greater, 8 MPa or greater, or 9 MPa or greater. In some embodiments, the initial relaxation modulus is not greater than about 15 MPa, 14 MPa, 13 MPa, 12 MPa, 11 MPa, or 10 MPa.

[0185] In selected embodiments, the orthodontic articles according to this disclosure optionally exhibit a relaxation modulus of 100 MPa or greater (e.g., at 30 minutes), as determined by immersion in water overnight at 37°C and 95% humidity using DMA, followed by an application of 1% strain for 11 hours, and then a 1-hour strain recovery measurement under 0 MPa stress. The DMA procedure for relaxation modulus is described in detail in the following examples, and the DMA procedure is performed on material samples of the orthodontic articles after water conditioning and initial relaxation modulus testing. Preferably, the orthodontic articles exhibit a relaxation modulus of 0.1 MPa or greater (e.g., at 11 hours).

[0186] In selected embodiments, the orthodontic articles according to this disclosure optionally exhibit a percentage loss of relaxation modulus of 70% or greater, as determined by DMA. This loss is determined by comparing the initial relaxation modulus with the relaxation modulus measured under conditions of 37°C, 95% humidity, and 1% strain. Studies have found that orthodontic articles according to at least some embodiments of this disclosure exhibit a greater loss of relaxation modulus after exposure to water than articles made of different materials. Preferably, the orthodontic articles exhibit a relaxation modulus loss of 99% or less, 90% or less, or 85% or less. In some embodiments, the relaxation modulus loss is 80%, 85%, or 90% or greater.

[0187] In at least some embodiments of the orthodontic articles disclosed herein, the articles are advantageously more resistant to staining than articles made from different, more hydrophilic components. For example, colorants and other colored substances in beverages are generally hydrophilic, and therefore they have a greater affinity for more hydrophilic compositions than for more hydrophobic compositions.

[0188] The aforementioned mechanical properties are particularly suitable for orthodontic products that require elasticity and flexibility, as well as sufficient abrasion resistance and long-term durability.

[0189] method

[0190] In a fourth aspect, this disclosure provides a method for manufacturing orthodontic articles. The method comprises: a) providing a photopolymerizable composition comprising: 30% to 60% by weight of at least one (meth)acrylate reactive diluent; a photoinitiator; and 30% to 60% by weight of a polymerization product comprising a urea-functionalized component or an acrylamide-functionalized component, wherein the photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP) when measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s; b) selectively curing the photopolymerizable composition; and c) repeating steps a) and b) to form a plurality of layers and produce an orthodontic article. The method optionally includes d) curing the remaining unpolymerized photopolymerizable composition after step c). The method also optionally includes e) removing at least a portion of the remaining unpolymerized photopolymerizable composition after step c). When both optional steps d) and e) are performed, step e) is typically performed before step d).

[0191] The polymerizable (e.g., photopolymerizable) components described herein can be mixed using known techniques. In some embodiments, for example, a method for preparing the photopolymerizable composition described herein includes the steps of: mixing all or substantially all components of the composition, heating the mixture, and optionally filtering the heated mixture. In some embodiments, softening of the mixture is carried out at about 50°C or at a temperature in the range of about 50°C to about 85°C. In some embodiments, the photopolymerizable composition described herein is prepared by placing all or substantially all components of the composition in a reaction vessel and heating the resulting mixture to a temperature of about 50°C to about 85°C with stirring. Heating and stirring are continued until the mixture reaches a substantially homogeneous state.

[0192] In many embodiments, the photopolymerizable composition is polymerized in a tank, as discussed in detail below.

[0193] The shape of the article is not limited and often includes molded, one-piece (e.g., monolithic) articles, where a single monolithic article offers more than one dimensional variation. For example, the article may include one or more channels, one or more undercuts, one or more perforations, or combinations thereof. Such features are typically not available in monolithic articles using conventional molding methods.

[0194] The components of the photopolymerizable (e.g., polymerizable) composition have been discussed in detail above. In many embodiments, photochemical radiation (including UV radiation, electron beam radiation, visible light radiation, or combinations thereof) is used to cure the photopolymerizable composition. Furthermore, the method optionally includes using photochemical radiation to post-cure the orthodontic article.

[0195] In some embodiments, the method includes tank polymerization of the photopolymerizable composition. When tank polymerization is used, radiation can penetrate the walls of the container (e.g., tank) holding the photopolymerizable composition, such as the side walls or bottom walls.

[0196] In some embodiments, the photopolymerizable compositions described herein in a cured state may exhibit one or more desired properties. The photopolymerizable compositions in a "cured" state may include photopolymerizable compositions comprising at least partially polymerized and / or crosslinked polymerizable components. For example, in some cases, the cured article is at least about 10% polymerized or crosslinked, or at least about 30% polymerized or crosslinked. In some cases, the cured polymerizable composition is at least about 50%, at least about 70%, at least about 80%, or at least about 90% polymerized or crosslinked. The cured polymerizable composition may also be about 10% to about 99% polymerized or crosslinked.

[0197] Manufacturing orthodontic products

[0198] Once prepared according to the method described above, the polymerizable (e.g., photopolymerizable) composition of this disclosure can be used in numerous additive manufacturing processes to produce a variety of, for example, orthodontic articles. A generalized method 100 for producing three-dimensional articles... Figure 1 The following is an illustration. Each step of the method will be discussed in more detail below. First, in step 110, a desired photopolymerizable composition (e.g., containing at least one (meth)acrylate reactive diluent) is provided and introduced into a reservoir, barrel, or other suitable container for use in an additive manufacturing apparatus. The additive manufacturing apparatus selectively cures the photopolymerizable composition in step 120 according to a set of computerized design instructions. In step 130, steps 110 and / or 120 are repeated to form multiple layers, thereby producing an article comprising a three-dimensional structure (i.e., an orthodontic article). Optionally, uncured photopolymerizable composition is removed from the article in step 140, further optionally, the article is subjected to additional curing in step 150 to polymerize the remaining uncured photopolymerizable components in the article, and also further optionally, the article is subjected to heat treatment in step 160.

[0199] The method for printing three-dimensional articles or objects described herein may include forming the article from multiple layers of the photopolymerizable composition described herein in a layer-by-layer manner. Furthermore, layers of the building material composition may be deposited based on an image of the three-dimensional article in a computer-readable format. In some or all embodiments, the photopolymerizable composition is deposited according to pre-selected computer-aided design (CAD) parameters.

[0200] Furthermore, it should be understood that the methods for manufacturing 3D articles described herein may include so-called “stereolithography / groove polymerization” 3D printing methods. Other techniques for 3D manufacturing are known and may be suitably adapted for use in the applications described herein. More generally, 3D manufacturing techniques continue to become available. All such techniques are suitable for use with the photopolymerizable compositions described herein, provided that they provide manufacturing viscosity and resolution compatible with the properties of the specified article. Manufacturing may be performed using any of the manufacturing techniques described herein, alone or in various combinations, using data representing the 3D object, which may be reformatted or otherwise adapted to specific printing or other manufacturing techniques as needed.

[0201] 3D articles can be formed from the photopolymerizable compositions described herein using tank polymerization (e.g., stereolithography). For example, in some cases, a method of printing a 3D article includes: holding the photopolymerizable composition described herein in a fluid state in a container, and selectively applying energy to the photopolymerizable composition in the container to solidify at least a portion of the fluid layer of the photopolymerizable composition, thereby forming a hardened layer defining the cross-section of the 3D article.

[0202] Furthermore, the method described herein may also include raising or lowering a hardened layer of the photopolymerizable composition to provide a new or second fluid layer of the unhardened photopolymerizable composition at the surface of the fluid in the container, followed by selectively applying energy again to the photopolymerizable composition in the container to solidify at least a portion of the new or second fluid layer of the photopolymerizable composition, thereby forming a second solidified layer defining a second cross-section of the 3D article. Furthermore, by applying energy for solidifying the photopolymerizable composition, the first and second cross-sections of the 3D article may be bonded or adhered to each other in the z-direction (or the construction direction corresponding to the aforementioned raising or lowering direction). Additionally, selectively applying energy to the photopolymerizable composition in the container may include applying photochemical radiation with sufficient energy to solidify the photopolymerizable composition, such as UV radiation, visible light radiation, or electron beam radiation. The method described herein may also include planarizing the provided new layer of the fluid photopolymerizable composition by raising or lowering a lifting platform. This planarization may, in some cases, be performed using a wiper, roller, or recoating machine. Planarization can correct the thickness of one or more layers by uniformly distributing the material before curing to remove excess material, and create a uniform, smooth, bare or flat, face-up surface on the printer's support platform.

[0203] It is important to further understand that the above process can be repeated a selected number of times to provide a 3D article. For example, in some cases, the process can be repeated "n" times. Furthermore, it should be understood that one or more steps of the method described herein, such as the step of selectively applying energy to a photopolymerizable composition layer, can be performed based on an image of a 3D article in a computer-readable format. Suitable stereolithography printers include the Viper Pro SLA, available from 3D Systems, Rock Hill, SC, South Carolina, and the Asiga PICO PLUS 39, available from Asiga USA, Anaheim Hills, CA.

[0204] Figure 2 An exemplary stereolithography apparatus (“SLA”) for use with the photopolymerizable compositions and methods described herein is illustrated. Typically, the SLA 200 may include a laser 202, optics 204, a steering lens 206, a lift 208, a platform 210, and a straight edge 212 located within a tank 214 filled with a photopolymerizable composition. In operation, the laser 202 is directed across the surface of the photopolymerizable composition to cure a cross-section of the composition, after which the lift 208 slightly lowers the platform 210 and cures another cross-section. The straight edge 212 may sweep across the surface of the cured composition between layers to smooth and normalize the surface before adding a new layer. In other embodiments, the tank 214 may be slowly filled with liquid resin while pulling the article layer by layer onto the top surface of the photopolymerizable composition.

