Photopolymerizable compositions containing polyurethane methacrylate polymers prepared using polycarbonate diols, articles, and methods

Abstract

The present disclosure provides a photopolymerizable composition. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a glass transition temperature of 125 degrees Celsius or greater. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate; iii) a polycarbonate diol; and iv) a catalyst. The polymerization reaction product includes a polyurethane methacrylate polymer. Often, the polycarbonate diol has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol, or the polyurethane methacrylate polymer has a weight average molecular weight of 8,000 g / mol or greater. Also provided is an article comprising a photopolymerizable composition reaction product. The present disclosure further provides an article and a method for manufacturing the article. A method is further provided that includes receiving, by a manufacturing device having one or more processors, a digital object including data defining the article, and generating the article based on the digital object using the manufacturing device by an additive manufacturing process. A system is also provided that includes a display that displays a 3D model of the article, and one or more processors that cause a 3D printer to create a physical object of the article in response to a 3D model selected by a user.

Description

[Technical Field]

[0001] TECHNICAL FIELD The present disclosure relates generally to polymerizable compositions, articles, and methods for making articles, such as additive manufacturing methods, that include polyurethane methacrylate polymers. [Background technology]

[0002] The use of stereolithography and inkjet printing to produce three-dimensional articles has been known for a relatively long time, and these processes are generally known as so-called 3D printing (or additive manufacturing) methods. In liquid bath polymerization techniques (stereolithography being one type of liquid bath polymerization technique), a desired 3D article is fabricated from a liquid curable composition using two alternating successive steps. In the first step, a layer of the liquid curable composition, one of whose boundaries is the surface of the composition, is cured with appropriate radiation at the height of this layer and in a surface area corresponding to the desired cross-sectional area of ​​the molded article to be formed. In the second step, the cured layer is covered with a new layer of liquid curable composition, and this series of steps is repeated until a so-called green body (i.e., a gelled article) of the desired shape is achieved. This green body is often not yet fully cured and usually requires post-curing. The mechanical strength of the green body immediately after curing is also known as green strength and is relevant for subsequent processing of the printed article.

[0003] Other 3D printing technologies use ink jetted as a liquid through a printhead to form various three-dimensional articles. During operation, the printhead may deposit a curable photopolymer layer by layer. Some jet printers deposit the polymer with a support material or binder. In some instances, the build material is solid at ambient temperature and changes to a liquid when raised to the jetting temperature. In other instances, the build material is liquid at ambient temperature. Summary of the Invention

[0004] Existing printable / polymerizable resins tend to be too brittle (e.g., low elongation, short-chain crosslinking, thermosetting compositions, and / or high glass transition temperatures) for elastic oral appliances such as aligners. Aligners or other appliances made with such resins can easily break in a patient's mouth during treatment, creating pieces of material that can abrade or puncture exposed tissue or be swallowed. Such breakage can, at a minimum, interrupt treatment and have serious health consequences for the patient. Therefore, a need exists for curable liquid resin compositions that are compatible and suitable for forming elastomeric articles using 3D printing (e.g., additive manufacturing) methods. Preferably, curable liquid resin compositions used in bath polymerization 3D printing processes have low viscosity, adequate cure rates, and excellent mechanical properties in the final cured article. In contrast, compositions for inkjet printing processes need to be much lower viscosities so they can be jetted through a nozzle, which is not the case with most bath polymerization resins.

[0005] In a first aspect, a photopolymerizable composition is provided. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. In formula (I), Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -O-C(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. In formula (II), each R2 and each R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23. The polycarbonate diol either has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0006] In a second aspect, an article is provided, the article comprising the photopolymerized reaction product of the photopolymerizable composition according to the first aspect.

[0007] In a third aspect, there is provided a method of making an article, the method comprising: a) providing a photopolymerizable composition according to the first aspect; and b) polymerizing the photopolymerizable composition.

[0008] In a fourth aspect, there is provided a method of making another article, the method comprising: a) providing a photopolymerizable composition according to the first aspect; and b) selectively curing the photopolymerizable composition to form the article.

[0009] In a fifth aspect, a photopolymerizable composition is provided. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. In formula (I), Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight of 8,000 grams per mole (g / mol) or greater. In formula (II), each R2 and each R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23.

[0010] In a sixth aspect, there is provided a non-transitory machine-readable medium comprising data representing a three-dimensional model of an article, the non-transitory machine-readable medium, when accessed by one or more processors interfacing with a 3D printer, causing the 3D printer to produce an article comprising a reaction product of a photopolymerizable composition according to the first aspect.

[0011] In a seventh aspect, a method is provided, the method including: (a) obtaining data representing a 3D model of an article from a non-transitory machine-readable medium; (b) executing, by one or more processors, a 3D printing application using the data to interface with a manufacturing device; and (c) generating, by the manufacturing device, a physical object of the article, the article comprising a reaction product of a photopolymerizable composition according to the first aspect.

[0012] In an eighth aspect, another method is provided, the method comprising: (a) receiving, by a manufacturing device having one or more processors, a digital object including data defining multiple layers of an article; and (b) generating, using the manufacturing device by an additive manufacturing process, an article based on the digital object, the article comprising a reaction product of a photopolymerizable composition according to the first aspect.

[0013] In a ninth aspect, there is provided a system comprising: a display that displays a 3D model of an article; and one or more processors that cause a 3D printer to create a physical object of the article in response to the 3D model selected by a user, the article comprising a reaction product of a photopolymerizable composition according to the first aspect.

[0014] In a tenth aspect, a compound is provided, the compound having formula (VI): [ka] It is of the type.

[0015] The compound of the tenth aspect can be advantageously used as an ultraviolet absorber in the photopolymerizable compositions, articles, and methods according to the first to eighth aspects.

[0016] In an eleventh aspect, a photopolymerizable composition is provided. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional (meth)acrylate of formula (X): HO-Q-(A1)2(X); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, and A1 is independently selected from (meth)acrylic functional groups of the formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol. The polymerization reaction product comprises a polyurethane methacrylate polymer.

[0017] Drawbars and transparent tray aligners manufactured in accordance with at least certain embodiments of the present disclosure have been found to exhibit low brittleness, good resistance to water, and good toughness.

[0018] The above summary of the present disclosure is not intended to describe each disclosed embodiment or every implementation of the present disclosure. The following description more particularly exemplifies exemplary embodiments. In several places throughout this application, guidance is provided by listing examples, which examples can be used in various combinations. In each instance, the recited items serve only as a representative group and should not be interpreted as an exclusive list. [Brief explanation of the drawings]

[0019] [Figure 1] FIG. 1 is a flow diagram of a process for constructing an article using the photopolymerizable composition disclosed herein. [Figure 2] FIG. 1 is a generalized schematic diagram of a stereolithography apparatus. [Figure 3] FIG. 1 is an isometric view of a printed transparent tray aligner according to one embodiment of the present disclosure. [Figure 4] FIG. 1 is an isometric view of a printed drawbar according to one embodiment of the present disclosure. [Figure 5] 1 is a generalized schematic diagram of an apparatus in which radiation is directed through a container. [Figure 6] FIG. 6 is a block diagram of a generalized system 600 for additive manufacturing of an article. [Figure 7] FIG. 1 is a block diagram of a generalized manufacturing process for an article. [Figure 8] FIG. 1 is a high-level flow diagram of an exemplary article manufacturing process. [Figure 9] FIG. 1 is a high-level flow diagram of an exemplary article additive manufacturing process. [Figure 10] 1 is a schematic front view of an exemplary computing device 1000. FIG.

[0020] While the above-identified figures illustrate several embodiments of the present disclosure, other embodiments are also contemplated as noted herein. The figures are not necessarily drawn to scale. In all cases, this disclosure presents the invention by way of representation and not limitation. It is to be understood that numerous other modifications and embodiments can be devised by those skilled in the art which are within the scope and spirit of the principles of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0021] As used herein, "aliphatic group" refers to a saturated or unsaturated straight-chain, branched-chain, or cyclic hydrocarbon group. This term is used to encompass, for example, alkyl, alkenyl, and alkynyl groups. The term "aliphatic / alicyclic" refers to a compound or polymer containing both aliphatic and alicyclic groups.

[0022] As used herein, "alkyl" means a straight or branched chain, cyclic or non-cyclic, saturated monovalent hydrocarbon having 1 to 32 carbon atoms, e.g., methyl, ethyl, 1-propyl, 2-propyl, pentyl, and the like.

[0023] As used herein, "alkylene" means a straight-chain saturated divalent hydrocarbon group having 1 to 12 carbon atoms or a branched-chain saturated divalent hydrocarbon group having 3 to 12 carbon atoms, e.g., methylene, ethylene, propylene, 2-methylpropylene, pentylene, hexylene, and the like.

[0024] As used herein, "alkenyl" refers to a monovalent straight- or branched-chain unsaturated aliphatic group having one or more carbon-carbon double bonds, e.g., vinyl. Unless otherwise specified, alkenyl groups typically contain 1 to 20 carbon atoms.

[0025] As used herein, the term "arylene" refers to a divalent group that is carbocyclic and aromatic. The group has 1 to 5 rings that are connected, fused, or a combination thereof. The other rings may be aromatic, non-aromatic, or a combination thereof. In some embodiments, the arylene group has up to 5 rings, up to 4 rings, up to 3 rings, up to 2 rings, or 1 aromatic ring. For example, the arylene group may be phenylene.

[0026] As used herein, "aralkylene" refers to a divalent group that is an alkylene group substituted with an aryl group or an alkylene group bonded to an arylene group. The term "alkarylene" refers to a divalent group that is an arylene group substituted with an alkyl group or an arylene group bonded to an alkylene group. Unless otherwise specified, the alkyl or alkylene portion in either group typically has 1 to 20 carbon atoms, 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms. Unless otherwise specified, the aryl or arylene portion in either group typically has 6 to 20 carbon atoms, 6 to 18 carbon atoms, 6 to 16 carbon atoms, 6 to 12 carbon atoms, or 6 to 10 carbon atoms.

[0027] As used herein, in the context of a composition being essentially free of a component, the term "essentially free" refers to a composition that contains less than 1 weight percent (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 the component, based on the total weight of the composition.

[0028] As used herein, the term "glass transition temperature" (Tg) of a polymer refers to the transition from a glassy state to a rubbery state of the polymer and can be measured using differential scanning calorimetry (DSC), for example, at a heating rate of 10°C per minute in a nitrogen stream. When the Tg of a monomer is referred to, this Tg refers to the Tg of a homopolymer of that monomer. The homopolymer must be of sufficiently high molecular weight so that the Tg reaches a limiting value, and it is generally understood that the Tg of a homopolymer increases to this limiting value with increasing molecular weight. A homopolymer is also understood to be substantially free of moisture, residual monomers, solvents, and other contaminants that may affect the Tg. Suitable DSC and analytical methods are as described in Matsumoto, A. et al., J. Polym. Sci. A., Polym. Chem. 1993, 31, 2531-2539.

[0029] As used herein, the term "hardenable" refers to a material that can be hardened or solidified, for example, by heating to remove solvent, by heating to cause polymerization, chemical crosslinking, radiation-induced polymerization, or crosslinking, etc.

[0030] As used herein, "curing" means hardening or partially hardening a composition by any mechanism, such as, for example, heat, light, radiation, electron beam, microwave, chemical reaction, or a combination thereof.

[0031] As used herein, "cured" refers to a material or composition that has been hardened or partially hardened (e.g., polymerized or crosslinked) by curing.

[0032] As used herein, "integral" refers to being manufactured at the same time or not being able to be separated without damaging one or more of the (integral) parts.

[0033] As used herein, "(meth)acrylate" is shorthand for acrylate, methacrylate, or a combination thereof; "(meth)acrylic acid" is shorthand for acrylic acid, methacrylic acid, or a combination thereof; and "(meth)acrylic" is shorthand for acrylic and methacrylic groups. "Acrylic" refers to derivatives of acrylic acid, such as acrylate and methacrylate. "(Meth)acrylic" refers to a monomer or oligomer having at least one acrylic or methacrylic group, and if it contains more than one group, it refers to a monomer or oligomer that is linked by an aliphatic segment. As used herein, a "(meth)acrylate-functional compound" is, inter alia, a compound containing a (meth)acrylate moiety.

[0034] As used herein, "polymerizable composition" refers to a hardenable composition that can be polymerized upon initiation (e.g., upon initiation of free radical polymerization). Typically, prior to polymerization (e.g., hardening), the polymerizable composition has a viscosity profile consistent with the requirements and parameters of one or more 3D printing systems. For example, in some embodiments, hardening involves exposure to actinic radiation having sufficient energy to initiate a polymerization or crosslinking reaction. For example, in some embodiments, ultraviolet (UV) radiation, electron beam radiation, or both can be used. When actinic radiation can be used, the polymerizable composition is referred to as a "photopolymerizable composition."

[0035] As used herein, "resin" includes 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.

[0036] As used herein, a "residue of a diisocyanate" is the structure of a diisocyanate after the -NCO group has been removed. For example, 1,6-hexamethylene diisocyanate has the structure OCN-(CH)-NCO, and its residue Rd1 after the isocyanate group has been removed is -(CH)-.

[0037] As used herein, a "residue of a polycarbonate polyol" refers to the structure of a polycarbonate polyol after removal of its -OH groups. For example, a polycarbonate diol having the structure H(O-R1-OC(=O))mO-R2-OH has a residue (e.g., RdOH) that is -R1-OC(=O)-(O-R1-OC(=O))m-1-O-R2- (wherein each R1 and R2 in each repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and m is 2 to 23) after removal of the terminal -OH groups. Examples of R2 and R3 groups include -CH2-CH2-CH(CH3)-CH2-CH2-, -CH2-C(CH3)2-CH2-, -(CH2)6-, -(CH2)9-, and -(CH2)10-.

[0038] As used herein, "thermoplastic" refers to a polymer that flows when heated sufficiently above its glass transition point and becomes solid when cooled.

[0039] As used herein, "thermoset" refers to a polymer that is permanently set upon curing and does not flow upon subsequent application of heat. Thermoset polymers are typically crosslinked polymers.

[0040] The words "preferred" and "preferably" refer to embodiments of the present disclosure that may provide certain benefits, under certain circumstances, although other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, and is not intended to exclude other embodiments from the scope of the present disclosure.

[0041] In this application, terms such as "a," "an," and "the" are not intended to refer only to a singular entity, but include general classes, specific examples of which may be used for illustration. The terms "a," "an," and "the" are used interchangeably with the term "at least one." The phrases "at least one of" and "including at least one of" following a list refer to any one of the items in the list, and any combination of two or more items in the list.

[0042] As used herein, the term "or" is generally used in its ordinary sense including "and / or" unless the content specifically dictates otherwise.

[0043] The term "and / or" means one or all of the listed elements or a combination of any two or more of the listed elements.

[0044] Also, herein, all numbers are intended to be modified by the term "about," and preferably by the term "exactly." As used herein, the term "about," in the context of a measured quantity, refers to the variation in that measured quantity that would be expected by one of ordinary skill in the art making the measurement and exercising a level of care commensurate with the purpose of the measurement and the precision of the measuring device being used. Also herein, the recitation of numerical ranges by endpoints includes all numbers subsumed within that range and those endpoints (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0045] When used herein as a modifier to a characteristic or attribute, the term "generally," unless otherwise specified, means that the characteristic or attribute would be readily recognized by one of ordinary skill in the art, but does not require absolute precision or perfect agreement (e.g., within + / - 20% for quantifiable characteristics). The term "substantially," unless otherwise specified, means a high degree of approximation (e.g., within + / - 10% for quantifiable characteristics), but again, does not require absolute precision or perfect agreement. Terms such as identical, equal, uniform, constant, exactly, etc., are understood to be within normal tolerances or measurement error applicable to the particular situation, but do not require absolute precision or perfect agreement.

[0046] In a first aspect, the present disclosure provides a photopolymerizable composition, the photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher; b) a photoinitiator; and c) a polymerization reaction product of component The ingredients are i) a diisocyanate; ii) Formula (I): HO-Q-(A)p (I) a hydroxy-functional methacrylate of the formula: wherein Q is a polyvalent organic linking group, A is a methacrylic functional group of the formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2; iii) Formula (II): H(O-R2-OC(=O))mO-R3-OH (II) a polycarbonate diol of formula (II), wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol has a number average molecular weight (Mn) of greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn of greater than 1,000 g / mol; iv) a catalyst; and Including, The polymerization reaction product comprises a blend comprising a polymerization reaction product of a component comprising a polyurethane methacrylate polymer.

[0047] In a fifth aspect, the present disclosure provides a photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher; b) a photoinitiator; and c) a polymerization reaction product of component The ingredients are i) a diisocyanate; ii) Formula (I): HO-Q-(A)p (I) a hydroxy-functional methacrylate of the formula: wherein Q is a polyvalent organic linking group, A is a methacrylic functional group of the formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2; iii) Formula (II): H(O-R2-OC(=O))mO-R3-OH (II) (wherein each R2 and R3 in each (O-R2-O-C(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 groups and R3 groups is 4 to 10, and m is 2 to 23), and iv) a catalyst; and Including, a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight of 8,000 grams per mole (g / mol) or greater; Including, including blends.

[0048] In an eleventh aspect, the present disclosure provides a photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher; b) a photoinitiator; and c) a polymerization reaction product of component: i) a diisocyanate; ii) Formula (X): HO-Q-(A1)2 (X) wherein Q is a polyvalent organic linking group and A1 is independently selected from (meth)acrylic functional groups of the formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H; and iii) Formula (II): H(O-R2-OC(=O))mO-R3-OH (II) a polycarbonate diol of formula (II), wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol has a number average molecular weight (Mn) of greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn of greater than 1,000 g / mol; iv) a catalyst; and Including, a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; Includes.

[0049] Components a) to c) and i) to iv) of each of the first, fifth, and eleventh aspects are described in detail below.

[0050] Monofunctional (meth)acrylate monomers In an optional embodiment, the photopolymerizable composition comprises 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, the monofunctional (meth)acrylate monomer having a high glass transition temperature (Tg), i.e., the cured homopolymer has a Tg of 125° C. or higher. In some embodiments, there is present a monofunctional (meth)acrylate monomer that results in a cured homopolymer having a Tg of 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. In selected embodiments, there is present a monofunctional (meth)acrylate monomer that results in a cured homopolymer having a Tg of 150° C. or higher, 170° C. or higher, or 180° C. or higher. The Tg of homopolymers of monofunctional (meth)acrylate monomers is typically about 260°C or less. For example, 1-adamantyl methacrylate decomposes at about 260°C. In some embodiments, the Tg of homopolymers of monofunctional (meth)acrylate monomers is 255°C, 250°C, 245°C, 240°C, 235°C, 230°C, 225°C, 220°C, 215°C, 210°C, 205°C, or 200°C or less. The inclusion of one or more monofunctional (meth)acrylate monomers in a photopolymerizable composition, whose cured homopolymer has a Tg of 125°C or greater, contributes to an increased relaxation modulus of the photopolymerized reaction product of the composition, as measured after immersion in deionized water. The Tg of the homopolymer of the monomer can often be found in the literature, such as Table 1 below. Table 1 includes the Tg of homopolymers of several monofunctional (meth)acrylate monomers and literature sources for the reported Tg.

