WO2018092889A1

WO2018092889A1 - Single-material-type tooth surface treatment material

Info

Publication number: WO2018092889A1
Application number: PCT/JP2017/041505
Authority: WO
Inventors: 憲司畑中; 直樹西垣
Original assignee: クラレノリタケデンタル株式会社
Priority date: 2016-11-18
Filing date: 2017-11-17
Publication date: 2018-05-24
Also published as: JP7142574B2; JPWO2018092889A1

Abstract

The present invention provides an easy-to-handle single-material-type tooth surface treatment material which suppresses hyperesthesia or suppresses the progress of tooth decay without damaging the surface aesthetics of the treated site. The present invention relates to the single-material-type tooth surface treatment material containing water and a complex ion (A) of an iodide ion and a silver ion.

Description

One material type tooth surface treatment material

The present invention relates to a tooth surface treatment material that is one-material type, easy to handle, excellent in storage stability, suppresses the progress of caries without impairing the aesthetic surface of the treatment site, and suppresses hypersensitivity.

The rate of remaining teeth among elderly people is increasing due to the improvement of dental treatment technology and enlightenment activities represented by the 8020 movement. However, with the onset of aging, dementia, and the like, the level of regular oral care is reduced, and the simultaneous increase in dental caries on the root surface and adjacent surface has become a clinical problem.

In many cases of such symptoms, it is difficult for the patient to open his / her mouth sufficiently for treatment, and therefore, filling and repairing treatment with a composite resin or the like becomes extremely difficult. As one of the treatment methods in such a situation, the progress of caries is suppressed by utilizing the antibacterial property of the silver compound. For example, a method of stopping caries by applying a drug such as saphoride (Beebrand Medico Dental Co., Ltd.) containing silver diammine fluoride has been performed. However, the conventional method has a clinical problem that the affected area to which the drug is applied turns black and greatly deteriorates aesthetics.

Patent Document 1 discloses a two-stage tooth in which a liquid containing a silver compound (first liquid) is applied to an affected area, and then a liquid containing an alkali metal halide or alkaline earth metal halide (second liquid) is applied. A face treatment method is described. According to this, secondary caries did not occur even after 6 months from the treatment, and no black discoloration was observed in the treatment area. However, in this treatment method, two chemicals are required. First, a liquid containing a silver compound is applied, dried, and then the second liquid is applied, so that an excess silver compound that causes discoloration is separated from another silver compound. However, a complicated operation of removing from the treatment portion was necessary.

Patent Document 2 describes a method for reducing caries by applying a composition containing silver diammine fluoride and a carrier that allows continuous release of silver diammonium fluoride and adheres to the tooth surface to the affected area. Has been. According to this, the caries are stopped after 6 months from the treatment. However, the treatment method does not solve the problem that the affected area turns black. Thus, it is difficult to achieve both the one-material type and not to change the affected area to black after the treatment, and there has been no tooth surface treatment material that satisfies both of these points.

US Pat. No. 6,461,161 US 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 with a single material type and 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 can be easily handled with a single material type and that can suppress hypersensitivity without impairing the aesthetic surface of the treatment site. Furthermore, an object of the present invention is to provide a one-material type tooth surface treatment material that has no ammonia smell and is excellent in the feeling of use. Another object of the present invention is to provide a one-part tooth surface treatment material that is excellent in storage stability. Furthermore, an object of the present invention is to provide a one-part tooth surface treatment material excellent in acid resistance.

The present invention provides a one-part tooth surface treatment material containing a complex ion (A) of silver ions and iodide ions (A) 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 relative to the mass of the one-material type tooth surface treatment material. preferable.

In one embodiment of the tooth surface treatment material of the present invention, the iodide ion is derived from an iodide salt (B), the silver ion is derived from a silver salt (C), and the silver salt is as follows. (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), It is at least one silver compound selected from the group consisting of silver sulfate (I), silver thiocyanate (I), silver vanadate, and organic silver salt, and the iodide salt (B) / silver salt (C) It is preferable that the molar ratio is not less than the lower limit value at which the silver salt (C) is completely dissolved in the one-material type tooth surface treatment material.

