Dental compositions and methods of making and using same

Abstract

The multi-component hardening dental composition includes a first component and a second component. The first component includes a monofunctional and / or polyfunctional component having one or more ethylenically unsaturated groups, acid-reactive glass particles, and an oxidizing agent. The second component includes a water-miscible polyacid, a reducing agent including a water-insoluble organic compound, and water.

Description

[Technical Field]

[0001] Two-component dental cements are described, for example, in WO 2011 / 081975, WO 2020 / 75007(A1), and U.S. Pat. No. 5,501,727. [Background technology]

[0002] Two-component glass ionomer cements have been used in dental applications for some time. These materials consist of an ionic polymer component and a reactive glass component, which, when combined in the presence of water, undergo a cement-setting reaction. These dental materials offer several desirable attributes, including long-term fluoride release, resistance to moisture and saliva, good mechanical properties, and excellent adhesion to dental hard tissue without pretreatments such as conditioners or adhesives. Powder-liquid, powder-paste, paste-paste, paste-liquid, and liquid-liquid two-component cements have been reported.

[0003] Known materials and methods have been found to have various drawbacks, including, for example, variability in mechanical strength, varying consistencies, insufficient working or setting times, cost per application, multiple dispensing and mixing steps, mechanical mixing equipment, and shelf life.

[0004] The above materials are available as multi-component systems, typically in two-component systems. They can be any combination of powder, liquid, or paste. The storage stability of the individual components is very important to prevent changes in viscosity, color, or any other properties during the material's shelf life (typically 2-4 years). At the time of use, the components are mixed together and then applied. Setting should occur quickly so that the procedure is comfortable for both the patient and the operator. The setting characteristics should allow sufficient time for the material to be mixed and applied to the abutment and / or dental prosthetic or orthodontic appliance in place in the oral cavity.

[0005] Glass ionomer cement systems targeted for stability have been developed as water-based compositions, which have unique redox chemistries. However, such compositions have certain drawbacks. For example, water-based pastes present challenges with moisture in the packaging and problems associated with "drying out" the paste. As another example, while tertiary amine and peroxide redox curing systems can provide effective curing of the resin in glass ionomer cement systems, amine / peroxide systems have been found to produce undesirable color changes in the compositions. While compositions have been developed that mitigate color change issues through the incorporation of encapsulated redox curing agents, such compositions involve additional complexities in chemistry and manufacturing. As a result, interest in alternative methods and compositions for more stable delivery of glass ionomer cements and related materials continues to grow. Summary of the Invention

[0006] The present disclosure is directed, at least in part, to such alternative methods and compositions. In general, the multi-component systems of the present disclosure utilize minimal amounts of water (or no water) in the first component to stabilize the water-soluble metal persulfate salt in such component without concerns about water loss (i.e., drying out of the paste). Furthermore, the dispersion of 1-benzyl-5-phenylbarbituric acid (BPBA) in an aqueous-based second component that does not contain polymerizable monomers provides stability to the second component, maintaining the reactivity of BPBA during storage. Furthermore, it has been discovered that BPBA-based redox cure systems do not produce color changes in the set cement (in contrast to the amine / peroxide-based curing compositions discussed above).

[0007] definition The term "water-soluble" refers to a material, such as a monomer, that is partially or completely water-soluble and that dissolves alone in water in an amount of at least 5 g per liter of water at 25°C.

[0008] The term "comprising" and variations thereof (e.g., comprises, includes, etc.) do not have a limiting meaning where these terms appear in the description and claims.

[0009] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably unless the context clearly dictates otherwise.

[0010] Also, in this specification, numerical ranges expressed by endpoints include all numbers subsumed within that range (e.g., a viscosity ratio range of 1:0.06 to 1:13 includes 1:0.06 to 1:13, 1:0.1 to 1:13, 1:0.25 to 1:13, 1:0.5 to 1:13, 1:0.6 to 1:13, 1:1 to 1:13, 1:0.06 to 1:10, 1:0.06 to 1:7.5, 1:0.06 to 1:5, 1:0.06 to 1:3.5, 1:0.06 to 1:1, 1:0.1 to 1:10, 1:0.25 to 1:7.5, 1:0.5 to 1:5, 1:0.6 to 1:3.5, 1:0.75 to 1:2, 1:0.9 to 1:1.1, etc.). DETAILED DESCRIPTION OF THE INVENTION

[0011] In some embodiments, the present disclosure is directed to a multi-component (e.g., two-component) hardenable dental composition (e.g., a glass ionomer cement), wherein a first component (sometimes referred to as Paste A) comprises (i) a liquid monofunctional and / or polyfunctional monomer, oligomer, or polymer, (ii) an oxidizing agent, and (iii) an acid-reactive glass, wherein the first component is free or substantially free of water, and a second component (sometimes referred to as Paste B) comprises (i) a reducing agent, (ii) a polyacid without polymerizable side groups, (iii) water, and (iv) optionally, a filler without surface-bound polymerizable groups.

