A stable, two-component dual-cure dental composition for storage.

Abstract

The present invention relates to two-component, dual-cure dental compositions that have improved stability towards discoloration and premature polymerization. The dental composition includes a base member and a catalyst member, wherein the base member comprises a polymerizable component without acidic moieties, optionally a polymerizable component with acidic moieties, a filler, a transition metal component, a peroxide component, and a stabilizer component including a free radical moiety, wherein the catalyst member comprises a polymerizable component having no acidic moieties, a filler, and It includes an ascorbic acid component, a photoinitiator system, and a stabilizer component that includes a phosphite or sulfite moiety. The dental composition is particularly useful as a bulk-fill dental composite, a dental resin cement, a core build-up dental material, or a self-cure and dual-cure dental adhesive. The present invention further relates to the use of an initiator system and a stabilizer comprising a free radical moiety.

Description

Technical Field

[0001] The present invention relates to a two-component dual-cure dental composition having improved stability towards discoloration and premature polymerization.

[0002] Dental compositions are particularly useful as bulk-fill dental composites, dental resin cements, core build-up dental materials, or self-curing and dual-cure dental adhesives. [[ID=IO]]

Background Art

[0003] Generally, one-component and two-component dental curable compositions are known.

[0004] To cure one-component or two-component dental compositions, different types of initiator systems have been proposed.

[0005] To prevent premature polymerization of the curable components, some of these compositions contain stabilizers or other means for improving storage stability.

[0006] J.M. Antonucci et al. describe in J.M. Antonucci, C.L. Grams, D.J. Termini: "New initiator systems for dental resins based on ascorbic acid", J. Dent. Res. 1979, 58, 1887 - 1899, the use of an initiator system containing peroxide, ascorbic acid derivatives, and copper salts.

[0007] U.S. Patent No. 5,501,727 (3M) relates to a dental curable composition containing ethylenically unsaturated moieties, an oxidizing agent, and metal complexed ascorbic acid.

[0008] U.S. Patent No. 5,688,883 (Dentsply) refers to a polymerizable composition formed by mixing a liquid and a powder composition, wherein the liquid comprises a peroxide and the powder comprises a proton donor (e.g., an ascorbic acid derivative) and a metal-containing compound.

[0009] U.S. Patent No. 6,998,111 (Dentsply) describes a storage-stable polymerizable composition comprising a peroxide, a metal-containing material, and a protected reducing agent (e.g., ascorbic acid supported with a protecting group).

[0010] U.S. Patent No. 5,847,025 (Ivoclar) describes a photocurable composite material characterized by its anaerobic stabilizer and / or stable organic radical content, which has low photosensitivity and improved vacuum stability.

[0011] European Patent No. 2374445(A2) (Voco) describes a dual-cure multi-component dental composition.

[0012] International Publication No. 2016 / 007453(A1)(3M) describes a two-component self-adhesive dental composition, its manufacturing process, and its use.

[0013] International Publication No. 2017 / 100231(A1)(3M) describes a two-component self-adhesive dental composition, a preservative stabilization initiator system, and its use.

[0014] German Patent No. 10 2010 003 883(A1) (Voco) describes a photopolymerizable dental composition comprising (a) a photopolymerizable monomer comprising acrylate and methacrylate, (b) a photoinitiator, (c) a molecular weight modifier comprising a compound that reacts with a radical of the monomer of component (a), wherein the reaction is carried out by abstracting a hydrogen radical from the molecular weight modifier at the allyl position, and (e) at least one inorganic filler.

[0015] U.S. Patent No. 2005 / 203199(A1) (Moszner et al.) refers to dental materials containing a radically polymerizable organic binder, a polymerization initiator, and a polymerization accelerator. In addition, the material may also contain a polymerizable UV absorber and a polymerization inhibitor to prevent premature spontaneous polymerization.

[0016] U.S. Patent No. 2018 / 0221249(A1) (Fik et al.) describes an aqueous dental adhesive composition comprising a polymerizable compound containing a polymerizable double bond, an initiator system, a solvent mixture, and a certain hydroquinone stabilizer. The use of other stabilizers may impart stability to the dental composition, but may cause discoloration problems. [Overview of the project]

[0017] In general, there is a need for dental curable compositions with an appropriate curing kinetics, particularly those that can cure fast enough to obtain products with appropriate physical properties such as flexural strength and E-modulus.

[0018] Furthermore, dental hardening compositions should be sufficiently stable for storage.

[0019] Sufficient storage stability is typically achieved by adding an appropriate amount of a suitable stabilizer.

[0020] To stabilize a curable composition containing a highly reactive initiator system, a large amount of stabilizer is typically required.

[0021] However, while using large amounts of stabilizers may help stabilize the composition from a rheological standpoint, it can also lead to other problems such as discoloration over time.

[0022] Therefore, there is a particular need for dental compositions that have sufficient storage stability and appropriate hardening properties that do not exhibit unacceptable discoloration during storage.

[0023] One or more of the above objectives are addressed by the present invention as described herein.

[0024] In one embodiment, the present invention is a dental composition comprising a base member and a catalyst member that are mixed before use, as described herein and in the claims. The base member is Polymerizable components that do not have an acidic portion, Optionally, a polymerizable component having an acidic portion, Filler and, Transition metal components, Peroxide components, A stabilizer component containing a free radical portion, The catalyst component, Polymerizable components that do not have an acidic portion, Filler and, Ascorbic acid component, Photoinitiator system, The dental composition is characterized by comprising a stabilizing component containing a phosphite or sulfite portion.

[0025] In another embodiment, the present invention relates to a dental composition for use in a process comprising the steps of: mixing a base member and a catalyst member to obtain a mixed member; applying at least a portion of the mixed member to the surface of tooth hard tissue; and optionally, applying radiation to a portion of the mixed member, as described herein and in the claims.

[0026] Further embodiments of the present invention, as described herein and in the claims, aim at a kit of components comprising a dental composition and at least one of the following items: dental filling composites, dental sealants, dental cements, dental mill blanks, dental etching agents, dental adhesives, dental try-in pastes, and dental fiber posts.

[0027] The present invention also relates to the use of stabilizers containing a free radical moiety to stabilize initiator systems that include a peroxide component in combination with a transition metal ion component.

[0028] Further embodiments relate to initiator systems comprising a transition metal component, a peroxide component, a stabilizer component including a free radical moiety, an ascorbic acid component, a photoinitiator system, and a stabilizer component including a phosphite or sulfite moiety, wherein the components are as described herein.

[0029] Unless otherwise defined, the following terms have the meanings set forth below in this specification.

[0030] A "dental composition," or "composition for dental use," or "composition used in the dental field" is a composition that can be used and is used in the dental field. In this regard, the composition should not be harmful to the patient's health and therefore should not contain harmful and toxic components that can migrate away from the composition.

[0031] Dental compositions are typically curable compositions that can be cured under ambient conditions including temperatures ranging from 15 to 50°C or 20 to 40°C within a time frame of 30 minutes, 20 minutes, or 10 minutes. Higher temperatures are not recommended as they may cause pain to the patient and could be harmful to the patient's health.

[0032] Dental compositions are typically supplied to physicians in relatively small volumes, i.e., in volumes ranging from 0.1 to 100 mL, 0.5 to 50 mL, or 1 to 30 mL. Therefore, the storage capacity of useful packaging devices falls within these ranges.

[0033] A "one-component composition" means that all components of the composition are present in the composition during storage and use. In other words, the composition applied or used is not prepared by mixing different components of the composition before use. In contrast to one-component compositions, two-component or multi-component compositions are typically formulated as powder / liquid, liquid / liquid, or paste / paste compositions and are supplied to physicians in the form of component kits.

[0034] The term "compound" refers to a chemical substance that has a specific molecular identity, or a chemical substance made from a mixture of such substances, including polymeric substances.

[0035] A "derivative" or "structural analog" is a chemical compound that exhibits a chemical structure closely related to the corresponding reference compound and contains all the structural elements characteristic of the corresponding reference compound, but has minor modifications compared to the corresponding reference compound, such as having additional chemical groups like an alkyl moiety, Br, Cl, or F, or lacking chemical groups like an alkyl moiety. In other words, a derivative is a structural analog of a reference compound. A derivative of a chemical compound is a compound that contains the chemical structure of the aforementioned chemical compound.

[0036] A "polymerizable component" is any component that can be cured or solidified, for example, by heating to induce polymerization or chemical crosslinking, or by radiation-induced polymerization or crosslinking, or by using a redox initiator, or by any other radical formation process. A radical polymerizable component may contain one, two, or three or more radical polymerizable groups. Typical examples of radical polymerizable groups include unsaturated carbon groups, such as vinyl groups present in (meth)acrylate groups.

[0037] A "monomer" is any chemical substance that can be characterized by a chemical formula having a radically polymerizable unsaturated group (including a (meth)acrylate group) that can increase its molecular weight by polymerization with an oligomer or polymer. Typically, the molecular weight of a monomer can be simply calculated based on the given chemical formula.

[0038] The terms "polymer" or "polymer material" are used interchangeably to refer to homopolymers, copolymers, terpolymers, etc.

[0039] As used herein, "(meth)acrylic" is an abbreviation for "acrylic" and / or "methacrylic". For example, "(meth)acrylicoxy" group is an abbreviation for either an acrylicoxy group (i.e., CH2=CH-C(O)-O-) and / or a methacrylicoxy group (i.e., CH2=C(CH3)-C(O)-O-).

[0040] "Polymerizable components having an acidic portion" is intended to include monomers, oligomers, and polymers having ethylenically unsaturated functional groups and acid and / or acid precursor functional groups.

[0041] Examples of acidic precursor functional groups include anhydrides, acid halides, and pyrophosphates.

[0042] The acidic group preferably includes one or more carboxylic acid residues such as -COOH or -CO-O-CO-, a phosphate residue such as -OP(O)(OH)OH, a phosphonic acid residue, a sulfonic acid residue such as -SO3H, or a sulfinic acid residue such as -SO2H.

[0043] Ingredients containing the "ascorbic acid portion" are ingredients that contain the following structural elements. [ka] (In the formula, the symbol "*" indicates a bond to another chemical part or atom.)

[0044] "Solvent" means a liquid in which the components can be at least partially dispersed or dissolved under ambient conditions (e.g., 23°C). Solvents are typically about 5 Pa * Less than s, or about 1 Pa * Less than s, or approximately 0.1 Pa * It has a viscosity of less than s.

[0045] As used herein, “hardening” or “curing” of a composition is used interchangeably and refers to polymerization and / or crosslinking reactions, for example, involving one or more materials contained in the composition, including photopolymerization and chemical polymerization techniques (e.g., ionic or chemical reactions that form radicals effective for polymerizing ethylenically unsaturated compounds).

[0046] "Self-hardening dental composite materials" refer to materials that can harden without the application of radiation. Such materials typically contain a redox initiator system that includes oxidizing components (such as peroxides) and reducing components (such as amines). During storage, self-hardening dental composite materials are typically supplied as kits of components in which the components of the redox initiator system are separated from each other.

[0047] "Dual-cure dental composite material" refers to a self-hardening dental composite material that further contains a photoinitiator system.

[0048] "Paste" refers to a soft, viscous mass (i.e., particles) of solid matter dispersed in a liquid.

[0049] As used herein, “tooth surface” or “hard tissue of the tooth” refers to the tooth structure (e.g., enamel, dentin, and cementum) and bone.

[0050] "Dental restorations" refer to materials used to restore the function of missing tooth structures. Examples of dental restorations include dental fillings, temporary crowns and bridge materials, dental crowns and bridges, inlays, onlays, veneers, root canal fillings, and dental posts.

[0051] A "self-etching composition" refers to a composition that adheres to the tooth surface without requiring pretreatment with an etching agent. Preferably, the self-etching composition can function as a self-adhesive primer without the need for another etching agent or primer, or it may be a self-adhesive composition itself.

