JP4533997B2 - Oral composition and method for producing calcium carbonate capsule - Google Patents

Description

  The present invention relates to oral compositions such as dentifrice, mouthwash, coating agent, chewing gum and the like that can prevent or ameliorate oral troubles such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface. .

  Oral troubles such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface cause loss of teeth and discomfort to other people, which is an obstacle to a healthy life. . To solve this problem, attempts have been made to prevent or ameliorate problems in the oral cavity by incorporating oral active ingredients such as enzymes and bactericides into dentifrices, mouthwashes, chewing gums, etc. In this case, it is difficult to maintain the effect of the active ingredient by rinsing the mouth and the active ingredient being washed away by saliva.

On the other hand, an attempt has been made to encapsulate an active ingredient for oral cavity in a capsule coated with a polymer such as gelatin or agar, a wax-like substance, or the like and mix it with dentifrice (for example, see Patent Documents 1 to 3). ). These capsules are comparatively large capsules of several tens to several hundreds of micrometers, and are characterized by breaking the capsules using physical force such as brushing with a toothbrush to release the active ingredients. Although the method can ensure storage stability such as prevention of leakage of active ingredients, the capsule does not break or the mouth is washed away when the mouth is rinsed, so the retention of the active ingredients in the oral cavity is poor and the effect persistence There were difficulties.
In addition, some use a finer organic capsule-like substance, and in Patent Document 4, the active ingredient is encapsulated in the liposome. It was destroyed by the surfactants and salts, and the stability was difficult.

  On the other hand, attempts have been made to utilize inorganic materials as drug-carrying components. In Patent Document 5, silica porous spheres or porous hollow spheres are exemplified as enzyme-supported solids, but the outside must be further covered with a water-soluble film-forming substance in order to prevent enzyme leakage, There was difficulty in releasing the contents. Patent Document 6 shows that porous calcium carbonate is impregnated with an active ingredient, but even if the active ingredient is supported on porous particles having a large porosity, it is isolated from the outside. However, the active ingredient was eluted in the preparation, and it was difficult to ensure the stability and effectiveness of the preparation for a long time.

  In the composition for oral cavity, calcium carbonate is mainly used as an abrasive. As an application other than the abrasive, there is a proposal in the above-mentioned Patent Document 6, but in Patent Document 7, by using extremely fine calcium carbonate, the acid produced by the caries plaque is neutralized, and the oral cavity is used. It has been proposed to suppress a decrease in internal pH. It has also been shown that calcium carbonate adsorbs well on carious plaques. However, the fine calcium carbonate shown here has almost no function of supporting an active ingredient because crystals are densely packed.

  As an inorganic capsule containing an oil component, for example, Patent Document 8 discloses a capsule containing an oil component. However, Patent Document 8 does not suggest application to the oral cavity field, particularly application to destruction of carious plaque.

  Accordingly, it is desired to develop an oral composition that can more effectively prevent or improve oral troubles such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface.

JP-A-1-275520 JP-A-8-169811 JP-A-10-67625 JP-A-4-273815 Japanese Patent Laid-Open No. 1-281085 JP-A-11-310522 JP 09-295924 A Japanese Examined Patent Publication No. 04-16212 Color material, 50 (2), 67 (1977) Chemical Engineering, 46 (10), 541 (1982) "Emulsification / dispersion process functions and applied technology" published by Science Forum, Inc. 134 (1995)

  The present invention has been made in view of the above circumstances, and exhibits stable and continuous effects on oral troubles such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface. It aims at providing the composition for oral cavity which can prevent or improve.

  As a result of intensive studies to achieve the above object, the present inventors have found that calcium carbonate capsules using calcium carbonate as a film material, particularly calcium carbonate capsules in which an active ingredient for oral cavity is encapsulated inside a film made of calcium carbonate. In the composition for oral cavity, at least one of the following (1) to (5) characteristics is exerted to prevent troubles in the oral cavity such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface. It has been found that it can be effectively prevented or improved, and the present invention has been made.

