Dental compositions and methods of making and using same

Abstract

A multi-component hardening dental composition, the first component comprising a mono- and / or poly-functional component having one or more ethylenically unsaturated groups, acid-reactive glass particles, and an oxidizing agent, the second component comprising a mono- and / or poly-functional component having one or more ethylenically unsaturated groups, a water-miscible polyacid, a reducing agent comprising an aromatic tertiary amine, an acid having a pKa lower than the pKa of the carboxylic acid, and a non-reactive filler.

Description

[Background technology]

[0001] Two-component dental cements are described, for example, in U.S. Pat. No. 6,982,288, WO 2020 / 075007, and WO 2011 / 081975. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0002] Two-component glass ionomer cements have been used for dental applications for some time. Such 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 tissues without pretreatment 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, inconsistent mechanical strength, varying consistencies, insufficient working or curing 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 powders, liquids, or pastes. The storage stability of the individual components is very important so that no changes in viscosity, color, or any other properties occur during the shelf life of the material (typically 2-4 years). At the time of use, the components are mixed and then applied. Setting should occur in a short time so that the procedure is neither uncomfortable for the patient nor the operator. The setting properties should allow sufficient time to mix the material and apply it to the abutment and / or dental prosthetic or orthodontic appliance in place in the oral cavity.

[0005] In conventional multi-component glass ionomer cement systems, a reducing agent (such as an aromatic tertiary amine) is paired with an oxidizing agent (such as a peroxide) in one component. In such systems, the electron-rich structure of the reducing agent can lead to undesirable self-hardening of resins containing reactive monomers and polymers during relatively short shelf lives. As a result, interest in alternative methods and compositions for more stable delivery of glass ionomer cements and related materials continues to grow.

[0006] 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.

[0007] The term "comprising" and variations thereof (e.g., comprises, includes, etc.) do not have a limiting meaning where these terms appear in the specification and claims.

[0008] As used herein, "a," "an," "the," "at least one," and "one or more" are used interchangeably unless the context clearly dictates otherwise.

[0009] Also, in this specification, the recitation of numerical ranges by endpoints includes 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.).

[0010] 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), where a first component comprises (i) a liquid (at room temperature) mono- 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 comprises (i) a liquid mono- and / or polyfunctional monomer, oligomer, or polymer, (ii) a reducing agent, (iii) a strong acid, (iv) a polyacid with or without polymerizable side groups, and (v) water.

[0011] 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 obtained. That is, by pairing the reducing agent with a polyacid in the second component (and pairing the reducing agent in the second component with another strong acid to form a latent catalyst), and by not including water (or at least not including a measurable amount of water) in the first component (containing the oxidizing agent), it has been discovered that a composition can be obtained that has all the advantages of known two-component cement compositions and has improved stability (e.g., shelf-life stability, e.g., even when subjected to handling errors (e.g., water loss that can occur due to loose capping or failure to recombine the cap and container in a timely manner).

[0012] In some embodiments, the first component of the multi-component settable composition may include (i) a liquid (at room temperature) 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 may include up to a small amount of water.

[0013] 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.

[0014] In some embodiments, the first component may include either or both of 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 other components of the solidifiable composition. That is, these components may be at least miscible enough to not substantially settle when combined with 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.

[0015] 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, which include 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.

[0016] 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 that provides some crosslinking in the composition when solidified. In some embodiments, the monomer may have a lower viscosity than bisphenol A-glycidyl methacrylate (Bis-GMA), or a viscosity 50 percent or less than that of Bis-GMA.

[0017] 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 (dimeth)acrylates include polyethylene glycol (dimeth)acrylates of various molecular weights, with the weight average molecular weight ranging from approximately 400 to 1000.

[0018] The components of the resin system can be selected to be miscible with the other components of the settable composition. That is, the components of the resin system can be at least sufficiently miscible that they do not substantially settle when combined with other ingredients of the composition (e.g., reducing and oxidizing agents). In some embodiments, the components of the resin system are miscible with water. The components of the resin system can be monomers, oligomers, polymers, or combinations thereof.