[0012] Surprisingly, it has been discovered that by separating the components of the ionic redox polymerization system (i.e., the reducing agent and the oxidizing agent) into different components, a more reliable two-component cement system can be achieved. That is, by pairing the reducing agent with a polyacid in the second component to form a dispersion of the reducing agent in water, thereby maintaining the reactivity of the reducing agent, and by making the first component (containing the water-soluble oxidizing agent) free of water (or at least free of appreciable amounts of water), a composition can be obtained that has all the advantages of known two-component cement compositions, but with improved stability (e.g., shelf-life stability, even when subjected to handling mishandling (e.g., potential water loss due to loose caps or failure to recap a container in a timely manner)).

[0013] In some embodiments, the first component of the multi-component settable composition can include (i) a liquid mono- and / or poly-functional component having ethylenically unsaturated groups (sometimes referred to herein as a "resin system"), (ii) an oxidizing agent, and (iii) an acid-reactive glass. In some embodiments, the first component can include no more than a small amount of water.

[0014] In some embodiments, the first component can be a paste, i.e., neither a powder nor a liquid, but a mixture of liquid and non-dissolvable powder / solid components having a generally uniform composition.

[0015] In some embodiments, the first component may include either or both a liquid monofunctional component and a liquid multifunctional (e.g., difunctional) component having an ethylenically unsaturated group. The liquid monofunctional or multifunctional component may include a monomer, oligomer, or polymer. In some embodiments, the liquid monofunctional or multifunctional component may be water-soluble. The liquid monofunctional or multifunctional component may also be selected to be miscible with the other components of the solidifiable composition. That is, these components may be at least sufficiently miscible that they do not substantially settle when combined with the other components of the composition. In some embodiments, the first component may include both a liquid monofunctional component and a liquid multifunctional (e.g., difunctional) component having an ethylenically unsaturated group.

[0016] In some embodiments, suitable ethylenically unsaturated groups include allyl, vinyl, acrylate, and methacrylate groups. In some embodiments, such monomers (or oligomers or polymers) have a relatively low molecular weight and contain only one ethylenically unsaturated group per monomer molecule. In some embodiments, the molecular weight of such monomers is from about 100 to about 1000. In some embodiments, including any one of the above embodiments that includes a water-soluble liquid monofunctional monomer having one ethylenically unsaturated group per monomer molecule, the water-soluble liquid monomer may be selected from the group consisting of 2-hydroxyethyl (meth)acrylate, glycerol mono(meth)acrylate, sugar methacrylate, and combinations thereof.

[0017] Also, as noted above, the multi-component solidifying compositions described herein may also, in certain embodiments, include a component having at least two ethylenically unsaturated groups per monomer molecule, which provides some crosslinking in the composition upon solidification. In some embodiments, this monomer may have a viscosity lower than bisphenol A-glycidyl methacrylate (Bis-GMA), or up to 50 percent of the viscosity of Bis-GMA.

[0018] In some embodiments, a suitable difunctional monomer may include glycerol dimethacrylate. Alternatively, or in addition, a water-soluble monomer may be used. Suitable water-soluble dimethacrylates include polyethylene glycol (dimeth)acrylates of various molecular weights, with a weight-average molecular weight ranging from approximately 400 to 1000.

[0019] The components of the resin system are selected to be miscible with the other components of the settable composition. That is, preferably, the components of the resin system are at least sufficiently miscible that they do not substantially settle when combined with the other ingredients of the composition (e.g., the reducing agent and oxidizing agent). Preferably, the components of the resin system are miscible with water. The components of the resin system can be monomers, oligomers, polymers, or combinations thereof.

[0020] The components of the resin system are selected to be miscible with the other components of the settable composition. That is, preferably, the components of the resin system are at least sufficiently miscible that they do not substantially settle when combined with the other ingredients of the composition (e.g., the reducing agent and oxidizing agent). Preferably, the components of the resin system are miscible with water. The components of the resin system can be monomers, oligomers, polymers, or combinations thereof.

