Calcium ion and fluoride ion releasing dental composition

Abstract

The present invention relates to a dental composition comprising a polymerizable component, an initiator suitable for curing the polymerizable component, a Ca ion-releasing component having a Ca ion-releasing ability of 400 mg / l (ppm) to 700 mg / l (ppm) in 24 hours when 2.5 g of the Ca ion-releasing component is introduced into 50 ml of deionized water at pH 2, and an F ion-releasing component having an F ion-releasing ability of 1,500 mg / l (ppm) to 3,500 mg / l (ppm) in 24 hours when 2.5 g of the F ion-releasing component is introduced into 50 ml of deionized water at pH 7. The present invention also relates to a parts kit comprising the dental composition according to the present invention and one or a combination of the following items: a dental adhesive, a dental milling block, a prefabricated dental crown. The dental composition is suitable for use in a method of remineralizing defective teeth in the oral cavity of a mammal, the method comprising the step of fixing a dental restoration to the surface of the defective teeth using the dental composition.

Description

Technical Field

[0001] The present invention relates to a dental composition, particularly a resin-modified glass ionomer cement (RM-GIC) having calcium ion and fluoride ion release properties.

[0002] Dental compositions can be used to bond dental restorations to tooth structures and to remineralize tooth structures to which dental restorations are bonded.

Background Art

[0003] Dental caries typically refers to tooth decay caused by bacteria located in the biofilm in a patient's oral cavity. These bacteria produce lactic acid, among other things, and lactic acid interacts with the hard tissues of the teeth.

[0004] The hard tissues of the teeth, particularly tooth enamel, contain a large amount of phosphate mineral apatite having the general formula Ca5(PO4)3(F, Cl, OH), where hydroxyapatite is the main component of tooth enamel. Fluoroapatite is said to be more resistant to acids compared to hydroxyapatite.

[0005] Therefore, in order to make the hard tissues of the teeth more resistant to acids, it has been proposed to treat the hard tissues of the teeth with a composition containing a fluoride-releasing component.

[0006] In this regard, various mouthwashes and toothpastes are available for daily practice.

[0007] In addition to these products, there are also dental restorative compositions containing a fluoride-releasing component or a phosphate-releasing component. These dental compositions are typically used by dentists when treating missing teeth.

[0008] For example, U.S. Patent Application Publication No. 2007 / 183984 (A1) (Wrigley) describes an oral composition for tooth calcification or remineralization, comprising a combination of calcium phosphate salts and acids having different solubilities in the oral cavity. The presence of the acid combination in the oral composition is said to maximize the release of calcium ions and phosphate ions from the oral composition over a long period to promote the precipitation of enamel-like crystals on or in the subsurface region of the tooth surface.

[0009] U.S. Patent No. 5,824,720 (Gangnus et al.) relates to a fluoride-releasing polymerizable dental composite material containing (a) one or more ethylenically unsaturated polymerizable monomers based on a difunctional or polyfunctional (meth)acrylate; (b) an initiator and optionally an activator; (c) a conventional filler, and optionally a pigment, a thixotropic agent, a plasticizer and other auxiliaries; and (d) one or more highly water-soluble inorganic fluoride complexes of the general formula A n MF m (wherein A is a monovalent cation, M is a metal of Group III-V or II-V sub-group, n is an integer from 1 to 3, and m is an integer from 3 to 6).

[0010] International Publication No. 2018 / 102484 (A1) (3M) describes a curable dental composition comprising a first part which is an encapsulated material (including, for example, a first part), the encapsulated material comprising a basic core material and an inorganic shell material comprising a metal oxide surrounding the core, and a second part which is an acidic component (including, for example, a second part) suitable for use as water or a biological carrier material.

[0011] International Publication No. 2014 / 148002 (A1) (Kuraray) describes a resin-reinforced glass ionomer cement which contains fluoroaluminosilicate glass particles, acidic calcium phosphate and basic calcium phosphate particles or calcium compound particles excluding phosphorus, polyalkenoic acid, a non-acidic polymerizable monomer, water and a polymerization initiator, and exhibits the release of calcium and fluoride ions.

[0012] U.S. Patent No. 4,746,686 (Waller) relates to a visible light-activated cavity liner that provides a source of leachable calcium and fluoride, and the composition includes a photopolymerizable matrix material, a photoinitiator, a reducing agent, a synthetic hydroxylapatite filler, and a powder glass ionomer filler.

SUMMARY OF THE INVENTION

[0013] However, there is still a need for curable dental compositions, particularly dental cements, that address the problem of more effectively or differently remineralizing defective tooth structures.

[0014] In particular, there is a desire for dental compositions that can release not only fluoride ions but also calcium ions.

[0015] Once released, calcium ions and fluoride ions typically form water-insoluble calcium fluoride, so it is important to provide such compositions.

[0016] It is also desirable for the dental composition to have good adhesive properties.

[0017] Furthermore, if possible, the dental composition should meet the aesthetic expectations of the practitioner.

[0018] Ideally, the dental composition should also be sufficiently storage stable.

[0019] One or more of the above objects can be achieved by the present invention described herein.

[0020] In one embodiment, the present invention features a dental composition comprising a polymerizable component, an initiator suitable for curing the polymerizable component, a Ca ion-releasing component that, when 2.5 g of the Ca ion-releasing component is introduced (steered) into 50 ml of deionized water at pH 2, has a Ca ion-releasing ability of 400 mg / l (ppm) to 700 mg / l (ppm) in 24 hours, and an F ion-releasing component that, when 2.5 g of the F ion-releasing component is introduced into 50 ml of deionized water at pH 7, has an F ion-releasing ability of 1,500 mg / l (ppm) to 3,500 mg / l (ppm) in 24 hours.

[0021] The dental composition is typically provided as a parts kit that includes an acidic portion and a non-acidic portion.

[0022] The present invention also relates to a parts kit comprising the dental composition described herein and one or a combination of the following items: a dental adhesive, a dental milling block, and a prefabricated dental crown.

[0023] The present invention also relates to a dental composition for use in a method of remineralizing a missing tooth in the oral cavity of a mammal, the method comprising the step of fixing a dental restoration to the surface of the missing tooth using the dental composition described herein.

[0024] Unless otherwise defined, as used herein, the following terms shall have the meanings set forth below.

[0025] The term "compound" or "component" is a chemical substance having a specific molecular identity or a chemical substance made from such substances, for example, a mixture of polymeric substances.

[0026] The "hardenable or curable or polymerizable component" is any component that can be hardened or cured in the presence of a photoinitiator by radiation-induced polymerization. The curable component may contain only one, two, three, or more polymerizable groups. Typical examples of polymerizable groups include, among others, unsaturated carbon groups such as vinyl groups present in (meth)acrylate groups.

[0027] As used herein, "(meth)acryl" is an abbreviation that refers to "acryl" and / or "methacryl". For example, the "(meth)acryloxy" group is an abbreviation that refers to either an acryloxy group (i.e., CH2=CH-C(O)-O-) and / or a methacryloxy group (i.e., CH2=C(CH3)-C(O)-O-).

[0028] As used herein, "curing" or "hardening" of a composition is used interchangeably and refers to polymerization and / or crosslinking reactions, including, for example, photopolymerization reactions and chemical polymerization techniques (e.g., ionic or chemical reactions that form radicals effective for polymerizing ethylenically unsaturated compounds) in which one or more materials contained in the composition are involved.

[0029] An "initiator" is a substance that can initiate or cause the hardening process of a polymerizable component or monomer, for example, by a redox / auto-cure chemical reaction, or by a reaction induced by radiation, or by a reaction induced by heat.

[0030] A "redox initiator system" is defined as a combination of a reducing agent and an oxidizing agent located on the application portion of the application device. When present, transition metal components are also considered components of the redox initiator system.

[0031] "Dental articles" mean articles used in the dental field, particularly as dental restorations or for manufacturing dental restorations. Dental articles typically have two different surface portions, an outer surface and an inner surface. The outer surface is typically a surface that does not permanently contact the tooth surface. In contrast, the inner surface is the surface used to attach or fix the dental article to the tooth. When the dental article has the shape of a dental crown, the inner surface typically has a concave shape, while the outer surface typically has a convex shape. Dental articles shall not contain components harmful to the patient's health and thus shall not contain harmful and toxic components that may leak from dental or orthodontic articles.

[0032] "Dental restorations" mean dental articles used to restore the teeth being treated. Examples of dental restorations include crowns, bridges, inlays, onlays, veneers, prefabrications, copings, crown-bridge frameworks, and parts thereof.

[0033] "Particles" mean substances that are solids with geometrically definable shapes. The shape may be regular or irregular. Particles can typically be analyzed, for example, with respect to particle size and particle size distribution.

[0034] The particle size (d50) of the powder can be obtained from the cumulative curve of the particle size distribution. Each measurement can be performed using a commercially available particle size analyzer (e.g., Malvern Mastersizer 2000). "D" represents the diameter of the powder particles, and "50" refers to the volume percentage of the particles. In some cases, 50% may be expressed as "0.5". For example, "(d50)=1μm" means that 50% of the particles have a size of 1μm or less.

[0035] "Paste" refers to a soft, viscous mass of solid dispersed in a liquid.

[0036] "Viscous" means a viscosity greater than 50 Pa * s at 23°C.

[0037] "Liquid" means any solvent or liquid that can at least partially disperse or dissolve components under ambient conditions (e.g., 23 °C). A liquid typically has a viscosity below 10 Pa * s, or below 8 Pa * s, or below 6 Pa * s.

[0038] "Glass ionomer cement" or "GIC" means a cement that cures or hardens by the reaction of an acid-reactive glass and a polyacid in the presence of water.

[0039] "Resin-modified glass ionomer cement" or "RM-GIC" means a GIC that further contains a polymerizable component, an initiator system, and typically a diluent such as 2-hydroxyethyl methacrylate (HEMA).

[0040] "Acid-reactive filler" means a filler that chemically reacts in the presence of (poly)acid to initiate a solidification reaction.

[0041] "Non-acid-reactive filler" means a filler that does not exhibit a chemical solidification reaction within about 30 minutes when mixed with (poly)acid under ambient conditions (e.g., 23 °C).

