JP7142574B2 - One material type tooth surface treatment material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a tooth surface treatment material that is easy to handle as a single material, has excellent storage stability, suppresses the progress of caries without impairing the aesthetic surface of the treatment site, and suppresses hypersensitivity.

Improvements in dental treatment techniques and enlightenment activities represented by the 8020 movement have increased the rate of remaining teeth in the elderly. However, as the level of regular oral care declines due to aging and the onset of dementia, simultaneous multiple caries on the tooth root surface and adjacent surface has become a clinical problem.

In many cases of such symptoms, it is difficult for the patient to fully open the mouth for treatment, which makes filling and repairing treatment with composite resin or the like extremely difficult. As one of the treatment methods in such a situation, the antibacterial properties of silver compounds are used to inhibit the progression of caries. For example, a method of stopping caries has been performed by applying a drug such as Sahoride (manufactured by Bebrand Medico Dental) containing silver diammine fluoride. However, the conventional method has a clinical problem that the affected area to which the drug is applied is discolored black, which greatly impairs the aesthetic appearance.

In Patent Document 1, a two-stage dental treatment is performed by applying a liquid containing a silver compound (first liquid) to an affected area and then applying a liquid (second liquid) containing an alkali metal halide or an alkaline earth metal halide. A surface treatment method is described. According to this, no secondary caries occurred even after 6 months from the treatment, and no black discoloration was observed in the treated area. However, in this treatment method, two chemicals are required. First, a liquid containing a silver compound is applied, and after drying, the second liquid is applied. It was necessary to perform a complicated operation of changing to the treatment site and removing it from the treatment site.

Patent Document 2 describes a method of reducing caries by applying a composition containing silver diammine fluoride and a carrier that enables sustained release of silver diammine fluoride and adheres to the tooth surface to the affected area. It is According to this, cessation of caries was observed after 6 months of treatment. However, this treatment method does not solve the problem that the affected area turns black. As described above, it is difficult to achieve both of being a single material and not discoloring the affected area black after treatment.

U.S. Pat. No. 6,461,161 U.S. Patent Application Publication No. 2010/0247456

The present invention has been made to solve the above problems, and provides a tooth surface treatment material that is easy to handle as a single material and that can suppress the progression of caries without impairing the aesthetic surface of the treatment site. for the purpose. Another object of the present invention is to provide a tooth surface treatment material that is easy to handle as a single material and that can suppress hypersensitivity without damaging the aesthetic surface of the treatment site. A further object of the present invention is to provide a one-material type tooth surface treatment material that does not have an ammonia odor and is excellent in feeling when used. Another object of the present invention is to provide a one-component tooth surface treatment material which is excellent in storage stability. A further object of the present invention is to provide a single material type tooth surface treatment material which is excellent in acid resistance.

The present invention provides a single material type tooth surface treatment material containing complex ions (A) of silver ions and iodide ions and water.

In the one-material type tooth surface treatment material of the present invention, the concentration of silver atoms present in a dissolved state in the solution is 10 to 125,000 mass ppm with respect to the mass of the one-material type tooth surface treatment material. preferable.

In one embodiment of the one-component tooth surface treatment material of the present invention, the iodide ions are derived from iodide salt (B), the silver ions are derived from silver salt (C), and the silver salt (C) is silver diammine fluoride, silver nitrate (I), silver fluoride (I), silver chloride (I), silver bromide (I), silver carbonate (I), silver iodide (I), silver oxide (I), silver chlorate (I), silver perchlorate (I), silver chromate (I), silver hexafluoroantimonate (V), silver hexafluorophosphate (I), silver nitrite (I), at least one silver compound selected from the group consisting of silver sulfate (I), silver thiocyanate (I), silver vanadate and organic silver salts, wherein the iodide salt (B)/silver salt (C) The molar ratio is preferably at least the lower limit at which the silver salt (C) is completely dissolved in the one-component tooth surface treatment material.

In another embodiment of the one-component tooth surface treatment material of the present invention, the iodide ions are derived from iodide salt (B), and the silver ions are supplied from silver salt (C), The silver salt (C) is at least one silver compound selected from the group consisting of silver iodide (I) and organic silver salts, and the iodide salt (B)/silver salt (C) molar ratio is preferably less than the lower limit at which the silver salt (C) is completely dissolved in the one-component tooth surface treatment material.

In the one-material type tooth surface treatment material of the present invention, the organic silver salt comprises silver (I) formate, silver (I) acetate, silver (I) citrate, silver (II) oxalate, silver gluconate, and propion. Silver acid (I), silver succinate (I), silver malonate (I), silver DL-tartrate (I), silver laurate (I), silver palmitate (I), N,N-diethyldithiocarbamic acid silver (I), silver 2-ethylhexanoate (I), silver lactate (I), silver methanesulfonate (I), silver salicylate (I), silver p-toluenesulfonate (I), silver trifluoroacetate ( I), silver trifluoromethanesulfonate (I) and silver stearate (I).

In the single material type tooth surface treatment material of the present invention, the iodide ion is derived from an iodide salt (B), and the iodide salt (B) is sodium iodide, potassium iodide, rubidium iodide, iodine. At least one compound selected from the group consisting of magnesium iodide, calcium iodide and strontium iodide is preferred.

The single material type tooth surface treatment material of the present invention does not turn black when it is applied to a hydroxyapatite plate and allowed to stand for 24 hours in an environment of 25° C. and illuminance of 1200 lux to evaporate water. is one of the features.