[0019] 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 weight percent, 3 to 40 weight percent, or 5 to 30 weight percent, based on the total weight of the first component.

[0020] In some embodiments, suitable oxidizing agents may include persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate and alkylammonium persulfate, hydroperoxides such as benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, tert-amyl hydroperoxide, and 2,5-dihydroperoxy-2,5-dimethylhexane, salts of copper (II) and iron (III), hydroxylamine, perborate and its salts, salts of permanganate anion, and combinations thereof. Hydrogen peroxide may also be used, but may interfere with the photoinitiator in some cases when present. In some embodiments, the oxidizing agent may include potassium persulfate (e.g., milled potassium persulfate). 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.

[0021] 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.

[0022] In some embodiments, the first component may include an acid-reactive glass. Suitable acid-reactive glasses may include, for example, ion-leaching glasses as described in U.S. Pat. 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 may be selected from borate glasses, phosphate glasses, and fluoroaluminosilicate glasses. In some embodiments, the acid-reactive glass may include fluoroaluminosilicate (FAS) glasses.

[0023] In embodiments that include FAS glass, the FAS glass may contain sufficient leachable cations so that a solidified dental composition is formed when the glass is mixed with the components of the settable composition. The glass may also contain sufficient leachable fluoride ions so that the solidified 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 particles that are sufficiently finely divided so that it can be conveniently mixed with other cement components and the resulting mixture will perform well when used in the mouth.

[0024] 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 wide variety of commercial sources, and 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 (Rishi Dental Industry Co., Ltd., Tokyo, Japan), and CHEMFILSuperior (Dentsply International, York, PA). Mixtures of fillers can be used if desired.

[0025] 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.

[0026] In some embodiments, any of the above-mentioned acid-reactive glass particles can be surface-treated. Suitable surface treatments include acid washing, treatment with phosphates, treatment with chelating agents such as tartaric acid, and treatment with silane or silanol coupling agents. 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.

[0027] In some embodiments, the acid-reactive glass can be present in the first component in an amount of from 1 to 80 weight percent, from 3 to 60 weight percent, or from 5 to 40 weight percent, based on the total weight of the first component.

[0028] 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.

[0029] In some embodiments, the second component of the multi-component solidifiable composition may include (i) a liquid mono- and / or polyfunctional monomer, oligomer, or polymer, (ii) a polyacid with or without polymerizable side groups, (iii) a reducing agent, (iv) a strong acid, and (v) water. Like the first component, in some embodiments, the second component may be in the form of a paste.

[0030] In some embodiments, the second component may include either or both of a liquid monofunctional component and a liquid multifunctional (e.g., difunctional) component having ethylenically unsaturated groups. The liquid monofunctional or multifunctional components may include monomers, oligomers, or polymers. Generally (but independently), the liquid monofunctional and multifunctional (e.g., difunctional) components of the second component may be of the same type as discussed with respect to the first component.

[0031] Additionally, in some embodiments, the resin system of the second component may include one or more acid-functional monomers, oligomers, or polymers (also referred to herein as acid-functional components). Such components may be ethylenically unsaturated compounds having acid functionality and may include oxyacid-functional derivatives of carbon, phosphorus, sulfur, and boron compounds and may be selected from those described in U.S. Pat. No. 7,156,911, columns 6-7, the entire disclosure of which is incorporated herein by reference. In some embodiments, the acid-functional components may include polymers including homopolymers and copolymers (i.e., polymers of two or more different monomers) of alkenoic acids such as acrylic acid, 2-chloroacrylic acid, 2-cyanoacrylic acid, aconitic acid, citraconic acid, fumaric acid, glutaconic acid, itaconic acid, maleic acid, mesaconic acid, methacrylic acid, and tiglic acid.