Moreover, the tooth surface treatment material of one material type of the present invention, as another embodiment, the iodide ion is derived from an iodide salt (B), and the silver ion is supplied from the 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 salt, and the molar ratio of the iodide salt (B) / the silver salt (C) However, it is preferable that the silver salt (C) is less than a lower limit value at which the silver salt (C) is completely dissolved in a one-material type tooth surface treatment material.

In one material type tooth surface treatment material of the present invention, the organic silver salt is silver formate (I), silver acetate (I), silver citrate (I), silver oxalate (II), silver gluconate, propion. Silver (I), silver (I) succinate (I), silver malonate (I), DL-silver 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 ( It is preferably at least one silver compound selected from the group consisting of I), silver trifluoromethanesulfonate (I) and silver stearate (I).

In the tooth surface treating material of one material type 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 It is preferably at least one compound selected from the group consisting of magnesium iodide, calcium iodide and strontium iodide.

The tooth surface treatment material of one material type according to the present invention should not turn black when applied to a hydroxyapatite plate and then left to stand for 24 hours in an environment with an illuminance of 1200 lux at 25 ° C. to evaporate water. Is one of the features.

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

The one-surface type tooth surface treatment material of the present invention is for preventing caries.

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

The present invention also provides an iodide aqueous solution having an iodide salt (B) concentration of 5 to 60% by mass and a silver salt (C) in a molar ratio of iodide salt (B) / silver salt (C). The manufacturing method of the one-material type tooth surface treatment material including the production | generation process of the complex ion (A) mixed so that it may become 0.5 or more is provided.

According to the present invention, it is possible to provide a tooth surface treatment material that is easy to handle with a single material type and can suppress the progress of dental 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 with a single material type 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 has no ammonia odor and is excellent in the feeling of use. Another object of the present invention is to provide a one-part tooth surface treatment material that is excellent in storage stability. Furthermore, this invention can provide the one-material type tooth surface processing material excellent in acid resistance.

It is an analysis chart which shows the result of the X-ray-diffraction analysis of the deposit which added the same quantity of water to the one-surface type tooth surface processing material which concerns on Example 2 of this invention, and was made to precipitate. It is an analysis chart which shows the result of the X-ray-diffraction analysis of the deposit which added the same quantity of water to the one-material type tooth surface processing material which concerns on Example 15 of this invention, and was made to precipitate.

DETAILED DESCRIPTION OF THE INVENTION The present invention is a one-part tooth surface treatment material characterized by containing complex ions (A) of silver ions and iodide ions (A) and water.

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

Since silver ions have a bactericidal power against bacteria, they are widely used as antibacterial agents, and are also applied as dental agents for the purpose of controlling caries. However, silver-based dental agents that have been used in the past produce silver (I) oxide (Ag ₂ O) in the air, and the treated area turns black. Furthermore, in order to avoid the formation of silver oxide (I), after applying a liquid containing a silver compound (first liquid), a liquid containing a halogenated alkali metal or an alkaline earth metal halide (second liquid) is applied. Although the method of apply | coating and chemically removing the silver compound which exists excessively in an affected part is also used, it is a two-material type | mold and operation is complicated (refer patent document 1).

On the other hand, 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 impairing the aesthetic surface of the treatment site, and suppresses hypersensitivity. A composition characterized by containing complex ions (A) of ions and iodide ions (A) and water, is easy to handle with a single material type, suppresses the progress of caries without damaging the aesthetic surface of the treatment site, It was also found that hypersensitivity can be suppressed.