The one-component tooth surface treatment material of the present invention preferably contains a water-soluble fluoride salt (D).

The single material type tooth surface treatment material of the present invention is for caries prevention.

The single material type tooth surface treatment material of the present invention is for suppressing hypersensitivity.

Further, in the present invention, an iodide aqueous solution having an iodide salt (B) concentration of 5 to 60% by mass and a silver salt (C) are mixed at a molar ratio of iodide salt (B)/silver salt (C) Provided is a method for producing a single material type tooth surface treatment material, which includes a step of generating complex ions (A) mixed so that A is 0.5 or more.

According to the present invention, it is possible to provide a tooth surface treatment material that is easy to handle as a single material and that can suppress the progression of caries without impairing the aesthetic surface of the treatment site. In addition, the present invention can provide a tooth surface treatment material that is easy to handle as a single material and suppresses hypersensitivity without impairing the aesthetic surface of the treatment site. Furthermore, the present invention can provide a one-material type tooth surface treatment material that does not have an ammonia odor and has excellent usability. Another object of the present invention is to provide a one-component tooth surface treatment material which is excellent in storage stability. Furthermore, the present invention can provide a single material type tooth surface treatment material that is excellent in acid resistance.

FIG. 5 is an analysis chart showing the results of X-ray diffraction analysis of precipitates precipitated by adding the same amount of water to the single material type tooth surface treatment material according to Example 2 of the present invention. FIG. FIG. 10 is an analysis chart showing the results of X-ray diffraction analysis of precipitates precipitated by adding the same amount of water to the one-component tooth surface treatment material according to Example 15 of the present invention. FIG.

The present invention is a one-component tooth surface treatment material characterized by containing complex ions (A) of silver ions and iodide ions and water.

In addition, in this specification, the upper limit and the lower limit of the numerical range (content of each component, etc.) can be appropriately combined.

Since silver ions have bactericidal activity against bacteria, they are widely used as antibacterial agents, and are also applied as dental agents for the purpose of inhibiting dental caries. However, conventionally used silver-based dental agents generate silver (I) oxide (Ag ₂ O) in the air, discoloring the treated area black. Furthermore, in order to avoid the formation of silver (I) oxide, after applying a liquid containing a silver compound (first liquid), a liquid containing an alkali metal halide or an alkaline earth metal halide (second liquid) is applied. A method of chemically removing silver compounds excessively present in the affected area by applying is also used, but it is a two-component type and the operation is complicated (see Patent Document 1).

In response to this, the present inventors have developed a tooth surface treatment material that is easy to handle with a single material type, suppresses the progression of caries without damaging the aesthetic surface of the treatment site, and suppresses hypersensitivity. A composition characterized by containing a complex ion (A) of an ion and an iodide ion and water is a single material type, is easy to handle, and suppresses the progress of caries without damaging the aesthetic surface of the treatment site, Moreover, it discovered that hyperesthesia can be suppressed.

The reason why the one-component tooth surface treatment material of the present invention is one-component, easy to handle, and capable of suppressing the progression of caries without impairing the aesthetic surface of the treatment site is considered as follows. First, in order to prevent the treated area from turning black due to the production of silver (I) oxide (Ag ₂ O), after applying the tooth surface treatment material, silver iodide (AgI), which does not easily turn black in the air, was applied. I decided to generate it. Next, in order to suppress the progress of caries, the silver compound must exist in the form of silver ions in the tooth surface treatment material, but silver iodide is almost insoluble in water. However, in an aqueous solution containing iodide salt (B), silver iodide can dissolve and exist as a complex ion (A) of silver ion and iodide ion. In the method described in Patent Document 1, excess silver compounds are removed in order to obtain the effect. By supplying it in the presence of silver chloride, it is present as complex ions (A) of silver ions and iodide ions, thereby obtaining an effect of inhibiting caries. For this reason, in the one-material type tooth surface treatment material of the present invention, silver is present in an ionic state in advance, and can be spread very easily even in places where it is difficult for an applicator to reach, such as adjacent surfaces of teeth. . As a result, an excellent caries-inhibiting effect is expected in any affected area. In addition, since the complex ions (A) of silver ions and iodide ions that permeate the affected area are precipitated as silver iodide in the dentin, the treated area does not turn black. Furthermore, the solution containing the complex ions (A) of silver ions and iodide ions itself is stable without blackening or reprecipitation, and can be easily stored and handled as a single material. In addition, the one-component tooth surface treatment material of the present invention has acid resistance necessary in the oral cavity.

In addition, as a means for generating silver iodide in the tooth substance after applying the tooth surface treatment material, silver iodide itself is dissolved in an aqueous solution containing iodide salt (B) as described above to obtain silver ions and iodide. Besides obtaining the ion complex ion (A), it is also effective to select a silver salt (C) other than silver iodide that is soluble in the aqueous solution containing the iodide salt (B). When silver salts (C) other than silver iodide are dissolved in an aqueous solution containing iodide salts (B), the Ag-I bond takes on a strong covalent bond, resulting in stable complex ions of silver ions and iodide ions. (A) is considered to be generated.