[0052] A "self-adhesive composition" refers to a composition that can adhere to a tooth surface without pretreatment with a primer or bonding agent. Preferably, the self-adhesive composition is also a self-etching composition that does not require the use of another etching agent.

[0053] "Untreated tooth surface" refers to a tooth or bone surface that has not been treated with an etching agent, primer, or bonding agent before the application of the self-etching adhesive or self-adhesive composition. However, this surface may be mechanically treated with a dental bur, grinding or polishing medium, pumice, etc.

[0054] An "unetched" tooth surface refers to a tooth or bone surface that has not been treated with an etching agent before the application of a self-etching adhesive or self-adhesive composition.

[0055] A "functionalized silane compound" is a silane compound having one or more moieties that can undergo chemical reactions beyond condensation with the OH moieties of other silanes or with the surface of a filler. Examples of functionalized silane compounds include amino or (meth)acrylate functionalized silanes such as 3-aminopropyltrimethoxysilane or 3-(meth)acrylooxypropyltrimethoxysilane.

[0056] The composition is characterized as a "dual-cure type" when it contains one or more initiator systems that cure the composition by radiation or by a redox reaction without radiation, i.e., by a self-curing mechanism.

[0057] "Radiation-curable" means that the components (or, in some cases, the composition) can be cured by the application of radiation, preferably electromagnetic radiation of wavelengths in the visible light spectrum, under ambient conditions and within a suitable time (e.g., within about 60, 30, or 10 seconds).

[0058] "Ambient conditions" means the conditions to which the compositions described herein are typically exposed during storage and handling. Ambient conditions may be, for example, a pressure of 900 to 1,100 mbar, a temperature of 10 to 40°C, and a relative humidity of 10 to 100%. In laboratories, ambient conditions are typically adjusted to 20 to 25°C and a relative humidity of about 50%.

[0059] A material or composition is considered "essentially or substantially free" of a particular component within the meaning of this invention if it does not contain that component as an essential characteristic. Therefore, the component is not intentionally added to the composition or material, either by itself, in combination with other components, or as a constituent of other components. A composition or material that is essentially free of a particular component typically contains that component in an amount of less than 1% by weight, less than 0.1% by weight, or less than 0.01% by weight relative to the whole of the composition or material. Ideally, the composition or material would contain no such component at all. However, it may not be possible to avoid the presence of small amounts of the component, for example, due to impurities.

[0060] As used herein, “a,” “an,” “the,” “at least one,” and “one or more” are interchangeable. Furthermore, in this specification, numerical ranges indicated by endpoints include all numbers contained within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0061] Adding "(s)" to a term means that the term should include both singular and plural forms. For example, the term "additive(s)" means one additive and two or more additives (e.g., two, three, four, etc.).

[0062] Unless otherwise indicated, all numbers representing the quantities and physical properties of substances contained herein, as well as those used in this specification and the claims, should be understood as numbers in themselves and modified by the term “approximately.”

[0063] The term "approximately" allows for some degree of variability in a value or range, for example, within 10%, 5%, or 1% of the limit of a given value or range.

[0064] The terms “contains” or “includes” and their variations shall not be limited in meaning when used herein and in the claims. The term “contains” also includes the terms “essentially consists of” and “consist of.” “Essentially consists of” means that there may be certain further components that do not substantially affect the essential properties of the article, composition or method. “Consists of” means that there are no further components.

[0065] "And / or" means one or both. For example, "expression component A and / or component B" refers to component A only, component B only, or both component A and component B. [Modes for carrying out the invention]

[0066] The dental compositions described herein have been found to possess several advantageous properties.

[0067] The dental composition contains an initiator system having high reactivity and a fast curing rate, making it particularly suitable for dental compositions in the dental field where rapid and reliable curing is desired.

[0068] In this respect, the initiator system includes two components, a photoinitiator system, and a redox initiator system.

[0069] The redox initiator system becomes active when the base component and the catalyst component are mixed.

[0070] Photoinitiator systems become active when the composition is exposed to radiation.

[0071] The combination of both systems enables rapid and reliable curing of dental compositions, even under challenging conditions.

[0072] However, using such highly reactive initiator systems can adversely affect the storage stability of the composition or its individual components.

[0073] This problem is typically addressed by adding a stabilizing component.

[0074] However, when well-known stabilizing components such as phenol stabilizers (e.g., butylated hydroxytoluene, BHT) or hydroquinone stabilizers (e.g., hydroquinone monomethyl ether, MEHQ) were used at normal concentrations up to several hundred ppm, the dental compositions or their respective components exhibited undesirable premature polymerization.

[0075] When the concentrations of these well-known stabilizing components increased, undesirable discoloration of the dental composition or its corresponding component was observed.

[0076] These problems can be addressed by using stabilizing components that include free radical moieties.

[0077] These stabilizing components were found to be particularly useful for stabilizing curable compositions containing peroxide components, even in the presence of transition metal components.

[0078] It was also found that only small amounts of these stabilizing components are needed to achieve the long-term stability of the composition and its individual components.

[0079] Therefore, the dental compositions and their corresponding components described herein are sufficiently stable and do not show discoloration even after long-term storage.

[0080] In addition to the stabilizing component containing the free radical moiety, the dental composition contains further stabilizing components. These further stabilizing components include sulfite or phosphite moieties.

[0081] These stabilizing components were found to be particularly useful in stabilizing initiator systems containing ascorbic acid components when combined with photoinitiator systems.

[0082] Furthermore, the dental composition obtained after curing exhibits appropriate physical properties such as flexural strength and E-modulus.

[0083] Therefore, the dental compositions described herein include a highly reactive initiator system comprising a curing component, a filler, a photoinitiator component, and a redox initiator component, as well as two types of stabilizer components.

[0084] The present invention as described herein comprises a base member and a catalyst member and can be considered a two-component dental composition.

[0085] The compositions contained in the base member and catalyst member are intended to be mixed before use to obtain a dental curable composition.

[0086] The base member and catalyst member are typically supplied in a mixing ratio of 10:1 to 1:1, 5:1 to 1:1, or 2:1 to 1:1 relative to their volume.

[0087] A 1:1 mixing ratio relative to volume may be preferable because it allows for a more homogeneous mixing of the corresponding components.

[0088] The dental composition obtained after mixing the base member and the catalyst member is typically heated to 10-70 Pa at 28°C. * It has a viscosity in the range of s.

[0089] Dental compositions having a viscosity in this range can be easily discharged from a static mixing cannula and applied to the surface of tooth structures.

[0090] Furthermore, dental compositions having such a viscosity range can be used as fluid bulk-fill dental composite materials, dental resin cements, or self-curing and dual-cure dental adhesive materials.

[0091] The composition contained in the base member typically has a viscosity in the range of 5 to 60 Pa·s at 23°C. *

[0092] A base member having a viscosity within such a range can be easily mixed by using a static mixing cannula.

[0093] The composition contained in the base member typically has a pH value in the range of 2 to 5 when contacted with water (e.g., wet pH-sensitive paper). Therefore, the composition contained in the base member is typically acidic.

[0094] The base member is typically provided as a paste.

[0095] The base member contains a polymerizable component that does not have an acidic moiety.

[0096] Suitable polymerizable components that do not have an acidic moiety are characterized by the following formula, A n BA m and can be characterized by, A is an ethylenically unsaturated group bonded to the backbone B such as a (meth)acryloyl moiety, B is selected from (i) a linear or branched C1 - C 12 alkyl, (ii) a C6 - C 12 aryl optionally substituted with other functional groups (e.g., OH), or (iii) an organic group having 4 to 20 carbon atoms bonded to each other by one or more ether, ester, amide, urethane, carbonyl, and / or sulfonyl bonds, m and n are independently selected from 0, 1, 2, 3, 4, 5, or 6, provided that n + m is greater than 0, that is, at least one A group is present.

[0097] ​Examples of such polymerizable materials include methyl acrylate, methyl methacrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, n-hexyl (meth)acrylate, stearyl (meth)acrylate, allyl (meth)acrylate, glycerol di(meth)acrylate, and UDMA (isomer, e.g., Rohm), which is a reaction product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate (TMDI). Diurethane dimethacrylate, glycerol tri(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, trimethylolpropane tri(meth)acrylate, 1,2,4-butanetriol tri(meth)acrylate, 1,4-cyclohexanediol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, sorbitol hexa(meth)acrylate, bis[1-(2-(meth)acrylooxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-methacrylooxy-2] Mono-, di-, or polyacrylates and methacrylates such as bis[1-(3-methacrylate)]-p-propoxyphenyldimethylmethane (BisGMA), bis[1-(3-methacrylate)]-p-propoxyphenyldimethylmethane, dimethacrylates of ethoxylated bisphenol A having 2 to 10 ethoxy units (e.g., BisEMA-6) and trishydroxyethyl-isocyanurate trimethacrylate; copolymerizable mixtures of polyethylene glycol bis-acrylates and bis-methacrylates with molecular weights of 200 to 500, acrylic monomers (see U.S. Patent No. 4,652,274 (Boettcher et al.)), and acrylic oligomers (see U.S. Patent No. 4,642,126 (Zador et al.)); and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate;Examples include urethane, urea, or polyfunctional (meth)acrylates containing amide groups.

[0098] Examples of polyether (meth)acrylates include dialkylene glycol mono(meth)acrylates, such as diethylene glycol mono(meth)acrylate, triethylene glycol mono(meth)acrylate, tetraethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate.

[0099] The molecular weights of these compounds are typically less than 20,000 g / mol, particularly less than 15,000 g / mol, and especially less than 10,000 g / mol.

[0100] Further examples of polymerizable components include di(meth)acrylates derived from tricyclodecane-dimethanol (which is typically a mixture of isomers), reaction products of tricyclodecane-dimethanol and isocyanatoethyl (meth)acrylate, reaction products of tricyclodecane-diisocyanate and hydroxyethyl (meth)acrylate or hydroxypropyl (meth)acrylate, e.g., bis[3[4]-methacrylic-oxymethyl-8(9)-tricyclo[5.2.1.0 2,6 Decylmethyl triglyceride, and bishydroxymethyltricyclo-(5.2.1.0 2,6 These are urethane (meth)acrylates and di(meth)acrylates of decane. These types of methacrylic esters are described in U.S. Patent No. 4,795,823 (Schmitt et al.).

[0101] Polymerizable monomers containing a hydroxyl moiety can also be added.

[0102] Suitable compounds include 2-hydroxyethyl methacrylate (HEMA), 2- or 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 1,2- or 1,3- and 2,3-dihydroxypropyl (meth)acrylate, 2-hydroxypropyl-1,3-di(meth)acrylate, 3-hydroxypropyl-1,2-di(meth)acrylate, N-(meth)acryloyl-1,2-dihydroxypropylamine, N-(meth)acryloyl-1,3-dihydroxypropylamine, 1-phenoxy-2-hydroxypropyl (meth)acrylate, and 1-naphthoxy-2-hydroxypropyl (meth)acrylate.

[0103] 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 2,3-dihydroxypropyl (meth)acrylate may be preferred.

[0104] If desired, brominated components such as those described in European Patent Application No. 17200519.1 may also be used. The contents of this reference are incorporated herein by reference.

[0105] When brominated components are desired, it has been found that components containing aromatic moieties selected from brominated resorcinol, catechol, tyrosol, benzoic acid, or phenolic moieties are particularly useful.

[0106] If desired, a mixture of two or more of these free radical polymerizable materials can be used.

[0107] Polymerizable components that do not contain acidic portions are typically present in the following amounts in the base material. Lower limit: at least 5, or at least 10, or at least 20% by weight, Upper limit: Maximum 70, or maximum 60, or maximum 50% by weight. Range: 5-70, or 10-60, or 20-50% by weight. The weight percentage is relative to the amount of the base material.

[0108] The base member may also contain a polymerizable component having an acidic portion.