[0021] In some embodiments, the liquid monofunctional and polyfunctional (e.g., difunctional) components having ethylenically unsaturated groups may be present in the first component in an amount of 1 to 50 wt %, 3 to 40 wt %, or 5 to 30 wt %, based on the total weight of the first component.

[0022] In some embodiments, suitable oxidizing agents include persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, and alkylammonium persulfates; hydroperoxides such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, and 2,5-dihydroperoxy-2,5-dimethylhexane; salts of cobalt(III) and iron(III); hydroxylamine; perborate and its salts; salts of permanganate anion; and combinations thereof. Hydrogen peroxide can also be used, but may interfere with the photoinitiator when present. In some embodiments, the oxidizing agent may include potassium persulfate (e.g., milled potassium persulfate having a small particle size for easy dispersion in the paste, such as an average particle size of less than 100 microns). The oxidizing agent may optionally be provided in an encapsulated form, as described in U.S. Pat. No. 5,154,762. The oxidizing agent may be selected to be miscible in the composition and / or miscible in water.

[0023] In some embodiments, the oxidizing agent may be present in the first component in an amount of 0.01 to 10 wt %, 0.1 to 4.0 wt %, or 0.5 to 2.0 wt %, based on the total weight of the first component.

[0024] In some embodiments, the first component can include an acid-reactive glass. Suitable acid-reactive glasses can include, for example, ion-leaching glasses such as those described in U.S. Patent Nos. 3,655,605, 3,814,717, 4,143,018, 4,209,434, 4,360,605, and 4,376,835. In some embodiments, the acid-reactive glass can be selected from borate glasses, phosphate glasses, and fluoroaluminosilicate glasses. In some embodiments, the acid-reactive glass can include fluoroaluminosilicate (FAS) glasses.

[0025] In embodiments including FAS glass, the FAS glass may contain sufficient leachable cations so that a hardened dental composition is formed when the glass is mixed with the components of the hardenable composition. The glass may also contain sufficient leachable fluoride ions so that the hardened composition has cariogenic properties. The glass may be made from a melt containing fluoride, alumina, and other glass-forming raw materials using techniques well known to those skilled in the art of FAS glass making. The FAS glass may be in the form of sufficiently finely divided particles so that it can be conveniently mixed with other cement components and the resulting mixture will perform well when used in the mouth.

[0026] In some embodiments, the average particle size (average longest dimension—typically diameter) of the FAS glass is 10 micrometers or less, or 5 micrometers or less, as measured, for example, using a sedimentation analyzer. Suitable FAS glasses are well known to those skilled in the art and are available from a variety of commercial sources; many are found in currently available glass ionomer cements, such as those sold under the trade names VITREMER, VITREBOND, RELY X LUTING CEMENT, and KETAC-FIL (3M ESPE Dental Products, St. Paul, MN), FUJI II, GC FUJI LC, and FUJI IX (Jizhi Dental Industry Co., Ltd., Tokyo, Japan), and CHEMFIL Superior (Dentsply International, York, PA). Mixtures of fillers can be used, if desired.

[0027] In some embodiments, the FAS glass can be surface treated. Suitable surface treatments include acid washing (e.g., treatment with phosphoric acid), treatment with phosphates, treatment with chelating agents such as tartaric acid, and treatment with silane or acidic or basic silanol solutions. Desirably, the pH of the treatment solution or treated glass is adjusted to neutral or near neutral, as this can increase the storage stability of the settable composition.

[0028] In some embodiments, any of the acid-reactive glass particles described above can be surface-treated. Suitable surface treatments include acid washing, treatment with phosphate, treatment with a chelating agent such as tartaric acid, or treatment with a silane or silanol coupling agent. In some embodiments, the acid-reactive glass particles can be silanol-treated fluoroaluminosilicate glass particles, as described in U.S. Pat. No. 5,332,429, the entire disclosure of which is incorporated herein by reference.

[0029] In some embodiments, the acid-reactive glass may be present in the first component in an amount of 1 to 80 wt %, 3 to 60 wt %, or 5 to 40 wt %, based on the total weight of the first component.

[0030] In some embodiments, the first component may be free of water or substantially free of water. In this regard, in some embodiments, the first component may comprise less than 5% by weight, less than 1% by weight, or less than 0.5% by weight of water, based on the total weight of the first component. In some embodiments, the first component may be free of water other than that unintentionally introduced by the various components comprising the first component (i.e., the first component may be free of any added water).

