JP6958012B2 - Oral composition - Google Patents

Description

The present invention relates to an oral composition having excellent fluorine retention on the tooth surface and improved uptake of fluorine ions into enamel.

Fluorine-containing compounds are blended in many oral preparations (dentifrices, etc.) as medicinal components having functions such as promoting remineralization and suppressing decalcification.
In order for the fluorine-containing compound in the oral preparation to act more effectively, it is effective to improve the retention of the fluorine-containing compound on the tooth surface. So far, it has been reported that a cationic polymer promotes electrostatic adsorption of fluorine on the tooth surface and improves the retention of fluorine on the tooth surface (Patent Document 1; Japanese Patent Application Laid-Open No. 62-145010). Gazette). Further, in Patent Document 2 (Japanese Unexamined Patent Publication No. 2002-3351), fluorine retention in the oral cavity is improved by using a specific fragrance component such as anethole and l-menthol within a specific ratio together with wax as a fluorine ion supply compound. It is improving.

In addition, it is important that fluorine is incorporated into tooth enamel in order for the effect of the fluorine-containing compound to work. In Patent Documents 3 and 4 (Japanese Patent Laid-Open Nos. 2001-342122 and 2002-173419), it is difficult to effectively take up fluorine on the tooth surface to which plaque is attached. Therefore, dextranase and hydroxyethyl cellulose are used. By using a dimethyldiallyl ammonium salt in combination or using a long-chain glyceryl ether sulfonate, the penetration of fluorine into the decalcified layer is promoted and the uptake into tooth enamel is improved.

Japanese Unexamined Patent Publication No. 62-145010 JP-A-2002-3351 Japanese Unexamined Patent Publication No. 2001-342122 Japanese Unexamined Patent Publication No. 2002-173419 Special Table 2012-522775 Japanese Unexamined Patent Publication No. 8-269954 Japanese Unexamined Patent Publication No. 2010-275271

However, since saliva is constantly secreted in the actual oral cavity, the fluorine-containing compound electrostatically adsorbed on the tooth surface may be washed away by the saliva over time, and fluorine is sufficiently retained on the tooth surface. It was difficult to incorporate it into enamel.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide an oral composition having excellent retention of fluorine on the tooth surface and improved uptake of fluorine ions into enamel.

As a result of diligent studies to achieve the above object, the present inventors have obtained colloidal particles in which at least a part of the surface is aluminum oxide, for example, aluminum oxide colloidal particles, in an oral composition containing a fluorine-containing compound. When at least a part of the surface of organic or inorganic colloidal nuclear particles is coated with aluminum oxide-coated colloidal particles, the electrostatic and physical retention of fluorine on the tooth surface is enhanced, and the enamel is formed. It has been found that the uptake of fluorine ions in aluminum is improved, and the present invention has been made.

That is, according to the present invention, by blending (A) a fluorine-containing compound and (B) colloidal particles in which at least a part of the surface is aluminum oxide, the colloidal particles are formed on the tooth surface. Physically adsorbed to the tooth surface and cationic aluminum oxide is electrostatically adsorbed on the fluorine ions, which significantly improves the retention of the fluorine-containing compound (A) on the tooth surface and constantly secretes saliva. Fluorine is strongly adsorbed on the tooth surface and has excellent retention even in the oral cavity, and fluorine ions are sufficiently and effectively taken into the enamel to increase the fluorine ion concentration of the enamel. be able to. Such an action effect cannot be obtained by using a cationized polymer, hydroxyethyl cellulose / dimethyldiallylammonium salt, or silica other than the component (B), for example, without using the component (B) ( It is peculiar to the component (B) (see the comparative example described later).
It is known that alumina-coated colloidal silica is used as an abrasive for an electronic substrate material or an electronic recording medium, but in the present invention, in the oral composition, the tooth surface retention of the component (A) depends on the component (B). Is improved, and the above-mentioned special action and effect are given.