[0051] In some embodiments, the monofunctional (meth)acrylate monomer comprises a cycloaliphatic monofunctional (meth)acrylate. Suitable monofunctional (meth)acrylate monomers include, for example, but are not limited to, 3,3,5-trimethylcyclohexyl methacrylate, butyl-cyclohexyl methacrylate (e.g., cis-4-tert-butyl-cyclohexyl methacrylate, 73 / 27 trans / cis-4-tert-butylcyclohexyl methacrylate, and / or trans-4-tert-butylcyclohexyl methacrylate), 2-decahydronaphthyl methacrylate, 1-adamantyl acrylate, dicyclopentadienyl methacrylate, dicyclopentanyl methacrylate, isobornyl methacrylate (e.g., d,l-isobornyl methacrylate), dimethyl-1-adamantyl methacrylate, bornyl methacrylate (e.g., d,l-bornyl methacrylate), 3-tetracyclo[4.4.0.1.1]dodecyl methacrylate, 1-adamantyl methacrylate, or combinations thereof. In one embodiment, the monofunctional (meth)acrylate monomer comprises isobornyl methacrylate.

[0052] In certain embodiments, the weight ratio of monofunctional (meth)acrylate monomer to polyurethane methacrylate polymer is 60:40 to 40:60, 55:45 to 45:55, or 50:50. In many cases, the monofunctional methacrylate monomer is present in an amount of 45 or more, 46 or more, 47 or more, 48 or more, 49 or more, 50 or more, 51 or more, 52 or more, 53 or more, 54 or more, or 55 or more parts by weight per 100 parts by weight of the total photopolymerizable composition, and 70 or less, 69 or less, 68 or less, 67 or less, 66 or less, 65 or less, 64 or less, 63 or less, 62 or less, 61 or less, 60 or less, 59 or less, 58 or less, 57 or less, or 56 or less parts by weight per 100 parts by weight of the total photopolymerizable composition.

[0053] In some embodiments of the present invention, the cured material will come into contact with an aqueous environment. In these cases, it is advantageous to utilize a material with a low affinity for water. The affinity of a certain (meth)acrylate monomer for water can be estimated by calculating the partition coefficient between water and an immiscible solvent such as octanol. This can serve as a quantitative descriptor of hydrophilicity or lipophilicity. The octanol / water partition coefficient can be calculated using the log P module in software programs such as ACD ChemSketch (Advanced Chemistry Development, Inc., Toronto, Canada). In some embodiments of the present 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 12.5 or less. In some embodiments, the calculated log P value is 12, 11.5, 11, 10.5, 10, 9.5, 9, 8.5, 8, 7.5, 7, 6.5, 6, or 5.5 or less. Furthermore, in some embodiments, the photopolymerizable composition is essentially free of monofunctional (meth)acrylate monomers having a log P value of less than 3, less than 2, or less than 1, thereby precluding the presence of significant amounts of hydrophilic (meth)acrylate monomers.

[0054] In some embodiments, the photopolymerizable composition comprises 25 wt% or less, e.g., 23 wt%, 21 wt%, 20 wt%, 19 wt%, 17 wt%, 15 wt%, 13 wt%, or 11 wt% or less, of a hydrophilic (meth)acrylate monomer or polymer (e.g., a hydrophilic urethane (meth)acrylate polymer) having a log P value of less than 3, less than 2, or less than 1, based on the total weight of the photopolymerizable composition, and the hydrophilic component is in an amount of 1 wt% or more, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 7 wt%, 9 wt%, or 10 wt% or more, e.g., 1 wt% to 25 wt%, based on the total weight of the photopolymerizable composition. In some embodiments, a combination of a hydrophilic component and a monofunctional (meth)acrylate monomer such that the cured homopolymer has a Tg of 150°C or greater can impart advantageous properties to the article, for example, the photopolymerizable composition may contain 20% by weight or greater, 22% by weight, 25% by weight, 27% by weight, 30% by weight, 32% by weight, 35% by weight, 37% by weight, 40% by weight, 42% by weight, 45% by weight, 47% by weight, or 50% by weight or greater of a monofunctional (meth)acrylate monomer such that the cured homopolymer has a Tg of 150°C or greater, when 1% by weight to 25% by weight of the hydrophilic component is present, each based on the total weight of the photopolymerizable composition. [Table 1]

[0055] Photoinitiator The photopolymerizable compositions of the present disclosure include at least one photoinitiator. Suitable exemplary photoinitiators are available from IGM Resins (Waalwijk, The Netherlands) under the trade name OMNIRAD, including 1-hydroxycyclohexyl phenyl ketone (OMNIRAD 184), 2,2-dimethoxy-1,2-diphenylethan-1-one (OMNIRAD 651), bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (OMNIRAD 819), 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one (OMNIRAD 2959), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone (OMNIRAD 369), 2-dimethylamino-2-(4-methyl-benzyl)-1-(4-morpholin-4-yl-phenyl)-butan-1-one (OMNIRAD 379), 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one (OMNIRAD 907), oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone]ESACURE ONE (Lamberti SpA, Gallarate, Italy), 2-hydroxy-2-methyl-1-phenylpropan-1-one (DAROCUR 1173), 2,4,6-trimethylbenzoyldiphenylphosphine oxide (OMNIRAD TPO), and 2,4,6-trimethylbenzoylphenylphosphinate (OMNIRAD TPO-L). Additional suitable photoinitiators include, for example, but are not limited to, benzil dimethyl ketal, 2-methyl-2-hydroxypropiophenone, benzoin methyl ether, benzoin isopropyl ether, anisoin methyl ether, aromatic sulfonyl chlorides, photoactive oximes, and combinations thereof.

[0056] 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 an amount 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 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 can be present in an amount of about 0.1 wt % to 5 wt %, 0.2 wt % to 5 wt %, 0.1 wt % to 2 wt %, 1.5 wt % to 3 wt %, or 0.5 wt % to 5 wt %, based on the total weight of the photopolymerizable composition.

[0057] Additionally, a thermal initiator may optionally be present in the photopolymerizable compositions described herein. In some embodiments, the thermal initiator is present in the photopolymerizable composition in an amount of up to about 5 wt %, based on the total weight of the polymerizable components in the photopolymerizable composition. In some cases, the thermal initiator is present in an amount of about 0.1 wt % to 5 wt %, based on the total weight of the polymerizable components in the photopolymerizable composition. Suitable thermal initiators include, but are not limited to, peroxides such as benzoyl peroxide, dibenzoyl peroxide, dilauryl peroxide, cyclohexane peroxide, methyl ethyl ketone peroxide, hydroperoxides such as tert-butyl hydroperoxide and cumene hydroperoxide, dicyclohexyl peroxydicarbonate, 2,2-azo-bis(isobutyronitrile), and t-butyl perbenzoate. Examples of commercially available thermal initiators include initiators available from DuPont Specialty Chemical (Wilmington, Del.) under the trade name VAZO, including VAZO 67 (2,2'-azo-bis(2-methylbutyronitrile)), VAZO 64 (2,2'-azo-bis(isobutyronitrile)), and VAZO 52 (2,2'-azo-bis(2,2-dimethylvaleronitrile)), and an initiator available from Elf Atochem North America, Philadelphia, Pa. under the trade name LUCIDOL 70.

[0058] In certain embodiments, the use of more than one initiator increases the percentage of monomer that is incorporated into the reaction product of the polymerizable components, thus helping to reduce the percentage of monomer that remains uncured.

[0059] component Articles according to the present disclosure comprise the polymerization reaction product of components including at least one diisocyanate, at least one hydroxy-functional methacrylate of formula (I), at least one polycarbonate diol, and at least one catalyst, each of which is discussed in detail below.

[0060] The suitable amounts of each of the diisocyanate, the hydroxy-functional methacrylate of Formula (I), and the polycarbonate diol present in the components are based on the molar ratio of each of these components to the other components. For example, the ratio of the diisocyanate (e.g., having two isocyanate equivalents per mole of isocyanate compound) to the polycarbonate diol typically ranges from 4 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of alcohol of the polycarbonate diol to 4 molar equivalents of isocyanate of the diisocyanate to 3 molar equivalents of alcohol of the polycarbonate diol. In other words, the ratio of the diisocyanate to the polycarbonate diol typically ranges from 4 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of alcohol of the polycarbonate diol to 1.3 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of alcohol of the polycarbonate diol. In selected embodiments, the ratio of diisocyanate to polycarbonate diol is 4 molar equivalents of isocyanate of the diisocyanate to 2 molar equivalents of alcohol of the polycarbonate diol, or stated another way, 2 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of alcohol of the polycarbonate diol. The closer the ratio of diisocyanate to polycarbonate diol is to 1 molar equivalent of isocyanate of the diisocyanate to 1 molar equivalent of alcohol of the polycarbonate diol, the higher the weight average molecular weight of the resulting polyurethane (meth)acrylate polymer produced in the polymerization reaction product of the components.

[0061] The ratio of diisocyanate to hydroxy-functional methacrylate of formula (I) typically ranges from 4 molar equivalents of isocyanate of the diisocyanate to 3 molar equivalents of hydroxy-functional methacrylate of formula (I) to 4 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of formula (I). In other words, the ratio of diisocyanate to hydroxy-functional methacrylate of formula (I) typically ranges from 1.3 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of formula (I) to 4 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of formula (I). In selected embodiments, the ratio of diisocyanate to hydroxy-functional methacrylate of Formula (I) is 4 molar equivalents of isocyanate of the diisocyanate to 2 molar equivalents of hydroxy-functional methacrylate of Formula (I), or stated another way, 2 molar equivalents of isocyanate of the diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0062] The ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) typically ranges from 1 molar equivalent of alcohol of polycarbonate diol to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 3 molar equivalents of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I). In other words, the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) typically ranges from 1 molar equivalent of alcohol of polycarbonate diol to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 1 molar equivalent of alcohol of polycarbonate diol to 0.3 molar equivalent of hydroxy-functional methacrylate of Formula (I). In selected embodiments, the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) is 1 molar equivalent of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0063] Diisocyanates The component (e.g., contained in the polymerization reaction product of the component) includes at least one diisocyanate. The diisocyanate that can be used in the component can be any organic isocyanate having two free isocyanate groups. This includes aliphatic, cycloaliphatic, aromatic, and araliphatic isocyanates. Any of the known diisocyanates can be used, such as alkyl and alkylene diisocyanates, cycloalkyl diisocyanates, and cycloalkylene diisocyanates, as well as combinations of alkylene diisocyanates and cycloalkylene diisocyanates. In some embodiments, diisocyanates having the formula Rdi(NCO)2 can be used, where Rdi is defined above.

[0064] Specific examples of suitable diisocyanates include, but are not limited to, 2,6-toluene diisocyanate (TDI), 2,4-toluene diisocyanate, methylenedicyclohexylene-4,4' diisocyanate (H12MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,6-diisocyanatohexane (HDI), tetramethyl-m-xylylene diisocyanate, 2,2,4-trimethyl-1,6-diisocyanatohexane, and 2,4,4-trimethyl -1,6-diisocyanatohexane (TMXDI), trans-1,4-hydrogenated xylylene diisocyanate (H6XDI), cyclohexyl-1,4-diisocyanate, 4,4'-methylenediphenyl diisocyanate, 2,4'-methylenediphenyl diisocyanate, mixtures of 4,4'-methylenediphenyl diisocyanate and 2,4'-methylenediphenyl diisocyanate, 1,5-naphthalene diisocyanate, 1,4-tetramethylene diisocyanate, 1,4-phenylene diisocyanate, 2,6 -Toluene diisocyanate and 2,4-toluene diisocyanate, 1,5-naphthylene diisocyanate, 2,4'-diphenylmethane diisocyanate and 4,4'-diphenylmethane diisocyanate, pentamethylene diisocyanate, dodecylmethylene diisocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, methyl 2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1 ,3-bis(isocyanatomethyl)cyclohexane, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether diisocyanate, 1,3-xylylene diisocyanate or 1,4-xylylene diisocyanate, lysine diisocyanate methyl ester, 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate, 3,3'-dimethyl-phenylene diisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1] Heptane, bis(2-isocyanatoethyl) fumarate, 4-diphenylpropane diisocyanate, trans-cyclohexane-1,4-diisocyanate, hydrogenated dimer acid diisocyanate, norbornene diisocyanate, methylene bis(6-isopropyl-1,3-phenyl)diisocyanate, and any combination thereof. In selected embodiments, the diisocyanate includes IPDI.

[0065] Hydroxy-functional methacrylate The components of the first and fifth aspects (e.g., included in the polymerization reaction product of the components) have the formula (I): HO-Q-(A)p (I) wherein Q is a polyvalent organic linking group and A is a methacryl functional group of formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms (e.g., R1 can be methyl); p is 1 or 2].

[0066] In some embodiments, in the hydroxy-functional methacrylate of Formula (I), Q is an alkylene group, p is 1, and in the methacryl functional group A, R 1 is methyl.

[0067] The component of the eleventh embodiment (e.g., included in the polymerization reaction product of the component) has the formula (X): HO-Q-(A1)2 (X) wherein Q is a polyvalent organic linking group and A1 is a (meth)acrylic functional group independently selected from (meth)acrylic functional groups of the formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H (e.g., R4 can be methyl).

[0068] Q can be a straight-chain, branched-chain, or ring-containing alkylene linking group. Q can optionally contain heteroatoms such as O, N, and S, and combinations thereof. Q can optionally contain heteroatom-containing functional groups such as carbonyl or sulfonyl, and combinations thereof. In some embodiments, Q is a straight-chain, branched-chain, or ring-containing linking group selected from arylene, aralkylene, and alkarylene. In still other embodiments, Q is a straight-chain, branched-chain, or ring-containing linking group containing heteroatoms such as O, N, and S and / or heteroatom-containing functional groups such as carbonyl and sulfonyl. In other embodiments, Q is a branched-chain or ring-containing alkylene group optionally containing heteroatoms selected from O, N, and S, and / or heteroatom-containing functional groups such as carbonyl and sulfonyl.

[0069] Suitable examples of hydroxy-functional methacrylates of formula (I) include, but are not limited to, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate (all isomers), hydroxybutyl methacrylate (all isomers), poly(e-caprolactone) mono[2-methacryloxyethyl] ester, glycerol dimethacrylate, 1-(acryloxy)-3-(methacryloxy)-2-propanol, 2-hydroxy-3-phenyloxypropyl methacrylate, 2-hydroxyalkyl methacryloyl phosphate, 4-hydroxycyclohexyl methyl methacrylate ... Examples of suitable methacrylates include cyclohexyl methacrylate, trimethylolpropane dimethacrylate, trimethylolethane dimethacrylate, 1,4-butanediol monomethacrylate, neopentyl glycol monomethacrylate, 1,6-hexanediol monomethacrylate, 3-chloro-2-hydroxypropyl methacrylate, 2-hydroxy-3-alkyloxy methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, ethylene oxide-modified phthalic acid methacrylate, and 4-hydroxycyclohexyl methacrylate.

[0070] Suitable hydroxy-functional methacrylates of formula (X) include, but are not limited to, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxypropyl methacrylate (all isomers), hydroxypropyl acrylate (all isomers), hydroxybutyl methacrylate (all isomers), hydroxybutyl acrylate (all isomers), caprolactone monoacrylate available from Sartomer (Exton, PA) under the tradename "SR-495," and other poly(e-caprolactone) mono[2-(meth)acryloxyethyl] esters, poly(e-caprolactone) mono[2-acryloxyethyl] esters, glycerol dimethacrylate (all isomers), glycerol diacrylate (all isomers), 1-(acryloxyethyl) esters, 1-(meth ... (methacryloxy)-3-(methacryloxy)-2-propanol, 2-hydroxy-3-phenyloxypropyl methacrylate, 2-hydroxy-3-phenyloxypropyl acrylate, 2-hydroxyalkyl methacryloyl phosphate, 2-hydroxyalkyl acryloyl phosphate, 4-hydroxycyclohexyl methacrylate, 4-hydroxycyclohexyl acrylate, trimethylolpropane dimethacrylate, trimethylolpropane diacrylate, trimethylolethane dimethacrylate, trimethylolethane diacrylate, 1,4-butanediol monomethacrylate, 1,4-butanediol monoacrylate, neopentyl glycol monomethacrylate, neopentyl glycol monoacrylate, 1,6-hexanediol monomethacrylate, 1,6-hexanediol monoacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl acrylate, 2-hydroxy-3-alkyloxy methacrylate, 2-hydroxy-3-alkyloxy acrylate, polyethylene glycol monomethacrylate, monomethoxypolyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, monomethoxypolyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, monomethoxypolypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, monomethoxypolypropylene glycol monoacrylate, ethylene oxide-modified phthalic acid methacrylate, ethylene oxide-modified phthalic acid acrylate, 4-hydroxycyclohexyl methacrylate, and 4-hydroxycyclohexyl methacrylate.

[0071] Polycarbonate Diol It has been found that the component (e.g., contained in the polymerization reaction product of the component) contains a polycarbonate diol, which contributes to less water absorption during contact with water than an article containing a polyurethane with another linking group, such as a polyether. Selected articles absorb less than 3%, less than 2.5%, less than 2%, less than 1.5%, less than 1%, or even less than 0.5% water when immersed in deionized water at 37°C for 7 days. The polycarbonate diol is represented by the formula (II): H(O-R2-OC(=O))mO-R3-OH (II) [wherein each R2 and R3 in each (O-R2-OC(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 groups and R3 groups is 4 to 10, and m is an integer from 2 to 23.] In other words, R1 and / or R2 of some repeating units may have a carbon number of less than 4 (e.g., 2 or 3), which is sufficient for the repeating units to have a carbon number high enough that the average carbon numbers of R1 and R2 of all repeating units in the polycarbonate diol of formula (II) fall within any of the following ranges: 4 to 10, or 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. In selected embodiments, at least one of R1 or R2 is -CH2CH2CH(CH3)CH2CH2-, -(CH2)6-, or -(CH2)4-, preferably a combination of -CH2CH2CH(CH3)CH2CH2- and -(CH2)6-.

[0072] In many cases, either the polycarbonate diol has a molecular weight greater than 1,000 grams per mole (g / mol), or the average molecular weight of all polycarbonate diols present in the component is greater than 1,000 g / mol. In other words, in some embodiments, when a component contains a single polycarbonate diol of formula (II), the polycarbonate diol has a molecular weight greater than 1,000 g / mol. When a component contains two or more polycarbonate diols (i.e., each of which is of formula (II)), the Mn of at least one of the polycarbonate diols may be 1,000 g / mol or less, provided that the weighted average of all Mn values ​​of the two or more polycarbonate diols is greater than 1,000 g / mol. For example, a component comprising two polycarbonate diols may comprise a molar ratio of 1 first polycarbonate diol having an Mn of about 500 g / mol to 2 second polycarbonate diols having an Mn of about 1,500 g / mol, resulting in a weighted average Mn of 1,167 g / mol. In certain embodiments, the polycarbonate diol (or the weighted average of all polycarbonate diols present in the component) has a number average molecular weight of 1,500 g / mol or greater.

[0073] In some embodiments, the hydroxyl group is 450 grams per mole (g / mol) or more, 500 g / mol or more, 550 g / mol or more, 600 g / mol or more, 650 g / mol or more, 700 g / mol or more, 750 g / mol or more, 800 g / mol or more, 850 g / mol or more, 900 g / mol or more, 950 g / mol or more, or 1,000 g / mol or more, and 3,200 g / mol or less, 3,100 g / mol or less, 3,000 g / mol or less, One or more polycarbonate diols are present that have an Mn of 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. In other words, the polycarbonate diol may have an Mn 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. On the other hand, the inclusion of a polycarbonate diol having an Mn of more than 3,200 g / mol may adversely affect the rigidity of the photopolymerization product of the photopolymerization composition by increasing the elastomeric properties of the photopolymerization product. In selected embodiments, the photopolymerizable composition is essentially free of diols having a lower Mn than one or more polycarbonate diols present in the composition.