[0031] In some embodiments, the second component of the multi-component solidifying composition can include (i) a polyacid (e.g., a polyacid without polymerizable side groups), (ii) a reducing agent including 1-benzyl-5-phenylbarbituric acid (BPBA), (iii) water, and (iv) optionally, a filler without polymerizable groups attached to the filler surface. Like the first component, in some embodiments, the second component can be in the form of a paste.

[0032] In some embodiments, the second component can include a polyacid. In some embodiments, the polyacid can be water-miscible. Suitable water-miscible polyacids can include homopolymers or copolymers of unsaturated mono-, di-, and tricarboxylic acids, such as homopolymers or copolymers of acrylic acid, itaconic acid, or maleic acid. In some embodiments, the water-miscible polyacid can include polymers having sufficient pendant ionic groups to undergo a setting reaction in the presence of reactive glass and water, and sufficient pendant nonionic polymerizable groups to allow the resulting mixture to cure via a redox curing mechanism and / or exposure to radiant energy.

[0033] In some embodiments, the polyacid can be a (co)polymer (the reaction product of a polyacid and a coupling agent), hi some embodiments, the polyacid can be the reaction product of a polymer selected from the group consisting of polyacrylic acid, copolymers of acrylic acid and itaconic acid, copolymers of acrylic acid and maleic acid, copolymers of methyl vinyl ether and maleic anhydride or maleic acid, copolymers of ethylene and maleic anhydride or maleic acid, copolymers of styrene and maleic anhydride or maleic acid, and combinations thereof.

[0034] In some embodiments, the polyacid can have Formula I: B(X) m (Y) n I where B is an organic backbone, each X is independently an ionic group capable of undergoing a setting reaction in the presence of water and acid-reactive glass particles, each Y is independently a nonionically polymerizable group, m is at least 2, and n is at least 1. In some embodiments, X is —COOH and Y is a copolymer group free of ethylenically unsaturated groups. In some embodiments, backbone B is a carbon-carbon bonded oligomeric or polymeric backbone optionally containing non-interfering substituents such as oxygen, nitrogen, or sulfur heteroatoms. The term “non-interfering” refers to substituents or linking groups that do not unduly interfere with ionic or non-ionic polymerization reactions. In some embodiments, B is a hydrocarbon backbone. The X and Y groups can be attached to backbone B directly or by any non-interfering linking group, such as a substituted or unsubstituted alkylene group, alkyleneoxyalkylene group, arylene group, aryleneoxyalkylene group, alkyleneoxyarylene group, arylenealkylene group, or alkylenearylene group. Alkylene and arylene refer to the divalent forms of alkyl and aryl, respectively. The linking group may also include bonds such as -OC(=O)-, -C(=O)NH-, -NH-C(=O)O-, -O-, etc., and combinations thereof, each of which may be used in either orientation. In some embodiments, Y is linked to B through an amide bond.

[0035] Polyacids of Formula I include, but are not limited to, (1) polyacids of Formula B(X): m+n (2) reacting the n X groups of the polymer of formula B(X) with a suitable compound to form n pendant Y groups; m (3) reacting a polymer of formula B(Y) with a suitable compound at a site other than the X group to form n pendant Y groups; m+n or B(Y) n (3) reacting the Y group or other moieties of the polymer with a suitable compound to form m pendant X groups; and (4) copolymerizing an appropriate monomer, e.g., a monomer containing one pendant X group with a monomer containing one pendant Y group. Synthetic route (1) above is preferred. Such groups can be reacted through the use of a "coupling compound," i.e., a compound containing both a Y group and a reactive group capable of reacting with the X groups of the polymer, thereby covalently attaching the Y group to the backbone B in a pendant manner. Suitable coupling compounds are organic compounds that optionally contain non-interfering substituents and / or non-interfering linking groups between the Y group and the reactive group.

[0036] In some embodiments, the polyacid may be present in the second component in an amount of 2 to 50 wt %, 5 to 35 wt %, or 10 to 15 wt %, based on the total weight of the second component.