[0032] In some embodiments, the liquid monofunctional and polyfunctional (e.g., difunctional) components having ethylenically unsaturated groups may be present in the second component in an amount of 1 to 50 weight percent, 3 to 40 weight percent, or 5 to 30 weight percent, based on the total weight of the second component.

[0033] In some embodiments, the second component may include a polyacid. In some embodiments, the polyacid may be water-miscible. Suitable water-miscible polyacids may include homo- or copolymers of unsaturated mono-, di-, and tricarboxylic acids, such as homo- or copolymers of acrylic acid, itaconic acid, and maleic acid. In some embodiments, the water-miscible polyacids may include polymers having sufficient pendant ionic groups to undergo a curing reaction in the presence of reactive glass and water, and sufficient pendant non-ionic polymerizable groups to allow the resulting mixture to cure by a redox curing mechanism and / or by exposure to radiant energy.

[0034] In some embodiments, the polyacid can be a functional acidic (co)polymer (the reaction product of a polyacid and a coupling agent). In 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 acid, copolymers of ethylene and maleic anhydride or acid, copolymers of styrene and maleic anhydride or acid, and combinations thereof, with a coupling compound selected from the group consisting of acryloyl chloride, methacryloyl chloride, vinyl azalactone, allyl isocyanate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, and 2-isocyanatoethyl methacrylate. In some embodiments, the polyacid can be the reaction product of 2-isocyanatoethyl methacrylate and a copolymer of acrylic acid and itaconic acid (acrylic-itaconic acid copolymer with pendant methacrylate side groups) prepared as described in Example 11 of U.S. Pat. No. 5,130,347.

[0035] In some embodiments, the polyacid has 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 curing reaction in the presence of water and acid-reactive glass particles, each Y is independently a non-ionically polymerizable group, m is at least 2, and n is at least 1. In some embodiments, X is -COOH and Y is an ethylenically unsaturated group. In some embodiments, the 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 the 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. In some embodiments, Y is an acryloyloxy, methacryloyloxy, acrylamide, or methacrylamide group.

[0036] 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) nThe polymers can be prepared according to a variety of synthetic routes, including (1) reacting the Y groups or other sites of the polymer with a suitable compound to form m pendant X groups, and (2) copolymerizing a suitable monomer, e.g., a monomer containing one or more pendant X groups with a monomer containing one or more pendant Y groups. Synthetic route (1) above is preferred. Such groups can be reacted by 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 linking the Y groups in a pendant manner to the backbone B. Suitable coupling compounds are organic compounds that optionally contain non-interfering substituents and / or non-interfering linking groups between the Y groups and the reactive groups.

[0037] As mentioned above, suitable coupling compounds for preparing the polyacids used herein include compounds containing at least one group capable of reacting with X to form a covalent bond and at least one polymerizable ethylenically unsaturated group. When X is carboxyl, many groups, including both electrophilic and nucleophilic groups, can react with X. Examples of such groups include hydroxyl, amino, isocyanato, halo, carboxyl, and oxiranyl. Examples of suitable coupling compounds include, but are not limited to, acryloyl chloride, methacryloyl chloride, vinyl azalactone, allyl isocyanate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, and 2-isocyanatoethyl methacrylate. Other examples of suitable coupling compounds include those described in U.S. Pat. Nos. 4,035,321 and 5,814,682, the disclosures of which are incorporated herein by reference.

[0038] In some embodiments, the polyacid may be present in the second component in an amount of 2 to 50 weight percent, 5 to 35 weight percent, or 10 to 15 weight percent based on the total weight of the second component.

[0039] In some embodiments, suitable reducing agents can include ascorbic acid, metal complexed ascorbic acid, aromatic amines such as dimethylaminophenanthol and dihydroxyethyl-p-toludine, cobalt(II) chloride, ferrous chloride, ferrous sulfate, hydrazine, hydroxylamine, oxalic acid, thiourea, alkylthioureas and salts of dithionous acid, 1-allyl-2-thiourea, thiosulfates, aromatic sulfinates such as benzenesulfinates and p-toluenesulfinates, sulfite anion, and combinations thereof.