The present invention exhibits at least one of the following.
(1) Calcium carbonate, which is a capsule membrane material, has excellent adsorbability to the oral mucosa, dental caries, or plaque causing periodontal disease, and therefore has excellent retention in the oral cavity.
(2) The calcium carbonate capsule of the present invention itself exhibits the ability to neutralize acids (such as lactic acid) produced by germs causing caries. The calcium carbonate capsule according to the present invention has a thin film thickness, for example, about 5 μm, and the capsule film is easily dissolved by an acid produced by a caries-causing fungus and exhibits an acid neutralizing ability. To do. Moreover, the dissolved calcium ion exhibits a function as a tooth remineralization component.
(3) Retention of the active ingredient in the oral cavity by encapsulating the active ingredient for oral cavity to prevent or ameliorate troubles in the oral cavity such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface. The effect of active ingredients such as the prevention of bad breath and the preventive effect can be exerted continuously by improving the properties and gradual release of the active ingredients through the pores of the calcium carbonate capsule membrane.
(4) The calcium carbonate capsule according to the present invention is excellent in the effect of preventing leakage and improving the stability of the active ingredient contained in the calcium carbonate capsule in the preparation. That is, since the calcium carbonate capsule forms an inorganic film, it has a higher ability to retain the encapsulated substance even when it is blended in the oral composition than when a porous or network gel structure supporting substance is used. It is hard to leak.
(5) The calcium carbonate capsule membrane is dissolved by the acid produced by the causative bacteria of the caries, and the encapsulated active ingredient can be released. In this case, since no physical force such as brushing is required to release the active ingredient encapsulated in the calcium carbonate capsule, the encapsulated active ingredient can be reliably released according to the change in the pH environment in the oral cavity. . In addition, since the active ingredient can be selectively released at the site where the carious plaque is present using this characteristic, there is a targeting property. For example, an effective sterilization / removal function of carious plaque can be exhibited by encapsulating a sterilizing agent or a liquid in which the sterilizing agent is dissolved in a capsule.

Accordingly, the present invention provides the following oral composition and method for producing calcium carbonate capsules .
[1]. An oral composition comprising a calcium carbonate capsule in which an active ingredient for oral cavity is encapsulated in a film made only of calcium carbonate .
[2]. The oral composition according to [1], wherein the oral active ingredient contained in the film is a sterilizing or antibacterial substance.
[3]. The composition for oral cavity according to [2], wherein the sterilizing or antibacterial substance is nonionic or cationic.
[4]. The oral composition according to [3], wherein the nonionic bactericidal or antibacterial substance is triclosan, isopropylmethylphenol, hinokitiol or bisabolol.
[5]. The oral composition according to [3], wherein the cationic bactericidal or antibacterial substance is chlorhexidine, chlorhexidine salt, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride, or decalinium chloride.

  The composition for oral cavity of the present invention has the ability to neutralize acids produced by caries-causing bacteria by blending the calcium carbonate capsule, and can function as a remineralization component of teeth, In addition, by encapsulating the oral active ingredient in the calcium carbonate capsule, the retention of the active ingredient in the oral cavity is improved, and the sustained release of the active ingredient is excellent in the sustainability of the effect derived from the active ingredient. Since the capsule membrane is dissolved by the acid produced by the fungus, the active ingredient can be selectively released to the diseased part such as caries, thus caries, periodontal disease, bad breath, and pigmentation on the tooth surface. It is possible to effectively prevent or improve intraoral troubles.

  Hereinafter, the present invention will be described in more detail. The composition for oral cavity of the present invention is characterized by comprising a calcium carbonate capsule.

  The calcium carbonate capsule according to the present invention is a capsule using calcium carbonate as a membrane material, and there is no particular limitation on the shape as long as the capsule has a hollow structure formed of calcium carbonate, but a hollow spherical capsule It is preferable that In addition, calcium carbonate capsules may have pores through which reactants or by-products pass in the capsule membrane in the process of production, but the pores are small and on the order of tens of nanometers, and the number of pores is small. The retention efficiency of the inclusion substance is high.

  As the capsule particle size decreases, the capsule strength increases and is less likely to be broken by external pressure. However, the particle size is preferably 0.01 to 50 μm, more preferably 0.05 to 30 μm, and still more preferably 0. The range is from 1 to 20 μm. In addition, the said particle size is a measured value by phase-contrast microscope observation or electron microscope observation.

  Taking into account that the capsule membrane can be dissolved by the acid produced by the causative bacteria of the caries present in the oral cavity, the capsule thickness is 2 μm or less on average, particularly 0.05 to 1 μm on average, as measured by transmission electron microscopy. In particular, the average is preferably 0.1 to 0.5 μm, and if it is less than 0.05 μm, the strength of the capsule is weakened and may be easily broken by external pressure. May not dissolve easily and the blending effect may not be exhibited.

