Carious tooth structure-restoring agent, carious tooth structure-restoring agent kit, and dental adhesive kit

Abstract

To provide a carious tooth structure-restoring agent that is convenient for treating multiple teeth at once, and can be used for preventive treatment of root caries and for early caries treatment in an aesthetic manner without discoloring the treated area.SOLUTION: A carious tooth structure-restoring agent comprises: a compound (a) having an acidic group represented by the following formula (I): R1-Xk [in formula (I), R1 represents an organic group having 40 or less carbon atoms, which may or may not have at least one (meth)acryloyloxy group; X represents an acidic group; k represents an integer of 1 or 2; when k is 2, the two acidic groups X are the same as or different from each other]; a metal ion (b); water (c); and a hydrophilic solvent (d); and is substantially free of a crosslinkable polymerizable monomer. The metal ion (b) comprises at least one metal ion selected from the group consisting of a strontium ion (b1) and an aluminum ion (b2).SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a dental caries dentin restorative agent, a dental caries dentin restorative agent kit, and a dental adhesive kit. More specifically, the present invention relates to a novel and useful dental caries dentin restorative agent, and a dental caries dentin restorative agent kit and a dental adhesive kit using the same.

Background Art

[0002] In recent years, due to the so-called 8020 movement of "maintaining more than 20 of one's own teeth even at the age of 80", the number of remaining teeth in the elderly has been increasing. However, the remaining teeth of the elderly are subject to gingival recession due to periodontal disease or the like, and are exposed to the root surface. The exposed root surface is susceptible to dental caries. That is, the increase in the number of remaining teeth in the elderly brings about the problem of root surface caries peculiar to the elderly caused by the exposure of the root surface. Therefore, in combination with the increase in the elderly population, dealing with root surface caries has become an urgent issue.

[0003] Currently, as a treatment method for root surface caries, filling and restoration with composite resin or glass ionomer cement are widely used in the same manner as the treatment of coronal caries. However, when the caries progresses below the gingival margin, it becomes extremely difficult to remove the caries and perform the filling operation. In addition, the caries may progress over the entire circumference of the root surface, and the restoration of such caries becomes even more difficult.

[0004] Root surface caries often occur in multiple teeth at once and generally require time for restoration. Therefore, not only the dental medical staff who perform the treatment, but also the physical and mental burdens borne by the patients who receive the treatment are large.

[0005]

[0006] ​Thus, root caries is a dental disease for which an appropriate treatment method has not yet been established, and there has been a demand for a new material suitable for this disease.

[0007] In addition, Patent Document 1 describes a treatment material or root canal filling material for hypersensitivity, which consists of two liquids, A and B, containing substances that rapidly form hardly soluble precipitates upon mixing. In Patent Document 1, it is described that the liquid A and then the liquid B are applied to the dentin, the liquid A is an aqueous solution of a mixture composed of one or more substances selected from sodium salts, potassium salts, and lithium salts of inorganic acids or organic acids, and the liquid B is a mixture composed of one or more substances selected from chlorides, nitrates, and acetates of calcium, zinc, strontium, magnesium, aluminum, barium, iron, copper, silver, lead, or tin, or an aqueous solution of calcium chloride, zinc chloride, or strontium chloride. Further, Patent Document 2 describes a pretreatment material composition for improving adhesiveness by applying it to carious dentin. And it is described that at least one acidic compound selected from the group consisting of nitric acid, phosphoric acid, citric acid, (meth)acrylic acid, and poly(meth)acrylic acid is used as a compound capable of demineralizing dentin to be included in the composition. Furthermore, Patent Document 3 proposes including a metal salt of a phosphate ester compound in a material for adhering dentin to a repair material such as metal, ceramic, or composite resin.

[0008] However, Patent Documents 1 to 3 do not describe restoring caries to a state close to sound dentin, and the inventions described in Patent Documents 1 to 3 did not consider the treatment of initial caries.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0010] As described above, root caries is a dental disease for which an appropriate treatment method has not yet been established, and a new material suitable for this disease has been demanded.

[0011] In view of the above problems, the present invention provides a caries-affected dentin restorative agent that has the simplicity of being able to treat multiple teeth at once, has excellent aesthetics without discoloration of the treatment site, and can perform preventive measures and initial caries treatment for root caries.

Means for Solving the Problems

[0012] As a result of intensive studies to solve the above problems, the present inventor has found a new finding that demineralized dentin is strengthened in a short time by applying a specific composition containing a compound having an acidic group, a strontium compound or an aluminum compound, water, and a hydrophilic solvent to the tooth surface. In addition, it has also been found that the tooth surface coated with the above specific composition can acquire caries resistance, and through further repeated studies, the present invention has been completed.

[0013] That is, the present invention includes the following inventions. [1] A compound (a) having an acidic group represented by the following formula (I), R 1 -X k ···Formula (I) [In formula (I), R 1 represents an organic group having 40 or fewer carbon atoms with or without at least one (meth)acryloyloxy group. X represents an acidic group. k represents an integer of 1 or 2. When k is 2, the two acidic groups X are the same as each other or different from each other.] containing metal ions (b), water (c), and a hydrophilic solvent (d), The metal ion (b) contains at least one metal ion selected from the group consisting of strontium ion (b1) and aluminum ion (b2). A dental caries-affected dentin restorative agent substantially free of a crosslinkable polymerizable monomer. [2] The dental caries-affected dentin restorative agent according to [1] above, wherein the compound (a) having an acidic group is represented by the following formula (II). R 1 -((X m- ) a ·(H + ) b ) k ··· Formula (II) [In formula (II), R 1 and k have the same meanings as defined in formula (I). X m- represents an m-valent acid anion group. m represents an integer of 1, 2, or 3. a and b represent integers of 1, 2, or 3 in the relationship of am = b. ] [3] The dental caries-affected dentin restorative agent according to [1] or [2] above, wherein the compound (a) having an acidic group is a compound represented by the following formula (III). R 2 -R 3 -O-P(=O)(-OH)2 ··· Formula (III) [In formula (III), R 2 represents a (meth)acryloyloxy group or hydrogen. R 3 represents an alkylene group having 6 to 20 carbon atoms. ] [4] The dental caries-affected dentin restorative agent according to any one of [1] to [3] above, wherein the strontium ion (b1) is derived from at least one strontium compound selected from the group consisting of compounds represented by the following formula (IV). (Sr 2+ ) c ·(Y n- ) d ··· Formula (IV) [In formula (IV), Y n- represents an anion that serves as a counter ion to the strontium ion. n represents an integer of 1, 2, or 3. c and d represent integers of 1, 2, or 3 in the relationship of 2c = nd. ] [5] The dental caries dentin restorative agent according to any one of [1] to [4] above, wherein the strontium ion (b1) is derived from at least one strontium compound selected from the group consisting of SrCl2, Sr(OH)2, and SrF2. [6] The dental caries dentin restorative agent according to any one of [1] to [3] above, wherein the aluminum ion (b2) is derived from at least one aluminum compound selected from the group consisting of the compounds represented by the following formula (V). (Al 3+ ) e ·(Z s- ) f ··· Formula (V) [In formula (V), Z s- represents an anion that serves as a counter ion to the aluminum ion. s represents an integer of 1, 2, or 3. e and f represent integers of 1, 2, or 3 that satisfy the relationship 3e = sf.] [7] The dental caries dentin restorative agent according to any one of [1] to [3] and [6] above, wherein the aluminum ion (b2) is derived from at least one aluminum compound selected from the group consisting of AlCl3, Al(OH)3, AlF3, and AlK(SO4)2. [8] The dental caries dentin restorative agent according to any one of [1] to [7] above, which is a dentin strengthening agent. [9] The dental caries dentin restorative agent according to any one of [1] to [8] above, wherein the organic compound other than the compound (a) having an acidic group and the hydrophilic solvent (d) is 5 parts by mass or less in 100 parts by mass of the dental caries dentin restorative agent.