[0074] Examples of polycarbonate diols suitable for use in the components include, but are not limited to, those commercially available from Kuraray Co. Ltd. (Tokyo, JP) under the trade name "KURARAY POLYOL", specifically, for example, each of the KURARAY POLYOL C series, i.e., C-590, C-1090, C-2050, C-2090, and C-3090, and those commercially available from Covestro LLC (Pittsburgh, PA) under the trade name "DESMOPHEN", for example, each of the Desmophen C series, i.e., C-2100, C-2200, and C XP-2613.

[0075] catalyst The components (e.g., contained in the polymerization reaction product of the components) include a catalyst for catalyzing the reaction of at least one isocyanate, at least one (meth)acrylate monool, and at least one polycarbonate diol. Typically, the catalyst is included in an amount of 0.01 wt % to 5 wt % based on the total weight of the polymerizable components.

[0076] Examples of suitable catalysts include, but are not limited to, dioctyl dilaurate (DOTDL), tin octoate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin mercaptide, dibutyltin thiocarboxylate, dibutyltin dimaleate, dioctyltin mercaptide, dioctyltin thiocarboxylate, lead 2-ethylhexanoate, tetraalkyl titanates such as tetrabutyl titanate (TBT), triethylamine, N,N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylhexylamine, N-methylpropional, N-ethylhexylamine, N-methylpropional, N-ethylpropional, N-methyl ... ethylmorpholine, N,N-dimethyl-p-toluidine, beta-(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-hexanediol-diamine, bis(N,N-dimethylamine), Bis(morpholinoethyl) ether, N'-cyclohexyl-N,N-dimethylformamide, N,N'-dimethylpiperazine, trimethylpiperazine, bis(aminopropyl)piperazine, N-(N,N'-dimethylaminoethyl)morpholine, bis(morpholinoethyl) ether, 1,2-dimethylimidazole, N-methylimidazole, 1,4-diamidine, 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), 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU), and salts such as phenol salts and octylate salts, N,N,N',N''-pentamethyldiethylenetriamine, N,N,N',N'-pentamethyldipropylenetriamine, tetramethylguanidine, N-cyclohexyl-N',N',N'',N''-tetramethylguanidine, N-methyl-N'-(2-dimethylaminoethyl)piperazine, and 1,3,5-tris(N,N-dimethyl-propyl)-hexahydro-1,3,5-triazine.

[0077] In optional embodiments, the catalyst comprises zinc, an amine, tin, zirconium, or bismuth. The catalyst may comprise tin, such as dibutyltin diacrylate. Preferably, however, the catalyst does not comprise tin, as tin catalysts may be undesirable in orthodontic articles that come into contact with the patient's oral cavity.

[0078] The catalyst may include an organometallic zinc complex free of 2-ethylhexyl carboxylate and 2-ethylhexanoic acid, such as the zinc catalyst commercially available from King Industries, Inc. (Norwalk, CT) under the trade name K-KAT XK-672, 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, available from Sigma-Aldrich (St. Louis, MO), and bismuth catalysts available from King Industries under the trade names K-KAT XK-651 and K-KAT 348. Available aluminum-based catalysts include K-KAT 5218 from King Industries. Additionally, zirconium-based catalysts include K-KAT 4205 and K-KAT 6212, both available from King Industries.

[0079] Polymerization reaction product of the components An article according to the present disclosure comprises a polymerization reaction product of the aforementioned components. The polymerization reaction product of the components contains at least one polyurethane methacrylate polymer. The urethane is prepared by the reaction of an isocyanate with an alcohol to form a carbamate bond. The polyurethane methacrylate polymer typically provides the final article with toughness (e.g., at least a minimum tensile strength and / or modulus) and flexibility (e.g., at least a minimum elongation at break). In addition to the urethane functional groups, the polyurethane methacrylate polymer further comprises a polycarbonate linking group. The linking group is a functional group that connects two or more urethane groups and may be divalent, trivalent, or tetravalent, preferably divalent. Additionally, the polyurethane methacrylate polymer optionally further comprises one or more functional groups selected from hydroxyl groups, carboxyl groups, amino groups, and siloxane groups. These functional groups can react with other components of the photopolymerizable composition during polymerization. The polyurethane methacrylate polymer preferably has a molecular weight of 3,000 g / mol or more, 4,000 g / mol or more, 5,000 g / mol or more, 6,000 g / mol or more, 6,000 g / mol or more, 7,000 g / mol or more, 8,000 g / mol or more, 9,000 g / mol or more, 10,000 g / mol or more, 11,000 g / mol or more, or 12,000 g / mol or more, and has a weight average molecular weight (Mw) of 50,000 g / mol or less, 45,000 g / mol or less, 40,000 g / mol or less, 35,000 g / mol or less, 32,000 g / mol or less, 30,000 g / mol or less, 28,000 g / mol or less, 25,000 g / mol or less, 23,000 g / mol or less, 20,000 g / mol or less, or 18,000 g / mol or less. In other words, the polyurethane methacrylate polymer can have a Mw of 8,000 g / mol or more, 10,000 g / mol or more, 3,000 g / mol to 50,000 g / mol, 6,000 g / mol to 40,000 g / mol, 6,000 g / mol to 18,000 g / mol, 6,000 g / mol to 35,000 g / mol, or 8,000 g / mol to 32,000 g / mol.The weight average molecular weight can be measured using gel permeation chromatography (GPC), for example, using the method described in the Examples below. Higher molecular weight polyurethane methacrylates will result in higher viscosity resin formulations with comparable composition and loading, making the formulation less flowable, while lower molecular weight polyurethane methacrylates will have less toughening effect on the cured article.

[0080] In some embodiments, the polyurethane methacrylate has formula (V): [ka] where A is of the formula -OC(=O)C(R1)=CH2, where R1 is an alkyl of 1 to 4 carbon atoms (e.g., methyl), p is 1 or 2, Q is a polyvalent organic linking group as described above, Rd1 is the residue of a diisocyanate, RdOH is the residue of a polycarbonate polyol, and r is an average of 1 to 15. In some embodiments, r is 15, 14, 13, 12, 11, or 10 or less. In some embodiments, r is an average of at least 2, 3, 4, or 5. In some embodiments, A is a methacrylic functional group, such as a methacrylate. In some embodiments, the polymerization reaction product of the components further comprises one or more side reaction products in addition to the polyurethane methacrylate polymer. Depending on the selectivity of the catalyst and / or the weight ratio of the components, oligomers of the reactants can be produced. The order of addition of the components when preparing the photopolymerizable composition affects the relative amounts of polymer and oligomer produced in the photopolymerization reaction product. For example, adding the isocyanate to the polycarbonate diol first, and then the monofunctional methacrylate, will result in a higher ratio of polyurethane methacrylate polymer to by-products such as oligomers than would, instead, adding the monofunctional (meth)acrylate to the isocyanate first, and then the polycarbonate diol.

[0081] Oligomers having the structure monofunctional (meth)acrylate monomer-isocyanate-monofunctional (meth)acrylate monomer have been found to be by-products of the polymerization reaction of the components in certain embodiments. The polyurethane methacrylate polymer can be purified to remove such by-products. Alternatively, additional by-products, such as oligomers, can be added to the polymerization reaction product, particularly if a particular reaction produces small amounts of one or more by-products. It has been discovered that some by-product components can improve at least one of the modulus or degree of crosslinking of the photopolymerizable composition after it has cured.

[0082] For example, the photopolymerizable composition may comprise a compound of formula (III): [ka] wherein Q, p, and R1 are as defined in Formula (I), and Rdi is the residue of a diisocyanate as defined above. Typically, the compound of Formula (III) is produced during polymerization of the components, as described above. The specific formulation of the components affects the amount of the compound of Formula (III) produced during polymerization of the components. For example, the specificity of the catalyst for catalyzing the formation of polyurethane methacrylate polymers can affect the amount of the compound of Formula (III) produced during polymerization of the components. In certain embodiments, a compound of Formula (III) is added to the photopolymerizable composition, particularly if a lower than desired amount of the compound of Formula (III) is produced by polymerization of the components. In any embodiment, the compound may advantageously improve crosslinking during the photopolymerization reaction, increasing the modulus or the photopolymerization product, or both. Whether the compound of Formula (III) is formed during polymerization of the components, added separately to the photopolymerizable composition, or both, in some embodiments, the compound of Formula (III) is present in an amount of 0.05 weight percent (wt%) or more, 0.1 wt% or more, 0.5 wt% or more, 1 wt% or more, 1.5 wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, 5 wt% or more, 6 wt% or more, 7 wt% or more, 8 wt% or more, or 9 wt% or more based on the weight of the polymerizable composition, and 20 wt% or less, 18 wt% or less, 16 wt% or less, 14 wt% or less, 12 wt% or less, or 10 wt% or less based on the weight of the polymerizable composition. In other words, the compound of Formula (III) may be present in the photopolymerizable composition in an amount of 0.05 weight percent to 20 weight percent (wt %), 1.5 wt % to 12 wt %, 2.5 wt % to 12 wt %, 5 wt % to 15 wt %, 5 wt % to 12 wt %, 7 wt % to 15 wt %, 7 wt % to 12 wt %, or 5 wt % to 20 wt %, based on the weight of the polymerizable composition.

[0083] In selected embodiments, the compound of formula (III) has formula (IV): [ka] It is of the type.

[0084] A second polymerization reaction product of the components: In an optional embodiment, the photopolymerizable composition further comprises a second polymerization reaction product of a component. The use of a second polyurethane (meth)acrylate polymer may provide the article with somewhat different mechanical properties than using a single polyurethane methacrylate polymer in the photopolymerizable composition. The second polymerization reaction product component is: 1) An isocyanate-functional (meth)acrylate compound of formula (VII): (A1) pQ-NCO (VII), wherein p and Q are as defined for formula (I), and A1 is a (meth)acrylic functional group of formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H; 2) Polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH (II) wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23; 3) a catalyst.

[0085] The second polymerization reaction product comprises a polyurethane (meth)acrylate polymer that is different from the first polyurethane methacrylate polymer. In selected embodiments, the second polymerization reaction product comprises a polyurethane (meth)acrylate polymer represented by Formula (VIII): [ka] wherein Q and p are as defined for formula (I), R2 and R3 are as defined for formula (II), and R4 is as defined for formula (VII).

[0086] The compound of formula (VIII) is typically obtained by reacting a polycarbonate diol with an isocyanate-functional (meth)acrylate compound in the presence of a catalyst. Examples of isocyanate-functional (meth)acrylates include isocyanatoethyl methacrylate, isocyanatoethoxyethyl methacrylate, isocyanatoethyl acrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate, which are commercially available, for example, from Showa Denko (Tokyo, Japan). As an example, the compound of formula (VIII) can be, in selected embodiments, a compound of formula (IX): [ka] In formula (IX), n is about 6.7 for a 1000 molecular weight polycarbonate diol based on hexanediol.

[0087] In some embodiments, the second polymerization reaction product has formula (XI): [ka] where Rdi is a residue of a diisocyanate as defined above. In embodiments where the diisocyanate is asymmetric, the orientation of the bond of the residue of the diisocyanate to the nitrogen atom of the carbamate bond changes during polymerization, and thus the polymerization reaction product contains multiple polyurethane methacrylate structures.

[0088] Bifunctional component The photopolymerizable compositions of the present disclosure optionally include at least one difunctional component, such as a difunctional (meth)acrylate monomer or oligomer. The difunctional component present in the photopolymerizable composition can co-react (e.g., undergo addition polymerization) with the polyurethane methacrylate polymer.

[0089] The difunctional component (e.g., monomer) is present in an amount of up to 15 wt % based on the total weight of the photopolymerizable composition, up to 12 wt %, up to 10 wt %, or up to 8 wt % based on the total weight of the photopolymerizable composition. Including more than 15 wt % of the difunctional component can result in more crosslinking than desired, reducing the elongation of the article.

[0090] Suitable difunctional monomers include, but are not limited to, those represented by formula (III): [ka] wherein Q, p, and R1 are as defined in formula (I) and Rdi is the residue of a diisocyanate as defined above, or Formula (VIII): [ka] wherein Q and p are as defined for formula (I), R2 and R3 are as defined for formula (II), and R4 is as defined for formula (VII). Further suitable bifunctional monomers include hydroxyethyl methacrylate diester of terephthalic acid, 1,12-dodecanediol dimethacrylate, alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, caprolactone-modified neopentyl glycol hydroxypivalate diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol diacrylate, dipropylene glycol diacrylate, ethoxylated (10) bisphenol A diacrylate, ethoxylated (3) bisphenol A diacrylate, Examples of suitable difunctional monomers include ethoxylated (30) bisphenol A diacrylate, ethoxylated (4) bisphenol A diacrylate, hydroxypivalaldehyde-modified trimethylolpropane diacrylate, neopentyl glycol diacrylate, polyethylene glycol (200) diacrylate, polyethylene glycol (400) diacrylate, polyethylene glycol (600) diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, or any combination thereof. Additional suitable difunctional monomers include the dimethacrylates of the above diacrylates.

[0091] Typically, photopolymerizable compositions are essentially free of trihydric alcohols, which are alcohols having three hydroxyl groups, because such alcohols increase the hydrophilicity of the photopolymerizable composition, which can result in undesirably high water absorption during use of articles prepared from the photopolymerizable composition.

[0092] additives The photopolymerizable compositions described herein, in some examples, further comprise one or more additives, such as one or more additives selected from the group consisting of inhibitors, stabilizers, sensitizers, absorption modifiers, fillers, and combinations thereof.

[0093] Additionally, the photopolymerizable material compositions described herein may further include one or more sensitizers that can increase the effectiveness of one or more photoinitiators that may also be present. In some embodiments, the sensitizer includes isopropylthioxanthone (ITX) or 2-chlorothioxanthone (CTX). Other sensitizers may also be used. When used in a photopolymerizable composition, the sensitizer can be present in an amount ranging from about 0.01 wt %, or about 1 wt %, based on the total weight of the photopolymerizable composition.

[0094] The photopolymerizable compositions described herein also optionally include one or more polymerization inhibitors or stabilizers. Polymerization inhibitors are often included in photopolymerizable compositions to provide additional thermal stability to the composition. In some examples, stabilizers include one or more antioxidants. Any antioxidant not inconsistent with the objectives of the present disclosure may be used. For example, in some embodiments, suitable antioxidants include various aryl compounds, including butylated hydroxytoluene (BHT), which can also be used as a polymerization inhibitor in the embodiments described herein. Additionally or alternatively, polymerization inhibitors include methoxyhydroquinone (MEHQ).

[0095] In some embodiments, when a polymerization inhibitor is used, the polymerization inhibitor is present in an amount of about 0.001% to 2%, 0.001% to 1%, or 0.01% to 1% by weight, based on the total weight of the photopolymerizable composition. Further, when a stabilizer is used, the stabilizer is present in the photopolymerizable compositions described herein in an amount of about 0.1% to 5%, about 0.5% to 4%, or about 1% to 3% by weight, based on the total weight of the photopolymerizable composition.

[0096] The photopolymerizable compositions described herein can also include one or more ultraviolet absorbers, such as dyes, optical brighteners, pigments, particulate fillers, and the like, to control the transmittance of actinic radiation. One particularly suitable ultraviolet absorber is Tinuvin 326, (2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol, available from BASF Corporation, Florham Park, NJ. Another particularly suitable absorption modifier is Tinopal OB, benzoxazole, 2,2'-(2,5-thiophenediyl)bis[5-(1,1-dimethylethyl)], also available from BASF Corporation. Another suitable ultraviolet absorber is an optical brightener comprising a compound of formula (VI): [ka]

[0097] Compounds of formula VI can be synthesized as described in detail in the Examples below.

[0098] When a UV absorber is used, the UV absorber may be present in an amount of about 0.001% to 5% by weight, about 0.01% to 1% by weight, about 0.1% to 3% by weight, or about 0.1% to 1% by weight, based on the total weight of the photopolymerizable composition.

[0099] The photopolymerizable composition may contain fillers, including nanoscale fillers. Examples of suitable fillers include naturally occurring or synthetic materials, including, but not limited to, silica (SiO (e.g., quartz)), alumina (AlO), zirconia, 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 (china clay), talc, zirconia, titania, and submicron silica particles (e.g., pyrogenic silicas such as those available under the trade name AEROSIL, including "OX50", "130", "150", and "200" silicas from Degussa Corp., Akron, OH, and CAB-O-SIL M5 and TS-720 silicas from Cabot Corp., Tuscola, IL). Organic fillers made from polymeric materials, such as those disclosed in WO 09 / 045752 (Kalgutkar et al.), are also possible.

[0100] The composition may further comprise a fibrous reinforcement material and a colorant, such as a dye, pigment, or pigment dye. Examples of suitable fibrous reinforcements include PGA microfibrils, collagen microfibrils, and other fibrous reinforcements described in U.S. Patent No. 6,183,593 (Narang et al.). Examples of suitable colorants described in U.S. Patent No. 5,981,621 (Clark et al.) include 1-hydroxy-4-[4-methylphenylamino]-9,10-anthracenedione (FD&C Purple No. 2), 6-hydroxy-5-[(4-sulfophenyl)oxo]-2-naphthalenesulfonic acid, disodium salt (FD&C Yellow No. 6), 9-(o-carboxyphenyl)-6-hydroxy-2,4,5,7-tetraiodo-3H-xanthen-3-one, disodium salt, monohydrate (FD&C Red No. 3), and the like.

[0101] Discontinuous fibers are also suitable fillers, such as fibers containing carbon, ceramic, 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, which are chopped or sheared to obtain discontinuous ceramic fibers. Ceramic fibers can be produced from various commercially available ceramic filaments. Examples of filaments useful for forming ceramic fibers include ceramic oxide fibers sold under the trademark NEXTEL (3M Company, St. Paul, MN). NEXTEL is a continuous filament ceramic oxide fiber with low elongation and shrinkage at operating temperatures, providing 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 aluminosilicates, and NEXTEL 610 is alumina. During manufacturing, NEXTEL filaments are coated with organic sizing or finishes, which function as fiber processing aids. Sizing can involve the use of starch, oil, wax, or other organic components applied to the filament strand for protection and handling aids. Sizing can be removed from ceramic filaments by thermally washing the filaments or ceramic fibers at temperatures of 700°C for 1 to 4 hours.

[0102] Ceramic fibers can be cut, crushed, or chopped to provide relatively uniform lengths. This can be achieved by cutting continuous filaments of ceramic material with mechanical shearing or laser cutting operations, among other cutting operations. Given the highly controlled nature of certain cutting operations, the size distribution of ceramic fibers can be very narrow, allowing for control of composite properties. For example, ceramic fiber length can be measured using an optical microscope (Olympus MX61, Tokyo, Japan) equipped with a CCD camera (Olympus DP72, Tokyo, Japan) and analysis software (Olympus Stream Essentials, Tokyo, Japan). Samples can be prepared by spreading a representative sample of ceramic fibers on a glass slide and measuring the lengths of at least 200 ceramic fibers at 10x magnification.