Moreover, although the hollow ratio of the calcium carbonate capsule according to the present invention (the volume ratio of the internal hollow portion with respect to the capsule volume is defined as the hollow ratio of the capsule) varies depending on the film thickness and particle size of the capsule, it is 15 to 85%. The range is suitable, and if it is less than 15%, the capsule membrane cannot be easily dissolved by the acid in the oral cavity, or the amount of the active ingredient cannot be sufficiently secured, and the blending effect may not be exhibited, and it exceeds 85% In some cases, the strength of the capsule is weakened, and the capsule is easily broken by external pressure.
In addition to direct observation with an electron microscope, it can be confirmed that the capsule suddenly increases (breaks) when a certain load is applied, in addition to direct observation with an electron microscope. . The hollow ratio can be obtained by calculation from the measured values of the capsule film thickness and the capsule particle diameter by observation with a transmission electron microscope.

  The calcium carbonate capsule preferably has an average breaking strength (measured value of strength at the time of capsule rupture by a micro compression tester manufactured by Shimadzu Corporation) of 10 to 100 MPa, particularly 15 to 50 MPa. Since the strength is weak, it may be easily broken by an external pressure. When the pressure exceeds 100 MPa, the capsule membrane may not be easily dissolved in the oral cavity and the blending effect may not be exhibited.

  In the calcium carbonate capsule according to the present invention, various active ingredients usually blended in the oral composition can be encapsulated in the hollow part of the capsule film. Here, as the active ingredient to be encapsulated, an active ingredient that can prevent or ameliorate oral troubles such as caries, periodontal disease, bad breath, pigmentation on the tooth surface is suitably formulated, for example, an enzyme, Examples include sterilizing or antibacterial components, fluorine compounds, anti-inflammatory agents, vitamins, plant extracts, antibiotics, peroxides, Maillard reaction inhibitors, and fragrances. In addition, there is no restriction | limiting in particular in the form of an active ingredient, It may be a solid at room temperature, or it may be liquid, and there is no restriction | limiting about solubility, even if it is water-soluble, it is a poorly water-soluble and oil-soluble ingredient. There may be. Specific active ingredients can be listed below, and one of these ingredients can be used alone or in combination of two or more.

[Enzyme] Dextranase, mutanase, lysozyme amylase, protease, lytic enzyme, superoxide dismutase, tannase and the like.
[Bactericidal or antibacterial component] Nonionic substances such as triclosan, isopropylmethylphenol, hinokitiol and bisabolol, and cationic substances such as chlorhexidine, chlorhexidine hydrochloride, chlorhexidine gluconate, benzethonium chloride, benzalkonium chloride Cetylpyridinium chloride, decalinium chloride, etc.
[Fluorine compound] Hydrogen fluoride, sodium monofluorophosphate, potassium monofluorophosphate, stannous fluoride and the like.
[Vitamins] Vitamin E, vitamin D, vitamin A, vitamin C and the like.
[Plant extract] Plant extracts such as rosemary, sage, mint, thyme and eucalyptus.
[Other active ingredients] Tranexamic acid, epsilon aminocaproic acid, aluminum chlorohydroxy allantoin, dihydrocholesterol, glycyrrhizic acid, glycyrrhetinic acid, glycerophosphate, chlorophyll, sodium chloride, water-soluble inorganic phosphate compound, l-menthol, palatinose, glycine , Proline and so on.
Of these active ingredients, particularly bactericidal or antibacterial ingredients are preferably used. Moreover, in order to encapsulate these active ingredients efficiently, ethanol, propylene glycol, glycerin, liquid paraffin, animal and vegetable oils and the like can be used in appropriate amounts as solvents.

  The encapsulation ratio of the active ingredient in the calcium carbonate capsule is preferably set in a range in which the effect of the active ingredient can be exerted, and is 0.5 to 50% by mass, particularly 1 to 20% by mass with respect to the amount of calcium carbonate in the capsule. If the amount is less than 0.5% by mass, the effect of the contained active ingredient may not be exhibited. If the amount exceeds 50% by mass, the capsule may exceed the hollow volume, making it difficult to encapsulate the active ingredient. is there.