[0109] Polymerizable components having an acidic portion are defined by the following formula: A n BC m It can be represented as (In the formula, B is a linear or branched chain C1-C optionally substituted with (i)OH) 12 C6-C atoms optionally substituted with alkyl or (ii)OH groups. 12 A skeleton group such as an organic group having 4 to 20 carbon atoms bonded to one or more ethers, thioethers, esters, thioesters, thiocarbonyls, amides, urethanes, carbonyl and / or sulfonyl bonds, each optionally substituted with an aryl and (iii)OH group, respectively. A is an ethylenically unsaturated group bonded to a skeletal group such as the (meth)acroyl moiety. C is an acidic group bonded to the skeletal group, m, n = 1, 2, 3, 4, 5, or 6, The acidic group includes one or more carboxylic acid or anhydride residues such as -COOH or -CO-O-CO-, a phosphate residue such as -OP(O)(OH)OH, a phosphonic acid residue, a sulfonic acid residue such as -SO3H, or a sulfinic acid residue such as -SO2H.

[0110] Specific examples of ethylenically unsaturated acidic compounds include glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl (meth)acrylate phosphate, bisglycerol phosphate di(meth)acrylate, bis((meth)acrylooxyethyl) phosphate, ((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxypropyl) phosphate, bis((meth)acrylooxy)propyl phosphate, (meth)acrylooxyhexyl phosphate, bis((meth)acrylooxyhexyl) phosphate, (meth)acrylooxy Examples include, but are not limited to, tyl phosphate, bis((meth)acryloxyoctyl) phosphate, (meth)acryloxydecyl phosphate, bis((meth)acryloxydecyl) phosphate, caprolactone methacrylate phosphate, di- or tri(meth)acrylic citric acid, poly(meth)acrylic oligomaleic acid, poly(meth)acrylic polymaleic acid, poly(meth)acrylic poly(meth)acrylic acid, poly(meth)acrylic polycarboxyl-polyphosphonic acid, poly(meth)acrylic polychlorophosphate, poly(meth)acrylic polysulfonate, and poly(meth)acrylic polyboric acid.

[0111] (Meth)acrylic acid and alkanediol reaction products (e.g., C2-C) 20 , or C2~C 12 , or C6~C 10 ), and the reaction products of phosphorus oxide were also found to be suitable.

[0112] Furthermore, monomers, oligomers, and polymers of unsaturated carboxylic acids such as (meth)acrylic acid and aromatic (meth)acrylicated acids (e.g., methacrylated trimellitic acid), as well as their anhydrides, can also be used.

[0113] Some of these compounds can be obtained, for example, as reaction products between isocyanatoalkyl (meth)acrylates and carboxylic acids. Additional compounds of this type having both an acidic functional component and an ethylenically unsaturated component are described in U.S. Patent No. 4,872,936 (Engelbrecht) and No. 5,130,347 (Mitra). A wide variety of such compounds containing both an ethylenically unsaturated moiety and an acidic moiety can be used. Mixtures of such compounds can be used if desired.

[0114] Furthermore, as an ethylenically unsaturated compound having an acidic functional group, for example, is the polymerizable bisphosphonic acid;AA:ITA:IEM (AA:ITA copolymer) disclosed in U.S. Patent Application No. 2004 / 0206932(A1) (Abuelyaman), which is prepared by reacting the AA:ITA copolymer with a sufficient amount of 2-isocyanatoethyl methacrylate to convert the acidic group portion of the copolymer into pendant methacrylate groups, such as the copolymer of acrylic acid:itaconic acid and pendant methacrylate, for example, U.S. Patent No. 5,130,347 (Mitra). Examples include those described in Example 11; and those described in U.S. Patent No. 4,259,075 (Yamauchi et al.), U.S. Patent No. 4,499,251 (Omura et al.), U.S. Patent No. 4,537,940 (Omura et al.), U.S. Patent No. 4,539,382 (Omura et al.), U.S. Patent No. 5,530,038 (Yamamoto et al.), U.S. Patent No. 6,458,868 (Okada et al.), and European Patent No. 0712622(A1) (Fuchigami et al.) and European Patent No. 1051961(A1) (Hino et al.).

[0115] Typical compositions also include ethylenically unsaturated acidic compounds having at least one phosphate group (e.g., a P-OH moiety).

[0116] Examples of preferred phosphate-containing polymerizable monomers include 6-(meth)acrylooxyhexyl dihydrogen phosphate, 7-(meth)acrylooxyheptyl dihydrogen phosphate, 8-(meth)acrylooxyoctyl dihydrogen phosphate, 9-(meth)acrylooxynonyl dihydrogen phosphate, 10-(meth)acrylooxydecyl dihydrogen phosphate, 11-(meth)acrylooxyundecyl dihydrogen phosphate, 12-(meth)acrylooxidedecyl dihydrogen phosphate, 16-(meth)acrylooxyhexadecyl dihydrogen phosphate, 20-(meth)acrylooxyeicosyl dihydrogen phosphate, bis[6-(meth)acrylooxyhexyl]hydrogen phosphate, bis[8-(meth)acrylooxyoctyl]hydrogen phosphate, and bis[9-(meth)acrylooxynonyl]hydrogen phosphate. Examples include hydrogen phosphate, bis[10-(meth)acryloxydecyl]hydrogen phosphate, 1,3-di(meth)acryloxypropyl dihydrogen phosphate, 2-(meth)acryloxyethylphenyl hydrogen phosphate, 2-(meth)acryloxyethyl-2-bromoethyl hydrogen phosphate, (5-methacryloxy)pentyl-3-phosphonopropionate, (6-methacryloxy)hexyl-3-phosphonopropionate, (10-methacryloxy)decyl-3-phosphonopropionate, (6-methacryloxy)hexyl-3-phosphonoacetate, (10-methacryl-oxy)-decyl-3-phosphonoacetate, 2-methacryloxyethyl (4-methoxyphenyl)hydrogen phosphate, and 2-methacryloxypropyl (4-methoxyphenyl)hydrogen phosphate, as well as mixtures thereof.

[0117] If desired, a mixture of different components, including an acidic portion, can be used.

[0118] The presence of polymerizable components with acidic portions helps to improve the etching properties of the composition.

[0119] If present, polymerizable components containing an acidic portion in the base material are typically present in the following amounts: Lower limit: at least 0.5, or at least 1, or at least 2% by weight. Upper limit: Maximum 20, or maximum 15, or maximum 10% by weight. Range: 0.5-20, or 1-15, or 2-10% by weight. The weight percentage is relative to the amount of the base material.

[0120] The base component further includes a filler.

[0121] The filling material may be selected from one or more of the wide variety of materials suitable for incorporation into compositions used in dental applications.

[0122] The fillers that can be used in the compositions herein are preferably pulverized. The fillers may have a unimodal or bimodal (e.g., bimodal) particle size distribution. The maximum particle size (maximum dimension of the particle, usually the diameter) of the filler is typically less than 20 μm, more typically less than 10 μm, and most preferably less than 5 μm. Typically, the mean primary particle size of the filler is less than 0.1 μm, and more typically less than 0.075 μm.

[0123] The filler should be non-toxic and suitable for use in the mouth or on a patient. The filler may be radiopaque or radiopaque. The filler is typically substantially insoluble in water.

[0124] The composition may include an inorganic material, or a filler that is essentially made of an inorganic material.

[0125] Suitable inorganic fillers include, but are not limited to, quartz, glass derived from Zr, Sr, Ce, Sb, Sn, Ba, Zn, and Al, feldspar, borosilicate glass, kaolin, talc, titania, low Mohs hardness fillers such as those described in U.S. Patent No. 4,695,251 (Randklev), and submicron silica particles (e.g., calcined silica), which are naturally occurring or synthetic materials.

[0126] Calcined silica or precipitated silica has been found to be particularly useful.

[0127] Suitable calcined silica fillers are typically 100-400 m 2 It has a specific surface area (BET) of 1 / g.

[0128] Examples of non-surface-treated fillers that can be used include AEROSIL™ containing "OX50", "90", "130", "150", "200", "300", and "380" silica (Evonik Industries AG, Essen, Germany); Cab-O-Sil containing "LM-150", "M-5", "H-5", and "EH-5" silica (Cabot Corp., Tuscola, IL); HDK™ containing "S13", "V15", "N20", "T30", and "T40" silica (Wacker-Chemie AG, Munich, Germany); and Orisil™ containing "200", "300", and "380" silica (Orisil, Lviv, Ukraine).

[0129] Suitable fillers also include nano-sized silica particles, nano-sized metal oxide particles, and combinations thereof. Nanofillers are described in U.S. Patent Publication No. 2005 / 0252413 (Kangas et al.), No. 2005 / 0252414 (Craig et al.), and No. 2005 / 0256223 (Kolb et al.).

[0130] Other suitable fillers are disclosed in U.S. Patent No. 6,387,981 (Zhang et al.) and No. 6,572,693 (Wu et al.), U.S. Patent No. 6,730,156 (Windisch), U.S. Patent No. 6,899,948 (Zhang), and International Publication No. 03 / 063804 (Wu et al.).

[0131] Heavy metal oxides and fluorides are examples of fillers that can be used to impart radiopaqueness to the materials described herein. As used herein, “radiopaqueness” refers to the ability of a solidified dental material to be distinguishable from tooth structures using conventional methods and standard dental radiography equipment. Radiopaqueness in dental materials is advantageous in certain cases where radiography is used to diagnose dental conditions. For example, radiopaque materials allow for the detection of secondary caries that may have formed in the tooth tissue surrounding the filler. The desired degree of radiopaqueness can be varied depending on the specific application and the physician's predictions regarding the radiographic film.

[0132] Oxides or fluorides of heavy metals having an atomic number greater than approximately 28 may be preferred. The heavy metal oxide or fluoride should be selected to avoid imparting undesirable color or shade to the hardened resin in which the filler is dispersed. For example, iron and cobalt are undesirable because they impart dark and contrasting colors to the intermediate shades of teeth in dental materials. More preferably, the heavy metal oxide or fluoride is an oxide or fluoride of a metal having an atomic number greater than 30. Suitable metal oxides include yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanide elements (i.e., elements with atomic numbers in the range of 57-71), cerium, and oxides of combinations thereof. Suitable metal fluorides include, for example, yttrium trifluoride and ytterbium trifluoride. More preferably, oxides or fluorides of heavy metals having an atomic number greater than 30 and less than 72 may be optionally included in the material of the present invention. Particularly preferred metal oxides that impart radiopaqueness include lanthanum oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide, and combinations thereof. The heavy metal oxide particles may aggregate. In this case, the average diameter of the aggregated particles is preferably less than 200 nm, and more preferably less than 90 nm.

[0133] Other suitable fillers for increasing radiopaqueness are salts of barium and strontium, in particular strontium sulfate and barium sulfate.

[0134] To strengthen the bond between the filler and the resin, the surface of the filler particles can be pre-treated with a silane coupling agent.

[0135] The filler contained in the base material is typically present in the following amounts: Lower limit: at least 10, or at least 15, or at least 20% by weight, Upper limit: Maximum 85, or maximum 80, or maximum 75% by weight, Range: 10-85, or 15-80, or 20-75% by weight. The weight percentage is relative to the amount of the base material.

[0136] The base material further contains transition metal components.

[0137] The properties and structure of the transition metal components are not particularly limited, as long as the desired results can be achieved.

[0138] Suitable transition metal components include organic and / or inorganic salts of vanadium, chromium, manganese, iron, cobalt, nickel, and / or copper, with copper, iron, and vanadium being sometimes preferred.

[0139] According to one embodiment, the transition metal component is a copper-containing component.

[0140] The oxidation stage of copper in the copper-containing component is preferably +1 or +2.

[0141] Typical examples of usable copper components include copper acetate, copper chloride, copper benzoate, copper acetylacetate, copper naphthenate, copper carboxylate, copper bis(1-phenylpentane-1,3-dione) complex (copper procetonate), copper ethylhexanoate, copper salicylate, copper-thiourea complexes, ethylenediaminetetraacetic acid, and / or mixtures thereof, as well as copper salts and complexes. The copper compounds may be used in hydrate form or without water.