[0037] In some embodiments, the reducing agent may include a water-insoluble organic reducing agent such as 1-benzyl-5-phenylbarbituric acid (BPBA) or ascorbyl palmitate. It has been discovered that such organic reducing agents generally maintain their redox-cure reactivity when dispersed in water to form a paste with other components in the second component. In contrast, water-soluble reducing agents lose their redox-cure reactivity over time when dissolved in water. The water-insoluble organic reducing agents of the present disclosure may be dispersed as particles in water to achieve such storage stability. Finally, these water-insoluble reducing agents may dissolve through interaction with the resin system (e.g., methacrylate resin) after mixing the two components. The redox couple from the first and second components can then generate free radicals to cure the resin system.

[0038] In some embodiments, the reducing agent may be present in the second component in an amount of 0.1 to 8.0 wt %, 0.25 to 5.0 wt %, or 0.5 to 3.0 wt %, based on the total weight of the second component.

[0039] In some embodiments, the second component may include water, which may be present in the second component in an amount of 1 to 70 wt %, 2 to 60 wt %, 2 to 50 wt %, 5 to 40 wt %, 5 to 30 wt %, or 7 to 20 wt %, based on the total weight of the second component.

[0040] In some embodiments, non-reactive fillers may also be included in the compositions described herein to control viscosity and for other reasons, such as to achieve a desired appearance, to impart desired strength properties, to impart radiopacity, etc. In some embodiments, including any one of the above embodiments, the first component, the second component, or both, may further comprise a non-reactive filler in an amount of 5-60 wt %, 10-50 wt %, or 15-40 wt %, based on the total weight of the respective component.

[0041] In some embodiments, the non-reactive filler can be selected from one or more materials suitable for incorporation into compositions used in medical applications, such as fillers currently used in dental restorative compositions, etc. In some embodiments, the filler can have a maximum particle size of less than 50 micrometers and an average particle size of less than about 10 micrometers. The filler can have a unimodal or multimodal (e.g., bimodal) particle size distribution.

[0042] In some embodiments, the non-reactive filler is selected from the group consisting of inorganic materials, cross-linked organic materials, and combinations thereof. Suitable cross-linked organic materials are insoluble in the composition and are optionally filled with inorganic fillers. The filler should be non-toxic and suitable for use in the mouth. The filler can be radiopaque, radiolucent, or non-radiopaque.

[0043] Examples of suitable non-reactive inorganic fillers are naturally occurring or synthetic materials such as quartz, nitrides (e.g., silicon nitride), glasses derived from, for example, Ce, Sb, Sn, Zr, Sr, Ba, and Al, colloidal silica, colloidal zirconia, feldspar, borosilicate glasses, kaolin, talc, titania, and zinc glasses; fillers with low Mohs hardness such as those described in U.S. Pat. No. 4,695,251; and submicron silica particles (e.g., pyrogenic silicas such as the "Aerosil" series "OX50," "130," "150," and "200" silicas sold by Degussa and the "Cab-O-Sil M5" silica sold by Cabot Corp.); metal powders such as those disclosed in U.S. Pat. No. 5,084,491, particularly at column 2, lines 52-65; and combinations thereof.

[0044] Examples of suitable non-reactive organic filler particles include filled or unfilled ground polycarbonates, polyepoxides, etc. Preferred non-reactive filler particles are quartz, submicron silica and zirconia, and non-vitreous microparticles of the type described in U.S. Patent No. 4,503,169. Mixtures of these non-reactive fillers, as well as combination fillers made from organic and inorganic materials, are also contemplated.

[0045] In some embodiments including a non-reactive filler, the non-reactive filler is selected from the group consisting of fumed silica, zirconia silica, quartz, non-pyrogenic silica, and combinations thereof.

[0046] In some embodiments, the surface of non-reactive filler particles may be treated with a coupling agent to enhance the bond between the filler and the polymerizable component when the composition is solidified. Suitable coupling agents include gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, SILQUEST A-1230 (Momentive Performance Chemicals), and the like.

[0047] Additional components suitable for use in the oral environment may optionally be used in the multi-component solidifying compositions described herein (either or both components). In one example, such components include solvents, co-solvents (e.g., alcohol), or diluents. In another example, indicators, dyes, pigments, inhibitors, accelerators, viscosity modifiers, humectants, tartaric acid, chelating agents, surfactants, buffers, stabilizers (including free radical stabilizers), submicron silica particles, additives that impart fluorescence and / or opalescence, modifiers that extend working time, and other materials apparent to those skilled in the art may be used. Additionally, drugs or other therapeutic substances may optionally be added to the compositions. Examples include whitening agents, breath fresheners, flavoring agents, fragrances, anti-caries agents (e.g., xylitol), fluoride sources, remineralizing agents (e.g., calcium phosphate compounds), enzymes, anesthetics, coagulants, acid neutralizing agents, chemotherapeutic agents, immune response modifiers, thixotropic agents, polyols, anti-inflammatory agents, antibacterial agents, antifungal agents, xerostomia treatment agents, desensitizing agents, and the like, of the type that may also be used in dental compositions. Combinations of any of the above additives can also be used in the compositions described herein. The selection and amount of any one such additive can be determined by one of skill in the art depending on the desired results.