  For the production of the calcium carbonate capsule, an encapsulation method by W / O / W emulsification is suitably employed. For example, the manufacture of calcium carbonate hollow capsules is described in Non-Patent Document 1 (Coloring Materials, 50 (2), 67 (1977)) and Non-Patent Document 2 (Chemical Engineering, 46 (10), 541 (1982)). It can be prepared by applying the described interfacial reaction method. This is based on W / O / W emulsification, and each of the two reaction components is dissolved in the inner aqueous phase and the outer aqueous phase, W / O emulsification using an organic solvent, and further W / O / W emulsification, In this method, an inorganic precipitation reaction is caused at the interface between the inner aqueous phase and the outer aqueous phase to form a film.

  In this case, when producing a calcium carbonate capsule, a predetermined amount of calcium salt is dissolved in one of the inner aqueous phase and the outer aqueous phase, and a predetermined amount of carbonate is dissolved in the other aqueous phase, There is no particular limitation as to whether each of the calcium salt and the carbonate is dissolved in the inner aqueous phase or the outer aqueous phase, and can be appropriately selected. Examples of calcium salts used in the reaction include water-soluble calcium chloride, calcium nitrate, calcium acetate and the like. Examples of the carbonate include water-soluble potassium carbonate, sodium carbonate, ammonium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate and the like.

As the organic solvent, those in which W / O emulsification and W / O / W emulsification are efficiently formed are preferable, and examples thereof include benzene, n-hexane, cyclohexane, liquid paraffin, and salad oil.
In order to improve the formability of W / O emulsification and W / O / W emulsification, it is preferable to add a small amount of a surfactant. Examples of the surfactant include sorbitan monopalmitate (Span 40), sorbitan monostearate (Span 60), sorbitan monooleate (Span 80), sorbitan trioleate (Span 85), and other polyoxyethylene sorbitan series. Polyoxyethylene sorbitan monopalmitate (Tween 40), polyoxyethylene sorbitan monostearate (Tween 60), polyoxyethylene sorbitan monooleate (Tween 80), polyoxyethylene trioleate (Tween 85), sucrose fatty acid ester Activators, polyglycerin fatty acid ester activators, and the like. These surfactants are preferably blended alone or in combination of two or more, and in particular, in order to efficiently form a W / O emulsifier, it is preferable to adjust the lipophilicity as a whole. . The addition amount of the surfactant is preferably about 0.5 to 5% by mass with respect to the organic solvent.

The components used in these encapsulation reactions are preferably components used in foods and oral pharmaceuticals and cosmetics.
The reaction conditions can be adjusted as appropriate, and the reaction temperature can be room temperature, but it may be heated or cooled, and the reaction time is from several minutes to several hours. After completion of the reaction, calcium carbonate hollow capsules can be obtained through separation of organic solvent, washing with water, washing with ethanol or methanol, and drying.

  The average particle diameter and film thickness of the calcium carbonate hollow capsule can be controlled by adjusting the type, concentration, ratio, and type and amount of the emulsifier used in the reaction.

  For the inclusion of the active ingredient in the calcium carbonate hollow capsule, a method according to the active ingredient to be encapsulated can be adopted. As an encapsulation method, for example, as described in Non-Patent Document 3 ("Functions and Application Technology of Emulsification / Dispersion Process", Science Forum, Inc., P. 134 (1995)), calcium carbonate hollow capsules are used. It can be carried out by impregnating a liquid oral active ingredient under reduced pressure or by impregnating a liquid obtained by diluting or dissolving the oral active ingredient with a solvent such as ethanol or propylene glycol or water. When using a solvent, the active ingredient may be encapsulated, and the solvent used may be removed by volatilization or may be encapsulated.

  As another encapsulation method, when the active ingredient is a water-soluble component, it can be encapsulated by dissolving in an inner aqueous phase at the time of W / O emulsification in the calcium carbonate capsule production process. When the active ingredient is a solid having good water dispersibility, it can be encapsulated by dispersing it in the inner aqueous phase during W / O emulsification in the calcium carbonate capsule production process. When the active ingredient is an oil-soluble ingredient, the active ingredient can be dissolved in liquid paraffin, salad oil or the like, and can be encapsulated using the production method described in Patent Document 8, specifically, at the time of capsule formation By pre-emulsifying an oil phase in which the active ingredient is dissolved in liquid paraffin or salad oil in the aqueous phase that is the inner aqueous phase, and forming an O / W / O / W type emulsion to make a capsule membrane Can be included.