[0142] Particularly preferred are, sometimes, copper(II) acetate, copper bis(1-phenylpentane-1,3-dione) complex (copper procetonate), and copper ethylhexanoate.

[0143] According to one embodiment, the transition metal component is an iron-containing component.

[0144] The oxidation level of iron in the iron-containing component is preferably +2 or +3.

[0145] Typical examples of iron-containing components that can be used include salts and complexes containing ferrous sulfate, ferric chloride, iron carboxylate, iron naphthenate, and iron(III) acetylacetonate (including hydrates of these salts).

[0146] According to one embodiment, the transition metal component is a vanadium-containing component.

[0147] The oxidation step of vanadium in the vanadium-containing component is preferably +4 or +5.

[0148] Typical examples of vanadium components that can be used include vanadium acetylacetonate, vanadyl acetylacetonate, vanadyl stearate, vanadium naphthenate, vanadium benzoylacetonate, vanadyl oxalate, bis(maltrate)oxovanadium(IV), oxobis(1-phenyl-1,3-butanedione)vanadium(IV), vanadium(V) oxytriisopropoxide, ammonium metavanadate(V), sodium metavanadate(V), vanadium pentoxide(V), divanadium tetroxide(IV), and vanadyl sulfate(IV), as well as vanadium salts and complexes and mixtures thereof, but vanadium acetylacetonate, vanadyl acetylacetonate, and bis(maltrate)-oxovanadium(IV) are sometimes preferred.

[0149] The transition metal components contained in the base material are typically present in the following amounts, calculated relative to the weight of the transition metal compound: Lower limit: at least 0.001, or at least 0.002, or at least 0.005% by weight. Upper limit: Maximum 0.1, or maximum 0.08, or maximum 0.05% by weight. Range: 0.001~0.1, or 0.002~0.08, or 0.005~0.05% by weight. The weight percentage is relative to the amount of the base material.

[0150] The base material further contains peroxide components, particularly organic peroxides.

[0151] Almost all organic peroxides can be used if they are suitable for achieving the desired results.

[0152] In contrast to inorganic peroxides, organic peroxides do not contain metals or metal ions. Therefore, organic peroxides typically contain only C, O, H, and optionally halogens (e.g., F, Cl, Br). Usable organic peroxides include diperoxides and hydroperoxides.

[0153] According to one embodiment, the organic peroxide is used in excess of the weight of the component containing the ascorbic acid portion.

[0154] According to one embodiment, the organic peroxide is a diperoxide, preferably a diperoxide comprising a portion R1-OO-R2-OO-R3, where R1 and R3 are independently H, alkyl (e.g., C1-C6), branched alkyl (e.g., C1-C6), cycloalkyl (e.g., C5-C6) 10 ), alkylaryl (for example, C7~C 12 ), or aryl (for example, C6~C) 10 ) is selected from and R2 is selected from alkyl (e.g., C1-C6) or branched alkyl (e.g., C1-C6).

[0155] Suitable examples of organic diperoxides include 2,2-di-(tert-butylperoxy)-butane and 2,5-dimethyl-2,5-di-(tert-butylperoxy)-hexane, as well as mixtures thereof.

[0156] According to another embodiment, the organic peroxide is a hydroperoxide, in particular, a structural portion. ROOH It is a hydroperoxide containing, R is (for example, C1~C 20 ) alkyl, (for example, C3~C20 ) Branched alkyl, (for example, C6~C 12 )Cycloalkyl, (for example, C7~C 20 ), alkylaryl (for example, C6~C 12 ) or aryl (for example, C6~C) 12 )

[0157] Examples of suitable organic hydroperoxides include t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinan hydroperoxide, p-methane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide, as well as mixtures thereof.

[0158] The use of hydroperoxides may be particularly preferable in the formulation of self-adhesive compositions.

[0159] Other peroxides that can be used include ketone peroxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates.

[0160] Examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methylcyclohexanone peroxide, and cyclohexanone peroxide.

[0161] Examples of peroxyesters include α-cumylperoxyneodecanoate, t-butylperoxypivalate, t-butylperoxyneodecanoate, 2,2,4-trimethylpentylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, di-t-butylperoxyisophthalate, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-3,3,5-trimethylhexanoate (TBPIN), t-butylperoxyacetate, t-butylperoxybenzoate, and t-butylperoxymaleic acid.

[0162] Examples of peroxydicarbonates include di-3-methoxyperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, bis(4-t-butylcyclohexyl)peroxydicarbonate, diisopropyl-1-peroxydicarbonate, di-n-propylperoxydicarbonate, di-2-ethoxyethyl-peroxydicarbonate, and diallylperoxydicarbonate.

[0163] Examples of diacyl peroxides include acetyl peroxide, benzoyl peroxide, decanoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0164] Examples of dialkylperoxides include di-t-butylperoxide, dicumylperoxide, t-butylcumylperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 1,3-bis(t-butylperoxyisopropyl)benzene, and 2,5-dimethyl-2,5-di(t-butylperoxy)-3-hexane.

[0165] Examples of peroxyketals include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexanoate, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)n-butyl valerate.

[0166] The organic peroxides contained in the base material are typically present in the following amounts: Lower limit: at least 0.1, or at least 0.2, or at least 0.5% by weight. Upper limit: Maximum 5, or maximum 4, or maximum 3% by weight. Range: 0.1-5% by weight, or 0.2-4% by weight, or 0.5-3% by weight. The weight percentage is relative to the amount of the base material.

[0167] If the amount of organic peroxide is too high, the curing of the composition may proceed too rapidly.

[0168] If the amount of organic peroxide is too small, the curing of the composition may take too long.

[0169] The base component further contains a stabilizer component that includes a free radical portion.

[0170] Adding stabilizers can help improve the storage stability of dental compositions, particularly those containing transition metal ion components, and especially those containing transition metal ion components combined with peroxides.

[0171] Stabilizers found to be useful include those containing a free radical moiety or those selected from anaerobic stabilizers.

[0172] The free radical portion is 2,2-diphenyl-1-picrylhydrazyl (DPPH), 4-Hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl (TEMPOL), 2,2,6,6-tetramethyl-piperidinyloxyl (TEMPO) 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl (garbinoxyl), It contains the triphenylmethyl radical portion.

[0173] Stabilizers containing structural components of TEMPOL or TEMPO as free radical moieties are sometimes preferred. If desired, these stabilizers can be characterized by one of the following formulas. [ka] (In the formula, X', X'', X''', Y and R have the following meanings independently of each other: X'=O, S X'', X''' = O, S, or nonexistent Y=C, H, or does not exist R=H, each having 1 to 12 carbon atoms (either an alkyl, alkenyl, aryl, alkylaryl, or arylalkyl group, or none at all).

[0174] In particular, the following stabilizers have been found useful: 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (Prostab® 5198), bis(2,2,6,6-tetramethylpiperidine-1-oxyl-4-yl)decandioate (Prostab® 5415), 4-methacryloyloxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-amino-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-1-oxyl, 2,2-diphenyl-1-picrylhydrazyl (DPPH), 2,2-di(4-tert-octylphenyl)-1-picrylhydrazyl, and mixtures thereof.

[0175] On the other hand, the following stabilizers were found to be ineffective in stabilizing curable compositions containing initiator systems that combine peroxide components with transition metal ion components: Butylated hydroxytoluene (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168), 4,6-bis(dodecylthiomethyl)-o-cresol (Irganox® 1726), 4,6-bis(octylthiomethyl)-o-cresol (Irganox® 1520L), octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox® 1076), thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (Irganox® 1035), didodecyl 3,3'-thiodipropionate (Irganox® PS 800FL), 2',3-bis[[3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyl]]propionohydrazide (Irganox® MD 1024), Flamestab® NOR 116 NOR-HALS such as FF, 3,5-di-tert-butyl-4-hydroxyanisole (2,6-di-tert-butyl-4-ethoxyphenol), 2,6-di-tert-butyl-4-(dimethylamino)methylphenol or 2,5-di-tert-butylhydroquinone, 2-(2'-hydroxy-5'-methylphenyl)-2H-benzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)-2H-benzotriazole, 2-hydroxy-4-methoxybenzophenone (UV-9), 2-(2'-hydroxy-4',6'-di-tert-pentylphenyl)-2H-benzotriazole, 2-hydroxy-4-n-octoxybenzophenone, and 2-(2'-hydroxy-5'-methacrylateoxyethylphenyl)-2H-benzotriazole.

[0176] Using excessive amounts of these stabilizers may cause undesirable discoloration during storage. Nevertheless, these stabilizers can be used further if desired.

[0177] The stabilizer containing free radicals in the base material is typically present in the following amounts: Lower limit: at least 0.005, or at least 0.01, or at least 0.02% by weight. Upper limit: Maximum 0.3, or maximum 0.2, or maximum 0.1% by weight. Range: 0.005~0.3, or 0.01~0.2, or 0.02~0.1% by weight. The weight percentage is relative to the amount of the base material.

[0178] The composition contained in the catalyst material is typically 5-60 Pa at 23°C. * It has a viscosity in the range of s.

[0179] Catalyst components having viscosities within this range can be easily mixed using a static mixing cannula.

[0180] The composition contained in the catalyst typically has a pH value in the range of 5 to 7 when in contact with water (e.g., damp pH-sensitive paper).

[0181] The catalyst component is typically supplied as a paste.

[0182] The catalyst component contains polymerizable components that do not have an acidic portion.

[0183] Polymerizable components without acidic portions contained in the catalyst member can be characterized by the same general formula used to describe polymerizable components without acidic portions contained in the base member.

[0184] Polymerizable components that do not contain acidic portions and are included in the catalyst member can also be selected from the examples described for the base member.

[0185] Polymerizable components without acidic portions contained in the catalyst material are typically present in the following amounts: Lower limit: at least 5, or at least 10, or at least 20% by weight, Upper limit: Maximum 70, or maximum 60, or maximum 50% by weight. Range: 5-70, or 10-60, or 20-50% by weight. The weight percentage refers to the amount of catalyst material.

[0186] The filler contained in the catalyst member may be the same as or different from the filler contained in the base member.

[0187] The fillers contained in the catalyst component are typically present in the following amounts: Lower limit: at least 10, or at least 15, or at least 20% by weight, Upper limit: Maximum 85, or maximum 80, or maximum 75% by weight, Range: 10-85, or 15-80, or 20-75% by weight. The weight percentage refers to the amount of catalyst material.

[0188] The catalyst component contains ascorbic acid.

[0189] Components containing the ascorbic acid portion include salts and esters of ascorbic acid, ethers, ketals, or acetals.

[0190] Suitable salts include alkali metal salts and alkaline earth metal salts such as Na, K, and Ca, as well as mixtures thereof.

[0191] As an ester of ascorbic acid, one or more of the hydroxyl functional groups of ascorbic acid are replaced with carboxylic acids, particularly C2-C2. 30 Examples include those produced by reacting with carboxylic acids.

[0192] C2~C 30Suitable examples of carboxylic acids include fatty acids such as caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linole-elaidic acid, alpha-linolenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid, and docosahexaenoic acid.

[0193] Ascorbic acid components that can be readily dissolved or mixed in the remaining resin matrix containing polymerizable components that do not have an acidic portion are particularly preferred.

[0194] In other words, it is sometimes preferable to use an ascorbic acid component having a hydrophobic moiety. Suitable hydrophobic moieties include saturated and unsaturated aliphatic residues (e.g., C2-C2). 30 or C 12 ~C 30 These are examples. These ascorbic acid derivatives can also function as surfactants (substances having a so-called "head / tail structure").

[0195] Particularly preferred are ascorbyl palmitate, ascorbyl stearate, mixtures thereof, and salts, especially their alkali and alkaline earth salts.