The reason why the one-material type tooth surface treatment material of the present invention is one-material type, easy to handle, and can suppress hypersensitivity without impairing the aesthetic surface of the treatment site is considered as follows. When the tooth surface treatment material penetrates into the dentinal tubules, it comes into contact with interstitial fluid present in the dentinal tubules. Silver ions are highly reactive, especially with thiol groups of proteins that constitute interstitial fluid. As a result of the reaction, the protein is denatured, which increases the viscosity of the interstitial fluid in the dentinal tubules. Physical blockade by silver iodide that precipitates in dentinal tubules is also considered to be effective in suppressing hypersensitivity. When the one-component tooth surface treatment material of the present invention is used for suppressing hypersensitivity, it preferably has a high dentinal tubule sealing rate. When used as a hypersensitivity suppressing material, the concentration of silver atoms dissolved in the solution is preferably 500 to 125,000 ppm by mass, preferably 2,000 to 125,000 ppm, based on the mass of the single-component tooth surface treatment material. 000 ppm by mass is more preferred, and 10,000 to 125,000 ppm by mass is even more preferred.

The one-material type tooth surface treatment material of the present invention contains complex ions (A) of silver ions and iodide ions and water. It is preferably 10 to 125,000 ppm by mass based on the mass of the tooth surface treatment material. When the silver atom concentration is less than 10 ppm by mass, the caries-inhibiting effect when the tooth surface treatment material is applied becomes considerably smaller than that of commercially available caries-inhibiting materials (eg, sahoride, etc.). The silver atom concentration is preferably 1000 mass ppm or more, more preferably 10000 mass ppm or more. On the other hand, when the concentration exceeds 125,000 mass ppm, the antibacterial effect does not change even if the concentration is higher than that. Since silver compounds are generally expensive, there is no merit in terms of cost. Moreover, the complex ions (A) of silver ions and iodide ions cannot be completely dissolved, and silver iodide may precipitate. The silver atom concentration is more preferably 120,000 mass ppm or less. The method for calculating the silver atom concentration is as described in Examples below.

The silver ions used in the one-component tooth surface treatment material of the present invention are derived from silver salt (C), and are not particularly limited. Also called silver diammine fluoride (Ag(NH ₃ ) ₂ F), silver nitrate (I), silver (I) fluoride, silver chloride (I), silver bromide (I), silver carbonate (I) , silver iodide (I), silver oxide (I), silver chlorate (I), silver perchlorate (I), silver chromate (I), silver hexafluoroantimonate (V), silver hexafluorophosphate (I), silver nitrite (I), silver sulfate (I), silver thiocyanate (I), silver vanadate (AgVO ₃ ) and at least one selected from the group consisting of organic silver salts are preferably used. Among these, silver iodide (I) is more preferable because it facilitates increasing the concentration of silver in the solution. When the silver salt (C) used in the tooth surface treatment material of the present invention is a suitable compound in the first embodiment, the iodide salt (B)/silver salt (C) molar ratio is It is preferable that the silver salt (C) is not less than the lower limit at which the silver salt (C) is completely dissolved in the one-component tooth surface treatment material. However, silver (I) iodide and organic silver salts are not limited to this, as will be described later. Here, "the lower limit at which the silver salt (C) is completely dissolved" means the lower limit of the iodide salt (B)/silver salt (C) molar ratio at which the silver salt (C) is visually dissolved.

The lower limit at which the silver salt (C) is completely dissolved varies depending on the type of silver salt (C). In the case of AgX (X means an atom or functional group to which the Ag atom is bound) type such as silver (I) fluoride, silver (I) bromide, silver (I) 2-ethylhexanoate, silver The lower limit at which the salt (C) is completely dissolved is 3.5 for the iodide salt (B)/silver salt (C) molar ratio. That is, in the case of the AgX type tooth surface treatment material of the first embodiment, the iodide salt (B)/silver salt (C) molar ratio is preferably 3.5 or more. However, in the case of AgX type silver iodide (I), the molar ratio of iodide salt (B)/silver salt (C) is preferably 1.9 or more. Next, in the case of Ag ₂ X type such as silver oxide, the lower limit for complete dissolution of silver salt (C) is the iodide salt (B)/silver salt (C) molar ratio of 7.5. . That is, in the case of the Ag ₂ X type tooth surface treatment material of the one material type of the first embodiment, the iodide salt (B)/silver salt (C) molar ratio is preferably 7.5 or more. Furthermore, in the case of Ag ₃ X type such as silver citrate, the lower limit for complete dissolution of silver salt (C) is 10 in the molar ratio of iodide salt (B)/silver salt (C). That is, in the case of the Ag ₃ X type tooth surface treatment material of the first embodiment, the iodide salt (B)/silver salt (C) molar ratio is preferably 10 or more. If the iodide salt (B)/silver salt (C) molar ratio is less than the lower limit for each type of silver salt (C), undissolved silver salt (C) is present in the tooth surface treatment material. . Therefore, depending on the type of silver salt (C), undissolved silver salt (C) may be oxidized and blackened when the tooth surface treatment material is applied.

When the silver salt (C) used in the one-material type tooth surface treatment material of the present invention is silver iodide (I) and an organic silver salt that themselves are difficult to blacken, iodide salt (B) /Silver salt (C) molar ratio may be less than the lower limit at which the silver salt (C) is completely dissolved in the one-component tooth surface treatment material. Therefore, in another embodiment (also referred to as "second embodiment"), the silver salt (C) is at least one silver compound selected from the group consisting of silver iodide (I) and organic silver salts. and wherein the iodide salt (B)/silver salt (C) molar ratio is less than the lower limit at which said silver salt (C) is completely soluble. Although there is undissolved silver salt (C) in the tooth surface treatment material, when the tooth surface treatment material is applied, since the silver salt (C) is silver iodide (I) or an organic silver salt, The one-material type tooth surface treatment material of the second embodiment is also resistant to blackening.