[0103] Suitable fibers include ceramic fibers available under the trade name NEXTEL (available from 3M Company, St. Paul, MN), such as NEXTEL 312, 440, 610, and 720. One preferred ceramic fiber herein comprises polycrystalline α-Al2O3. Suitable alumina fibers are described, for example, in U.S. Pat. No. 4,954,462 (Wood et al.) and U.S. Pat. No. 5,185,299 (Wood et al.). A representative alpha alumina fiber is commercially available under the trade name NEXTEL 610 (3M Company, St. Paul, MN). In some embodiments, the alumina fibers are polycrystalline alpha alumina fibers and, on a theoretical oxide basis, comprise greater 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 alpha alumina fibers comprise alpha alumina having an average particle size of less than 1 micrometer (or even, in some embodiments, less than 0.5 micrometer). In some embodiments, the polycrystalline alpha 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. Pat. No. 4,047,965 (Karst et al.). Exemplary aluminosilicate fibers are commercially available under the tradenames NEXTEL 440 and NEXTEL 720 from 3M Company (St. Paul, MN). Aluminoborosilicate fibers are described, for example, in U.S. Pat. No. 3,795,524 (Sowman). Exemplary aluminoborosilicate fibers are commercially available under the tradename NEXTEL 312 from 3M Company. Boron nitride fibers can be made, for example, as described in U.S. Pat. No. 3,429,722 (Economy) and U.S. Pat. No. 5,780,154 (Okano et al.).

[0104] 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). Aluminoborosilicate 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 a number of commercial suppliers.

[0105] Examples of useful pigments include, but are not limited to, white pigments such as titanium oxide, zinc phosphate, zinc sulfide, zinc oxide, and lithopone; red and red-orange pigments such as iron oxide (maroon, red, bright red), iron / chromium oxide, cadmium sulfoselenide, and mercury cadmium sulfide (maroon, red, orange); ultramarine (blue, pink, and purple), chromium tin (pink), manganese (purple), cobalt (purple); barium titanate, cadmium sulfide (yellow), chromium (orange, yellow), molybdate (orange), zinc chromate (yellow), nickel titanate (yellow), iron oxide. Orange, yellow, and buff pigments such as nickel tungsten titanium, zinc ferrite, and chromium titanate; brown pigments such as iron oxide (buff, brown), manganese oxide / antimony oxide / titanium oxide, manganese titanate, natural sienna (amber), and titanium tungsten manganese; blue-green pigments such as chromium aluminate (blue), chromium cobalt alumina (turquoise), 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 generally used to achieve the desired color tone in the cured composition.

[0106] The use of fluorescent dyes and pigments can also be useful to make printed compositions visible under invisible light. A particularly useful hydrocarbon-soluble fluorescent dye is 2,5-bis(5-tert-butyl-2-benzoxazolyl)-1-thiophene. Fluorescent dyes such as rhodamines can also be attached to cationic polymers and incorporated as part of the resin.

[0107] If desired, the compositions of the present disclosure may contain other additives, such as indicators, accelerators, surfactants, humectants, antioxidants, tartaric acid, chelating agents, buffers, and other similar ingredients that will be apparent to those skilled in the art. Additionally, pharmaceutical or other therapeutic substances can optionally be added to the photopolymerizable composition. Examples include, but are not limited to, fluoride sources, whitening agents, anti-caries agents (e.g., xylitol), mineral supplements (e.g., calcium phosphate compounds and other calcium and phosphate sources), enzymes, breath fresheners, anesthetics, coagulants, acid neutralizers, chemotherapeutic agents, immune response modifiers, thixotropes, polyols, anti-inflammatory agents, antibacterial agents, antifungal agents, dry mouth treatment agents, desensitizing agents, and the like, types often used in dental compositions.

[0108] Combinations of any of the above additives may be used, and one of ordinary skill in the art can select any one of such additives and the amount thereof to achieve the desired result without undue experimentation.

[0109] The photopolymerizable composition materials herein can also exhibit a variety of desirable properties as uncured, cured, and post-cured articles. When uncured, the photopolymerizable composition has a viscosity profile that conforms to the requirements and parameters of one or more additive manufacturing devices (e.g., 3D printing systems). Advantageously, in many embodiments, the photopolymerizable composition contains minimal amounts of solvent. For example, the composition may contain 95% to 100% solids, preferably 100% solids. In some cases, the photopolymerizable compositions described herein exhibit a dynamic viscosity, when uncured, of about 0.1 to 1,000 Pa·s, about 0.1 to 100 Pa·s, or about 1 to 10 Pa·s, measured at 40°C and a shear rate of 0.1 [1 / s] using a TA Instruments AR-G2 magnetic bearing rheometer using a 40 mm cone-plate measurement system. In some cases, the photopolymerizable compositions described herein exhibit a dynamic viscosity, when uncured, of less than about 10 Pa·s.

[0110] Goods In a second aspect, the present disclosure provides an article, the article comprising the polymerization reaction product of a photopolymerizable composition according to the first or fifth aspect.

[0111] The shape of the article is not limited and may include a film or a molded one-piece article. For example, it can be easily prepared by casting a photopolymerizable composition according to the first aspect and then subjecting the cast composition to actinic radiation to polymerize the photopolymerizable composition. In many embodiments, the article comprises a molded one-piece article in which two or more dimensional variations are achieved in a single one-piece article. For example, the article may include one or more channels, one or more undercuts, one or more perforations, or a combination thereof. Such features are typically not possible to achieve in a one-piece article using conventional molding methods. In selected embodiments, the article comprises an orthodontic article. Orthodontic articles are described in more detail below.

[0112] The suitability and durability of cured articles made from the photopolymerizable compositions of the present disclosure can be judged, in part, by standard tensile, modulus, and / or elongation tests. Photopolymerizable compositions, after hardening, can typically be characterized by at least one of the following parameters:

[0113] The article preferably exhibits at least one desirable physical property, including the following: initial relaxed modulus, elongation to break, tensile strength, relaxed modulus at 30 minutes, percent loss in relaxed modulus, weight percent extractables, and temperature-separated peaks in loss modulus and tan δ, and weight percent water absorption. Preferably, the article exhibits at least two different desirable physical properties, more preferably at least three different desirable physical properties, and most preferably at least initial relaxed modulus, elongation to break, and tensile strength. Values ​​for these different physical properties are described below.

[0114] The article optionally exhibits an initial relaxed modulus of 100 megapascals (MPa) or greater, measured by dynamic mechanical analysis (DMA) at 37°C and 2% strain after conditioning (i.e., immersion) a sample of the article's material in deionized water at room temperature (i.e., 22-25°C) for 48 hours ("water conditioning"). The DMA procedure is described in detail in the Examples below. Preferably, the article exhibits an initial relaxed modulus of 200 MPa or greater, 300 MPa or greater, 400 MPa or greater, 500 MPa or greater, 600 MPa or greater, 700 MPa or greater, 800 MPa or greater, 900 MPa or greater, 1,000 MPa or greater, 1,100 MPa or greater, or even 1,200 MPa or greater. In some embodiments, the initial relaxed modulus is about 3,000, 2,500, 2,000, or 1,500 MPa or less.

[0115] The article optionally exhibits a (e.g., 30-minute) relaxed modulus of 100 MPa or greater at 37°C and 2% strain, as measured by DMA after immersion in water for 30 minutes. The DMA procedure for relaxed modulus is described in detail in the Examples below and is performed on a sample of the article's material after water conditioning and initial relaxed modulus testing. Preferably, the article exhibits a (30-minute) relaxed modulus of 200 MPa or greater, 300 MPa or greater, 400 MPa or greater, 500 MPa or greater, 600 MPa or greater, 700 MPa or greater, 800 MPa or greater, 900 MPa or greater, or even 1,000 MPa or greater. In some embodiments, the (e.g., 30-minute) relaxed modulus is about 1500, 1200, 1000, or 800 MPa or less.

[0116] The article optionally exhibits a percent loss in relaxed modulus of 70% or less as determined by DMA. The loss is determined by comparing the initial relaxed modulus with the relaxed modulus at 37°C and 2% strain (e.g., after 30 minutes). Articles according to at least certain embodiments of the present disclosure have been found to exhibit a lower loss in relaxed modulus after exposure to water than articles made from different materials. Preferably, the article exhibits a loss in relaxed modulus of 65% or less, 60% or less, 55% or less, 50% or less, 45% or less, 40% or less, or even 35% or less. In some embodiments, the loss in relaxed modulus is 10%, 15%, or 20% or more.

[0117] The article optionally exhibits a printed article elongation to break of 20% or greater, as determined in accordance with the Examples section below, after conditioning (i.e., immersing) a sample of the orthodontic article material in phosphate buffered saline at pH 7.4 at a temperature of 37°C for 24 hours ("PBS conditioning"). A high elongation to break helps prevent the article from being too brittle and potentially breaking during use. One potential use is as an orthodontic article, which, if too brittle, could break in the patient's mouth during use. Preferably, the orthodontic article exhibits an elongation to break of 25% or more, 30% or more, 35% or more, 40% or more, 45% or more, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, 75% or more, 80% or more, 85% or more, 90% or more, 95% or more, 100% or more, 110% or more, or even 120% or more. In some embodiments, the elongation to break is 250%, 240%, 230%, 220%, 210%, 200%, 190%, 180%, 170%, 160%, 150%, or 140% or less.

[0118] The article optionally exhibits a yield tensile strength of 14 MPa or greater, measured according to ASTM-D638-14 using specimen V after PBS conditioning. Yield strength (i.e., yield strength) is defined as the maximum tensile stress a material can handle before permanently deforming. Tensile strength at break refers to the point on a stress-strain curve at which the material breaks. As used herein, a yielding specimen has a distinct peak on the stress-strain curve. However, the stress-strain curve of a brittle material does not have a yield point, is often linear throughout the entire strain range, and ultimately fails at the maximum tensile strength without appreciable plastic flow. High tensile strength contributes to the article having a degree of strength that allows it to remain elastic during use in a patient's mouth. Preferably, the article exhibits a tensile strength at yield of 15 MPa or more, 17 MPa or more, 20 MPa or more, 25 MPa or more, 30 MPa or more, 35 MPa or more, 40 MPa or more, 45 MPa or more, 50 MPa or more, or even 55 MPa or more. In some embodiments, the tensile strength is 100 MPa, 95 MPa, 90 MPa, 85 MPa, 80 MPa, 75 MPa, or 70 MPa or less.

[0119] In selected embodiments, the article exhibits an initial relaxed modulus of 100 MPa, an elongation at break of 20% or greater, and a tensile strength at yield of 14 MPa or greater. Similarly, the article may exhibit any combination of the above preferred values ​​for each of the initial relaxed modulus, elongation at break, and tensile strength at yield. It has been unexpectedly discovered that photopolymerizable compositions according to at least certain embodiments can be formed into articles possessing all three of these physical properties simultaneously.

[0120] In selected embodiments, dynamic mechanical analysis of the articles demonstrated a particular type of response, providing high elongation accompanied by a high relaxation modulus at 30 minutes. When measured at a frequency of 1 Hz and a temperature heating ramp rate of 2°C / min from below -40°C to above 200°C, some embodiments according to the present disclosure exhibit a loss modulus peak below 20°C, more preferably below 15°C, and most preferably below 10°C. In some embodiments, the loss modulus peak temperature is at least -70°C, -60°C, or -50°C. The term peak does not necessarily refer to a maximum value of the loss modulus; it can be a local maximum or a shoulder on a larger peak. These articles tend to exhibit high levels of elongation to break. In other embodiments, the articles may also exhibit a Tan δ peak of >80°C, more preferably >100°C, and most preferably >110°C. In some embodiments, the peak Tan δ temperature is equal to or lower than 150°C, 140°C, 135°C, or 130°C. Articles that exhibited a high 30-minute relaxation modulus exhibited a Tan δ peak >80° C. Articles that exhibited both a high elongation at break and a high 30-minute relaxation modulus exhibited a loss modulus peak below 20° C. and a Tan δ peak above 80° C. Loss modulus and Tan δ are explained, for example, in Sepe, MP (1998 Dynamic Mechanical Analysis for Plastics Engineering. William Andrew Publishing / Plastics Design Library).

[0121] In at least certain embodiments of the articles of the present disclosure, the articles are advantageously more resistant to staining than articles made from different, more hydrophilic components. For example, dyes and other coloring materials in aqueous compositions such as beverages are typically hydrophilic and therefore have a greater affinity for more hydrophilic compositions than for more hydrophobic compositions.

[0122] In certain embodiments, the article contains 2% or less, 1% or less, 0.75% or less, 0.5% or less, or even 0.1% or less extractable components by weight, based on the total weight of the article. As described in more detail in the examples below, the components can be extracted using either organic solvents or water. Post-treatment of the article to assist in achieving low extractable component articles is described in more detail below.

[0123] The above mechanical properties are particularly well suited for orthodontic articles that require resilience and flexibility along with adequate wear strength and low moisture absorption.

[0124] method In a third aspect, the present disclosure provides a method of making an article, the method comprising: a) providing a photopolymerizable composition according to the first aspect; and b) polymerizing the photopolymerizable composition.

[0125] In a fourth aspect, the present disclosure provides a method of making an article, the article comprising the reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the entire photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher; b) a photoinitiator; and c) a polymerization reaction product of component The ingredients are i) a diisocyanate; ii) Formula (I): HO-Q-(A)p (I) a hydroxy-functional methacrylate of the formula: wherein Q is a polyvalent organic linking group, A is a methacrylic functional group of the formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2; iii) Formula (II): H(O-R2-OC(=O))mO-R3-OH (II) a polycarbonate diol of formula (II), wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst, and a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer. Alternatively, instead of the polycarbonate diol having the above Mn, the polyurethane methacrylate may have a weight average molecular weight (Mw) of 8,000 g / mol or greater (i.e., similar to the fifth embodiment of the present disclosure).

[0126] Components a) through c) and i) through iv) are as described in detail above. In many embodiments, the photopolymerizable composition of the article is bath polymerized, as described in detail below. Optionally, when formed using additive manufacturing methods, the article comprises multiple layers.

[0127] The photopolymerizable compositions described herein can be mixed using known techniques. In some embodiments, for example, a method for preparing the photopolymerizable compositions described herein includes mixing all or substantially all of the components of the photopolymerizable composition, heating the mixture, and optionally filtering the heated mixture. Softening the mixture, in some embodiments, is carried out at a temperature of about 50°C or a temperature in the range of about 50°C to about 85°C. In some embodiments, the photopolymerizable compositions described herein are prepared by placing all or substantially all of the components of the composition in a reaction vessel and heating the resulting mixture to a temperature in the range of about 50°C to about 85°C with stirring. Heating and stirring are continued until the mixture reaches a substantially homogenized state.

[0128] In many embodiments, the photopolymerizable composition is bath polymerized, as discussed in detail below.

[0129] The shape of the article is not limited, and typically includes molded one-piece articles, including molded one-piece articles in which two or more dimensional variations are provided by a single one-piece article. For example, the article may include one or more channels, one or more undercuts, one or more perforations, or a combination thereof. Such features are typically not possible to achieve in one-piece articles using conventional molding methods. Specific orthodontic articles are described in more detail below.

[0130] In a sixth aspect, the present disclosure provides a method of manufacturing an article, the method comprising: a) 1) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the entire photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher; 2) a photoinitiator; and 3) A polymerization reaction product of a component, wherein the component is: i) a diisocyanate; ii) Formula (I): HO-Q-(A)p (I) a hydroxy-functional methacrylate of the formula: wherein Q is a polyvalent organic linking group, A is a methacrylic functional group of the formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2; iii) Formula (II): H(O-R2-OC(=O))mO-R3-OH (II) a polycarbonate diol of formula (II), wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst; and Including, obtaining a photopolymerizable composition comprising: a polymerization reaction product of components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; b) selectively curing the photopolymerizable composition to form an article; and c) repeating steps a) and b) to form multiple layers and produce an article comprising a three-dimensional structure; Includes:

[0131] Alternatively, instead of the polycarbonate diol having the above Mn, the polyurethane methacrylate may have a weight average molecular weight (Mw) of 8,000 g / mol or more (i.e., similar to the fifth aspect of the present disclosure). The photopolymerizable composition components are as discussed in detail above. In many embodiments, the photopolymerizable composition is cured using actinic radiation, including ultraviolet light, electron beam radiation, visible radiation, or a combination thereof. Furthermore, the method optionally further includes post-curing the article using actinic radiation or heat.

[0132] In certain embodiments, the method comprises bath polymerization of the photopolymerizable composition. When bath polymerization is employed, radiation may be directed through a wall of a container (e.g., a bath) that holds the photopolymerizable composition, such as a side wall or bottom wall.

[0133] The photopolymerizable compositions described herein in their cured state can, in some embodiments, exhibit one or more desirable properties. A "cured" photopolymerizable composition can include a photopolymerizable composition comprising a polymerizable component that is at least partially polymerized and / or crosslinked. For example, in some instances, the cured article is at least about 10% polymerized or crosslinked, or at least about 30% polymerized or crosslinked. In some instances, the cured photopolymerizable composition is at least about 50%, at least about 70%, at least about 80%, or at least about 90% polymerized or crosslinked. The cured photopolymerizable composition can also be from about 10% to about 99% polymerized or crosslinked.

[0134] Manufacture of goods Once prepared as described above, the photopolymerizable compositions of the present disclosure can be used in a variety of additive manufacturing processes, including casting films or articles, to produce a variety of articles. A generalized method 100 for producing three-dimensional articles is shown in FIG. 1. Each step of the method is described in detail below. First, in step 110, a desired photopolymerizable composition (e.g., comprising a monofunctional (meth)acrylate monomer and a polyurethane methacrylate polymer) is provided and introduced into a reservoir, cartridge, or other suitable container for use by or within an additive manufacturing device. The additive manufacturing device selectively cures the photopolymerizable composition according to a set of computerized design instructions in step 120. In step 130, steps 110 and / or 120 are repeated to form multiple layers to produce an article (e.g., a tensile bar) comprising a three-dimensional structure. Optionally, in step 140, the uncured photopolymerizable composition is removed from the article, and further optionally, in step 150, the article is subjected to additional curing to polymerize any remaining uncured photopolymerizable components within the article, and still further optionally, the article is subjected to a heat treatment in step 160.

[0135] Methods of printing three-dimensional articles or objects described herein can include forming an article from multiple layers of the photopolymerizable compositions described herein in a layer-by-layer manner. Further, layers of the material composition to be built can be deposited according to an image of the three-dimensional article in computer-readable form. In some or all embodiments, the photopolymerizable composition is deposited according to preselected computer-aided design (CAD) parameters.

[0136] It is further understood that the methods for producing 3D articles described herein can include so-called "stereolithography / vapour polymerization" 3D printing methods. Other techniques for three-dimensional fabrication are known and may be appropriately adapted for use in the applications described herein. More generally, three-dimensional fabrication techniques are becoming increasingly available. All such techniques can be adapted for use with the photopolymerizable compositions described herein, so long as they provide fabrication viscosities and resolution consistent with the specified article characteristics. Fabrication may be performed using any of the fabrication techniques described herein, alone or in various combinations, using data representing the three-dimensional object, which can be reformatted or otherwise adapted as needed for a particular printing or other fabrication technique.