[0042] To distinguish an acid-reactive filler from a non-acid-reactive filler, the following test may be or will be conducted. Agent A and Agent B are mixed at a mass ratio of 3:1 to prepare a composition, where Agent A consists of 100 wt% of the filler to be analyzed, and Agent B consists of 43.6 wt% of poly(acrylic acid-co-maleic acid) (Mw: about 20,000 ± 3,000), 47.2 wt% of water, 9.1 wt% of tartaric acid, and 0.1 wt% of benzoic acid.

[0043] "Polyacid" or "polyalkenoic acid" means a polymer having a plurality of (e.g., more than 10, or more than 20, or more than 50) acidic repeating units. That is, the acidic repeating units are either bonded to the polymer backbone or pendant therefrom.

[0044] A "storage stable composition" is a composition that can be stored for a suitable period (e.g., at least 12 months under ambient conditions or 3 months under accelerated aging conditions) without exhibiting significant performance issues (e.g., a decrease in flexural strength or compressive strength), and / or does not solidify over time, and / or does not separate over time.

[0045] As used herein, "tooth surface" refers to tooth structures (e.g., enamel, dentin, and cementum) and bone.

[0046] A "self-etching" composition refers to a composition that adheres to the tooth surface without pretreatment of the tooth surface with an etching agent. Preferably, a self-etching composition can also function as a self-adhesive primer without using another etching agent or primer.

[0047] A "self-adhesive" composition refers to a composition that can adhere to the tooth surface without pretreatment of the tooth surface with a primer or bonding agent. Preferably, a self-adhesive composition is also a self-etching composition that does not use another etching agent.

[0048] "Self-curing composition" means a composition that cures by a redox reaction without the application of radiation.

[0049] An "untreated" tooth surface refers to a tooth or bone surface that has not been treated with an etching agent, primer, conditioner, or bonding agent prior to the application of a self-etching adhesive or self-adhesive composition.

[0050] The tooth surface of "unetched" refers to the tooth or bone surface that has not been treated with an etching material before the application of a self-etching adhesive or a self-adhesive composition.

[0051] "Surrounding conditions" means the conditions to which the compositions described in this specification are normally exposed during storage and handling. The surrounding conditions may be, for example, a pressure of 900 mbar to 1,100 mbar, a temperature of 10 °C to 40 °C, and a relative humidity of 10% to 100%. In the laboratory, the surrounding conditions are typically adjusted to 20 °C to 25 °C and 1,000 mbar to 1,025 mbar (at sea level).

[0052] As used herein, "a", "an", "the", "at least one", and "one or more" are used interchangeably. Also, in this specification, the description of a numerical range by endpoints includes all numbers included within that range (for example, 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0053] Appending "(s)" to a term means that the term should include both the singular and plural forms. For example, the term "additive(s)" means one additive and two or more additives (for example, 2, 3, 4, etc.).

[0054] Unless otherwise indicated, all numbers representing the amounts of ingredients and the measured values of physical properties, such as those described below, used in this specification and the claims should be understood to be modified in all instances by the term "about".

[0055] The terms "comprising" or "containing" and their variations, when used in this specification and the claims, do not have a limiting meaning. "Consisting essentially of" means that certain additional components may be present, i.e., components that do not substantially affect the essential characteristics of the article or composition. "Consisting of" means that no additional components should be present. The term "comprising" shall also include the terms "consisting essentially of" and "consisting of".

[0056] If a composition does not contain a particular component as an essential feature, the composition is "essentially or substantially free of" this component. Thus, this component is not intentionally added to the composition, either alone or in combination with other components or substances containing other components. A composition that is essentially free of a particular component usually does not contain any of this component at all. However, for example, due to impurities contained in the raw materials used, it may not be possible to avoid the presence of a small amount of this component.

DETAILED DESCRIPTION OF THE INVENTION

[0057] The compositions described herein have been found to have several advantageous properties.

[0058] Dental compositions can release a combination of calcium ions and fluoride ions.

[0059] Since the presence of fluoride is thought to correlate with improved oral hygiene, the release of fluoride ions from dental materials and toothpastes is considered beneficial. It is thought that by applying fluoride ions, the hardness of the tooth surface structure can be improved.

[0060] This can typically be achieved by using fluoride ion-releasing reactive glasses that are often present in RM-GICs, or by adding fluoride ion-containing compounds such as sodium fluoride to the dental composition.

[0061] It is also assumed that the application of calcium ions to the tooth surface can contribute to the remineralization of the tooth structure.

[0062] This can typically be achieved by adding a water-soluble calcium salt. However, not all types of Ca ion-releasing components or F ion-releasing components are suitable.

[0063] It has been found that it is difficult to provide a significant release of calcium in the presence of fluoride, probably due to the in-situ formation of insoluble calcium fluoride. In fact, it has been found that RM-GIC formulations containing sodium fluoride release less calcium than formulations without sodium fluoride.

[0064] While not wishing to be bound by any particular theory, each component is thought to have a kind of delayed ion release ability so as not to exceed the solubility product of calcium fluoride during the preparation of the dental composition and during its application to the prepared tooth structure.

[0065] Thus, Ca ions and F ions remain available for incorporation into the hard tissues of the tooth and can therefore contribute to the remineralization of the hard tissues of the tooth over time.

[0066] Due to this property, the dental composition can also be regarded as a so-called bioactive material.

[0067] Furthermore, depending on the nature of the initiator system used, the dental composition can also be easily cured by applying radiation, or is self-curing, or can be cured by using a combination of different curing reactions.

[0068] The dental compositions described herein are also sufficiently storage-stable and, when formulated as a self-adhesive composition, have sufficient adhesion properties (e.g., shear bond strength).

[0069] By selecting appropriate components, the aesthetic aspects of the dental composition can also be addressed.

[0070] If desired, the dental compositions described herein typically have the following properties: a) Viscosity: 10 Pa * s to 5,000 Pa * s, or 100 Pa * s to 2,000 Pa * s (measured at a frequency of 1.25 Hz and a deflection of 1.75% 60 seconds after the start of mixing of the composition); b) pH value: 1 to 6 when measured with a moist pH-sensitive test paper or stick; c) Shear bond strength to dentin: 1 MPa to 10 MPa; d) Setting time: Characterizable by being within 10 minutes when measured at 28°C, either alone or in combination.

[0071] Combinations of the following features: a) and b); a) and c); b) and c) may be preferred.

[0072] The dental composition contains a polymerizable component. The polymerizable component includes a component having at least one or two polymerizable moieties such as a (meth)acrylate moiety. Crosslinking or polymerization of the polymerizable component can be initiated by using a redox initiator system and / or by using a photoinitiator system.

[0073] In some embodiments, the polymerizable component contains an acidic group or moiety.

[0074] The polymerizable component having an acid moiety typically has the following formula A n BC m (wherein A is an ethylenically unsaturated group such as a (meth)acrylic moiety, B is a linear or branched C1-C optionally substituted with (i) another functional group (e.g., halide (including Cl, Br, I), OH, or a mixture thereof)12 alkyl, (ii) C6-C optionally substituted with other functional groups (e.g., halides, OH, or mixtures thereof) 12 aryl, (iii) a spacer group such as an organic group having 4 to 20 carbon atoms bonded to each other by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl, and / or sulfonyl bonds, C is an acidic group, or a precursor of an acidic group such as an acid anhydride, m and n are independently selected from 1, 2, 3, 4, 5, or 6, The acidic group includes one or more carboxylic acid residues such as -COOH or -CO-O-CO-, phosphate residues such as -O-P(O)(OH)OH, phosphonic acid residues such as C-P(O)(OH)(OH), sulfonic acid residues such as -SO3H, or sulfinic acid residues such as -SO2H) can be represented by

[0075] Examples of the polymerizable component having an acid moiety include glycerol phosphate mono(meth)acrylate, glycerol phosphate di(meth)acrylate, hydroxyethyl (meth)acrylate (e.g., HEMA) phosphate, bis((meth)acryloyloxyethyl) phosphate, (meth)acryloyloxy-propyl phosphate, bis((meth)acryloyloxypropyl) phosphate, bis((meth)acryloyloxy)propyloxy phosphate, (meth)acryloyloxyhexyl phosphate, bis((meth)acryloyloxyhexyl) phosphate, (meth)acryloyloxyoctyl phosphate, bis((meth)acryloyloxyoctyl) phosphate, (meth)acryloyloxydecyl phosphate, bis((meth)acryloyloxydecyl) phosphate, caprolactone methacrylate phosphate, di- or tri-methacrylate of citric acid, but are not limited thereto. Derivatives of these curable components having an acid moiety that can easily react with water to form the above specific examples such as acid halides or anhydrides are also contemplated.

[0076] The polymerizable component having an acidic group is typically present in the following amounts, by weight % based on the weight of the dental composition: namely, at least 0.5 wt% or 1 wt% or 2 wt%; up to 15 wt% or 10 wt% or 8 wt%, in the range: 0.5 wt% to 15 wt% or 2 wt% to 10 wt% or 3 wt% to 8 wt%.

[0077] In some embodiments, the polymerizable component does not contain an acidic group.

[0078] The polymerizable component having no acidic moiety is typically a free-radically polymerizable material comprising an ethylenically unsaturated monomer, monomer or oligomer or polymer.

[0079] Suitable polymerizable components having no acidic moiety are of the following formula: A n BA m (wherein A is an ethylenically unsaturated group such as a (meth)acrylic moiety, B is selected from (i) a linear or branched C1-C alkyl optionally substituted with other functional groups (e.g., halides (including Cl, Br, I), OH, or mixtures thereof), (ii) a C6-C aryl optionally substituted with other functional groups (e.g., halides, OH, or mixtures thereof), or (iii) an organic group having 4 to 20 carbon atoms bonded to each other by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl, and / or sulfonyl bonds, 12 alkyl, (ii) a C6-C aryl optionally substituted with other functional groups (e.g., halides, OH, or mixtures thereof), or (iii) an organic group having 4 to 20 carbon atoms bonded to each other by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl, and / or sulfonyl bonds, 12 aryl, or (iii) an organic group having 4 to 20 carbon atoms bonded to each other by one or more ether, thioether, ester, thioester, thiocarbonyl, amide, urethane, carbonyl, and / or sulfonyl bonds, m, n are independently selected from 0, 1, 2, 3, 4, 5, or 6, provided that n + m is greater than 0, i.e., at least one A group is present) and can be characterized by.

