Powder mixture for spraying onto tooth surfaces or into gingival sulci / periodontal pockets.

Abstract

This powder mixture, which is for spraying, and for spraying, via a powder spraying device, into supragingival or subgingival tooth surfaces, or into a gingival sulcus and a periodontal pocket, is characterized by comprising: (a) at least one selected from the group consisting of a saccharide, a sugar alcohol, an amino acid, a phosphate compound, a carbonate compound, and a calcium compound; and (b) a hydrophobic fine particle silica.

Description

Technical Field

[0001] The present invention relates to a jet powder mixture, and particularly to a jet powder mixture that is mixed with air in a powder / air mixing chamber of a powder jet device, and then jetted onto supragingival or subgingival tooth surfaces, or into gingival sulci and periodontal pockets.

Background Art

[0002] Periodontal disease refers to all diseases occurring in periodontal tissue composed of gingiva, cementum, periodontal ligament and alveolar bone. It is an inflammatory disease mainly caused by oral bacteria in plaque, and is roughly divided into gingivitis and periodontitis. Inflammation localized to the gingiva is called "gingivitis", and a condition where inflammation extends beyond the gingiva to the periodontal ligament and alveolar bone, causing damage and destruction of these sites, is called "periodontitis". In the case of gingivitis, even though inflammation is observed in periodontal tissue, the inflammation does not spread to the periodontal ligament or alveolar bone, so the disease can be cured by mechanically removing the causative plaque. However, when symptoms progress from gingivitis to periodontitis, tooth mobility, damage and destruction of the periodontal ligament and alveolar bone occur; if the condition becomes more severe, it is difficult to restore the original healthy state even if plaque is mechanically removed.

[0003] In recent years, periodontal disease has been classified as a lifestyle-related disease, prevalent in approximately 80% of adults, and is the leading cause of tooth loss in adults. In addition, recent studies have suggested the association between periodontal disease and serious systemic diseases (diabetes, arteriosclerosis, heart disease, preterm birth, low birth weight delivery, cerebrovascular disease, etc.), and it has become clear that periodontal disease is a risk factor. Furthermore, the characteristics of periodontal disease are inflammation of soft tissues around the teeth, exposure of the root surface, formation of periodontal pockets, and progressive destruction of the fibrous tissues supporting teeth and alveolar bone. If periodontal disease is left untreated, it will eventually lead to tooth loss. Caries and periodontal disease have long been regarded as the two major diseases in dentistry. While the incidence of caries has gradually decreased, periodontal disease shows no tendency to decline because it is an intractable disease, and countermeasures against it are considered important and urgent issues in preventive medicine. For this reason, it is important to detect periodontal disease as early as possible and provide immediate treatment to prevent it from becoming severe.

[0004] To prevent periodontal disease, it is necessary to remove as much plaque and tartar as possible that has adhered not only to the tooth surface above the gum line, but also to the gingival sulcus below the gum line and the narrow areas within the periodontal pocket. Traditionally, this periodontal treatment has mainly involved mechanical cleaning using curettes, sonic or ultrasonic scalers. However, the use of these instruments requires a high level of skill from the user, and it could not be denied that it caused discomfort to the patient. Furthermore, repeated mechanical cleaning could wear down the tooth roots, leading to the risk of developing hypersensitivity and weakening of the tooth roots.

[0005] To prevent and treat such periodontal diseases, it has been reported that a spray powder mixture is sprayed together with water from a powder spraying device to clean the tooth surface (for example, U.S. Patent No. 4,174,571, U.S. Patent No. 4,595,365, Japanese Patent Publication No. 4418,113, U.S. Patent No. 6,126,444, U.S. Patent No. 5,810,587, and Japanese Patent Publication No. 5,846,720, etc.). [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent Publication No. 4174571 [Patent Document 2] U.S. Patent No. 4,595,365 [Patent Document 3] Patent Publication No. 4418113 [Patent Document 4] U.S. Patent No. 6126444 [Patent Document 5] U.S. Publication No. 5810587 [Patent Document 6] Patent Publication No. 5846720 [Overview of the project] [Problems that the invention aims to solve]

[0007] However, the conventional powder mixtures for injection described above, while possessing excellent fluidity that allows for easy discharge from a powder injection device, were unable to adequately prevent damage to the tooth surface.

[0008] The present invention aims to provide a powder mixture for a powder spraying device that has superior fluidity when discharged from the powder spraying device and low abrasiveness that does not damage the tooth surface, in order to solve the aforementioned problems of the conventional invention. [Means for solving the problem]

[0009] In other words, the present invention is A powder mixture for spraying onto the tooth surface above or below the gingival margin, or into the gingival sulcus and periodontal pocket, using a powder spraying device, (a) at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds, (b) Hydrophobized silica particles A powder mixture for spraying containing the following To provide. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a powder mixture composition for a powder spraying device that has superior fluidity when discharged from the spraying device and low abrasiveness that does not damage the tooth surface. [Brief explanation of the drawing]

[0011] [Figure 1] Figure 1 shows the external appearance of an angle of repose measuring instrument. [Figure 2] Figure 2 shows the angle of repose. [Modes for carrying out the invention]

[0012] The following describes a powder mixture for spraying, which is an embodiment for carrying out the present invention.

[0013] Unless otherwise specified with terms such as "less than", "smaller than" or "larger than", the numerical ranges mentioned in the present specification are intended to include the lower limit and upper limit per se. That is, taking a numerical range from 1 to 100 as an example, the numerical range is interpreted to include the lower limit "1" and the upper limit "100".

[0014] [Mechanism of Action] An embodiment of the present invention (hereinafter referred to as "the present embodiment") is A powder mixture for spraying by a powder jet device onto a supragingival or subgingival tooth surface, or into a gingival sulcus and periodontal pocket, (a) at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds, and (b) hydrophobized fine-particle silica, which is a spraying powder mixture comprising the above components. The spraying powder mixture according to the present embodiment has both superior fluidity and low abrasiveness. The reason for this, while not being bound by any particular theory, is presumed as follows. The spraying powder mixture according to the present embodiment comprises (a) at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds, and (b) hydrophobized fine-particle silica. Here, since component (a) has relatively high hydrophilicity, the component (a) particles tend to aggregate with each other. However, when component (b) intervenes between component (a) particles, it suppresses a significant increase in particle size caused by aggregation of component (a). For this reason, the spraying powder mixture according to the present embodiment has superior fluidity. Furthermore, since the increase in particle size of component (a) is suppressed, the impact applied to the tooth surface can be reduced. Therefore, the spraying powder mixture according to the present embodiment has superior low abrasiveness. From the above, it is considered that the spraying powder mixture according to the present embodiment has both superior fluidity and low abrasiveness. Here, it is assumed that the superior fluidity of the powder mixture for injection contributes particularly to more uniform mixing with air in the powder / air mixing chamber installed in the powder injection device, passage through the connecting portion connecting the main body of the powder injection device and the injection nozzle, suppression of clogging occurrence at the injection nozzle, and more uniform and stable injection from the injection nozzle to the tooth surface above or below the gingival margin or into the gingival sulcus and periodontal pocket. In addition, it is assumed that the superior low abrasiveness of the powder mixture for injection contributes particularly to the suppression of damage to the tooth surface caused by the powder mixture for injection injected from the powder injection device onto the tooth surface above or below the gingival margin.

[0015] [Background of the Present Invention] The present inventors have intensively studied the reason why the powder mixture for injection in the prior art cannot have both excellent fluidity and low abrasiveness, and as a result, obtained the following technical findings. For example, in the case of a powder for injection consisting only of component (a), since component (a) itself is relatively soft, it would seem at first consideration that the impact on the tooth surface can be reduced. However, while component (a) is relatively soft, it tends to aggregate easily, and the particle size of the particulate form (e.g., particles) in the powder for injection tends to increase. For this reason, the impact of the powder for injection on the tooth surface increases, and as a result, damage to the tooth surface cannot be sufficiently suppressed. In addition, the increase in particle size also affects the decrease in fluidity, and as a result, for example, inhibits mixing in the powder injection device and discharge from the injection nozzle. As described above, the present inventors have obtained the technical finding that the root cause of the inability to have both superior fluidity and low abrasiveness lies in the aggregability of the particulate form constituting the powder for injection.

[0016] The present inventors have further studied based on the above technical findings, and focused on the fact that the aggregability of particles is caused by the hydrophilicity of component (a). Accordingly, the inventors found that by adding hydrophobized silica fine particles (component (b)) as the second component to component (a), component (b) enters between the particles of component (a) and significantly reduces the aggregability of the powder mixture for injection. It was found that this suppresses a significant increase in the particle size of component (a) in the powder mixture for injection, and suppresses the decrease in low abrasiveness and fluidity. In this way, the inventors have come to realize that the spray powder mixture according to this embodiment is characterized by containing a combination of a specific (a) component (at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds) and a specific (b) component (hydrophobized silica fine particles).

[0017] [Insights derived from prior art, etc.] The present inventors have obtained the following knowledge from the prior art. Powder mixtures for spraying and powder spraying devices for preventing and treating periodontal disease have been studied. For example, a powder spraying device and powder used therein have been disclosed (Patent Document 1: U.S. Patent No. 4,174,571, Patent Document 2: U.S. Patent No. 4,595,365) that can efficiently clean the tooth surface above the gingival margin by spraying a water-soluble abrasive mixed with air together with water. In this prior art, sodium bicarbonate is used as the water-soluble abrasive mixed with air and sprayed onto the tooth surface. While the use of this abrasive does not pose a problem in cleaning tooth enamel, it causes significant damage to the dentin where the tooth root is exposed, leading to serious clinical problems, thus limiting its scope of use. Patent Document 1 (U.S. Patent No. 4,174,571) discloses sodium glutamate or sodium gluconate as abrasives for powder spraying devices, which have lower abrasiveness and cause less damage to the enamel surface and tooth root surface compared to conventionally used abrasives. Furthermore, Patent Document 3 (Japanese Patent Publication No. 4418113) discloses a water-soluble, tooth-friendly powder, such as amino acids, sugars, or organic acids and their salts, for cleaning the subgingival area, including the root dentin, and the powder has a density of 2.0 g / cm³. 3The following is characterized by an average particle size of 45 μm or less. Furthermore, Patent Document 4 (U.S. Patent No. 6,126,444) discloses that the easily damaged subgingival root surface is treated with a water-insoluble particulate polysaccharide powder, such as cellulose, starch, or agar. It is important that these powders do not remain in the oral cavity, especially in the gingival sulcus and periodontal pockets, after being sprayed onto the tooth surface. If they remain in the oral cavity, they not only cause discomfort to the patient but the powder remaining in the gingival sulcus, periodontal pockets, and gums can become a foothold for bacteria and cause infection.