[0137] It is entirely possible to form 3D articles from the photopolymerizable compositions described herein using liquid vat 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 that defines a cross-section of the 3D article. Additionally, the methods described herein can further include raising and lowering the hardened layer of photopolymerizable composition to provide a new or second fluid layer of unhardened photopolymerizable composition on the surface of the fluid in the container, and subsequently selectively applying energy to the photopolymerizable composition in the container again to solidify at least a portion of the new or second fluid layer of the photopolymerizable composition to form a second solidified layer that defines a second cross-section of the 3D article. Furthermore, the application of energy to solidify the photopolymerizable composition can bond or adhere the first and second cross sections of the 3D article to each other in the z-direction (i.e., the build direction corresponding to the lifting direction described above). Furthermore, selectively applying energy to the photopolymerizable composition in the container can include applying actinic radiation, such as ultraviolet, visible, or electron beam radiation, having sufficient energy to cure the photopolymerizable composition. The methods described herein can also include planarizing the new layer of fluid photopolymerizable composition provided by raising and lowering the elevator platform. Such planarization can, in some cases, be achieved by utilizing a wiper, roller, or recoater. Planarization involves flattening the dispensed material to remove excess material and create a uniform, smooth, exposed, or flat, upward-facing surface on the printer's support platform, thereby correcting the thickness of one or more layers before the material is cured.

[0138] It is further understood that the above-described 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. It is further understood that one or more steps of the methods described herein, such as selectively applying energy to a layer of a photopolymerizable composition, can be performed according to a computer-readable image of the 3D article. Suitable stereolithography printers include the Viper Pro SLA, available from 3D Systems, Rock Hill, SC, and the Asiga PICO PLUS39, available from Asiga USA, Anaheim Hills, CA.

[0139] FIG. 2 shows an example of a stereolithography apparatus ("SLA") that may be used with the photopolymerizable compositions and methods described herein. Generally, SLA 200 may include a laser 202, optics 204, a steering lens 206, an elevator 208, a platform 210, and a linear edge 212 within a bath 214 filled with the photopolymerizable composition. During operation, laser 202 is steered across the surface of the photopolymerizable composition to cure a cross-section of the photopolymerizable composition, after which elevator 208 slightly lowers platform 210 to cure another cross-section. Linear edge 212 may sweep across the surface of the cured composition between layers to smooth and normalize the surface before depositing a new layer. In other embodiments, bath 214 may be slowly filled with liquid resin while an article is drawn layer by layer on top of the photopolymerizable composition.

[0140] A related technique, bath polymerization by digital light processing ("DLP"), also uses a reservoir of curable polymer (e.g., a photopolymerizable composition). However, DLP-based systems project a two-dimensional cross-section onto the curable material, curing the desired portion of the entire plane orthogonal to the projected beam at once. All such curable polymer systems that may be adapted for use with the photopolymerizable compositions described herein are intended to be within the scope of the term "bath polymerization system" as used herein. In certain embodiments, equipment adapted for use in a continuous mode, such as that commercially available from Carbon 3D, Inc. (Redwood City, CA), may be used, as described, for example, in U.S. Pat. Nos. 9,205,601 and 9,360,757 (both to DeSimone et al.).

[0141] 5, a schematic diagram of another SLA apparatus that may be used with the photopolymerizable compositions and methods described herein is provided. Generally, apparatus 500 may include a laser 502, optics 504, a steering lens 506, an elevator 508, and a platform 510 within a bath 514 filled with a photopolymerizable composition 519. During operation, laser 502 is directed through a wall 520 (e.g., a floor) of bath 514 toward the photopolymerizable composition, curing a cross section of photopolymerizable composition 519 to form article 517, after which elevator 508 slightly raises platform 510 and another cross section is cured.

[0142] More generally, photopolymerizable compositions are typically cured using actinic radiation, such as ultraviolet radiation, electron beam radiation, visible radiation, or any combination thereof. One of ordinary skill in the art can select a suitable radiation source and wavelength range for a particular application without undue experimentation.

[0143] After the 3D article is formed, it is typically removed from the additive manufacturing apparatus and cleaned (e.g., ultrasonically, foam, or spray-cleaned in a solvent that dissolves a portion of the uncured photopolymerizable composition but not the cured solid-state article (e.g., substrate)). Any other conventional method may also be used to clean the article and remove uncured material from the surface of the article. At this stage, the three-dimensional article typically has sufficient green strength for handling in any remaining steps of method 100.

[0144] In certain embodiments of the present disclosure, it is expected that the formed article resulting from step 120 will shrink (i.e., decrease in volume), resulting in smaller dimensions of the article after (optional) step 150 than anticipated. For example, the cured article may shrink in volume by less than 5%, less than 4%, less than 3%, less than 2%, or even less than 1%, as opposed to other compositions that result in articles that shrink in volume by approximately 6-8% upon optional post-curing. The amount of volumetric shrinkage typically does not result in significant distortion of the final object shape. Therefore, it is specifically contemplated that the dimensions in the digital representation of the final cured article may be scaled up according to an overall scaling factor to compensate for this shrinkage. For example, in some embodiments, at least a portion of the digital article representation may be at least 101%, 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% of the desired size of the printed orthosis.

[0145] The overall magnification can be calculated for a given photopolymerizable composition formulation by creating a calibration part according to the above steps 110 and 120. The dimensions of the calibration article can be measured before post-cure.

[0146] Typically, the three-dimensional article formed by the initial additive manufacturing process of step 120 is not fully cured, as described above, meaning that not all of the photopolymerizable material in the composition is polymerized, even after washing. Some uncured photopolymerizable material is typically removed from the surface of the printed article during the washing process (e.g., optional step 140). The article surface, and the bulk article itself, typically still retains uncured photopolymerizable material, indicating further curing. Removing residual uncured photopolymerizable composition is particularly useful if the article is subsequently post-cured to minimize uncured residual photopolymerizable composition from undesirably curing directly on the article.

[0147] Further curing can be achieved by further exposure to actinic radiation, heating, or both. Exposure to actinic radiation can be from any convenient radiation source, typically ultraviolet, visible, and / or electron beam radiation, for a time ranging from about 10 minutes to more than 60 minutes. Heating is generally carried out under an inert atmosphere at a temperature ranging from about 75°C to 150°C for a time ranging from about 10 minutes to more than 60 minutes. So-called post-cure ovens, which combine ultraviolet and thermal energy, are particularly suitable for use in the post-cure process of step 150 and / or step 160. Generally, post-curing improves the mechanical properties and stability of the three-dimensional article compared to the same three-dimensional article that has not been post-cured.

[0148] One particularly attractive opportunity for 3D printing is the direct formation of clear tray aligners for orthodontics. These trays, also known as aligners or polymer or shell appliances, come in sets and are intended to be worn continuously over several months to gradually move teeth in incremental steps toward a desired target position. Some types of clear tray aligners have a row of tooth-shaped receptacles that receive each tooth in the patient's dental arch, with the receptacles oriented in slightly different positions from one appliance to the next to incrementally move each tooth toward the desired target position via the elastic properties of the polymer material. Various methods have been proposed to manufacture clear tray aligners and other elastic appliances. Typically, additive manufacturing methods, such as the aforementioned stereolithography, are used to create positive arch models for each dental arch. A sheet of polymer material is then placed over each arch model and formed to fit the model teeth in each model arch using heat, pressure, and / or negative pressure. The formed sheet is cleaned, trimmed as necessary, and the resulting arch-shaped appliance is shipped to a treating professional along with the desired number of other appliances.

[0149] Aligners or other elastic appliances formed directly by 3D printing would eliminate the need to print a dental arch mold and then thermoform the appliances. Furthermore, new aligner designs would become possible, increasing flexibility in treatment planning. Exemplary methods for directly printing clear tray aligners and other elastic orthodontic appliances are described in PCT Publication Nos. WO 2016 / 109660 (Raby et al.), WO 2016 / 148960 (Cinader et al.), and WO 2016 / 149007 (Oda et al.), as well as U.S. Patent Publication Nos. 2011 / 0091832 (Kim et al.) and 2013 / 0095446 (Kitching).

[0150] Similar techniques and the photopolymerizable compositions of the present disclosure can be used to make a variety of dental and orthodontic articles, including, but not limited to, removable appliances with occlusal windows as described in International Application Publication No. 2016 / 109660 (Raby et al.), removable appliances with palatal plates as described in U.S. Patent Publication No. 2014 / 0356799 (Cinader et al.), and resilient polymeric dental arch members as described in International Application Publication Nos. 2016 / 148960 and 2016 / 149007 (Oda et al.), and U.S. Patent Publication No. 2008 / 0248442 (Cinader et al.). Additionally, the photopolymerizable compositions can be used to make indirect bonding trays, such as those described in WO 2015 / 094842 (Paehl et al.) and U.S. Patent Application Publication No. 2011 / 0091832 (Kim et al.), as well as other dental articles, including, but not limited to, crowns, bridges, veneers, inlays, onlays, fillings, and prostheses (e.g., partial or complete dentures). Other orthodontic appliances and devices include, but are not limited to, orthodontic brackets, buccal tubes, lower retainers, orthodontic bands, Class II and Class III braces, sleep apnea devices, mouth gag devices, buttons, cleats, and other accessory devices.

[0151] In some embodiments, in accordance with at least certain aspects of the present disclosure, a (e.g., non-transitory) machine-readable medium is used in additive manufacturing of an article. Data is typically stored on the machine-readable medium. The data represents a three-dimensional model of the article, which model is accessible by at least one computer processor interfaced with additive manufacturing equipment (e.g., a 3D printer, a manufacturing device, etc.). The data is used to cause the additive manufacturing equipment to fabricate an article comprising a reaction product of a photopolymerizable composition, the photopolymerizable composition comprising a blend of a) 40-60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, b) a photoinitiator, and c) the polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of the components includes i) a diisocyanate, ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I), iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II), and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is an integer between 2 and 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol. Components a) to c) and i) to iv) are as described in detail above.

[0152] Data representing the article may be generated using computer modeling, such as computer-aided design (CAD) data. Image data representing the design of the (e.g., polymer) article can be exported to an additive manufacturing machine in STL format or any other suitable computer-processable format. Scanning methods for scanning three-dimensional objects can also be used to create the data representing the article. One exemplary technique for acquiring data is digital scanning. Any other suitable scanning technique can be used to scan the article, including 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.). The initial digital dataset, which may include both raw data from the scanning operation and data representing the article derived from the raw data, can be processed to separate the design of the article from any surrounding structures (e.g., supports for the article). In embodiments in which the article is an orthodontic article, scanning techniques may include, for example, scanning a patient's oral cavity to customize the orthodontic article for the patient.

[0153] In many cases, machine-readable media is provided as part of a computing device. A computing device may have one or more processors, volatile memory (RAM), a device for reading the machine-readable media, and input / output devices such as a display, a keyboard, and a pointing device. Additionally, a computing device may also include other software, such as an operating system and other application software, firmware, or a combination thereof. A computing device may be, for example, a workstation, laptop, personal digital assistant (PDA), server, mainframe, or any other general-purpose or special-purpose computing device. A computing device may read executable software instructions from a computer-readable medium (such as a hard drive, CD-ROM, or computer memory) or may receive instructions from another source logically connected to the computer, such as another networked computer. Referring to FIG. 10 , a computing device 1000 often 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. In FIG. 10 , a drawbar 1130 is displayed on the display 1100.

[0154] Referring to FIG. 6 , in certain embodiments, the present disclosure provides a system 600. The system 600 includes a display 620 that displays a 3D model 610 of an article (e.g., a drawbar 1130 as displayed in the display 1100 of FIG. 10 ) and one or more processors 630 that cause a 3D printer / additive manufacturing device 650 to create a physical object of the article 660 in response to the 3D model 610 selected by a user. Often, 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, specifically for user selection of the 3D model 610. The article 660 includes the reaction product of a photopolymerizable composition that includes a blend of a) 40-60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, b) a photoinitiator, and c) the polymerization reaction product of components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group; A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms); and p is 1 or 2. The polymerization reaction product includes a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeating unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is an integer from 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol. Components a) to c) and i) to iv) are as described in detail above.

[0155] 7, a processor 720 (or two or more processors) is in communication with each of a machine-readable medium 710 (e.g., a non-transitory medium), a 3D printer / additive manufacturing device 740, and, optionally, a display 730 for viewing by a user. The 3D printer / additive manufacturing device 740 is configured to manufacture one or more articles 750 based on instructions from the machine-readable medium 710 from the processor 720, which provides data representing a 3D model of the article 750 (e.g., including a drawbar 1130 as displayed on the display 1100 of FIG. 10).

[0156] Referring to FIG. 8 , for example, but not by way of limitation, an additive manufacturing method includes obtaining 810 data representing a 3D model of an article according to at least one embodiment of the present disclosure from a (e.g., non-transitory) machine-readable medium. The method further includes executing 820, by one or more processors, an additive manufacturing application that interfaces with a modeling device using the data, and generating 830, by the modeling device, a physical object of the article. The additive manufacturing equipment can selectively cure a photopolymerizable composition to form the article. The article includes a reaction product of a photopolymerizable composition that includes a blend of a) 40-60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, b) a photoinitiator, and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125° C. or greater. The polymerization reaction product of the components includes i) a diisocyanate, ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I), iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II), and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is an integer between 2 and 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol. Components a)-c) and i)-iv) are as described in detail above. One or more of various optional post-processing steps 840 may be performed. Typically, any remaining unpolymerized photopolymerizable components may be cured. In certain embodiments, the article comprises an orthodontic article.

[0157] 9, a method of manufacturing an article includes receiving 910, by a manufacturing device having one or more processors, a digital object including data defining multiple layers of the article, and generating 920, using the manufacturing device by an additive manufacturing process, an article based on the digital object. Again, the article may be subjected to one or more steps of post-processing 930.

[0158] Selected Embodiments of the Present Disclosure Embodiment 1 is a photopolymerizable composition. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or higher. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group; A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms; and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0159] Embodiment 2 is the photopolymerizable composition of embodiment 1, further comprising Formula (III): [ka] wherein Q, p, and R1 are as defined for formula (I), and Rdi is the residue of a diisocyanate.

[0160] Embodiment 3 is the photopolymerizable composition of embodiment 2, wherein the compound of formula (III) is produced during polymerization of the components.

[0161] Embodiment 4 is the photopolymerizable composition of embodiment 2 or embodiment 3, wherein a compound of formula (III) is added to the photopolymerizable composition.

[0162] Embodiment 5 is the photopolymerizable composition of any one of embodiments 2-4, wherein the compound of Formula (III) is present in an amount of 0.05 weight percent to 20 weight percent (wt %), based on the weight of the polymerizable composition.

[0163] Embodiment 6 is the photopolymerizable composition of any one of embodiments 2-5, wherein the compound of Formula (III) is present in an amount of 1.5% to 12% by weight, based on the weight of the polymerizable composition.

[0164] Embodiment 7 is the photopolymerizable composition of any one of embodiments 2-5, wherein the compound of formula (III) is present in an amount of 5% to 20% by weight, based on the weight of the polymerizable composition.

[0165] Embodiment 8 is the photopolymerizable composition of any one of embodiments 2-7, wherein Q in the compound of formula (III) is divalent.

[0166] Embodiment 9 is the photopolymerizable composition of any one of embodiments 2-8, wherein the compound of formula (III) is of formula (IV): [ka]

[0167] Embodiment 10 is the photopolymerizable composition of any one of embodiments 1-9, further comprising a difunctional (meth)acrylate monomer or oligomer.

[0168] Embodiment 11 is the photopolymerizable composition of any one of embodiments 1-10, wherein the monofunctional (meth)acrylate monomer is selected from the group consisting of 3,3,5-trimethylcyclohexyl methacrylate, butylcyclohexyl methacrylate (e.g., cis-4-tert-butylcyclohexyl methacrylate, 73 / 27 trans / cis-4-tert-butylcyclohexyl methacrylate, and / or trans-4-tert-butylcyclohexyl methacrylate), 2-decahydronaphthyl methacrylate, 1-adamantyl acrylate, dicyclopentadienyl methacrylate, isobornyl methacrylate (e.g., d,l-isobornyl methacrylate), dimethyl-1-adamantyl methacrylate, bornyl methacrylate (e.g., d,l-bornyl methacrylate), 3-tetracyclo[4.4.0.1.1]dodecyl methacrylate, 1-adamantyl methacrylate, and combinations thereof.

[0169] Embodiment 12 is the photopolymerizable composition according to any one of embodiments 1 to 11, wherein the weight ratio of the (meth)acrylate monomer to the polyurethane methacrylate polymer is 60:40 to 40:60.

[0170] Embodiment 13 is the photopolymerizable composition according to any one of embodiments 1 to 12, wherein the weight ratio of the (meth)acrylate monomer to the polyurethane methacrylate polymer is 55:45 to 45:55.

[0171] Embodiment 14 is the photopolymerizable composition of any one of embodiments 1-13, wherein the diisocyanate is selected from the group consisting of 2,6-toluene diisocyanate (TDI), methylenedicyclohexylene-4,4'-diisocyanate (H12MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,6-diisocyanatohexane (HDI), tetramethyl-m-xylylene diisocyanate, a mixture of 2,2,4-trimethyl-1,6-diisocyanatohexane and 2,4,4-trimethyl-1,6-diisocyanatohexane (TMXDI), trans-1,4-hydrogenated xylylene diisocyanate (H6XDI), and combinations thereof.

[0172] Embodiment 15 is the photopolymerizable composition of any one of embodiments 1-14, wherein the diisocyanate comprises IPDI.

[0173] Embodiment 16 is the photopolymerizable composition according to any one of embodiments 1 to 15, wherein in the polycarbonate diol of formula (II), the average number of carbon atoms in the combination of all R2 groups and R3 groups is 4 to 10.

[0174] Embodiment 17 is the photopolymerizable composition of any one of embodiments 1 to 16, wherein in the hydroxy-functional methacrylate of formula (I), Q is an alkylene group, p is 1, and in the methacryl functional group A, R1 is methyl.

[0175] Embodiment 18 is the photopolymerizable composition of any one of embodiments 1 through 17, wherein the polycarbonate diol has an Mn of greater than 1,000 grams per mole (g / mol) to 3,200 g / mol, greater than 1,000 g / mol to 2,000 g / mol, greater than 1,000 g / mol to 2,600 g / mol, or 1,800 g / mol to 2,200 g / mol.

[0176] Embodiment 19 is the photopolymerizable composition of any one of embodiments 1 to 18, having a solids content of 95% to 100% solids.

[0177] Embodiment 20 is the photopolymerizable composition of any one of embodiments 1-19, wherein the monofunctional (meth)acrylate monomer has a logarithm of the octanol / water partition coefficient (log P) value greater than 3, greater than 2, or greater than 1.

[0178] Embodiment 21 is the photopolymerizable composition of any one of embodiments 1 through 20, essentially free of monofunctional (meth)acrylate monomers having a log P value less than 3, less than 2, or less than 1.

[0179] Embodiment 22 is the photopolymerizable composition of any one of embodiments 1 to 21, further comprising an ultraviolet absorber comprising a fluorescent brightener in an amount of 0.001 wt % to 5 wt %, based on the total weight of the photopolymerizable composition.

[0180] Embodiment 23 is the photopolymerizable composition of any one of embodiments 1 to 22, further comprising an inhibitor in an amount of 0.001 wt % to 1 wt %, based on the total weight of the photopolymerizable composition.

[0181] Embodiment 24 is the photopolymerizable composition of any one of embodiments 1 to 23, wherein the photoinitiator is present in an amount of 0.2% to 5% by weight, based on the weight of the photopolymerizable composition.