It is considered as follows that the one-surface type tooth surface treatment material of the present invention is easy to handle and can suppress the progression of caries without impairing the aesthetic surface of the treatment site. First, in order to prevent the treatment portion from being discolored black due to the generation of silver oxide (I) (Ag ₂ O), silver iodide (AgI), which does not easily turn black in the air, is applied after applying the tooth surface treatment material. It was decided to generate. Next, in order to suppress the progress of caries, the silver compound needs to be present in a state of silver ions in the tooth surface treatment material, but silver iodide is hardly dissolved in water. However, in an aqueous solution containing an iodide salt (B), silver iodide can be dissolved and exist as a complex ion (A) of silver ions and iodide ions. In the method described in Patent Document 1, excess silver compound is removed to obtain the effect, whereas in the present invention, the silver compound is iodine in the form of an aqueous solution containing an iodide salt (B). By supplying in the presence of silver halide, a caries inhibitory effect is obtained by making it exist as a complex ion (A) of silver ions and iodide ions. For this reason, in the one-surface type tooth surface treatment material of the present invention, silver is present in an ionic state in advance, and it can be easily distributed to places where the applicator such as the adjacent surface of the tooth is difficult to reach. . Thereby, an excellent caries-suppressing effect is expected in any affected part. Further, the complex ion (A) of silver ions and iodide ions that have penetrated into the affected area is precipitated as silver iodide in the tooth, and therefore the treated area does not turn black. Furthermore, since the solution containing the complex ion (A) of silver ions and iodide ions is stable without blackening or re-precipitation, it can be easily stored and handled as a one-material type. Further, the one-surface type tooth surface treatment material of the present invention has acid resistance necessary in the oral cavity.

Further, as means for generating silver iodide in the tooth after applying the tooth surface treatment material, silver ion and iodide are dissolved by dissolving silver iodide itself in an aqueous solution containing iodide salt (B) as described above. In addition to obtaining the complex ion (A) of ions, it is also effective to select a silver salt (C) other than silver iodide that can be dissolved in an aqueous solution containing an iodide salt (B). When the silver salt (C) other than silver iodide is dissolved in an aqueous solution containing the iodide salt (B), the Ag—I bond has a strong covalent bond, and therefore, a stable complex ion of silver ion and iodide ion. (A) is considered to be generated.

It is considered as follows that the one-surface type tooth surface treatment material of the present invention is a one-material type, is easy to handle, and can suppress hypersensitivity without impairing the aesthetic surface of the treatment site. When the tooth surface treatment material penetrates into the dentinal tubule, it comes into contact with the tissue fluid present in the dentinal tubule. Silver ions are particularly reactive with thiol groups of proteins that make up tissue fluids. As a result of the reaction, the protein is denatured, the viscosity of the tissue fluid in the dentinal tubule increases, and the movement of the tissue fluid in the dentinal tubule is suppressed, so that it is considered that hypersensitivity is suppressed. In addition, physical blockage by silver iodide precipitated in dentinal tubules is considered to be effective in combination with suppression of hypersensitivity. When the one-surface type tooth surface treatment material of the present invention is for suppressing hypersensitivity, it is preferable that the dentinal tubule sealing rate is high. When used as a material for suppressing hypersensitivity, the concentration of silver atoms present in a solution in the solution is preferably 500 to 125,000 ppm by mass, preferably 2,000 to 125,000, based on the mass of the one-surface type tooth surface treatment material. 000 ppm by mass is more preferable, and 10,000 to 125,000 ppm by mass is more preferable.

The tooth surface treatment material of one material type of the present invention contains complex ions (A) of silver ions and iodide ions (A) and water, but the concentration of silver atoms present in the solution in the solution state is that of one material type. It is preferably 10 to 125,000 mass ppm with respect to the mass of the tooth surface treatment material. When the silver atom concentration is less than 10 ppm by mass, the caries-suppressing effect when the tooth surface treatment material is applied is considerably smaller than that of a commercially available caries-suppressing material (for example, saholide). The silver atom concentration is preferably 1000 ppm by mass or more, and more preferably 10,000 ppm by mass or more. On the other hand, when the concentration exceeds 125,000 ppm by mass, the antibacterial effect does not change even when the concentration is higher than that. Since silver compounds are generally expensive, there is no merit in terms of cost. Further, the complex ion (A) of silver ions and iodide ions cannot be completely dissolved and silver iodide may be precipitated. The silver atom concentration is more preferably 120,000 mass ppm or less. The calculation method of the silver atom concentration is as in the examples described later.