[0018] In this type of powder-spray tooth surface cleaning, larger powder particles result in greater impact force and improved cleaning efficiency, but there is a concern that this may increase damage to the cleaned tooth surface. On the other hand, if the powder particles are small, the impact force is small, and the desired cleaning efficiency cannot be achieved. Patent document 5 (U.S. Patent No. 5810587) discloses a powder composition that combines cleaning efficiency with minimal damage to the tooth surface by having a group of very fine aluminum oxide particles in the range of 0.01 to 5 μm aggregate to form larger particles of 10 to 200 μm in size, which then rupture and decompose upon impact with the tooth surface. Furthermore, patent document 6 (Japanese Patent Publication No. 5846720) discloses a powder containing algitol, a sugar alcohol, as an abrasive for tooth surfaces, characterized by a Mohs hardness of 4 or less and an average particle size of 45 μm or less.

[0019] In the spray cleaning of tooth surfaces using powder mixed with air in the powder / air mixing chamber of a powder spray device, it is important to efficiently remove plaque and tartar adhering to the tooth surface while minimizing damage to the tooth surface, and after spray cleaning, the powder must dissolve in water and be completely discharged from the oral cavity. From the standpoint of spray cleaning efficiency, the larger the powder particles used for spray cleaning, the higher the spray cleaning efficiency, but conversely, the greater the damage to the tooth surface. Two methods have been proposed to overcome this. One is to use powder made by agglomerating small particles to create larger particles, and the other is to use water-soluble sugar alcohols or other soft organic materials as powder, which are less affected by particle size. However, when the particle size of the powder becomes smaller, its surface area increases further, or the powder surface of water-soluble organic materials has OH groups that have a high affinity for water, so the powder itself exhibits hydrophilicity, resulting in significant agglomeration and consequently a decrease in the fluidity of the powder. In this case, the powder / air mixing chamber attached to the powder spraying device would not be uniformly mixed with air, which could lead to clogging inside the powder / air mixing chamber attached to the powder spraying device, in the connecting parts through which the powder flows to the spray nozzle, and in the spray nozzle itself. There was also a risk of problems such as uneven and unstable spraying from the spray nozzle onto the tooth surface.

[0020] Furthermore, after spray cleaning, the powder must be completely expelled from the oral cavity, and therefore, it is preferable that the powder used be water-soluble. However, the gingival sulcus and periodontal pockets are narrow, moist areas with little moisture, so there is a possibility that partially dissolved or undissolved material may remain in these areas, potentially becoming a breeding ground for bacteria and inducing diseases such as periodontal disease. For this reason, techniques using highly water-soluble powders have been proposed. However, the tooth surface in the oral cavity is under a temperature environment of around 37°C, unlike the powder / air mixing chamber of the powder spraying device, and when spraying the tooth surface, the powder is mixed with water sprayed from a separate route and sprayed together onto the tooth surface. As a result, problems such as reduced spray cleaning efficiency exist because the powder has already softened by the time it hits the tooth surface.

[0021] [Knowledge and other information that formed the basis of this invention] Based on the knowledge derived from prior art, the inventors diligently studied to solve the above problems and found the following new findings (1) to (4). (1) It is known that the fluidity of a powder is influenced by the shape, particle size, and surface properties of the powder itself. However, in this embodiment, we have found that by mixing fine silica particles that have undergone a specific hydrophobic treatment as a second component with a powder that is highly hydrophilic and cohesive, the state in which each powder exists in the powder mixture changes, and as a result, the fluidity of the powder mixture is greatly improved.

[0022] (2) Furthermore, the ability to remove tartar and plaque adhering to the tooth surface and the reduction of damage to the tooth surface after removal are conflicting characteristics. In conventional technology, while the removal of tartar and plaque adhering to the tooth surface is improved when the powder has a large particle size, high hardness, and is water-insoluble, the problem is that it causes significant damage to the tooth surface after removal. There are prior arts that use soft organic materials to overcome this problem, but these powders have problems such as poor fluidity due to their high hydrophilicity and high cohesiveness, which leads to the formation of large secondary particles, and have not been able to overcome the aforementioned problem. However, in this embodiment, we have found a second new finding that the spray powder mixture in item (1) maintains a good balance not only in fluidity but also in the conflicting characteristics that were the challenge of the present invention, because the state of existence of each particle changes.

[0023] (3) Focusing on the structure and operation of the powder spraying device using the powder mixture for spraying according to this embodiment, it was found that in the process of spraying the powder from the nozzle tip, it is sprayed together with water that has flowed out from another path, and therefore on the tooth surface it becomes mixed with water. As a result, it became clear that the ability to remove tartar and plaque adhering to the tooth surface being sprayed is also affected by the solubility of the powder mixture in water. A third new finding was discovered: it is not simply a matter of whether the powder dissolves or does not dissolve in water, but the solubility is also important because it is affected by the oral temperature when the powder reaches the tooth surface. In other words, these powder mixtures exist in a powder state immediately after spraying onto the tooth surface and are involved in the removal of tartar and plaque adhering to the tooth surface, and after spraying and cleaning, they need to be easily dissolved in water by rinsing and discharged from the oral cavity. If the solubility in water is too high, it will soften when sprayed onto the tooth surface and will not be able to achieve the original purpose of removing tartar and plaque adhering to the tooth surface. Conversely, if the cleaning agent has low solubility in water, it can remain on the tooth surface, in the gingival sulcus, and in periodontal pockets after spray cleaning, potentially becoming a breeding ground for bacteria and leading to disease.

[0024] (4) Furthermore, after spraying and cleaning the tooth surface and gingival sulcus / periodontal pockets using a powder spraying device, even after rinsing, the oral cavity, especially the gingival sulcus and periodontal pockets, is a narrow, moist area with little moisture, so there is a possibility that partially dissolved or undissolved material may remain. As mentioned above, since the powder is water-soluble, it may adhere to various parts of the oral cavity as undissolved or partially dissolved material in the moist environment of the oral cavity, which can serve as a foothold for bacterial infection and thus may induce oral diseases. Therefore, in this embodiment, we have found as a fourth new finding that by including ion-sustaining glass as a third component in the powder mixture, it is possible to prevent the onset of oral diseases by slowly releasing various ions. As a result, even if the powder mixture does not completely dissolve in water and remains in the oral cavity in a partially dissolved or undissolved state, it is possible to suppress bacterial adhesion and proliferation, and furthermore, due to the sustained release effect of these ions, it is expected that caries and periodontal disease will be suppressed by strengthening the tooth structure of the tooth surface and the barrier function of the soft tissue in the periodontal pockets.

[0025] [Implementations derived based on new findings, etc.] Based on the above-mentioned new findings, the inventors have clarified several embodiments of the present invention and their effects. For example, in the spray powder mixture according to this embodiment, it is preferable to include (c) ion-releasing glass in addition to components (a) and (b). Furthermore, it has been revealed that in the spray powder mixture according to this embodiment, by mixing components (a) and (b), the fluidity of the powder mixture is improved because the hydrophobic smaller particles of component (b) coat the larger particles of component (a). In particular, when sugar alcohol, which is component (a), is mixed with trialkylsilylated fine silica particles, which is component (b), this effect was clearly observed due to the interaction between the particle surfaces. Furthermore, it has become clear that this improvement in fluidity makes it possible to achieve both the ability to remove tartar and plaque adhering to the tooth surface and the reduction of damage to the tooth surface after removal, which are contradictory properties. This effect was particularly noticeable when a sugar alcohol, preferably a sugar alcohol obtained by reducing disaccharides, and more preferably a sugar alcohol having a solubility in water at 20°C of 30% by weight or less, was used as component (a).

[0026] Furthermore, in order to maintain the above-mentioned conflicting properties, it is preferable that component (a) in the powder mixture be water-soluble. However, even when rinsing after spraying the powder onto the tooth surface using a powder spraying device, the oral cavity, especially the gingival sulcus and periodontal pockets, are narrow areas with little moisture and are in a moist state, so there is a possibility that partially dissolved or undissolved material may remain in those areas. These undissolved or partially dissolved materials remaining in the oral cavity could become a breeding ground for bacteria and pose a risk of inducing diseases such as periodontal disease. Therefore, in this embodiment, by including ion-sustaining glass as component (c) in the powder mixture, it is characterized by the sustained release of various ions, especially at least one of fluoride ions, strontium ions, borate ions, and aluminum ions. As a result, even if undissolved or partially dissolved material remains in the oral cavity, these ions are continuously released, which can suppress bacterial adhesion and proliferation. Furthermore, it is expected that this will help to strengthen tooth enamel on the tooth surface and provide a barrier function to the soft tissues in periodontal pockets during powder spraying cleaning, thereby helping to suppress the onset of caries and periodontal disease.

[0027] The components (a) and (b) of the spray powder mixture according to this embodiment, as well as any other components including component (c), will be described in detail below.

[0028] [(a) component] The spray powder mixture according to this embodiment comprises component (a). Component (a) allows for efficient removal of plaque and tartar adhering to the tooth surface while reducing damage to the tooth surface (especially the dentin) when the spray powder mixture is sprayed onto the tooth surface by a spraying device.

[0029] (a) Component is at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds. Component (a) may be a mixture thereof. Among these, component (a) is preferably sugars, sugar alcohols, and carbonate compounds, and more preferably sugar alcohols, from the viewpoint of further improving the fluidity and low abrasiveness of the spray powder mixture. Among sugar alcohols, it is even more preferably a sugar alcohol obtained by reducing disaccharides, and particularly preferably a sugar alcohol having a solubility in water at 20°C of 30% by weight or less, from the viewpoint of improving the removeability by the spray powder mixture. If the solubility of a sugar alcohol is 30% by weight or less at 20°C, then the sugar alcohol has relatively low solubility in water. Therefore, when a powder mixture for spraying is sprayed by a powder spraying device at room temperature (approximately 20°C), the sugar alcohol contained in the powder mixture does not easily dissolve in the water it is sprayed with, and can impact the tooth surface in powder (solid) form. Thus, in such cases, the powder mixture for spraying has excellent removal properties and can efficiently remove plaque and tartar that are adhering to the tooth surface.

[0030] (Sugars) Any type of sugar can be used as long as it is in powder form at room temperature, regardless of its powder form. Examples of sugars include monosaccharides, disaccharides, trisaccharides, and polysaccharides, and mixtures thereof can also be used without any restrictions. Specifically, examples of monosaccharides include monosaccharides called aldoses, which have one aldehyde group (-CHO) at the intramolecular end of a chain structure; monosaccharides called ketoses, which have one ketone group (=CO) in the molecule of a chain structure; and monosaccharides that are deoxy sugars in which one of the hydroxyl groups in the molecule is reduced and replaced by a hydrogen atom.