[0205] Related technologies, namely, tank polymerization with digital light processing (“DLP”), also use containers for curable polymers (e.g., photopolymerizable compositions). However, in DLP-based systems, a two-dimensional cross-section is projected onto the curable material to cure a desired segment transverse to the entire plane of the projected beam in a single pass. All such curable polymer systems suitable for the photopolymerizable compositions described herein are intended to fall within the scope of the term “tank polymerization system” as used herein. In some embodiments, equipment suitable for continuous operation may be employed, such as equipment commercially available from Carbon 3D, Inc., Redwood City, CA, such as that described in U.S. Patent Nos. 9,205,601 and 9,360,757 (both granted to DeSimone et al.).

[0206] refer to Figure 5This provides a general schematic diagram of another SLA apparatus that can be used with the photopolymerizable compositions and methods described herein. Typically, apparatus 500 may include a laser 502, optics 504, a steering lens 506, a lift 508, and a platform 510 located within a tank 514 filled with a photopolymerizable composition 519. In operation, the laser 502 is directed through the wall 520 (e.g., a base plate) of the tank 514 and into the photopolymerizable composition to cure a cross-section of the photopolymerizable composition 519 to form an article 517, after which the lift 508 slightly raises the platform 510 and cures another cross-section.

[0207] More generally, photochemical radiation (such as UV radiation, electron beam radiation, visible light radiation, or any combination thereof) is typically used to cure photopolymerizable compositions. Skilled practitioners can select the appropriate radiation source and wavelength range for a specific application without excessive experimentation.

[0208] After a 3D article has been formed, it is typically removed from the additive manufacturing apparatus and cleaned (e.g., by ultrasonic cleaning, bubbling cleaning, or spray rinsing in a solvent, which dissolves a portion of the uncured photopolymerizable composition but not the cured solid article (e.g., green article)). Any other conventional method for cleaning the article and removing uncured material from its surface may also be used. In some embodiments, removing uncured material from the article involves directing pressurized gas onto the uncured photopolymerizable composition to force at least a portion of the composition away from the article surface, for example, using an air knife. In some embodiments, removing uncured material from the article surface involves moving the article to generate a mass inertial force in the uncured photopolymerizable composition disposed on the article, thereby forming a coating of the uncured photopolymerizable composition on the article. This mass inertial force can be generated using a centrifuge, shaker, or mixer that spins along one or more axes. Suitable methods for generating mass inertial forces are described, for example, in International Publication WO 2020 / 157598 (Chakraborty et al.), the full text of which is incorporated herein by reference. For example, a centrifuge, shaker, or mixer that spins along one or more axes can be used to generate a source of mass inertia. In some embodiments, the movement of the object is either rotation or spin. Therefore, mass inertia can be generated by centrifugal force. A suitable mixer that spins along more than one axis is a dual-asymmetric centrifugal mixer, such as the DAC 400 FVZ, available from Flacktek, Landrum, SC, South Carolina. Dual-asymmetric centrifugal mixers provide simultaneous biaxial spin, which automatically reorients the article during spin, tending to pull the uncured composition from the concave features of the article within a short time period (e.g., 20 seconds, 15 seconds, or 10 seconds or less). At this stage, the three-dimensional article typically has sufficient green strength for processing in the remaining optional steps of method 100.

[0209] In some embodiments of this disclosure, the molded article obtained in step 120 is expected to shrink (i.e., its volume decreases), such that the size of the article after (optionally) step 150 will be smaller than expected. For example, the cured article may shrink by less than 5% by volume, less than 4% by volume, less than 3% by volume, less than 2% by volume, or even less than 1% by volume, in contrast to other compositions that provide articles that shrink by about 6% to 8% by volume upon optional post-curing. The amount of volume shrinkage percentage generally does not cause significant deformation of the final object shape. Therefore, it is particularly contemplated that the dimensions in the digital model of the final cured article may be adjusted by a global scaling factor to compensate for this shrinkage. For example, in some embodiments, at least a portion of the digital article may be at least 101% of the desired size of the printed apparatus, in some embodiments at least 102%, in some embodiments at least 104%, in some embodiments at least 105%, and in some embodiments at least 110%.

[0210] For any given photopolymerizable composition formulation, its global scaling factor can be calculated by fabricating a calibration article according to steps 110 and 120 above. The dimensions of the calibration article can be measured before post-curing.

[0211] Typically, as described above, the three-dimensional article formed by the initial additive manufacturing in step 120 is not fully cured, meaning that even after rinsing, not all photopolymerizable materials in the composition have polymerized. Some uncured photopolymerizable material is usually removed from the surface of the printed article during a cleaning process (e.g., optional step 140). The article surface and the block article itself often still retain uncured photopolymerizable material, indicating the need for further curing.

[0212] Removing residual uncured photopolymerizable composition is particularly useful when the article is subsequently post-cured, in order to minimize the undesirable direct curing of the uncured residual photopolymerizable composition on the article.

[0213] Further curing can be achieved by further irradiation with photochemical radiation, heating, or both. Exposure to photochemical radiation can be performed using any convenient radiation source, typically UV radiation, visible light radiation, and / or electron beam radiation, for a duration ranging from approximately 10 minutes to over 60 minutes. Heating is typically carried out in an inert atmosphere at temperatures ranging from approximately 75°C to 150°C for a duration ranging from approximately 10 minutes to over 60 minutes. So-called post-curing ovens, which combine UV radiation and heat, are particularly suitable for the post-curing processes of steps 150 and / or 160. Generally, post-curing improves the mechanical properties and stability of the three-dimensional article compared to the same article that has not been post-cured.

[0214] 3D printing technology holds particularly promising applications in the direct manufacture of dental prosthetic tools or molds. Dental prosthetic tools are custom-designed and pre-formed for specific teeth (or groups of teeth) of a particular patient. When used as dental prosthetic tools or molds, the photopolymerizable resin used must possess sufficiently high printing resolution to achieve the forming of minute features such as interproximal fins / spacers and hinges. Furthermore, the cured resin must have sufficient elastic modulus to resist the deformation stress generated when the restorative material fills the mold. The cured resin must also possess sufficient toughness to prevent breakage during operation and when bonded to the teeth. Preferably, the material does not undergo rapid physical or chemical aging and embrittlement. In some cases, the cured material must exhibit at least one of the following: a Young's modulus of 500 MPa or greater, a tensile strain at break of 4% or greater, or a tensile stress at break of 25 MPa or greater, each determined according to ASTM D638-14. In some cases, the cured material exhibits at least two, or even all three, of these physical properties.

[0215] In some examples, 3D printing technology can be used to produce such custom tools. Tools can also be produced using other methods that create physical objects from digital data, such as CAD / CAM milling. In other examples, vacuum forming technology can be used to produce tools.

[0216] In one example, the tool for forming a dental restoration includes: a pre-formed mold body configured to achieve a personalized fit to at least one tooth of a patient to be restored, the mold body being configured to align with a portion of the surface of the at least one tooth; the mold body being configured to engage with the at least one tooth to define a mold cavity surrounding at least a portion of the desired tooth structure of the at least one tooth to be restored, wherein the portion of the desired tooth structure of the at least one tooth to be restored defines a transition from the supragingival surface to the subgingival surface of the at least one tooth.

[0217] Custom tools can be formed based on a digital model of an individual patient's teeth and oral cavity, generated via intraoral 3D scanning (such as an intraoral scanner). In a specific example, the custom tool can be digitally designed using CAD software, such as solid modeling software based on a digital model of the planned dental arch to be restored. The custom tool can be designed to fit onto one or more teeth to be restored (the restoration portion) and portions of adjacent teeth (the mortise portion). Production may optionally include additional steps such as curing (e.g., in a UV chamber) and / or cleaning (e.g., in an alcohol solution). The mortise portion can be located in an area corresponding to the tooth's extension region. In the digital model, the design can be divided into two parts (a facial mold body and a lingual mold body) to allow for the final assembly of the tool components onto the teeth, selecting specific geometric interferences based on the arch length to provide the desired clamping force. In the digital model, the mortise portion is designed with a specific interlocking geometry, its overall height selected based on the specific location of the mortise portion within the patient's oral cavity. The parts within the CAD software can be converted into 3D point mesh files or other formats to facilitate production using, for example, a 3D printer. In some cases, dental restorative tools or molds contain polymer reaction products of photopolymerizable compositions according to at least some embodiments described herein.

[0218] Suitable dental prosthetic tools and molds, and methods of their preparation, are described in detail in U.S. Patents 10,722,331, 11,123,165, 11,185,392 (each granted to Hansen et al.) and 11,547,530 (Dingeldein et al.); U.S. Publications 2019 / 0083208, 2023 / 0042808 (each granted to Hansen et al.), 2019 / 0298489, and 2021 / 0290349 (each granted to Dingeldein et al.); and International Publications WO2023 / 031771, WO2023 / 031761, and WO2023 / 031766 (each granted to Hansen et al.).

[0219] Another application of 3D printing is the direct fabrication of orthodontic clear tray appliances. These trays (also known as aligners, polymer appliances, or shell appliances) are supplied in series and worn sequentially over several months to gradually move the teeth towards the desired alignment. Some types of clear tray appliances feature rows of tooth cavities to support each tooth in the patient's arch, with slight variations in the orientation of these cavities between different appliances to gradually push each tooth toward its desired position using the elastic properties of the polymer material. Various methods have been proposed in the past for manufacturing clear tray appliances and other flexible appliances. Typically, an orthodontic arch model is created for each arch using additive manufacturing methods such as stereolithography as described above. A sheet of polymer material is then placed on each arch model and shaped under heat, pressure, and / or vacuum to fit the model teeth of each arch. The shaped sheet is cleaned and trimmed, and the final arched appliance is shipped to a processing professional along with the desired number of other appliances.