In addition, Patent Document 5 (Japanese Patent Laid-Open No. 2012-522775) describes the treatment of erosive damage to the tooth enamel surface by cationically modified silica, and Patent Document 6 (Japanese Unexamined Patent Publication No. 8-269954). ) Is the adsorption and removal of endotoxin derived from periodontal pathogens by a water-insoluble solid on which octadecylpropyl dimethylammonium is immobilized. We are proposing improvements in polishability and cleanability by using acid salts. On the other hand, the present invention is to improve the retention of fluorine on the tooth surface and thereby to improve the uptake into enamel by using the component (B) in combination with the component (A). The effects of the present invention cannot be predicted from Patent Documents 5 to 7.

Therefore, the present invention provides the following oral compositions.
[1]
An oral composition comprising (A) a fluorine-containing compound and (B) colloidal particles in which at least a part of the surface is aluminum oxide.
[2]
(B) The oral composition according to [1], wherein the colloidal particles in which at least a part of the surface is aluminum oxide are aluminum oxide colloidal particles.
[3]
(B) The aluminum oxide-coated colloidal particles in which at least a part of the surface is aluminum oxide is an aluminum oxide-coated colloidal particle in which at least a part of the surface of an organic or inorganic colloidal nuclear particle is coated with aluminum oxide. Oral composition.
[4]
The oral composition according to [3], wherein the organic or inorganic colloidal nuclear particles are inorganic oxides.
[5]
The oral composition according to [4], wherein the inorganic oxide is colloidal silica.
[6]
The oral composition according to any one of [3] to [5], wherein the content ratio of the organic or inorganic colloidal nuclear particles to aluminum oxide is 100/1 to 100/30 as a mass ratio.
[7]
(B) The oral composition according to any one of [1] to [6], wherein the colloidal particles in which at least a part of the surface is aluminum oxide has a volume average particle diameter of 0.1 to 1,000 nm.
[8]
(B) The oral composition according to any one of [1] to [7], wherein the colloidal particles in which at least a part of the surface is aluminum oxide has a BET specific surface area of 90 to 4,000 mm ^{2 / g.}
[9]
The oral composition according to any one of [1] to [8], which contains 500 to 1,500 ppm of the component (A) as a fluorine ion and 1 to 10% by mass of the component (B).
[10]
The oral composition according to any one of [1] to [9], which further contains (C) an anionic surfactant in an amount of 0.05 to 2% by mass.
[11]
The oral composition according to any one of [1] to [10], which further contains (D) one or more enzymes selected from dextranase and mutanase.
[12]
The oral composition according to any one of [1] to [11], further comprising (E) 2 to 50% by mass of a silica-based abrasive having a volume average particle diameter (median diameter) of 5 to 40 μm.
[13]
The oral composition according to any one of [1] to [12], which is a dentifrice.

According to the present invention, it is possible to provide an oral composition having excellent retention of fluorine on the tooth surface and improved uptake of fluorine ions into enamel.

Hereinafter, the present invention will be described in more detail. The oral composition of the present invention is characterized by containing (A) a fluorine-containing compound and (B) colloidal particles in which at least a part of the surface is aluminum oxide.

(A) The fluorine-containing compound is a medicinal component that promotes remineralization of teeth and prevents caries. Sodium fluoride, sodium monofluorophosphate, etc. can be used, and one type alone or two types can be used. It may be combined. Of these, sodium fluoride is preferable.

The blending amount of the fluorine-containing compound (A) is preferably 500 to 1,500 ppm, particularly preferably 500 to 1,450 ppm, as fluorine ions with respect to the entire composition.
The amount of fluorine ions can be adjusted within the above range according to the purpose of use. For example, it may be 500 ppm for children, 700 ppm or more, and further 900 ppm or more.
When sodium fluoride is used within the range of the amount of fluorine ions, the amount of sodium fluoride is 0.1 to 0.3% (mass%, the same applies hereinafter) of the entire composition (500 to 1, 500 ppm) is preferable, and when sodium monofluorophosphate is used, the blending amount thereof is preferably 0.4 to 1.1% (500 to 1,500 ppm) of the entire composition.