[0080] 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, a reaction product of 2-hydroxyethyl methacrylate (HEMA) and 2,2,4-trimethylhexamethylene diisocyanate (TMDI) called UDMA, a diurethane dimethacrylate (a mixture of isomers, e.g., Rohm Plex 6661-0), 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)acryloxy)]-p-ethoxyphenyldimethylmethane, bis[1-(3-methacryloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane (BisGMA), bis[1-(3-acryloxy-2-hydroxy)]-p-propoxy-phenyldimethylmethane, and tris-hydroxyethyl-isocyanurate trimethacrylate; mono-, di-, or poly-acrylates and methacrylates; bis-acrylates and bis-methacrylates of polyethylene glycol with a molecular weight of 200 to 500, a copolymerizable mixture of acrylated monomers (see U.S. Patent No. 4,652,274), and acrylated oligomers (see U.S. Patent No. 4,642,126); and vinyl compounds such as styrene, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate;Examples include polyfunctional (meth)acrylates containing urethane, urea, or amide groups. If desired, mixtures of two or more of these free-radical polymerizable materials can be used.;

[0081] Further polymerizable components that may be present include di(meth)acrylates of ethoxylated bis-phenol A, such as 2,2'-bis(4-(meth)acryloxytetraethoxyphenyl)propane, urethane (meth)acrylate, and (meth)acrylamide. The monomers used can further be esters of [alpha]-cyanoacrylic acid, crotonic acid, cinnamic acid, and sorbic acid.

[0082] It is also possible to use the methacrylic esters described in European Patent No. 0235826, such as bis[3[4]-methacryloyloxymethyl-8(9)-tricyclo[5.2.1.0 2,6 decylmethyltriglycolate. 2,2-bis-4(3-methacryloyloxy-2-hydroxypropoxy)phenylpropane (Bis-GMA), 2,2-bis-4(3-methacryloyloxypropoxy)phenylpropane, 7,7,9-trimethyl-4,13-dioxo-3,14-dioxa-5,12-diazhexadecane-1,16-dioxodimethacrylate (UDMA), urethane (meth)acrylate, and bis-hydroxymethyltricyclo-(5.2.1.0 2,6 )decane di(meth)acrylate are also suitable.

[0083] These ethylenically unsaturated monomers can be used alone or in combination with other ethylenically unsaturated monomers in dental compositions. In addition to or in addition to their components, other curable components that can be added include oligomeric or polymeric compounds such as polyester (meth)acrylate, polyether (meth)acrylate, polycarbonate (meth)acrylate, and polyurethane (meth)acrylate. The molecular weights of these compounds are typically less than 20,000 g / mol, particularly less than 15,000 g / mol, and particularly less than 10,000 g / mol.

[0084] The polymerizable component having no acidic group is typically present in the following amounts, by weight % based on the weight of the dental composition: namely, at least 1% by weight or 5% by weight or 10% by weight; up to 50% by weight or 45% by weight or 40% by weight; range: 1% by weight to 50% by weight or 5% by weight to 45% by weight or 10% by weight to 40% by weight.

[0085] The dental composition contains an initiator suitable for curing the polymerizable component. Different types of initiator systems can be used.

[0086] The dental composition may contain a photoinitiator or photoinitiator system and / or a redox initiator system.

[0087] According to certain embodiments, the dental composition contains a photoinitiator.

[0088] As the photoinitiator, those capable of polymerizing the polymerizable monomer by the action of visible light having a wavelength in the range of 350 nm to 500 nm are preferred.

[0089] Suitable photoinitiators often contain an alpha-diketone moiety, an anthraquinone moiety, a thioxanthone moiety or a benzoin moiety.

[0090] Examples of photoinitiators include camphorquinone, 1-phenylpropane-1,2-dione, benzyl, diacetyl, benzyldimethyl ketal, benzyldiethyl ketal, benzyldi(2-methoxyethyl) ketal, 4,4'-dimethylbenzyldimethyl ketal, anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis(4-dimethyl-aminophenyl) ketone, 4,4'-bisdiethylaminobenzophenone.

[0091] It has also been found that using acylphosphine oxides is similarly useful.

[0092] Suitable acylphosphine oxides have the following formula (R 9 )2-P(=O)-C(=O)-R 10 (wherein each R 9 may independently be a hydrocarbyl group such as alkyl, cycloalkyl, aryl, and aralkyl, any of which may be substituted with a halo-, alkyl-, or alkoxy group, or two R 9 groups may combine to form a ring with the phosphorus atom, and R 10 is a hydrocarbyl group, an S-, O-, or N-containing 5- or 6-membered heterocyclic group, or a -Z-C(=O)-P(=O)-(R 9 )2 group, and Z represents a divalent hydrocarbyl group such as alkylene or phenylene having 2 to 6 carbon atoms). It can be characterized by.

[0093] Suitable systems are also described, for example, in U.S. Patent No. 4,737,593 (Ellrich et al.), the content of which is incorporated herein by reference.

[0094] Preferred acylphosphine oxides are those in which the R 9 and R 10 groups are phenyl, or lower alkyl- or lower alkoxy-substituted phenyl. "Lower alkyl" and "lower alkoxy" mean groups having from 1 to 4 carbon atoms. In particular, 2,4,6-trimethylbenzoyldiphenylphosphine oxide has been found to be useful (Lucirin™ TPO, BASF).

[0095] More specific 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, bis-(2,6-dichlorobenzoyl)-2-naphthylphosphine oxide, 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-dimethylphenylphosphine 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.,

[0096] The acylphosphine oxide bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (formerly known as IRGACURE™ 819, available from Ciba Specialty Chemicals) may be preferred in some cases.,

[0097] The photoinitiator can be present in the following amounts, by weight % based on the weight of the dental composition: namely, at least 0 wt% or 0.005 wt% or 0.01 wt%; up to 2 wt% or 1.5 wt% or 1 wt%, in the range: 0 wt% to 2 wt% or 0.001 wt% to 1.5 wt% or 0.01 wt% to 1 wt%.,

[0098] According to certain embodiments, the dental composition includes a redox initiator system.,

[0099] The redox initiator system typically includes an oxidizing agent, a reducing agent, and optionally a transition metal component.,

[0100] Suitable oxidizing agents include organic peroxides and persulfate components, and mixtures thereof.,

[0101] Organic peroxides that can be used include hydroperoxides, ketone peroxides, diacyl peroxides, dialkyl peroxides, peroxyketals, peroxy esters, and peroxydicarbonates.,

[0102] Examples of diperoxides that can be used include diperoxides containing the moiety R1-O-O-R2-O-O-R3, where R1 and R3 are independently selected from H, alkyl (e.g., C1-C6), branched alkyl (e.g., C1-C6), cycloalkyl (e.g., C5-C 10 ), alkylaryl (e.g., C7-C 12 ), or aryl (e.g., C6-C 10 ), and R2 is selected from alkyl (e.g., (C1-C6) or branched alkyl (e.g., C1-C6).

[0103] Examples of ketone peroxides include methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, methyl cyclohexanone peroxide, and cyclohexanone peroxide.

[0104] Examples of peroxy esters include cumyl peroxy neodecanoate, t-butyl peroxy pivalate, t-butyl peroxy neodecanoate, 2,2,4-trimethylpentyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxy-2-ethylhexanoate, di-t-butyl peroxy isophthalate, di-t-butyl peroxy hexahydroterephthalate, t-butyl peroxy-3,3,5-trimethylhexanoate, t-butyl peroxy acetate, t-butyl peroxy benzoate, and t-butyl peroxy maleate.

[0105] Examples of peroxydicarbonates include di-3-methoxy peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, bis(4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl-1-peroxydicarbonate, di-n-propyl peroxydicarbonate, di-2-ethoxyethyl-peroxydicarbonate, and diallyl peroxydicarbonate.

[0106] Examples of diacyl peroxides include acetyl peroxide, benzoyl peroxide, decanoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, 2,4-dichlorobenzoyl peroxide, and lauroyl peroxide.

[0107] Examples of dialkyl peroxides include di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, 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.

[0108] Examples of peroxyesters include 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2,2-bis(t-butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, and 4,4-bis(t-butylperoxy)valeric acid n-butyl ester.

[0109] According to one embodiment, the organic peroxide is a hydroperoxide, particularly a hydroperoxide containing the structural moiety R-O-O-H, where R is, for example, C1-C 20 ) alkyl, (e.g., C3-C 20 ) branched alkyl, (e.g., C6-C 12 ) cycloalkyl, (e.g., C7-C 20 ) alkylaryl, or (e.g., C6-C 12 ) aryl.

[0110] Examples of suitable organic hydroperoxides include t-butyl hydroperoxide, t-amyl hydroperoxide, p-diisopropylbenzene hydroperoxide, cumene hydroperoxide, pinane hydroperoxide, p-methane hydroperoxide, and 1,1,3,3-tetramethylbutyl hydroperoxide.

[0111] Suitable peroxodisulfate components and / or peroxodiphosphate components and / or mixtures thereof that can be used include organic and / or inorganic components.

[0112] Suitable examples include ammonium, sodium, and potassium peroxodisulfate components and / or peroxodiphosphate components. Sodium peroxodisulfate may be preferred in some cases.

[0113] Suitable transition metal components include organic and / or inorganic salts selected from titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, and / or zinc, and copper and iron may be preferred in some cases.

[0114] Useful salts include acetates, chlorides, sulfates, benzoates, acetylacetonates, naphthenates, carboxylates, bis(1-phenylpentane-1,3-dione) complexes, salicylates, complexes with ethylenediaminetetraacetic acid, and mixtures thereof of any of the transition metals.

[0115] According to one embodiment, the transition metal component is in an oxidized state, which enables the component to be reduced. Useful oxidation states include, as appropriate, +2, +3, +4, +5, +6, and +7.

[0116] The copper component may be preferred in some cases. The oxidation state of copper in the copper component is preferably +1 or +2.

[0117] Typical examples of copper components that can be used include copper salts and complexes containing copper acetate, copper chloride, copper benzoate, copper acetylacetonate, copper naphthenate, copper carboxylate, copper bis(1-phenylpentane-1,3-dione) complex (copper procetonate), copper salicylate, complex with thiourea, complex of copper with ethylenediaminetetraacetic acid, and / or mixtures thereof. The copper compound may be used in hydrated form or may be anhydrous. Copper acetate is particularly preferred.

[0118] The amount of transition metal component that can be used is not particularly limited. The transition metal salt must be used in an amount sufficient to achieve the intended purpose.

[0119] Examples of the reducing agent include ascorbic acid component, tertiary amine component, sulfinate component, sulfuric acid component, borane component, (thio)urea component, and (thio)barbituric acid component, saccharin, and metal salts thereof.