The organic silver salt used in the one-component tooth surface treatment material of the present invention is not particularly limited, but is silver formate (I), silver acetate (I), silver citrate (I), and silver oxalate (II). , silver gluconate, silver propionate (I), silver succinate (I), silver malonate (I), silver DL-tartrate (I), silver laurate (I), silver palmitate (I), N, Silver N-diethyldithiocarbamate (I), silver 2-ethylhexanoate (I), silver lactate (I), silver methanesulfonate (I), silver salicylate (I), silver p-toluenesulfonate (I) , silver trifluoroacetate (I), silver trifluoromethanesulfonate (I) and silver stearate (I). Among these, silver formate (I), silver citrate (I), silver oxalate (II), silver propionate (I), silver succinate (I), 2-ethyl Silver (I) hexanoate, silver (I) lactate, silver (I) salicylate, and silver (I) N,N-diethyldithiocarbamate are more preferred.

The iodide ion used in the present invention is derived from iodide salt (B) and is not particularly limited, but iodide salt (B) is sodium iodide, potassium iodide, rubidium iodide, magnesium iodide, At least one selected from the group consisting of calcium iodide and strontium iodide is preferably used. Among these, sodium iodide and potassium iodide are more preferable from the viewpoint of the solubility of the silver salt (C).

The one-material type tooth surface treatment material of the present invention forms silver (I) inside and on the surface of the tooth structure when water is evaporated after it is applied to the tooth structure, so that the tooth surface treatment material can be used for 24 hours or more after the treatment. does not turn black. The degree of blackening was quantified by the method described in Examples. The value obtained by subtracting the L value after applying the tooth surface treatment material from the L value before applying the tooth surface treatment material, that is, the color difference (ΔL*) before and after applying the tooth surface treatment material is 20 or less. is preferred. It is preferably 15 or less, more preferably 10 or less. The method for measuring the color difference is as described in Examples below.

From the standpoint of acid resistance, the one-component tooth surface treatment material of the present invention preferably further contains a water-soluble fluoride salt (D) in one embodiment. The water-soluble fluoride salt (D) is not particularly limited, but sodium fluoride, potassium fluoride, ammonium fluoride, lithium fluoride, cesium fluoride, magnesium fluoride, calcium fluoride, strontium fluoride, barium fluoride. , copper fluoride, zirconium fluoride, aluminum fluoride, tin fluoride, sodium monofluorophosphate, potassium monofluorophosphate, hydrofluoric acid, sodium titanium fluoride, potassium titanium fluoride, hexylamine hydrofluoride, Laurylamine hydrofluoride, glycine hydrofluoride, alanine hydrofluoride, fluorosilanes and the like. Among them, sodium fluoride, potassium fluoride, sodium monofluorophosphate, and tin fluoride are preferably used from the viewpoint of safety to the living body.

In the one-material type tooth surface treatment material of the present invention, the concentration of the water-soluble fluoride salt (D) is preferably 0.01 to 5.0% in terms of converted fluorine ion concentration. If the concentration is less than 0.01%, the acid resistance of the tooth coated with the tooth surface treatment material may not be improved. The concentration is more preferably 0.02% or higher. On the other hand, when the concentration exceeds 5.0%, there is a possibility that the safety to the living body is impaired. The concentration of water-soluble fluoride salt (D) is more preferably 4.5% or less.

The method for producing the one-material type tooth surface treatment material of the present invention is not particularly limited, but for example, a method of mixing and dissolving iodide salt (B), silver salt (C) and water; iodide salt (B). silver ion and iodide by adding and dissolving silver salt (C) in a solution of silver salt (C) and water; It includes a step of generating a complex ion (A) of ions. The means for dissolving the above components after mixing is not particularly limited, but can be achieved by methods such as stirring dissolution using stirring blades, vibration dissolution, ultrasonic dissolution, and rotation-revolution-type stirring dissolution.

As a method for producing a one-component tooth surface treatment material of the present invention, for example, in the case of a method of adding and dissolving a silver salt (C) in a solution of an iodide salt (B) and water, the iodide salt ( An iodide aqueous solution having a concentration of B) of 5 to 60% by mass and a silver salt (C) are mixed so that the iodide salt (B)/silver salt (C) molar ratio is 0.5 or more. It is preferable to include a step of generating a complex ion (A) that allows The concentration of the iodide salt (B) is preferably 10% by mass or more, more preferably 20% by mass or more, from the viewpoint of the solubility of the silver salt (C). On the other hand, if it exceeds 60% by mass, the iodide salt (B) becomes undissolved, so the content is preferably 55% by mass or less. The iodide salt (B)/silver salt (C) molar ratio is preferably 1.0 or more, more preferably 2.0 or more, from the viewpoint of the solubility of the silver salt (C). be.

The one-material type tooth surface treatment material of the present invention comprises a complex ion (A) of silver ion and iodide ion, an iodide salt (B), a silver salt (C), and a water-soluble It may contain other components other than the divalent fluoride salt (D) and water. For example, thickeners, solvents, coloring agents, perfumes, etc. can be blended. The content of other components is not particularly limited, but is preferably less than 10% by mass, more preferably less than 5% by mass, and even more preferably less than 1% by mass in the one-component tooth surface treatment material.