The component (B) is a colloidal particle in which at least a part of the surface is aluminum oxide. Examples of the component (B) include aluminum oxide colloidal particles (Ba) and aluminum oxide-coated colloidal particles (Bb) in which at least a part of the surface of the organic or inorganic colloidal nuclear particle surface is coated with aluminum oxide. It can be preferably used.
Further, in the aluminum oxide-coated colloidal particles (Bb), preferable organic or inorganic colloidal nuclear particles include inorganic oxides, and inorganic oxides other than aluminum oxide can be used, and colloidal silica can be used. More preferred. That is, the aluminum oxide-coated colloidal particles (Bb) are preferably alumina-coated colloidal silica in which at least a part of the silica surface is coated with alumina.
As the alumina-coated colloidal silica, colloidal silica whose silica surface is surface-treated with alumina may be used, and it is sufficient that alumina adheres to at least a part of the silica surface and is coated with alumina.

Further, in the aluminum oxide-coated colloidal particles (Bb), it is preferable that the amount ratio of the organic or inorganic colloidal nuclear particles and the aluminum oxide coated on the surface thereof is within a specific range as a mass ratio. Specifically, in the alumina-coated colloidal silica, the mass ratio of silica / alumina showing the amount ratio of silica as nuclei particles to the alumina coated on the surface thereof is preferably 100/1 to 100/30, more preferably 100. It is / 3 to 100/25, more preferably 100/5 to 100/20. When the ratio is within this range, the retention of fluorine on the tooth surface is further increased, and the uptake into the enamel is further improved. If the ratio of alumina to silica 100 is less than 1, it becomes difficult for fluorine to be adsorbed on the silica surface, and sufficient retention may not be obtained. If the ratio of alumina to 100 silica exceeds 30, anionic surfactants and the like may also be adsorbed on the silica surface, and not only may the retention of fluorine not be sufficiently obtained, but also free surfactants may be produced. It may be reduced and the original performance of the surfactant, especially the foaming as a dentifrice, may be impaired.

The component (B) preferably has a volume average particle size of 0.1 to 1,000 nm, more preferably 1 to 500 nm, particularly preferably 1 to 100 nm, and particularly preferably 5 to 100 nm. When the volume average particle size is 0.1 nm or more, it is easy to handle in manufacturing, and when it is 1,000 nm or less, it is preferable without the possibility of damaging the teeth. The volume average particle size is the volume average particle size obtained by the dynamic light scattering method, and the diffusion count was calculated by measuring the temporal fluctuation of the scattered light intensity and obtained by the Einstein-Stokes formula. This is the value obtained by calculating the average value of the particle size (the same applies hereinafter). Specifically, the measurement was performed using a nanoparticle analyzer (nano Partica SZ-100, manufactured by HORIBA).

The BET specific surface area of the component (B) ^{is preferably 90 to 4,000 mm 2} / g, more preferably 100 to 800 mm ² / g, and particularly preferably 120 to 400 mm ² / g. When it is 90 mm ² / g or more, the adsorption force of the component (A) can be sufficiently obtained. When it is 4,000 mm ² / g or less, the strength as particles is sufficiently maintained and it can be prevented from collapsing.
The BET specific surface area is a value measured at 25 ° C. using a specific surface area measuring device (manufactured by Nikkiso Co., Ltd., automatic specific surface area meter, BET multipoint method, measurement gas; nitrogen).

The component (B) is supplied as an acidic sol whose surface is cationic, mainly as an aqueous dispersion, and a commercially available product can be used. Specifically, the following aluminum oxide colloidal particles, aluminum oxide-coated colloidal particles (colloidal silica surface-treated with alumina), and the like can be used.
Aluminum colloidal particles Alumina sol AS-200 (manufactured by Nissan Chemical Industries, Ltd.)
Volume average particle size: 7 to 15 nm, BET specific surface area: 120 mm ² / g
Colloidal silica surface-treated with alumina Snowtex AK (manufactured by Nissan Chemical Industries, Ltd.)
Silica / alumina mass ratio = 9/1 = 100/11
Volume average particle size: 17 nm, BET specific surface area: 130 to 280 mm ² / g
Silica Doll 20P (manufactured by Nippon Chemical Industrial Co., Ltd.)
Silica / alumina mass ratio = 8/1 = 100/13
Volume average particle size: 20 nm, BET specific surface area: 160 mm ² / g

The blending amount of the component (B) is preferably 1 to 10%, more preferably 3 to 7% of the entire composition. When it is 1% or more, the retention of fluorine is increased, and the uptake into enamel is sufficiently improved. When it is 10% or less, the hardness of the pharmaceutical product can be maintained appropriately and good usability can be maintained. If it exceeds 10%, it may become too hard, especially in the dentifrice composition, and cause poor extrusion from the container.