[0031] Monosaccharides with a single aldehyde group (-CHO) at the intramolecular end of a chain structure called an aldose include, but are not limited to, glyceraldehyde, arabinose, lyxose, allose, altrose, glucose, and mannose. Monosaccharides with a single ketone group (=CO) in a chain structure called a ketose include, but are not limited to, dihydroxyacetone, psicose, fructose, sorbose, and tagatose. Furthermore, monosaccharides that are deoxy sugars in which one of the intramolecular hydroxyl groups is reduced and replaced by a hydrogen atom include, but are not limited to, deoxyribose, fucose, and rhamnose.

[0032] Disaccharides can be specifically exemplified by, but are not limited to, sucrose, lactose, maltose, trehalose, turanose, cellobiose, and palatinose. Among these, from the perspective of emphasizing the suppression of caries development, examples of disaccharides include lactose, maltose, trehalose, turanose, cellobiose, and palatinose, with trehalose and palatinose being preferred.

[0033] Furthermore, there are no restrictions whatsoever on trisaccharides and polysaccharides (more specifically, oligosaccharides of three saccharides or more), and any oligosaccharide can be used. Note that some of the above sugars have chiral carbons within their molecules and thus have stereoisomers, but these are all included under the names given.

[0034] Among these, sugars may be those that are abundant in nature or have become industrially available, from the perspective of prioritizing cost reduction. Furthermore, from the perspective of prioritizing the ability to suppress the onset of dental caries (anti-cariogenic properties) in addition to the above-mentioned emphasis on cost reduction, trehalose, fructose, tagatose, maltose, and palatinose (isomaltulose), which are commonly used in food products, may also be used.

[0035] (Sugar alcohol) Any sugar alcohol can be used as long as it is in powder form (solid), regardless of its powder shape. Examples of sugar alcohols include monosaccharides and disaccharides, and mixtures thereof can also be used without any restrictions. Among these sugar alcohols, monosaccharides are, for example, sugar alcohols produced by reducing the carbonyl group of aldoses and ketoses, which are monosaccharides described above. Specific examples of monosaccharide sugar alcohols called alditols (sugar alcohols obtained by reducing aldoses, which are sugars having an aldehyde group (-CHO) in the molecule of a chain structure, to a hydromethyl group) include erythritol, threitol, ribitol, xylitol, arabinitol, glucitol (sorbitol), and mannitol, but the use is not limited to these. Specific examples of disaccharide sugar alcohols (i.e., sugar alcohols obtained by reducing disaccharides) include lactitol, maltitol, and reduced palatinose, but the use is not limited to these. Furthermore, some of the sugar alcohols mentioned above have chiral carbons in their molecules and exist as stereoisomers, but all of these are included under the names given. Among these, sugar alcohols are those that are abundant in nature or that can be industrialized, from the perspective of prioritizing cost reduction. In addition to prioritizing cost reduction, from the perspective of also prioritizing anti-caries properties, sugar alcohols may also be, for example, erythritol, xylitol, glucitol (sorbitol), mannitol, maltitol, and reduced palatinose, and preferably erythritol, mannitol, and reduced palatinose. Among these, sugar alcohols are more preferably erythritol, xylitol, maltitol, and reduced palatinose, which are approved as Foods for Specified Health Uses.Furthermore, reduced palatinose is also known as isomalt, reduced isomaltulose, or palatinite. The precursor, palatinose, has a reducing group in the fructose portion of the molecule, and the α-1,6-glucosidic bond is stable. Under hydrogenation conditions, hydrolysis does not occur, and the reaction is completed while maintaining the basic molecular structure of the disaccharide. As a result, the final product is an equimolar mixture of α-D-glucopyranosyl-1,6-mannitol and its stereoisomer, α-D-glucopyranosyl-1,6-sorbitol. Because it possesses properties intermediate between the two, it is the most preferred sugar alcohol.

[0036] (amino acid) Any amino acid can be used, regardless of its powder form (solid), as long as it is in powder form. Examples of amino acids include acidic amino acids having two carboxyl groups in their molecule, basic amino acids having two or more amino groups in their molecule, and neutral amino acids having characteristic groups other than carboxyl and amino groups (more specifically, hydroxyl groups, amide groups, and aromatic groups), moieties (more specifically, alkyl chains, etc.), or atoms (more specifically, sulfur atoms) in their molecule. Mixtures of these can also be used without any restrictions. Specific examples of amino acids include aspartic acid and glutamic acid as acidic amino acids having two carboxyl groups in their molecule; lysine, arginine, and histidine as basic amino acids having two or more amino groups in their molecule; glycine, alanine, valine, leucine, and isoleucine as neutral amino acids having alkyl chains in their molecule; and serine and threonine as neutral amino acids having hydroxyl groups in their molecule. Examples of amino acids that contain a sulfur atom in their molecule and are neutral include cysteine ​​and methionine. Examples of amino acids that contain an amide group in their molecule and are neutral include asparagine and glutamine. Examples of amino acids that contain an imino group in their molecule and are neutral include proline. Examples of amino acids that contain an aromatic group in their molecule include phenylalanine, tyrosine, and tryptophan, but are not limited to these. Some of the above amino acids have chiral carbons in their molecules and thus have stereoisomers, but these are all included in the names given. Among these, amino acids may also include, for example, histidine, tryptophan, lysine, methionine, phenylalanine, threonine, valine, leucine, and isoleucine, which are classified as essential amino acids that animals cannot synthesize in their bodies, as well as glycine, which is abundant in collagen, an animal protein.

[0037] (Phosphate compounds) Any phosphate compound can be used, regardless of its form, as long as it is in powder (solid) form. Examples of phosphate compounds include tricalcium phosphate, calcium dihydrogen phosphate, calcium monohydrogen phosphate, and calcium hydroxide phosphate (synthetic hydroxyapatite), and mixtures of these can be used without any problems, but the use is not limited to these. Among these, the phosphate compound may be, for example, calcium hydroxide phosphate (synthetic hydroxyapatite), which is composed of the same components as natural hydroxyapatite found in tooth enamel and dentin.

[0038] (Carbonate compounds) Any carbonate compound can be used, regardless of its form, as long as it is in powder (solid) form. Examples of carbonate compounds include heavy calcium carbonate (natural calcium carbonate) obtained by crushing and / or classifying limestone, light calcium carbonate (more specifically, synthetic calcium carbonate and precipitated calcium carbonate, etc.) obtained by precipitating fine crystals in liquid through chemical reactions, calcium bicarbonate, sodium bicarbonate (baking soda), and sodium carbonate. Mixtures of these can also be used without any restrictions, but are not limited to these. Among these, the carbonate compound may also be sodium bicarbonate (baking soda), which has a proven track record of being used as a powder raw material in conventional powder spraying devices.

[0039] (Calcium compounds) Any calcium compound can be used, regardless of its form, as long as it is in powder (solid) form. Examples of calcium compounds include, but are not limited to, calcium oxide, calcium hydroxide (slaked lime), and calcium fluoride. Among these, it is preferable to use calcium fluoride, which can strengthen tooth structure by fluorinating the natural hydroxyapatite contained in tooth enamel and dentin.

[0040] (a) The components can be classified into organic powders and inorganic powders. The former includes sugars, sugar alcohols, and amino acids, while the latter includes phosphate compounds, carbonate compounds, and calcium compounds. Because the hardness of the materials differs among these classified powders, even with the same particle size, the impact force when removing tartar and plaque adhering to the tooth surface changes, which can affect the ease of removing tartar and plaque and the damage inflicted on the tooth surface. Therefore, from the viewpoint of prioritizing the improvement of the removeability and low abrasiveness of the spray powder mixture, an appropriate particle size can be selected depending on the type of classified powder. More specifically, since organic powders such as sugars, sugar alcohols, and amino acids are softer and have lower hardness compared to inorganic powders, their average particle size (D50) may be, for example, 0.1 to 200.0 μm, preferably 1.0 to 100.0 μm, more preferably 5.0 to 80.0 μm, even more preferably 10.0 to 50.0 μm, and particularly preferably 20.0 to 35.0 μm. On the other hand, inorganic powders such as phosphate compounds, carbonate compounds, and calcium compounds are harder materials with higher hardness compared to organic powders. Therefore, their average particle size (D50) may be, for example, 0.1 to 100.0 μm, preferably 1.0 to 80.0 μm, more preferably 5.0 to 70.0 μm, even more preferably 10.0 to 70.0 μm, and particularly preferably 30.0 to 70.0 μm.

[0041] In this specification, the "average particle size (D50)" can be measured using the laser diffraction-scattering method. In other words, the average particle size (D50) is the integrated 50% particle size value from the smallest particle size distribution obtained by the laser diffraction-scattering method. However, since many of the components (a) contained in the spray powder mixture according to this embodiment are water-soluble, it is more appropriate to determine the average particle size (D50) by a dry particle size measurement method. If the average particle size (D50) falls below the above range, the fluidity of the spray powder mixture according to this embodiment deteriorates. As a result, the powder and air do not mix uniformly in the powder / air mixing chamber attached to the powder spraying device. This can lead to clogging inside the powder / air mixing chamber attached to the powder spraying device, in the connecting parts through which the powder flows to the spray nozzle, and in the spray nozzle itself. It can also cause problems such as uneven and unstable spraying from the spray nozzle onto the tooth surface. Furthermore, if the particle size is small, the impact force is low, resulting in unsatisfactory results in the removal of tartar and plaque adhering to the tooth surface. On the other hand, if the average particle size (D50) exceeds the above range, the impact force increases due to the larger particle size, which is undesirable as it can damage the tooth surface after the removal of adhering tartar and plaque.

[0042] In the spray powder mixture according to this embodiment, in order to maintain a good balance between the ability to remove tartar and plaque adhering to the tooth surface and the degree to which damage to the tooth surface occurs after spray cleaning, it is preferable to include organic powders such as sugars, sugar alcohols, and amino acids as component (a), which are less affected by the hardness of the material and can be controlled solely by the average particle size (D50).

[0043] Furthermore, while the tooth surface from which plaque and tartar are removed is hydrophilic due to the presence of moisture, in the spray powder mixture according to this embodiment, hydrophobic fine silica particles of component (b) are mixed in to provide fluidity, making the entire spray powder mixture hydrophobic. Therefore, this spray powder mixture has a property that makes it difficult to adhere to the tooth surface to which it is sprayed, and the removal of plaque and tartar adhering to the tooth surface largely relies on the impact force during powder spraying. However, in the spray powder mixture according to this embodiment, by using a highly hydrophilic material as the mother particle of component (a), collision and adhesion to the hydrophilic tooth surface occur simultaneously during spray cleaning, making it possible to efficiently remove tartar and plaque adhering to the tooth surface, and further reducing damage to the tooth surface. Therefore, in one preferred embodiment, the spray powder mixture according to this embodiment includes a hydrophilic sugar alcohol as component (a) among the organic powders. Examples of such hydrophilic sugar alcohols include sugar alcohols that have many OH groups with high affinity for water in their molecule, and can be obtained by reducing the carbonyl group of sugars and hydrogenating them.