[10] A dental caries dentin restorative agent kit comprising a liquid A and a liquid B, wherein the liquid B and the liquid A are applied to the tooth surface in this order, The liquid A is the dental caries dentin restorative agent [A] according to any one of [1] to [9] above, The liquid B is a liquid [B] containing calcium ions (e1) and water, which is a dental caries dentin restorative agent kit.

[11] The dental caries dentin restorative agent kit according to

[10] above, wherein the calcium ion (e1) is derived from at least one calcium compound selected from the group consisting of the compounds represented by the following formula (VII). (Ca 2+ ) g·(W r- ) h ···Formula (VII) [In Formula (VII), W r- represents an anion that is a counter ion of calcium ion (e1). r represents an integer of 1, 2, or 3. g and h represent integers of 1, 2, or 3 that satisfy the relationship 2g = rh.]

[12] The dental caries-affected dentin restorative agent kit according to

[10] or

[11] above, wherein the calcium ion (e1) is derived from at least one calcium compound selected from the group consisting of CaCl2, CaBr2, CaI2, CaSO4, Ca(HCO3)2, and Ca(CH3COO)2.

[13] A dental adhesive kit comprising the dental caries-affected dentin restorative agent according to any one of [1] to [9] above and a dental adhesive [C].

[14] A dental adhesive kit comprising the dental caries-affected dentin restorative agent kit according to any one of

[10] to

[12] above and a dental adhesive [C]. [Advantages of the Invention]

[0014] According to the present invention, it is possible to provide a dental caries-affected dentin restorative agent that can restore the dentin that has been demineralized and weakened by dental caries to a strength closer to that of sound dentin while ensuring high aesthetics by a simple procedure of applying it to the tooth surface. [Modes for Carrying Out the Invention]

[0015] In this specification, the "strength" in the case of "the dentin is strong" means mechanical strength and resistance to demineralization by acid. Also, in this specification, the upper limit value and the lower limit value of a numerical range (content of each component, value calculated from each component, and each physical property, etc.) can be appropriately combined. Also, in this specification, the "dental caries-affected dentin restorative agent" means a dental material that can restore the dentin that has been demineralized and weakened by dental caries to be closer to sound dentin when applied to the dentin, and is a dental material that brings about at least the repair of the initially demineralized dentin in incipient dental caries. The "dental caries-affected dentin restorative agent" may further have an action of strengthening the dentin and an action of preventing dental caries of the dentin.

[0016] [Dental caries dentin restorative agent] The dental caries dentin restorative agent according to an embodiment of the present invention contains a compound (a) having an acidic group, R 1 -X k ··· Formula (I) [In Formula (I), R 1 represents an organic group having 40 or fewer carbon atoms which may or may not have at least one (meth)acryloyloxy group. X represents an acidic group. k represents an integer of 1 or 2. When k is 2, the two acidic groups X are the same as or different from each other.] contains a metal ion (b), water (c), and a hydrophilic solvent (d), the metal ion (b) contains at least one metal ion selected from the group consisting of strontium ion (b1) and aluminum ion (b2), and substantially does not contain a crosslinkable polymerizable monomer. In the present specification, “(meth)acryloyloxy” is a general term for methacryloyloxy and acryloyloxy. The same applies to other similar terms.

[0017] The mechanism by which the effects of the present invention are obtained by the above dental caries dentin restorative agent is not limited to this, but the present inventor presumes as follows. By applying the above dental caries dentin restorative agent to the tooth surface, deposits are formed on the entire coated tooth surface. This deposit is formed when an acidic mixture composed of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d) demineralizes the smear layer and the dentin surface layer portion of the dentin and penetrates into the dentin, and the compound (a) having an acidic group, strontium ion (b1) or aluminum ion (b2), and the inorganic components of the demineralized dentin are complexed and precipitated on the tooth surface. It is considered to be a substance formed by this formation, and it is presumed that this formation enhances the mechanical strength of the dentin and further imparts an anti-caries effect.

[0018] Generally, in the case of dental caries with substantial defects, it is necessary to restore the crown form with a restorative material. At this time, by using the above-mentioned dental caries dentin restorative agent, since the dentin decalcified and weakened by dental caries can be restored to a strength close to that of healthy dentin, the adhesion of the restorative material to the dentin can be made more stable, and a highly reliable restoration can be achieved.

[0019] In this specification, the action of enhancing the mechanical strength of carious dentin and the action of enhancing the resistance of sound dentin to acid decalcification brought about by the above-mentioned dental caries dentin restorative agent may be collectively referred to as "dentin strengthening".

[0020] <Compound (a) having an acidic group> The compound (a) having an acidic group represented by the above formula (I) is a compound having an acidic group in which an acidic composition mixed with water (c) and a hydrophilic solvent (d) exhibits an acid etching effect and a primer treatment effect on dentin, and is a component that gives a decalcifying action and a penetrating action.

[0021] The compound (a) having an acidic group represented by the above formula (I) is preferably represented by the following formula (II). R 1 -((X m- ) a ·(H + ) b ) k ···Formula (II) [In formula (II), R 1 and k have the same meaning as defined in formula (I). X m- represents an m-valent acid anion group. m represents an integer of 1, 2, or 3. a and b represent integers of 1, 2, or 3 in the relationship of am = b.]

[0022] Examples of the compound (a) having an acidic group include compounds having at least one acidic group such as a phosphate group, a pyrophosphate group, a thiophosphate group, a phosphonic acid group, a sulfonic acid group, and a carboxylic acid group. Specific examples of the compound (a) having an acidic group are given below.

[0023] Examples of the phosphate group-containing compounds include octyl dihydrogen phosphate, decyl dihydrogen phosphate, dodecyl dihydrogen phosphate, tetradecyl dihydrogen phosphate, hexadecyl dihydrogen phosphate, octadecyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl dihydrogen phosphate, 3-(meth)acryloyloxypropyl dihydrogen phosphate, 4-(meth)acryloyloxybutyl dihydrogen phosphate, 5-(meth)acryloyloxypentyl dihydrogen phosphate, 6-(meth)acryloyloxyhexyl dihydrogen phosphate, 7-(meth)acryloyloxyheptyl dihydrogen phosphate, 8-(meth)acryloyloxyoctyl dihydrogen phosphate, 9-(meth)acryloyloxynonyl dihydrogen phosphate, 10-(meth)acryloyloxydecyl dihydrogen phosphate, 11-(meth)acryloyloxyundecyl dihydrogen phosphate, 12-(meth)acryloyloxydodecyl dihydrogen phosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen phosphate, 20-(meth)acryloyloxyicosyl dihydrogen phosphate, bis[2-(meth)acryloyloxyethyl] hydrogen phosphate, bis[4-(meth)acryloyloxybutyl] hydrogen phosphate, bis[6-(meth)acryloyloxyhexyl] hydrogen phosphate, bis[8-(meth)acryloyloxyoctyl] hydrogen phosphate, bis[9-(meth)acryloyloxynonyl] hydrogen phosphate, bis[10-(meth)acryloyloxydecyl] hydrogen phosphate, 1,3-di(meth)acryloyloxypropyl dihydrogen phosphate, 2-(meth)acryloyloxyethyl phenyl hydrogen phosphate, 2-(meth)acryloyloxyethyl-2-bromoethyl hydrogen phosphate, and bis[2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl] hydrogen phosphate.

[0024] Examples of the pyrophosphate group-containing compounds include bis[2-(meth)acryloyloxyethyl] pyrophosphate, bis[4-(meth)acryloyloxybutyl] pyrophosphate, bis[6-(meth)acryloyloxyhexyl] pyrophosphate, bis[8-(meth)acryloyloxyoctyl] pyrophosphate, and bis[10-(meth)acryloyloxydecyl] pyrophosphate.