In the present invention, it is preferable to further add (C) anionic surfactant. When the (C) anionic surfactant is added, not only the foaming is improved, but also the retention of fluorine on the tooth surface is further improved.

Examples of the anionic surfactant include α-olefin sulfonates such as sodium tetradecene sulfonate, alkyl sulfoacetates such as sodium lauryl sulfoacetate, alkyl sulfates such as sodium lauryl sulfate, and sodium lauroyl methyl taurine. Examples thereof include an acyl taurine salt of, and an acyl sarcosine salt such as sodium lauroyl sarcosin. These may be used individually by 1 type or in combination of 2 or more types. Of these, α-olefin sulfonate is preferable in terms of the retention effect of fluorine on the tooth surface.
As the α-olefin sulfonic acid salt, alkali metal salts such as sodium and potassium of α-olefin sulfonic acid having 14 to 16 carbon atoms can be used, and α-olefin sulfonic acid salt having 14 carbon atoms is preferable. It is a sodium salt (generic name; sodium tetradecene sulfonate). Commercially available products that can be used for oral compositions can be obtained, and for example, the trade name "K Liporan PJ-400CJ" manufactured by Lion Specialty Chemicals Co., Ltd. can be used.

The blending amount of the anionic surfactant (C) is preferably 0.05 to 2%, more preferably 0.2 to 0.6% of the total composition. When it is 0.05% or more, the retention of fluorine is sufficiently improved. When it is 2% or less, the development of its own bitterness can be sufficiently prevented.

In the present invention, when the enzyme (D) is further added, the retention of fluorine on the tooth surface is further improved.
Examples of the enzyme include dextranase and mutanase, and dextranase is particularly preferable.
The amount of the enzyme blended into the composition is preferably in the range of 1 to 260 units / g (U / g), particularly 2 to 130 units / g, and particularly preferably 10 to 130 units / g. When 13,000 units / g of dextranase is used, the blending amount thereof is preferably 0.01 to 2%, more preferably 0.02 to 1%, and particularly 0.1 to 1% of the total composition. Is. In the above range, it is preferable because it is excellent in the retention of fluorine and the suppression of offensive odor peculiar to the enzyme.

The oral composition of the present invention is particularly suitable as a dentifrice composition for toothpaste and the like. Further, if necessary, in addition to the above-mentioned components, other known components according to the dosage form and the like can be blended within a range that does not interfere with the effects of the present invention. For example, in toothpaste, abrasives, surfactants other than anionic surfactants, thickeners, binders, and if necessary, sweeteners, preservatives, fragrances, fluorine-containing compounds, and active ingredients other than enzymes are blended. Can be done.

As the abrasive, a general abrasive for a dentifrice can be used. For example, silica-based abrasives such as silica gel, precipitated silica, and aluminosilicate, calcium dihydrate dihydrate and anhydride, calcium phosphate-based compounds such as calcium phosphate tertiary, calcium carbonate, aluminum hydroxide, and synthetic resin-based abrasives. And so on. Of these, silica-based abrasives are preferable.
As for the average particle size of the abrasive, particularly the silica-based abrasive, the median diameter (d50) using the volume average is preferably 5 to 40 μm, particularly preferably 10 to 30 μm. The median diameter is a value measured using a particle size distribution measuring device (Nikkiso Co., Ltd., Microtrack particle size distribution meter, dispersion medium; water).
The blending amount of the abrasive is usually 0 to 50%, particularly 2 to 50%, particularly 2 to 40% of the total composition. Generally, the blending amount in toothpaste is 10 to 50%.