[0044] As mentioned above, it is preferable that component (a) is hydrophilic in the spray powder mixture according to this embodiment. In such cases, from the viewpoint of emphasizing the suppression of periodontal disease, it is preferable that component (a) has moderate hydrophilicity, neither too high nor too low. If component (a) has moderate hydrophilicity (water solubility), when spraying the powder, it is sprayed onto the tooth surface together with water that has flowed out from a separate path of the powder spraying device. Therefore, even in the oral cavity, which is under a temperature environment of around 37°C (unlike inside the powder spraying device), component (a) in the spray powder mixture sprayed onto the tooth surface does not easily dissolve in water. For this reason, component (a) tends not to soften easily, which can suppress a decrease in the removal ability of tartar and plaque adhering to the tooth surface. On the other hand, after spray cleaning, it is necessary to completely discharge the spray residue outside the oral cavity. If the solubility of the sprayed powder is too low, some of it will dissolve only partially, and this partially dissolved material will adhere to and remain in the oral cavity, making it impossible to completely discharge the residue outside the oral cavity. This can become a foothold for bacteria to adhere to, potentially leading to periodontal disease.

[0045] Therefore, it has become clear that even sugar alcohols that are hydrophilic to water can have their effects affected by their type, molecular structure, and resulting solubility. Specifically, the solubility of sugar alcohols in water (amount dissolved in 100 mL of water at 20°C) is as follows: for monosaccharide sugar alcohols, sorbitol: 72% by weight, xylitol: 66% by weight, mannitol: 18% by weight, and erythritol: 33% by weight; for disaccharide sugar alcohols, maltitol: 60% by weight, and reduced palatinose: 28% by weight. Therefore, while the use of sugar alcohols is preferable in this embodiment, to further enhance the effects of the present invention, disaccharide sugar alcohols are preferable to monosaccharides, which have excessively high solubility in water, and it is even more preferable that the solubility in water (amount dissolved in 100 mL of water at 20°C) is 30% by weight or less. Furthermore, regarding solubility in water, from the perspective of dissolving in the oral cavity and completely expelling it from the oral cavity, if the solubility in water is too low, there is a risk of residue remaining after spray cleaning. Therefore, the most preferable embodiment is one in the range of 20 to 30% by weight in water.

[0046] The content of component (a) in the total amount of the spray powder mixture according to this embodiment is 100 parts by weight, for example, may be 80 parts by weight or more, preferably 90 parts by weight or more, and more preferably 95 parts by weight or more.

[0047] [(b) Component] (b) Component imparts hydrophobicity to the spray powder mixture. The hydrophobic silica fine particles of component (b) are primary particles diameterFine silica particles measuring 0.01 to 1000 nm can be used without any limitations, as long as they are hydrophobized by surface treatment with an organic compound, either in the form of primary particles or processed into aggregated or agglomerated particles. The primary silica particles may be, for example, 0.01 to 1000 nm, 1 to 100 nm, or 5 to 20 nm. Furthermore, there are no particular limitations on the method of producing the fine silica particles, including dry methods (high-temperature hydrolysis method) for producing dry silica using silicon tetrachloride as a raw material, wet methods for producing precipitated silica using water glass as a raw material, and sol-gel methods for producing sol-gel silica using alkoxide compounds as a raw material. law Any silica microparticle produced by any of these manufacturing methods can be used, and there are no restrictions whatsoever even if it is a mixed silica microparticle containing silica produced by different manufacturing methods. It can be used Furthermore, there are no particular restrictions on crystallinity; crystalline, amorphous, or mixed fine silica particles are all acceptable. Among these, those manufactured by the dry process are primary particles. diameter It is preferable to use amorphous fine silica particles obtained by processing fine silica particles of 1 to 100 nm into aggregated or agglomerated particles. The specific surface area of ​​the fine silica particles that have been processed into aggregated or agglomerated particles by the BET method is, for example, 20 to 400 (m²). 2 It may be / g), preferably 50-300 (m 2 / g) and more preferably 100~300(m 2 The value is ( / g). These silica particles can be used individually or in combination with other particles.

[0048] In this embodiment, a crucial requirement is to hydrophobize the fine silica particles by surface treatment with an organic compound. However, there are no restrictions on the organic compound as long as it can hydrophobize the particles; any organic compound can be used. By treating the surface of these fine silica particles with an organic compound, the hydrophilic surface properties of the fine silica particles can be modified to hydrophobic. However, the degree of hydrophobization varies depending on conditions such as the surface treatment method and the amount of organic compound used for surface treatment. Therefore, in this embodiment, hydrophobization is defined as the fine silica particles being hydrophobized if they float even slightly on the surface of the water when added to water. There are no restrictions on the organic compound that can be used in this hydrophobization process; any organic compound can be used. However, it is preferable to use a silane compound that can react with the OH groups on the surface of the fine silica particles through a condensation reaction.

[0049] Examples of hydrophobic treatments include dimethylsilylation, trimethylsilylation, alkylsilylation, trialkylsilylation, dimethylpolysiloxane, aminoalkylsilylation, methacrylatesilylation, and methacrylatealkylsilylation. Among these, hydrophobic treatment by dialkylsilylation or trialkylsilylation is preferred, more preferably by dimethylsilylation or trimethylsilylation, and even more preferably by trimethylsilylation. Examples of silane compounds that can be used for hydrophobic treatment include dimethyldichlorosilane, trimethylchlorosilane, and hexamethyldisilazane. These hydrophobic silica particles can be used individually or in combination of several types. Furthermore, hydrophobic silica particles with larger particle sizes can be used without any limitations by further granulation or aggregation.

[0050] Furthermore, fine titania, fine alumina, other oxide fine particles, or mixtures thereof, which are manufactured using the same method as the fine silica fine particles used in this embodiment and have similar particle sizes and specific surface areas, can also be used in this embodiment after hydrophobic treatment. In addition, a mixture of these oxide fine particles and the aforementioned fine silica fine particles, which has been hydrophobic treated, or a mixture of each hydrophobic treated fine particle can be used as a powder mixture for spraying according to this embodiment.

[0051] (b) There are no particular restrictions on the content (mixing ratio) of hydrophobic fine silica particles in component (b), and hydrophobic fine silica particles can be mixed in any ratio. The content of hydrophobic fine silica particles in component (b) may be, for example, 0.001 parts by weight to 10.0 parts by weight per 100 parts by weight of component (a), preferably 0.01 parts by weight to 8.0 parts by weight, and more preferably 0.1 parts by weight to 5.0 parts by weight. When the content of hydrophobic fine silica particles per 100 parts by weight of component (a) is 0.001 parts by weight or more, the fluidity of the spray powder mixture is improved. In other words, the spray powder mixture is more likely to be uniformly mixed with air in the powder / air mixing chamber attached to the powder spraying device, making it less likely for clogging to occur inside the powder / air mixing chamber attached to the powder spraying device, in the connecting parts through which the powder flows to the spray nozzle, and in the spray nozzle, and also reducing the risk of problems such as uneven and unstable spraying from the spray nozzle to the tooth surface. do not have On the other hand, if the content of hydrophobic fine silica particles relative to 100 parts by weight of component (a) is 10.0 parts by weight or less, the effects of the present invention can be maintained while suppressing a decrease in workability. Specifically, in this case, since there is no excess hydrophobic fine silica particles in the spray powder mixture, the volume of the spray powder mixture does not tend to increase, and handling difficulties such as difficulty in filling operations when transferring it into the powder / air mixing chamber are less likely to occur.

[0052] [(c) component] (c) Ion-sustaining glass continuously releases ion species based on its glass composition. The spray powder mixture according to this embodiment preferably further comprises (c) ion-sustaining glass. When the spray powder mixture further comprises (c) ion-sustaining glass, (c) ion-sustaining glass imparts sustained release properties of ion species to the spray powder mixture. In this case, the sustained ion release effect can be exerted on tooth structure above and below the gingival margin, as well as on soft tissues in the gingival sulcus and periodontal pockets, resulting in strengthening of tooth structure and suppression of bacterial activity. (c) The ion-releasing glass preferably releases at least one of the following: fluoride ions, strontium ions, borate ions, and aluminum ions. When the (c) ion-releasing glass releases one of the above ions, it can further exhibit effects such as strengthening of tooth structure and suppression of bacterial activity. In a more preferred embodiment, the (c) ion-releasing glass releases the above multiple ion species simultaneously.

[0053] Any ion-releasing glass can be used without any limitations, as long as it contains one or more glass skeleton-forming elements that form the glass skeleton and one or more glass-modifying elements that modify the glass skeleton. These ion-releasing glasses can be used individually or in combination of multiple ion-releasing glasses. In this embodiment, glass amphoteric elements that have the role of either a glass skeleton-forming element or a glass-modifying element depending on the glass composition are included in the category of glass skeleton-forming elements. Specific examples of glass skeleton-forming elements included in ion-releasing glasses include silica, aluminum, boron, and phosphorus, and these can be used individually or in combination of multiple elements. Specific examples of glass-modifying elements include halogen elements such as fluorine, bromine, and iodine, alkali metal elements such as sodium and lithium, and alkaline earth metal elements such as calcium and strontium, and these can be used individually or in combination of multiple elements. Among these, it is preferable that the glass contains silica, aluminum, and boron as glass framework forming elements, and fluorine, sodium, and strontium as glass modifying elements. Specifically, examples include silica glass containing strontium and sodium, fluoroaluminosilicate glass, fluoroborosilicate glass, and fluoroaluminoborosilicate glass. Furthermore, from the viewpoint of gradually releasing fluoride ions, strontium ions, borate ions, and aluminum ions, for example, fluoroaluminoborosilicate glass containing strontium may also be used. Specific examples of the glass composition range include SiO2 15-35% by mass, Al2O3 15-30% by mass, B2O3 5-20% by mass, SrO 20-45% by mass, F 5-15% by mass, and Na2O 0-10% by mass. This glass composition can be confirmed using instrumental analysis such as elemental analysis, Raman spectroscopy, and X-ray fluorescence analysis, but there is no problem as long as the measured values ​​match these composition ranges in any of the analytical methods.

[0054] There are no particular limitations on the manufacturing method of these ion-releasing glasses, and they can be manufactured by methods such as melting or sol-gel methods. Among these, the melting method using a melting furnace is preferred in terms of the ease of designing the glass composition, including the selection of raw materials. The ion-releasing glass used in the spray powder mixture according to this embodiment has an amorphous structure, but there is no problem if it contains some crystalline structure, and there is no problem even if it is a mixture of glass having an amorphous structure and glass having a crystalline structure. Whether or not the glass structure is amorphous can be confirmed using analytical instruments such as X-ray diffraction analysis or transmission electron microscopes. Among these, the ion-releasing glass used in this embodiment is preferably an amorphous structure, which is a homogeneous structure, because various ions are released slowly in equilibrium with the ion concentration in the external environment.