[0040] In some embodiments, the reducing agent may include a tertiary aromatic amine. In some embodiments, the tertiary aromatic amine has the following structural formula:

[0041] [ka] (wherein R1, R2, and R3 are independently a hydrogen atom, an alkyl group, an alkyl alcohol group, an alkyl group containing an ester or amide bond, an ester group, an amide group, or a utethane group having 1 to 8, 1 to 6, or 1 to 4 carbon atoms. In some embodiments, the tertiary aromatic amine may have the following:

[0042] [ka] or any derivative of such a tertiary aromatic amine.

[0043] In some embodiments, the reducing agent (e.g., a tertiary aromatic amine) 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.

[0044] As previously discussed, the second component may include a strong acid in addition to a reducing agent to form a latent catalyst for the multi-component solidifying composition. In general, the strong acid may act to suppress the reactivity of the reducing agent. More specifically, the strong acid may react with the reducing agent (e.g., aromatic tertiary amine) in water to form a salt (e.g., an amine salt), dramatically reducing the electron density of the nitrogen atom with a bond to a proton, thereby reducing the reducing ability of the aromatic tertiary amine to form free radicals. This avoids undesirable / premature self-curing of the second component. In some embodiments, a suitable strong acid may be an acid that is stronger than a carboxylic acid (i.e., an acid with a pKa lower than the pKa of the carboxylic acid). In some embodiments, suitable strong acids can include phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, and monomers containing one or more phosphate groups, such as methacryloyloxydecyl dihydrogen phosphate (MDP) or methacryloyloxyhecyl dihydrogen phosphate (MHP).

[0045] It should be understood that in some embodiments, after mixing of the first and second components, the reducing agent that reacted with the strong acid to form a salt can be regenerated. That is, after mixing, the aqueous resin system and polyacid of the second component are coupled with the resin system and oxidizing agent of the first component, the oxidizing agent may be dissolved in the water of the second component, and (in embodiments using a tertiary aromatic amine as the reducing agent) the aromatic tertiary amine phosphate (of the second component) can be converted to an aromatic tertiary amine after mixing with the acid-reactive filler and any other components in the first component. The regenerated aromatic tertiary amine can then dissolve in the water / resin solution to form a normal peroxide / amine redox couple and form free radicals to initiate the hardening of the multi-component settable composition.

[0046] In some embodiments, the second component may include water. Water may be present in the second component in an amount of 1 to 40% by weight, 2 to 30% by weight, or 5 to 20% by weight, based on the total weight of the second component.

[0047] 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 obtain 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.

[0048] In some embodiments, the non-reactive filler may 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 may have a maximum particle size of less than 50 micrometers and an average particle size of less than about 10 micrometers. The filler may have a unimodal or polymodal (e.g., bimodal) particle size distribution.

[0049] 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.

[0050] 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 "Cab-O-Sil M5" silica sold by Cabot Corp.); metal powders such as those disclosed in U.S. Pat. No. 5,084,491, especially at column 2, lines 52-65; and combinations thereof.

[0051] 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 are also contemplated, as well as combination fillers made from organic and inorganic materials.

[0052] 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.

[0053] In some embodiments, the surface of the 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 for use include gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, SILQUEST A-1230 (Momentive Performance Chemicals), and the like.

[0054] Additional components suitable for use in the oral environment may be optionally used in the multi-component solidifying compositions (either or both components) described herein. 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 that will be apparent to those skilled in the art may be used. In addition, drugs or other therapeutic substances may be optionally added to the composition. Examples include whitening agents, breath fresheners, flavoring agents, fragrances, anticaries (e.g., xylitol), fluoride sources, remineralization agents (e.g., calcium phosphate compounds), enzymes, anesthetics, coagulants, acid neutralizers, 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 may be used in the compositions described herein. The selection and amount of any one such additive may be determined by one of skill in the art depending on the desired results.