[0182] Embodiment 25 is the photopolymerizable composition of any one of embodiments 1 to 24, wherein the catalyst comprises zinc.

[0183] Embodiment 26 is the photopolymerizable composition of any one of embodiments 1-25, wherein the catalyst comprises an organometallic zinc complex and does not comprise 2-ethylhexyl carboxylate or 2-ethylhexanoic acid.

[0184] Embodiment 27 is the photopolymerizable composition of any one of embodiments 1-26, wherein the catalyst does not contain tin.

[0185] Embodiment 28 is the photopolymerizable composition of any one of embodiments 1 to 27, wherein the catalyst comprises bismuth.

[0186] Embodiment 29 is the photopolymerizable composition of any one of embodiments 1 to 28, wherein the polyurethane methacrylate polymer has a weight average molecular weight (Mw) of 6,000 g / mol to 35,000 g / mol.

[0187] Embodiment 30 is the photopolymerizable composition of any one of embodiments 1 through 29, further comprising a difunctional monomer in an amount of up to 15 weight percent, based on the total weight of the photopolymerizable composition.

[0188] Embodiment 31 is the photopolymerizable composition of embodiment 30, wherein the difunctional monomer comprises hydroxyethyl methacrylate diester of terephthalic acid, 1,12-dodecanediol dimethacrylate, or a combination thereof.

[0189] Embodiment 32 is the photopolymerizable composition of embodiment 30 or 31, wherein the difunctional monomer comprises a hydroxyethyl methacrylate diester of terephthalic acid.

[0190] Embodiment 33 is the photopolymerizable composition of any one of embodiments 1 to 32, wherein the ratio of diisocyanate to polycarbonate diol ranges from 4 molar equivalents of isocyanate of diisocyanate to 1 molar equivalent of alcohol of polycarbonate diol to 4 molar equivalents of isocyanate of diisocyanate to 3 molar equivalents of alcohol of polycarbonate diol.

[0191] Embodiment 34 is the photopolymerizable composition of embodiment 33, wherein the ratio of diisocyanate to polycarbonate diol is 4 molar equivalents of isocyanate of the diisocyanate to 2 molar equivalents of alcohol of the polycarbonate diol.

[0192] Embodiment 35 is the photopolymerizable composition of any one of embodiments 1 through 34, wherein the ratio of diisocyanate to hydroxy-functional methacrylate of Formula (I) ranges from 4 molar equivalents of isocyanate of diisocyanate to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 4 molar equivalents of isocyanate of diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0193] Embodiment 36 is the photopolymerizable composition of any one of embodiments 1 through 35, wherein the ratio of diisocyanate to hydroxy-functional methacrylate of Formula (I) is 4 molar equivalents of isocyanate of diisocyanate to 2 molar equivalents of hydroxy-functional methacrylate of Formula (I).

[0194] Embodiment 37 is the photopolymerizable composition of any one of embodiments 1 to 36, wherein the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) ranges from 1 molar equivalent of alcohol of polycarbonate diol to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 3 molar equivalents of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0195] Embodiment 38 is the photopolymerizable composition of any one of embodiments 1 through 37, wherein the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) is 1 molar equivalent of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0196] Embodiment 39 is a method for preparing a polyurethane methacrylate having formula (V): [ka] 39. The photopolymerizable composition of any one of embodiments 1 to 38, wherein A has the formula -OC(=O)C(R1)=CH2, where R1 is alkyl of 1 to 4 carbon atoms (e.g., methyl), p is 1 or 2, Q is a polyvalent organic linking group as defined above, Rdi is the residue of a diisocyanate, RdOH is the residue of a polycarbonate polyol, and r is an average of 1 to 15.

[0197] Embodiment 40 is the photopolymerizable composition of any one of embodiments 1 to 39, further comprising a compound of Formula (VI). [ka]

[0198] Embodiment 41 is the photopolymerizable composition of any one of embodiments 1 through 40, further comprising a second polymerization reaction product of the component comprising: 1) an isocyanate-functional (meth)acrylate compound of formula (VII): (A1)pQ-NCO(VII), where p and Q are as defined for formula (I), and A1 is a (meth)acrylic functional group of formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H; 2) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(I); and 3) a catalyst. Each R3 and each R3 in each (O-R3-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 g / mol, or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0199] Embodiment 42 is an embodiment of the present invention, wherein the second polymerization reaction product is a copolymer having a structure represented by Formula (VIII): [ka] wherein Q and p are as defined for Formula (I), R2 and R3 are as defined for Formula (II), and R4 is as defined for Formula (VII).

[0200] Embodiment 43 is a method for treating a compound of formula (VIII) comprising administering to a patient a compound of formula (IX): [ka] 43. The photopolymerizable composition of embodiment 42, wherein n is about 6.7 for a 1000 molecular weight polycarbonate diol based on hexanediol.

[0201] Embodiment 44 is the photopolymerizable composition of any one of embodiments 1-43, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 155° C. or greater.

[0202] Embodiment 45 is the photopolymerizable composition of any one of embodiments 1-44, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 170°C or greater, or 180°C or greater.

[0203] Embodiment 46 is the photopolymerizable composition of any one of embodiments 1-45, essentially free of diol compounds having a lower molecular weight than any polycarbonate diol present in the composition.

[0204] Embodiment 47 is the photopolymerizable composition of any one of embodiments 1-46, essentially free of trihydric alcohols.

[0205] Embodiment 48 is an article comprising the photopolymerized reaction product of the photopolymerizable composition of any one of embodiments 1-47.

[0206] Embodiment 49 is the article of embodiment 48, exhibiting an initial relaxation modulus greater than or equal to 100 megapascals (MPa) measured at 37° C. and 2% strain.

[0207] Embodiment 50 is the article of embodiment 48 or embodiment 49, exhibiting a percent loss in relaxed modulus of 70% or less.

[0208] Embodiment 51 is the article of any one of embodiments 48-50, exhibiting a percent loss in relaxed modulus of 40% or less.

[0209] Embodiment 52 is the article of any one of embodiments 48-51, exhibiting a relaxed modulus of 100 MPa or greater.

[0210] Embodiment 53 is the article of any one of embodiments 48-52, wherein the printed article exhibits an elongation at break of 20% or greater, or 70% or greater.

[0211] Embodiment 54 is the article of any one of embodiments 48-53, exhibiting a tensile strength at yield of 14 MPa or greater, or 25 MPa or greater.

[0212] Embodiment 55 is the article of any one of embodiments 48-54, comprising 1% or less by weight of extractable components.

[0213] Embodiment 56 is the article of any one of embodiments 48-55, exhibiting two glass transition temperatures (Tg).

[0214] Embodiment 57 is the article of claim 56, wherein the first Tg is 20° C. or less and the second Tg is 80° C. or more.

[0215] Embodiment 58 is a method of making an article. The method includes: a) obtaining a photopolymerizable composition; and b) polymerizing the photopolymerizable composition. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0216] Embodiment 59 is a method of making an article. The method includes: a) obtaining a photopolymerizable composition; and b) selectively curing the photopolymerizable composition to form an article. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0217] Embodiment 60 is the method of embodiment 59, further comprising repeating steps a) and b) to form multiple layers to create an article having a three-dimensional structure.

[0218] Embodiment 61 is the method of embodiment 59 or embodiment 60, wherein the photopolymerizable composition is cured using actinic radiation, including ultraviolet radiation, electron beam radiation, visible radiation, or a combination thereof.

[0219] Embodiment 62 is the method of embodiment 61, wherein the actinic radiation is directed through a wall of a container holding the photopolymerizable composition.

[0220] Embodiment 63 is the method of embodiment 61 or 62, wherein 90% or more of the actinic radiation is absorbed over a distance of 150 micrometers of the photopolymerizable composition.

[0221] Embodiment 64 is the method of any one of embodiments 59-63, wherein the photopolymerizable composition is cured through the floor of a container holding the photopolymerizable composition.

[0222] Embodiment 65 is the method of any one of embodiments 59-64, further comprising post-curing the article with actinic radiation.

[0223] Embodiment 66 is the method of any one of embodiments 59-65, comprising bath polymerization of the photopolymerizable composition.

[0224] Embodiment 67 is the method of any one of embodiments 59-66, wherein the article comprises a film or a molded integral article.

[0225] Embodiment 68 is the method of any one of embodiments 59-67, wherein the article comprises one or more channels, one or more undercuts, one or more perforations, or a combination thereof.

[0226] Embodiment 69 is the method of any one of embodiments 59-68, further comprising subjecting the article to a heat treatment.

[0227] Embodiment 70 is the method of any one of embodiments 58-69, wherein the photopolymerizable composition further comprises at least one filler.

[0228] Embodiment 71 is the method of any one of embodiments 58-70, wherein the photopolymerizable composition further comprises at least one filler selected from silica, alumina, zirconia, and discontinuous fibers.

[0229] Embodiment 72 is the method of embodiment 71, wherein the discontinuous fibers comprise carbon, ceramic, glass, or a combination thereof.

[0230] Embodiment 73 is a compound of formula (III): [ka] 73. The method of any one of claims 58 to 72, further comprising a compound of the formula: (wherein Q, p, and R1 are as defined for formula (I), and Rdi is a residue of a diisocyanate).

[0231] Embodiment 74 is the method of embodiment 73, wherein the compound of formula (III) is produced during polymerization of the components.

[0232] Embodiment 75 is the method of embodiment 73 or 74, wherein the compound of Formula (III) is added to the photopolymerizable composition.

[0233] Embodiment 76 is the method of any one of embodiments 73 to 75, wherein the compound of Formula (III) is present in an amount of 0.05 weight percent to 20 weight percent (wt %), based on the weight of the polymerizable composition.

[0234] Embodiment 77 is the method of any one of embodiments 73 to 76, wherein the compound of Formula (III) is present in an amount of 1.5% to 12% by weight, based on the weight of the polymerizable composition.

[0235] Embodiment 78 is the method of any one of embodiments 73 to 77, wherein the compound of Formula (III) is present in an amount of 5% to 20% by weight, based on the weight of the polymerizable composition.

[0236] Embodiment 79 is the method of any one of embodiments 73 to 78, wherein Q in the compound of Formula (III) is divalent.

[0237] Embodiment 80 is the method of any one of embodiments 73 to 79, wherein the compound of Formula (III) is of Formula (IV): [ka]

[0238] Embodiment 81 is the method of any one of embodiments 58-80, wherein the photopolymerizable composition further comprises a difunctional (meth)acrylate monomer or oligomer.

[0239] Embodiment 82 is the method of any one of embodiments 58 to 81, wherein the monofunctional (meth)acrylate monomer is selected from the group consisting of 3,3,5-trimethylcyclohexyl methacrylate, butyl-cyclohexyl methacrylate (e.g., cis-4-tert-butyl-cyclohexyl methacrylate, 73 / 27 trans / cis-4-tert-butylcyclohexyl methacrylate, and / or trans-4-tert-butylcyclohexyl methacrylate), 2-decahydronaphthyl methacrylate, 1-adamantyl acrylate, dicyclopentadienyl methacrylate, isobornyl methacrylate (e.g., d,l-isobornyl methacrylate), dimethyl-1-adamantyl methacrylate, bornyl methacrylate (e.g., d,l-bornyl methacrylate), 3-tetracyclo[4.4.0.1.1]dodecyl methacrylate, 1-adamantyl methacrylate, and combinations thereof.

[0240] Embodiment 83 is the method of any one of embodiments 58 to 82, wherein the weight ratio of (meth)acrylate monomer to polyurethane methacrylate polymer is from 60:40 to 40:60.

[0241] Embodiment 84 is the method of any one of embodiments 58 to 83, wherein the weight ratio of (meth)acrylate monomer to polyurethane methacrylate polymer is 55:45 to 45:55.

[0242] Embodiment 85 is the method of any one of embodiments 58 to 84, wherein the diisocyanate is selected from the group consisting of 2,6-toluene diisocyanate (TDI), methylenedicyclohexylene-4,4'-diisocyanate (H12MDI), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,6-diisocyanatohexane (HDI), tetramethyl-m-xylylene diisocyanate, a mixture of 2,2,4-trimethyl-1,6-diisocyanatohexane and 2,4,4-trimethyl-1,6-diisocyanatohexane (TMXDI), trans-1,4-hydrogenated xylylene diisocyanate (H6XDI), and combinations thereof.

[0243] Embodiment 86 is the method of any one of embodiments 58 to 85, wherein the diisocyanate comprises IPDI.

[0244] Embodiment 87 is the method of any one of embodiments 58 to 86, wherein in the polycarbonate diol of Formula (II), the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10.

[0245] Embodiment 88 is the method of any one of embodiments 58-87, wherein in the hydroxy-functional methacrylate of Formula (I), Q is an alkylene group, p is 1, and in the methacryl functional group A, R2 is methyl.

[0246] Embodiment 89 is the method of any one of embodiments 58 to 88, wherein the polycarbonate diol has a Mn of greater than 1,000 grams per mole (g / mol) to 3,200 g / mol, greater than 1,000 g / mol to 2,000 g / mol, greater than 1,000 g / mol to 2,600 g / mol, or 1,800 g / mol to 2,200 g / mol.

[0247] Embodiment 90 is the method of any one of embodiments 58 to 89, wherein the photopolymerizable composition has a solids content of 95% to 100% solids.

[0248] Embodiment 91 is the method of any one of embodiments 58-90, wherein the monofunctional (meth)acrylate monomer has a log P value greater than 3, greater than 2, or greater than 1.

[0249] Embodiment 92 is the method of any one of embodiments 58-91, essentially free of monofunctional (meth)acrylate monomers having a log P value of less than 3, less than 2, or less than 1.

[0250] Embodiment 93 is the method of any one of embodiments 58 to 92, wherein the photopolymerizable composition further comprises an ultraviolet absorber comprising an optical brightener in an amount of 0.001 wt.% to 5 wt.%, based on the total weight of the photopolymerizable composition.

[0251] Embodiment 94 is the method of any one of embodiments 58 to 93, wherein the photopolymerizable composition further comprises an inhibitor in an amount of 0.001 wt % to 1 wt %, based on the total weight of the photopolymerizable composition.

[0252] Embodiment 95 is the method of any one of embodiments 58 to 94, wherein the photoinitiator is present in an amount of 0.2 wt.% to 5 wt.%, based on the weight of the photopolymerizable composition.

[0253] Embodiment 96 is the method of any one of embodiments 58 to 95, wherein the catalyst comprises zinc.

[0254] Embodiment 97 is the method of any one of embodiments 58 to 96, wherein the catalyst comprises an organometallic zinc complex and does not comprise 2-ethylhexyl carboxylate or 2-ethylhexanoic acid.

[0255] Embodiment 98 is the method of any one of embodiments 58 to 97, wherein the catalyst does not contain tin.

[0256] Embodiment 99 is the method of any one of embodiments 58 to 98, wherein the catalyst comprises zinc.

[0257] Embodiment 100 is the method of any one of embodiments 58-99, wherein the polyurethane methacrylate polymer has a weight average molecular weight (Mw) of 6,000 g / mol to 35,000 g / mol.

[0258] Embodiment 101 is the method of any one of embodiments 58-100, wherein the photopolymerizable composition further comprises a difunctional monomer in an amount of up to 15 wt %, based on the total weight of the photopolymerizable composition.

[0259] Embodiment 102 is the method of embodiment 101, wherein the difunctional monomer comprises hydroxyethyl methacrylate diester of terephthalic acid, 1,12-dodecanediol dimethacrylate, or a combination thereof.

[0260] Embodiment 103 is the method of embodiment 101 or embodiment 102, wherein the difunctional monomer comprises a hydroxyethyl methacrylate diester of terephthalic acid.

[0261] Embodiment 104 is the method of any one of embodiments 58-103, wherein the ratio of diisocyanate to polycarbonate diol ranges from 4 molar equivalents of isocyanate of diisocyanate to 1 molar equivalent of alcohol of polycarbonate diol to 4 molar equivalents of isocyanate of diisocyanate to 3 molar equivalents of alcohol of polycarbonate diol.

[0262] Embodiment 105 is the method of embodiment 104, wherein the ratio of diisocyanate to polycarbonate diol is 4 molar equivalents of isocyanate of the diisocyanate to 2 molar equivalents of alcohol of the polycarbonate diol.

[0263] Embodiment 106 is the method of any one of embodiments 58 to 104, wherein the ratio of diisocyanate to hydroxy-functional methacrylate of Formula (I) is in the range of 4 molar equivalents of isocyanate of diisocyanate to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 4 molar equivalents of isocyanate of diisocyanate to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0264] Embodiment 107 is the method of any one of embodiments 58-106, wherein the ratio of diisocyanate to hydroxy-functional methacrylate of Formula (I) is 4 molar equivalents of isocyanate of diisocyanate to 2 molar equivalents of hydroxy-functional methacrylate of Formula (I).

[0265] Embodiment 108 is the method of any one of embodiments 58 to 107, wherein the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) ranges from 1 molar equivalent of alcohol of polycarbonate diol to 3 molar equivalents of hydroxy-functional methacrylate of Formula (I) to 3 molar equivalents of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0266] Embodiment 109 is the method of any one of embodiments 58-108, wherein the ratio of polycarbonate diol to hydroxy-functional methacrylate of Formula (I) is 1 molar equivalent of alcohol of polycarbonate diol to 1 molar equivalent of hydroxy-functional methacrylate of Formula (I).

[0267] Embodiment 110 is a method for preparing a polyurethane methacrylate having formula (V): [ka] 109. The method of any one of embodiments 58-109, wherein A has the formula -OC(=O)C(R1)=CH2, where R1 is alkyl of 1 to 4 carbon atoms (e.g., methyl), p is 1 or 2, Q is a polyvalent organic linking group as defined above, Rdi is the residue of a diisocyanate, RdOH is the residue of a polycarbonate polyol, and r is an average of 1 to 15.

[0268] Embodiment 111 is the method of any one of embodiments 58 to 110, further comprising a compound of formula (VI). [ka]

[0269] Embodiment 112 is the method of any one of embodiments 58-111, wherein the polymerization reaction product of the components has an addition order of the polycarbonate diol component first and the monofunctional methacrylate component second.

[0270] Embodiment 113 is the method of embodiment 112, wherein the order of addition of components includes the diisocyanate third.

[0271] Embodiment 114 is an embodiment in which the photopolymerizable composition comprises a compound of Formula (VIII): [ka] wherein Q and p are as defined for formula (I), R2 and R3 are as defined for formula (II), and R4 is as defined for formula (VII).

[0272] Embodiment 115 is the case where the compound of formula (VIII) is a compound of formula (IX): [ka] 115. The method of embodiment 114, wherein the compound is: wherein n is about 6.7 for a 1000 molecular weight polycarbonate diol based on hexanediol.

[0273] Embodiment 116 is the method of any one of embodiments 58-115, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 155° C. or greater.

[0274] Embodiment 117 is the method of any one of embodiments 58-116, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 170°C or greater, or 180°C or greater.

[0275] Embodiment 118 is the method of any one of embodiments 58-117, wherein the photopolymerizable composition is essentially free of diol compounds having a lower molecular weight than any polycarbonate diol present in the composition.

[0276] Embodiment 119 is the method of any one of embodiments 58-118, wherein the photopolymerizable composition is essentially free of trihydric alcohols.