  The composition for oral cavity of the present invention is obtained by blending the calcium carbonate capsules thus obtained in an arbitrary ratio, such as toothpaste, toothpaste, toothpaste such as liquid toothpaste, mouthwash, application It can be prepared as an agent, dental floss, tablet, chewing gum, gummi, candy, troche and the like.

  In this case, the compounding quantity of a calcium carbonate capsule is 0.1-30 mass% of the whole composition for oral cavity, Especially 0.5-10 mass% is preferable. If the blending amount is less than 0.1% by mass, a satisfactory blending effect may not be obtained, and even if it exceeds 30% by mass, no further effect may be expected.

  In addition, the calcium carbonate capsule-containing oral composition of the present invention can be produced by a normal method for preparing an oral composition, and there are no particular restrictions on the method of blending the calcium carbonate capsule, but various components are blended. It is preferable to add and mix calcium carbonate capsules at the final stage in order to prevent the capsules from being broken by mechanical force.

  In the composition for oral cavity of the present invention, as other optional components, components usually used depending on the dosage form can be blended as necessary. For example, in the case of dentifrice, various abrasives, wetting agents, binders, surfactants, sweeteners, fragrances, coloring agents, preservatives, other active ingredients, etc., alone or in combination of two or more. The usual amount can be used as long as the effects of the present invention are not impaired.

  As abrasives, precipitated silica, silica gel, aluminosilicate, zeolite, zirconosilicate, dicalcium phosphate dihydrate and anhydride, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, magnesium carbonate, tertiary phosphorus Examples thereof include magnesium acid, insoluble sodium metaphosphate, insoluble potassium metaphosphate, titanium oxide, hydroxyapatite, and synthetic resin-based abrasive (mixing amount: usually 5 to 50% by mass with respect to the entire composition).

  Examples of the wetting agent include glycerin, sorbitol, propylene glycol, polyethylene glycol, and 1,3-butylene glycol (blending amount: usually 10 to 50% by mass with respect to the entire composition).

  As binder, carrageenan, hydroxyethylcellulose sodium, carboxymethylcellulose sodium, hydroxyethylcellulose, hydroxypropylcellulose, methylcellulose, hydroxypropylmethylcellulose, sodium alginate, propylene glycol ester alginate, polyacrylic acid, sodium polyacrylate, xanthan gum, tara gum, Guam gum, locust bean gum, gellan gum, gelatin, curdlan, gum arabic, agar, pectin, polyvinyl alcohol, polyvinyl pyrrolidone, pullulan, etc. (blending amount: usually 0.1 to 5% by mass with respect to the total composition) ).

  As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant and the like can be blended, specifically, sodium lauryl sulfate, sodium α-olefin sulfonate, N-acyl glutamate, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-acyl taurate, sucrose fatty acid ester, alkylol amide, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester, polyoxyethylene polyoxy Examples include propylene glycol, polyoxyethylene sorbitan monostearate, sodium lauroyl sarcosine, alkyl polyglucoside, polyoxyethylene alkyl ether sulfosuccinate (blending amount; usually 0.5 to 5 mass based on the entire composition) ).

Examples of the sweetening agent include saccharin sodium, stevioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyl hydrochalcone, and perilartin. Examples of the colorant include blue No. 1, yellow No. 4, titanium dioxide and the like. Examples of the preservative include paraoxybenzoic acid ester and sodium benzoate.
Examples of the fragrances include terpenes such as l-menthol, carvone, anethole and limonene, or derivatives thereof, peppermint oil, and the like.

  In addition, to the oral composition of the present invention, as an active ingredient, in addition to the active ingredient encapsulated in the capsule, one or more of the oral active ingredients exemplified above as the encapsulating ingredient of the capsule are added, Can be blended.

  Furthermore, gum base, xylitol, citrate, dibutylhydroxytoluene, malic acid, pH adjuster, ethanol, water and the like can be blended as necessary as other optional components other than the above.

  EXAMPLES Hereinafter, although an experiment example and an Example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, the average particle diameter measured by the particle diameter of 100 capsules by phase-contrast microscope observation, and computed by arithmetic mean.