[0220] Orthodontic appliances or other flexible devices that can be directly manufactured using 3D printing eliminate the need for printing molds for the dental arch and further thermoforming the appliances. This technology also enables novel appliance designs, providing greater flexibility in treatment planning. Exemplary methods for directly printing transparent tray appliances and other flexible orthodontic devices are described in PCT Publications WO2016 / 109660 (Raby et al.), WO2016 / 148960 (Cinader et al.), and WO2016 / 149007 (Oda et al.), as well as US Publications US2011 / 0091832 (Kim et al.) and US2013 / 0095446 (Kitching).

[0221] The following describes the use of a transparent tray orthodontic appliance as a printing device 300 ( Figure 3The general methods described herein. However, similar techniques and photopolymerizable compositions of this disclosure can be used to fabricate other dental and orthodontic products. Representative examples include, but are not limited to, removable appliances with occlusal windows described in International Application Publication No. WO2016 / 109660 (Raby et al.); removable appliances with palatal plates described in U.S. Application Publication No. 2014 / 0356799 (Cinader et al.); resilient polymer arched members described in International Applications WO2016 / 148960 and WO2016 / 149007 (Oda et al.) and U.S. Application Publication No. 2008 / 0248442 (Cinader et al.); and molding techniques and tools for forming dental restorations in the oral cavity described in WO2016 / 094272 (Hansen et al.) and U.S. Application Publication No. 2019 / 0083208 (Hansen et al.). In addition, photopolymerizable compositions can be used to manufacture indirect bonding trays, such as those described in International Publication WO2015 / 094842 (Paehl et al.) and U.S. Publication 2011 / 0091832 (Kim et al.), as well as other dental products, including but not limited to crowns, bridges, veneers, inlays, onlays, fillings, and dentures (e.g., partial or complete dentures). Other orthodontic appliances and devices include, but are not limited to, orthodontic brackets, buccal tubes, lingual retainers, orthodontic bands, Class II and Class III appliances, sleep apnea devices, bite openers, buttons, splints, and other attachment devices.

[0222] Manufacturing orthodontic appliances using photopolymerizable compositions

[0223] exist Figure 3 The text describes a particularly interesting implementation of the article. The additively manufactured article 300 is a clear tray orthodontic appliance and is removably positioned on some or all of a patient's teeth. In some embodiments, the appliance 300 is one of a plurality of incremental adjustment appliances. The appliance 300 may include a housing having a cavity. The cavity is shaped to accommodate teeth and resiliently reposition teeth from one dentition position to a subsequent dentition position. The cavity may include a plurality of slots, each adapted to connect to and accommodate a corresponding tooth of the patient's dental arch. These slots are spaced apart from each other along the length of the cavity, although the adjoining areas of adjacent slots may communicate with each other. In some embodiments, the housing is fitted onto all teeth of the maxilla or mandible. Typically, only specific teeth are repositioned, while other teeth provide a base or anchorage area to hold the dental appliance in place while applying a resilient repositioning force to the one or more teeth to be treated.

[0224] To facilitate adjustment of the patient's tooth position, when the patient wears the appliance 300, at least one cavity can be aligned to apply rotational and / or translational forces to the corresponding tooth, ultimately aligning the tooth to a new desired position. In some specific examples, the appliance 300 may be configured to provide only compressive or linear forces. In the same or different examples, the appliance 300 may be configured to apply translational forces to one or more teeth within the cavity.

[0225] In some implementations, the housing of the appliance 300 is fitted onto some or all of the anterior teeth of the maxilla or mandible. Typically, only specific teeth are repositioned, while other teeth provide a base or anchorage area, holding the appliance in place while applying a resilient repositioning force to the one or more teeth requiring repositioning. Therefore, the appliance 300 can be designed such that any cavity is shaped to facilitate holding the tooth in a specific position to maintain its current position.

[0226] The method 400 for manufacturing orthodontic appliances using the photopolymerizable compositions of this disclosure may include, for example: Figure 4 The general steps outlined herein are described below. Various aspects of the process are discussed in further detail below. The process includes generating a treatment plan for repositioning the patient's teeth. In short, the treatment plan may include obtaining data representing an initial arrangement of the patient's teeth (step 410), which typically includes obtaining impressions or scan data of the patient's teeth prior to the commencement of treatment. The treatment plan will also include determining the final or target arrangement of the patient's anterior and posterior teeth (step 420), as well as multiple planned successive or intermediate tooth arrangements for moving at least the anterior teeth along the treatment path from the initial arrangement to the selected final or target arrangement (step 430). One or more appliances may be virtually designed based on the treatment plan (step 440), and image data representing the appliance design may be exported to an additive manufacturing apparatus (e.g., a 3D printer system) in STL format or any other suitable computer-processable format (step 450). The appliances may be manufactured using the photopolymerizable compositions of this disclosure retained in the additive manufacturing apparatus (step 460).

[0227] In some embodiments, according to at least some aspects of this disclosure, a machine-readable medium (e.g., non-transitory) is used in the additive manufacturing of the article. Data is typically stored on this machine-readable medium. This data represents a three-dimensional model of the article, which can be accessed by at least one computer processor interfaced with additive manufacturing equipment (e.g., a 3D printer, manufacturing apparatus, etc.). This data is used to enable the additive manufacturing equipment to produce an article comprising a reaction product of a photopolymerizable composition comprising a blend of: 30% to 60% by weight of at least one (meth)acrylate reactive diluent, a photoinitiator, and 30% to 60% by weight of a polymerization reaction product including a urea-functionalized component or an acrylamide-functionalized component. The cured homopolymer of at least one (meth)acrylate reactive diluent has a Tc of 50°C or higher. g The polymerization product of this photopolymerizable composition has the shape of an orthodontic article. Details of this photopolymerizable composition are as described above.

[0228] Data representing an article can be generated using computer modeling, such as computer-aided design (CAD) data. Image data representing an article (e.g., a polymer) design can be exported to an additive manufacturing apparatus in STL format or any other suitable computer-processable format. Data representing an article can also be created using scanning methods that scan three-dimensional objects. An exemplary technique for acquiring this data is digital scanning. Any other suitable scanning techniques can be used to scan articles, including X-ray radiography, laser scanning, computed tomography (CT), magnetic resonance imaging (MRI), and ultrasound imaging. Other possible scanning methods are described, for example, in U.S. Patent Application Publication No. 2007 / 0031791 (Cinader, Jr. et al.). An initial digital dataset can be processed, which may include raw data from the scanning operation and data representing an article derived from the raw data to separate the article design from any surrounding structures, such as supports for the article. In an alternative embodiment, the scanning technique may include, for example, scanning a patient's oral cavity to customize an orthodontic article for that patient. Typically, a machine-readable medium is set up as part of a computing device. The computing device may have one or more processors, volatile memory (RAM), means for reading machine-readable media, and input / output devices such as a display, keyboard, and pointing devices. Furthermore, the computing device may include other software, firmware, or combinations thereof, such as an operating system and other application software. The computing device may be, for example, a workstation, laptop computer, personal digital assistant (PDA), server, mainframe, or any other general-purpose or special-purpose computing device. The computing device may read executable software instructions from computer-readable media such as hard disk drives, CD-ROMs, or computer memory, or may receive instructions from another source logically connected to the computer, such as another networked computer. (Reference) Figure 10 The computing device 1000 typically includes an internal processor 1080, a display 1100 (e.g., a monitor), and one or more input devices such as a keyboard 1140 and a mouse 1120. Figure 10 In the image, the orthodontic appliance article 1130 is shown on the display 1100.

[0229] refer to Figure 6 In some embodiments, this disclosure provides a system 600. System 600 includes a display 620 (e.g., such as a 3D model 610 of an article of manufacture) that displays the 3D model 610 of the article of manufacture. Figure 10 The display 620 shows an orthodontic appliance 1130; and one or more processors 630, which, in response to a 3D model 610 selected by the user, cause a 3D printer / additive manufacturing apparatus 650 to produce a physical object of an article 660. Typically, an input device 640 (e.g., a keyboard and / or mouse) is used in conjunction with the display 620 and at least one processor 630, particularly for user selection of the 3D model 610. The article 660 comprises a reaction product of a photopolymerizable composition comprising a blend of: 30% to 60% by weight of at least one (meth)acrylate reactive diluent and 30% to 60% by weight of a polymerization reaction product including a urea-functionalized component or an acrylamide-functionalized component, wherein the photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP) when measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s. The polymerization reaction product of the photopolymerizable composition has the shape of an orthodontic article. The details of the photopolymerizable composition are as described above.