Although the silver ion used for the tooth surface treatment material of the one material type | mold of this invention originates in silver salt (C) and is not specifically limited, silver salt (C) is a certain embodiment ("1st embodiment"). In addition, silver diammine fluoride (Ag (NH ₃ ) ₂ F), 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 At least one selected from the group consisting of (I), silver nitrite (I), silver sulfate (I), silver thiocyanate (I), silver vanadate (AgVO ₃ ), and organic silver salt is preferably used. Among these, silver iodide (I) is more preferable because it easily increases the silver concentration 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 molar ratio of iodide salt (B) / silver salt (C) is: It is preferable that the silver salt (C) is not less than a lower limit value at which the silver salt (C) is completely dissolved in the one-material type tooth surface treatment material. However, silver iodide (I) and organic silver salts are not limited as described later. Here, the “lower limit value for complete dissolution” means the lower limit value of the molar ratio of iodide salt (B) / silver salt (C) in which the silver salt (C) is visually dissolved.

About the lower limit which a silver salt (C) melt | dissolves completely, it changes with types of silver salt (C). Silver (I), silver bromide (I), silver 2-ethylhexanoate (I) and other AgX (X means an atom or a functional group to which Ag atoms are bonded) type silver The lower limit value for completely dissolving the salt (C) is that the molar ratio of iodide salt (B) / silver salt (C) is 3.5. That is, as the tooth surface treatment material of one material type of the first embodiment, in the case of AgX type, the molar ratio of iodide salt (B) / silver salt (C) is preferably 3.5 or more. However, in the case of silver iodide (I) even in the AgX type, 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 value for completely dissolving the silver salt (C) is that the molar ratio of iodide salt (B) / silver salt (C) is 7.5. . That is, in the case of the Ag ₂ X type, the one-type tooth surface treatment material of the first embodiment preferably has an iodide salt (B) / silver salt (C) molar ratio of 7.5 or more. Furthermore, in the case of an Ag ₃ X type such as silver citrate, the lower limit value for completely dissolving the 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, the one-type tooth surface treatment material of the first embodiment preferably has an iodide salt (B) / silver salt (C) molar ratio of 10 or more. When the molar ratio of iodide salt (B) / silver salt (C) 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. . For this reason, depending on the type of the silver salt (C), when the tooth surface treatment material is applied, the undissolved silver salt (C) may be oxidized and blackened.

In the case where the silver salt (C) used in the one-surface type tooth surface treatment material of the present invention is silver iodide (I) and an organic silver salt which are not easily blackened, the iodide salt (B) The molar ratio of / silver salt (C) may be less than the lower limit value at which the silver salt (C) is completely dissolved in the one-surface type tooth surface treatment material. Therefore, as 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 salt. There is an embodiment in which the molar ratio of iodide salt (B) / silver salt (C) is less than the lower limit value at which the silver salt (C) is completely dissolved. Although undissolved silver salt (C) is present in the tooth surface treatment material, when the tooth surface treatment material is applied, the silver salt (C) is silver iodide (I) or an organic silver salt. The tooth surface treatment material of one material type of the second embodiment is also difficult to turn black.

Although it does not specifically limit as organic silver salt used for the tooth surface treatment material of one material type of this invention, Silver formate (I), Silver acetate (I), Silver citrate (I), Silver oxalate (II) , Silver gluconate, silver propionate (I), silver succinate (I), silver malonate (I), DL-silver 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) At least one selected from the group consisting of silver (I) trifluoroacetate, silver (I) trifluoromethanesulfonate and silver (I) stearate is preferably used. Among these, from the viewpoint of safety to living bodies, silver formate (I), silver citrate (I), silver oxalate (II), silver propionate (I), silver succinate (I), 2-ethyl Silver hexanoate (I), silver lactate (I), silver salicylate (I), and silver N, N-diethyldithiocarbamate (I) are more preferred.

The iodide ion used in the present invention is derived from the iodide salt (B) and is not particularly limited, but the 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 tooth surface treatment material of one material type of the present invention produces silver (I) in the inside and surface of the tooth when water is evaporated after being applied to the tooth, etc., and more than 24 hours have passed after the treatment. Will not turn black. The degree of blackening was quantified by the method described in the 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 application of the tooth surface treatment material is 20 or less. Is preferred. It is preferably 15 or less, more preferably 10 or less. The method of measuring the color difference is as described in the examples described later.