[0048] Modifiers that can extend the time between the initiation of the setting reaction in the restoration and the point at which sufficient hardening has occurred to allow subsequent clinical treatment of the restoration surface include, for example, alkanolamines, such as ethanolamine and triethanolamine, as well as mono-, disodium hydrogen phosphate, and trisodium hydrogen phosphate. Modifiers can be added to either Component A or Component B. When used, the modifier is present in a concentration of about 0.1 to 10 weight percent, based on the total weight of the composition.

[0049] Certain stabilizers provide color stability, such as oxalic acid, sodium metabisulfite, sodium bisulfite, sodium thiosulfate, metaphosphoric acid, and combinations thereof.

[0050] Free radical stabilizers can be used with photoinitiators to prevent premature polymerization or to adjust the working time of free radical initiated compositions. Suitable examples of free radical stabilizers include, for example, butylated hydroxytoluene (BHT) and methyl ethyl hydroquinone (MEHQ).

[0051] Viscosity modifiers include thickeners. Suitable thickeners include hydroxypropyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose and its various salts, such as the sodium salt, and combinations thereof.

[0052] In some embodiments, either or both of the first and second components may include a photoinitiator, which may be present not primarily to enable hardening, but rather to allow the practitioner to quickly harden excess portions of the hardenable composition during use (e.g., excess material present after a dental crown is placed on a prepared tooth).

[0053] Generally, photoinitiators can function as a source of free radicals when activated by heat or light. Such initiators can be used alone or in combination with one or more accelerators and / or sensitizers. Suitable photoinitiators (i.e., photoinitiator systems containing one or more compounds) include binary and ternary photoinitiators. In one example, a ternary photoinitiator can include an iodonium salt, a photosensitizer, and an electron donor compound, as described in U.S. Pat. No. 5,545,676 (Palazzotto et al.). Examples of iodonium salts include diaryliodonium salts, such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, diphenyliodonium tetrafluoroborate, and tolylcumyliodonium tetrakis(pentafluorophenyl)borate. Examples of photosensitizers include monoketones and diketones that absorb some light within the range of approximately 400 to 520 nanometers, preferably 450 to 500 nanometers. Alpha-diketones that absorb light within these ranges are preferred. Examples of such photosensitizers include camphorquinone, benzil, furil, 3,3,6,6-tetramethylcyclohexanedione, phenanthraquinone, 1-phenyl-1,2-propanedione, and other 1-aryl-1-alkyl-1,2-ethanediones, as well as cyclic alpha-diketones. Camphorquinone is most preferred. Preferred electron donor compounds include substituted amines, such as ethyl dimethylaminobenzoate.

[0054] When utilized, a photoinitiator should be present in an amount sufficient to provide the desired rate of polymerization, which amount will depend in part on the light source, the thickness of the layer to be exposed to radiant energy, and the extinction coefficient of the photoinitiator.

[0055] In some embodiments, each component of the multi-component hardening dental compositions described herein can have a balanced viscosity relative to the other components of the composition. In some embodiments, including any one of the above embodiments, the first component and the second component can each independently have a viscosity of 6 Pascal-seconds (Pa·s) or greater and 100 Pa·s or less. In some embodiments, the ratio of the viscosity of the second component to the first component is 1:0.06 to 1:13, 1:0.6 to 1:3.5, or 1:0.9 to 1:1.6. For purposes of this disclosure, viscosity is measured at room temperature at a shear rate of 20 s−1 using a simple shear method with a TA instrument (AR G2).

[0056] Method for producing hardened dental material The multi-component solidifying composition of the present disclosure can be formed by combining a first component and a second component. Any conventional mixing or combining technique can be used. For example, the first and second components can be dispensed onto a mix pad and mixed by hand, using an automix tip, or by a rotary device.