[0055] The average particle size (D50) of the ion-sustaining glass affects the fluidity of the spray powder mixture according to this embodiment, the ability to remove tartar and plaque adhering to the tooth surface and the resulting damage to the tooth surface, and the ion-sustaining properties that strengthen tooth structure and suppress bacterial activity in periodontal pockets. In this specification, "average particle size (D50)" can be used without particular limitation, regardless of the measurement principle, such as laser diffraction / scattering, dynamic light scattering, or centrifugal sedimentation, and is obtained from any particle size measurement method. In other words, it is the 50% cumulative particle size from the smallest particle size distribution obtained by any particle size measurement method. This average particle size (D50) of the ion-sustaining glass can be controlled during manufacturing processes such as wet and / or dry grinding, classification, and sieving. The average particle size (D50) of the ion-sustaining glass can be, for example, 0.01 to 50.0 μm. mIt may be as follows, preferably 0.1 to 10.0 μm, and more preferably 0.5 to 5.0 μm. If the average particle size (D50) of the ion-sustaining glass is 0.01 μm or more, the specific surface area of ​​the ion-sustaining glass becomes smaller and the amount of ions released decreases, but the decrease in the fluidity of the spray powder mixture according to this embodiment can be suppressed. As a result, it is easier to achieve a uniform mixing state with air in the powder / air mixing chamber attached to the powder spraying device, making it less likely for clogging to occur inside the powder / air mixing chamber attached to the powder spraying device, in the connecting parts through which the powder flows to the spray nozzle, and in the spray nozzle, and also making it less likely for problems such as uneven and unstable spraying from the spray nozzle to the tooth surface to occur. On the other hand, if the average particle size (D50) of the ion-sustaining glass is 50.0 μm or less, when the spray powder mixture according to this embodiment is sprayed onto the tooth surface, the ability to remove tartar and plaque adhering to the tooth surface decreases, but the damage to the removed tooth surface can be reduced. Furthermore, the shape of the ion-releasing glass may be any shape, such as spherical, plate-shaped, fragmented, or flaky, and there are no particular restrictions, but it is preferably spherical or fragmented.

[0056] (c) There are no particular restrictions on the content of the ion-sustaining glass, and it can be mixed in any proportion, but for example, it may be 0.01 parts by weight to 30.0 parts by weight per 100 parts by weight of component (a), preferably 0.1 parts by weight to 20.0 parts by weight, more preferably 0.5 parts by weight to 10.0 parts by weight, and even more preferably 1.0 part by weight to 10.0 parts by weight. When the content of the ion-sustaining glass per 100 parts by weight of component (a) is 0.01 parts by weight or more, an extreme decrease in the amount of ion-sustaining release is suppressed, and the adhesion and proliferation of bacteria can be suppressed when the spray powder mixture according to this embodiment remains in the oral cavity in an undissolved or semi-dissolved state. Furthermore, it can be expected that the tooth surface will be strengthened and a barrier function will be expressed for the soft tissue in the periodontal pocket when the powder is sprayed, and the onset of caries and periodontal disease can be suppressed. On the other hand, if the content of (c) ion-releasing glass is 30.0 parts by weight or less, although the removal of tartar and plaque adhering to the tooth surface is not greatly improved when the spray powder mixture according to this embodiment is sprayed onto the tooth surface, the risk of increased damage to the tooth surface after removal is reduced. Furthermore, because the fluidity of the spray powder mixture according to this embodiment does not deteriorate easily, it is easier to achieve a uniform mixing state with air in the powder / air mixing chamber attached to the powder spraying device, which suppresses clogging inside the powder / air mixing chamber attached to the powder spraying device, in the connecting parts through which the powder flows to the spray nozzle, and in the spray nozzle, and reduces the risk of problems such as uneven and unstable spraying from the spray nozzle to the tooth surface.

[0057] In one preferred embodiment, with an emphasis on further enhancing the ion-releasing properties from the ion-releasing glass, which is component (c), the ion-releasing glass may be surface-treated, for example. By surface-treating the surface of the ion-releasing glass, it can be functionalized and its ion-releasing properties can be improved. Examples of surface treatment materials used for surface treatment include surfactants, fatty acids, organic acids, inorganic acids, monomers, polymers, various coupling materials, silane compounds, metal alkoxide compounds and their partial condensates. These surface treatment materials may be used individually or in combination of two or more. Among these surface treatment materials, it is preferable to perform a composite surface treatment using an acidic polymer and a silane compound.

[0058] This composite surface treatment involves coating an ion-releasing glass surface with a silane compound, followed by surface treatment using an acidic polymer, which will be explained in detail below. In an aqueous dispersion containing ion-releasing glass that has been finely ground to a desired average particle size (D50) by grinding or the like, the general formula (I):

[0059] [ka] A silane compound represented by the general formula (I) (wherein Z represents RO-, X represents a halogen, Y represents -OH, R is an organic group with 8 or fewer carbon atoms, n, m, and L are integers from 0 to 4, and n+m+L=4) is mixed, hydrolyzed or partially hydrolyzed in situ to obtain a silanol compound, which is then condensed to obtain a polysiloxane, and then coated with an ion-releasing glass surface to obtain a polysiloxane-coated ion-releasing glass.

[0060] In general formula (I), examples of organic groups with 8 or fewer carbon atoms represented by R include alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, and phenyl groups. Alkyl groups having 1 to 8 carbon atoms are linear or branched, and examples include methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, s-butyl groups, t-butyl groups, pentyl groups, isopentyl groups, neopentyl groups, n-hexyl groups, n-heptyl groups, and n-octyl groups. Alkyl groups having 1 to 8 carbon atoms are preferably alkyl groups having 1 to 4 carbon atoms (more specifically, methyl groups, ethyl groups, propoxy groups, and butyl groups), more preferably alkyl groups having 1 to 2 carbon atoms (more specifically, methyl groups and ethyl groups), and even more preferably methyl groups. Alkenyl groups, having 2 to 8 carbon atoms, can be linear or branched, and examples include ethenyl (vinyl) groups, propenyl groups, butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, and octenyl groups.

[0061] Examples of halogens represented by X in general formula (I) include fluorine, chlorine, bromine, and iodine. The halogen is preferably chlorine.

[0062] In general formula (1), n, which represents the number of Z groups in one molecule of the silane compound, is preferably an integer from 1 to 4, more preferably an integer from 2 to 4, even more preferably an integer from 3 to 4, and particularly preferably 4. The larger the value of n, the greater the number of RO groups in the silane compound represented by general formula (1). Fine particle silica treated with a silane compound represented by general formula (1) with a large value of n has high hydrophobicity.

[0063] Examples of silane compounds represented by general formula (I) include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraalyloxysilane, tetrabutoxysilane, tetrakis(2-ethylhexyloxy)silane, trimethoxychlorosilane, triethoxychlorosilane, triisopropoxychlorosilane, trimethoxyhydroxysilane, diethoxydichlorosilane, tetraphenoxysilane, tetrachlorosilane, and silicon hydroxide (silicon oxide hydrate), with tetramethoxysilane and tetraethoxysilane being preferred.

[0064] Furthermore, it is more preferable that the compound is a low-condensation compound of a silane compound represented by general formula (I). For example, a low-condensation silane compound obtained by partially hydrolyzing and condensing tetramethoxysilane and tetraethoxysilane. These compounds can be used alone or in combination. Furthermore, organosilane compounds can be added as part of the silane compounds represented by general formula (I) during polysiloxane treatment.

[0065] The polysiloxane-coated ion-releasing glass obtained in the previous step can be subjected to an acidic polymer treatment, in which it is reacted with an acidic polymer to obtain an ion-releasing glass which is a particularly preferred component (c) to be mixed into the spray powder mixture according to this embodiment. The acidic polymer treatment can be carried out using equipment commonly used in the industry, such as a dry fluidized bed agitator. ye Examples include Lumixer, Supermixer, and High-Speed ​​Mixer. The reaction of an acidic polymer with an ion-releasing glass coated with a polysiloxane film can be carried out by contacting it with an acidic polymer solution by impregnation or spraying. For example, the polysiloxane-coated ion-releasing glass can be dry-flowed, and an acidic polymer solution can be dispersed from above while it is flowing, and then thoroughly stirred. There are no particular restrictions on the method of dispersing the acidic polymer solution, but a dropping or spraying method that allows for uniform dispersion is more preferable.

[0066] The solvent used to prepare the acidic polymer solution for the reaction is not limited as long as it is a solvent in which the acidic polymer dissolves, and examples include water, ethanol, and acetone. Of these, water is particularly preferred, as it allows the acidic groups of the acidic polymer to dissociate and react uniformly with the polysiloxane-coated ion-releasing glass. The weight-average molecular weight of the acidic polymer dissolved in the acidic polymer solution may be, for example, 2,000 to 50,000, preferably 5,000 to 40,000. Surface treatment with an acidic polymer having a weight-average molecular weight of 2,000 or more facilitates the formation of an acidic polymer reaction phase in the polysiloxane-coated ion-sustaining glass, resulting in a tendency for higher ion-sustaining properties. On the other hand, surface treatment with an acidic polymer having a weight-average molecular weight of 50,000 or less prevents the viscosity of the acidic polymer solution from becoming too high, making it easier to homogeneously treat the polysiloxane-coated ion-sustaining glass. The concentration of the acidic polymer in the acidic polymer solution is, for example, 3 to 25 parts by weight, preferably 8 to 20 parts by weight. When the acidic polymer concentration is 3 parts by weight or more, the acidic polymer reaction phase described above is less likely to become fragile, and the effect of improved ion-sustaining properties is easily obtained. Furthermore, when the acidic polymer concentration is 25 parts by weight or less, it diffuses easily into the polysiloxane layer (porous) in a uniform state, making it easier to obtain a homogeneous acidic polymer reaction phase. Also, since the reaction does not occur immediately upon contact with the polysiloxane-coated ion-releasing glass, problems such as the formation of strongly reacted aggregates are less likely to occur. The amount of acidic polymer solution added to the polysiloxane-coated ion-releasing glass may be 6 to 40 parts by weight, preferably 10 to 30 parts by weight. For example, when calculated using this amount, the amount of acidic polymer relative to the polysiloxane-coated ion-releasing glass is preferably 1 to 7 parts by weight, and the amount of water is preferably 10 to 25 parts by weight.