[0277] Embodiment 120 is a non-transitory machine-readable medium. The non-transitory machine-readable medium contains data representing a three-dimensional model of an article, and when accessed by one or more processors interfaced with a 3D printer, causes the 3D printer to produce an article comprising the reaction product of a photopolymerizable composition. The photopolymerizable composition comprises a blend of a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of components comprises i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms or H), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0278] Embodiment 121 is a method comprising: 1) obtaining data representing a 3D model of an article from a non-transitory machine-readable medium; 2) executing, by one or more processors, a 3D printing application that interfaces with a manufacturing device using the data; and 3) generating, by the manufacturing device, a physical object of the article, wherein the article comprises a reaction product of a photopolymerizable composition comprising a blend of: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125° C. or greater. The polymerization reaction product of the components includes i) a diisocyanate, ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p (I), iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH (II), and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms or H), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0279] Embodiment 122 is another method. The method includes: 1) receiving, by a manufacturing device having one or more processors, a digital object including data defining multiple layers of an article; and 2) generating, using the manufacturing device by an additive manufacturing process, an article based on the digital object, the article including a reaction product of a photopolymerizable composition. The photopolymerizable composition includes a blend of: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125° C. or greater. The polymerization reaction product of the components includes i) a diisocyanate, ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I), iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II), and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms or H), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0280] Embodiment 123 is a system comprising: 1) a display displaying a 3D model of an article; and 2) one or more processors for causing a 3D printer to create a physical object of the article in response to a 3D model selected by a user, the article comprising the reaction product of a photopolymerizable composition comprising a blend of a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components, the cured homopolymer of the monofunctional (meth)acrylate monomer having a Tg of 125°C or greater. The polymerization reaction product of the components comprises: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2 (where R1 is a lower alkyl of 1 to 4 carbon atoms or H), and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in the combination of all R2 and R3 groups is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0281] Embodiment 124 is a compound of formula (VI): [ka] is a compound of

[0282] Embodiment 125 is a photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; and b) a compound of formula (VI): [ka] The composition includes a polymerization product of the following components: (i) an optical brightener of formula (I): (a) a photoinitiator; (b) a photoinitiator; and (c) a polymerization product of component (I): (b) a photoinitiator; and (c) a polymerization product of component (I): (c) a photoinitiator; and (d) a polymerization product of component (I): (a) a photoinitiator; and (b) a polymerization product of component (I): (b) a photoinitiator; and (c) a polymerization product of component (I): (c) a photoinitiator; and (d) a polymerization product of component (I): (c) a photoinitiator; and (e) a polymerization product of component (I): (c) a photoinitiator; and (f ... Each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0283] Embodiment 126 is an article comprising the polymerization reaction product of the photopolymerizable composition of embodiment 125.

[0284] Embodiment 127 is a method of making an article. The method includes: a) providing a photopolymerizable composition; and b) selectively curing the photopolymerizable composition to form the article. The photopolymerizable composition includes: a) 40 to 60 parts by weight, per 100 parts by weight of the total photopolymerizable composition, of a monofunctional (meth)acrylate monomer; and b) a compound of Formula (VI): [ka] The composition includes a polymerization reaction product of: (i) an optical brightener of formula (I): (II ... Each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol.

[0285] Embodiment 128 is the method of embodiment 127, further comprising repeating steps a) and b) to form multiple layers to create an article having a three-dimensional structure.

[0286] Embodiment 129 is a photopolymerizable composition. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of the components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of the components includes: i) a diisocyanate; ii) a hydroxy-functional methacrylate of formula (I): HO-Q-(A)p(I); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group; A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms; and p is 1 or 2. The polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight of 8,000 g / mol or greater, wherein each R2 and R3 in each (O-R2-O-C(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23.

[0287] Embodiment 130 is a photopolymerizable composition. The photopolymerizable composition includes: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition; b) a photoinitiator; and c) a polymerization reaction product of components. The cured homopolymer of the monofunctional (meth)acrylate monomer has a Tg of 125°C or greater. The polymerization reaction product of components includes: i) a diisocyanate; ii) a hydroxy-functional (meth)acrylate of formula (X): HO-Q-(A1)2(X); iii) a polycarbonate diol of formula (II): H(O-R2-OC(=O))mO-R3-OH(II); and iv) a catalyst. Q is a polyvalent organic linking group, and A1 is independently selected from (meth)acrylic functional groups of the formula -OC(=O)C(R4)=CH2, where R4 is a lower alkyl of 1 to 4 carbon atoms or H. Each R2 and R3 in each (O-R2-OC(=O)) repeat unit is independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, the average number of carbon atoms in all R2 and R3 groups combined is 4 to 10, and m is 2 to 23. The polycarbonate diol either has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol), or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol. The polymerization reaction product comprises a polyurethane methacrylate polymer.

[0288] Embodiment 131 is the photopolymerizable composition of embodiment 130, further comprising a hydroxy-functional methacrylate of formula (I):HO-Q-(A)p(I), where Q is a polyvalent organic linking group, A is a methacrylic functional group of formula -OC(=O)C(R1)=CH2, where R1 is a lower alkyl of 1 to 4 carbon atoms, and p is 1 or 2.

[0289] Embodiment 132 is the photopolymerizable composition of any one of embodiments 1-20 or 22-46, further comprising at least one hydrophilic monomer or polymer having a log P less than 3, present in an amount from 1 wt% to 25 wt%, based on the total weight of the photopolymerizable composition.

[0290] Embodiment 133 is the photopolymerizable composition of embodiment 132, wherein the photopolymerizable composition comprises at least one monofunctional (meth)acrylate monomer whose homopolymer has a Tg of 150°C or greater in an amount of 20% by weight or greater, based on the total weight of the photopolymerizable composition.

[0291] Embodiment 134 is the method of any one of embodiments 58-91 or 93-119, wherein the photopolymerizable composition comprises at least one hydrophilic monomer or polymer having a log P of less than 3, present in an amount of 1 wt% to 25 wt%, based on the total weight of the photopolymerizable composition.

[0292] Embodiment 135 is the method of embodiment 134, wherein the photopolymerizable composition comprises at least one monofunctional (meth)acrylate monomer whose homopolymer has a Tg of 150°C or greater in an amount of 20% by weight or greater, based on the total weight of the photopolymerizable composition.

[0293] Example Objects and advantages of the present disclosure are further illustrated by the following examples; however, the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit the present disclosure.

[0294] material Unless otherwise noted, all parts, percentages, ratios, etc. in the examples and elsewhere in this specification are by weight. The Table of Materials (below) lists the materials used in the examples and their suppliers. [Table 2-1] [Table 2-2] [Table 2-3]

[0295] Preliminary Example Preparation of naphthalimide acrylate (NapA) [ka]

[0296] A 1 L three-necked round-bottom flask was charged with 4-chloronaphthalic anhydride (100.0 g, 0.4299 mol, 1.0 equiv.), ethanolamine (26.26 g, 0.4299 mol, 1.0 equiv.), and iPrOH (516.7 g). The flask was equipped with a temperature probe, overhead stirrer, and reflux condenser. The reaction mixture was heated to 80 °C with stirring for 6 h and then cooled to 10 °C in an ice bath. The resulting yellow solid was collected by filtration and stirred with a mixture of water (300 g), iPrOH (300 g), and concentrated HCl (10 g). The resulting solid was filtered, washed with water / iPrOH (1:1, 500 g), and air-dried to give alcohol 2 (102 g, 86%). [ka]

[0297] A 2 L, three-necked round-bottom flask was charged with alcohol 2 (100.0 g, 0.3627 mol, 1.0 equiv.), KOH (40.71 g, 0.7255 mol, 2.0 equiv.), and methanol (581 g). The flask was equipped with a temperature probe, overhead stirrer, and reflux condenser. The reaction mixture was heated to 65 °C with stirring for 36 h and then cooled to 10 °C in an ice bath. The resulting yellow solid was collected by filtration and stirred with a mixture of water (300 g), MeOH (300 g), and concentrated HCl (10 g). The resulting solid was filtered, washed with water / MeOH (1:1, 600 g), and air-dried to give alcohol 3 (86.5 g, 88%). [ka]

[0298] A 1 L, three-necked round-bottom flask was charged with alcohol 3 (80.00 g, 0.2949 mol, 1.0 equiv.), chloroform (704 g), and triethylamine (35.81 g, 0.3539 mol, 1.2 equiv.). The flask was equipped with a Claisen adapter, an overhead stirrer, and a pressure-equalizing addition funnel. The Claisen adapter was equipped with a temperature probe and a reflux condenser. The reaction mixture was stirred and heated to 40 °C. Acryloyl chloride (29.36 g, 0.3244 mol, 1.1 equiv.) was added dropwise via the addition funnel, ensuring that the reaction temperature did not exceed 45 °C. After the addition was complete, the reaction was stirred for 30 min. Triethylamine (6.00 g, 0.0593 mol, 0.2 equiv.) was added, followed by the dropwise addition of acryloyl chloride (5.00 g, 0.0552 mol, 0.19 equiv.). The reaction was stirred at 40 °C for an additional 30 minutes. The reaction flask was then fitted with a distillation head, a condenser, and a receiving flask. The reaction mixture was heated to strip off most of the chloroform. EtOH (500 g) was added and stripping continued until the distillation head temperature reached 78 °C. The reaction mixture was cooled to 10 °C in an ice bath and filtered. The resulting solid was washed with water / HCl (10:1, 500 mL), water / NaCO (10:1, 500 mL), and water / EtOH (1:1, 500 mL). The solid was dried to give product 4 as a pale yellow solid (92.5 g, 96%).

[0299] Preparation of Adamantyl-1-methacrylate (AdMA) A 2 L three-neck round-bottom flask was fitted with a Dean-Stark trap equipped with a condenser, magnetic stir bar, and thermometer. 1-Adamantanol (252 g, 1.650 mol), hydroquinone (0.3 g), methacrylic acid (455 g, 5.28 mmol), and methylcyclohexane (400 g) were added and the mixture was stirred. Next, sulfuric acid (10.5 g) was added to the mixture, and dry air was then slowly bubbled through the mixture. The mixture was heated to reflux under constant air bubbling for 26 hours, during which time the reaction product water was removed using a trap. The mixture was then cooled to room temperature and slowly added to a mechanically stirred, ice-bath-cooled mixture of 350 g of KOH (6.2 mol) in 1000 g of deionized water and 500 g of hexane. After the addition was complete, the resulting mixture was separated using a separatory funnel and extracted with 1 x 500 mL of hexane. The combined organic extracts were washed with saturated aqueous sodium bicarbonate, and then 20 mg of phenothiazine was added to the organic phase. This was then dried over anhydrous magnesium sulfate, filtered, and concentrated by rotary evaporation. The concentrate was then distilled under vacuum (BP = 87-90 °C, 0.3 Torr) to give 320 g of liquid in a receiving flask containing 15 mg of 4-hydroxy-TEMPO. BHT (48 mg) was then added, and dry air was bubbled through for 30 seconds to give a clear product, which was then stored. H NMR: 5.99 (m, 1H), 5.45 (m, 1H), 2.14 (m, 9H), 1.87 (m, 3H), 1.64 (m, 6H). C NMR: 168.5, 138.1, 124.3, 80.4, 41.3, 36.3, 30.9, 18.4. Purity by GC = 98.4%.

[0300] Characterization of the above materials by nuclear magnetic resonance spectroscopy (NMR) H NMR (500 MHz) and C NMR (125 MHz) spectra were obtained using an Ultrashield 500 Plus FT NMR instrument from Bruker (Billerica, MA). Chemical shifts (δ) are reported in ppm relative to CDCl. Splitting pattern abbreviations are as follows: s (singlet), d (doublet), t (triplet), q (quartet), m (multiplet), br (broad line), app (apparent line), and combinations of these abbreviations.

[0301] Preparation of 4-tert-butylcyclohexyl methacrylate (cis / trans mixture) (tBuCHMA) A 2 L, three-necked, round-bottom flask was equipped with a 250 mL addition funnel, a magnetic stir bar, and a thermometer. 4-tert-butylcyclohexanol (150 g, 960 mmol), dichloromethane (600 g), triethylamine (178 g, 1760 mmol), and DMAP (6.4 g, 52 mmol) were added to the flask, followed by dropwise addition of methacrylic anhydride (263 g, 1710 mmol), maintaining the temperature below 35°C. The mixture was stirred at room temperature for 24 hours, after which 150 mL of water was added and stirred overnight. Dichloromethane (500 g) was then added, and the organic phase was washed with 200 mL of water, 200 mL of 0.1 M HCl, and 200 mL of saturated sodium bicarbonate. The organic phase was dried over anhydrous magnesium sulfate, and 20 mg of phenothiazine was added. The mixture was filtered and concentrated by rotary evaporation. The concentrate was then distilled under vacuum (BP = 73-90 °C, 0.3 Torr) to obtain 170 g of liquid in a receiving flask containing 7 mg of 4-hydroxy-TEMPO. BHT (26 mg) was then added, and dry air was bubbled through for 30 seconds to obtain a clear product, which was then stored. H NMR was consistent with a mixture of 72% trans and 28% cis isomers as described in Macromolecules, 1993, 26, 1659-1665. GC analysis indicated a total of 96% of the two isomers in a ratio of 73% trans / 27% cis.

[0302] Characterization of the above materials by gas chromatography (GC) Sample purity and product ratios were determined by gas chromatography (GC) using a Hewlett Packard (Palo Alto, CA) 6890 Series Plus gas chromatograph equipped with a flame ionization detector and an HP G1530A digital integrator. Sample injection was performed using a 7683 Series injector with a 2 microliter injection volume, an injection port temperature of 250 °C, and a 20:1 split ratio. A 30 m × 0.53 mm × 5 micrometer column obtained from Restek Corp. (Bellefonte, PA) under the trade name "RESTEX RTX-1" was used. He was used as the carrier gas at a flow rate of 12.4 mL / min, with a temperature program from 50 °C to 230 °C at 15 °C / min, from 230 °C to 280 °C at 50 °C / min, and then held at 280 °C for 2 minutes.

[0303] Preparation of diol diacrylate Preparation of C-590 diol diacrylate [ka] C-590 diol (50 g, 90.79 mmol), acrylic acid (19.8 g, 275 mmol), and p-toluenesulfonic acid (1.96 g, 11.3 mmol) were charged to a 250 mL three-neck flask equipped with a magnetic stir bar, thermocouple, and condenser. The mixture was heated to 85 °C. Vacuum (15–20 Torr) was applied for 2 minutes every 15–20 minutes to remove any formed water from the reaction. This was repeated for 4 hours, during which time there was no sign of HO formation or condensation on the flask walls. Heating was discontinued. After cooling to room temperature, the mixture was dissolved in 130 mL of an ethyl acetate / petroleum ether mixture (10:3 ratio). The mixture was extracted with 10% aqueous NaOH (100 mL) and then HO (200 mL). The organic layer was dried (over NaSO) and then concentrated to give a clear liquid in 91% yield.

[0304] Preparation of C-590 Diol Dimethacrylate (C-590 Diol MA) [ka] This material was prepared according to the procedure described above for the preparation of C-590 diol diacrylate, except that methacrylic acid was used instead of acrylic acid. The product was isolated as a low-viscosity liquid in 88-93% yield.

[0305] Preparation of C-2050 Diol Dimethacrylate (C-2050 Diol MA) [ka] This material was prepared according to the procedure described above for the preparation of C-590 diol diacrylate, except that methacrylic acid was used instead of acrylic acid and C-2050 diol was used instead of C-590 diol.

[0306] Preparation of polycarbonate diol-based urethane (meth)acrylates Urethane acrylates are of three main types. 1) Polycarbonate diols reacted with diisocyanates end-capped with (meth)acrylate monools such as HEA and HEMA. The idealized structure of such a material is shown below for a hexanediol-based polycarbonate diol: [ka] 2) Polycarbonate diol end-capped with isocyanate-(meth)acrylate, which is represented by hexanediol-based polycarbonate diol and IEM; [ka] 3) (meth)acrylate monool-terminated diisocyanates, [ka]

[0307] Type 1: 4 IPDI / 2 C-2050 / 2 HEMA(PE-1) A 1 L, three-necked round-bottom flask was charged with 514.75 g of C-2050 (0.52285 equiv., 984.5 hydroxide equivalents (OH EW)) and heated to approximately 45° C., followed by the addition of 116.19 g of IPDI (1.0457 equiv.), 0.280 g of BHT (400 ppm), and 0.175 g of DBTDL (250 ppm). The reaction was heated to an internal setpoint of 105° C. under dry air (temperature reached in approximately 20 minutes). At 1 hour and 20 minutes, 69.06 g of HEMA (0.5307 equiv., 130.14 MW, 1.5% excess) was added via addition funnel at a steady rate over 1 hour and 10 minutes. The reaction was heated at 105°C for approximately 2.5 hours, after which an aliquot was checked by Fourier transform infrared spectroscopy (FTIR), which showed the absence of the -NCO peak at 2265 cm-1, and the product was isolated as a clear, viscous material.

[0308] Type 2: C-2050 / 2 IEM (PE-2) A 1 L, three-necked round-bottom flask was charged with 431.93 g of C-2050 (0.43873 eq, 984.5 OH EW), 0.200 g of BHT (400 ppm), and 0.125 g of DBTDL (250 ppm) and heated to an internal temperature of approximately 60 °C under dry air. Next, 68.07 g of IEM (0.43873 eq, 155.15 MW) was added via addition funnel over approximately 1 hour and 20 minutes. At 1 hour and 30 minutes, an aliquot was analyzed by FTIR, which showed no -NCO peak at 2265 cm-1. At 1 hour and 38 minutes, 1.32 g of IEM was added, and an aliquot was analyzed by FTIR, which showed no -NCO peak at 2265 cm-1. After 4 hours of reaction, the reaction was stopped and the product was isolated as a clear, viscous material.

[0309] Type 3: IPDI / HEMA (PE-3) A 1 L, three-necked round-bottom flask was charged with 319.80 g of IPDI (2.878 equivalents), 0.280 g of BHT, and 0.175 g of bismuth neodecanoate (250 ppm based on solids) and heated under dry air to an internal temperature of approximately 55° C. 380.20 g (2.921 equivalents) of HEMA was then added over 1 hour 45 minutes, and the internal temperature was allowed to increase up to 90° C. An aliquot was checked by FTIR after 2 hours 25 minutes, which showed the absence of the -NCO peak at 2265 cm.

[0310] The samples in Table 2 below were prepared according to methods Types 1-3 above, using the amounts and types of ingredients indicated in the table. [Table 3-1] [Table 3-2]

[0311] Measurement of HEMA-IPDI-HEMA oligomer concentration. Measurement of the concentration of HEMA-IPDI-HEMA oligomers was performed by liquid chromatography-mass spectrometry (LC / MS) on an Agilent 1260 Infinity Series liquid chromatography system (Agilent Technologies, Waldbronn, Germany) using an Agilent Poroshell 120 SB-C8 2.1 mm × 50 mm 2.7 micrometer column at 40 °C with a flow rate of 0.5 mL / min. Two microliter samples were injected and eluted with the linear gradient described below. Water was Omnisolv HPLC grade from EMD Millipore, part of Merck KGaA. Re-equilibration time between runs was 5 min. Detection was performed using an Agilent 6130 Quadrupole LC / MS detector with electrospray ionization. Sample quantification was performed by integration of the chromatographic peak detected at m / z 500.3 (M-NH4+). Mass spectrometer parameters were atmospheric pressure ionization-electrospray (API-ES) mode: capillary voltage 4 kV, nebulizer gas pressure 50 psig (345 kPa gauge), drying gas flow rate 10 liters / min, drying gas temperature 300°C. [Table 4]

[0312] Calibration samples were prepared by dissolving 0.1009 g of the material polyurethane acrylate PE-33 in a 100 mL volumetric flask using ethyl acetate. This solution was then diluted to 1 mL in a 100 mL volumetric flask using acetonitrile to produce Dilution 1. Dilution 1 was further diluted in acetonitrile to concentrations of approximately 2.02, 0.505, 0.101, and 0.0121 ppm and filtered through a 0.22 micron PTFE syringe filter (Fisher Brand, Thermo Fisher Scientific, Hampton, NH). The calibration curve was linear from 2.02 to 0.0121 ppm. Calibration was performed immediately prior to the analytical sample.