[0057] In some embodiments, the methods, devices, and compositions described herein are well suited for many dental applications, such as luting cements used to secure or hold prosthetic devices (e.g., crowns, bridges, inlays, onlays, posts, abutments, veneers, artificial teeth, etc.) in place in the oral cavity; restorative or filling materials used to fill cavities; thin films used as dentin and enamel liners or enamel sealants or sealing materials; orthodontic bracket adhesives; and band cements. In some embodiments, the multi-component hardenable dental composition is selected from the group consisting of a liner material, a luting material, a restorative material, an endodontic material, and a sealing material. In certain embodiments, including any one of the above embodiments, the multi-component hardenable dental composition is an orthodontic bracket adhesive or band cement.

[0058] In some embodiments, the present disclosure provides methods of making and using the multi-component settable compositions described herein. For example, the settable compositions of the present disclosure (after mixing) can be used in methods of bonding or cementing dental articles (e.g., crowns, bridges, orthodontic appliances) to teeth or bone (either intraorally or extraorally), and in methods of filling teeth.

[0059] Objects and advantages of the present disclosure are further illustrated by the following examples, but 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. [Example]

[0060] [Table 1] Resin-Modified Glass Ionomer (RMGI) cements are two-component systems that react and harden (set) when combined. The following RMGI examples were prepared as paste-paste RMGIs, i.e., two-component reactive systems (Paste "A" and Paste "B").

[0061] Preparation of "Paste A" for resin-modified glass ionomer (RMGI) dental compositions For the preparation of Paste A, the HEMA / GDMA / BHT / CPQ were first combined and dissolved together, then the other ingredients were added to make a total of 100 grams of Paste A, mixed in a speed mixer at 3000 rpm for 2 minutes, and repeated (2 cycles) to form a uniform paste. [Table 2] * HEMA did not have the reactivity to the mixed paste A / B, which has a short hardening time suitable for RMGI cement.

[0062] Example EXA1 Paste A1 was prepared and stored at ambient conditions at room temperature for 35 months and was still a stable paste A without premature self-polymerization and was still able to react properly with various pastes B (see below).

[0063] Example EXA2 Paste A2 was considered a control sample in the sense that it was prepared without potassium persulfate. When EXA2 Paste A2 was combined with EXB1 Paste B1, which contained BPBA, it formed Comparative Example C.EX-RMGI-1, which showed no hardening even after 10 minutes (see below).

[0064] Preparation of "Paste B" for resin-modified glass ionomer (RMGI) dental compositions To prepare Paste B, the AA-MA copolymer was first dissolved in water, then BPBA was mixed into the copolymer solution, and finally the other ingredients were added to a total amount of 100 grams. Paste B was mixed using a speed mixer at 3000 rpm for 2 minutes and repeated (2 cycles) to form a uniform paste. [Table 3]

[0065] Preparation of an Example of Resin-Modified Glass Ionomer (RMGI) Cement Two-component resin-modified glass ionomer (RMGI) cements were prepared using the example Pastes "A" and "B" described above. Selected Paste "A" and Paste "B" samples were hand-mixed on a mixing pad using a dental spatula for 20 seconds in a 6:5 component ratio (A:B; e.g., 0.42 grams of Paste A and 0.35 grams of Paste B, respectively). The mixed examples were then placed in a 37°C oven to cure and harden (set). The mixture was tapped with the spatula to ensure it had set, and the set time was recorded and reported below. [Table 4] [Table 5] [Table 6]

[0066] Light curing test Individually, Example Paste A and Paste B could not be cured with a 3M ELIPAR DeepCure-S LED curing light (430-480 nm wavelength range) after 20 seconds of exposure due to the lack of a photoinitiator component in each paste. When Example Paste A and Paste B were mixed together (0.42 grams of Paste A and 0.35 grams of Paste B for 20 seconds on a mixing pad), thereby introducing all of the photoinitiator components into the RMGI mixture, the mixture could be photocured to a rubbery or solid state after 20 seconds of exposure. [Table 7]

Claims

1. 1. A multi-component hardenable dental composition comprising: monofunctional and / or polyfunctional components having one or more ethylenically unsaturated groups; acid-reactive glass particles; a first component comprising an oxidizing agent; a water-miscible polyacid; a reducing agent comprising a water-insoluble organic compound; a second component comprising water; 1. A multi-component hardenable dental composition comprising:

2. 2. The multi-component hardenable dental composition of claim 1, wherein the water-insoluble organic compound comprises 1-benzyl-5-phenylbarbituric acid.

3. 3. The multi-component hardenable dental composition of claim 1, wherein the oxidizing agent comprises a peroxide.