The thickening agent is not particularly limited, and includes fine particle silica, carboxymethylcellulose, sodium carboxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, polyvinyl alcohol, polyacrylic acid, polystyrenesulfonic acid, polystyrenesulfonate, polyglutamic acid, and polyglutamic acid. salt, polyaspartic acid, polyaspartate, poly-L-lysine, poly-L-lysine salt, starch other than cellulose, alginic acid, alginate, carrageenan, guar gum, xanthan gum, cellulose gum, hyaluronic acid, hyaluronate, One or two selected from polysaccharides such as pectin, pectin salts, chitin and chitosan, acidic polysaccharide esters such as propylene glycol alginate, and polymers such as proteins such as collagen, gelatin and derivatives thereof The above are mentioned.

The solvent is not particularly limited, but water-soluble tetrahydrofuran, 1,4-dioxane, ethanol, methanol, 1-propanol, isopropyl alcohol, tert-butyl alcohol, ethylene glycol, glycerin, acetone, 1,2-dimethoxyethane, Acetonitrile, dimethylformamide and the like can be mentioned. Among these, ethanol, 1-propanol, acetone, and glycerin, which are highly safe to living bodies, are preferred.

Sugar alcohols such as xylitol, sorbitol and erythritol; artificial sweeteners such as aspartame, acesulfame potassium, licorice extract, saccharin and saccharin sodium may also be added, if necessary. Furthermore, any pharmacologically acceptable drug or the like can be blended. antibacterial agents typified by cetylpyridinium chloride; disinfectants; anticancer agents; antibiotics; Bone marrow-derived stem cells; embryonic stem (ES) cells; induced pluripotent stem (iPS) cells that are dedifferentiated and prepared by gene introduction of differentiated cells such as fibroblasts; Cells and the like that promote tissue formation can be blended.

The single material type tooth surface treatment material of the present invention is obtained as a solution containing at least complex ions (A) of silver ions and iodide ions and water, is excellent in operability, and inhibits the progression of caries and inhibits hypersensitivity. Moreover, since the affected area does not turn black, aesthetic treatment is possible. In addition, it has no smell of ammonia, no irritation to the gums, and is excellent in use. Further, the one-material type tooth surface treatment material of the present invention can be stably stored as a one-material type, and is excellent in storage stability. In addition, the one-material type tooth surface treatment material of the present invention is excellent in acid resistance necessary in the oral cavity.

The present invention includes various combinations of the above configurations within the technical scope of the present invention as long as the effects of the present invention are exhibited.

Next, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by these Examples, and many modifications can be made in the art within the technical concept of the present invention. It is possible by a person with ordinary knowledge.

The following raw materials were used for Examples and Comparative Examples.
Potassium iodide: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Sodium iodide: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) iodide: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) fluoride: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) bromide: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) oxide: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) citrate: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Silver (I) 2-ethylhexanoate: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
Potassium fluoride: A product of Wako Pure Chemical Industries, Ltd. was used as it was.
An aqueous solution containing 38% by mass of silver diammine fluoride: Saphoride (product of Biebrand Medico) was used as it was.

[Example 1]
3.65 g of potassium iodide was added to 3.65 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 2.7 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 2]
3.8 g of potassium iodide was added to 3.8 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 2.4 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 3]
4.88 g of potassium iodide was added to 4.88 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 0.24 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 4]
4.988 g of potassium iodide was added to 4.988 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 0.024 g of silver (I) iodide was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 5]
4.998 g of potassium iodide was added to 4.998 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. 0.004 g of silver (I) iodide was further added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 6]
3.14 g of potassium iodide was added to 5.82 g of water and dissolved with stirring to prepare a 35% by mass potassium iodide aqueous solution. Further, 1.04 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 7]
2.3 g of potassium iodide was added to 6.88 g of water and dissolved with stirring to prepare a 25% by mass potassium iodide aqueous solution. Further, 0.82 g of silver (I) iodide was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 8]
1.49 g of potassium iodide was added to 8.462 g of water and dissolved with stirring to prepare a 15% by mass potassium iodide aqueous solution. 0.048 g of silver (I) iodide was further added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 9]
0.7 g of potassium iodide was added to 9.29 g of water and dissolved with stirring to prepare a 7% by mass potassium iodide aqueous solution. 0.01 g of silver (I) iodide was further added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 10]
4.23 g of potassium iodide was added to 3.07 g of water and dissolved with stirring to prepare a 58% by mass potassium iodide aqueous solution. Further, 2.7 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 11]
3.8 g of sodium iodide was added to 3.8 g of water and dissolved with stirring to prepare a 50 mass % sodium iodide aqueous solution. Further, 2.4 g of silver iodide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 12]
4.55 g of potassium iodide was added to 4.55 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 0.9 g of silver (I) fluoride was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 13]
4.31 g of potassium iodide was added to 4.31 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 1.38 g of silver bromide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 14]
4.61 g of potassium iodide was added to 4.61 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 0.78 g of silver oxide (I) was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 15]
4.36 g of potassium iodide was added to 4.36 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 1.28 g of silver (I) citrate was added to this solution and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. This material is a single material type.