[0196] The ascorbic acid component, including the ascorbic acid portion contained in the catalyst material, is typically present in the following amounts: Lower limit: at least 0.05, or at least 0.1, or at least 0.2% by weight. Upper limit: Maximum 5, or maximum 3, or maximum 2% by weight. Range: 0.05-5, or 0.1-3, or 0.2-2% by weight. The weight percentage refers to the amount of catalyst material.

[0197] If the amount of ascorbic acid is too high, the hardening of the composition may proceed too rapidly.

[0198] If the amount of ascorbic acid is too low, the composition may take too long to harden.

[0199] The catalyst component includes a photoinitiator system.

[0200] The properties and structure of the photoinitiator system are not particularly limited, as long as the intended purpose is not adversely affected.

[0201] By incorporating a photoinitiator system, a composition can be obtained that is characterized as a "dual-cure type," that is, this composition contains a redox initiator system suitable for solidifying the composition without radiation ("dark curing or self-curing") and a photoinitiator system suitable for solidifying the composition by irradiation with radiation ("photocuring").

[0202] Photoinitiator systems suitable for free radical polymerization are generally known to those skilled in the art who handle dental materials.

[0203] A suitable photoinitiator system often contains a sensitizer comprising an α-α-dikete moiety, an anthraquinone moiety, a thioxanthone moiety, or a benzoin moiety. Sensitizers containing an α-α-dikete moiety are often preferred.

[0204] A typical photoinitiator system includes a combination of a sensitizer and a reducing agent or donor component, often referred to as a photoinitiator system.

[0205] As a sensitizer, it is preferable to use one that can polymerize polymerizable monomers through the action of visible light having a wavelength of 390 nm to 830 nm.

[0206] Examples of sensitizers that can be used include camphorquinone, benzyl, diacetyl, benzyldimethylketal, benzyldiethylketal, benzyldi(2-methoxyethyl)ketal, 4,4'-dimethylbenzyldimethylketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone Examples include oxanthones, 2-methylthioxanthones, 2,4-dimethylthioxanthones, 2,4-diethylthioxanthones, 2,4-diisopropylthioxanthones, 2-chloro-7-trifluoromethylthioxanthones, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethylaminophenyl) ketone, and 4,4'-bisdiethylaminobenzophenone.

[0207] Tertiary amines are generally used as reducing agents or donor components. Suitable examples of tertiary amines include N,N-dimethyl-p-toluidine, N,N-dimethylaminoethyl methacrylate, triethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, methyldiphenylamine, and isoamyl 4-dimethylaminobenzoate.

[0208] Furthermore, ternary photopolymerization initiator systems comprising a sensitizer, an electron donor, and an onium salt, as described in U.S. Patents 6,187,833, 6,025,406, 6,043,295, 5,998,495, 6,084,004, 5,545,676, and International Publication No. 2009 / 151957 and U.S. Patent 6,765,036, can be used. These references are incorporated herein by reference.

[0209] In the ternary photoinitiator system, the first component is an iodonium salt, specifically a diaryliodonium salt.

[0210] Iodonium salts are preferably soluble in monomers and have storage stability (i.e., they do not spontaneously promote polymerization) when dissolved in monomers in the presence of sensitizers and donors. Therefore, the selection of a particular iodonium salt may vary to some extent depending on the specific monomer, polymer or oligomer, sensitizer, and donor selected. Suitable iodonium salts are described in U.S. Patents 3,729,313, 3,741,769, 3,808,006, 4,250,053, and 4,394,403, the disclosures relating to iodonium salts in these patents are incorporated herein by reference. Iodonium salts are monosalts (e.g., Cl - , Br - , I - , or C4H5SO3 - (Containing anions such as) or metal complex salts (e.g., SbF5OH) - Or AsF6 - It may contain ( ). A mixture of iodonium salts can be used if desired. Preferred iodonium salts include diphenyliodonium salts, such as diphenyliodonium chloride, diphenyliodonium hexafluorophosphate, and diphenyl-iodonium tetrafluoroborate.

[0211] The second component of the ternary photoinitiator system is a sensitizer.

[0212] The sensitizer is preferably soluble in the monomer and capable of absorbing light in a wavelength range of over 400 to 1200 nm, more preferably over 400 to 700 nm, and most preferably over 400 to 600 nm.

[0213] Suitable sensitizers include compounds in the following categories: ketones, coumarin dyes (e.g., ketocoumarins), xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds, aminotrialylmethane, merocyanines, squarylium dyes, and pyridinium dyes. Ketones (e.g., monoketones or α-diketones), ketocoumarins, aminoaryl ketones, and p-substituted aminostyryl ketone compounds are preferred sensitizers.

[0214] For example, a preferred type of ketone sensitizer is one with the chemical formula: ACO(X) b B is present (wherein X is CO or CR) 5 R 6 And R 5 and R 6 (A and B may be the same or different and may be hydrogen, alkyl, alkaryl, or aralkyl, b may be 0 or 1, and A and B may be different and may be substituted (having one or more non-interfering substituents), the same, or may be an unsubstituted aryl group, alkyl group, alkaryl group, or aralkyl group, or A and B may both form a cyclic structure that can be a substituted or unsubstituted alicyclic, aromatic, heteroaromatic, or condensed aromatic ring.)

[0215] Suitable ketones for the above formula include monoketones (b=0), such as 2,2-, 4,4- or 2,4-dihydroxybenzophenone, di-2-pyridyl ketone, di-2-furanyl ketone, di-2-thiophenyl ketone, benzoin, fluorenone, chalcone, Michler ketone, 2-fluoro-9-fluorenone, 2-chlorothioxanthone, acetophenone, benzophenone, 1- or 2-acetonaphthone, 9-acetylanthracene, 2-, 3- or 9-acetylphenanthrene, 4-acetylbiphenyl, propiophenone, n-butyrophenone, valerophenone, 2-, 3- or 4-acetylpyridine, and 3-acetylcoumarin. Suitable diketones include aralkyl diketones such as anthraquinone, phenanthrenequinone, o-, m- and p-diacetylbenzene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7- and 1,8-diacetylnaphthalene, and 1,5-, 1,8- and 9,10-diacetylanthracene. Suitable α-diketones (b=1 and X=CO) include 2,3-butanedione, 2,3-pentanedione, 2,3-hexanedione, 3,4-hexanedione, 2,3-heptanedione, 3,4-heptanedione, 2,3-octanedione, 4,5-octanedione, benzyl, 2,2'-3,3'- and 4,4'-dihydroxylbenzyl, furyl, di-3,3'-indolylethanedione, 2,3-bornanedione (camphorquinone), biacetyl, 1,2-cyclohexanedione, and 1,2-naphthaquinone.

[0216] The third component of the ternary initiator system is the donor.

[0217] Preferred donors include, for example, amines (including aminoaldehydes and aminosilanes), amides (including phosphoramides), ethers (including thioethers), ureas (including thioureas), ferrocenes, sulfinic acids and their salts, ferrocyanates, ascorbic acids and their salts, dithiocarbamic acids and their salts, xanthogenic acids, salts of ethylenediaminetetraacetic acid, and salts of tetraphenylboronic acid. The donors may be unsubstituted or substituted with one or more non-interfering substituents. Particularly preferred donors contain electron-donating atoms such as nitrogen, oxygen, phosphorus, or sulfur atoms, and abstractable hydrogen atoms bonded to carbon or silicon atoms at the α-position relative to the electron-donating atoms. Various types of donors are disclosed in U.S. Patent No. 5,545,676, which is incorporated herein by reference.

[0218] Alternatively, free radical initiators useful for the present invention include acylphosphine oxides and bisacylphosphine oxides.

[0219] Suitable acylphosphine oxides can be described by a general formula. (R 9 )2-P(=O)-C(=O)-R 10 (In the formula, each R 9 Each of these may be a hydrocarbyl group such as alkyl, cycloalkyl, aryl, and aralkyl, and any of them may be substituted with a halo-, alkyl-, or alkoxy group, or two R 9 The group can bond and form a ring with the phosphorus atom, R 10 This is a hydrocarbyl group, an S-, O-, or N-containing 5 or 6-membered heterocyclic group, or -ZC(=O)-P(=O)-(R 9 ) There are two groups (wherein Z represents a divalent hydrocarbyl group such as alkylene or phenylene having 2 to 6 carbon atoms).

[0220] A preferred acylphosphine oxide is R 9 and R 10The group is phenyl, or a lower alkyl- or lower alkoxy-substituted phenyl. "Lower alkyl" and "lower alkoxy" refer to such groups having 1 to 4 carbon atoms. For example, see U.S. Patent No. 4,737,593.

[0221] Suitable bisacylphosphine oxides can be described by a general formula. [ka] (In the formula, n is 1 or 2, R 4 , R 5 , R 6 and R 7 R is H, C1-4 alkyl, C1-4 alkoxyl, F, Cl or Br, and 2 and R 3 is the same or different, representing a cyclohexyl, cyclopentyl, phenyl, naphthyl, or biphenylyl radical, cyclopentyl, cyclohexyl, phenyl, naphthyl, or a biphenylyl radical substituted with F, Cl, Br, I, C1-4 alkyl and / or C1-4 alkoxyl, or representing an S or N-containing 5-membered or 6-membered heterocycle, or R 2 and R 3 These atoms bond to form a ring containing 4 to 10 carbon atoms, optionally substituted with 1 to 6 C1-4 alkyl radicals.

[0222] Further examples include bis-(2,6-dichlorobenzoyl)phenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-ethoxyphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-biphenylylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-propylphenylphosphine oxide, and bis-(2,6-dichlorobenzoyl)-2-naphthyl Bis-(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-chlorophenylphosphine oxide, bis-(2,6-dichlorobenzoyl)-2,4-dimethoxyphenylphosphine oxide, bis-(2,6-dichlorobenzoyl)decylphosphine oxide, bis-(2,6-dichlorobenzoyl)-4-octylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,5-dimethyl Tylphenylphosphine oxide, bis-(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis-(2,4,6-trimethylbenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro-3,4,5-trimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis-(2,6-dichloro-3,4,5-trimethoxybenzoyl)-4-ethoxyphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-2,5 -Dimethylphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)phenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-4-biphenylylphosphine oxide, bis-(2-methyl-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-2-naphthylphosphine oxide, bis-(2-methyl-1-naphthoyl)-4-propylphenylphosphine oxide, bis-(2-methyl-1-naphthoyl)-2,Examples include 5-dimethylphosphine oxide, bis-(2-methoxy-1-naphthoyl)-4-ethoxyphenylphosphine oxide, bis-(2-methoxy-1-naphthoyl)-4-biphenylylphosphine oxide, bis-(2-methoxy-1-naphthoyl)-2-naphthylphosphine oxide, and bis-(2-chloro-1-naphthoyl)-2,5-dimethylphenylphosphine oxide.

[0223] Acylphosphine oxide bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (formerly known as Irgacure® 819, Ciba) is sometimes preferred.

[0224] A tertiary amine reducing agent may be used in combination with an acylphosphine oxide. Specific examples of tertiary amines useful in the present invention include ethyl-4-(N,N-dimethylamino)benzoate and N,N-dimethylaminoethyl methacrylate.

[0225] Commercially available phosphine oxide photoinitiators capable of initiating free radicals when irradiated at wavelengths exceeding 400 nm and up to 1200 nm include: a 25:75 weight mixture of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (formerly known as Irgacure® 1700, Ciba); 2-benzyl-2-(N,N-dimethylamino)-1-(4-morpholinophenyl)-1-butanone (formerly known as Irgacure® 369, Ciba); and bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl) titanium (formerly known as Irgacure® 784). Examples include DC (formerly known as Ciba), a 1:1 weight mixture of bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2-hydroxy-2-methyl-1-phenylpropan-1-one (formerly known as Darocur® 4265, Ciba), ethyl-2,4,6-trimethylbenzylphenylphosphine oxide (formerly known as Lucirin® LR8893X, BASF), and bis(2,4,6-trimethylbenzoyl)-diphenylphosphine oxide (formerly known as Irgacure® 819, BASF).