[0025] Examples of the thiophosphate group-containing compounds include 2-(meth)acryloyloxyethyl dihydrogen thiophosphate, 3-(meth)acryloyloxypropyl dihydrogen thiophosphate, 4-(meth)acryloyloxybutyl dihydrogen thiophosphate, 5-(meth)acryloyloxypentyl dihydrogen thiophosphate, 6-(meth)acryloyloxyhexyl dihydrogen thiophosphate, 7-(meth)acryloyloxyheptyl dihydrogen thiophosphate, 8-(meth)acryloyloxyoctyl dihydrogen thiophosphate, 9-(meth)acryloyloxynonyl dihydrogen thiophosphate, 10-(meth)acryloyloxydecyl dihydrogen thiophosphate, 11-(meth)acryloyloxyundecyl dihydrogen thiophosphate, 12-(meth)acryloyloxydodecyl dihydrogen thiophosphate, 16-(meth)acryloyloxyhexadecyl dihydrogen thiophosphate, and 20-(meth)acryloyloxyicosyl dihydrogen thiophosphate.

[0026] Examples of the phosphonate group-containing compounds include 2-(meth)acryloyloxyethyl phenylphosphonate, 5-(meth)acryloyloxypentyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl-3-phosphonopropionate, 10-(meth)acryloyloxydecyl-3-phosphonopropionate, 6-(meth)acryloyloxyhexyl phosphonoacetate, and 10-(meth)acryloyloxydecyl phosphonoacetate.

[0027] Examples of the sulfonic acid group-containing compound include 2-(meth)acrylamide-2-methylpropanesulfonic acid, styrenesulfonic acid, and 2-sulfoethyl (meth)acrylate.

[0028] Examples of the carboxylic acid group-containing compound include a compound having one carboxy group in the molecule and a compound having a plurality of carboxy groups in the molecule.

[0029] Examples of the compound having one carboxy group in the molecule include (meth)acrylic acid, N-(meth)acryloylglycine, N-(meth)acryloylaspartic acid, O-(meth)acryloyltyrosine, N-(meth)acryloyltyrosine, N-(meth)acryloylphenylalanine, N-(meth)acryloyl-p-aminobenzoic acid, N-(meth)acryloyl-o-aminobenzoic acid, p-vinylbenzoic acid, 2-(meth)acryloyloxybenzoic acid, 3-(meth)acryloyloxybenzoic acid, 4-(meth)acryloyloxybenzoic acid, N-(meth)acryloyl-5-aminosalicylic acid, N-(meth)acryloyl-4-aminosalicylic acid, 2-(meth)acryloyloxyethyl hydrogen succinate, 2-(meth)acryloyloxyethyl hydrogen phthalate, and 2-(meth)acryloyloxyethyl hydrogen maleate.

[0030] Examples of the compound having a plurality of carboxy groups in the molecule include 6-(meth)acryloyloxyhexane-1,1-dicarboxylic acid, 9-(meth)acryloyloxynonane-1,1-dicarboxylic acid, 10-(meth)acryloyloxydecane-1,1-dicarboxylic acid, 11-(meth)acryloyloxyundecane-1,1-dicarboxylic acid, 12-(meth)acryloyloxydodecane-1,1-dicarboxylic acid, 13-(meth)acryloyloxytetradecane-1,1-dicarboxylic acid, 4-(meth)acryloyloxyethyl trimellitate, 4-(meth)acryloyloxybutyl trimellitate, 4-(meth)acryloyloxyhexyl trimellitate, 4-(meth)acryloyloxydecyl trimellitate, 2-(meth)acryloyloxyethyl-3'-(meth)acryloyloxy-2'-(3,4-dicarboxybenzoyloxy)propyl succinate.

[0031] The compound (a) having an acidic group may be a compound represented by the following formula (III). R 2 -R 3 -O-P(=O)(-OH)2 ··· Formula (III) [In formula (III), R 2 represents a (meth)acryloyloxy group or hydrogen. R 3 represents an alkylene group having 6 to 20 carbon atoms.]

[0032] Among the compounds (a) having these acidic groups, phosphate group- or pyrophosphate group-containing compounds are preferable because they exhibit better deposit formation on dentin, and particularly, phosphate group-containing compounds are preferable. Among them, in terms of showing high dentin demineralization and high deposit formation, a divalent phosphate group-containing compound having an alkyl group with 6 to 20 carbon atoms as the main chain in the molecule, or a divalent phosphate group-containing compound having an alkylene group with 6 to 20 carbon atoms as the main chain in the molecule like the compound represented by the above formula (III) is more preferable, and a divalent phosphate group-containing compound having an alkyl group or an alkylene group with 8 to 12 carbon atoms as the main chain in the molecule such as dodecyl dihydrogen phosphate and 10-methacryloyloxydecyl dihydrogen phosphate is most preferable.

[0033] The compound (a) having an acidic group may be used alone or in combination of two or more. From the viewpoint of easily ensuring the effects of the present invention, the content of the compound (a) having an acidic group is preferably 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more with respect to the total 100% by mass of the compound (a) having an acidic group, water (c), and hydrophilic solvent (d) in the above dental caries-affected dentin restorative agent. Also, it is preferably 70% by mass or less, and more preferably 60% by mass or less. In other words, the content of the compound (a) having an acidic group is preferably 10 to 70% by mass with respect to the total 100% by mass of the compound (a) having an acidic group, water (c), and hydrophilic solvent (d).

[0034] <Metal ion (b)> As described above, the metal ion (b) contains at least one metal ion selected from the group consisting of strontium ion (b1) and aluminum ion (b2). The metal ion (b) includes strontium ion (b1) and may or may not include aluminum ion (b2), or may include aluminum ion (b2) and may or may not include strontium ion (b1), or may include both strontium ion (b1) and aluminum ion (b2). Among these, it is preferable to include strontium ion (b1) and not include aluminum ion (b2), or to include both aluminum ion (b2) and strontium ion (b1). In addition, the metal ion (b) may include metal ions other than strontium ion (b1) and aluminum ion (b2), but from the viewpoints of preventing dental caries and suppressing the progression of dental caries, etc., it is preferable that it is only strontium ion (b1), only aluminum ion (b2), or only strontium ion (b1) and aluminum ion (b2).

[0035] (Strontium ion (b1) and strontium compound (b01)) The strontium ion (b1) is derived from the strontium compound (b01). When the strontium compound (b01) is dissolved by the compound (a) having an acidic group, the strontium ion (b1) is contained in the above dental caries-affected dentin restorative agent. The strontium ion (b1) is preferably derived from at least one strontium compound selected from the group consisting of compounds represented by the following formula (IV). (Sr 2+ ) c ·(Y n- ) d ···Formula (IV) [In formula (IV), Y n- represents an anion that becomes a counter ion of the strontium ion. n represents an integer of 1, 2, or 3. c and d represent integers of 1, 2, or 3 that satisfy the relationship 2c = nd.]

[0036] Specific strontium compounds (b01) include at least one strontium compound selected from the group consisting of SrCl2, Sr(OH)2, and SrF2, and preferably SrCl2. The strontium compound (b01) used when preparing the above dental caries dentin restorative agent may be used alone or in combination of two or more. Therefore, the strontium ions (b1) in the dental caries dentin restorative agent may be a single type or two or more types.

[0037] The amount of the strontium compound (b01) incorporated into the above dental caries dentin restorative agent is preferably 0.3% by mass or more, more preferably 0.6% by mass or more, and still more preferably 1.0% by mass or more, based on the total mass (100% by mass) of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d), from the viewpoint of facilitating the formation of deposits for dentin strengthening. Also, from the viewpoint of suppressing excessive neutralization of the acidic groups of the compound (a) having an acidic group and ensuring good demineralization and penetration effects, it is preferably 10% by mass or less, more preferably 7.0% by mass or less, and still more preferably 5.0% by mass or less. In other words, the content of the strontium compound (b01) is preferably 0.3 to 10% by mass based on the total mass of 100% by mass of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d).