[Example 16]
4.13 g of potassium iodide was added to 4.13 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. To this solution, 1.74 g of silver (I) 2-ethylhexanoate was further added and dissolved with stirring at room temperature to obtain a colorless and transparent tooth surface treatment material containing complex ions (A) of silver ions and iodide ions. Obtained. This material is a single material type.

[Example 17]
3.5 g of potassium iodide was added to 3.5 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. 3.0 g of silver iodide (I) was further added to this solution and stirred at room temperature to obtain a tooth surface treatment material containing undissolved silver iodide and complex ions (A) of silver ions and iodide ions. got This material is a single material type.

[Example 18]
3.5 g of potassium iodide was added to 3.5 g of water and dissolved with stirring to prepare a 50% by mass potassium iodide aqueous solution. Further, 2.4 g of silver iodide (I) and 0.6 g of potassium fluoride were added to this solution and dissolved with stirring at room temperature to obtain a colorless transparent tooth containing complex ions (A) of silver ions and iodide ions. A surface treatment material was obtained. This material is a single material type.

[Example 19]
2.71 g of potassium iodide was added to 5.04 g of water and dissolved with stirring to prepare a 35% by mass potassium iodide aqueous solution. Further, 0.9 g of silver iodide (I) and 1.35 g of potassium fluoride were added to this solution and dissolved with stirring at room temperature to obtain a colorless transparent tooth containing complex ions (A) of silver ions and iodide ions. A surface treatment material was obtained. This material is a single material type.

[Comparative Example 1]
Saphoride was used as an aqueous solution containing 38% by mass of silver diammine fluoride. This material is a single material type.

[Comparative Example 2]
As liquid A, safforide was used as an aqueous solution containing 38% by mass of silver diammine fluoride. As liquid B, 4.0 g of potassium iodide was added to 6.0 g of water and dissolved with stirring. This material is a two-material type. When it was subjected to the test, the liquid A was first applied, washed with water and dried, and then the liquid B was applied, washed with water and dried.

[Antibacterial activity test (inhibition circle formation test)]
It was evaluated according to the qualitative test (halo method) of JIS L 1902:2008 "Antibacterial test method and antibacterial effect of textile products".
(1) Cultivation of test bacterial solution After mixing and dissolving 5.0 g of meat extract, 10.0 g of peptone and 5.0 g of sodium chloride in 1000 mL of purified water, 0.1 mol / A bouillon medium was prepared by preparing with L sodium hydroxide solution and autoclaving. A platinum loop of Streptococcus mutans was transplanted to this broth medium and cultured at 37° C. for 24 hours to adjust the bacterial concentration to 7.1×10 ⁶ cells/mL.

(2) Preparation of pour plate medium Put 1 mL of the bacterial solution obtained in (1) above in a sterilized petri dish, add 15 mL of nutrient agar medium kept at 45 ° C. to the petri dish, mix well, and leave at room temperature. Allow the agar to solidify. This was inverted and allowed to stand at room temperature for an additional hour to dry excess moisture.

(3) Placement and culture of test piece A paper disc (diameter 10 mm) pre-impregnated with 0.05 mL of the solution prepared in Examples and Comparative Examples is placed in the center of the pour plate medium obtained in (2) above. made it adhere. After that, it was cultured at 37° C. for 24 hours.

(4) Measurement of Inhibition Circle After culturing, the width of the inhibition circle formed around the paper disc is calculated from the bottom side of the Petri dish based on the following.
W=(TD)/2
(Wherein, W represents the width (mm) of the blocking circle (halo), T represents the sum of the length of the paper disc and the width of the blocking circle (mm), and D represents the length (mm) of the paper disc. .)

[Discoloration test (blackening)]
(1) Application of tooth surface treatment material 0.01 mL of tooth surface treatment material was collected on a hydroxyapatite plate (manufactured by HOYA Technosurgical Co., Ltd.) having a length and width of 10 mm and a thickness of 2 mm. ) for 10 seconds so as to cover the entire surface of the hydroxyapatite plate. After that, it was allowed to stand for 24 hours under an environment of 25° C. and an illumination of 1200 lux to evaporate the water.

(2) Evaluation of discoloration Spectrophotometer (manufactured by Konica Minolta Japan Co., Ltd., model number CM-3610d, JIS Z 8722: 2009 , compliant with condition c, light source D65, white background) L value (JIS Z 8781-4 when measuring chromaticity with a standard white plate behind the sample: 2013 L * a * b * in the color system The lightness representing the lightness index L*) was measured, and the color difference (ΔL*) from the L value (initial value) before applying the tooth surface treatment material was obtained to evaluate the blackening.

[Acid resistance test]
(1) Preparation of bovine tooth test piece The center of the buccal side of a healthy bovine incisor was polished with water-resistant abrasive paper of No. 80 and then No. 1000 to expose the dentin, and the exposed surface (flat surface) of the dentin was wrapped. The exposed surface of the dentin was mirror-finished by polishing with films (manufactured by 3M Japan Co., Ltd.) with No. 1200, No. 3000 and No. 8000 in that order. Then, it was immersed in a 5-fold diluted solution of 0.5 M EDTA solution (manufactured by Wako Pure Chemical Industries, Ltd.) for 30 seconds and washed with water for 60 seconds. The prepared bovine tooth test piece was coated with nail polish except for a 3 mm×3 mm square test window in the center.