[0055] Modifiers that may extend the time between the initiation of the setting reaction in the restoration and the time when sufficient hardening has occurred to permit subsequent clinical treatment of the surface of the restoration include, for example, alkanolamines such as ethanolamine and triethanolamine, as well as monosodium hydrogen phosphate, disodium hydrogen phosphate, and trisodium hydrogen phosphate. Modifiers may be added to either Component A or Component B. When used, the modifiers are present in a concentration of about 0.1 to 10 weight percent, based on the total weight of the composition.

[0056] Certain stabilizers provide color stability, such as oxalic acid, sodium metabisulfite, sodium bisulfite, sodium thiosulfate, metaphosphoric acid, and combinations thereof.

[0057] 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).

[0058] Viscosity modifiers include thickening agents. Suitable thickening agents include hydroxypropyl cellulose, hydroxymethyl cellulose, carboxymethyl cellulose and its various salts, such as sodium, and combinations thereof.

[0059] In some embodiments, either or both of the first and second components may include a photoinitiator. In some embodiments, a photoemitter may not be present primarily to enable hardening, but rather to allow the practitioner to rapidly harden excess portions of the hardenable composition during use (e.g., excess amounts of material present after a dental crown is placed on a prepared tooth).

[0060] In general, 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 that include 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 triylcumyliodonium tetrakis(pentafluorophenyl)borate. Examples of photosensitizers include monoketones and diketones that absorb some light in the range of about 400 nanometers 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.

[0061] Photoinitiators, when utilized, 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.

[0062] 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 more 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.

[0063] For purposes of this disclosure, viscosity is the viscosity measured at room temperature at a shear rate of 20 / s using the simple shear method on a TA instrument (AR G2).

[0064] In some embodiments, upon mixing the first and second components, the hardenable dental composition can have a set time of less than 10 minutes, less than 7 minutes, or less than 5 minutes. As used herein, "set time" refers to the time at room temperature without heat or light activation at which sufficient hardening has occurred to obtain essentially the properties of the final hardened state of the composition.

[0065] The multi-component solidifying composition of the present disclosure can be formed by combining the first and second components. 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, mixed using an automix tip, or mixed by a rotary device.

[0066] 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; band cements, etc. In some embodiments, the multi-component hardening dental composition is selected from the group consisting of liner materials, luting materials, restorative materials, endodontic materials, and sealing materials. In certain embodiments, including any one of the above embodiments, the multi-component hardening dental composition is an orthodontic bracket adhesive or band cement.

[0067] 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 intra- or extra-orally) and in methods of filling teeth.

[0068] 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. EXAMPLES

[0069] [Table 1]

[0070] "Paste B" preparation for resin-modified glass ionomer (RMGI) dental compositions 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").

[0071] Comparative Examples CEx.B1 and CEx.B2 did not contain a strong acid and therefore formed gels after standing overnight, despite being solutions when first mixed, and therefore were unacceptable for use as Paste "B" in the RMGI composition.

[0072] [Table 2] "Yes" = gel formed overnight; not acceptable for RMGI paste "B". "None" = no gel formed overnight and is acceptable as Paste "B" for RMGI.

[0073] [Table 3] "None" = no gel formed overnight and is acceptable as Paste "B" for RMGI.

[0074] "Paste A" preparation for resin-modified glass ionomer (RMGI) dental compositions

[0075] [Table 4]

[0076] [Table 5]

[0077] [Table 6]

[0078] [Table 7]

[0079] Preparation of Examples of Resin-Modified Glass Ionomer (RMGI) Cement Two-component resin-modified glass ionomer (RMGI) cements were prepared using Example Paste "A" and Paste "B" above. Selected Paste "A" and Paste "B" samples were hand mixed on a mixing pad using a dental spatula for 20 seconds in a component ratio of 6:5 (A:B, respectively). The mixed examples were then placed in a 37°C oven to cure and harden (set). The mixture was tapped with a spatula to ensure it set, and the setting time was recorded and reported in Table 8 below.