[0038] Also, the content of the strontium ions (b1) in the above dental caries dentin restorative agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and still more preferably 0.3% by mass or more, based on the total mass (100% by mass) of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d), from the same viewpoint. Also, it is preferably 8.0% by mass or less, more preferably 5.6% by mass or less, and still more preferably 4.0% by mass or less. In other words, the content of the strontium ions (b1) is preferably 0.1 to 8.0% by mass based on the total mass of 100% by mass of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d). The content of strontium ions (b1) in the dental caries dentin restorative agent can be calculated based on the blending amount of the strontium compound (b01), and can also be determined by measuring the content of strontium ions (b1) with an ICP emission spectroscopic analyzer and then calculated therefrom.

[0039] (Aluminum ions (b2) and aluminum compound (b02)) Aluminum ions (b2) are derived from the aluminum compound (b02). When the aluminum compound (b02) is dissolved by the compound (a) having an acidic group, aluminum ions (b2) are contained in the above dental caries dentin restorative agent. Aluminum ions (b2) are preferably derived from at least one aluminum compound (b02) selected from the group consisting of compounds represented by the following formula (V). (Al 3+ ) e ·(Z s- ) f ···Formula (V) [In formula (V), Z s- represents an anion that becomes a counter ion of aluminum ions. s represents an integer of 1, 2, or 3. e and f represent integers of 1, 2, or 3 that satisfy the relationship 3e = sf.]

[0040] Specific examples of the aluminum compound (b02) include at least one aluminum compound (b02) selected from the group consisting of AlCl3, Al(OH)3, AlF3, and AlK(SO4)2, and preferably AlCl3 and Al(OH)3. The aluminum compound (b02) used when preparing the above dental caries dentin restorative agent may be used alone or in combination of two or more. Therefore, the aluminum ions (b2) in the dental caries dentin restorative agent may be a single type or two or more types.

[0041] The amount of the aluminum compound (b02) formulated in the above dental caries dentin restorative agent is preferably 0.3% by mass or more, more preferably 0.6% by mass or more, still more preferably 1.0% by mass or more, from the viewpoint of facilitating the formation of deposits for dentin strengthening, with respect to the total mass (100% by mass) of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d). Also, from the viewpoint of suppressing excessive neutralization of the acidic group of the compound (a) having an acidic group and ensuring good demineralization and penetration effects, it is preferably 10% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.0% by mass or less. In other words, the content of the aluminum compound (b02) is preferably 0.3 to 10% by mass with respect to the total 100% by mass of the masses of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d).

[0042] Also, the content of aluminum ions (b2) in the above dental caries dentin restorative agent is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.3% by mass or more, from the same viewpoint, with respect to the total mass (100% by mass) of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d). Also, it is preferably 8.0% by mass or less, more preferably 5.6% by mass or less, still more preferably 4.0% by mass or less. In other words, the content of aluminum ions (b2) is preferably 0.1 to 8.0% by mass with respect to the total 100% by mass of the masses of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d). The content of aluminum ions (b2) in the dental caries dentin restorative agent can be calculated based on the blending amount of the aluminum compound (b02), and can also be determined by measuring the content of aluminum ions (b2) with an ICP emission spectroscopic analyzer and calculating from it.

[0043] <Water (c)> Water (c) preferably does not contain impurities that have an adverse effect, and distilled water or ion-exchanged water is preferred. The content of water (c) in the above dental caries dentin restorative agent is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass with respect to the total 100% by mass of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d).

[0044] <Hydrophilic solvent (d)> The hydrophilic solvent (d) means an organic compound having a solubility in water at 25 ° C of 10% by mass or more, preferably having a solubility of 30% by mass or more, and more preferably being soluble in water at any ratio at 25 ° C.

[0045] The hydrophilic solvent (d) may be a single compound or a mixture of a plurality of compounds.

[0046] Examples of the hydrophilic solvent (d) include ethanol, 2-propanol, 2-methyl-2-propanol, acetone, tetrahydrofuran, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,3-dihydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, 2-((meth) acryloyloxy) ethyltrimethylammonium chloride, polyethylene glycol di (meth) acrylate (having 9 or more oxyethylene groups), N, N-dimethylaminoethyl methacrylate, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N, N-bis (2-hydroxyethyl) (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-ethoxymethyl (meth) acrylamide, diacetone (meth) acrylamide, 4-(meth) acryloylmorpholine, N-trimethylolmethyl-N-methyl (meth) acrylamide, N-[3-(dimethylamino) propyl] acrylamide, and (meth) acrylamide represented by the following formula (VI).

[0047] [Chemical formula] [In the above formula (VI), R 3 and R 4 are each independently an alkyl group having 1 to 3 carbon atoms which may have a substituent (such as a hydroxyl group, etc.) (such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, etc.), and R 5 is a hydrogen atom or a methyl group.]

[0048] Among these hydrophilic solvents (d), ethanol, 2-propanol, 2-methyl-2-propanol, acetone, tetrahydrofuran, 2-hydroxyethyl (meth)acrylate, 2,3-dihydroxypropyl (meth)acrylate, N,N-dimethylaminoethyl methacrylate, diacetone (meth)acrylamide and hydrophilic monofunctional (meth)acrylamide monomers are preferred, and ethanol, 2-propanol, 2-hydroxyethyl (meth)acrylate, N,N-dimethylaminoethyl methacrylate, and the monofunctional (meth)acrylamide monomer represented by formula (VI) are more preferred. The hydrophilic solvent (d) may be blended alone or in combination of two or more.

[0049] The hydrophilic solvent (d) functions as a co-solvent for the compound (a) having an acidic group and water (c). The content of the hydrophilic solvent (d) in the above dental caries-affected dentin restorative agent is preferably 1 to 90% by mass, more preferably 5 to 80% by mass, and even more preferably 10 to 70% by mass with respect to the total mass of 100% by mass of the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d).

[0050] [Organic compounds other than the compound (a) having an acidic group and the hydrophilic solvent (d)] The above-mentioned dental caries dentin restorative agent substantially does not contain a crosslinkable polymerizable monomer which is an organic compound other than the compound (a) having an acidic group and the hydrophilic solvent (d). Here, "substantially does not contain" specifically means that in 100 parts by mass of the above-mentioned dental caries dentin restorative agent, the crosslinkable polymerizable monomer is 5 parts by mass or less, preferably 3 parts by mass or less. Examples of the crosslinkable polymerizable monomer include hydrophobic crosslinkable polymerizable monomers having no acidic group, such as aromatic bifunctional monomers, aliphatic bifunctional monomers, and trifunctional or higher functional monomers. The dental caries dentin restorative agent according to the embodiment of the present invention substantially does not contain a crosslinkable polymerizable monomer, thereby avoiding inhibiting the action of complexing the compound (a) having an acidic group, the strontium ion (b1) or the aluminum ion (b2), and the inorganic components of the demineralized dentin, and promoting the formation of deposits by these.

[0051] Examples of the aromatic difunctional monomer include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-(meth)acryloyloxy-2-hydroxypropoxy)phenyl]propane, 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxyethoxyphenyl)propane, 2-(4-(meth)acryloyloxydiethoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2-(4-(meth)acryloyloxydipropoxyphenyl)-2-(4-(meth)acryloyloxytriethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypropoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxyisopropoxyphenyl)propane.

[0052] Examples of the aliphatic difunctional monomer include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,3 - butanediol di(meth)acrylate, 1,5 - pentanediol di(meth)acrylate, 1,6 - hexanediol di(meth)acrylate, 1,10 - decanediol di(meth)acrylate, 1,2 - bis(3 - methacryloyloxy - 2 - hydroxypropoxy)ethane, 2,2,4 - trimethylhexamethylene bis(2 - carbamoyloxyethyl)di(meth)acrylate, N - methacryloyloxyethyl acrylamide, N - methacryloyloxypropyl acrylamide, N - methacryloyloxybutyl acrylamide, N-(1 - ethyl-(2 - methacryloyloxy)ethyl)acrylamide, N-(2-(2 - methacryloyloxyethoxy)ethyl)acrylamide.