(2) Application of tooth surface treatment material, preparation of acid immersion sample 0.01 mL of tooth surface treatment material is dropped on a test window of 3 mm × 3 mm square, and applied using a regular microbrush (manufactured by Microbrush). ℃ for 4 minutes. Thereafter, the tooth surface treatment material applied to the bovine tooth test piece was washed with distilled water and immersed in distilled water at 37°C for 24 hours. After that, the bovine tooth test piece was further immersed in a separate container containing 20 mL of lactic acid buffer (pH=2.75) at 37° C. for 8 hours with the test window facing upward. Thereafter, the bovine tooth test piece was washed with distilled water and then dried.

(3) Evaluation of Acid Resistance From the bovine tooth test piece prepared in (2) above, the manicure coated in (1) above was carefully removed with a razor. Using the periphery of the test window protected with nail polish as a reference plane, the vertical distance between the bottom surface of the test window demineralized by acid immersion and the reference plane as the demineralization depth, a 3D laser microscope (VK-9710, Keyence Corporation (manufactured). The measurement was performed on each side of a 3 mm×3 mm square test window, and the average value was obtained. The smaller the demineralization depth, the better the acid resistance. It was 103 μm when the tooth surface treatment material was not applied.

[Storage stability test]
5 g of the liquids obtained from Examples 1 to 19 and Comparative Examples 1 and 2 were accurately weighed into a glass sample tube and allowed to stand at 25°C. The storage stability was evaluated according to the following evaluation criteria.
A: Over one month after preparation, it maintains a transparent property without any sediment or discoloration.
B: Up to 1 month after preparation, it maintains a transparent property without any sediment or discoloration.
C: Precipitation or discoloration occurs after preparation, and good properties cannot be maintained.

[Concentration of silver atoms dissolved in the solution]
(1) System in which Silver Salt (C) is Completely Dissolved Based on the blending ratio (mass ratio) of the silver salt (C) in the composition, the silver atom concentration (mass ppm) was calculated.

(2) System in which silver salt (C) is undissolved A silver ion meter (manufactured by KDD Corporation) was used to measure the concentration of silver atoms dissolved in the solution. Add the coloring reagent attached to the silver ion meter to the solution to be measured, and mix by sufficiently shaking. The colored solution was set in a silver ion meter to measure the silver atom concentration. When the silver atom concentration exceeds the upper limit of the measurement range of the measuring instrument, the composition is diluted with a 50% by mass potassium iodide aqueous solution and measured again.

[Component Analysis of Deposits Generated by Addition of Water]
(1) Sample preparation for X-ray diffraction analysis The same mass of water is added to the compositions prepared in the examples. The resulting precipitate was filtered, washed with water and dried to prepare a powder sample for X-ray diffraction analysis.

(2) X-ray diffraction analysis The powder sample obtained above was filled in a sample plate made of SiO ₂ and placed in an X-ray diffraction analyzer (SmartLab, manufactured by Rigaku Co., Ltd.), and the tube voltage and tube current were 45 kV. -200 mA, the detector was a one-dimensional semiconductor detector, and composition analysis was performed.

[Examples 1 to 19]
Antibacterial activity, discoloration, acid resistance, storage stability, and deposits upon addition of water were evaluated according to the procedures described above. The obtained evaluation results are shown in Tables 1-4. In addition, the precipitation at the time of water addition was performed only for Examples 2 and 15. Analytical charts obtained by X-ray diffraction analysis of precipitates precipitated by adding the same amount of water to the tooth surface treatment materials obtained in Examples 2 and 15 are shown in FIGS. In both Examples 2 and 15, the main component of the precipitate was silver (I) iodide, which was confirmed to be a mixture of two types of crystal structures, hexagonal and cubic.

[Comparative Examples 1 and 2]
Antibacterial activity, discoloration, acid resistance, and storage stability were evaluated by the same procedure as in the above examples. The obtained evaluation results are shown in Tables 5 and 6.

Regarding Examples 1 to 19 and Comparative Example 1, the dentinal tubule sealing rate was measured by the following method. Table 7 shows the results.

[Dental tubule sealing rate test]
(1) Preparation of bovine tooth disk The center of the buccal side of a healthy bovine incisor tooth was polished with water-resistant abrasive paper in the order of No. 80 and No. 1000 to expose the dentin and form a disk with a diameter of about 7 mm and a thickness of 2 mm. . The polished surface of the bovine tooth was further polished with a lapping film (manufactured by Sumitomo 3M Co., Ltd.) with No. 1200, No. 3000 and No. 8000 in this order. Then, after being immersed in a 5-fold diluted solution of 0.5 M EDTA solution (manufactured by Wako Pure Chemical Industries, Ltd.) for 30 seconds, washed with water for 60 seconds, 10% sodium hypochlorite solution (Neo Cleaner "Sekine", Neo Pharmaceutical Industry Co., Ltd.) was applied for 60 seconds, and then washed with water for 60 seconds.

(2) Preparation of artificial saliva Sodium chloride (8.77 g, 150 mmol), monopotassium dihydrogen phosphate (122 mg, 0.9 mmol), calcium chloride (166 mg, 1.5 mmol), Hepes (4.77 g, 20 mmol) Each was weighed into a weighing dish and sequentially added to a 2000 ml beaker containing about 800 ml of distilled water while stirring. After confirming that the solute was completely dissolved, while measuring the acidity of this solution with a pH meter (F55, Horiba, Ltd.), a 10% sodium hydroxide aqueous solution was gradually added to adjust the pH to 7.0.