[0230] refer to Figure 7 The processor 720 (or more processors) communicates with each of the machine-readable medium 710 (e.g., a non-transitory medium), the 3D printer / additive manufacturing apparatus 740, and optionally a display 730 for viewing by a user. The 3D printer / additive manufacturing apparatus 740 is configured to manufacture one or more articles 750 based on instructions from the processor 720, these instructions being used to obtain representations of the articles 750 from the machine-readable medium 710 (e.g., such as...). Figure 10 Data of a 3D model of the orthodontic appliance (1130) shown on the display 1100. (Reference) Figure 8For example, but not limited to, according to at least one embodiment of this disclosure, the additive manufacturing method includes retrieving data representing a 3D model of an article from (e.g., a non-transitory) machine-readable medium 810. The method also includes executing an additive manufacturing application 820 interfaced with a manufacturing apparatus using the data by one or more processors; and generating a physical object of the article 830 by the manufacturing apparatus. The additive manufacturing equipment can selectively cure a photopolymerizable composition to form an article. The article comprises a reaction product of a photopolymerizable composition comprising a blend of the following components: 30% to 60% by weight of at least one (meth)acrylate reactive diluent, a photoinitiator, and 30% to 60% by weight of a polymerization reaction product comprising a urea-functionalized component or an acrylamide-functionalized component. The cured homopolymer of at least one (meth)acrylate reactive diluent has a Tc of 50°C or higher. g Cured homopolymers of at least one monofunctional (meth)acrylate monomer have a Tc of 30°C or higher. g The polymerization product of this photopolymerizable composition has the shape of an orthodontic article. Details of the photopolymerizable composition are as described above. One or more optional post-processing steps 840 may be performed. Typically, the remaining unpolymerized photopolymerizable component can be cured. The article includes an orthodontic article.

[0231] Additionally, refer to Figure 9 A method of manufacturing an article includes: receiving a digital object 910, comprising data specifying multiple layers of an orthodontic article, by a manufacturing apparatus having one or more processors; and generating an article 920 based on the digital object using the manufacturing apparatus via an additive manufacturing process. The article may also undergo one or more post-processing steps.

[0232] This disclosure selects an implementation scheme.

[0233] Embodiment 1 is a photopolymerizable composition. This photopolymerizable composition comprises 30% to 60% by weight of at least one (meth)acrylate reactive diluent, a photoinitiator, and 30% to 60% by weight of a polymerization product comprising a urea-functionalized component or an acrylamide-functionalized component. When measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s, this photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP).

[0234] Implementation Scheme 2 is a photopolymerizable composition according to Implementation Scheme 1, wherein the photopolymerizable composition exhibits a dynamic viscosity of less than 2000 cP at 40°C.

[0235] Implementation scheme 3 is a photopolymerizable composition according to implementation scheme 1 or implementation scheme 2, wherein the photopolymerizable composition exhibits a dynamic viscosity of less than 400 cP at 60°C.

[0236] Embodiment 4 is a photopolymerizable composition according to Embodiments 1 to 3, wherein the photopolymerizable composition contains 5% by weight or less of a polyurethane component.

[0237] Embodiment 5 is a photopolymerizable composition according to Embodiments 1 to 4, wherein the photopolymerizable composition comprises 45% to 60% by weight of at least one (meth)acrylate reactive diluent based on the total weight of the photopolymerizable composition, 30% to 50% by weight of a first polymerization product based on the total weight of the photopolymerizable composition, and optionally up to 10% by weight of a component having a glass transition temperature (T0) of 50°C or higher. g The first polymerization product comprises a crosslinking agent and optionally up to 12% by weight of the component based on the total weight of the photopolymerizable composition. The first polymerization product comprises a first polyether polyamine and an olefinically unsaturated isocyanate functional monomer. The second polymerization product comprises a second polyether polyamine and an olefinically unsaturated isocyanate functional monomer.

[0238] Embodiment 6 is a photopolymerizable composition according to Embodiments 1 to 5, wherein the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product of the component, and the composition comprises no more than 5% by weight of a second polymerization product of the component.

[0239] Embodiment 7 is a photopolymerizable composition according to Embodiments 1 to 6, wherein the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product and a crosslinking agent, and the composition comprises no more than 5% by weight of a second polymerization product.

[0240] Embodiment 8 is a photopolymerizable composition according to Embodiments 1 to 7, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, and then the composition comprises at least one of 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, 5% to 10% by weight of a crosslinking agent, or 1% to 10% by weight of methacrylic acid.

[0241] Embodiment 9 is a photopolymerizable composition according to Embodiments 1 to 8, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component and 55% to 60% by weight of a (meth)acrylate reactive diluent.

[0242] Embodiment 10 is a photopolymerizable composition according to Embodiments 1 to 9, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, and 5% to 10% by weight of a crosslinking agent.

[0243] Embodiment 11 is a photopolymerizable composition according to Embodiments 1 to 10, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the components, 55% to 60% by weight of a (meth)acrylate reactive diluent and 1% to 10% by weight of methacrylic acid.

[0244] Embodiment 12 is a photopolymerizable composition according to Embodiments 1 to 11, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent and 5% to 12% by weight of a second polymerization product of the component.

[0245] Embodiment 13 is a photopolymerizable composition according to Embodiments 1 to 12, wherein the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, and 5% to 10% by weight of a crosslinking agent.

[0246] Embodiment 14 is a photopolymerizable composition according to Embodiments 1 to 13, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, and 1% to 10% by weight of methacrylic acid.

[0247] Embodiment 15 is a photopolymerizable composition according to Embodiments 5 to 14, wherein the first polymerization product of the component comprises a polyether polyamine having a weight-average molecular weight (M) of 300 g / mol to 6,500 g / mol as determined by gel permeation chromatography. w ) of polyether triamine.

[0248] Embodiment 16 is a photopolymerizable composition according to Embodiment 15, wherein the polyether polyamine is a polyether triamine having the structure of Formula II:

[0249] Where n is 1 to 10; x is 1 to 84; y is 1 to 84; and z is 1 to 84.

[0250] Embodiment 17 is a photopolymerizable composition according to Embodiments 5 to 14, wherein the first polymerization product of the component comprises a polyether polyamine having an M content of 200 g / mol to 4,000 g / mol as determined by gel permeation chromatography. n Polyether diamine.

[0251] Embodiment 18 is a photopolymerizable composition according to Embodiment 17, wherein the polyether polyamine is a polyether diamine having the structure of Formula I:

[0252] Where x ranges from 4 to 90.

[0253] Embodiment 19 is a photopolymerizable composition according to Embodiments 1 to 18, wherein the first polymerization product of the component is present in an amount of 40% to 50% by weight based on the total weight of the photopolymerizable composition.

[0254] Embodiment 20 is a photopolymerizable composition according to Embodiments 1 to 19, wherein the first polymerization product of the component is present in an amount of 30% by weight to less than 40% by weight based on the total weight of the photopolymerizable composition.

[0255] Embodiment 21 is a photopolymerizable composition according to Embodiments 1 to 20, wherein the (meth)acrylate reactive diluent is present in an amount of 55% to 60% by weight based on the total weight of the photopolymerizable composition.

[0256] Embodiment 22 is a photopolymerizable composition according to Embodiments 20 to 21, wherein the second polymerization product of the component is present in an amount of 5% to 12% by weight based on the total weight of the photopolymerizable composition.

[0257] Embodiment 23 is a photopolymerizable composition according to Embodiments 20 to 22, wherein the crosslinking agent is present in an amount of 5% to 10% by weight based on the total weight of the photopolymerizable composition.

[0258] Embodiment 24 is a photopolymerizable composition according to Embodiments 1 to 4, wherein the photopolymerizable composition comprises 30% to 50% by weight of a (meth)acrylate reactive diluent and 40% to 60% by weight of the polymerization product of the component. The polymerization product of the component comprises a polymeric glycol and acrylonitrile.

[0259] Embodiment 25 is a photopolymerizable composition according to Embodiment 24, wherein the acrylonitrile includes 2-vinyl-4,4-dimethylacylonitrile.

[0260] Embodiment 26 is a photopolymerizable composition according to Embodiments 23 to 25, wherein the photopolymerizable composition further comprises a crosslinking agent.

[0261] Embodiment 27 is a photopolymerizable composition according to Embodiment 26, wherein the crosslinking agent comprises the polymerization product of polyamine and acrylonitrile.

[0262] Embodiment 28 is a photopolymerizable composition according to Embodiments 24 to 27, wherein the polymeric diol has a number-average molecular weight (Mn) of 200 g / mol to 5,000 g / mol or 400 g / mol to 3,000 g / mol as determined by gel permeation chromatography. n ).

[0263] Embodiment 29 is a photopolymerizable composition according to Embodiments 24 to 28, wherein the polymerizable diol includes polyester diol, polycarbonate diol, polyether diol, polyolefin diol, or a combination thereof.

[0264] Embodiment 30 is a photopolymerizable composition according to Embodiments 24 to 29, wherein the polymerizable diol includes polycarbonate diol.

[0265] Embodiment 31 is a photopolymerizable composition according to Embodiments 24 to 30, wherein the polymerizable diol comprises a polycarbonate diol of Formula III.

[0266] Each of R1 and R2 in each (O-R1-OC(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and the average number of carbon atoms in all combinations of R1 and R2 groups is 4 to 10, and m is an integer from 2 to 23.

[0267] Embodiment 32 is a photopolymerizable composition according to Embodiments 24 to 31, wherein the photopolymerizable composition further comprises acrylonitrile.

[0268] Scheme 33 is a photopolymerizable composition according to Schemes 1 to 32, wherein the (meth)acrylate reactive diluent includes at least one of isoborneol methacrylate, isoborneol acrylate, methyl methacrylate, tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate or tricyclodecanediethanol diacrylate.

[0269] Implementation scheme 34 is a photopolymerizable composition according to implementation schemes 1 to 33, wherein the (meth)acrylate reactive diluent is isobornyl methacrylate.

[0270] Embodiment 35 is a photopolymerizable composition according to Embodiments 1 to 34, wherein the photopolymerizable composition further comprises at least one of methacrylic acid, an antioxidant, or a UV absorber.