[0053] Examples of the trifunctional or higher functional monomers include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, N,N-(2,2,4 - trimethylhexamethylene)bis[2-(aminocarboxy)propane - 1,3 - diol]tetra(meth)acrylate, 1,7 - diacryloyloxy - 2,2,6,6 - tetra(meth)acryloyloxymethyl - 4 - oxyheptane.

[0054] It is preferable that the above-mentioned dental caries dentin restorative agent substantially does not contain organic compounds other than the above-mentioned crosslinkable polymerizable monomer, the compound (a) having an acidic group, and the hydrophilic solvent (d). Specifically, "substantially does not contain" here means that in 100 parts by mass of the above-mentioned dental caries dentin restorative agent, the organic compounds other than the compound (a) having an acidic group and the hydrophilic solvent (d) are 5 parts by mass or less, preferably 3 parts by mass or less. Examples of substances other than the compound (a) having an acidic group and the hydrophilic solvent (d) among the organic compounds other than the crosslinkable polymerizable monomer include, for example, · Photoinitiators such as (bis)acylphosphine oxides, thioxanthones, or quaternary ammonium salts of thioxanthones, ketals, α-diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, α-aminoketone-based compounds; · Polymerization accelerators such as aldehydes, thiol compounds, and aminobenzoic acid ester compounds; · Antibacterial substances such as cetylpyridinium chloride, benzalkonium chloride, (meth)acryloyloxydodecylpyridinium bromide, (meth)acryloyloxyhexadecylpyridinium chloride, (meth)acryloyloxydodecylammonium chloride, triclosan, and 12-methacryloyloxydodecylpyridinium bromide; · Monofunctional polymerizable monomers such as 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, and octafluoropentyl (meth)acrylate; may be mentioned.

[0055] Examples of the (bis)acylphosphine oxides used as the above-mentioned photoinitiator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and sodium salt of 2,4,6-trimethylbenzoylphenylphosphine oxide. Examples of α-diketones used as the above photoinitiator include diacetyl, benzyl, camphorquinone, 2,3-pentanedione, 2,3-octanedione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, and acenaphthenequinone.

[0056] Specific examples of aldehydes used as the above polymerization accelerator include terephthalaldehyde and benzaldehyde derivatives. Examples of benzaldehyde derivatives include dimethylaminobenzaldehyde, p-methoxybenzaldehyde, p-ethoxybenzaldehyde, p-n-octyloxybenzaldehyde, and the like. Specific examples of thiol compounds used as the above polymerization accelerator include 2-mercaptobenzoxazole, decanethiol, 3-mercaptopropyltrimethoxysilane, and thiobenzoic acid. Specific examples of amino benzoate compounds used as the above polymerization accelerator include ethyl 4-(N,N-dimethylamino)benzoate, methyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-N,N-(dimethylamino)benzoate, 2-[(meth)acryloyloxy]ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, and n-butyl 4-(N,N-dimethylamino)benzoate.

[0057] <Other Components> The above dental caries dentin restorative may further contain one or more other components. Examples of such other components include pH adjusters, polymerization inhibitors, ultraviolet absorbers, thickeners, colorants (dyes, pigments, etc.), fluorescent agents, fragrances, and the like. Further, the above dental caries dentin restorative may contain, as the above other component, a fluoride ion-releasing substance such as sodium fluoride, potassium fluoride, sodium monofluorophosphate, lithium fluoride, ytterbium fluoride, and the like. Further, the above dental caries dentin restorative may contain a metal compound such as calcium hydroxide, calcium chloride, silver oxide, and the like. There are no particular limitations on the blending amount of other components, and an amount that can achieve the necessary effects may be used. However, from the perspective of easily ensuring the effectiveness of dentin strengthening and the treatment of initial caries, in 100 parts by mass of the above-mentioned caries-dentin restorative agent, it is preferably 0.01 to 1 part by mass, more preferably 0.05 to 0.5 part by mass, and even more preferably 0.07 to 0.3 part by mass. However, when the other component is an organic compound, its blending amount is 5 parts by mass or less, more preferably 3 parts by mass or less, in 100 parts by mass of the above-mentioned caries-dentin restorative agent.

[0058] In addition, as the caries-dentin restorative agent according to an embodiment of the present invention, as long as the effects of the present invention are achieved, as the other component, it may contain calcium ions. However, from the perspective of more easily achieving the effects of the present invention, it is preferably substantially free of calcium ions. Since the above-mentioned caries-dentin restorative agent is substantially free of calcium ions, in the process of forming deposits caused by the above-mentioned caries-dentin restorative agent, at least one of the action of precipitation by the complexation of the compound (a) having an acidic group, strontium ion (b1) or aluminum ion (b2), and the inorganic components of the demineralized dentin, and the action of depositing on the dentin surface, the involvement of calcium ions can be reduced, and it is presumed that the deposits can be formed more efficiently.

[0059] The above-mentioned calcium ions are derived from calcium compounds. When the calcium compound is dissolved by the compound (a) having an acidic group, calcium ions are contained in the caries-dentin restorative agent. The calcium ions are derived from, for example, the same calcium compound as the calcium ions contained in the liquid B described later. More specific calcium compounds that can be a source of calcium ions contained in the caries-dentin restorative agent as other components include at least one calcium compound selected from the group consisting of CaO, CaCl2, Ca(OH)2, and CaF2.

[0060] Here, "substantially free of calcium ions" specifically means that the calcium ion content in 100% by mass of the above-mentioned dental caries-affected dentin restorative agent is 5% by mass or less, preferably 3% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and even more preferably 0.05% by mass or less. In other words, in this specification, "substantially free of calcium ions" means that the calcium ion content is 0 to 5% by mass in 100% by mass of the dental caries-affected dentin restorative agent, preferably 0 to 3% by mass, more preferably 0 to 1% by mass, still more preferably 0 to 0.1% by mass, and even more preferably 0 to 0.05% by mass. Also, in this specification, the calcium ion content in the above-mentioned dental caries-affected dentin restorative agent can be calculated from the blending amount of the calcium compound that generates calcium ions. It can also be determined by measurement using an ICP emission spectroscopic analyzer.

[0061] [Method for producing dental caries-affected dentin restorative agent] As a method for producing the dental caries-affected dentin restorative agent according to an embodiment of the present invention, the compound (a) having an acidic group, the strontium compound (b01) or the aluminum compound (b02), water (c), and the hydrophilic solvent (d) can be added in any order, and finally, the solid component, the strontium compound (b01) or the aluminum compound (b02), is dissolved in the liquid mixture composition containing the compound (a) having an acidic group, water (c), and the hydrophilic solvent (d) to obtain the above-mentioned dental caries-affected dentin restorative agent.

[0062] [Use of dental caries-affected dentin restorative agent] The above-mentioned dental caries-affected dentin restorative agent can be provided as a liquid of one dosage form and can be applied to the dentin using a cotton ball, a small piece of sponge, a small brush, an applicator brush, etc. If necessary after application, air is blown with a three-way syringe or the like, and the treatment is completed by drying the evaporating components. Since it is a simple surgical procedure, even when treating a large number of teeth, the stress on both the operator and the patient is minimal.

[0063] Since the dentin-strengthening effect brought about by the dental caries-affected dentin restorative agent according to the embodiment of the present invention is particularly remarkable for dentin, the above dental caries-affected dentin restorative agent can be preferably applied as a "dentin-strengthening agent".

[0064] In addition, the dental caries-affected dentin restorative agent according to the embodiment of the present invention can be suitably used for the uses of preventing the onset of dental caries, suppressing the progression of incipient dental caries, suppressing secondary dental caries, and suppressing a dental hypersensitivity floor.

[0065] In the above dentin-strengthening agent, from the viewpoint of making it difficult to inhibit the action of complexing the compound (a) having an acidic group, the metal ion (b), and the inorganic components of the demineralized dentin, in 100 parts by mass of the dental caries-affected dentin restorative agent, the organic compound other than the compound (a) having an acidic group and the hydrophilic solvent (d) is preferably 5 parts by mass or less, more preferably 4.9 parts by mass or less, still more preferably 4.8 parts by mass or less. There is no particular limitation on the lower limit, and it may be 0 parts by mass. Also, it may be more than 0 parts by mass, 1 part by mass or more, or 2 parts by mass or more.