In one embodiment, the one-surface type tooth surface treatment material of the present invention preferably further contains a water-soluble fluoride salt (D) from the viewpoint of acid resistance. Although it does not specifically limit as water-soluble fluoride salt (D), 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, Examples include laurylamine hydrofluoride, glycine hydrofluoride, alanine hydrofluoride, and fluorosilanes. Of these, sodium fluoride, potassium fluoride, sodium monofluorophosphate, and tin fluoride are preferably used from the viewpoint of safety to the living body.

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

Although the manufacturing method of the tooth surface treatment material of the one material type | mold of this invention is not specifically limited, For example, iodide salt (B), the method of mixing silver salt (C) and water, and dissolving; iodide salt (B) Silver ion and iodide can be dissolved by adding silver salt (C) to a solution of water and water; by adding iodide salt (B) to a mixed solution of silver salt (C) and water and dissolving. A step of generating complex ions (A) of ions. The means for dissolving the components after mixing them is not particularly limited, but can be achieved by methods such as stirring dissolution using a stirring blade, vibration dissolution, ultrasonic dissolution, rotation and revolution stirring stirring and dissolution.

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

The tooth surface treatment material of one material type of the present invention is a complex ion (A) of silver ion and iodide ion, iodide salt (B), silver salt (C), water-soluble within a range not inhibiting the effects of the present invention. Fluoride salt (D) and other components other than water may be contained. For example, a thickener, a solvent, a coloring agent, a fragrance | flavor, etc. can be mix | 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 a single-tooth type tooth surface treatment material.

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

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, Examples include acetonitrile and dimethylformamide. Among these, ethanol, 1-propanol, acetone, and glycerin that are highly safe for living bodies are preferable.

If necessary, sugar alcohols such as xylitol, sorbitol and erythritol; artificial sweeteners such as aspartame, acesulfame potassium, licorice extract, saccharin and saccharin sodium may be added. Furthermore, any pharmacologically acceptable drug or the like can be blended. Antibacterial agents typified by cetylpyridinium chloride, etc .; antiseptics; anticancer agents; antibiotics; blood circulation improving agents such as actosine and PGE1; growth factors such as bFGF, PDGF and BMP; osteoblasts; odontoblasts; Bone marrow-derived stem cells; embryonic stem (ES) cells; induced pluripotent stem (iPS) cells obtained by dedifferentiation and production of differentiated cells such as fibroblasts by gene transfer, and cells such as differentiated cells Cells or the like that promote tissue formation can be added.

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

The present invention includes embodiments in which the above configurations are combined in various ways within the technical scope of the present invention as long as the effects of the present invention are exhibited.

EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples, and many modifications are possible in the art within the technical idea of the present invention. This is possible by those with ordinary knowledge.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

[Antimicrobial test (inhibition circle formation test)]
Evaluation was performed according to the qualitative test (Hello method) of JIS L 1902: 2008 “Antimicrobial 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 with respect to 1000 mL of purified water, 0.1 mol / kg so that the pH becomes 7.0. Prepared with L sodium hydroxide solution and pasteurized with high pressure steam to prepare bouillon medium. One mutans bacterium was transplanted into this broth medium and cultured at 37 ° C. for 24 hours to adjust the bacterium concentration to 7.1 × 10 ⁶ cells / mL.

(2) Preparation of pour plate medium After putting 1 mL of the bacterial solution obtained in (1) above into a sterilized petri dish, add 15 mL of a normal agar medium kept at 45 ° C. to the petri dish, and mix well. Leave it to solidify the agar. This was inverted and left at room temperature for an additional hour to dry excess moisture.

(3) Placement and culture of test pieces Place a paper disk (diameter 10 mm) pre-impregnated with 0.05 mL of the solution prepared in the examples and comparative examples in the center of the pouch plate medium obtained in (2) above. Adhered. Then, it culture | cultivated for 24 hours at 37 degreeC.