4. The multi-component hardenable dental composition according to any one of claims 1 to 3, wherein the oxidizing agent comprises a persulfate.

5. The multi-component hardenable dental composition according to any one of claims 1 to 4, wherein the oxidizing agent comprises potassium persulfate.

6. 6. The multi-component hardenable dental composition of claim 1, wherein the oxidizing agent is present in the first component in an amount of 0.1 to 4.0 wt. %, based on the total weight of the first component.

7. The multi-component hardenable dental composition of any one of claims 1 to 6, wherein the acid-reactive glass comprises a fluoroaluminosilicate (FAS) glass.

8. 8. The multi-component hardenable dental composition of claim 1, wherein the acid-reactive glass is present in the first component in an amount of 3 to 60 wt. %, based on the total weight of the first component.

9. 9. The multi-component hardenable dental composition of claim 1, wherein water, if present in the first component, is present in an amount of less than 0.5 wt. %, based on the total weight of the first component.

10. The multi-component hardenable dental composition of any one of claims 1 to 9, wherein the polyacid comprises a homopolymer or copolymer of acrylic acid, itaconic acid, or maleic acid.

11. The polyacid has the formula: B(X) ｍ (Y) ｎ wherein B is an organic backbone, each X is independently an ionic group capable of undergoing a setting reaction in the presence of water and the acid-reactive glass particles, each Y is independently a nonionic polymerizable group, m is at least 2, and n is at least 1. The multi-component hardenable dental composition according to any one of claims 1 to 10,

12. 12. The multi-component hardenable dental composition of claim 11, wherein X is --COOH and Y is a copolymer group containing no ethylenically unsaturated groups.

13. 13. The multi-component hardenable dental composition of claim 1, wherein the polyacid is present in the second component in an amount of 5 to 35 wt %, based on the total weight of the second component.

14. 14. The multi-component hardenable dental composition of claim 1, wherein the reducing agent is present in the second component in an amount of 0.25 to 5.0 wt. %, based on the total weight of the second component.

15. 15. The multi-component hardenable dental composition of claim 1, wherein water is present in the second component in an amount of 1 to 70 wt. %, based on the total weight of the second component.

16. 16. The multi-component hardenable dental composition of claim 1, wherein the first component, the second component, or both the first component and the second component comprise a non-reactive filler in an amount of 1 to 40 wt. %, based on the total weight of the components including the non-reactive filler.

17. The multi-component hardenable dental composition of any one of claims 1 to 16, wherein the second component further comprises a non-reactive filler.

18. The multi-component hardenable dental composition of any one of claims 1 to 17, wherein the non-reactive filler comprises an inorganic material, a cross-linked organic material, and combinations thereof.

19. 19. The multi-component hardenable dental composition of claim 1, wherein the second component comprises the non-reactive filler in an amount of 30 to 40 weight percent, based on the total weight of the second component.

20. 20. The multi-component hardenable dental composition of any one of claims 1 to 19, wherein the non-reactive filler comprises fumed silica, zirconia silica, quartz, non-pyrogenic silica, or a combination thereof.

21. 21. The multi-component hardenable dental composition of any one of claims 1 to 20, wherein the mono- and / or poly-functional components of the first component are liquid at room temperature and water-miscible.

22. 22. The multi-component hardenable dental composition of claim 1, wherein the first component includes both monofunctional and polyfunctional components having ethylenically unsaturated groups.

23. 23. The multi-component hardenable dental composition according to any one of claims 1 to 22, wherein the monofunctional and polyfunctional components having an ethylenically unsaturated group of the first component are present in the first component in an amount of 3 to 40 wt%, based on the total weight of the first component.

24. The multi-component hardenable dental composition of any one of claims 1 to 23, which upon mixing has a setting time of less than 10 minutes.

25. The multi-component hardenable dental composition of any one of claims 1 to 24, selected from the group consisting of liner materials, luting materials, restorative materials, endodontic materials, and sealing materials.

26. The multi-component hardening dental composition according to any one of claims 1 to 25, wherein either or both of the first component and the second component are in a paste form.

27. A method of using the multi-component hardenable dental composition according to any one of claims 1 to 26, comprising: Adhering a dental article to a tooth or bone using the multi-component hardening dental composition according to any one of claims 1 to 26; or A method comprising at least partially filling a dental cavity with the multi-component hardenable dental composition of any one of claims 1 to 26.

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