[0226] The sensitizer and reducing agent are typically present together in one of the components of the component kit described herein. Alternatively, the components of the photoinitiator system may be diffused into the base component and the catalyst component.

[0227] For stability reasons, it is sometimes preferable that the photoinitiator system be contained in the catalyst component, i.e., the component containing the ascorbic acid component.

[0228] The catalyst component contains a stabilizer component that includes a phosphite or sulfite portion.

[0229] Sometimes, organic stabilizers, i.e., stabilizers other than salts, are preferred.

[0230] While not bound by any particular theory, it is considered necessary to consider the solubility of the stabilizer in the composition and / or the pKs value of the stabilizer.

[0231] It may be preferable to use a stabilizer with high solubility. Similarly, it is also preferable to use a smaller amount of acidic stabilizer.

[0232] It has been found that the stabilizing effect of organic sulfite or organic phosphite stabilizers is sometimes better than that of inorganic sulfite or inorganic phosphite stabilizers.

[0233] According to one embodiment, the stabilizer has a molecular weight of 80 to 800 or 120 to 700 g / mol.

[0234] The stabilizer containing the phosphite or sulfite portion in the catalyst component is typically present in the following amounts: Lower limit: at least 0.01% by weight, or at least 0.05% by weight, or at least 0.1% by weight. Upper limit: Maximum 5 or maximum 3 or maximum 1% by weight, Range: 0.01-5% by weight, or 0.05-3% by weight, or 0.1-1% by weight. The weight percentage refers to the weight of the catalyst component.

[0235] Examples of inorganic phosphites include calcium hypophosphate, sodium phosphate, and mixtures thereof.

[0236] Examples of organic phosphites include alkyl or aryl or alkyl-aryl phosphites (e.g., C1-C12). 40)(e.g., di-ethyl phosphite, di-butyl phosphite, di-iso-propyl phosphite, di-n-propyl phosphite, tri-phenyl phosphite, tri-allyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite (commercially available as Irgafos™ 168), bis(2,4-dicumylphenyl) pentaerythritol diphosphate (commercially available as Doverphos™ S-9228), bis-(2,4-di-t-butylphenol) pentaerythritol diphosphite (commercially available as Irgafos™ 126), phosphorus trichloride, the reaction product of 1,1'-biphenyl and 2,4-bis(1,1-dimethylethyl)phenol (commercially available as Hostanox™ P-EPQ), and mixtures thereof).

[0237] If desired, a mixture of an organic phosphite and an inorganic phosphite can also be used.

[0238] Examples of inorganic sulfites include lithium sulfite, sodium sulfite, potassium sulfite, calcium sulfite, sodium hydrogen sulfite, and mixtures thereof.

[0239] Examples of organic sulfites include di-alkyl or aryl sulfite (e.g., C1-C 12 )(e.g., di-ethyl sulfite, di-n-propyl sulfite, di-iso-propyl sulfite, glycol sulfite, 1,3-propylene sulfite), diallyl sulfite, and mixtures thereof.

[0240] If desired, a mixture of an organic sulfite and an inorganic sulfite can also be used.

[0241] If desired, a mixture of an organic phosphite and an inorganic phosphite and a mixture of an organic sulfite and an inorganic sulfite can also be used.

[0242] According to one embodiment, it is preferable to use a stabilizer selected from organic sulfites, organic phosphites, and mixtures thereof.

[0243] The ratio of the stabilizer component containing the free radical to the peroxide component is typically in the range of 1:100 to 1:5 or 1:50 to 1:10 in terms of molar amount.

[0244] Such ratios may be beneficial for improving the reactivity of dental compositions.

[0245] The ratio of the stabilizer component containing the free radical moiety to the transition metal component, calculated relative to the weight of the transition metal ions, is typically in the range of 100:1 to 5:1 or 75:1 to 10:1 by weight.

[0246] Such ratios may be beneficial for improving the color stability of dental compositions.

[0247] The following ratio combinations have been found to be particularly beneficial in obtaining dental compositions that are stable for storage: The ratio of the stabilizer component containing the free radical to the peroxide component is in the range of 1:100 to 1:5 in terms of molar amount. The ratio of the stabilizer component containing the free radical moiety to the transition metal component, calculated relative to the weight of the transition metal ions, is in the range of 100:1 to 5:1.

[0248] According to one embodiment, when the base member and the catalyst member are mixed, the dental composition contains, or essentially consists of, each component in the following amounts: Polymerizable components with acidic portion: 0-20% by weight, Polymerizable components that do not contain acidic parts: 5-50% by weight, Filler: 5-80% by weight, Transition metal component: 0.0005~0.05% by weight, Peroxide component: 0.05-2.5% by weight Stabilizer components including free radical moieties: 0.0025~0.15% by weight, Ascorbic acid content: 0.025-2.5% by weight Photoinitiator system: 0.05-2.5% by weight, Stabilizer component containing phosphite or sulfite portion: 0.005-2.5% by weight The weight percentage refers to the total weight of the composition.

[0249] According to another embodiment, when the base member and the catalyst member are mixed, the dental composition contains, or essentially consists of, each component in the following amounts: Polymerizable components with acidic portion: 1-20% by weight, Polymerizable components that do not contain acidic parts: 5-50% by weight, Filler: 20-80% by weight, Transition metal component calculated relative to the weight of the transition metal compound: 0.0005 to 0.05% by weight. Peroxide component: 0.05-2.5% by weight Stabilizer components including free radical moieties: 0.025-0.15% by weight Ascorbic acid content: 0.025-2.5% by weight Photoinitiator system: 0.05-2.5% by weight, Stabilizer component containing phosphite or sulfite portion: 0.05-2.5% by weight The weight percentage refers to the total weight of the composition.

[0250] The dental compositions described herein may also contain a solvent.

[0251] The addition of a solvent or co-solvent may help to adjust the viscosity and viscosity of the composition.

[0252] Examples of solvents include, but are not limited to, linear, branched, or cyclic saturated or unsaturated alcohols, ketones, esters, ethers, or mixtures of two or more of these solvents having 2 to 10 carbon atoms. Preferred alcoholic solvents include methanol, ethanol, isopropanol, and n-propanol.

[0253] Other suitable organic solvents are THF, acetone, methyl ethyl ketone, cyclohexanol, toluene, alkanes, and alkyl acetates, especially ethyl acetate.

[0254] The above solvents can be used alone or, if the solvent mixture does not impair the adhesion properties to the extent that the desired results are not obtained, can be used as a mixture of two or more of any of these solvents.

[0255] If present, the solvent can be present in the base member or the catalyst member or both.

[0256] If present, the solvent is typically present in the following amounts: Lower limit: at least 1, or at least 2, or at least 5 wt%, Upper limit: at most 20, or at most 15, or at most 10 wt%, Range: 1 - 20, or 2 - 15, or 5 - 10 wt%, The wt% is based on the amount of the dental composition.

[0257] The dental compositions described herein may also contain the following additives alone or in combination.

[0258] Additive adjuvants that can be used include fluoride release agents, photo - bleachable colorants, dyes, and other components well - known to those skilled in the art.

[0259] Examples of photo - bleachable colorants include rose bengal, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyl eosin, eosin blueish, eosin B, erythrosine B, erythrosine yellowish - ish blend, toluidine blue, 4’,5’ - dibromofluorescein, and blends thereof. Further examples of photo - bleachable colorants can be found in U.S. Patent No. 6,444,725 (Tom et al.).

[0260] Examples of fluoride stripping agents include naturally occurring or synthetic fluoride minerals such as simple and complex inorganic fluoride salts like sodium fluoride, potassium zinc fluoride, and potassium hexafluorotianoate, simple and complex organic fluoride salts like tetraethylammonium tetrafluoroborate, or combinations thereof. These fluoride sources may optionally be treated with surface treatment agents.

[0261] If present, the additive may be present in the base component, the catalyst component, or both.

[0262] If present, the additive should be in the following quantities: Lower limit: at least 0.01, or at least 0.1, or at least 0.2% by weight. Upper limit: Maximum 5, or maximum 3, or maximum 2% by weight. Range: 0.01-5, or 0.1-3, or 0.2-2% by weight. Weight percentages refer to the amount of the dental composition.

[0263] The dental compositions described herein may also be characterized, individually or in combination, after mixing and curing the base member and the catalyst member, by the following characteristics: flexural strength in accordance with ISO 4049:2010:80-200 MPa, and / or E-modulus in accordance with ISO 4049:2010:3,000-7,000 MPa.

[0264] Further embodiments of the present invention are described below.

[0265] Embodiment 1 is a dental composition comprising a base member and a catalyst member that are mixed before use, The base member is A polymerizable component having an acidic portion in an amount of 0-20% by weight, A polymerizable component that does not have an acidic portion, in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, A transition metal component selected from organic salts of copper, vanadium, and iron, and mixtures thereof, A peroxide component selected from diperoxides, hydroperoxides, ketone peroxides, peroxyesters, peroxydicarbonates, diacylperoxides, dialkylperoxides, peroxyketals, and mixtures thereof, A stabilizer component containing a free radical moiety, selected from 2,2-diphenyl-1-picrylhydrazyl (DPPH), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPOL), 2,2,6,6-tetramethyl-piperidinyloxyl (TEMPO), 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl (garbinoxyl), and triphenylmethyl radical, Optionally, it may include or be essentially composed of additives. The catalyst component, A polymerizable component that does not have an acidic portion, in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, C2-C of ascorbic acid 30 Ascorbic acid components selected from carboxylic acid esters, alkali and alkaline earth salts of ascorbic acid, and mixtures thereof, A photoinitiator system containing a sensitizer and a reducing agent or donor component, A stabilizer component comprising a phosphite or sulfite portion selected from organic phosphates, organic sulfites, and mixtures thereof, Optionally, it may include or be essentially composed of additives. The aim is to provide dental compositions in which the weight percentage is relative to the total weight of the composition.

[0266] Embodiment 2 is a dental composition comprising a base member and a catalyst member that are mixed before use, The base member is A polymerizable component having an acidic portion in an amount of 0.5 to 20% by weight, A polymerizable component that does not have an acidic portion, in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, A transition metal component selected from organic copper salts and mixtures thereof, A peroxide component selected from diperoxides, hydroperoxides, and mixtures thereof, A stabilizer component containing a free radical moiety, selected from 2,2-diphenyl-1-picrylhydrazyl (DPPH), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPOL), 2,2,6,6-tetramethyl-piperidinyloxyl (TEMPO), 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl (garbinoxyl), and triphenylmethyl radical, Optionally, it may include or be essentially composed of additives. The catalyst component, A polymerizable component that does not have an acidic portion, in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, C2-C of ascorbic acid 30 Ascorbic acid components selected from carboxylic acid esters, alkali and alkaline earth salts of ascorbic acid, and mixtures thereof, A photoinitiator system containing a sensitizer and a reducing agent or donor component, A stabilizer component comprising a phosphite or sulfite portion selected from organic phosphates, organic sulfites, and mixtures thereof, Optionally, it may include or be essentially composed of additives. The aim is to provide dental compositions in which the weight percentage is relative to the total weight of the composition.

[0267] Embodiment 3 is a dental composition comprising a base member and a catalyst member that are mixed before use, The base member is A polymerizable component having an acidic portion, Polymerizable components that do not have an acidic portion, Filler and, A transition metal component selected from organic copper salts and mixtures thereof, A peroxide component selected from diperoxides, hydroperoxides, and mixtures thereof, A stabilizer component containing a free radical moiety, selected from 2,2-diphenyl-1-picrylhydrazyl (DPPH), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPOL), 2,2,6,6-tetramethyl-piperidinyloxyl (TEMPO), 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl (garbinoxyl), and triphenylmethyl radical, Optionally, it may include or be essentially composed of additives. The catalyst component, Polymerizable components that do not have an acidic portion, Filler and, C2-C of ascorbic acid 30 Ascorbic acid components selected from carboxylic acid esters and mixtures thereof, A photoinitiator system containing a sensitizer and a reducing agent or donor component, A stabilizer component containing the phosphite portion, The aim is to provide dental compositions that optionally include or essentially consist of additives.