[0067] The acidic polymer that can be used to form an acidic polymer reaction phase on the surface of polysiloxane-coated ion-releasing glass by the above method can be any copolymer or homopolymer derived from a polymerizable monomer having an acidic group (more specifically, at least one acidic group selected from the group consisting of phosphate residues, pyrophosphate residues, thiophosphate residues, carboxylic acid residues, and sulfonic acid groups, etc.), without any problems. Examples of these polymerizable monomers include acrylic acid, methacrylic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, aconitic acid, mesaconic acid, maleic acid, itaconic acid, fumaric acid, glutaconic acid, citraconic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic acid, 4-(meth)acryloyloxyethoxycarbonylphthalic anhydride, 5-(meth)acryloylaminopentyl carboxylic acid, 11-(meth)acryloyloxy-1,1-undecanedicarboxylic acid, 2-(meth)acryloyloxyethyl dihydrogen phosphate, and 10-(meth)acryloyloxydecyl dihydrogen Examples include phosphates, 20-(meth)acryloyloxyeicosyldihydrogen phosphate, 1,3-di(meth)acryloyloxypropyl-2-dihydrogen phosphate, 2-(meth)acryloyloxyethylphenyl phosphate, 2-(meth)acryloyloxyethyl 2'-bromoethyl phosphate, (meth)acryloyloxyethylphenyl phosphonate, di(2-(meth)acryloyloxyethyl) pyrophosphate, 2-(meth)acryloyloxyethyl dihydrogen dithiophosphophosphate, and 10-(meth)acryloyloxydecyldihydrogen thiophosphate. Among polymers (co)polymerized using these polymerizable monomers, homopolymers or copolymers derived from α-β unsaturated carboxylic acids that exhibit relatively slow acid-base reactions with acid-reactive elements contained in polysiloxane-coated ion-sustaining glass are preferred. Examples of such α-β unsaturated carboxylic acids include acrylic acid polymers, acrylic acid-maleic acid copolymers, and acrylic acid-itaconic acid copolymers.

[0068] Ion-releasing glass is characterized by its ability to continuously release ionic species based on its glass composition. The following method can be used to determine whether or not the ion-releasing glass used in the spray powder mixture according to this embodiment has ion-releasing properties.

[0069] When 0.1 g of ion-releasing glass is added to 100 g of distilled water and stirred for 1 hour, the ion concentration (F1) or elemental concentration (F1) released into the distilled water and the ion concentration (F2) or elemental concentration (F2) released into the distilled water after stirring for 2 hours satisfy the relationship shown in equation (1) below, in which case it can be considered to have ion-releasing properties. F2 > F1...Equation (1) Furthermore, if there are multiple ions being released from the ion-releasing glass, it is not necessary for all ion concentrations or elemental concentrations due to the ion species to satisfy equation (1). The glass can be considered to have ion-releasing properties even if at least one ion concentration or elemental concentration due to the ion species satisfies equation (1).

[0070] [Any component other than (c) component] The spray powder mixture according to this embodiment comprises components (a) to (b). The spray powder mixture may also comprise any component other than component (c). Examples of optional components include antimicrobial agents that control bacterial activity, colorants that provide distinctiveness, and fragrances that provide flavor and a refreshing sensation. The spray powder mixture may contain any of these components to the extent that they do not impair the effects of the present invention.

[0071] Examples of colorants include inorganic white pigments (more specifically, titanium dioxide and zinc oxide); inorganic red pigments (more specifically, iron oxide (red iron oxide) and iron titanate); inorganic brown pigments (more specifically, γ-iron oxide); inorganic yellow pigments (more specifically, yellow iron oxide and ochre); inorganic black pigments (more specifically, black iron oxide and lower titanium oxide); inorganic purple pigments (more specifically, mango violet and cobalt violet); inorganic green pigments (more specifically, chromium oxide, chromium hydroxide, and cobalt titanate); inorganic blue pigments (more specifically, ultramarine and Prussian blue); pearl pigments (more specifically, titanium dioxide coated mica, titanium dioxide coated bismuth oxychloride, titanium dioxide coated talc, etc.). Examples include colored titanium oxide coated mica, bismuth oxychloride, and fish scale foil; metal powder pigments (more specifically, aluminum powder and copper powder); organic pigments such as zirconium, barium, and aluminum lake (more specifically, organic pigments such as Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, and Blue 404, as well as Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3, and Blue 1); and natural pigments (more specifically, chlorophyll and β-carotene). These colorants can be used individually or in combination.

[0072] Examples of antibacterial agents include benzoic acid, sodium benzoate, isopropyl parahydroxybenzoate, isobutyl parahydroxybenzoate, ethyl parahydroxybenzoate, methyl parahydroxybenzoate, butyl parahydroxybenzoate, propyl parahydroxybenzoate, isopropylmethylphenol, sodium sulfite, sodium hyposulfite, potassium pyrosulfite, sorbic acid, potassium sorbate, sodium dehydroacetate, piroctone olamine, thujaplicin, Aralia cordata extract, Styrax japonica extract, Artemisia capillaris extract, Sillago japonica protein extract, enzymatically hydrolyzed Coix lacryma-jobi extract, bamboo extract, allyl mustard oil, protamine, tea extract, grapefruit seed extract, lysozyme, and chitosan. These antibacterial agents can be used individually or in combination.

[0073] Fragrances include, for example, musk, lemon oil, 1-heptanol, α-methyl ionone, aldehyde C-10, aldehyde C-11, aldehyde C-9, allyl heptanoate, anisaldehyde, benzaldehyde, benzacetate, benzylacetate, butyl propionate, cedar leaf oil, cedrol, cedyl acetate, cinnamic alcohol, cinnamon leaf, citronella oil, citronellal, glove bud oil, cyclamenaldehyde, ethyl butyrate, ethyl caproate, ethyl isobutyrate, ethyl isobalate, ethyl propionate, eucalyptus oil, eugenol, farnesol, geraniol, hep Cylaldehyde, heptylformate, hexylacetate, hydrotropic aldehyde, isobornyl acetate, isoamylformate, limonene, linalool, linalyl acetate, methylheptenone, nonylaldehyde, organum oil, p-cresyl acetate, p-methylacetophenone, phenylacetaldehyde, propylpropionate, spearmint oil, terpenyl acetate, linalool, tetrahydrolinalool, thymol, isobornyl acetate, α-ionone, β-ionone, acetylcedrene, acetyl eugenol, alcohol C-10, alcohol C-11 undecylenic, alcohol C-12, aldehyde C-14 Examples include aldehyde C-18, anise alcohol, anisyl acetate, benzyl benzoate, benzyl isobalate, benzyl salicylate, cinnamyl acetate, citronellol, citronellyl isobutyrate, citronellyloxyacetaldehyde, coumarin, ethyl cinnamate, ethyl vanillin, geranyl isobutyrate, geranyl triglyceride, heliotropin, hexyl cinnamic aldehyde, hydroxycitronellal, indole, isoamyl cinnamic aldehyde, isoamyl salicylate, jasmone, methyl anthranilate, methyl cinnamate, muscone, musk ketone, nerolidol, pentalide, phenyl acetate acid, lavender oil, menthol, and vanillin. These fragrances can be used individually or in combination.

[0074] (Method for manufacturing powder mixture for spraying) The spray powder mixture according to this embodiment can be produced by mixing component (a), component (b), and any other component as needed. There are no restrictions on the mixing of component (a), which is at least one selected from the group consisting of sugars, sugar alcohols, amino acids, phosphate compounds, carbonate compounds, and calcium compounds, with component (b), which is hydrophobized fine silica particles, and any mixing method can be used without any problems. Furthermore, there are no restrictions on the type of mixer used, nor on the mixing method or conditions, and they can be freely selected. In one preferred embodiment, the primary particle size of component (b) is considerably smaller than that of component (a), but in this case there are no particular restrictions on the mixing state of these two components, and any mixing state, such as a coated state or a dispersed state in clumps, is acceptable, and the effects of the present invention can be recognized simply by the presence of the two components together.

[0075] For example, the effects described herein are merely illustrative and not necessarily limited to these effects, and additional effects may also exist. Furthermore, for example, the spray powder mixture described in this embodiment comprises component (a) and component (b), but the presence of components that may inevitably or accidentally be mixed in during the preparation, storage, and / or use of the spray powder mixture (for example, trace or minute amounts of components that can be recognized as trace or minute amounts by those skilled in the art) is permissible.

[0076] The present invention is not limited to the embodiments described above, and design modifications are possible without departing from the spirit of the invention. [Examples]

[0077] The present invention will be described in more detail and specifically below using examples, but the present invention is not limited to these examples. The units of the numerical values ​​in Tables 2 to 4 are g (parts by mass).

[0078] <Preparation of powder mixture for spraying> The materials used in the examples and comparative examples, along with their abbreviations, are shown below. (a) component • Sugars: Trehalose, Palatinose (disaccharides) • Sugar alcohols: Erythritol, reduced palatinose, mannitol (sugar alcohol) • Carbonate compounds: Sodium bicarbonate (baking soda)

[0079] (b) Ingredients: Fine particle silica • Fine particle silica A: Dimethylsilylated hydrophobic silica (primary particle size 16 nm) • Fine particle silica B: Trimethylsilylated hydrophobic silica (primary particle size 12 nm) • Fine particle silica C: Trimethylsilylated hydrophobic silica (primary particle size 7 nm) • Fine particle silica D: Non-hydrophobic silica (primary particle size 12 nm)

[0080] (c) Components: Ion-releasing glass • Ion-releasing glass 1 • Ion-releasing glass 2 • Ion-releasing glass 3 • Ion-releasing glass 4 • Ion-releasing glass 5

[0081] Ion-releasing glass samples 1-5 were prepared according to the following procedure. (Manufacturing of ion-releasing glass 1) A mixture was obtained by mixing various raw materials: silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate. The resulting mixture was then melted at 1400°C to obtain glass A (glass composition: SiO2 22.5% by mass, Al2O3 20.0% by mass, B2O3 12.3% by mass, SrO 35.7% by mass, Na2O 2.5% by mass, and F 7.0% by mass). Next, the obtained glass A was pulverized using a vibratory mill for 100 hours. The resulting pulverized material was designated as ion-sustaining glass A. 500 g of this ion-sustaining glass A and 1105 g of a low-condensation silane compound (Mitsubishi Chemical Corporation's "MS51SG1" (SiO2 content 16%, degree of polymerization 2-6)) were placed in a universal mixer and stirred for 90 minutes. Afterward, the mixture was heat-treated at 140°C for 30 hours to obtain the heat-treated product. This heat-treated material was crushed using a Henschel mixer to obtain polysiloxane-coated ion-sustaining glass A. 500g of this polysiloxane-coated glass A was taken and placed in a Henschel mixer. While stirring, an acidic polymer aqueous solution (polyacrylic acid aqueous solution: polymer concentration 13 parts by weight, weight-average molecular weight 20000; manufactured by Nacalai Tesque) was sprayed from above. Subsequently, it was heat-treated at 100°C for 3 hours to obtain ion-sustaining glass 1. The obtained ion-sustaining glass 1 was an ion-sustaining glass with a composite surface treatment.

[0082] The average particle size (D50) of this ion-releasing glass 1 was measured using a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and was found to be 0.5 μm. The elemental concentrations (fluoride ions converted to fluorine element concentration) of various ions released from this composite surface-treated ion-releasing glass 1 were measured, and the presence or absence of ion-releasing performance was confirmed by its conformance to equation (1). The results are shown in Table 1.