[0120] A thiourea component containing a polymerizable moiety, particularly a (meth)acrylate moiety, is also preferred.

[0121] The polymerizable thiourea component contains a thiourea moiety bonded to the (meth)acrylate moiety via a spacer unit containing an alkyl chain, preferably a C 3~11 alkyl chain.

[0122] The molecular weight of the polymerizable thiourea component is typically in the range of 200 g / mol to 400 g / mol. This molecular weight range seems to be an appropriate compromise to enable sufficient molecular mobility and reactivity within the curable composition to be cured.

[0123] The polymerizable thiourea component has the following formula: MA-S-TU-R (wherein, MA: (meth)acrylate, S: C 3~11 linear alkyl, or C 3~8 linear alkyl, or C 3~6 linear alkyl, TU: thiourea, R: C1-C6 alkyl or cycloalkyl (C 3~6 , preferably C 5~6 )) and can be characterized by.

[0124] The polymerizable thiourea component typically does not contain an allyl moiety (H2C=CH-CH2-) and a carbamate moiety (-O-CO-NH-).

[0125] A suitable polymerizable thiourea component typically exhibits an average water contact angle in the range of greater than 10° or greater than 15° when measured over a period of 0 to 12 seconds after placing a water droplet on a surface coated with the polymerizable thiourea component.

[0126] Preferred polymerizable thiourea components include N-(5-methacryloyloxypentyl)-N'-ethylthiourea, N-(5-methacryloyloxypentyl)-N'-cyclohexylthiourea, N-(5-methacryloyloxyundecyl)-N'-ethylthiourea, and mixtures thereof.

[0127] When an oxidizing agent comes into contact with a reducing agent, a redox reaction typically begins. Such a redox reaction is suitable for initiating the curing of the curable component and resulting in crosslinking of the curable component.

[0128] When a redox initiator system comprising an oxidizing component, a reducing component, and optionally a transition metal component is present, it is typically present in the following amounts, by weight % based on the weight of the entire dental composition: namely, at least 0.1 wt% or 0.2 wt% or 0.3 wt%; up to 5 wt% or 4 wt% or 3 wt%, range: 0.1 wt% to 5 wt% or 0.2 wt% to 4 wt% or 0.3 wt% to 3 wt%.

[0129] The dental composition contains a calcium ion-releasing component.

[0130] The Ca ion-releasing component has a Ca ion-releasing ability of 400 mg / L to 700 mg / L when 2.5 g of the compound is stirred in 50 mL of deionized water at pH = 2 for 24 hours.

[0131] The Ca ion-releasing component is typically present in the following amounts, by weight % based on the weight of the dental composition: namely, at least 0.5 wt% or 1 wt% or 2 wt%; up to 30 wt% or 25 wt% or 20 wt%, range: 0.5 wt% to 30 wt% or 1 wt% to 25 wt% or 2 wt% to 20 wt%.

[0132] According to some embodiments, the Ca ion releasing component includes a basic core material that releases Ca ions and an inorganic shell material that includes a metal oxide surrounding the basic core material.

[0133] The basic core material is a material that provides a pH greater than 7 when dissolved in deionized water.

[0134] Examples of the basic core material include oxides and hydroxides of alkali and alkaline earth metals, and strongly basic salts such as alkali phosphates.

[0135] Specific examples of the basic core material include oxides and hydroxides of Na, K, Ca, Sr, and Ba; silicates of Na, K, Ca, Sr, and Ba; and aluminates of Na, K, Ca, Sr, and Ba. Basic silicates and glasses typically contain at least 1, 2, or 3 moles of a basic core compound (e.g., CaO) per mole of silica on a cation molar basis. Similarly, basic aluminates typically contain at least 1, 2, or 3 moles of a basic core compound (e.g., CaO) per mole of alumina on a cation molar basis.

[0136] In some embodiments, the core includes CaO having a pKa of 11.6 and is prepared therefrom. The amount of CaO is typically at least 5, 10, 15, 20, or 25 wt% and can range up to 75 wt% or more.

[0137] Specific examples of basic core materials containing CaO include Portland cement (reported to contain 60 wt% - 70 wt% CaO), tricalcium silicate (containing about 75 wt% CaO), and bioactive glass such as that available from 3M Advanced Material Division (containing about 25 wt% CaO and about 25 wt% Na2O).

[0138] Conventional natural (e.g., Portland) cement and synthetic cement typically contain a large amount of calcium silicate (e.g., 3CaO-SiO2, 2CaO-SiO2) alone or in combination with one or more calcium aluminates (e.g., 3CaO-Al2O3, 4CaO-Al2O3-Fe2O3) and are hardenable or self-hardening when mixed with water. Portland cement typically contains about 61% - 69% CaO, about 18% - 24% SiO2, about 2% - 6% Al2O3, about 1% - 6% Fe2O3, and about 0.5% - 5% MgO.

[0139] The Ca ion release component provides basic core particles and can be manufactured by encapsulating the basic core particles with an inorganic coating (e.g., a continuous non-particulate) using at least one of the vapor deposition techniques. Examples of vapor deposition methods include chemical vapor deposition (CVD) such as atmospheric pressure chemical vapor deposition (APCVD), hydrolytic CVD, and plasma CVD.

[0140] Advantages of vapor deposition techniques for providing coatings include that the coatings are constructed from molecular-sized species without interference from solvents or liquid media. Some coating methods (e.g., ALD and CVD) tend to result in coatings composed of conformal layers on irregular materials (e.g., powders or porous microparticles).

[0141] ALD and CVD are coating processes involving chemical reactions, and the chemical reactants used are called chemical precursors. That is, they are precursors to the coating material to be formed (e.g., a metal oxide coating) (i.e., coating precursors). In some embodiments, a single coating precursor is used, while in other embodiments, at least two coating precursors are used. At least one coating precursor contains at least one metal cation required for the coating (e.g., a metal oxide coating).

[0142] An effective coating method for producing the encapsulated materials described herein is atmospheric pressure CVD (APCVD). APCVD can be carried out with simple equipment such as glass products. In some embodiments, a hydrolysis reaction is used to form a (e.g., continuous) metal oxide coating at a temperature in the range from room temperature (about 22 °C~) up to about 180 °C.

[0143] Exemplary precursors for ALD and CVD processes include metal alkyls (e.g., trimethyl or triethyl aluminum, diethyl zinc), volatile metal chlorides (titanium tetrachloride, silicon tetrachloride, aluminum trichloride), silanes, metal alkoxides (titanium isopropoxide, aluminum isopropoxide, silicon ethoxide), compounds having mixed alkyl, halide, hydride, alkoxy, and other groups, and other volatile metal organic compounds, and coating precursors (e.g., metal oxide precursors) containing at least one metal cation. Exemplary co-reactants for coating precursors containing at least one metal cation (e.g., metal oxide precursors containing at least one metal cation) include water, oxygen, ozone, ammonia, and alkylamines. In addition to metal oxides, other inorganic, non-metal coating materials are deposited using a chemical reaction between a coating precursor and a co-reactant for the coating precursor (e.g., a metal nitride coating is deposited using a metal nitride precursor containing at least one metal cation and a co-reactant for the metal nitride precursor).

[0144] Exemplary (e.g., continuous) coatings include non-metallic inorganic materials such as metal (e.g., Al, Si, Ti, Zr, Mg, and Zn) oxides. In some embodiments, the shell material comprises at least 50, 60, 70, 80, 90, or 100 weight % of a single metal oxide, or combinations thereof. Exemplary metal oxides can include forms such as hydroxides and oxyhydroxides, as well as forms containing mixed anions (e.g., in addition to oxides, halides, hydroxyls, small amounts of alkyl or carboxylates, etc.). The shell material is primarily an inorganic material having a carbon content of 20, 10, 5, or 1 weight % or less. Further, the encapsulated basic material can also have a carbon content of 20, 10, 5, or 1 weight % or less. The shell material may further include metal nitrides, metal sulfides, metal oxysulfides, and metal oxynitrides. The coating can be amorphous, crystalline, or a mixed single-phase or multiphase, and can contain one or more cations and one or more anions. In some embodiments, the coating is amorphous alumina with or without some hydroxyls or bound water.

[0145] In some embodiments, the shell has an average thickness of at least 5, 10, 15, 20, or 25 nm. The thickness of the shell can range up to 250, 500, 750, or 1000 nm (1 micrometer). In some embodiments, for example, in the case of an encapsulated dental filling, the thickness of the shell typically ranges up to 100, 150, or 200 nm.

[0146] On a weight % basis, the shell material is typically at least 0.1, 0.2, 0.3, 0.4, or 0.5 weight % of the total encapsulated material. The amount of shell material on a weight % basis can range up to a maximum of 15 or 20 weight % or less of the total encapsulated material, but more typically 10, 9, 8, 7, 6, or 5 weight % or less.

[0147] Particularly useful calcium ion releasing components include basic core materials containing a CaO component, particularly calcium silicates such as 3CaO - SiO2 and 2CaO - SiO2, the surface of which is covered with an inorganic shell material containing Al2O3 or SiO2.

[0148] Suitable calcium ion releasing components are also described in International Publication No. WO 2018 / 102484 (A1) (3M). The content of this reference is incorporated herein by reference.

[0149] The dental composition contains a fluoride ion releasing component.

[0150] The F ion releasing component herein has an F ion releasing ability of 1,500 mg / l (ppm) to 3,500 mg / l (ppm) in 24 hours when 2.5 g of the F ion releasing component is introduced into 50 ml of deionized water.

[0151] The F ion releasing component can typically be characterized by the following features: molecular weight: 110 - 300 g / mol; water solubility: 3 - 20 g / l in water at 23°C, either alone or in combination.

[0152] If the molecular weight of the F ion releasing component is too low, the water solubility is often too high.

[0153] The F ion releasing component is typically present in the following amounts, by weight % relative to the weight of the dental composition: i.e., at least 0.1 wt% or 0.5 wt% or 1 wt%; up to 20 wt% or 15 wt% or 10 wt%, range: 0.1 wt% - 20 wt% or 0.5 wt% - 15 wt% or 1 wt% - 10 wt%.

[0154] Suitable F ion releasing components that can be used include the following formula A n MF m (wherein A is an alkali metal ion or NR4 + and R is C1 - C 18It is alkyl, phenyl or substituted phenyl, M is selected from Ti, Zr, Al, Zn, P, n is from 1 to 3, m is from 3 to ) and those having are exemplified.