As the surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be blended.
Examples of the nonionic surfactant include polyoxyethylene fatty acid esters such as polyoxyethylene hydrogenated castor oil, sugar fatty acid esters such as sucrose fatty acid esters, sugar alcohol fatty acid esters such as multitoll fatty acid esters, sorbitan fatty acid esters, and glycerin fatty acid esters. , Polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene higher alcohol ether and the like.
Examples of the cationic surfactant include alkylammonium and alkylbenzylammonium salts, and examples of the amphoteric surfactant include betaine acetate type, betaine type and imidazoline type.
The blending amount of the surfactant is preferably 0.001 to 10%, particularly 0.01 to 5% of the total composition.

Examples of the thickener include sugar alcohols such as sorbitol and xylit, and polyhydric alcohols such as glycerin and propylene glycol. The blending amount of these is preferably 5 to 50%, particularly 20 to 45% of the total composition.

As the binder, an organic or inorganic binder can be blended. Specifically, cellulose derivatives such as sodium carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose, alginic acid derivatives such as sodium alginate, gums such as xanthan gum, organic binders such as sodium polyacrylate, and gelling silica. , Inorganic binders such as gelling aluminum silica. The blending amount of the binder is usually 0.1 to 10% of the total composition. In the present invention, an organic binder is particularly preferable, and the blending amount of the organic binder is preferably 0.1 to 5%, particularly 0.5 to 3% of the entire composition. The inorganic binder, particularly the viscous silica, is preferably 5% or less, particularly 2% or less, particularly 1% or less of the entire composition when blended in terms of the retention of fluorine.

Examples of the sweetener include sodium saccharin and the like, and examples of the preservative include benzoic acid or a salt thereof, paraoxybenzoic acid ester and the like.

As fragrances, peppermint oil, spare mint oil, anis oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamon oil, coriander oil, mandarin oil, Lime oil, lavender oil, rosemary oil, laurel oil, camomill oil, caraway oil, majorum oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, grapefruit oil, sweetie Natural fragrances such as oil, yuzu oil, iris concrete, absolute peppermint, absolute rose, orange flower, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, distilling, liquid extraction, essence, powder Fragrances (such as fragrances) and menthol, carboxylic, anator, cineole, methyl salicylate, synamic aldehyde, eugenol, 3-l-mentoxypropane-1,2-diol, timol, linalol, linaryl acetate, limonene, Menton, Menthyl Acetate, N-Substituted Paramentan-3-Carboxamide, Pinen, Octylaldehyde, Citral, Pregon, Calvier Acetate, Anisaldehyde, Ethyl Acetate, Ethyl Butyrate, Allyl Cyclohexane Propionate, Methyl Anthranilate, Ethyl Single flavors such as methylphenylglycidate, vanillin, undecalactone, hexanal, butanol, isoamyl alcohol, hexenol, dimethylsulfide, cycloten, furfural, trimethylpyrazine, ethyllactate, ethylthioacetate, as well as strawberry flavor, apple flavor, banana Although known flavoring materials used in oral compositions can be used in combination, such as flavors, pineapple flavors, grape flavors, mango flavors, butter flavors, milk flavors, fruit mix flavors, tropical fruit flavors and other blended flavors. , The fragrance is not limited to the fragrances described in the examples.
Further, the blending amount is not particularly limited, but it is preferable to use 0.000001 to 1% of the above-mentioned fragrance material in the composition. Further, as a perfume for perfume using the above perfume material, it is preferable to use 0.1 to 2% in the composition.

Examples of the active ingredient include nonionic bactericides such as isopropylmethylphenol, cationic bactericides such as cetylpyridinium chloride, anti-inflammatory agents, water-soluble phosphoric acid compounds, potassium nitrate, aluminum lactate, vitamins, plant extracts and the like. Be done. The blending amount of the active ingredient is an effective amount within a range that does not interfere with the effect of the present invention.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples,% indicates mass% unless otherwise specified. The silica / alumina ratio is a mass ratio.
The method for measuring physical properties is shown below.
Volume average particle size; measured by a nanoparticle analyzer (nanoPartica SZ-100, manufactured by HORIBA).
BET specific surface area; measured at 25 ° C. using a specific surface area measuring device (manufactured by Nikkiso Co., Ltd., automatic specific surface area meter, BET multipoint method, measurement gas; nitrogen).