[Experiment 1]
(A) Preparation of calcium carbonate hollow capsule According to the preparation method described in Non-Patent Document 1, a hollow capsule using calcium carbonate as a membrane material was prepared. The preparation process and reaction conditions are as follows.
Step 1: W / O emulsification solvent (0.336 g sorbitan monooleate (Span 80) and 0.672 g polyoxyethylene sorbitan monooleate (Tween 80)) in a solvent (n-hexane 64 mL) at room temperature The oil phase was dissolved. This oil phase was stirred at 8,000 rpm using a homogenizer (ULTRA-TURRAX T25basic manufactured by TKA-WERKE), and 32 mL (3 mol / L) of an aqueous potassium carbonate solution was added in 3 seconds, and 1 at 8,000 rpm. Emulsification for a minute gave a W / O emulsion.
Step 2: W / O / W emulsification The obtained W / O emulsion is added to 640 mL (0.3 mol / L) of calcium chloride aqueous solution stirred at 400 rpm using three downward propeller blades in 3 seconds. , W / O / W emulsification was carried out, and the mixture was reacted at room temperature for 1 hour to form a calcium carbonate capsule membrane.

  Thereafter, the mixture obtained in Step 2 was allowed to stand for 15 minutes to separate into a hexane layer and an aqueous layer, and then the hexane layer was removed by decantation. The remaining aqueous layer was suction filtered through a 1 μm pore filter paper. The solid content remaining on the filter paper was dispersed in 200 mL of water and stirred for 5 minutes with a stirrer, and then suction filtered through a 1 μm pore filter paper again. This water dispersion and filtration operation was repeated once more. The solid content remaining on the filter paper was dispersed in 200 mL of ethanol and stirred with a stirrer for 5 minutes, followed by suction filtration through a 1 μm pore filter paper. The remaining solid was allowed to stand at 100 ° C. overnight and dried to obtain a calcium carbonate hollow capsule. When the particle size of the obtained capsule was measured by phase contrast microscopy, it was 3 to 10 μm (average particle size 6.2 μm). When the sliced surface of the capsule was observed with a transmission electron microscope, the thickness of the capsule film was 0.1 to 0.9 μm. As a result of calculating the hollowness of the capsule from the particle diameter observed with a transmission electron microscope and the capsule film thickness, it was 47%. Moreover, when the fracture strength of this capsule was measured using a micro compression tester manufactured by Shimadzu Corporation, the average was 31.4 MPa.

  1 and 2 show transmission electron micrographs (magnification: 14000 times) of the sliced surface of the obtained calcium carbonate hollow capsule. In the figure, the portion of the capsule surface that appears as a white solid coating is determined as the capsule membrane.

(B) Evaluation of acid neutralization ability Using the calcium carbonate hollow capsule obtained by the above method, the neutralization ability of the acid produced by the caries causing the caries was evaluated by the following method.
That is, 4 mL of a suspension containing Streptococcus mutans, a caries-related bacterium, at a concentration of 1 × 10 ⁸ cells / mL, calcium carbonate capsules at a final concentration of 0.8% (W / V), and sugar solution at a final concentration The suspension was added to 1% (W / V), and the pH of the suspension was measured over time. At this time, calcium carbonate for abrasives having an approximately the same particle diameter (average particle diameter of 5.8 μm (according to laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by Horiba, Ltd.)) was used as a comparative example. The control is a system without addition of calcium carbonate. The result is shown in FIG.

  From the results of FIG. 3, it was found that the one administered with the calcium carbonate hollow capsule had an effect of suppressing the decrease in pH caused by the activity of caries bacteria compared to the one administered with the calcium carbonate for abrasive. . This is probably because the calcium carbonate hollow capsule has a thin capsule thickness, so that it is easily dissolved by the acid produced by the cariogenic bacteria and has an excellent neutralizing effect.

[Experiment 2]
(A) Preparation of calcium carbonate capsule containing triclosan 2 g of calcium carbonate hollow capsule obtained in Experimental Example 1 was placed in a pear-shaped flask and stirred with a magnetic stirrer, under reduced pressure (aspirator suction, 2,700 Pa) Then, 2.5 g of an ethanol solution of triclosan (concentration: 17% by mass) was gradually dropped from a nozzle into a pear-shaped flask to impregnate a calcium carbonate hollow capsule with the ethanol solution of triclosan. Then, ethanol was volatilized and removed overnight using a vacuum dryer at a reduced pressure of 1 Pa to obtain triclosan-encapsulated calcium carbonate capsules. The amount of triclosan incorporated into the capsule was quantified using ¹ H-NMR.