[0155] Particularly useful F-ion releasing components found include KZnF3, K2TiF6, and mixtures thereof.

[0156] These F-ion releasing components have been found to be suitable for meeting the aesthetic expectations for dental compositions as they do not adversely affect the opacity of the hardened dental composition.

[0157] Ca-ion releasing components are typically contained in the dental composition in a greater amount (by weight) compared to the amount of the F-ion releasing component.

[0158] The ratio of the Ca-ion releasing component to the F-ion releasing component contained in the dental composition is in the range of 1:0.9 to 1:0.1 or 1:0.7 to 1:0.3 by weight.

[0159] The Ca-ion releasing component and the F-ion releasing component are typically present in the dental composition in an amount sufficient to enable the release of at least 10 ppm of F ions per gram of the hardened composition stored in deionized water at 36°C for 30 days, and at least 2 ppm of Ca ions per gram of the hardened composition stored in deionized water at 36°C for 30 days.

[0160] In certain embodiments, the Ca-ion releasing component and the F-ion releasing component are present in the dental composition in an amount sufficient to enable the release of F ions in the range of 10 ppm to 25 ppm per gram of the hardened composition stored in deionized water at 36°C for 30 days, and Ca ions in the range of at least 2 ppm to 10 ppm per gram of the hardened composition stored in deionized water at 36°C for 30 days.

[0161] The above amount or range is considered sufficient to achieve the desired remineralization effect on the hard tissues of teeth.

[0162] The dental composition may also contain one or more fillers. Suitable fillers include acid-reactive fillers, particularly acid-reactive glasses, and non-acid-reactive fillers.

[0163] The acid-reactive glass can undergo a glass ionomer cement reaction.

[0164] According to one embodiment, the acid-reactive glass has the following characteristics: a) Average particle size: 1 μm to 25 μm, b) (d10 / μm): 0.5 μm to 3 μm, (d50 / μm): 2 μm to 7 μm, (d90 / μm): 6 μm to 30 μm, c) pH value of the dispersion of 1 g of filler stirred in 10 mL of deionized water for 5 minutes: 5 to 10, and can be characterized by the individual or combined values.

[0165] Combinations of features a) and b), or a) and c) may be preferred in some cases.

[0166] If the average particle size of the acid-reactive glass exceeds the range outlined above, the viscosity of the composition obtained when the compositions contained in each part of the parts kit described herein are mixed may not be appropriate, and the desired mechanical properties may be adversely affected.

[0167] If the average particle size of the acid-reactive glass is below the range outlined above, the curing time may be too fast.

[0168] Suitable acid-reactive glasses include aluminosilicate glasses and fluoroaluminosilicate glasses (FAS glasses).

[0169] Acid-reactive glass can be made from a melt containing fluoride, silica, alumina, and other glass-forming elements using techniques well known to those skilled in the art of FAS glass manufacturing.

[0170] Since FAS glass is typically in the form of sufficiently finely divided particles, it can be well mixed with other cement components and functions well when the resulting mixture is used in the oral cavity.

[0171] Suitable FAS glasses are well known to those skilled in the art and are available from a variety of commercial sources, many of which are found in currently available glass ionomer cements such as those marketed under the trade names Ketac™-Molar, or Ketac™-Fil Plus (3M Oral Care), and FUJI™ IX (GC).

[0172] Useful acid-reactive glasses can also be characterized by their Si / Al ratio. Fillers having an Si / Al ratio (by weight %) of less than 1.5 or 1.4 or 1.3 have been found to be particularly useful.

[0173] Suitable acid-reactive glasses are also commercially available, for example, from Schott AG (Germany) or Speciality Glass (US).

[0174] If the amount of acid-reactive glass is too high, it may become more difficult to mix the paste in the parts kit described herein. Further, similarly, it may become difficult to obtain the appropriate viscosity and acceptable mechanical properties of the resulting composition.

[0175] If the amount of acid-reactive glass is too low, it may become more difficult to formulate a suitable paste. Further, the mechanical properties may be inferior.

[0176] The acid-reactive glass is typically present in the following amounts, by weight % relative to the weight of the dental composition: namely, at least 5 wt% or 8 wt% or 10 wt%; up to 70 wt% or 60 wt% or 50 wt%, in the range: 5 wt% to 70 wt% or 8 wt% to 60 wt% or 10 wt% to 50 wt%.

[0177] According to one embodiment, the non-acid-reactive filler has the following characteristics: a) Average particle size: 10 nm to 500 nm, or 10 nm to 200 nm, b) Does not contain particles larger than 2 μm, c) pH value of a dispersion of 1 g of the filler stirred for 5 minutes in 10 mL of deionized water: 4 to 9, and can be characterized by the sole or combined of these.

[0178] Combinations of features a) and b), or b) and c) may be preferred in some cases.

[0179] If the average particle size of the non-acid-reactive filler exceeds the range outlined above, the viscosity of the resulting paste may not be appropriate, and in addition, it may be difficult to obtain the desired mechanical properties.

[0180] If the average particle size of the non-acid-reactive filler is below the range outlined above, the desired viscosity of the resulting paste may not be appropriate.

[0181] Examples of suitable non-acid-reactive fillers are natural or synthetic materials, including but not limited to: kaolin; silica particles (e.g., those available under the trade name "AEROSIL®" such as "OX 50", "130", "150", and "200" silica from Evonic, as well as HDK® such as "H15", "H20", "H2000" from Wacker, and CAB-O-SIL M5 silica from Cabot Corp., etc., submicron fired silica), alumina, titania, and zirconia particles.

[0182] Mixtures of these non-acid-reactive fillers are also envisioned.

[0183] The non-acid-reactive filler may also be provided as a dispersion or sol of particles in a liquid (such as water).

[0184] When the filler is provided as an aqueous dispersion or sol, the amount of water in the aqueous dispersion or sol must be taken into account when the amounts of water and filler in the composition are calculated or measured.

[0185] Suitable non-acid-reactive fillers are also commercially available as aqueous dispersions, for example, under the trade name Levasil® from Obermeier, Bad Berleburg, Germany, starting with type "50 / 50%" (% values indicate the filler content by weight).

[0186] If desired, the particle surface of the non-acid-reactive filler can be surface-treated. Suitable surface treatment agents include silanes, such as trimethoxysilane having an organic functional group for modifying the chemical properties of the particles. Suitable silanes are, for example, silanes that modify acidic properties (having an amino group or a carboxylic acid group), or silanes that modify hydrophobicity / hydrophilicity (having an alkane chain or a polyethylene glycol chain).

[0187] The non-acid-reactive filler may also be X-ray visible and includes particles of metal oxides and metal fluorides. Oxides or fluorides of heavy metals having an atomic number greater than 28 and less than 72 may be preferred. Suitable metal oxides are oxides of yttrium, strontium, barium, zirconium, hafnium, niobium, tantalum, tungsten, bismuth, molybdenum, tin, zinc, lanthanide elements (i.e., elements having an atomic number in the range of 57 to 71, including the end values), cerium, and combinations thereof.

[0188] Particularly preferred metal oxides for imparting radiopacity include lanthanum oxide, zirconium oxide, yttrium oxide, ytterbium oxide, barium oxide, strontium oxide, cerium oxide, and combinations thereof.

[0189] Suitable metal fluorides are, for example, yttrium trifluoride and ytterbium trifluoride.

[0190] According to one embodiment, the non-acid-reactive filler is selected from silica, (alumino)silicate, alumina, and mixtures thereof.

[0191] The non-acid-reactive filler is typically present in the following amounts, by weight % based on the weight of the dental composition: namely, at least 0 wt% or 4 wt% or 6 wt%; up to 40 wt% or 35 wt% or 30 wt%; range: 0 wt% to 40 wt% or 4 wt% to 35 wt% or 6 wt% to 30 wt%.

[0192] The dental composition may also contain a polyacid.

[0193] The polyacid should have a molecular weight sufficient to impart good storage, handling, and mixing properties in glass ionomer materials and to provide good material properties.

[0194] According to one embodiment, the polyacid has the following characteristics being solid (at 23 °C); molecular weight (Mw): about 2,000 g / mol to about 250,000 g / mol or about 4,000 g / mol to about 100,000 g / mol (evaluated against sodium polyacrylate salt standard using gel permeation chromatography) and can be characterized by the sole or combined thereof.

[0195] If the molecular weight of the polyacid is too large, it may be difficult to make the viscosity of the paste obtained when mixing the compositions contained in the parts kit described herein workable. Further, the preparation of the composition may also become difficult. In addition, the resulting mixture or composition may become too sticky (i.e., adhere to the dental instrument used for application).

[0196] If the molecular weight of the polyacid is too low, the viscosity of the resulting paste may be too low and the mechanical properties may be poor.

[0197] Typically, a polyacid is a polymer having a plurality of acidic repeating units.

[0198] The polyacid used for the cement composition described herein substantially does not contain polymerizable groups.

[0199] The polyacid need not be completely water-soluble, but is typically at least sufficiently water-miscible so as not to substantially sediment when combined with other aqueous components.

[0200] The polyacid is curable, for example, in the presence of acid-reactive glass and water, but does not contain ethylenically unsaturated groups.

[0201] That is, the polyacid is a polymer obtained by polymerizing an unsaturated acid. However, by this production method, the polyacid may still contain unavoidable trace amounts (e.g., up to 1, or 0.5, or 0.3 wt% relative to the amount of monomer used) of free monomer.

[0202] Typically, the unsaturated acid is an oxyacid (i.e., an oxygen-containing acid) of carbon, sulfur, phosphorus, or boron. More typically, it is an oxyacid of carbon.

[0203] Suitable polyacids include, for example, polyalkenoic acids, such as homopolymers and copolymers of unsaturated mono-, di-, or tricarboxylic acids.

[0204] Polyalkenoic acids can be prepared by homopolymerization and copolymerization of unsaturated aliphatic carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, glutaconic acid, aconitic acid, citraconic acid, mesaconic acid, fumaric acid, and tiglic acid.

[0205] Suitable polyacids also include alternating copolymers of maleic acid and ethylene (such as those with a molar ratio of 1:1).

[0206] Suitable polyacids are also described in the following documents: U.S. Patent No. 4,209,434 (Wilson et al.) and U.S. Patent No. 4,360,605 (Schmitt et al.). The content regarding the description of the polyacids in these documents is incorporated herein by reference.