[0271] Embodiment 36 is an orthodontic article. The orthodontic article comprises a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises 45% to 60% by weight of at least one (meth)acrylate reactive diluent based on the total weight of the photopolymerizable composition, 30% to 50% by weight of a first polymerization product based on the total weight of the photopolymerizable composition, and optionally up to 10% by weight of a component having a glass transition temperature (T0) of 50°C or higher. g The first polymerization product comprises a crosslinking agent and optionally up to 12% by weight of a second polymerization product based on the total weight of the photopolymerizable composition. The first polymerization product comprises a first polyether polyamine and an olefinically unsaturated isocyanate functional monomer. The second polymerization product comprises a second polyether polyamine and an olefinically unsaturated isocyanate functional monomer. The polymerization product has a Tg of 50°C or higher. g .

[0272] Embodiment 37 is an orthodontic article according to Embodiment 36, wherein the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product of the component, and the composition comprises no more than 5% by weight of a second polymerization product of the component.

[0273] Embodiment 38 is an orthodontic article according to Embodiments 36 to 37, wherein the photopolymerizable composition comprises 40% to 50% by weight of a first polymerization product of the components and a crosslinking agent, and the composition comprises no more than 5% by weight of a second polymerization product of the components.

[0274] Embodiment 39 is an orthodontic article according to Embodiments 36 to 38, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, and then the composition comprises at least one of 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, 5% to 10% by weight of a crosslinking agent, or 1% to 10% by weight of methacrylic acid.

[0275] Embodiment 40 is an orthodontic article according to Embodiments 36 to 39, wherein the photopolymerizable composition comprises 30% to 40% by weight of the first polymerization product of the component and 55% to 60% by weight of (meth)acrylate reactive diluent.

[0276] Embodiment 41 is an orthodontic article according to Embodiments 36 to 40, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, and 5% to 10% by weight of a crosslinking agent.

[0277] Embodiment 42 is an orthodontic article according to Embodiments 36 to 41, wherein the photopolymerizable composition comprises 30% to 40% by weight of the first polymerization product of the component, 55% to 60% by weight of (meth)acrylate reactive diluent and 1% to 10% by weight of methacrylic acid.

[0278] Embodiment 43 is an orthodontic article according to Embodiments 36 to 42, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent and 5% to 12% by weight of a second polymerization product of the component.

[0279] Embodiment 44 is an orthodontic article according to Embodiments 36 to 43, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 45% to 60% by weight of a (meth)acrylate reactive diluent, a photoinitiator, 5% to 12% by weight of a second polymerization product of the component, and 5% to 10% by weight of a crosslinking agent.

[0280] Embodiment 45 is an orthodontic article according to Embodiments 36 to 44, wherein the photopolymerizable composition comprises 30% to 40% by weight of a first polymerization product of the component, 55% to 60% by weight of a (meth)acrylate reactive diluent, 5% to 12% by weight of a second polymerization product of the component, and 1% to 10% by weight of methacrylic acid.

[0281] Embodiment 46 is an orthodontic article according to Embodiments 36 to 45, wherein the first polymerization product of the component comprises a polyether polyamine having a weight-average molecular weight (M) of 300 g / mol to 6,500 g / mol as determined by gel permeation chromatography. w ) of polyether triamine.

[0282] Implementation scheme 47 is an orthodontic article according to implementation scheme 46, wherein the polyether polyamine is a polyether triamine having the structure of formula II:

[0283] Where n is 1 to 10; x is 1 to 84; y is 1 to 84; and z is 1 to 84.

[0284] Embodiment 48 is an orthodontic article according to Embodiments 36 to 45, wherein the first polymerization product of the component comprises a polyether polyamine having an M content of 200 g / mol to 4,000 g / mol as determined by gel permeation chromatography. n Polyether diamine.

[0285] Implementation scheme 49 is an orthodontic article according to implementation scheme 48, wherein the polyether polyamine is a polyether diamine having the structure of formula I:

[0286] Where x ranges from 4 to 90.

[0287] Embodiment 50 is an orthodontic article according to Embodiments 36 to 49, wherein the first polymerization product of the component is present in an amount of 40% to 50% by weight based on the total weight of the photopolymerizable composition.

[0288] Embodiment 51 is an orthodontic article according to Embodiments 36 to 50, wherein the first polymerization product of the component is present in an amount of 30% to less than 40% by weight based on the total weight of the photopolymerizable composition.

[0289] Embodiment 52 is an orthodontic article according to Embodiments 36 to 51, wherein the (meth)acrylate reactive diluent is present in an amount of 55% to 60% by weight based on the total weight of the photopolymerizable composition.

[0290] Embodiment 53 is an orthodontic article according to embodiments 36 to 52, wherein the second polymerization product of the component is present in an amount of 5% to 12% by weight based on the total weight of the photopolymerizable composition.

[0291] Embodiment 54 is an orthodontic article according to embodiments 36 to 53, wherein the crosslinking agent is present in an amount of 5% to 10% by weight based on the total weight of the photopolymerizable composition.

[0292] Embodiment 55 is an orthodontic article according to embodiments 36 to 54, wherein the polymerization product of the photopolymerizable composition exhibits each of 15 MPa or greater tensile stress at break, 300 MPa or greater Young's modulus, and 65% or greater tensile strain at break.

[0293] Embodiment 56 is an orthodontic article. This orthodontic article is a polymerization product of a photopolymerizable composition. The photopolymerizable composition comprises 30% to 50% by weight of a (meth)acrylate reactive diluent and 40% to 60% by weight of a component polymerization product. The component polymerization product comprises a polymeric glycol and acrylonitrile. The photopolymerizable composition polymerization product has a Tg of 50°C or higher, more preferably above 80°C or 90°C. g .

[0294] Implementation scheme 57 is an orthodontic article according to implementation scheme 56, wherein acrylonitrile includes 2-vinyl-4,4-dimethylacylonitrile.

[0295] Embodiment 58 is an orthodontic article according to Embodiments 56 to 57, wherein the photopolymerizable composition further comprises a crosslinking agent.

[0296] Implementation scheme 59 is an orthodontic article according to implementation scheme 58, wherein the crosslinking agent includes the polymerization product of polyamine and acrylonitrile.

[0297] Embodiment 60 is an orthodontic article according to Embodiments 56 to 59, wherein the polymeric diol has a number-average molecular weight (Mn) of 200 g / mol to 5,000 g / mol or 400 g / mol to 3,000 g / mol as determined by gel permeation chromatography. n ).

[0298] Implementation scheme 61 is an orthodontic article according to implementation schemes 56 to 60, wherein the polymeric diol includes polyester diol, polycarbonate diol, polyether diol, polyolefin diol or a combination thereof.

[0299] Implementation scheme 62 is an orthodontic article according to implementation schemes 56 to 61, wherein the polymeric diol includes polycarbonate diol.

[0300] Implementation scheme 63 is an orthodontic article according to implementation schemes 56 to 62, wherein the polymeric diol includes polycarbonate diol of formula III.

[0301] Each of R1 and R2 in each (O-R1-OC(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and the average number of carbon atoms in all combinations of R1 and R2 groups is 4 to 10, and m is an integer from 2 to 23.

[0302] Embodiment 64 is an orthodontic article according to embodiments 56 to 63, wherein the photopolymerizable composition further comprises acrylonitrile.

[0303] Embodiment 65 is an orthodontic article according to embodiments 56 to 64, wherein the photopolymerizable composition further comprises 2-vinyl-4,4-dimethylacyl lactone (VDM).

[0304] Implementation Scheme 66 is an orthodontic product according to Implementation Schemes 56 to 65, wherein the (meth)acrylate reactive diluent includes at least one of isobornyl methacrylate, isobornyl acrylate, methyl methacrylate, tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate or tricyclodecanediethanol diacrylate.

[0305] Embodiment 67 is an orthodontic article according to Embodiments 36 to 66, wherein the photopolymerizable composition further comprises at least one of methacrylic acid, an antioxidant, or a UV absorber.

[0306] Embodiment 68 is an orthodontic article according to Embodiments 56 to 67, wherein the polymerization product of the photopolymerizable composition exhibits each of a tensile stress at break of 15 MPa or greater and a tensile strain at break of 65% or greater.

[0307] Embodiment 69 is an orthodontic article according to Embodiments 56 to 68, wherein the polymerization product of the photopolymerizable composition exhibits a Young's modulus of 175 MPa or greater.

[0308] Implementation Scheme 70 is an orthodontic article according to Implementation Schemes 56 to 69, wherein the polymerization product of the photopolymerizable composition exhibits a water absorption rate of no more than 1.5% by weight after being soaked in deionized water at a temperature of 20°C to 25°C for 72 hours.

[0309] Implementation scheme 71 is an orthodontic article according to implementation schemes 56 to 70, wherein the polymerization product of the photopolymerizable composition exhibits a peak loss modulus at a temperature below 20°C and a tanδ peak value > 70°C.

[0310] Embodiment 72 is a method for manufacturing an orthodontic article. The method includes a) obtaining a photopolymerizable composition; b) selectively curing the photopolymerizable composition; and c) repeating steps a) and b) to form multiple layers and produce an orthodontic article. The photopolymerizable composition includes the composition according to the embodiments herein.

[0311] Embodiment 73 is the method according to Embodiment 72, wherein the method optionally includes curing the remaining unpolymerized photopolymerizable composition after step (c).

[0312] Embodiment 74 is the method according to Embodiment 73 or Embodiment 74, wherein the method optionally further includes removing at least a portion of the remaining unpolymerized photopolymerizable composition after step (c).

[0313] Embodiment 75 is the method according to Embodiments 72 to 74, wherein photochemical radiation (including UV radiation, electron beam radiation, visible light radiation, or combinations thereof) is used to cure the photopolymerizable composition.

[0314] Implementation scheme 76 is the method according to implementation scheme 75, wherein photochemical radiation can penetrate the wall of the container holding the photopolymerizable composition.