(4) Measurement of inhibition circle After incubation, the inhibition circle width is calculated from the bottom side of the petri dish based on the following for the inhibition circle formed around the paper disk.
W = (TD) / 2
Where W represents the width (mm) of the blocking circle (halo), T represents the sum of the length of the paper disk and the width of the blocking circle (mm), and D represents the length of the paper disk (mm). .)

[Discoloration test (black discoloration)]
(1) Application of tooth surface treatment material 0.01 mL of tooth surface treatment material was sampled on a hydroxyapatite plate (manufactured by HOYA Techno Surgical Co., Ltd.) 10 mm in length and width, and 2 mm in thickness, and micro brush regular (manufactured by Microbrush) ) Was applied for 10 seconds so as to spread over the entire surface of the hydroxyapatite plate. Then, it left still for 24 hours in 25 degreeC and the illumination intensity of 1200 lux, and water was evaporated.

(2) Evaluation of discoloration A spectrocolorimeter (manufactured by Konica Minolta Japan Co., Ltd., model number CM-3610d, JIS Z 8722: 2009) was applied to the portion of the hydroxyapatite plate obtained in (1) to which the tooth surface treatment material was applied. In the L * a * b * color system of JIS Z 8781-4: 2013 when the chromaticity is measured in accordance with condition c, light source D65, white background) and a standard white plate placed behind the sample to measure chromaticity Blackness was evaluated by measuring a color difference (ΔL *) from the L value (initial value) before applying the tooth surface treatment material by measuring a lightness index L *.

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

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

(3) Evaluation of acid resistance The nail polish covered with the above (1) was carefully peeled off with a razor from the bovine tooth test piece prepared in the above (2). 3D laser microscope (VK-9710, Keyence Corporation) with the vertical distance from the bottom and the reference surface of the test window deashed by acid dipping as the reference surface around the test window protected by the nail polish Manufactured). The measurement was performed for each side of a 3 mm × 3 mm square test window, and the average value was obtained. The smaller the decalcification depth value, the better the acid resistance. When the tooth surface treatment material was not applied, the thickness was 103 μm.

[Storage stability test]
5 g of the liquid material obtained from Examples 1 to 19 and Comparative Examples 1 and 2 was precisely 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: More than 1 month after the preparation, no precipitates and no discoloration are maintained and the transparent properties are maintained.
B: From 1 to 1 month after preparation, the precipitate and the discoloration are maintained and the transparent property is maintained.
C: Precipitation or discoloration occurs after preparation, and good properties cannot be maintained.

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

(2) System in which silver salt (C) is not dissolved The silver atom concentration dissolved in the solution was measured using a silver ion meter (manufactured by KDD Corporation). Add the coloring reagent attached to the silver ion meter to the solution to be measured, and mix well by shaking. The colored solution was set on a silver ion meter, and the silver atom concentration was measured. When the silver atom concentration exceeds the upper limit of the measuring range of the measuring instrument, the composition is diluted with a 50 mass% potassium iodide aqueous solution and measured again.

[Component analysis of precipitates generated by water addition]
(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 off, 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 is filled in a sample plate made of SiO _{2 and} installed in an X-ray diffraction analysis apparatus (SmartLab, manufactured by Rigaku Corporation), and the tube voltage and tube current are 45 kV. -200 mA, the detector was a one-dimensional semiconductor detector, and the composition analysis was performed.

[Examples 1 to 19]
By the procedure shown above, antibacterial activity, discoloration, acid resistance, storage stability, and precipitates upon addition of water were evaluated. The obtained evaluation results are shown in Tables 1 to 4. In addition, the precipitation at the time of water addition was performed only about Example 2 and 15. FIGS. 1 and 2 show analysis charts obtained by performing X-ray diffraction analysis on the precipitates obtained by adding the same amount of water to the tooth surface treatment materials obtained in Examples 2 and 15 and precipitating them. In 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.

For Examples 1 to 19 and Comparative Example 1, the dentinal tubule blockage rate was measured by the following method. The results are shown in Table 7.