[0313] Samples for analysis were prepared by dissolving 0.1–0.3 g of material in a 100 mL volumetric flask using ethyl acetate. This solution was then diluted to 1 mL in a 100 mL volumetric flask using acetonitrile to produce Dilution 1. Dilution 1 was filtered through a 0.22 micron PTFE syringe filter (Fisher Brand) and analyzed as described above. The results for each sample are shown in Table 4. [Table 5]

[0314] General Procedure for Formulation Preparation The formulations were prepared by weighing the ingredients (shown in Tables 5-18) into an amber jar, followed by rolling on a roller (manufactured by Olde Midway and having the trade name "OLDE MIDWAY PRO18") at 60°C until mixed. [Table 6] [Table 7] [Table 8] [Table 9] [Table 10] [Table 11] [Table 12] [Table 13] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18] [Table 19]

[0315] Polymer / Oligomer Molecular Weight Characterization Method: The molecular weights of oligomers and polymers were characterized using gel permeation chromatography (GPC). The GPC instrument consisted of an e2695 separation module and a 2414 dRI detector, both from Waters Corporation (Milford, MA). Tetrahydrofuran was used as the eluent and operated at a flow rate of 0.6 mL / min. The GPC column was also an HSPgel HR MB-M column from Waters Corporation. The column compartment and refractive index detector were set at 35°C. Molecular weight standards were EasiVial PMMA from Agilent Technologies (Mp values ​​of the PMMA molecular weight standards used in the calibration curve ranged from 550 D to 1,568,000 g / mol). The relative number-average molecular weights (Mn) and weight-average molecular weights (Mn) of selected oligomers / polymers are listed in kilodaltons (kD) in Table 19 below. [Table 20]

[0316] General Procedure for Casting and Curing Formulations Each formulation listed in Tables 5-18 was poured into a silicone dogbone mold (1 mm thick Type V mold, ASTM D638-14) for preparing tensile specimens and a rectangular mold measuring 9.4 mm x 25.4 mm x 1 mm for preparing DMA three-point bend specimens. A 2 mil (0.05 mm) polyethylene terephthalate (PET) release liner (obtained from 3M Company, St. Paul, MN, under the trade name "SCOTCHPAK") was wrapped around the filled mold, and the filled mold with the liner was placed between two glass plates held together with binder clips. The formulation was cured for 30 minutes in an Asiga Pico Flash post-cure chamber (obtained from Asiga USA, Anaheim Hills, CA). The specimens were removed from the mold and subsequently exposed to light for 30 minutes using the Asiga Pico Flash post-cure chamber. The specimens were then placed in an oven set at 100°C for 30 minutes. Dog-bone specimens were conditioned in phosphate buffered saline (PBS, 1×, pH=7.4) for 24 hours at 37° C. DMA three-point bend specimens were conditioned in deionized (DI) water at room temperature for 48 hours.

[0317] General Procedure for Measuring Loss Modulus and Tan δ Using Dynamic Mechanical Analysis Dynamic mechanical analysis (DMA) was performed on rectangular cured specimens (approximately 25.4 mm x 9.4 mm x 1 mm) using a TA Instruments Model Q800 Dynamic Mechanical Analyzer (TA Instruments, Newcastle, DE) in controlled strain mode, 0.2% strain, 0.02 N preload force, 125% force track, and 1 Hz tension clamps. The temperature was swept from -40°C to 200°C at a rate of 2°C / min. The specimens were immersed in deionized water at 37°C for at least 24 hours, at which point they were thoroughly saturated with water before testing and were tested immediately after removal from the water. [Table 21]

[0318] Additive manufacturing of compounded resins Unless otherwise noted, all 3D printed examples were produced on either an Asiga Pico 2 HD or Asiga Max liquid bath polymerization 3D printer available from Asiga USA, Anaheim Hills, CA.

[0319] Each formulation listed in Tables 21-24 was photopolymerized on an Asiga 3D printer equipped with a 385 nm LED light source. Type V tensile bars and DMA 3-point bend specimens according to ASTM D638-14 (2014) were produced. The printer's resin bath was heated to 35-50°C prior to photopolymerization to reduce the viscosity so that tensile bars could be produced. The following settings were used for printing: slice thickness = 50 μm, burn-in layers = 1, separation speed = 1.5 mm / s, separation distance = 10 mm, and approach speed = 1.5 mm / s. The Asiga Pico 2 HD used one slide per layer at a speed of 7 mm / min. Table 23 further lists the printer type used to print the formulations listed in Tables 21-24, as well as the exposure time, burn-in time, and temperature. The printed parts were washed with propylene carbonate, followed by isopropanol to remove unreacted resin. The printed parts were then post-cured for 90 minutes on each side using an Asiga Pico Flash post-cure chamber, followed by heating in an oven at 100°C for 30 minutes. Dogbone specimens were conditioned in phosphate-buffered saline (PBS, 1X, pH=7.4) at 37°C for 24 hours. DMA three-point bend specimens were conditioned in DI water at room temperature for 48 hours. [Table 22] [Table 23] [Table 24] [Table 25] [Table 26]

[0320] General Procedure for Tensile Testing The PBS-conditioned dog bones were tested on an Instron 5944 (Instron, Norwood, MA) equipped with a 500 N load cell. The test speed was 5 mm / min. The gauge length was set at 1 inch (2.5 cm). Five replicate specimens were tested for each formulation, and the average value is reported. Tensile strength at yield was measured according to ASTM D638-14(2014) and is shown below in Tables 26 and 27. For specimens that did not yield, the ultimate tensile strength was measured. The elongation at break was determined from the crosshead travel of the grips.

[0321] General procedure for measuring relaxation modulus using dynamic mechanical analysis Rectangular specimens were water-conditioned by immersion in deionized water at room temperature (22-25°C) for 48 hours and tested on a TA Q800 DMA equipped with a submerged three-point bending clamp. The water-conditioned rectangular specimens were placed in a water-filled submersion fixture and equilibrated at 37°C for 10 minutes. After equilibration, a 2% strain was applied and data collection began. Relaxation modulus was measured for 30 minutes using TA Advantage software. The first data point collected was the initial relaxed modulus, and the final data point collected at 30 minutes was the 30-minute relaxed modulus. The percentage loss of relaxation modulus from the initial value compared to the relaxed modulus at 30 minutes (referred to as the percentage loss of relaxation modulus after 30 minutes) was calculated as follows: 100 - ((Relaxed modulus at 30 minutes / Initial relaxed modulus) * 100)). This data is reported in Tables 26 and 27. [Table 27-1] [Table 27-2] [Table 28]

[0322] Additive manufacturing of aligner articles from compounded resins The EX-51 formulation was photopolymerized using an AsigaMax printer equipped with a 385 nm LED light source. The stereolithography file format (STL file) of the aligner was loaded into Asiga Composer software to generate the support structure. The printer's resin bath was heated to 40 °C prior to photopolymerization to reduce the viscosity so that the article could be fabricated. The following settings were used for printing: slice thickness = 50 μm, burn-in (fixing) layer = 1, separation speed = 1.5 mm / s, burn-in exposure time = 10 s, and exposure time = 3 s. The printed parts were cleaned with propylene carbonate, followed by isopropanol to remove unreacted resin. The printed specimens were then post-cured for 90 minutes on each side using an Asiga Pico Flash post-cure chamber. The photopolymerized aligner fit a model demonstrating the accuracy of the additively manufactured part. The aligner had acceptable strength and flexibility.

[0323] Test Procedure for Gravimetric Analysis of Extractables from Printed Articles Articles molded as five consecutive rows of teeth (30.4 mm x 9.24 mm x 8.17 mm) were printed using the EX-51 and EX-52 formulations and post-processed according to the procedure described above. The article thickness was 0.49 mm. A 3 x 5-tooth article (total surface area 45 cm) was placed in a 40 mL glass vial and weighed. 15 mL of solvent (either heptane or 5% ethanol / Milli-Q water) was added to the vial, with one 15 mL blank (a vial without an article) for each solvent. The vial was covered with a Teflon cap, and the sample was kept at 37 °C for 24 hours while shaking at 80 RPM in a LabLine Benchtop Incubator Shaker Model 4628. After the sample cooled, the extraction solution was transferred to a new 20 mL glass vial. 5 mL aliquots were transferred to pre-weighed 8 mL glass vials and set to evaporate under a nitrogen purge. Once the solvent was dried and free of water, the vial was weighed until a constant weight was reached. The residue (%) was calculated using the following formula: The test was performed in triplicate, all performed simultaneously. The results shown are the average of the three replicates.

number

[0324] All of the above patents and patent applications are expressly incorporated herein by reference. The above-described embodiments are illustrative of the invention, and other constructions are possible. Accordingly, the present invention should not be deemed limited to the embodiments described in detail above and illustrated in the accompanying drawings, but rather should be limited only by the fair scope of the following claims, including equivalents.

Claims

1. 1. A photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a T of 125° C. or higher. ｇ and a monofunctional (meth)acrylate monomer having a logarithm of the octanol / water partition coefficient (log P) value greater than 3; b) a photoinitiator present in an amount of 0.5% to 5% by weight; c) a polymerization reaction product of component The component is i) a diisocyanate; and ii) Formula (I): HO-Q-(A) ｐ (I) wherein Q is a polyvalent organic linking group and A is a group of formula -OC(=O)C(R １ ) = CH ２ (In the formula, R １ is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2; iii) Formula (II): H(O-R) ２ -O-C(=O)) ｍ -O-R ３ -OH (II) (In the formula, each (OR ２ Each R in the —O—C(═O) repeating unit ２ and R ３ are independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and all of the R ２ group and the R ３ wherein the average number of carbon atoms in combination with groups is 4 to 10, and m is 2 to 23, and wherein the polycarbonate diol either has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol) or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst; and Including, the ratio of said isocyanate to said polycarbonate diol ranges from 4 molar equivalents of isocyanate of said diisocyanate to 1 molar equivalent of alcohol of said polycarbonate diol to 4 molar equivalents of isocyanate of said diisocyanate to 3 molar equivalents of alcohol of said polycarbonate diol; a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; 1. A photopolymerizable composition comprising:

2. 1. A photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a T of 125° C. or higher. ｇ and a monofunctional (meth)acrylate monomer having a logarithm of the octanol / water partition coefficient (log P) value greater than 3; b) a photoinitiator present in an amount of 0.5% to 5% by weight; c) a polymerization reaction product of component The component is i) a diisocyanate; and ii) Formula (I): HO-Q-(A) ｐ (I) wherein Q is a polyvalent organic linking group and A is a group of formula -OC(=O)C(R １ ) = CH ２ (In the formula, R １ is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2; iii) Formula (II): H(O-R) ２ -O-C(=O)) ｍ -O-R ３ -OH (II) (In the formula, each (OR ２ Each R in the —O—C(═O) repeating unit ２ and R ３ are independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and all of the R ２ group and the R ３ the average number of carbon atoms in combination with the group is 4 to 10, and m is 2 to 23; iv) a catalyst; and Including, the ratio of said isocyanate to said polycarbonate diol ranges from 4 molar equivalents of isocyanate of said diisocyanate to 1 molar equivalent of alcohol of said polycarbonate diol to 4 molar equivalents of isocyanate of said diisocyanate to 3 molar equivalents of alcohol of said polycarbonate diol; a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer having a weight average molecular weight (Mw) of 8,000 g / mol or greater; 1. A photopolymerizable composition comprising:

3. Formula (III): 【Chemical 1】 (Wherein, Q and R １ is as defined for formula (I), and R ｄｉ The photopolymerizable composition of claim 1 or 2, further comprising a compound of the formula:

4. 4. The photopolymerizable composition of claim 1, wherein the monofunctional (meth)acrylate monomer is selected from the group consisting of 3,3,5-trimethylcyclohexyl methacrylate, cis-4-tert-butyl-cyclohexyl methacrylate, 2-decahydronaphthyl methacrylate, 1-adamantyl acrylate, 73 / 27 trans / cis-4-tert-butylcyclohexyl methacrylate, dicyclopentadienyl methacrylate, dicyclopentanyl methacrylate, trans-4-tert-butylcyclohexyl methacrylate, d,l-isobornyl methacrylate, dimethyl-1-adamantyl methacrylate, d,l-bornyl methacrylate, 3-tetracyclo[4.4.0.1.1]dodecyl methacrylate, 1-adamantyl methacrylate, and combinations thereof.

5. In the hydroxy-functional methacrylate of formula (I), Q is an alkylene group, p is 1, and in the methacryl functional group A, R １ The photopolymerizable composition of any one of claims 1 to 4, wherein is methyl.

6. 6. The photopolymerizable composition of claim 1, further comprising an ultraviolet absorber comprising an optical brightener in an amount of 0.001 wt % to 5 wt %, based on the total weight of the photopolymerizable composition.

7. The fluorescent whitening agent is represented by formula (VI): 【Chemistry 2】 The photopolymerizable composition of claim 6 comprising a compound of formula:

8. The photopolymerizable composition of any one of claims 1 to 7, further comprising an inhibitor in an amount of 0.001% to 1% by weight.

9. The photopolymerizable composition of any one of claims 1 to 8, essentially free of monofunctional (meth)acrylate monomers having a logarithm of the octanol / water partition coefficient (log P) value of less than 3.

10. An article comprising a photopolymerized reaction product of the photopolymerizable composition of any one of claims 1 to 9.

11. 11. The article of claim 10, wherein the article exhibits at least two properties selected from the group consisting of an initial relaxation modulus at 37°C and 2% strain of 100 megapascals (MPa) or greater, a percent loss in relaxation modulus of 70% or less, a 30-minute relaxation modulus of 100 MPa or greater, an elongation to break of the printed article of 20% or greater, and a tensile strength at yield of 14 MPa or greater.

12. 1. A method of manufacturing an article, comprising: a) a photopolymerizable composition, 1) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a T of 125° C. or higher. ｇ and a monofunctional (meth)acrylate monomer having a logarithm of the octanol / water partition coefficient (log P) value greater than 3; 2) a photoinitiator present in an amount of 0.5% to 5% by weight; 3) a polymerization reaction product of component The component is i) a diisocyanate; and ii) Formula (I): HO-Q-(A) ｐ (I) wherein Q is a polyvalent organic linking group and A is a group of formula -OC(=O)C(R １ ) = CH ２ (In the formula, R １ is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2; iii) Formula (II): H(O-R) ２ -O-C(=O)) ｍ -O-R ３ -OH (II) (In the formula, each (OR ３ Each R in the —O—C(═O) repeating unit ２ and R ３ are independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and all of the R ２ group and the R ３ the average number of carbon atoms in combination with groups is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol) or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst; and Including, the ratio of said isocyanate to said polycarbonate diol ranges from 4 molar equivalents of isocyanate of said diisocyanate to 1 molar equivalent of alcohol of said polycarbonate diol to 4 molar equivalents of isocyanate of said diisocyanate to 3 molar equivalents of alcohol of said polycarbonate diol; a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; obtaining a photopolymerizable composition comprising: b) selectively curing the photopolymerizable composition to form the article; and c) repeating steps a) and b) to form multiple layers to produce said article comprising a three-dimensional structure; A method comprising:

13. a) receiving, by a manufacturing device having one or more processors, a digital object including data defining a plurality of layers of an article; b) generating the article based on the digital object using the manufacturing device by an additive manufacturing process, The article comprises the reaction product of a photopolymerizable composition, the photopolymerizable composition comprising: 1) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a T of 125° C. or higher. ｇ and a monofunctional (meth)acrylate monomer having a logarithm of the octanol / water partition coefficient (log P) value greater than 3; 2) a photoinitiator present in an amount of 0.5% to 5% by weight; 3) a polymerization reaction product of component The component is i) a diisocyanate; and ii) Formula (I): HO-Q-(A) ｐ (I) wherein Q is a polyvalent organic linking group and A is a group of formula -OC(=O)C(R １ ) = CH ２ (In the formula, R １ is a lower alkyl of 1 to 4 carbon atoms), and p is 1 or 2; iii) Formula (II): H(O-R) ２ -O-C(=O)) ｍ -O-R ３ -OH (II) (In the formula, each (OR ２ Each R in the —O—C(═O) repeating unit ２ and R ３ are independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and all of the R ２ group and the R ３ the number of carbon atoms in combination with the aryl groups is 4 to 10, and m is 2 to 23, wherein the polycarbonate diol either has an Mn greater than 1,000 grams per mole (g / mol) or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst; and Including, the ratio of said isocyanate to said polycarbonate diol ranges from 4 molar equivalents of isocyanate of said diisocyanate to 1 molar equivalent of alcohol of said polycarbonate diol to 4 molar equivalents of isocyanate of said diisocyanate to 3 molar equivalents of alcohol of said polycarbonate diol; a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; and generating a blend of A method comprising:

14. 1. A photopolymerizable composition comprising: a) 40 to 60 parts by weight of a monofunctional (meth)acrylate monomer per 100 parts by weight of the total photopolymerizable composition, wherein the cured homopolymer of the monofunctional (meth)acrylate monomer has a T of 125° C. or higher. ｇ and a monofunctional (meth)acrylate monomer having a logarithm of the octanol / water partition coefficient (log P) value greater than 3; b) a photoinitiator present in an amount of 0.5% to 5% by weight; c) a polymerization reaction product of component The component is i) a diisocyanate; and ii) Formula (X): HO-Q-(A １ ) ２ (X) [wherein Q is a polyvalent organic linking group, A １ is represented by the formula -OC(=O)C(R ４ ) = CH ２ (In the formula, R ４ is a lower alkyl of 1 to 4 carbon atoms or H); and iii) Formula (II): H(O-R) ２ -O-C(=O)) ｍ -O-R ３ -OH (II) (In the formula, each (OR ２ Each R in the —O—C(═O) repeating unit ２ and R ３ are independently an aliphatic, alicyclic, or aliphatic / alicyclic alkylene group, and all of the R ２ group and the R ３ wherein the average number of carbon atoms in combination with groups is 4 to 10, and m is 2 to 23, and wherein the polycarbonate diol either has a number average molecular weight (Mn) greater than 1,000 grams per mole (g / mol) or the weighted average of all polycarbonate diols present in the component has an Mn greater than 1,000 g / mol; iv) a catalyst; and Including, the ratio of said isocyanate to said polycarbonate diol ranges from 4 molar equivalents of isocyanate of said diisocyanate to 1 molar equivalent of alcohol of said polycarbonate diol to 4 molar equivalents of isocyanate of said diisocyanate to 3 molar equivalents of alcohol of said polycarbonate diol; a polymerization reaction product of the components, wherein the polymerization reaction product comprises a polyurethane methacrylate polymer; 1. A photopolymerizable composition comprising:

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