[0083] (Manufacturing of ion-releasing glass 2) A mixture was obtained by mixing various raw materials: silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate. The resulting mixture was then melted at 1400°C to obtain glass B (glass composition: SiO2 23.8% by mass, Al2O3 16.2% by mass, B2O3 10.5% by mass, SrO 35.6% by mass, Na2O 2.3% by mass, and F 11.6% by mass). Next, the obtained glass B was pulverized using a vibratory mill for 40 hours. The resulting pulverized material was designated as ion-releasing glass 2.

[0084] The average particle size (D50) of this ion-releasing glass 2 was measured using a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and was found to be 1.2 μm. The elemental concentrations (fluoride ions converted to fluorine element concentration) of various ions released from this ion-releasing glass 2 were measured, and the presence or absence of ion-releasing performance was confirmed by its conformance to equation (1). The results are shown in Table 1.

[0085] (Manufacturing of ion-releasing glass 3) 500 g of the above-mentioned ion-sustaining glass 2 and 1105 g of a low-condensation silane compound (Mitsubishi Chemical Corporation's "MS51SG1" (SiO2 content 16%, degree of polymerization 2-6)) were placed in a universal mixer and stirrer and stirred for 90 minutes. Then, the mixture was heat-treated at 140°C for 30 hours to obtain a heat-treated product. This heat-treated product was crushed using a Henschel mixer to obtain polysiloxane-coated ion-sustaining glass 3. 500 g of this polysiloxane-coated ion-sustaining glass 3 was taken and placed in a Henschel mixer. While stirring, an acidic polymer aqueous solution (polyacrylic acid aqueous solution: polymer concentration 13 parts by weight, weight-average molecular weight 20000; manufactured by Nacalai Tesque) was sprayed from above. Then, the mixture was heat-treated at 100°C for 3 hours to obtain ion-sustaining glass 3. The obtained ion-sustaining glass 3 was an ion-sustaining glass with a composite surface treatment.

[0086] The average particle size (D50) of this ion-releasing glass 3 was measured using a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and was found to be 1.3 μm. The elemental concentrations (fluoride ions converted to fluorine element concentration) of various ions released from this composite surface-treated ion-releasing glass 3 were measured, and the presence or absence of ion-releasing performance was confirmed by its conformance to equation (1). The results are shown in Table 1.

[0087] (Manufacturing of ion-releasing glass 4) A mixture was obtained by mixing various raw materials: silicon dioxide, aluminum oxide, boron oxide, sodium fluoride, and strontium carbonate. The resulting mixture was then melted at 1400°C to obtain glass C (glass composition: SiO2 19.8% by mass, Al2O3 19.8% by mass, B2O3 11.7% by mass, SrO 35.0% by mass, Na2O 2.3% by mass, and F 11.4% by mass). Next, the obtained glass C was pulverized using a vibratory mill for 10 hours. The resulting pulverized material was designated as ion-sustaining glass C. 500 g of this ion-sustaining glass C and 1660 g of a low-condensation silane compound (Mitsubishi Chemical Corporation's "MS51SG1" (SiO2 content 16%, degree of polymerization 2-6)) were placed in a universal mixer and stirred for 90 minutes. Subsequently, the mixture was heat-treated at 140°C for 30 hours to obtain the heat-treated product. This heat-treated material was crushed using a Henschel mixer to obtain polysiloxane-coated ion-sustaining glass C. 500g of this polysiloxane-coated glass B was taken and placed in a Henschel mixer. While stirring, an acidic polymer aqueous solution (polyacrylic acid aqueous solution: polymer concentration 13 parts by weight, weight-average molecular weight 20,000; manufactured by Nacalai Tesque) was sprayed from above. Subsequently, it was heat-treated at 100°C for 3 hours to obtain ion-sustaining glass 4. The obtained ion-sustaining glass 4 was an ion-sustaining glass with a composite surface treatment.

[0088] The average particle size (D50) of this ion-releasing glass 4 was measured using a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and was found to be 3.1 μm. The elemental concentrations (fluoride ions converted to fluorine element concentration) of various ions released from this composite surface-treated ion-releasing glass 4 were measured, and the presence or absence of ion-releasing performance was confirmed by its conformance to equation (1). The results are shown in Table 1.

[0089] (Manufacturing of ion-releasing glass 5) Ion-releasing glass 5 was obtained using the same manufacturing method as ion-releasing glass 4, except that glass C was pulverized for 6 hours using a vibrating mill.

[0090] The average particle size (D50) of this ion-releasing glass 5 was measured using a laser diffraction particle size analyzer (Microtrac SPA: manufactured by Nikkiso Co., Ltd.) and found to be 5.1 μm. The elemental concentrations (fluoride ions converted to fluorine element concentration) of various ions released from this composite surface-treated ion-releasing glass 5 were measured, and the presence or absence of ion-releasing performance was confirmed by its conformation to equation (1). The results are shown in Table 1.

[0091] [Table 1]

[0092] <Preparation of powder mixture for spraying> (Examples 1-32 and Comparative Examples 1-6) The spray powder mixtures for the examples and comparative examples were prepared by mixing each component according to the compositions listed in Tables 2-4. Commercially available powder spray mixtures (Airflow Powder Plus: EMS, Periomate Powder: Nakanishi, Lunos: Dürdental) were used as reference examples.

[0093] <Measurement Method and Evaluation Method> The test methods (measurement methods and evaluation methods) used in the examples and comparative examples are as follows. The results of the test methods are shown in Table 1 and Tables 5 to 7, respectively.

[0094] [Evaluation of ion-sustaining glass's ion-sustaining properties] 0.1 g of ion-sustaining glass was added to 100 mL of distilled water and stirred for 1 hour. The mixture was then filtered using an analytical syringe filter (Chromatodisk 25A, pore size 0.2 μm: GL Sciences Co., Ltd.), and the elemental concentrations due to each ion slowly released in the filtrate were measured. The obtained measured value was designated as F1. Similarly, 0.1 g of ion-sustaining glass was added to 100 mL of distilled water and stirred for 2 hours. The mixture was then filtered in the same manner, and the elemental concentrations due to each ion slowly released in the filtrate were measured. The obtained measured value was designated as F2. The suitability of equation (1) was confirmed from these values ​​of F1 and F2 (the respective elemental concentrations) to determine whether or not the glass exhibited ion-sustaining properties. F2 > F1...Equation (1)

[0095] The specific method for measuring elemental concentrations is as follows: For the measurement of fluorine element concentration, fluoride ions were measured using a fluoride ion composite electrode (Model 9609: Orion Research Co., Ltd.) and an ion meter (Model 720A: Orion Research Co., Ltd.), and this value was converted to the fluorine element concentration. 0.5 mL of TISABIII (Orion Research Co., Ltd.) was added as an ion strength adjuster during measurement. Calibration curves were created using standard solutions of 0.1, 1, 10, and 50 ppm. Meanwhile, for the measurement of other elements (B, Al, and Sr), elemental concentrations were calculated using an inductively coupled plasma atomic emission spectrometer (ICPS-8000: Shimadzu Corporation). Calibration curves were created using standard solutions of 0, 10, 25, and 50 ppm. If the measured element fell outside the calibration curve range, it was diluted as appropriate before measurement.

[0096] [Evaluation of the fluidity of powder mixtures for spraying] (Measurement of the angle of repose of powder mixtures for spraying) The angle of repose of the spray powder mixtures prepared according to each example and comparative example was measured using the angle of repose measuring instrument shown in Figure 1, and evaluated as an indicator of fluidity. Further details were provided in accordance with the test methods described below. -Test Method- The spray powder mixtures obtained in each example and comparative example were poured into the funnel section shown in Figure 1 and allowed to fall in sufficient quantities to overflow from the lower stage. As a result, a mound of spray powder mixture was formed on the stage. The inclination angle of the resulting mound (Figure 2) was measured using a dedicated protractor. This operation was repeated twice, and the average of the obtained angles was calculated as the angle of repose (°). A smaller value for the angle of repose indicates better fluidity of the spray powder mixture.

[0097] (Evaluation of dynamic fluidity of powder mixture for injection) The dynamic fluidity of the spray powder mixtures prepared in each example and comparative example was evaluated as an indicator of fluidity according to the following test method. -Test Method- A fixed amount (80 mL) of the spray powder mixture obtained in each example and comparative example was placed in a 100 mL plastic container along with one pebble (20 mm in diameter). The container was shaken up and down 10 times, then left to stand upright on a table. Immediately afterward, the plastic container was slowly tilted 90°, and the movement of the spray powder mixture inside the container was visually observed. Based on the observed results, the dynamic fluidity of the spray powder mixture was evaluated according to the evaluation criteria below. -Evaluation Criteria- ◎(Excellent): After the plastic container tips over, the spray powder mixture moves until it is parallel to the table surface (more than 80% of the spray powder mixture moves). ○ (Good): After the plastic container tips over, the spray powder mixture moves (the spray powder mixture is not parallel to the table surface but has an inclined surface, and 20-80% of the spray powder mixture moves). × (Poor): Even after the plastic container is tipped over, the spray powder mixture hardly moves (more than 80% of the spray powder mixture remains stationary).

[0098] (Evaluation of hydrophobicity of powder mixtures) The spray powder mixtures prepared in each example and comparative example were evaluated as an indicator of hydrophobicity according to the following test method. -Test Method- One spoonful (0.2 mL) of the spray powder mixture obtained in each example and comparative example was taken and added to a 50 mL glass container of water, then stirred for 5 seconds using a plastic spatula. After stirring, the state (appearance) of the added spray powder mixture was observed visually. Based on the observation results, the hydrophobicity of the spray powder mixture was evaluated according to the following evaluation criteria. -Evaluation Criteria- ◎(Excellent): The spray powder mixture does not mix with water at all, and more than 60% by volume floats on the liquid surface. ○(Good): A portion of the spray powder mixture is compatible with water, and more than 0% by volume but less than 60% by volume is suspended. × (Bad): The spray powder mixture is compatible with water, disperses or dissolves completely in the water, and no floating spray mixture can be observed.

[0099] (Overall liquidity assessment) Based on the evaluation results of the angle of repose, dynamic fluidity, and hydrophobicity related to fluidity, an overall evaluation of the fluidity of the spray powder mixture was performed according to the following evaluation criteria. -Evaluation Criteria- ◎ (Excellent): The angle of repose is 40° or less, and both the dynamic fluidity and hydrophobicity evaluation results are excellent. ○ (Good): The angle of repose is 50° or less, and at least one of the evaluation results for dynamic fluidity and hydrophobicity is ○, and neither is ×. × (Bad): Either the angle of repose is greater than 50°, or at least one of the dynamic fluidity and hydrophobicity evaluation results is ×.