[0066] [Dental caries-affected dentin restorative agent kit] The dental caries-affected dentin restorative agent kit according to the embodiment of the present invention comprises a liquid A and a liquid B, and is a dental caries-affected dentin restorative agent kit in which the above liquid B and liquid A are applied to the tooth surface in this order. The above liquid A is any of the above-described dental caries-affected dentin restorative agents, and the above liquid B contains calcium ions (e1) and water.

[0067] By using the above dental composition kit, the liquid B, which is a liquid containing calcium ions and water, is applied to the tooth surface, particularly to the site affected by incipient dental caries on the exposed root surface, and further, the liquid A containing the above components (a) to (d) and substantially free of a crosslinkable polymerizable monomer is applied thereon, whereby it becomes easier to restore the dental caries-affected dentin.

[0068] In the above dental caries-affected dentin restorative agent kit, from the viewpoint of promoting the restoration of dental caries, it is preferable that the calcium ions (e1) are derived from at least one calcium compound selected from the group consisting of the compounds represented by the following formula (VII). (Ca 2+ ) g ·(W r- ) h ···Formula (VII) [In Formula (VII), W r- represents an anion that serves as a counter ion to calcium ion (e1). r represents an integer of 1, 2, or 3. g and h represent integers of 1, 2, or 3 that satisfy the relationship 2g = rh.]

[0069] Also, in the above dental caries dentin restorative agent kit, from the viewpoint of promoting the restoration of dental caries, it is preferable that the calcium ion (e1) contained in the liquid B is derived from at least one calcium compound selected from the group consisting of CaCl2, CaBr2, CaI2, CaSO4, Ca(HCO3)2, and Ca(CH3COO)2.

[0070] [Dental adhesive kit] The first dental adhesive kit according to an embodiment of the present invention includes a dental caries dentin restorative agent [A] and a dental adhesive [C] when the above-described dental caries dentin restorative agent is used as the dental caries dentin restorative agent [A]. The dental adhesive [C] is not particularly limited, and various known dental adhesives as dental bonding materials can be used. The dental adhesive [C] is usually an adhesive composition containing an acidic component and water, and may further contain a polymerizable monomer, a polymerization initiator, a solvent, and other compounding agents as necessary. Particularly preferred examples of the dental adhesive [C] include dental bonding materials containing an acidic group-containing (meth)acrylic polymerizable monomer, a water-soluble polymerizable monomer, and a polymerization initiator, as described in International Publication No. 2013 / 145621, International Publication No. 2015 / 190099, etc. The dental adhesive [C] may be of a one-component type that can be used as it is, or of a two-component type in which the A component and the B component are mixed immediately before use. Examples of commercially available products of the dental adhesive [C] include the dental bonding material "Clearfil (registered trademark) Universal Bond QuickER" manufactured by Kuraray Noritake Dental Co., Ltd.

[0071] Since the dental adhesive kit described above has the dental caries dentin restorative agent [A] containing the above components (a) to (d) and substantially no organic compounds other than components (a) and (d), application to the dental treatment site brings about strengthening of dentin and repair of incipient demineralized dentin. Then, by supplying the dental adhesive [C] to the application surface of the dental caries dentin restorative agent [A], it becomes possible to firmly adhere filling materials such as composite resin and coating materials, etc. that are further supplied later, and thus repair the tooth well. Also, in these operations, at least the dental caries dentin restorative agent [A] only requires a simple treatment such as application, and it is also possible to ensure high aesthetics.

[0072] The second dental adhesive kit according to an embodiment of the present invention includes the above-described dental caries dentin restorative agent kit and the dental adhesive [C]. Since the dental caries dentin restorative agent kit consists of the dental caries dentin restorative agent [A] and the liquid [B] containing calcium ions and water, application to the dental treatment site in the order of [B], [A] brings about strengthening of dentin and repair of incipient demineralized dentin at a higher level. Therefore, by supplying the dental adhesive [C] to the application surfaces of [B] and [A], and firmly adhering filling materials such as composite resin and coating materials, etc. that are further supplied later, the tooth can be repaired better.

[0073] In the above second dental adhesive kit, the details of the dental caries dentin restorative agent [A], the liquid [B] containing calcium ions and water, and the dental adhesive [C] are as described above.

[0074] The present invention includes embodiments in which the above configurations are variously combined within the scope of the technical idea of the present invention as long as the effects of the present invention are achieved.

Examples

[0075] Hereinafter, the dental caries dentin restorative agent according to the present invention, the dental caries dentin restorative agent kit according to the present invention, and the dental adhesive kit according to the present invention will be specifically described using examples, but these are not limited to the following examples.

[0076] [Preparation of Test Samples for Dentin Tensile Test (Sound Dentin)] The labial surface of bovine mandibular incisors was polished with #80 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water to expose a flat surface of dentin. Subsequently, polishing was performed in the same manner from the lingual surface to obtain plate-shaped dentin. The obtained plate-shaped dentin was polished with #1000 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water until it reached a thickness of 1 mm. Subsequently, the 1-mm-thick dentin was cut into a width of 1 mm using an automatic precision cutting machine Isomet (manufactured by BUEHLER), and prismatic sound dentin samples with a thickness of 1 mm × width of 1 mm × length of approximately 15 mm were prepared.

[0077] [Preparation of Test Specimens for Dentin Tensile Test (Carious Model Dentin)] Prismatic sound dentin samples formed into a thickness of 1 mm × width of 1 mm × length of approximately 15 mm were immersed in 0.5 M acetate buffer (pH 4.6) at 37°C for 24 hours to prepare prismatic carious model dentin samples with a thickness of 1 mm × width of 1 mm × length of approximately 15 mm.

[0078] [Measurement of Tensile Strength of Sound Dentin and Carious Model Dentin] Prismatic sound and carious model dentin samples formed into a thickness of 1 mm × width of 1 mm × length of approximately 15 mm were each fixed to a jig for micro tensile test with a cyanoacrylate-based adhesive. Using a small benchtop universal testing machine (manufactured by Shimadzu Corporation), the tensile strength of dentin was measured under the condition of a crosshead speed of 1 mm / min. Five samples were measured for each condition, and the average value was taken as the tensile strength. The tensile strength of sound dentin was 109 MPa, and the tensile strength of carious model dentin was 44 MPa.

[0079] The abbreviations of various components used in the examples and comparative examples are as follows. [Compound (a) Having an Acidic Group] MHP: 6-Methacryloyloxyhexyl Dihydrogen Phosphate MDP: 10-Methacryloyloxydecyl Dihydrogen Phosphate M12P: 12-Methacryloyloxydodecyl dihydrogen phosphate

[0080] [Hydrophilic solvent (d)] HEMA: 2-Hydroxyethyl methacrylate DEAA: N,N-Diethylacrylamide (compound represented by formula (VI))

[0081] [Organic compound other than compound (a) having an acidic group and hydrophilic solvent (d)] CPC: Cetylpyridinium chloride Bis-GMA: 2,2-Bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane

[0082] [Preparation and evaluation of dental caries dentin restorative agent] <Examples 1 to 15 and Comparative Examples 1 to 5> By mixing each material with the formulation described in Table 1-1 and Table 1-2, the dental caries dentin restorative agents of each example and each comparative example were prepared. Then, samples were prepared using each dental caries dentin restorative agent by the following procedure, and measurements were performed using the samples by the following procedure. For Comparative Example 4, since the compound having an acidic group was insoluble in water and the hydrophilic solvent, the measurement of tensile strength could not be performed.