[Examples, comparative examples]
The dentifrice compositions having the compositions shown in Tables 1 to 3 were prepared by a conventional method, and the retention of fluorine on the tooth surface was evaluated by the method shown below. The results are also shown in the table.

Details of the raw materials used are shown below.
(A1) Sodium Fluoride; Purified Sodium Fluoride (A2) Sodium Monofluorophosphate, manufactured by Stella Chemifer Co., Ltd .;
Phoskadent Na211 manufactured by ICLJAPAN Co., Ltd.
(B)
(Ba) Alumina colloid;
AS-200 manufactured by Nissan Chemical Industries, Ltd.
Cation species: Al ₂ O ₃
Volume average particle size: 12 nm, BET specific surface area: 120 mm ² / g
(Bb) Alumina-coated colloidal silica I;
Snowtex AK, manufactured by Nissan Chemical Industries, Ltd.
Cation species: Al ₂ O ₃
Abundance ratio with silica: Mass ratio of silica / alumina: 100 / 9.1
Volume average particle size: 17 nm, BET specific surface area: 200 mm ² / g
(Bb) Alumina-coated colloidal silica II;
Silica Doll 20P manufactured by Nippon Chemical Industrial Co., Ltd.
Cation species: Al ₂ O ₃
Abundance ratio with silica: Mass ratio of silica / alumina: 100 / 8.1
Volume average particle size: 20 nm, BET specific surface area: 160 mm ² / g
Cachisel (comparative ingredient);
Hydroxyethyl cellulose dimethyldiallyl ammonium salt rice wax manufactured by AkzoNobel Co., Ltd. (comparative ingredient);
Rice wax S-100 manufactured by Yokoseki Yushi Kogyo Co., Ltd.
Colloidal silica (comparative ingredient);
JGC Catalysts and Chemicals Co., Ltd., Cataloid SI-50, Volume Average Particle Size: 25 nm
Synthetic amorphous aluminum-bonded silicate (comparative component);
Synthetic amorphous aluminum-bonded silicate described in JP-A-2010-275271 (aluminum is 0.5 to 7.5% with respect to SiO _{2 as Al 2} O _{3 and the amount of OH group is 2. with} respect to SiO 2. Synthetic amorphous aluminum-bonded silicates from 0 to 3.5%)
Silica / alumina mass ratio: 98/2 = 100 / 2.04
Volume average particle size: 20 μm
Silicic anhydride (viscous silica);
DSL Japan Co., Ltd., CARPLEX # 67, volume average particle size: 6 μm
Silicic anhydride (abrasive silica);
Zirconosilicate average particle size (median diameter using volume average): 12 μm, manufactured by TAKI CHEMICAL CO., LTD.
Dextranase;
Daiichi Sankyo Propharma Co., Ltd., 13,000 units (unit) / g

<Evaluation method>
Experimental method Take 1 g of the dentifrice composition with a toothbrush, brush it for 3 minutes, rinse it 3 times with 60 mL of water, collect 1 g of saliva, and add water to make a total of 10 mL of fluorine contained in the saliva diluent. Ions were measured using a fluorine electrode (manufactured by Thermo Fisher Scientific Co., Ltd.), and the fluorine ion concentration was determined (the value is the average value of 4 subjects). Fluorine ions were measured immediately after rinsing with water and 6 hours after rinsing with water, and the respective fluorine ion concentrations were determined. In this case, the high concentration of fluorine ions in saliva indicates that the fluorine does not flow out during rinsing or aging, and the retention on the tooth surface is high.