[0315] Embodiment 77 is the method according to Embodiment 75 or Embodiment 76, wherein the photopolymerizable composition absorbs 90% or more of photochemical radiation at a distance of 150 micrometers.

[0316] Embodiment 78 is the method according to any one of Embodiments 72 to 77, wherein the photopolymerizable composition is cured through the bottom plate of a container containing the photopolymerizable composition.

[0317] Implementation scheme 79 is a method according to any one of implementation schemes 72 to 78, the method further comprising post-curing the orthodontic article using photochemical radiation.

[0318] Implementation scheme 80 is the method of any one of implementation schemes 72 to 79, wherein the method includes the tank polymerization of the photopolymerizable composition.

[0319] Implementation scheme 81 is a method according to any one of implementation schemes 72 to 80, the method further comprising subjecting the orthodontic article to heat treatment.

[0320] Embodiment 82 is a method according to any one of Embodiments 72 to 81, wherein the orthodontic article exhibits each of a tensile stress at break of 15 MPa or greater, a Young's modulus of 300 MPa or greater, and a tensile strain at break of 65% or greater.

[0321] Implementation scheme 83 is the method according to any one of implementation schemes 72 to 82, wherein the orthodontic article exhibits a Young's modulus of 175 MPa or greater.

[0322] Implementation scheme 84 is the method according to any one of implementation schemes 72 to 83, wherein the orthodontic article exhibits a water absorption rate of no more than 1.5% by weight after being soaked in deionized water at a temperature of 20°C to 25°C for 72 hours.

[0323] Embodiment 85 is the method according to any one of Embodiments 72 to 84, wherein the polymerization product of the photopolymerizable composition exhibits a peak loss modulus at a temperature below 20°C and a tanδ peak value > 70°C.

[0324] Implementation scheme 86 is a method according to any one of implementation schemes 72 to 85, wherein the orthodontic article contains 1.5% by weight or less of an extractable component.

[0325] Implementation scheme 87 is a method according to any one of implementation schemes 72 to 86, wherein the orthodontic product includes dental restoration tools, molds, dentures, retainers or orthodontic appliances.

[0326] Implementation scheme 88 is a method according to any one of implementation schemes 72 to 87, wherein the orthodontic product includes dental prosthetic tools or molds.

[0327] Embodiment 89 is a method comprising a) receiving a digital object by a manufacturing apparatus having one or more processors, the digital object including data specifying multiple layers of an orthodontic article; and b) generating an orthodontic article based on the digital object using the manufacturing apparatus via an additive manufacturing process. The orthodontic article includes reaction products of a photopolymerizable composition according to embodiments herein. The polymerization reaction products of the photopolymerizable composition have the shape of the orthodontic article.

[0328] Embodiment 90 is a system comprising a) a display showing a 3D model of an orthodontic article; and b) one or more processors that, in response to a user-selected 3D model, cause a 3D printer to create a physical object of the orthodontic article. The orthodontic article comprises reaction products of a photopolymerizable composition according to embodiments herein. The polymerization reaction products of the photopolymerizable composition have the shape of the orthodontic article.

[0329] Embodiment 91 is a dental restoration tool or mold comprising a polymerization product of a photopolymerizable composition according to embodiments herein.

[0330] Embodiment 92 is a non-transitory machine-readable medium comprising data representing a three-dimensional model of an orthodontic article, which, when accessed by one or more processors interfaced with a 3D printer, causes the 3D printer to produce the orthodontic article, the orthodontic article comprising reaction products of a photopolymerizable composition according to embodiments herein. The polymerization reaction products of the photopolymerizable composition have the shape of the orthodontic article.

[0331] Embodiment 93 is a method comprising: a) retrieving data representing a 3D model of an orthodontic article from a non-transitory machine-readable medium; b) executing a 3D printing application interfaced with a manufacturing apparatus using the data by one or more processors; and c) generating a physical object of an orthodontic article by the manufacturing apparatus. The orthodontic article comprises reaction products of a photopolymerizable composition according to embodiments herein. The polymerization reaction products of the photopolymerizable composition have the shape of an orthodontic article.

[0332] Example

[0333] The following embodiments further illustrate the purpose and advantages of this disclosure, but the specific materials and quantities listed in these embodiments, as well as other conditions and details, should not be construed as unduly limiting this disclosure.

[0334] Material

[0335] Unless otherwise specified, all parts, percentages, ratios, etc., in the embodiments and the remainder of the specification are by weight. Table 1 below lists the materials used in the embodiments and their sources.

[0336]

[0337] Preparation Examples

[0338] Synthesis of urea functional components

[0339] Synthesis of polypropylene glycol-based polyurea (meth)acrylate polymers

[0340] The urea functional component of the composition was prepared by the methods explained herein, as shown in Schemes 1 and 2. Scheme 1 illustrates the synthesis of a polymerization product from polyether diamine and isocyanate monomers, wherein the molar ratio of polyether diamine to isocyanate monomers is 1:2. Similarly, Scheme 2 illustrates the synthesis of a polymerization product from polyether triamine and isocyanate monomers, wherein the molar ratio of polyether triamine to isocyanate monomers is 1:3.

[0341]

[0342] Preparation of urea methacrylate T3000 (PE1)

[0343] Urea methacrylate T3000 (PE1) was prepared by the synthetic method described in Scheme 2 above. Jeffamine T3000 (30.00 g, 10.0 mmol) was added to a two-necked round-bottom flask equipped with a top stirrer and a dropping funnel. The flask was then immersed in a water bath at room temperature. IEM (pure, 4.75 g, 30.06 mmol) was added dropwise to the flask with stirring. After adding the IEM, the reaction solution was stirred for 30 minutes. The resulting product was then subjected to... 1 ¹H NMR analysis showed that the amine reacted completely to form PE1. PE1 can be used without further purification.

[0344] Similarly, the samples in Table 2 below were prepared by the methods described above, as shown in Scheme 1 or 2, with the amounts and types of materials used as described herein. PE3 to PE6 were prepared by Scheme 1; and PE2 and PE7 were prepared by Scheme 2.

[0345]

[0346] Synthesis of Acrylamide Functional Components

[0347] Acrylamide-functionalized polymer (PE8) was synthesized in a solvent from C-2050 glycol and VDM.

[0348] Kuraray C-2050 diol (50.1 g, 0.051 mol -OH), VDM (8.3 g, 0.0593 mol, 1.17 equivalents relative to -OH), DBU (0.15 mL, 0.155 g, 0.02 equivalents relative to -OH), and 280 mL DCM were added to a round-bottom flask equipped with a magnetic stirrer. The flask was also equipped with a reflux condenser, a dry air inlet, and a bubbler, and the reaction mixture was heated to reflux. 1 ¹H NMR was used to monitor the crude reaction using the resonance corresponding to the -CH₂-OH end group of the methylene polymer, and incomplete reaction was detected after 24 hours. At this point, additional DBU (0.15 mL, 0.155 g, 0.02 equivalents relative to -OH) was added. The reaction mixture was then heated for another 4 hours, and the reaction was monitored by ¹H NMR. 1 1H NMR analysis revealed that the end groups of the polymer were fully functionalized. Solvent removal under vacuum yielded a pure acrylamide-functionalized polymer (PE8).

[0349] Acrylamide-functionalized polymer (PE9) was synthesized from C-2050 diol and pure VDM.

[0350] Kuraray C-2050 diol (136 g, 0.139 mol -OH), VDM (22.4 g, 0.161 mol, 1.16 equivalents relative to -OH), DBU (0.5 mL, 0.51 g, 0.0033 mol, 0.024 equivalents relative to -OH), and 100 mL DCM were added to a 250 mL round-bottom flask equipped with a magnetic stirrer. The flask was also equipped with a reflux condenser, a dry air inlet, and a bubbler, and the reaction mixture was heated to 80 °C. 1 ¹H NMR was used to monitor the crude reaction using the resonance corresponding to the -CH₂-OH end group of the methylene polymer, and after 4 hours the reaction was found to be >95% complete, thus yielding the acrylamide-functionalized polymer (PE9). At this point, the reaction mixture was diluted with IBOMA (111 g, target 41 wt%), and the mixture was used to prepare the resin composition.

[0351] Synthesis of crosslinking agents

[0352] Acrylamide crosslinking agent (PE10) synthesized from polyamines and VDM.

[0353] Baxxodur EC301 (5.0 g, 0.043 mol - NH2) and VDM (6.35 g, 0.045 mol, 1.05 equivalent to NH2) were added to a three-necked round-bottom flask. The flask was equipped with a top stirrer, a dry air inlet / bubbler, and a thermocouple, and the reaction mixture was heated to 80°C. 1 ¹H NMR was used to monitor the crude reaction using the resonance corresponding to the -CH₂-NH₂ end group of the methylene polymer, and incomplete reaction was detected after 24 hours. At this point, additional DBU (0.15 mL, 0.155 g, 0.02 equivalents relative to -OH) was added. The reaction mixture was then heated for another 4 hours, and the reaction was monitored by ¹H NMR. 1 H NMR revealed that >95% of the end groups of the polymer were functionalized, thus producing the PE10 crosslinking agent.

[0354] succinic anhydride-derived amides - Synthesis of methacrylates

[0355] Synthesis of C-2050-amide-methacrylate using succinic anhydride (PE11)

[0356] 10.0 g of C-2050 diol and 10.0 g of IBOMA as a diluent were placed in a round-bottom flask equipped with a top stirrer to obtain a viscous, clear solution. 0.98 g of succinic anhydride and 0.0093 g (1%) of p-toluenesulfonic acid were added to this solution. The reaction mixture was then heated at 65 °C and stirred overnight. A small amount of succinic anhydride sublimated to the neck of the flask and was removed after the solution cooled to room temperature. Based on the final product... 1 The conversion was calculated using the ratio of the resonance of the terminal methylene group derived from succinic anhydride in the product at 2.58 ppm to 2.75 ppm to the resonance of unreacted succinic anhydride at 3.02 ppm in the 1H NMR spectrum. Overnight reaction yields reached 95% to 98%. Unreacted succinic anhydride was quenched by adding 1 equivalent of hexylamine to the product. The final product... 1 The disappearance of the resonance of succinic anhydride in H NMR confirms that the succinic anhydride has been completely consumed and the product polyol C2050-acid has been fully formed.