[0100] [Evaluation of low abrasiveness of powder mixtures for spraying] (Measurement of average particle size of powder mixture for spraying) The average particle size (μm) of the spray powder mixtures prepared according to each example and comparative example was measured by dry dispersion using a laser diffraction particle size distribution analyzer (Mastersizer 3000: Malvern Panalytical). In this example and comparative example, in the spray powder mixtures, component (a) had a much larger content (approximately 20 times or more) and a larger particle size (approximately 1000 times or more) compared to component (b). Therefore, the average particle size of the spray powder mixture substantially reflected the average particle size of component (a).

[0101] (Evaluation of the degree of aggregation of the powder mixture for spraying) An evaluation was conducted to confirm the state of existence, including the aggregation status, of the spray powder mixtures. Specifically, the particle size distribution of the spray powder mixtures prepared in each example and comparative example was measured by dry dispersion using a laser diffraction particle size distribution analyzer (Mastersizer 3000: Malvern Panalytical). The shape of the obtained particle size distribution was observed, and the number of peaks was counted. If there were two peaks, the volume ratio of the particles in the spray powder mixture belonging to the second peak was calculated from the particle size distribution. The degree of aggregation of the spray powder mixture was evaluated according to the following criteria based on the number of peaks and volume ratio in the obtained particle size distribution. -Evaluation Criteria- ◎ (Excellent): There is only one peak, and no aggregation is observed. ○ (Good): A second peak, likely due to aggregation, is present at 100 μm or higher, and is less than 10% by volume. × (Bad): A second peak, likely due to aggregation, is present at 100 μm or higher, and its volume is 10% or more.

[0102] (Evaluation of the damaging properties of powder mixtures for spraying onto dentin using a powder spraying device) The spray powder mixtures prepared in each example and comparative example were evaluated for their ability to damage dentin according to the following test method. -Test Method- The powder mixtures for spraying obtained in each example and comparative example were sprayed onto dentin surfaces using a powder spraying device (product name: Airflow Master, manufactured by EMS Corporation) under conditions of 50% powder output and 100% water content, at an injection distance of 3 mm and an angle of 45°. The treated dentin surfaces were observed using a benchtop scanning electron microscope (Phenom-World "G2pro"). Based on the observation results, the damage potential of the powder mixtures to dentin was evaluated according to the evaluation criteria below. This procedure was repeated three times for an overall evaluation. -Evaluation Criteria- ◎(Excellent): No changes were observed on the dentin surface before and after the spray treatment, and no scratches or other damage were found on the dentin surface. ○(Good): Some minor scratches or other damage are visible on the dentin surface, but there is no unevenness or peeling of the dentin. △(Acceptable): After spray treatment, some roughness (unevenness, etc.) is observed on the dentin surface, and damage such as scratches is present on the dentin surface, but no dentin delamination is observed. × (Bad): Damage such as scratches is observed on the dentin surface after spraying, including unevenness and peeling.

[0103] (Overall evaluation of low abrasiveness) Based on the evaluation results of the degree of cohesion and damage to dentin, an overall evaluation of low abrasiveness was performed according to the evaluation criteria below. -Evaluation Criteria- ◎ (Excellent): Both the degree of cohesion and the evaluation results for damage to dentin are excellent. ○ (Good): The evaluation result for cohesion level is ○, or the evaluation result for damage to dentin is ○ or △, and neither is ×. × (Bad): At least one of the evaluation results for cohesiveness and dentin damage is ×.

[0104] [Overall evaluation of fluidity and low abrasiveness] Based on the overall evaluation results for both fluidity and low abrasiveness, a comprehensive evaluation of fluidity and low abrasiveness was conducted according to the following evaluation criteria. -Evaluation Criteria- ◎ (Excellent): The overall evaluation results for both fluidity and low abrasiveness are both excellent. ○ (Good): At least one of the overall evaluation results for fluidity and low abrasiveness is ○, and neither is ×. × (Poor): At least one of the results of the overall evaluation of fluidity and low abrasiveness is ×.

[0105] [Evaluation of ion sustained release properties from powder mixtures for spraying] The ion sustained release properties from the spray powder mixtures prepared in each example and comparative example were evaluated according to the following test method. -Test Method- A fixed amount (2.5 g) of the spray powder mixture obtained in each example and comparative example was added to 15 mL of distilled water in a plastic container and stirred with a plastic spatula for 5 seconds. Then, the liquid below the powder suspended on the surface was collected as the test solution. The collected test solution was filtered using an analytical syringe filter (Chromatodisk 25A, pore size 0.2 μm: GL Sciences Co., Ltd.), and the elemental concentrations due to each sustained-release ion contained in the filtrate were measured. The specific method for measuring elemental concentrations is as follows: For measuring the fluorine element concentration, fluoride ions were measured using a fluoride ion composite electrode (Model 9609: Orion Research Co., Ltd.) and an ion meter (Model 720A: Orion Research Co., Ltd.), and this value was converted to the fluorine element concentration. 0.5 mL of TISABIII (Orion Research Co., Ltd.) was added as an ion strength adjuster during measurement. Calibration curves were created using standard solutions of 0.1, 1, 10, and 50 ppm. On the other hand, the values ​​of other elements (B, Al, and Sr) were calculated using an inductively coupled plasma atomic emission spectrometer (ICPS-8000: Shimadzu Corporation). Calibration curves were created using standard solutions of 0, 1, 5, and 10 ppm. If the measured element fell outside the calibration curve range, the solution was diluted as appropriate before measurement.

[0106] [Table 2]

[0107] [Table 3]

[0108] [Table 4]

[0109] The prepared powder mixture compositions and commercially available powder mixtures for powder spraying were evaluated according to the method described above for angle of repose, dynamic flowability, hydrophobicity, particle size, dentin damage, and ion sustained release. The test results are shown in Tables 5-7.

[0110] [Table 5]

[0111] [Table 6]

[0112] [Table 7]

[0113] As shown in Tables 2-4, the spray powder mixtures of Examples 1-32 contain both component (a) and component (b). Therefore, the spray powder mixtures of Examples 1-32 are examples that fall within the scope of the invention according to claim 1. As shown in Tables 5-7, the spray powder mixtures of Examples 1-32 received either an excellent (◎) or a good (○) overall evaluation for fluidity and low abrasiveness.

[0114] As shown in Table 4, Comparative Examples 1 to 6 do not contain component (b). Specifically, the spray powder mixture of Comparative Example 1 contains only component (a) and does not contain hydrophobized fine silica particles of component (b). The spray powder mixtures of Comparative Examples 2 to 4 contain component (a) and non-hydrophobized fine silica particles. The spray powder mixtures of Comparative Examples 5 to 6 contain component (a) and non-hydrophobized fine silica particles, as well as ion-releasing glass. Therefore, the spray powder mixtures of Comparative Examples 1 to 6 are examples outside the scope of the invention according to claim 1. As shown in Table 7, the spray powder mixtures of Comparative Examples 1 to 7 all received a failing grade in the overall evaluation of both fluidity and low abrasiveness.

[0115] Therefore, it is clear that the spray powder mixture of the example possesses superior fluidity and low abrasiveness compared to the spray powder mixture of the comparative example.

[0116] As shown in Tables 3-4, the spray powder mixtures of Examples 16-26 and 28-32 further contain component (c) in addition to components (a) and (b). Therefore, the spray powder mixtures of Examples 16-26 and 28-32 are examples that fall under the inventions of claims 2-3. As shown in Tables 6-7, the elemental concentrations of B, Al, Sr, and F were measured in the spray powder mixtures of Examples 16-26 and 28-32. This confirmed the sustained release properties of ions composed of B, Al, Sr, and F.

[0117] As shown in Tables 2-3, the spray powder mixtures of Examples 1-15 and 28 contain component (a) and component (b), but do not further contain component (c). The spray powder mixtures of Examples 1-15 and 27 are examples that fall within the scope of the invention of claim 1, but outside the scope of the invention of claims 2-3. As shown in Tables 5-6, the elemental concentrations of B, Al, Sr, and F were not measured in the spray powder mixtures of Examples 1-15 and 27. Therefore, the sustained release properties of ions containing B, Al, Sr, and F could not be confirmed.

[0118] Therefore, it is clear that the spray powder mixtures of Examples 16-26 and 27-32 possess not only superior fluidity and low abrasiveness, but also ion sustained release properties compared to the spray powder mixtures of Examples 1-15 and 27. As a result, it is believed that the ion sustained release effect can strengthen tooth structure and suppress bacterial activity on supragingival and subgingival tooth structure, gingival sulcus, and soft tissue within periodontal pockets.

[0119] [Cross-reference of related applications] This application claims priority based on Japanese Patent Application No. 2020-205830, filed on 11 December 2020, the entire contents of which are incorporated herein by reference. [Industrial applicability]

[0120] The powder mixture for spraying of the present invention enables stable spray cleaning onto the tooth surface above or below the gingival margin, or into the gingival sulcus and periodontal pocket, by uniform mixing with air in the powder / air mixing chamber of a powder spraying device. It also allows for efficient removal of tartar and plaque adhering to the tooth surface without damaging the tooth surface. Furthermore, the sustained ion release effect can strengthen tooth structure and suppress bacterial activity on the tooth structure above and below the gingival margin, as well as on the hard and soft tissues within the gingival sulcus and periodontal pocket.

Claims

1. A powder mixture for spraying onto the tooth surface above or below the gingival margin, or into the gingival sulcus and periodontal pocket, using a powder spraying device, (a) at least one sugar alcohol selected from the group consisting of erythritol, mannitol and reduced palatinose, and (b) Hydrophobized silica particles, It includes, A powder mixture for spraying, wherein the angle of repose of the powder mixture is 30° or more and 50° or less.

2. (c) The spray powder mixture according to claim 1, further comprising ion-releasing glass.

3. A powder mixture for spraying onto the tooth surface above or below the gingival margin, or into the gingival sulcus and periodontal pocket, using a powder spraying device, (a) At least one sugar alcohol selected from the group consisting of erythritol, mannitol and reduced palatinose, (b) Hydrophobized silica particles, and (c) Ion-releasing glass It includes, The powder mixture for spraying has an average particle size (D50) of ion-releasing glass of 0.01 to 50.0 μm, and the angle of repose of the powder mixture is 30° or more and 50° or less.

4. The powder mixture for spraying according to claim 2 or 3, wherein the (c) ion-releasing glass releases at least one of fluoride ions, strontium ions, borate ions, and aluminum ions in a sustained manner.

5. The spray powder mixture according to any one of claims 1 to 4, wherein the component in (a) is a sugar alcohol obtained by reducing a disaccharide.

6. The spray powder mixture according to any one of claims 1 to 5, wherein the solubility of the sugar alcohol in water at 20°C is 30% by weight or less.

7. The spray powder mixture according to any one of claims 1 to 6, wherein the hydrophobized fine silica particles in (b) are trialkylsilylated fine silica particles.

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