The amount of fluorine incorporated into enamel was measured by the method of Kin et al. (Journal of the Japanese Society for Oral Health, 48.8-19 (1998)).
The preparation and operation of the enamel sample was carried out as follows.
The organic matter and deposits on the crown of the cow tooth were removed with an abrasive, and a 20 mm ² window was prepared on the enamel surface with inlay wax, which was used as an enamel sample. By culturing this enamel sample in BMM medium ^{* 1} , a model biofilm ^{* 2} (plaque) was formed on the window surface.
1 g of the dentifrice composition was diluted and suspended in 3 times the amount of distilled water, and the enamel sample to which the plaque was attached was placed in this suspension and immersed in a constant temperature bath at 37 ° C. for 24 hours. The soaked enamel sample was rinsed with distilled water, immersed in a plastic container containing 0.4 mL of 0.5 mol / L perchloric acid for 60 seconds, and immediately immediately 1.6 mL of 0.5 mol / L sodium citrate. The solution was added to bring the total volume to 2.0 mL. The fluorine ion concentration (ppm) in this solution (decalcified solution) was measured with a fluorine ion electrode, and this was taken as the fluorine ion concentration in the inner layer of enamel (the value is an average value of n = 3).
In this case, the high concentration of fluorine ions in the inner layer of the enamel means that the uptake of fluorine into the enamel was effectively performed.
An enamel sample treated with human unstimulated saliva filtered through a 0.45 μm filter for 4 hours was used as a carrier for producing a model biofilm.

* 1: The composition of the BMM medium (basal medium mucin culture solution, BMM) used in the culture solution is as follows.
Composition of BMM medium (expressed by mass in 1 liter)
Proteose Pepton (manufactured by Becton and Dickinson):
4g / L
Tryptone (manufactured by Becton and Dickinson): 2 g / L
Yeast extract (manufactured by Becton and Dickinson):
2g / L
Mucin (manufactured by Sigma): 5 g / L
Hemin (manufactured by Sigma): 2.5 mg / L
Vitamin K (manufactured by Wako Pure Chemical Industries, Ltd.): 0.5 mg / L
KCl (manufactured by Wako Pure Chemical Industries, Ltd.): 1 g / L
Cysteine (manufactured by Wako Pure Chemical Industries, Ltd.): 0.2 g / L
Distilled water: Residual (Messed up to a total volume of 1 L and autoclaved at 121 ° C for 20 minutes.)

* 2: The strains used to prepare the model biofilm were Actinomyces viscosus ATCC43146, Veillonella parbula (Velilonella parvula) C Oralis (Streptococcus oralis) ATCC10557 and Streptococcus mutans ATCC25175 were used. These 5 strains were inoculated into a Rotating Disk Reactor (culture tank) containing 3,000 mL of BMM in advance at 1 × 10 ⁷ cfu / mL (cfu: colony forming units), and aerobically at 37 ° C. together with a carrier treated with saliva. The cells were cultured for 18 hours under specific conditions (5 vol% carbon dioxide, 95 vol% nitrogen). Then, under the same conditions, BMM medium was continuously supplied at a substitution rate of 5 vol% / hour, and the cells were cultured for 10 days to form a model biofilm containing 5 strains on the enamel sample.

Claims (10)

Aluminum oxide-coated colloidal particles (Bb) in which at least a part of the surface of (A) a fluorine-containing compound and (B) aluminum oxide colloidal particles (Ba) and colloidal nuclear particles of an inorganic oxide other than aluminum oxide is coated with aluminum oxide. ), The composition for oral use, which comprises one or more kinds selected from. Inorganic oxide other than aluminum oxide, oral composition according to claim 1 is colloidal silica. (Bb) component, orally according to claim 1 or 2 content ratio of colloidal core particles of inorganic oxides other than aluminum oxide and aluminum oxide are of 100 / 1-100 / 30 as a mass ratio Composition. The oral composition according to any one of claims 1 to 3 , wherein the component (B) has a volume average particle diameter of 0.1 to 1,000 nm. (B) component, the oral composition according to any one of claims 1-4 is of the BET specific surface area 90~4,000mm ² / g. The oral composition according to any one of claims 1 to 5 , which contains 500 to 1,500 ppm of the component (A) as a fluorine ion and 1 to 10% by mass of the component (B). The oral composition according to any one of claims 1 to 6 , further comprising (C) an anionic surfactant in an amount of 0.05 to 2% by mass. The oral composition according to any one of claims 1 to 7 , further comprising (D) one or more enzymes selected from dextranase and mutanase. The oral composition according to any one of claims 1 to 8 , further comprising (E) 2 to 50% by mass of a silica-based abrasive having a volume average particle diameter (median diameter) of 5 to 40 μm. The oral composition according to any one of claims 1 to 9 , which is a dentifrice.