[0357]

[0358] To synthesize polyol C2050 amide ester dimethacrylate, 10.5 g of the previous product (5 g equivalent of polyol C2050-acid) was added to a brown vial equipped with a stir bar. The vial was then heated at 60 °C with stirring. 0.69 g of 2-isocyanoethyl methacrylate (IEM) was added dropwise to the flask to initiate the reaction. The viscosity of the reaction mixture decreased with the addition of IEM. After a few minutes, bubble formation was observed, and the viscosity of the reaction mixture slowly increased. The reaction was maintained at 60 °C overnight. 1 ¹H NMR spectroscopy was used to track the reaction progress by observing the disappearance of the IEM resonance. Overnight conversion reached >99%, and excess IEM was quenched by adding 1 equivalent of hexylamine. The exact percentages of IBOMA and polyol C-2050-amide dimethacrylate were determined by thermogravimetric analysis (TGA), in which approximately 5 mg of product was heated to 450 °C at a rate of 10 °C / min. The weight percentage of IBOMA was calculated based on the first weight loss percentage from the TGA curve, and the weight percentage of polyol C-2050-amide dimethacrylate was based on the remaining weight loss percentage.

[0359] Amide-methacrylate (PE12) was synthesized from Jeffamine T3000 and succinic anhydride.

[0360] Jeffamine T3000 (10.0 g) and succinic anhydride (1.0 g) were added to a brown vial equipped with a stir bar. The reaction mixture was then heated at 65°C and stirred overnight. Based on the final product... 1The conversion was calculated using the ratio of the resonance of the terminal methylene group derived from succinic anhydride in the product at 2.58 ppm to 2.75 ppm to the resonance of unreacted succinic anhydride at 3.02 ppm in the 1H NMR spectrum. Overnight reaction yields reached 95% to 98%. Unreacted succinic anhydride was quenched by adding 1 equivalent of hexylamine to the product. The final product... 1 The disappearance of the resonance of succinic anhydride in H NMR confirmed that the succinic anhydride had been completely consumed and that Jeffamine T3000-acid had been formed.

[0361] To synthesize Jeffamine T3000 amide ester dimethacrylate, 10.5 g of the previous product (5 g equivalent of Jeffamine T3000-acid) was added to a brown vial equipped with a stir bar. The vial was then heated at 60 °C with stirring. 0.69 g of 2-isocyanoethyl methacrylate (IEM) was added dropwise to the flask, initiating the reaction. The viscosity of the reaction mixture decreased with the addition of IEM. After a few minutes, bubble formation was observed, and the viscosity of the reactants slowly increased. The reaction mixture was then kept at 60 °C overnight. 1 1H NMR technology tracks the reaction progress by observing the disappearance of IEM resonances. Overnight conversion reached >99%, and excess IEM was quenched by adding 1 equivalent of hexylamine.

[0362] Used in the preparation of formulations / General procedures for photopolymerizable compositions

[0363] General procedure for preparing urea-based compositions

[0364] The composition is prepared by weighing the components (shown in Tables 3 to 7) in an amber-colored wide-mouth bottle and then rolling them on a roller (OLDE MIDWAY PRO 18) at room temperature until they are completely mixed.

[0365]

[0366] General procedure for preparing acrylamide-based compositions

[0367] To prepare the resin for casting, acrylamide-functionalized polymer, IBOMA, TPO, BHT, and Tinuvin 326 were added to a 10-ounce brown bottle. To completely dissolve the solids and mix the resin, the bottle was capped and left overnight on a tubular roller at room temperature before use.

[0368] All the following resins were prepared using the same procedure, with appropriate amounts added to prepare copolymers having the weight percentage of each monomer as shown in Tables 8 to 9.

[0369]

[0370] General procedures for casting and curing

[0371] To prepare samples for mechanical testing, the formulated composition (resin mixture) was poured into either a silicone dog-bone mold (1 mm thick V-shaped mold, ASTM D638-14) for tensile testing or a silicone rectangular mold (1 mm thick, trimmed to 20 mm × 6 mm × 1 mm before use) for dynamic mechanical thermal analysis (DMTA) and dynamic mechanical analysis (DMA). The filled mold was placed between two glass plates and cured for 120 seconds in an Asiga Pico Flash post-curing apparatus. After demolding, the sample was cured on the back side for another 120 seconds in the same apparatus. The sample was then cured in a Clearstone CA3200 controlled atmosphere curing chamber equipped with 365 nm, 385 nm, and 405 nm LEDs, through which nitrogen gas was passed. The sample was then held in an oven set to 100 °C for 1 hour to remove any residual unreacted monomers.

[0372] General procedure for tensile testing

[0373] Using an Instron 6800 general-purpose testing system (Instron, Norwood, MA) equipped with a 5kN force sensor, the instrument was tested at 5mm min. -1 The tensile strength of dog-bone shaped specimens was determined by uniaxial tensile testing (ASTM D638-14 Type V) at the displacement rate. The initial clamps were 1 inch (2.5 cm), and the gauges were also set to 1 inch (2.5 cm). Six replicates of each composition were tested, and the average value was reported. The data were analyzed, and the ultimate tensile strength (tensile stress at break), tensile strain at break, and Young's modulus were determined using Bluehill general-purpose software. The tensile testing method is very similar to ASTM D638-14; however, in all embodiments, the Young's modulus was approximated by using crosshead velocity to approximate strain rather than by using an extensometer.

[0374]

[0375] General procedure for using dynamic mechanical analysis to terminate loss modulus and tanδ

[0376] DMTA was performed using a DMA 850 instrument (TA instrument) to obtain the storage modulus (E'), loss modulus (E"), tanδ, and glass transition temperature (T). g T g The peak value of tanδ is defined, and the data for each sample are summarized in Table 12.

[0377]

[0378] General Procedure for Terminating Stress Relaxation and Strain Recovery Using Dynamic Mechanical Analysis

[0379] Stress relaxation and strain recovery of selected samples were measured on a DMA 850 (TA instrument) at 95% humidity and 37°C. Samples were immersed overnight in DI water, then equilibrated in a DMA chamber with a 0N preload for 5 minutes at 95% humidity and 37°C. Stress relaxation was then measured at 1% strain for 11 hours, followed by strain recovery at 0 MPa stress for 1 hour at 95% humidity and 37°C. The results are summarized in Tables 13 and 14.

[0380]

[0381] Water absorption test of acrylamide samples

[0382] Water swelling tests were conducted on crosslinked resin formulations EX-24, EX-25, and EX-26. The resins were cured using the procedure described for preparing dog bone specimens for mechanical testing. For each resin composition, three specimens were weighed, dried, and then immersed in deionized water. After 72 hours, the specimens were removed, patted dry, and reweighed. The percentage of water absorption was obtained by dividing the weight difference by the original weight of the rod. The results are shown in Table 15 below.

[0383]

[0384] General Procedures for Urea-Based Additive Manufacturing Resin Formulations

[0385] The formulation is prepared by weighing the components (shown in Table 16) in an amber-colored wide-mouth bottle and then rolling them on a roller (OLDE MIDWAY PRO 18) at room temperature until they are completely mixed.

[0386]

[0387] General procedures for formulating resins for additive manufacturing

[0388] Unless otherwise specified, all 3D printed embodiments were fabricated on an Asiga Max X printer (Asiga USA, Anaheim Hills, California) with a 385nm LED light source or a Rapidshape D90 (Rapid Shape GmbH, Heimsheim, Germany) using a 385nm LED light source. The project's STL file was loaded into the software, and the support structure was generated as needed. The Asiga printer settings were as follows: slice thickness = 100μm, burn-in layers = 5, separation speed = 1.5mm / s, and 1 slide per layer. For the Asiga Max X printer, the normal exposure time was determined through a cure depth study of the printing resin, in which the resin pool was exposed to the printer light source for a period of time to cure a solid disk with a diameter of 0.5cm. Exposure times ranged from 1s to 15s, with 1s intervals between each exposure. The cured disk was then washed with iPA to remove excess resin and allowed to dry. The thickness of the cured disc was measured using a thickness gauge (Mitutoyo 543, MiSUMi USA, Schaumburg, IL). Normal exposure time was determined to be the time during which the cured thickness was measured to be 100 μm, and burn-in exposure time was twice the normal exposure time. Typical normal exposure time was 4.0 s, and typical burn-in exposure time was 8.0 s. Printing parameters for the Rapidshape D90 are listed in Table 17. After printing, the photopolymer was centrifuged at 800 rpm for 4 minutes in a Beckman Coulter Avanti J-20 XP (GMI, Ramsey, MN), and then post-cured in a Clearstone CA3200 controlled atmosphere curing chamber equipped with 365 nm, 385 nm, and 405 nm LEDs, with nitrogen passing through the chamber for 5 minutes. Finally, the printed object is baked in a vacuum oven at 100°C for 1 hour to remove any unreacted monomers.

[0389]

[0390] Measurement of resin viscosity

[0391] The resin viscosity of composition EX-23 was measured on a TA Instruments Discovery DHR rheometer equipped with a 40 mm 2° upper cone and Peltier heating / cooling enabled on the base plate. The sample was equilibrated at the set temperature for a holding time of 1 minute, followed by frequency sweeps between 1 / s and 100 / s. The viscosity reported at each temperature represents the best fit of the frequency sweep. The results are reported in Table 18 below.