(3) Sealing of dentin tubules 0.1 ml of a tooth surface treatment material was dropped onto the buccal dentin surface of the bovine tooth disk obtained in (1) above, and left to stand for 3 minutes. Thereafter, the surface of the bovine tooth disc was washed with distilled water and immersed in the artificial saliva obtained in (2) above at 37°C for 24 hours to obtain a test piece for SEM observation.

(4) SEM observation The test piece obtained in (3) above is dried at room temperature under reduced pressure for 1 hour and subjected to metal vapor deposition treatment, and then any three points on the surface treated with the tooth surface treatment material are scanned with a scanning electron Observations were made using a microscope (S-3500N, manufactured by Hitachi High-Technologies Corporation) at a magnification of 3000 times. The dentinal tubule sealing rate in each observation field was calculated according to the following formula, and the values of 3 points were averaged. The test was performed with n=5, and the values obtained in each test were averaged to obtain the dentinal tubule sealing rate. The dentinal tubule sealing rate of the test piece was determined by the following formula.
Dentin tubule blocking rate (%) = {(number of blocked dentinal tubules)/(number of dentinal tubules)} × 100

The single material type tooth surface treatment material of the present invention is easy to handle and is useful for suppressing the progression of caries and suppressing hypersensitivity without impairing the aesthetic surface of the treatment site. In addition, the one-component tooth surface treatment material of the present invention has no smell of ammonia, is excellent in feeling when used, and can be suitably used as a material for inhibiting caries progression, a material for inhibiting hypersensitivity, and the like. Furthermore, the one-component tooth surface treatment material of the present invention is excellent in acid resistance and storage stability.

Claims (10)

Containing complex ions (A) of silver ions and iodide ions and water,
The concentration of silver atoms present in a dissolved state in the solution is 500 to 125,000 ppm by mass with respect to the mass of the single material type tooth surface treatment material ,
A single material type tooth surface treatment material that does not turn black even after 24 hours or more after treatment. The iodide ion is derived from iodide salt (B), the silver ion is derived from silver salt (C), and the silver salt (C) is silver diammine fluoride, silver nitrate (I), silver fluoride ( I), silver chloride (I), silver bromide (I), silver carbonate (I), silver iodide (I), silver oxide (I), silver chlorate (I), silver perchlorate (I), Silver chromate (I), silver hexafluoroantimonate (V), silver hexafluorophosphate (I), silver nitrite (I), silver sulfate (I), silver thiocyanate (I), silver vanadate and organic silver A tooth surface treatment material comprising at least one silver compound selected from the group consisting of salts, wherein the molar ratio of the iodide salt (B)/the silver salt (C) is the same as the silver salt (C). 2. The one-material type tooth surface treatment material according to claim 1, which is at least the lower limit value for completely dissolving in . The iodide ion is derived from an iodide salt (B), the silver ion is derived from a silver salt (C), and the silver salt (C) is selected from the group consisting of silver iodide (I) and an organic silver salt. At least one silver compound is selected, and the molar ratio of the iodide salt (B)/the silver salt (C) is such that the silver salt (C) is completely dissolved in the single-component tooth surface treatment material. 2. The one-component tooth surface treatment material according to claim 1, which is less than the lower limit. The organic silver salt is silver formate (I), silver acetate (I), silver citrate (I), silver oxalate (II), silver gluconate, silver propionate (I), silver succinate (I), Silver malonate (I), silver DL-tartrate (I), silver laurate (I), silver palmitate (I), silver N,N-diethyldithiocarbamate (I), silver 2-ethylhexanoate (I) ), silver lactate (I), silver methanesulfonate (I), silver salicylate (I), silver p-toluenesulfonate (I), silver trifluoroacetate (I), silver trifluoromethanesulfonate (I) and stearin 4. The one-component tooth surface treatment material according to claim 2 or 3, which is at least one silver compound selected from the group consisting of silver acid (I). The iodide ion is derived from an iodide salt (B), and the iodide salt (B) is a group consisting of sodium iodide, potassium iodide, rubidium iodide, magnesium iodide, calcium iodide and strontium iodide. 5. The single material type tooth surface treatment material according to any one of claims 1 to 4, which is at least one compound selected from: 6. The composition according to any one of claims 1 to 5, which does not turn black when it is applied to a hydroxyapatite plate and allowed to stand for 24 hours under an environment of 25°C and an illumination intensity of 1200 lux to evaporate water. Single material type tooth surface treatment material. The one-component tooth surface treatment material according to any one of claims 1 to 6, further comprising a water-soluble fluoride salt (D). The one-component tooth surface treatment material according to any one of claims 1 to 7, which is for caries prevention. The single-component tooth surface treatment material according to any one of claims 1 to 7, which is for suppressing hypersensitivity. An iodide aqueous solution having an iodide salt (B) concentration of 5 to 60% by mass and a silver salt (C) are mixed so that the iodide salt (B)/silver salt (C) molar ratio is 0.5 or more. including a step of generating a complex ion (A) mixed so that
The concentration of silver atoms present in a dissolved state in the solution is 500 to 125,000 ppm by mass with respect to the mass of the single material type tooth surface treatment material ,
10. The method for producing a one-component tooth surface treatment material according to any one of claims 1 to 9, wherein the tooth surface treatment material does not turn black even after 24 hours or more after treatment .

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