[0268] Each of the components is as described herein.

[0269] The dental compositions described herein typically do not contain, either alone or in combination, the following components: A quantity of water exceeding 2% by weight, or exceeding 1% by weight, A halogenated solvent in an amount exceeding 2% by weight, or exceeding 1% by weight, or exceeding 0.5% by weight, Thiourea components in amounts exceeding 2% by weight, or exceeding 1% by weight, or exceeding 0.5% by weight, The weight percentage refers to the weight percentage relative to the entire composition.

[0270] These components are typically not added in sufficient quantities to dental compositions and are therefore absent. However, dental compositions may contain trace amounts of these components, and their presence is sometimes unavoidable because they may be present in the raw materials used to prepare the dental compositions described herein.

[0271] The present invention also relates to a process for producing the dental compositions described herein.

[0272] The compositions described herein are as follows: To provide the components of the composition, It can be manufactured by mixing the ingredients.

[0273] The temperature at which this manufacturing process can be carried out is not particularly limited.

[0274] The temperature used should be below the boiling point of the composition at normal pressure (1,013 mbar). Typically, the process can be carried out at temperatures in the range of 5°C to 100°C, or 10°C to 80°C. It is also possible to carry out the process at ambient temperature (e.g., about 23°C).

[0275] The atmosphere in which this manufacturing process is carried out is also not limited to any one of the above.

[0276] Typically, the manufacturing process is carried out under ambient conditions. Depending on the components used, it may be recommended to carry out the manufacturing process under inert conditions. In this regard, a nitrogen or argon atmosphere may be useful.

[0277] The pressure at which the manufacturing process of the present invention can be carried out is also not particularly limited. However, this method is typically carried out under ambient pressure (about 10¹³ mbar).

[0278] The method and order of adding the components are not particularly limited. However, typically, the manufacturing process begins by providing liquid components (such as polymerizable components without an acidic portion and polymerizable components with an acidic portion), adding stabilizer components and initiator components, and then adding fillers.

[0279] The mixing or dispersion of components can be achieved using equipment such as magnetic stirrs, mechanical stirrers, dissolving machines, ball mills, attritor mills, or high-shear devices.

[0280] The catalyst and base components of dental compositions are typically stored in a packaging device during storage.

[0281] The catalyst and base components described herein may be housed in separate, sealable containers (for example, made of plastic or glass).

[0282] For use, a physician may take an appropriate portion of the contained composition from the container and mix that portion manually on a mixing plate.

[0283] According to a preferred embodiment, the catalyst member and the base member are contained in separate compartments of the storage device.

[0284] The storage device typically comprises two compartments for storing each component, each compartment having a nozzle for delivering the component and a piston that can move within the compartment. Once the appropriate amount has been delivered, the components can then be mixed manually on a mixing plate.

[0285] According to another preferred embodiment, the storage device has an interface for receiving static mixing chips. The mixing chips are used to mix the respective pastes. Static mixing chips are commercially available, for example, from SulzerMixpac company.

[0286] Suitable storage devices include cartridges, syringes, and tubing.

[0287] The cartridges that can be used are described, for example, in U.S. Patent Application Publication 2007 / 0090079(A1) or U.S. Patent No. 5,918,772, and their disclosures are incorporated by reference. Some of the usable cartridges are commercially available, for example, from SulzerMixpac, Inc. (Switzerland). The static mixing chips that can be used are described, for example, in U.S. Patent Application Publication 2006 / 0187752(A1) or U.S. Patent No. 5,944,419, and their disclosures are incorporated by reference. The mixing chips that can be used are also commercially available from SulzerMixpac, Inc. (Switzerland).

[0288] Other suitable storage devices are described, for example, in International Publication No. 2010 / 123800(A1)(3M), International Publication No. 2005 / 016783(A1)(3M), International Publication No. 2007 / 104037(A1)(3M), International Publication No. 2009 / 061884(A1)(3M) (in particular the device shown in Figure 14 of International Publication No. 2009 / 061884(3M)), or International Publication No. 2015 / 073246(3M) (in particular the device shown in Figure 1 of International Publication No. 2015 / 07346). These storage devices have the shape of a syringe. The contents of these references are also incorporated herein by reference.

[0289] Alternatively, although not preferred, the paste / paste composition described herein may be dispensed in two separate syringes, and the individual pastes may be mixed by hand before use.

[0290] Accordingly, the present invention also aims to provide an apparatus for storing a kit of components described herein, comprising two compartments, namely compartment A and compartment B, wherein compartment A houses catalyst components and compartment B houses base components, and both compartments A and B are provided with an interface for receiving an entrance orifice for a nozzle or static mixing tip.

[0291] The mixing ratio of the base member to the catalyst member is typically 5:1 to 1:1, preferably 2:1 to 1:2, and more preferably 1:1, as a volume ratio.

[0292] The present invention also relates to a process for curing the dental compositions described herein.

[0293] Such a process typically includes the following steps: providing a catalyst member and a base member; mixing the catalyst member and the base member; and applying the resulting mixture to the surface of the tooth.

[0294] When the components are brought into contact with each other, the redox initiator components contained in each component initiate the curing of the curable components of the curable composition.

[0295] In addition, the curing of the curable composition can be further accelerated by applying radiation having a wavelength suitable for the photoinitiator system used.

[0296] Therefore, the dental compositions described herein are intended for use in the process of treating or restoring the hard tissue of teeth in living humans or animals, and this process is A step of mixing a base member and a catalyst member to obtain a mixed member, A step of applying a portion of the mixed material to the surface of the hard tissue of the tooth, The process optionally includes the step of applying radiation to a portion of the mixed material.

[0297] Therefore, the dental compositions described herein are so-called dual-cure compositions, that is, compositions containing two curing systems, a redox curing system, and a photoinitiator system.

[0298] The dental compositions described herein are particularly useful as bulk-fill dental composites, dental resin cements, core-build-up dental materials, or self-curing and dual-cure dental adhesives. Therefore, by providing the dental compositions in the form of bulk-fill dental composites, dental resin cements, core-build-up dental materials, or self-curing and dual-cure dental adhesives, the dental compositions can be used in the process of treating or restoring the hard tissues of human or animal teeth.

[0299] The present invention also aims to include, or essentially consist of, or kits comprising, the following items, either alone or in combination with, the dental compositions described herein: dental filling composites, dental sealants, dental cements, dental mill blanks, dental etching agents, dental try-in pastes, dental fiber posts, dental adhesives, and / or instructions for use. A combination of the dental compositions described herein with a dental filling composite or dental cement is sometimes preferred.

[0300] Further aspects of the present invention aim to use stabilizers that include a peroxide component in combination with a transition metal ion component, optionally in combination with a photoinitiator system as described herein, or essentially consist of these, or include a free radical moiety for stabilizing an initiator system consisting of these.

[0301] Further embodiments of the present invention relate to initiator systems described herein that can be used to cure compositions comprising polymerizable components having an acidic portion.

[0302] Such initiator systems include a transition metal component, a peroxide component, a stabilizer component containing a free radical moiety, an ascorbic acid component, a photoinitiator system, and a stabilizer component containing a phosphite or sulfite moiety, the components of which are as described herein.

[0303] A preferred embodiment of such an initiator system is: A transition metal component selected from organic salts of copper, vanadium, and iron, and mixtures thereof, preferably organic salts of copper, Diperoxides, hydroperoxides, ketone peroxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxyesters, and peroxydicarbonates, preferably peroxide components selected from diperoxides and hydroperoxides, A stabilizer component containing a free radical moiety, selected from 2,2-diphenyl-1-picrylhydrazyl (DPPH), 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (TEMPOL), 2,2,6,6-tetramethyl-piperidinyloxyl (TEMPO), 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl (garbinoxyl), triphenylmethyl radical, and mixtures thereof, Ascorbic acid component, preferably an ester of ascorbic acid, A photoinitiator system containing a sensitizer and a donor component, A stabilizing component containing a phosphite or sulfite moiety, preferably a stabilizing component containing a phosphite moiety, comprises, essentially consists of, or consists of these.

[0304] All disclosures of patents, patent documents, and publications cited herein are incorporated by reference as if each were incorporated individually. The above-mentioned specification, examples, and data provide a description of the manufacture and use of compositions relating to the present invention and methods. The present invention is not limited to the embodiments disclosed herein. Those skilled in the art will understand that many alternative embodiments of the present invention can be carried out without departing from the spirit and scope of the invention.

[0305] The following examples are given to illustrate the present invention. [Examples]

[0306] Unless otherwise specified, all parts and percentages are based on weight, all water is deionized water, and all molecular weights are weight-average molecular weights. Furthermore, unless otherwise specified, all experiments were conducted under ambient conditions (23°C, 10¹³ mbar).

[0307] method Viscosity of a single paste If desired, viscosity can be measured using a Physica MCR 301 Rheometer (Anton Paar, Graz, Austria) with a cone / plate-shaped PP15 under controlled shear rate at 23°C. The diameter is 15 mm. The shear rate is 0.001 seconds. -1 1,000 seconds -1 The number of data points increases logarithmically until a total of 60 data points are collected. 100 seconds -1 The viscosity measured is used for characterization.

[0308] Viscosity of mixed paste If desired, viscosity can be measured using a Physica MCR 301 Rheometer (Anton Paar, Graz, Austria) under controlled shear rate at 28°C with a plate / plate shape PP8. The diameter is 8 mm. Viscosity is measured in 10 seconds. -1 The viscosity is measured at a constant shear rate, and a total of 17 data points are collected. The viscosity at the 17 data points is used for characterization.

[0309] pH determination If desired, the pH can be determined by using moistened pH-sensitive paper.

[0310] Bending strength (FS) and E-modulus of elasticity (EM) This measurement was performed in accordance with ISO 4049:2010.

[0311] Color Value Measurement (CVM) A Delrin model with a height of 1.5 mm and a diameter of 15 mm was filled with approximately 0.6 g of base paste using two cover slips.* a * , b * The opacity values ​​were measured using a Gretag McBeth Color i7 device with the following parameters: Ulbricht sphere; D65, 10° viewer; aperture: 10 mm; area view: 6 mm; remission; wavelength: 360-750 nm.

[0312] Base paste b in the range of 0-15 * Value and base paste saving delta b in the range of 0-7 * The values ​​were found to meet the requirements for aesthetic dental compositions.

[0313] Autopolymerization Stability Test (APT) The base paste was stored in a PE cartridge at 50°C and visually inspected. If the paste could no longer be extruded from the cartridge, it was considered polymerized.

[0314] material Abbreviation: GPDM: Glycerol Phosphate Dimethacrylate Methacrylate: A mixture of urethane dimethacrylate (Plex® 6661) and triethylene glycol dimethacrylate. UDMA: Urethane dimethacrylate (Plex® 6661) YbF3: Ytterbium trifluoride Sr glass: Silane-treated, Schott GM32087 R805: Silane-treated fumed silica manufactured by Evonik AG Pigments: Color pigments, fluorescent pigments Copper procetonate: Copper bis(1-phenylpentane-1,3-dinate) Copper ethylhexanoate: copper bis(2-ethylhexanoate) TBPIN: tert-butylperoxy-3,5,5-trimethylhexanoate CPQ:D,L-Camphorquinone EDMAB: Ethyl 4-dimethylaminobenzoate Accelerator: Amine hydrochloride ASP: Palmitate Ascorbate TEMPOL:4-Hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl BHT: 2,6-di-tert-butyl-4-methylphenol (butylated hydroxytoluene) PMP-OH: Pentamethyl-4-piperidinol Hostanox (trademark): Reaction product of phosphorus trichloride, 1,1-biphenyl, and 2,4-bis(1,1-dimethylethyl)phenol. TPP: Triphenylphosphite

[0315] The following base pastes were prepared by mixing each component (amounts are given in parts by weight): [Table 1]

[0316] The following catalyst pastes were prepared by mixing each component (amounts are given in parts by weight): [Table 2]

[0317] To obtain a curable composition for measuring flexural strength and E-modulus, an equal volume portion of the base paste was mixed with a catalyst paste. [Table 3]

[0318] As can be seen from Table 3, all compositions yielded flexural strength values ​​in the range of 120 MPa (photocuring mode) and >100 MPa (self-curing mode), and E-modulus values ​​in the range of 6,000 MPa (photocuring mode) and >4,600 MPa (self-curing mode).