[0080] [Table 8]

[0081] Stability of resin-modified glass ionomer (RMGI) cements prepared with Paste A and Paste B components stored at elevated temperatures over time. A first stability experiment was conducted to test the stability of selected Example Paste B stored in a polypropylene syringe clicker at 45° C. for 26 days. A commercially available 3M RelyX™ Luting Plus Cement Clicker™ dispenser was emptied and used as a storage container for selected Example Paste B. One cylinder of the clicker was filled with Experimental Paste B and stored at 45° C. for 26 days. After the storage period, Example Paste B was extruded from the tip of the syringe and dispenser to ensure that Paste B was still extrudable and visually evaluated for any signs of premature self-hardening. The results are reported in Table 9.

[0082] Additionally, each Example Paste B stored at 45°C for 26 days was then mixed with Example Paste EXA6 and Paste A6 to form resin modified glass ionomers (RMGIs). Paste A and Paste B were mixed by hand on a mixing pad using a dental spatula for 20 seconds in a component ratio of 6:5 (A:B; 0.42 grams of Paste A mixed with 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 a spatula to ensure it had reacted and set. The setting times for each RMGI example were recorded and are reported in Table 9 below.

[0083] [Table 9]

[0084] A second stability experiment was conducted to test the stability of selected Example Paste B stored in a polypropylene syringe clicker at 45° C. for two months. A commercially available 3M RelyX™ Luting Plus Cement Clicker™ dispenser was emptied and used as a storage container for selected Example Paste B. One cylinder of the clicker was filled with Experimental Paste B and stored at 45° C. for two months. After the storage period, Example Paste B was extruded from the tip of the syringe and dispenser to ensure that Paste B was still extrudable and visually evaluated for any signs of premature self-hardening. The results are reported in Table 10.

[0085] Additionally, each Example Paste B stored at 45° C. for 2 months was then mixed with Example EXA7 Paste A7 stored at room temperature (ambient laboratory conditions) for 32 months to form a resin modified glass ionomer (RMGI). The aged Example EXA7 Paste A7 and each Paste B were mixed by hand for 20 seconds on a mixing pad using a dental spatula in a 6:5 component ratio (A:B; 0.42 grams of Paste A mixed with 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 a spatula to ensure it had reacted and set. The cure time for each example was recorded and is reported in Table 10.

[0086] [Table 10] * EXA7 Paste A7 stored at RT for 32 months

[0087] A third stability study was conducted in a similar manner to RMGI example EX-RMGI-28-32 above, except that EXA5 paste A5 stored for 1 month at 45° C. and EXB13 paste B13 stored for 2 months at 45° C. were used. The results are reported in Table 11.

[0088] [Table 11] * EXA5 Paste A5 stored at 45℃ for one month

Claims

1. 1. A multi-component hardenable dental composition comprising: mono- and / or poly-functional components having one or more ethylenically unsaturated groups; Acid-reactive glass particles; a first component comprising an oxidizing agent; mono- and / or poly-functional components having one or more ethylenically unsaturated groups; a water-miscible polyacid; a reducing agent comprising an aromatic tertiary amine; an acid having a pKa lower than the pKa of the carboxylic acid; and a second component comprising a non-reactive filler.

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

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

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

5. 5. 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.

6. The multi-component hardenable dental composition of any one of claims 1 to 5, wherein the acid-reactive glass comprises a fluoroaluminosilicate (FAS) glass.

7. 7. 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.

8. The polyacid has the formula: B(X) ｍ (Y) ｎ 8. The multi-component hardenable dental composition according to claim 1, which is a polyacid of the formula: (wherein B is a hydrocarbon backbone, X is -COOH, Y is an ethylenically unsaturated group, m is at least 2, n is at least 1, and Y is bonded to B via an amide bond).