[0083] [Tensile strength [Y] after artificial caries treatment after treatment on sound dentin] Prismatic sound dentin samples shaped to a thickness of 1 mm × width of 1 mm × length of approximately 15 mm were coated with the carious dentin restorative agents of each example and each comparative example using an applicator brush, and immediately subjected to an air blow treatment. Thereafter, each sample was immersed in a 0.5 M acetic acid buffer solution (pH 4.6) at 37°C for 24 hours to form an artificial caries treatment group. Each sample was fixed to a jig for a micro tensile test with a cyanoacrylate-based adhesive. Using a small desktop universal testing machine (manufactured by Shimadzu Corporation), the tensile strength of the dentin was measured under the condition of a crosshead speed of 1 mm / min. Five samples were measured for each condition, and the arithmetic mean value was taken as the "tensile strength [Y] after artificial caries treatment after treatment on sound dentin".

[0084] (Tensile strength [Z] after treatment on carious model dentin) Prismatic carious model dentin samples shaped to a thickness of 1 mm × width of 1 mm × length of approximately 15 mm were coated with the carious dentin restorative agents of each example and each comparative example using an applicator brush, and immediately subjected to an air blow treatment. Each sample was fixed to a jig for a micro tensile test with a cyanoacrylate-based adhesive. Using a small desktop universal testing machine (manufactured by Shimadzu Corporation), the tensile strength of the dentin was measured under the condition of a crosshead speed of 1 mm / min. Five samples were measured for each condition, and the arithmetic mean value was taken as the "tensile strength [Z] after treatment on carious model dentin".

[0085] The results of the "tensile strength [Y] after artificial caries treatment after treatment on sound dentin" and the "tensile strength [Z] after treatment on carious model dentin" were summarized in Table 1-1 and Table 1-2. Also, the ratio of [Y] to the "tensile strength of sound dentin (109 MPa)" was summarized in Table 1. The ratio of [Z] to the "tensile strength of carious model dentin (44 MPa)" was also summarized in Table 1-1 and Table 1-2.

[0086]

Table 1-1

[0087]

Table 1-2

[0088] From the results in Table 1-1 and Table 1-2, it can be seen that the sound dentin treated with the caries-affected dentin restorative agent containing the above components (a) to (d) and substantially free of organic compounds other than components (a) and (d) maintains a certain tensile strength even after artificial caries treatment and has acquired caries resistance. In addition, it can be seen that the tensile strength can be restored by treating the caries model dentin whose tensile strength has decreased by artificial caries treatment with the caries-affected dentin restorative agent containing the above components (a) to (d) and substantially free of organic compounds other than components (a) and (d).

[0089] On the other hand, the compositions of Comparative Examples 1 and 2 containing crosslinkable polymerizable monomers, the composition of Comparative Example 3 containing no strontium ions and aluminum ions, and the composition of Comparative Example 5 containing no compound (a) having an acidic group all have significantly smaller values of the tensile strength [Y] after artificial caries treatment after treating sound dentin and the tensile strength [Z] after treating caries model dentin compared to the caries-affected dentin restorative agent of the examples, and it can be seen that the caries restoration ability for carious dentin is not recognized either.

[0090] [Effect on the color tone of dentin] <Example 1A> The caries-affected dentin restorative agent of Example 1 described above was applied to the root part of the bovine mandibular anterior teeth using an applicator brush and air blown. After immersing in distilled water and storing at 37 °C for 24 hours, when the applied part was visually observed, no color tone change was recognized. The results are shown in Table 2.

[0091] <Comparative Example 6> The silver diamine fluoride preparation "Safforide Solution for Dentistry 38%" (manufactured by Bee Brand Medical Dental Co., Ltd.) was applied to the root part of the bovine mandibular anterior teeth according to the usage and dosage described in the attached document. After immersing in distilled water and storing at 37 °C for 24 hours, when the applied part was visually observed, an obvious color tone change to brown was recognized. The results are shown in Table 2.

[0092] [Table 2]

[0093] As is clear from the comparison between Example 1A and Comparative Example 6 shown in Table 2, the dental caries dentin restorative agent containing the above components (a) to (d) and substantially free of organic compounds other than components (a) and (d) has no color change to black or brown at the application site that occurs when using the silver diamine fluoride preparation, and can ensure high aesthetics.

[0094] [Combined use of the dental caries dentin restorative agent as Liquid A and Liquid B (dental caries dentin restorative agent kit)] [Example 16] The dental caries dentin restorative agent prepared in Example 1 was used as Liquid A (hereinafter, also referred to as "dental caries dentin restorative agent [A]"). Further, each material was mixed according to the formulation described in Table 3 to prepare Liquid B (hereinafter, also referred to as "liquid containing calcium ions and water [B]" or simply "liquid [B]"), which is a liquid containing calcium ions (e1) and water. Thus, a dental caries dentin restorative agent kit composed of Liquid A and Liquid B was obtained. Then, samples were prepared using this dental caries dentin restorative agent kit according to the following procedure, and measurements and evaluations were performed using the samples according to the following procedure.

[0095] The dental composition kit was applied to sound dentin and carious model dentin according to the following procedure. First, Liquid B was applied to sound dentin or carious model dentin, left standing for 10 seconds, dried with an air blow, and then Liquid A was applied, left standing for 10 seconds, and dried with an air blow. For the dried test pieces, the above tensile strengths [Y] and [Z] were measured according to the same procedure as described above. The results are shown in Table 3.

[0096] [Table 3]

[0097] From the results of Example 16 shown in Table 3, it can be seen that the dental caries dentin restorative agent kit of Example 16, in which a liquid B containing calcium ions and water and a liquid A, which contains the above components (a) to (d) and substantially does not contain organic compounds other than components (a) and (d), are applied to the tooth surface in this order, can further increase both the tensile strength [Y] after artificial caries treatment and the tensile strength [Z] after treatment on carious model dentin, after treatment on sound dentin.

[0098] [Combined use of dental caries dentin restorative agent and dental adhesive (first dental adhesive kit)] <Example 17> Assuming a treatment in which the above dental caries dentin restorative agent is applied to the tooth surface in the filling and restoration of dental caries cavities, an adhesion test to artificially carious dentin was carried out. That is, first, the labial surface of bovine mandibular anterior teeth was polished with #80 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water to obtain a sample with a flat dentin surface exposed. The obtained sample was further polished with #1000 silicon carbide paper (manufactured by Nippon Kenji Co., Ltd.) under running water. After polishing, the water on the surface was dried by air blowing. Next, the tooth surface excluding the central part (4 mm × 4 mm) of the dentin exposed surface was coated with a nail varnish, and then immersed in a 0.5 M acetic acid buffer solution (pH 4.6) at 37°C for 24 hours to form carious model dentin on the dentin exposed surface. The carious model dentin prepared as described above was washed under running water and dried by air blowing the water on the surface. A pressure-sensitive adhesive tape with a thickness of about 150 μm having a round hole with a diameter of 3 mm was adhered to the smooth surface (the part where carious model dentin was formed) after drying to define the adhesion area.

[0099] The dental caries dentin restorative agent prepared in Example 1 above was applied into the above round hole using an applicator brush, and then immediately dried by air-blowing the surface. Subsequently, a dental bonding agent (manufactured by Kuraray Noritake Dental Co., Ltd., trade name "Clearfil (registered trademark) Universal Bond QuickER") was applied into the above round hole using an applicator brush, rubbed for 10 seconds, and then dried by air-blowing the surface until the fluidity of the applied dental bonding agent disappeared. Subsequently, the applied dental bonding agent was cured by irradiating light for 3 seconds with a dental LED light irradiator (manufactured by Morita Corporation, trade name "Pentacure 2000").

[0100] A dental filling composite resin (manufactured by Kuraray Noritake Dental Co., Ltd., trade name "Clearfil (registered trademark) AP-X") was filled onto the surface of the cured product of the obtained dental bonding agent and covered with a release film (polyester). Next, a slide glass was placed on the release film and pressed to smooth the application surface of the dental filling composite resin. Subsequently, the dental filling composite resin was cured by irradiating light for 20 seconds with a dental LED light irradiator (manufactured by Morita Corporation, trade name "Pentacure 2000") through the release film.