[0319] The base paste using a sterically hindered amine as a stabilizer (PMP-OH; Comparative Example 2; Table 1) showed no substantial discoloration during storage (6.21 delta b). * The compound underwent autopolymerization after 14 days at 50°C.

[0320] Base pastes using phenol stabilizer (BHT) and different copper salts (Comparative Examples 1 and 3; Table 1) did not autopolymerize even after more than 92 days at 50°C, but showed discoloration during storage (see 51.2 and 62.45 b, respectively). * value).

[0321] Base pastes using stabilizers containing free radicals (TEMPOL; Example 1; Table 1) showed no substantial discoloration during storage (12.89 b). * The compound did not undergo autopolymerization even after more than 92 days at 50°C. The present invention encompasses the following embodiments. (Item 1) A dental composition comprising a base member and a catalyst member that are mixed before use, The base member is Polymerizable components that do not have an acidic portion, Optionally, a polymerizable component having an acidic portion, Filler and, Transition metal components, Peroxide components, A stabilizer component containing a free radical portion, The catalyst member, Polymerizable components that do not have an acidic portion, Filler and, Ascorbic acid component, Photoinitiator system, A dental composition comprising a stabilizing component containing a phosphite or sulfite portion. (Item 2) The dental composition according to item 1, wherein the ratio of the stabilizer component containing the free radical portion to the peroxide component is in the range of 1:100 to 1:5 in terms of molar amount. (Item 3) The dental composition according to item 1 or 2, wherein the base member and the catalyst member are provided in a volume ratio of 10:1 to 1:1. (Item 4) The dental composition according to any one of items 1 to 3, wherein the stabilizing component comprises a free radical moiety containing a portion selected from 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 2,2,6,6-tetramethyl-piperidinyloxyl, 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl, triphenylmethyl radical, and mixtures thereof. (Item 5) The dental composition according to any one of items 1 to 4, wherein the stabilizing component comprises a phosphite or sulfite portion selected from an organic phosphite stabilizer, an organic sulfite stabilizer, and a mixture thereof. (Item 6) The dental composition according to any one of items 1 to 5, wherein the peroxide component is selected from diperoxides, hydroperoxides, ketone peroxides, peroxyesters, peroxydicarbonates, diacylperoxides, dialkylperoxides, peroxyketals, and mixtures thereof. (Item 7) The dental composition according to any one of items 1 to 6, wherein the transition metal ion component is selected from organic and inorganic salts of vanadium, chromium, manganese, iron, cobalt, nickel, and copper, and mixtures thereof. (Item 8) Each ingredient in the following amounts: Polymerizable components that do not contain acidic parts: 5-50% by weight, Polymerizable components with acidic portion: 0-20% by weight, Filler: 5-80% by weight, Transition metal component: 0.0005~0.05% by weight, Peroxide component: 0.05-2.5% by weight Stabilizer components containing free radicals: 0.0025~0.15% Ascorbic acid content: 0.025-2.5% by weight Photoinitiator system: 0.05-3% by weight, Stabilizing component containing phosphite or sulfite portion: Contains 0.005 to 2.5% by weight. A dental composition according to any one of items 1 to 7, wherein the weight percentage is relative to the total weight of the composition. (Item 9) The base member is A polymerizable component having an acidic portion in an amount of 0-20% by weight, A polymerizable component that does not have an acidic portion, in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, A transition metal component selected from organic salts of copper, vanadium, and iron, and mixtures thereof, Peroxide components selected from diperoxides, hydroperoxides, ketone peroxides, peroxyesters, peroxydicarbonates, diacylperoxides, dialkylperoxides, peroxyketals, and mixtures thereof, It contains a stabilizer component comprising a free radical moiety selected from 2,2-diphenyl-1-picrylhydrazyl, 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 2,2,6,6-tetramethyl-piperidinyloxyl, 2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadiene-1-ylidene)-p-tolyloxyl, and triphenylmethyl radical, The catalyst member, A polymerizable component that does not have an acidic portion in an amount of 5-70% by weight, A filler in an amount of 10-85% by weight, C of ascorbic acid 2 ~C 30 Ascorbic acid components selected from carboxylic acid esters, alkaline and alkaline earth salts of ascorbic acid, alkaline and alkaline earth salts of ascorbic acid esters, and mixtures thereof, A photoinitiator system containing a sensitizer and a reducing agent or donor component, A stabilizer component comprising an organic phosphite, an organic sulfite, and a phosphite or sulfite portion selected from mixtures thereof, A dental composition according to any one of items 1 to 8, wherein the weight percentage is relative to the total weight of the composition. (Item 10) A dental composition according to any one of items 1 to 9, housed in a storage device, wherein the storage device comprises two compartments for storing each component, and each compartment comprises a nozzle for delivering the respective component and a piston movable within the compartment. (Item 11) A dental composition according to any one of items 1 to 10 for use in a process of treating or restoring the hard tissue of a human or animal tooth, wherein the process is A step of mixing the base member and the catalyst member to obtain a mixed member, The steps include applying at least a portion of the mixed material to the surface of the hard tissue of the tooth, A dental composition comprising the step of optionally applying radiation to a portion of the mixed material. (Item 12) A dental composition according to any one of items 1 to 11 for use in a process of treating or restoring the hard tissue of a human or animal tooth, wherein the dental composition is used as a bulk-fill dental composite, a dental resin cement, a core build-up dental material, or a self-curing and dual-cure dental adhesive. (Item 13) A kit of components comprising a dental composition described in any of items 1 to 12, and at least one of the following items: dental filling composite, dental sealant, dental cement, dental mill blank, dental etching agent, dental adhesive, dental try-in paste, or dental fiber post. (Item 14) Transition metal components, Peroxide components, Stabilizer components containing free radical moieties, Ascorbic acid component, Photoinitiator system, A stabilizer component containing a phosphite or sulfite portion, Initiator systems whose components are as described in any of items 1 to 13. (Item 15) Use of a stabilizer containing a free radical moiety to stabilize an initiator system containing a peroxide component in combination with a transition metal component, wherein the stabilizer, the peroxide component, and the transition metal component are as described in any of items 1 to 14.

Claims

1. A dental composition comprising a base member and a catalyst member that are mixed before use, The base member is Polymerizable components that do not have an acidic portion, Any polymerizable component having an acidic portion, Filler and, Transition metal components, Peroxide components, A stabilizer component containing a free radical portion, wherein the free radical portion is a 2,2,6,6-tetramethyl-piperidine-1-oxyl portion, The catalyst member, Polymerizable components that do not have an acidic portion, Filler and, Ascorbic acid component, Photoinitiator system, A dental composition comprising a stabilizing component containing a phosphite or sulfite portion.

2. The dental composition according to claim 1, wherein the ratio of the stabilizer component containing the free radical portion to the peroxide component is in the range of 1:100 to 1:5 in terms of molar amount.

3. The dental composition according to claim 1 or 2, wherein the base member and the catalyst member are provided in a volume ratio of 10:1 to 1:

1.

4. The dental composition according to any one of claims 1 to 3, wherein the stabilizing component comprises a free radical moiety selected from 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 2,2,6,6-tetramethyl-piperidine-1-oxyl, bis(2,2,6,6-tetramethylpiperidine-1-oxyl-4-yl)decandioate, 4-methacryloyloxy-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-amino-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-acetamido-2,2,6,6-tetramethyl-piperidine-1-oxyl, 4-oxo-2,2,6,6-tetramethyl-piperidine-1-oxyl, and mixtures thereof.

5. The dental composition according to any one of claims 1 to 4, wherein the stabilizing component comprises a phosphite or sulfite portion selected from an organic phosphite stabilizer, an organic sulfite stabilizer, and a mixture thereof.

6. The dental composition according to any one of claims 1 to 5, wherein the peroxide component is selected from diperoxides, hydroperoxides, ketone peroxides, peroxyesters, peroxydicarbonates, diacylperoxides, dialkylperoxides, peroxyketals, and mixtures thereof.

7. The dental composition according to any one of claims 1 to 6, wherein the transition metal ion component is selected from organic and inorganic salts of vanadium, chromium, manganese, iron, cobalt, nickel, and copper, and mixtures thereof.

8. Each ingredient in the following amounts: Polymerizable components that do not contain acidic portions: 5-50% by weight, Polymerizable components having an acidic portion: 0-20% by weight, Filler: 5-80% by weight, Transition metal component: 0.0005 to 0.05% by weight, Peroxide component: 0.05-2.5% by weight Stabilizer components including free radical moieties: 0.0025-0.15% Ascorbic acid content: 0.025-2.5% by weight Photoinitiator system: 0.05 to 3% by weight, Stabilizing component containing phosphite or sulfite portion: Contains 0.005 to 2.5% by weight. The dental composition according to any one of claims 1 to 7, wherein the weight percentage is relative to the total weight of the composition.

9. The base member is A polymerizable component having an acidic portion in an amount of 0 to 20% by weight, A polymerizable component that does not have an acidic portion, in an amount of 5 to 70% by weight, A filler in an amount of 10 to 85% by weight, A transition metal component selected from organic salts of copper, vanadium, and iron, and mixtures thereof, Peroxide components selected from diperoxides, hydroperoxides, ketone peroxides, peroxyesters, peroxydicarbonates, diacylperoxides, dialkylperoxides, peroxyketals, and mixtures thereof, A stabilizer component comprising a free radical moiety selected from 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl and 2,2,6,6-tetramethyl-piperidine-1-oxyl, The catalyst member, A polymerizable component that does not have an acidic portion in an amount of 5 to 70% by weight, A filler in an amount of 10 to 85% by weight, C of ascorbic acid ２ ~C ３０ Ascorbic acid components selected from carboxylic acid esters, alkaline and alkaline earth salts of ascorbic acid, alkaline and alkaline earth salts of ascorbic acid esters, and mixtures thereof, A photoinitiator system containing a sensitizer and a reducing agent or donor component, A stabilizer component comprising an organic phosphite, an organic sulfite, and a phosphite or sulfite portion selected from mixtures thereof, The dental composition according to any one of claims 1 to 8, wherein the weight percentage is relative to the total weight of the composition.

10. A dental composition according to any one of claims 1 to 9, housed in a storage device, wherein the storage device comprises two compartments for storing each component, and each compartment comprises a nozzle for delivering the respective component and a piston movable within the compartment.

11. A dental composition according to any one of claims 1 to 10 for use in a process of treating or restoring the hard tissue of a human or animal tooth, wherein the process is: A step of mixing the base member and the catalyst member to obtain a mixed member, The steps include applying at least a portion of the mixed material to the surface of the hard tissue of the tooth, A dental composition comprising the step of optionally applying radiation to a portion of the mixed material.

12. A dental composition according to any one of claims 1 to 11 for use in a process of treating or restoring the hard tissue of a human or animal tooth, wherein the dental composition is used as a bulk-fill dental composite, a dental resin cement, a core build-up dental material, or a self-curing and dual-cure dental adhesive.

13. A kit of components comprising a dental composition according to any one of claims 1 to 12, and at least one of the following items: dental filling composite, dental sealant, dental cement, dental mill blank, dental etching agent, dental adhesive, dental try-in paste, and dental fiber post.

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