[0207] Suitable polyacids are also included as an aqueous solution in the liquid component of commercially available products such as those manufactured by 3M Oral Care (such as Ketac™ Fil Plus Handmix) or GC (such as Fuji™ IX GP Handmix).

[0208] The amount of polyacid should be sufficient to react with the acid-reactive glass and provide an ionomer composition with the desired setting properties.

[0209] If the amount of polyacid is too high, it may be difficult to make the viscosity of the paste obtained when mixing the compositions contained in the parts kit described herein workable. Furthermore, the preparation of the composition may become difficult. In addition, the resulting mixture or composition may become too sticky (i.e., adhere to the dental instruments used for application).

[0210] The polyacid is typically present in the following amounts, by weight % relative to the weight of the dental composition: i.e., at least 1 wt% or 4 wt% or 6 wt%; up to 25 wt% or 20 wt% or 15 wt%, in the range: 1 wt% - 25 wt% or 4 wt% - 20 wt% or 6 wt% - 15 wt%.

[0211] The dental composition may also contain water. Typically, deionized water is used.

[0212] If the amount of water is too low, the hardening of the glass ionomer cement reaction may be affected.

[0213] If the amount of water is too high, it may be difficult to obtain a workable viscosity of the resulting paste. Furthermore, it becomes difficult to achieve the desired mechanical properties, and the paste may separate during storage.

[0214] When water is present, the water is typically present in weight % relative to the weight of the dental composition, in the following amounts: namely, at least 0.25 wt% or 0.5 wt% or 1 wt%; up to 20 wt% or 15 wt% or 10 wt%, in the range: 0.25 wt% to 20 wt% or 0.5 wt% to 15 wt% or 1 wt% to 10 wt%.

[0215] The dental composition can also contain additives.

[0216] Examples of additives that can be added include dyes, pigments, photo bleachable colorants, stabilizers, plasticizers, retarders, and mixtures thereof.

[0217] Examples of dyes or pigments that can be used include titanium dioxide or zinc sulfide (lithopone), red iron oxide 3395, Bayferrox™ 920 Z Yellow, Neazopon™ Blue 807 (copper phthalocyanine-based dye) or Helio™ Fast Yellow ER. These additives can be used for individual coloring of the dental composition.

[0218] Examples of photobleachable colorants that may be present include rose bengal, methylene violet, methylene blue, fluorescein, eosin yellow, eosin Y, ethyl eosin, eosin blueish, eosin B, erythrosine B, erythrosine yellowish blend, toluidine blue, 4’,5’-dibromofluorescein, and blends thereof. Further examples of photobleachable colorants can be found in U.S. Patent No. 6,444,725.

[0219] Additional additives that can be added include stabilizers, particularly free radical scavengers such as substituted and / or unsubstituted hydroxyaromatic compounds (e.g., butylated hydroxytoluene (BHT), hydroquinone, hydroquinone monomethyl ether (MEHQ), 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, 2-(2’-hydroxy-5’-methacryloyloxyethylphenyl)-2H-benzotriazole, and phenothiazine).

[0220] Further additives that can be added include inhibitors (e.g., 1,2-diphenylethylene), and plasticizers (including polyethylene glycol derivatives, polypropylene glycol, low molecular weight polyesters, dibutyl phthalate, dioctyl, dinonyl and diphenyl, di(isononyl adipate), tricresyl phosphate, paraffin oil, glycerol triacetate, bisphenol A diacetate, ethoxylated bisphenol A diacetate, and silicone oil).

[0221] Additives need not be present and may be completely absent. However, if present, they are typically present in amounts that are not harmful to the intended purpose.

[0222] Additives are typically present in weight percentages relative to the weight of the dental composition, in the following amounts: i.e., at least 0 wt% or 0.05 wt% or 0.1 wt%; up to 15 wt% or 10 wt% or 5 wt%, range: 0 wt% - 15 wt% or 0.05 wt% - 10 wt% or 0.1 wt% - 5 wt%.

[0223] In certain embodiments, the dental composition has the following amounts of each component: Polymerizable component having an acidic moiety: 0.5 wt% - 15 wt%, Polymerizable component having no acidic moiety: 1 wt% - 50 wt%, Polyacid: 1 wt% - 25 wt%, Water: 0.25 wt% - 20 wt%, Acid-reactive glass: 5 wt% - 70 wt%, Non-acid-reactive filler: 0 wt% - 40 wt%, Ca ion-releasing component: 0.5 wt% - 30 wt%, F ion-releasing component: 0.1 wt% - 20 wt%, Redox initiator system including an oxidizing agent, a reducing agent and optionally a transition metal component: 0.1 wt% - 5 wt%, Photoinitiator: 0 wt% - 2 wt%, Additives: 0 wt% - 15 wt%, and wt% are relative to the weight of the dental composition.

[0224] In certain embodiments, the dental composition comprises the following amounts of each component: Polymeric component having an acidic moiety: 1 wt% to 10 wt%, Polymeric component having no acidic moiety: 5 wt% to 40 wt%, Polyacid: 4 wt% to 20 wt%, Water: 0.5 wt% to 15 wt%, Acid-reactive glass: 5 wt% to 50 wt%, Non-acid-reactive filler: 4 wt% to 35 wt%, Ca ion-releasing component: 1 wt% to 25 wt%, F ion-releasing component: 0.5 wt% to 15 wt%, Redox initiator system comprising an oxidizing agent, a reducing agent and optionally a transition metal component: 0.3 wt% to 5 wt%, Photoinitiator: 0.01 wt% to 1 wt%, Additives: 0 wt% to 10 wt%, and wt% is based on the weight of the dental composition.

[0225] The dental composition is typically provided as a parts kit comprising an acidic part or paste and a non-acidic part or paste.

[0226] The acidic part and the non-acidic part are typically provided in a ratio of 3:1 to 1:3 or 2:1 to 1:2 by volume. A ratio of 1:1 by volume may be preferred.

[0227] The components of the parts kit are typically provided in a form that avoids unwanted reactions or interactions between them.

[0228] The acidic part or paste typically comprises a polymeric component having an acidic moiety, preferably in an amount of 1 wt% to 20 wt%, optionally, a polymeric component having no acidic moiety, preferably in an amount of 0 wt% to 50 wt% or 5 wt% to 40 wt%, a hydroperoxide component, preferably in an amount of 0.1 wt% to 5 wt%, Optionally, a transition metal component is included in an amount preferably of 0 wt% to 0.5 wt% or 0.001 wt% to 0.5 wt%. A polyacid is included in an amount preferably of 1 wt% to 30 wt%. Optionally, a non-acid-reactive filler is included in an amount preferably of 0 wt% to 50 wt% or 5 wt% to 50 wt%. Water is included in an amount preferably of 0.5 wt% to 20 wt% or 1 wt% to 20 wt%, and Optionally, an additive is included in an amount of 0 wt% to 10 wt%. The wt% is based on the amount of the acidic part or the paste. The non-acidic part or the paste typically includes a polymerizable component having no acidic part in an amount preferably of 1 wt% to 60 wt% or 5 wt% to 40 wt%.

[0229] Optionally, a photoinitiator is included in an amount preferably of 0 wt% to 2 wt% or 0.01 wt% to 1 wt%. A polymerizable thiourea component is included in an amount preferably of 0.1 wt% to 3 wt%. Acid-reactive glass is included in an amount preferably of 15 wt% to 70 wt%. Optionally, a non-acid-reactive filler is included in an amount preferably of 0 wt% to 30 wt% or 1 wt% to 20 wt%. Optionally, an additive is included in an amount preferably of 0 wt% to 10 wt%. A Ca ion-releasing component is included in an amount preferably of 5 wt% to 50 wt%, and An F ion-releasing component is included in an amount preferably of 1 wt% to 30 wt%. These are based on the non-acidic part or the paste.

[0230] According to certain embodiments, the dental composition includes the following components: NaF in an amount greater than 0.5 or 0.2 wt%, anhydrous AlF3 in an amount greater than 0.5 or 0.2 wt%, CaCO3 in an amount greater than 0.5 or 0.2 wt%, CaCl2 in an amount greater than 0.5 or 0.2 wt%, Does not contain, either alone or in combination, an amount of Ca(OH)2 that exceeds 0.5 or 0.2 wt%, where wt% is relative to the weight of the dental composition.

[0231] The presence of these components can increase the release of calcium ions and fluoride ions from the dental composition in an undesirable manner, resulting in exceeding the solubility product of calcium fluoride and forming insoluble calcium fluoride.

[0232] The dental composition can be used by combining and mixing the respective components to form the composition. If desired, a speed mixer or kneader can be used. If necessary, the manufacturing is carried out under savelight conditions.

[0233] The dental compositions described herein are typically stored within a suitable packaging material or device.

[0234] If the dental composition is provided as a parts kit containing two different parts or pastes, the parts or pastes may be contained in separate sealable vessels or receptacles (e.g., made from plastic or glass).

[0235] For use, the physician can take an appropriate amount of the contained composition from the vessel and manually mix that amount on a mixing plate.

[0236] According to a preferred embodiment, the different parts or pastes are contained in separate compartments of a storage device.

[0237] The storage device typically comprises two compartments for storing the respective parts, and each compartment is equipped with a nozzle for delivering the respective part. Once an appropriate amount has been delivered, the part can then be manually mixed on a mixing plate.

[0238] According to another preferred embodiment, the storage device has an interface for receiving a static mixing chip. The mixing chips are used to mix the respective pastes. Static mixing chips are commercially available, for example, from the SulzerMixpac company.

[0239] Suitable storage devices include cartridges, syringes and tubes.

[0240] The storage device typically comprises two housings or compartments, which have a front end with a nozzle, and a rear end, and at least one piston movable within the housing or compartment.

[0241] Usable cartridges are described, for example, in US Patent Application Publication No. 2007 / 0090079 (A1) (Keller), or US Patent No. 5,918,772 (Keller et al.), the disclosures of which are incorporated by reference. Some of the cartridges that can be used are commercially available, for example, from Sulzer Mixpac AG (Switzerland). Usable static mixing chips are described, for example, in US Patent Application Publication No. 2006 / 0187752 (A1) (Keller), or US Patent No. 5,944,419 (Streiff), the disclosures of which are incorporated by reference. The mixing chips that can be used are also commercially available from Sulzer Mixpac AG (Switzerland).