[0101] One end face (circular cross-section) of a stainless steel cylindrical rod (diameter 7 mm, length 2.5 cm) was adhered to the surface of the cured product of the obtained dental filling composite resin using a commercially available dental resin cement (manufactured by Kuraray Noritake Dental Co., Ltd., trade name "Panavia (registered trademark) 21"). After adhesion, the sample was allowed to stand at room temperature for 30 minutes and then immersed in distilled water to obtain an adhesion test specimen. Five such adhesion test specimens were prepared and allowed to stand in a thermostat maintained at 37°C for 24 hours while immersed in distilled water.

[0102] The measurement of the tensile adhesive strength was performed using a universal testing machine (manufactured by Shimadzu Corporation) with the crosshead speed set at 2 mm / min. The arithmetic mean value of the obtained values was taken as the tensile adhesive strength. The tensile adhesive strength was 17 MPa. The results are shown in Table 4.

[0103] <Comparative Example 6> In Example 17, the same operations as in Example 17 were performed except that the operation of "applying the dental caries dentin restorative agent prepared in Example 1 into the above round hole using an applicator brush and then drying the surface immediately by air blowing" was omitted, and the tensile adhesive strength of the dental bonding agent to the carious model dentin was measured. The tensile adhesive strength was 9 MPa. The results are shown in Table 4.

[0104]

Table 4

[0105] As is clear from the comparison between Example 17 and Comparative Example 6 shown in Table 4, the tensile adhesive strength of the dental bonding agent to the carious model dentin treated with the dental caries dentin restorative agent containing the above components (a) to (d) and substantially free of organic compounds other than components (a) and (d) is significantly higher compared to the tensile adhesive strength to the untreated carious model dentin.

[0106] [Combined Use of Dental Caries Dentin Restorative Agent Kit and Dental Adhesive (Second Dental Adhesive Kit)] <Example 18> The dental caries dentin restorative agent kit of Example 16 and the same dental adhesive "Quick ER" used in Example 17 were prepared to constitute a dental adhesive kit. Then, the tensile strength to the carious model dentin was evaluated using the dental adhesive kit. Specifically, first, Liquid B was applied to the carious model dentin, allowed to stand for 10 seconds, and then dried by air blowing. Subsequently, Liquid A was applied, allowed to stand for 10 seconds, and then dried by air blowing. Then, for the dried test piece, an adhesion test was performed in the same procedure as in Example 17, and the tensile strength to the carious model dentin was measured. The results are shown in Table 5. For reference, Comparative Example 6 described above is also shown in Table 5.

[0107]

Table 5

[0108] As is clear from the comparison between Example 18 shown in Table 5 and Comparative Example 6, the tensile adhesive strength of the dental bonding agent to the carious model dentin treated with the carious dentin restorative agent containing the above components (a) to (d) and substantially free of organic compounds other than components (a) and (d) is found to be significantly higher compared to the tensile adhesive strength to the untreated carious model dentin.

Industrial Applicability

[0109] The carious dentin restorative agent of the present invention can be suitably used particularly for preventive treatment of root caries and restorative treatment of initial caries, since it can provide strengthening of dentin and repair of initially demineralized dentin while ensuring high aesthetics with a simple procedure.

Claims

1. A caries-affected dentin restorative agent containing a compound (a) having an acidic group represented by the following formula (I), R １ -X ｋ ... Formula (I) [In formula (I), R １ represents an organic group having at least one (meth)acryloyloxy group or not having the same and having 40 or less carbon atoms. X represents an acidic group. k represents an integer of 1 or 2. When k is 2, the two acidic groups X are the same as each other or different from each other.] a metal ion (b), water (c), and a hydrophilic solvent (d), wherein the metal ion (b) contains at least one metal ion selected from the group consisting of strontium ions (b1) and aluminum ions (b2), and substantially free of a crosslinkable polymerizable monomer.

2. The caries-affected dentin restorative agent according to Claim 1, wherein the compound (a) having an acidic group is represented by the following formula (II). R １ -((X ｍ－ )) ａ ·(H ＋ )) ｂ )) ｋ ... Formula (II) [In formula (II), R １ and k have the same meanings as defined in formula (I). X ｍ－ represents an m-valent acid anion group. m represents an integer of 1, 2, or 3. a and b represent integers of 1, 2, or 3 that satisfy the relationship am = b.]

3. The caries-affected dentin restorative agent according to Claim 1 or 2, wherein the compound (a) having an acidic group is a compound represented by the following formula (III). R ２ -R ３ -O-P(=O)(-OH) ２ ... Formula (III) [In formula (III), R ２ represents a (meth)acryloyloxy group or hydrogen. R ３ represents an alkylene group having 6 to 20 carbon atoms.]

4. The caries-affected dentin restorative agent according to Claim 1 or 2, wherein the strontium ion (b1) is derived from at least one strontium compound selected from the group consisting of compounds represented by the following formula (IV). (Sr ２＋ ) ｃ ・ (Y ｎ－ ) ｄ ・・・ Formula (IV) [In formula (IV), Y ｎ－ represents an anion that serves as a counterion for strontium ions. n represents an integer of 1, 2, or 3. c and d represent integers of 1, 2, or 3 that satisfy the relationship 2c = nd.]

5. Strontium ion (b1) is SrCl ２ , Sr(OH) ２ , and SrF ２ The dental caries dentin restorative agent according to claim 1 or 2, which is derived from at least one strontium compound selected from the group consisting of

6. The caries-affected dentin restorative agent according to Claim 1 or 2, wherein the aluminum ion (b2) is derived from at least one aluminum compound selected from the group consisting of compounds represented by the following formula (V). (Al ３＋ ) ｅ · (Z ｓ－ ) ｆ · · · Formula (V) [In formula (V), Z ｓ－ represents an anion that serves as a counter ion for an aluminum ion. s represents an integer of 1, 2, or 3. e and f represent integers of 1, 2, or 3 that satisfy the relationship 3e = sf.]

7. The aluminum ion (b2) is from at least one aluminum compound selected from the group consisting of AlCl ３ , Al(OH) ３ , AlF ３ , and AlK(SO ４ ) ２ The dental caries dentin restorative agent according to claim 1 or 2, which is derived from.

8. The caries-affected dentin restorative agent according to Claim 1 or 2, which is a dentin strengthening agent.

9. The caries-affected dentin restorative agent according to Claim 1 or 2, wherein the organic compound other than the compound (a) having an acidic group and the hydrophilic solvent (d) is 5 parts by mass or less per 100 parts by mass of the caries-affected dentin restorative agent.

10. A caries-affected dentin restorative agent kit comprising a liquid A and a liquid B, wherein the liquid B and the liquid A are applied to the tooth surface in this order, wherein the liquid A is the caries-affected dentin restorative agent [A] according to Claim 1 or 2, and the liquid B is a liquid [B] containing calcium ions (e1) and water.

11. The caries-affected dentin restorative agent kit according to Claim 10, wherein the calcium ion (e1) is derived from at least one calcium compound selected from the group consisting of compounds represented by the following formula (VII). (Ca ２＋ ) ｇ ・ (W ｒ－ ) ｈ ・・・ Formula (VII) [In formula (VII), W ｒ－ represents an anion that serves as a counter ion for calcium ions (e1). r represents an integer of 1, 2, or 3. g and h represent integers of 1, 2, or 3 that satisfy the relationship 2g = rh.]

12. Calcium ions (e1) are CaCl ２ , CaBr ２ , CaI ２ , CaSO ４ , Ca(HCO ３ ), ２ and Ca(CH ３ COO) ２ The caries dentin restorative agent kit according to claim 10, which is derived from at least one calcium compound selected from the group consisting of

13. A dental adhesive kit comprising the caries-affected dentin restorative agent according to Claim 1 or 2 and a dental adhesive [C].

14. A dental adhesive kit comprising the caries-affected dentin restorative agent kit according to Claim 10 and a dental adhesive [C].

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