[Ivory tubule blockage rate test]
(1) Preparation of a bovine tooth disc The center of the cheek side of a healthy bovine incisor was polished with water-resistant abrasive paper in the order of No. 80 and No. 1000 to expose the dentin, and a disc having a diameter of about 7 mm and a thickness of 2 mm was formed. . The bovine tooth polishing surface was further polished with a lapping film (manufactured by Sumitomo 3M Limited) in the order of 1200, 3000, and 8000. Next, after immersing in a 5-fold diluted solution of 0.5M EDTA solution (manufactured by Wako Pure Chemical Industries, Ltd.) for 30 seconds, washed with water for 60 seconds, 10% sodium hypochlorite solution (Neocleaner “SEKINE”, Neo Pharmaceutical Industries) Made 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 added sequentially to a 2000 ml beaker containing about 800 ml of distilled water with stirring. After confirming that the solute was completely dissolved, the acidity of this solution was measured with a pH meter (F55, HORIBA, Ltd.), and a 10% sodium hydroxide aqueous solution was appropriately adjusted to pH 7.0.

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

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

The single-surface tooth surface treatment material of the present invention is easy to handle and is useful for suppressing the progression of caries and hypersensitivity without impairing the aesthetic surface of the treatment site. In addition, the one-surface type tooth surface treatment material of the present invention does not have an ammonia odor, has an excellent feeling of use, and can be suitably used as a caries progress inhibitor, a hypersensitivity inhibitor, or the like. Furthermore, the one-surface type tooth surface treatment material of the present invention is excellent in acid resistance and storage stability.

Claims

One-material tooth surface treatment material containing silver ion and iodide complex ion (A) and water.
The single-part tooth surface treatment material according to claim 1, wherein the concentration of silver atoms present in the solution in a dissolved state is 10 to 125,000 mass ppm relative to the mass of the single-material type tooth surface treatment material. .
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 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 (I) chromate, silver hexafluoroantimonate (V), silver (I) hexafluorophosphate, silver (I) nitrite, silver (I) sulfate, silver (I) thiocyanate, silver vanadate and organic silver A tooth surface treatment material, which is at least one silver compound selected from the group consisting of salts, wherein the iodide salt (B) / silver salt (C) has a molar ratio of the silver salt (C). The tooth surface treatment material of one material type according to claim 1 or 2, wherein the tooth surface treatment material is at least a lower limit value that completely dissolves in the material.
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 a group consisting of silver iodide (I) and an organic silver salt. It is at least one selected silver compound, and the molar ratio of the iodide salt (B) / the silver salt (C) is such that the silver salt (C) is completely dissolved in a single tooth type tooth surface treatment material. The single-surface type tooth surface treatment material according to claim 1 or 2, wherein the tooth surface treatment material is less than a lower limit value.
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), DL-silver 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 The single-surface type tooth surface treatment material according to claim 3 or 4, which is at least one silver compound selected from the group consisting of acid silver (I).
The iodide ion is derived from an iodide salt (B), and the iodide salt (B) is composed of sodium iodide, potassium iodide, rubidium iodide, magnesium iodide, calcium iodide and strontium iodide. The one-surface type tooth surface treatment material according to any one of claims 1 to 5, which is at least one compound selected from the group consisting of:
7. After applying to a hydroxyapatite plate, it does not turn black when it is allowed to stand for 24 hours in an environment with an illuminance of 1200 lux at 25 ° C., and does not turn black. One material type tooth surface treatment material.
The one-surface type tooth surface treatment material according to any one of claims 1 to 7, further comprising a water-soluble fluoride salt (D).
The single-surface type tooth surface treatment material according to any one of claims 1 to 8, which is used for preventing caries.
The one-surface type tooth surface treatment material according to any one of claims 1 to 8, which is used for suppressing hypersensitivity.
An iodide aqueous solution having a concentration of iodide salt (B) of 5 to 60% by mass and a silver salt (C) have an iodide salt (B) / silver salt (C) molar ratio of 0.5 or more. The method for producing a one-surface type tooth surface treatment material according to any one of claims 1 to 10, further comprising a step of producing complex ions (A) to be mixed.