[0242] Other suitable storage devices are described, for example, in WO 2010 / 123800 (3M), WO 2005 / 016783 (3M), WO 2007 / 104037 (3M), WO 2009 / 061884 (3M) (in particular, the device shown in FIG. 14 of WO 2009 / 061884 (3M)) or WO 2015 / 073246 (3M) (in particular, the device shown in FIG. 1 of WO 2015 / 07346). These storage devices have the shape of a syringe. The contents of these references are hereby incorporated by reference into this specification.

[0243] Alternatively, although less preferably, the paste / paste composition described herein may be provided in two individual syringes, and the individual pastes may be mixed by hand prior to use.

[0244] Accordingly, the present invention also relates to a device for storing the parts kit described herein, the device comprising two compartments, compartment A and compartment B, compartment A containing the non-acidic part or paste, compartment B containing the acidic part or paste, the non-acidic part or paste and the acidic part or paste being as described herein, and both compartment A and compartment B comprising an interface for receiving the entrance orifice of a nozzle or a static mixing tip.

[0245] The mixing ratio of the non-acidic part or paste to the acidic part or paste is typically from 3:1 to 1:3, preferably from 2:1 to 1:2, more preferably 1:1, by volume.

[0246] The contents of the above-mentioned references are hereby incorporated by reference into this specification.

[0247] The present invention also relates to a parts kit.

[0248] The parts kit includes, alone or in combination, the dental composition described herein and the following items: a dental milling block; a dental crown; a hybrid chip; a dental adhesive or adhesive system; a conditioning liquid for crown material or tooth material.

[0249] Suitable dental milling blocks typically include a porous zirconia material containing yttria as a phase stabilizing component and a coloring component. Examples of dental milling blocks are described in U.S. Patent Application Publication No. 2017 / 020639 (Jahns et al.) and U.S. Patent Application Publication No. 2015 / 238291 (A1) (Hauptmann et al.).

[0250] A suitable dental adhesive is an acidic dental composition having a fairly low viscosity (e.g., 0.01 Pa * s to 3 Pa * s) at 23°C. The dental adhesive interacts directly with the enamel or dentin surface of the tooth. The dental adhesive is typically a one-component composition, is radiation curable, and includes an ethylenically unsaturated component having an acidic moiety, an ethylenically unsaturated component having no acidic moiety, water, a sensitizer, a reducing agent, and additives. Examples of dental adhesives are described in U.S. Patent Application Publication No. 2020 / 0069532 (A1) (Thalacker et al.) and U.S. Patent Application Publication No. 2017 / 0065495 (A1) (Eckert et al.), U.S. Patent Application Publication No. 2019 / 231494 (A1) (Dittmann et al.).

[0251] Accordingly, the parts kit contains parts or components that can be used together in a method for restoring a missing tooth.

[0252] The dental milling block is used to machine a dental restoration, the dental adhesive is used to treat the tooth surface to be restored, and the dental composition described herein is used to bond a dental restoration machined from the dental milling block.

[0253] Examples of commercially available dental crowns that can be used include stainless steel crowns (3M Oral Care), or plastic crowns made of polyacetal, polyacrylate, polymethacrylate (PMMA), polyaryl ether ketone (PAEK), polyether ketone (PEK), polyether ether ketone (PEEK), polyether imide (PEI), polyether sulfone (PES), and polysulfone (PSU).

[0254] Suitable commercially available dental crowns are also described in U.S. Patent No. 8,651,867 (B2) (Zilberman), International Publication No. 2007 / 098485 (A2) (Nusmile), International Publication No. 2008 / 033758 (A2) (3M), and U.S. Patent Application Publication No. 2007 / 0196792 (A1) (Johnson et al.). The contents of the above-mentioned references are incorporated herein by reference.

[0255] Examples of commercially available dental adhesives or adhesive systems that can be used include Scotchbond™ Universal Adhesive (3M Oral Care), Scotchbond™ Universal Plus Adhesive (3M Oral Care).

[0256] Examples of commercially available conditioners that can be used include Ketac™ conditioner (3M Oral Care) and Cavity Conditioner (GC).

[0257] The dental composition is typically provided as RM-GIC.

[0258] Dental compositions are typically used to bond dental restorations to the surface of prepared teeth. Dental restorations typically have the shape of a dental crown or bridge, veneer, onlay or inlay. The material of the dental restoration may comprise, consist essentially of, or consist of ceramic (e.g., zirconia, alumina), glass-ceramic (e.g., lithium disilicate), metal (e.g., gold), metal alloy or composite material.

[0259] Due to the presence of Ca ions and F ion-releasing components, dental compositions can be useful in contributing to a method of remineralizing defective teeth in the oral cavity of a mammal by releasing calcium and fluoride ions onto the surface of the defective teeth.

[0260] The entire disclosures of the patents, patent documents, and publications cited herein are incorporated by reference in their entirety as if each was individually incorporated. Various modifications and variations of the present invention will be apparent to those skilled in the art without departing from the scope and spirit of the present invention. The above specification, examples and data provide a description of the manufacture and use of the compositions of the invention and the 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 practiced without departing from the spirit and scope of the present invention.

[0261] The following examples are given to illustrate the present invention.

Examples

[0262] Unless otherwise indicated, all parts and percentages are by weight, all water is deionized water, and all molecular weights are weight average molecular weights. Further, unless otherwise indicated, all experiments were carried out under ambient conditions (23 °C, 1013 mbar).

[0263] Method Viscosity of a single part If desired, the viscosity of the single part of the composition / paste composition can be measured at 23 °C under a controlled shear rate using a Physica MCR301 rheometer (Anton Paar, Graz, Austria) having a plate / plate geometry. The plate diameter is 15 mm and the separation gap between the plates is 0.5 mm. The shear rate is 20 s -1 -1.

[0264] Viscosity of the two-component composition If desired, the viscosity of the two-component composition can be measured using a Physica MCR 301 rheometer (Anton Paar, Graz, Austria) having a plate / plate geometry under controlled vibration at 28 °C. The plate diameter is 8 mm and the separation gap between the plates is 0.75 mm. The vibration frequency is 1.25 Hz and the deflection is 1.75%.

[0265] Particle size (suitable for micro-sized particles) If desired, the particle size distribution, including the volume-based particle size (d50), can be determined by laser diffraction using a Mastersizer 2000 (Malvern) particle size detection device that applies the Fraunhofer approximation. During the measurement, the sample is typically accurately dispersed using ultrasonic waves. In the case of water-insoluble particles, water is typically used as the dispersant.

[0266] Particle size (suitable for nano-sized particles) If desired, particle size measurements can be carried out using a light scattering particle size analyzer equipped with a red laser having a wavelength of 633 nm (obtained from Malvern Instruments Inc., Westborough, MA under the trade name "ZETA SIZER-Nano Series, Model ZEN3600"). Each sample is analyzed in a 1 square centimeter polystyrene sample cuvette. The sample is diluted 1:100, for example, 1 g of the sample is added to 100 g of deionized water and mixed. The sample cuvette is filled with approximately 1 gram of the diluted sample. Next, the sample cuvette is placed in the instrument and equilibrated at 25°C. The instrument parameters are set as follows: refractive index of the dispersant 1.330, viscosity of the dispersant 0.8872 mPa * s, refractive index of the material 1.43, and absorption value of the material 0.00 units. Next, the automatic particle size measurement procedure is executed. The instrument automatically adjusts the laser beam position and attenuator settings to obtain the best measured particle size values.

[0267] The light scattering particle size analyzer irradiates the sample with a laser and analyzes the intensity fluctuations of the light scattered from the particles at an angle of 173 degrees. To calculate the particle size, the method of Photon Correlation Spectroscopy (PCS) by the instrument can be used. PCS uses the intensity of the fluctuating light to measure the Brownian motion of the particles in the liquid. Next, the particle size is calculated as the diameter of a sphere moving at the measured velocity.

[0268] The intensity of the light scattered by the particles is proportional to the sixth power of the particle diameter. The Z-average size or cumulant average is the average calculated from the intensity distribution, and the calculation is based on the assumptions that the particles are unimodal, monodisperse, and spherical. The relevant function calculated from the intensity of the fluctuating light is the intensity distribution and its average. The average of the intensity distribution is calculated based on the assumption that the particles are spherical. Both the Z-average size and the intensity distribution average are more sensitive to larger particles than to smaller particles.

[0269] The volume distribution indicates the percentage of the total volume of particles corresponding to particles within a given size range. The volume average particle size is the particle size corresponding to the average of the volume distribution. Since the volume of a particle is proportional to the cube of the diameter, this distribution is less sensitive to larger particles than the Z-average size. Thus, the volume average is typically a smaller value than the Z-average size. Within the scope of this document, the Z-average size is referred to as the "average particle size".

[0270] pH value If desired, the pH value of the paste can be measured as follows: Contact a wet pH-sensitive paper or test stick with the composition to be analyzed.

[0271] Testing of buffer solution 0.4 g of the material to be tested was added to a glass beaker. Then, 24 mL of deionized water and 16 mL of pH 4 buffer solution (BDH 5018, VWR International, Radnor, PA) were added to the beaker using an 800 Dosino dosing unit (Metrohm, Herisau, Switzerland), and mechanically stirred using an 802 stirring unit (Metrohm). The pH of the solution was continuously measured using an InLab Expert pH meter (51343100, Mettler Toledo, Columbus, OH) until it exceeded 8, at which point the test was terminated and the time to pH = 8 was recorded.

[0272] Shear bond strength (SBS) Bovine teeth were ground flat to expose dentin, polished (grit 320 sandpaper), rinsed with water, and gently air-dried. A sandblasted and silanized steel rod (diameter = 4 mm) was bonded to the prepared teeth using the paste mixture to be tested. A load of 20 g / mm 2 was applied to the bonded rod at 36 °C for 10 minutes and then removed. The samples were then stored for 22 hours. Then, a shear bond strength (SBS) test was performed on the specimens using a Zwick 010 (Germany) tensile testing machine (speed = 0.75 mm / min).

[0273] Measurement of fluoride and calcium release of individual components Introduce 2.5 g of the Ca ion release component into 50 ml of deionized water having a pH of 2 at a temperature of 23 °C for 24 hours. The concentration of Ca ions is then measured using a Ca ion selective electrode.

[0274] Introduce 2.5 g of the F ion release component into 50 ml of deionized water having a pH of 7 at a temperature of 23 °C for 24 hours. The concentration of F ions is then measured using a Ca ion selective electrode.