[0392]

[0393] Weight-average molecular weight (Mw) was determined using gel permeation chromatography (GPC).

[0394] The GPC apparatus consisted of an Agilent Technologies 1260 Infinity II liquid chromatography system (comprised of an isocratic pump, autosampler, column chamber, and variable wavelength UV / vis detector) from Agilent Technologies, Santa Clara, CA, operating at a flow rate of 1.0 mL / min. The SEC column assembly comprised two PLgel 5 μm MIXED-C columns (300 mm long × 7.5 mm inner diameter) and a PLgel 5 μm guard column (50 mm long × 7.5 mm inner diameter), all from Agilent Technologies. Detection was performed using a miniDAWN 3-angle light scattering detector and an OPTILAB differential refractive index detector, both from Wyatt Technology Corporation, Santa Barbara, CA. Data were collected and analyzed using ASTRA software version 8 from Wyatt Technologies. The column chamber, UV / vis detector, and differential refractive index detector were all set to 40 °C. Solvents and eluents (or mobile phases) consisted of OMNISOLV grade tetrahydrofuran (stabilized with 250 ppm butylated hydroxytoluene) (from EMD Millipore Corporation, Burlington, MA). Relative molar mass data were determined from DIR data and are reported relative to EasiCal PS-1 PL2010-0501 and PL2010-0505 polystyrene standards (PS) from Agilent Technologies, in the range of Mp = 580 to Mp = 2,403,000 g / mol. Calibration curves were constructed in ASTRA software using all PS standards except Mp = 6,570,000, as this exceeded the upper limit of the column's molecular weight resolution.

[0395]

[0396] Baxxodur EC301 is reported to have a molecular weight of 230 g / mol, and Jeffamine T5000 has a molecular weight of 5000. As shown in Table 19 above, the measured Mw may differ slightly from the value reported by the manufacturer.

[0397] All patents and patent applications mentioned above are expressly incorporated herein by reference. The above embodiments are illustrative of the invention and other configurations are also possible. Therefore, the invention should not be considered limited to the embodiments described in detail above and shown in the accompanying drawings, but only by the reasonable scope of the appended claims and their equivalents.

Claims

1. A photopolymerizable composition, said photopolymerizable composition comprising: At least one (meth)acrylate reactive diluent, ranging from 30% to 60% by weight; Photoinitiators; and Polymerization products comprising 30% to 60% by weight of components including urea-functionalized or acrylamide-functionalized components. When measured by a cone-plate rheometer at a temperature of 20°C and a shear rate of 1 1 / s, the photopolymerizable composition exhibits a dynamic viscosity of less than 5000 centipoise (cP).

2. The photopolymerizable composition according to claim 1, wherein the component comprises 5% by weight or less of a polyurethane component.

3. The photopolymerizable composition according to claim 1 or claim 2, wherein the photopolymerizable composition comprises: Based on the total weight of the photopolymerizable composition, 45% to 60% by weight of the at least one (meth)acrylate reactive diluent; The first polymerization product comprises 30% to 50% by weight of the component based on the total weight of the photopolymerizable composition, said component including: First polyether polyamine; and Alkene unsaturated isocyanate functional monomers; Optionally up to 10% by weight of a glass transition temperature (T) of 50°C or higher g Crosslinking agents; and Optionally, a second polymerization product comprising up to 12% by weight of a component based on the total weight of the photopolymerizable composition, said component comprising: Second polyether polyamine; and Alkene unsaturated isocyanate functional monomers; The conditions are: A) When the first polymerization product of the component is present in an amount of 40% to 50% by weight, the composition comprises no more than 5% by weight of the second polymerization product of the component; and B) When the first polymerization product of the component is present in an amount of 30% by weight to less than 40% by weight, the composition comprises at least one of the following: i) 55% to 60% by weight of the (meth)acrylate reactive diluent; ii) 5% to 12% by weight of the second polymerization product; iii) 5% to 10% by weight of the crosslinking agent; or iv) 1% to 10% by weight of methacrylic acid.

4. The photopolymerizable composition according to claim 3, wherein the polyether polyamine has a weight-average molecular weight (M) of 300 g / mol to 6,500 g / mol as determined by gel permeation chromatography. w ) of polyether triamine.

5. The photopolymerizable composition according to any one of claims 3 to 4, wherein the polyether polyamine is a polyether triamine having the structure of formula II: ； Where n is 1 to 10; x is 1 to 84; y is 1 to 84; and z is 1 to 84.

6. The photopolymerizable composition according to claim 3, wherein the polyether polyamine is a polyether diamine having a Mn content of 200 g / mol to 4,000 g / mol as determined by gel permeation chromatography.

7. The photopolymerizable composition according to any one of claims 3 to 4 or 6, wherein the polyether polyamine is a polyether diamine having the structure of formula I: ； Where x ranges from 4 to 90.

8. The photopolymerizable composition according to any one of claims 1 to 7, wherein the first polymerization product of the component is present in an amount of 40% to 50% by weight based on the total weight of the photopolymerizable composition.

9. The photopolymerizable composition according to any one of claims 3 to 7, wherein the first polymerization product of the component is present in an amount of 30% by weight to less than 40% by weight based on the total weight of the photopolymerizable composition.

10. The photopolymerizable composition according to claim 9, wherein the (meth)acrylate reactive diluent is present in an amount of 55% to 60% by weight based on the total weight of the photopolymerizable composition.

11. The photopolymerizable composition according to claim 9 or claim 10, wherein the second polymerization product of the component is present in an amount of 5% to 12% by weight based on the total weight of the photopolymerizable composition.

12. The photopolymerizable composition according to any one of claims 9 to 11, wherein the crosslinking agent is present in an amount of 5% to 10% by weight based on the total weight of the photopolymerizable composition.

13. The photopolymerizable composition according to claim 1 or claim 2, wherein the photopolymerizable composition comprises: 30% to 50% by weight of the (meth)acrylate reactive diluent; and The polymerization product comprising 40% to 60% by weight of a component, wherein the component comprises: Polymeric diols; and Acetyl lactone.

14. The photopolymerizable composition of claim 13, wherein the acrylonitrile comprises 2-vinyl-4,4-dimethylacylonitrile.

15. The photopolymerizable composition according to claim 13 or claim 14, wherein the photopolymerizable composition further comprises a crosslinking agent.

16. The photopolymerizable composition according to claim 15, wherein the crosslinking agent comprises the polymerization product of a polyamine and an acrylonitrile.

17. The photopolymerizable composition according to any one of claims 13 to 16, wherein the polymeric diol has a number-average molecular weight (Mn) of 200 g / mol to 5,000 g / mol or 400 g / mol to 3,000 g / mol as determined by gel permeation chromatography.

18. The photopolymerizable composition according to any one of claims 13 to 17, wherein the polymerizable diol comprises polyester diol, polycarbonate diol, polyether diol, polyolefin diol, or a combination thereof.

19. The photopolymerizable composition according to any one of claims 13 to 17, wherein the polymerizable diol comprises polycarbonate diol.

20. The photopolymerizable composition according to any one of claims 13 to 19, wherein the photopolymerizable composition further comprises acrylonitrile.

21. The photopolymerizable composition according to any one of claims 1 to 20, wherein the (meth)acrylate reactive diluent comprises at least one of isoborneol methacrylate, isoborneol acrylate, methyl methacrylate, tert-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate or tricyclodecanediethanol diacrylate.

22. The photopolymerizable composition according to any one of claims 1 to 21, wherein the photopolymerizable composition further comprises at least one of methacrylic acid, an antioxidant, or a UV absorber.

23. An orthodontic article comprising a polymerization product of a photopolymerizable composition, the photopolymerizable composition comprising: Based on the total weight of the photopolymerizable composition, at least one (meth)acrylate reactive diluent comprises 45% to 60% by weight. Photoinitiator; The first polymerization product comprises 30% to 50% by weight of the component based on the total weight of the photopolymerizable composition, said component including: First polyether polyamine; and Alkene unsaturated isocyanate functional monomers; Optionally up to 10% by weight of a glass transition temperature (T) of 50°C or higher g Crosslinking agents; and Optionally, a second polymerization product comprising up to 12% by weight of a component based on the total weight of the photopolymerizable composition, said component comprising: Second polyether polyamine; and Alkene unsaturated isocyanate functional monomers; The conditions are: A) When the first polymerization product of the component is present in an amount of 40% to 50% by weight, the composition comprises no more than 5% by weight of the second polymerization product of the component; and B) When the first polymerization product of the component is present in an amount of 30% by weight to less than 40% by weight, the composition comprises at least one of the following: i) 55% to 60% by weight of the (meth)acrylate reactive diluent; ii) 5% to 12% by weight of the second polymerization product; or iii) 5% to 10% by weight of the crosslinking agent; or iv) 1% to 10% by weight of methacrylic acid; The polymerization product has a T value of 50°C or higher. g .

24. The orthodontic article of claim 23, wherein the polymerization product of the photopolymerizable composition exhibits each of 15 MPa or greater tensile stress at break, 300 MPa or greater Young's modulus, and 65% or greater tensile strain at break.

25. An orthodontic article or dental prosthetic tool, said orthodontic article or dental prosthetic tool comprising a polymerization product of a photopolymerizable composition, said photopolymerizable composition comprising: 30% to 50% by weight of (meth)acrylate reactive diluent; Photoinitiator; and The polymerization product comprising 40% to 60% by weight of a component, said component comprising: Polymeric diols; and Acetyl lactone, The polymerization product has a T value of 50°C or higher. g .

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