9. 9. The multi-component hardening dental composition of any one of claims 1 to 8, wherein the polyacid comprises a reaction product of (i) a polymer selected from the group consisting of polyacrylic acid, a copolymer of acrylic acid and itaconic acid, a copolymer of acrylic acid and maleic acid, a copolymer of methyl vinyl ether and maleic anhydride or maleic acid, a copolymer of ethylene and maleic anhydride or maleic acid, a copolymer of styrene and maleic anhydride or maleic acid, and combinations thereof, and (ii) a coupling compound selected from the group consisting of acryloyl chloride, methacryloyl chloride, vinyl azalactone, allyl isocyanate, 2-hydroxyethyl methacrylate, 2-aminoethyl methacrylate, and 2-isocyanatoethyl methacrylate.

10. 10. 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% by weight, based on the total weight of the second component.

11. The aromatic tertiary amine has the following structural formula: 【Chemistry 1】 (wherein R1, R2, and R3 are independently (i) a hydrogen atom, or (ii) an alkyl group having 1 to 8 carbon atoms, an alkyl alcohol group, an alkyl group containing an ester or amide bond, an ester group, an amide group, or a urethane group).

12. 12. The multi-component hardening dental composition of claim 1, wherein the aromatic tertiary amine 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.

13. The multi-component hardenable dental composition of any one of claims 1 to 12, wherein the acid comprises phosphoric acid, sulfuric acid, nitric acid, hydrochloric acid, or one or more monomers containing one or more phosphoric acid groups.

14. 14. The multi-component hardenable dental composition according to any one of claims 1 to 13, wherein water is present in the second component in an amount of 2 to 30% by weight, based on the total weight of the second component.

15. 15. The multi-component hardenable dental composition of claim 1, wherein the first component, the second component, or both the first and second components 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, and the non-reactive filler comprises an inorganic material, a crosslinked organic material, and combinations thereof.

16. 16. 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.

17. 17. The multi-component hardenable dental composition according to any one of claims 1 to 16, wherein the mono-functional and / or poly-functional components of the first and second components are liquid at room temperature and water-miscible.

18. The multi-component hardenable dental composition of any one of claims 1 to 17, wherein the first component includes both mono-functional and poly-functional components having ethylenically unsaturated groups.

19. 19. The multi-component hardenable dental composition of any one of claims 1 to 18, wherein the mono- and polyfunctional components having ethylenically unsaturated groups of the first and second components are independently present in each component in an amount of 3 to 40 wt%, based on the total weight of each component.

20. The multi-component hardenable dental composition of any one of claims 1 to 19, wherein the second component further comprises an acid-functional component.

21. The multi-component hardenable dental composition according to any one of claims 1 to 20, wherein the monofunctional and polyfunctional components having an ethylenically unsaturated group of the first component or the second component include 2-hydroxyethyl methacrylate, glycerol mono(meth)acrylate, or sugar methacrylate.

22. The multi-component hardenable dental composition of any one of claims 1 to 21, selected from the group consisting of liner materials, bonding materials, restorative materials, endodontic materials, and sealing materials.

23. The multi-component hardening dental composition according to any one of claims 1 to 22, wherein either or both of the first component and the second component are in a paste form.

24. 24. The multi-component hardenable dental composition of any one of claims 1 to 23, wherein the first component comprises water in an amount of less than 5 wt.%, less than 1 wt.%, or less than 0.5 wt.%, based on the total weight of the first component.

25. A method of using the multi-component hardenable dental composition according to any one of claims 1 to 24, comprising the steps of: Adhering a dental article to a tooth or bone using the multi-component hardening dental composition according to any one of claims 1 to 24; or A method comprising at least partially filling a dental cavity with the multi-component hardenable dental composition according to any one of claims 1 to 24.

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