[0275] The F ion and Ca ion release capacities (ppm; in mg / l) of specific components are shown in Table 2 below.

[0276] Measurement of fluoride and calcium release of hardened samples The release of calcium ions was measured using an inductively coupled plasma optical spectrometer (ICP; Optima (trademark) 8000, Perkin Elmer (registered trademark)). The release of fluoride was measured using a fluoride selective electrode (FSE; Titrando (trademark), Metrohm (trademark)).

[0277] ICP: First, three standard solutions were measured for calibration (eluent: 65% HNO3). Then, the extractant was tested. Two disk-shaped test pieces (diameter 15 mm; height 1.5 mm) were prepared by manually mixing on a mixing pad for 20 seconds (SF-S:SF-G = 1.00:1.15 weight / weight). The test pieces were clamped and cured at 36 °C and 100% humidity for 1 hour. Then, the samples were demolded and stored at 36 °C for 23 hours. Thereafter, two disk-shaped test pieces (total weight approximately 1.4 g) were placed in 50 ml of deionized water and stored at 36 °C. After 1 day, the extractant was analyzed. The sample was nebulized and ionized in an argon plasma. The individual elements were excited by interaction with excited state argon in the plasma. When each atom returned from the excited state to the ground state, they emitted light at wavelengths characteristic of the elements from which they originated. After the test, the two disk-shaped test pieces were immersed again in fresh deionized water until the next test.

[0278] FSE: First, four standard (buffer) solutions were measured for calibration. The reference electrode was Ag / AgCl. Two disc-shaped test pieces (diameter 15 mm; height 1.5 mm) were prepared by manually mixing on a mixing pad for 20 seconds (SF-S:SF-G = 1.00:1.15 weight / weight). The test pieces were clamped and cured at 36 °C and 100% humidity for 1 hour. Then, the samples were demolded and stored at 36 °C for 23 hours. Thereafter, two disc-shaped test pieces (total weight approximately 1.4 g) were placed in 50 ml of deionized water and stored at 36 °C. After one day, the extractant was analyzed. 10 ml of the sample solution was mixed with 10 ml of the buffer solution and the test was conducted.

[0279] The ion amount was measured after one day, one week, and one month. The cumulative value after one month is shown in Table 6.

[0280] Water contact angle If desired, the water contact angle can be measured as follows: A droplet of a 10 wt% ethanol solution of the component to be tested is applied onto the surface of a dental mixing pad. The ethanolic solvent is evaporated to obtain a coated surface (approximately 4 cm 2 in size). A water droplet is placed on that surface and the progress of the water contact angle is analyzed at 23 °C (Kruess Advance software 1.13.1.31401). The average value obtained within 0 seconds to 12 seconds after the placement of the droplet is taken.

[0281] Curing time If desired, the curing time can be measured by recording the viscosity of the curing mixture over time. The viscosity is measured using a Physica MCR 301 rheometer (Anton Paar, Graz, Austria) having a plate / plate geometry at 28 °C. From the recorded graph 2, two measurement points indicating the start and end of curing are taken. The two measurement points are: A) Start of curing = the time when the viscosity becomes three times the starting viscosity (measured 60 seconds after the start of mixing). B) Curing time = the time when the shear stress reaches 100,000 Pa.

[0282]

Table 1

[0283]

Table 2

[0284] General procedure The paste was prepared by first weighing all the components and then mixing them at high speed.

[0285] Example 1 The following paste was prepared:

[0286]

Table 3

[0287]

Table 4

[0288]

Table 5

[0289]

Table 6

[0290] The use of a combination of a composite F-ion releasing component and a CaO-containing filler encapsulated resulted in a higher calcium ion release than the combination of a CaO-containing filler encapsulated with NaF, although the same amount of fluoride ions was added to both formulations (Examples 2 and 3).

[0291] While not wishing to be bound by any particular theory, it is thought that the aqueous solubility of each component may have an impact. In particular, the aqueous solubility and / or ion release ability of the F-ion releasing component should not be too high in order to reduce the risk of formation of insoluble CaF2.

Claims

1. A dental composition comprising: a polymerizable component; an initiator suitable for curing the polymerizable component; a Ca ion-releasing component having a Ca ion-releasing ability of 400 mg / l to 700 mg / l in 24 hours when 2.5 g of the Ca ion-releasing component is introduced into 50 ml of deionized water at pH 2; an F ion-releasing component having an F ion-releasing ability of 500 mg / l to 3,500 mg / l in 24 hours when 2.5 g of the F ion-releasing component is introduced into 50 ml of deionized water at pH 7; and wherein the amount of the Ca ion-releasing component contained in the dental composition is greater in weight than the amount of the F ion-releasing component.

2. The dental composition according to claim 1, wherein the Ca ion-releasing component comprises a basic core material that releases Ca ions and an inorganic shell material comprising a metal oxide surrounding the core.

3. The Ca ion-releasing component is a basic core material containing a calcium silicate such as a CaO component, particularly 3CaO-SiO ２ and 2CaO-SiO ２ and an inorganic shell material containing Al ２ O ３ or SiO ２ surrounding the core, and the dental composition according to claim 1 or 2.

4. The dental composition according to any one of claims 1 to 3, wherein the F ion-releasing component is characterized by the following features: molecular weight: 110 to 300 g / mol; water solubility: 3 to 20 g / l at 23 °C, either alone or in combination.

5. wherein the F ion-releasing component is represented by formula A ｎ MF ｍ (wherein A is an alkali metal ion or NR ４ ＋ and R is C １ to C １８ alkyl, phenyl or substituted phenyl, M is selected from Ti, Zr, Al, Zn, P, n is 1 to 3, and m is 3 to 6) The dental composition according to any one of claims 1 to 4, having

6. The F ion-releasing component is KZnF ３ , K ２ TiF ６ , and the dental composition according to any one of claims 1 to 5, which is selected from the group consisting of these and mixtures thereof.

7. The dental composition according to any one of claims 1 to 6, wherein the ratio of the Ca ion-releasing component contained in the dental composition to the F ion-releasing component is in the range of 1:0.9 to 1:0.1 by weight.

8. The Ca ion-releasing component and the F ion-releasing component are present in the dental composition in an amount sufficient to enable the release of: at least 10 ppm of F ions per gram of the cured composition stored in deionized water at 36 °C for 30 days, and at least 2 ppm of Ca ions per gram of the cured composition stored in deionized water at 36 °C for 30 days, The dental composition according to any one of claims 1 to 7.

9. The dental composition according to any one of claims 1 to 8, wherein the initiator comprises a redox initiator system comprising an oxidizing agent, a reducing agent, and optionally a transition metal component, and the reducing agent is a thiourea component containing a (meth)acrylate moiety.

10. The dental composition comprises: a polymerizable component having an acidic moiety; a polymerizable component having no acidic moiety; a polyacid; water; an acid-reactive glass; A Ca ion-releasing component comprising a basic core containing a material that releases Ca ions and an inorganic shell material containing a metal oxide surrounding the core, Formula A ｎ MF ｍ (wherein A is an alkali metal ion or NR ４ ＋ and R is C １ ~ C １８ alkyl, phenyl or substituted phenyl, M is selected from Ti, Zr, Al, Zn, P, n is 1 to 3, and m is 3 to 6), and an F ion-releasing component having A redox initiation system comprising an oxidizing agent, a reducing agent, and optionally a transition metal component, Optionally, a non-acid-reactive filler, Optionally, an additive A resin-modified glass ionomer cement composition comprising the same, a dental composition, particularly the dental composition according to any one of claims 1 to 9.

11. The following amounts of the components: A polymerizable component having an acidic moiety in an amount of 0.5% to 15% by weight, A polymerizable component having no acidic moiety in an amount of 1% to 50% by weight, A polyacid in an amount of 1% to 25% by weight, An acid-reactive glass in an amount of 5% to 70% by weight, Water in an amount of 0.25% to 20% by weight, A non-acid-reactive filler in an amount of 0% to 40% by weight, A Ca ion-releasing component comprising a basic core containing a material that releases Ca ions and an inorganic shell material containing a metal oxide surrounding the core, in an amount of 0.5% to 30% by weight, An F-ion releasing component having, in an amount of 0.1% to 20% by weight, of formula A ｎ MF ｍ wherein A is an alkali metal ion or NR ４ ＋ wherein R is C １ to C １８ alkyl, phenyl or substituted phenyl, M is selected from Ti, Zr, Al, Zn, P, n is 1 to 3, and m is 3 to 6), and A redox initiation system comprising an oxidizing agent, a reducing agent, and optionally a transition metal component, in an amount of 0.2% to 6% by weight, A photoinitiator in an amount of 0% to 15% by weight, An additive in an amount of 0% to 15% by weight, Including, wherein the weight percentages are based on the weight of the entire composition, the dental composition according to any one of claims 1 to 10.

12. The following components: NaF in an amount of more than 0.5% by weight, An amount of AlF anhydride exceeding 0.5% by weight ３ , An amount of CaCO exceeding 0.5% by weight ３ , An amount of CaCl exceeding 0.5% by weight ２ , An amount of Ca(OH) exceeding 0.5% by weight ２ , Not included alone or in combination, wherein the weight percentages are based on the weight of the entire composition, the dental composition according to any one of claims 1 to 11.

13. Provided as a parts kit including an acidic part and a non-acidic part, wherein the acidic part and the non-acidic part are preferably provided in a ratio of 3:1 to 1:3 by volume, The acidic part is, A polymerizable component having an acidic moiety, A polymerizable component having no acidic moiety, An oxidizing component, A polyacid, A non-acid-reactive filler, Water, Including, The non-acidic part is, A polymerizable component having no acidic moiety, Optionally, a photoinitiator, A reducing agent, preferably a (polymerizable) thiourea reducing agent, An acid-reactive glass, A Ca ion-releasing component, An F ion-releasing component, Including, the dental composition according to any one of claims 1 to 12.

14. A parts kit comprising the dental composition according to any one of claims 1 to 13 and the following items: a dental adhesive, a dental milling block, a prefabricated dental crown, alone or in combination.

15. A dental composition for use in a method of remineralizing missing teeth in the oral cavity of a mammal, the dental composition according to any one of claims 1 to 13, wherein the method comprises the step of fixing a dental restoration to the surface of the missing tooth using the dental composition according to any one of claims 1 to 13.

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