  That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were placed in an NMR tube, and about 0.4 mL of deuterated methanol was added as a solvent. Further, 3 drops of 35% by mass deuterated hydrochloric acid was added to completely dissolve the calcium carbonate film, and triclosan was extracted. The peak at 6.5 ppm was 1,1,2,2-tetrachloroethane, and when this integrated value was 2, the peak area at 7.5 ppm of triclosan was 0.29. When the content of triclosan was calculated from this value, it was 17% by mass with respect to the total amount of the capsule.

(B) Release behavior of encapsulated triclosan by acid addition Using the obtained triclosan encapsulated calcium carbonate capsule, the release behavior of triclosan encapsulated by acid addition was measured. Here, an intraoral demineralization model solution was used as the acid to be added. The composition of the intraoral demineralization model solution is shown below.
Intraoral demineralization model solution composition: Inorganic salts shown below are dissolved in water so as to have the following concentrations.
Calcium chloride 300mmol / L
Potassium dihydrogen phosphate 500mmol / L
Sodium chloride 2mol / L
Lactic acid 1mol / L
Acetic acid 1 mol / L
Furthermore, pH was adjusted to 4.5 using 1 mol / L sodium hydroxide aqueous solution.

Triclosan-encapsulated calcium carbonate capsules (120 mg) were placed in a vial, 10 g of water was added, and the mixture was dispersed with a stirring bar. The oral demineralization model liquid was dripped there, and the relationship between an oral demineralization model liquid drop amount and liquid pH was measured. Regarding the amount of triclosan released, 120 mg of triclosan-encapsulated calcium carbonate capsules were placed in a vial, 10 g of water was added and dispersed with a stirrer, and the oral decalcification model solution was added dropwise to a predetermined pH. Then, 2 g of a 1,1,2,2-tetrachloroethane hexane solution (0.48% by mass) was added and stirring was continued for 2 minutes to extract triclosan eluted from the capsule into the hexane layer. After separation for 1 minute, a part of the hexane layer was put into an NMR tube, hexane was distilled off by heating, deuterated chloroform was added, and triclosan peak appearing at 7.5 ppm by ¹ H-NMR and 6 The amount of triclosan was determined from the peak of 1,1,2,2-tetrachloroethane appearing at 0.0 ppm, and the ratio of the released mass to the encapsulated mass in the initial capsule was calculated as the triclosan release rate (%).

  FIG. 4 shows the relationship between the dripping amount of the oral decalcification model solution, the pH transition, and the triclosan release rate. From this figure, it became clear that triclosan was released from the triclosan-encapsulated calcium carbonate capsule as the pH became acidic. In addition, it is understood that triclosan is released at 60% or more at a pH of about 5.7 or less at which demineralization starts in the oral cavity, and it is considered that an excellent bactericidal effect is exhibited.

(C) Evaluation of the bactericidal effect of caries bacteria Using the obtained triclosan-encapsulated calcium carbonate capsule, the bactericidal effect of the causative bacteria of caries was evaluated by the following method.
Streptococcus mutans, a caries-causing bacterium, was tilted in a test tube using a Todd Hebbit broth medium to form artificial plaques on the test tube wall and used as a sample. The artificial plaque was washed twice with 2 mL of physiological saline, and 1 mL of physiological saline in which 5% by mass of triclosan-encapsulated calcium carbonate capsules were dispersed was added and shaken for 3 minutes. After washing, a Todd Hebbit broth medium solution containing 1% by mass sugar was further added and incubated at 37 ° C. After 10 minutes, 60 minutes, and 120 minutes, plaques were dispersed with ultrasonic waves, the dispersion was smeared on an agar plate, and the number of viable bacteria was counted after incubation. Similarly, a system using a calcium carbonate capsule not containing triclosan and a system without adding a capsule (control) were simultaneously evaluated. The results are shown in Table 1.

  From the results in Table 1, the growth of the fungus occurred in the system without the addition of the calcium carbonate capsule, whereas the growth of the fungus was suppressed in the system to which the calcium carbonate capsule without the inclusion substance was added. In the system to which the calcium carbonate capsule was added, the reduction of bacteria was confirmed. In the system in which the calcium carbonate capsule containing triclosan is added, the calcium carbonate capsule film is dissolved by the acid produced by the causative bacteria of the caries, and the content of triclosan is released, so that the bactericidal effect is exhibited. From this, the usefulness of the calcium carbonate capsule and the calcium carbonate capsule containing the active ingredient was found.

[Experiment 3]
(A) Preparation of calcium carbonate capsule encapsulating l-menthol 0.9 g of calcium carbonate hollow capsule obtained in Experimental Example 1 was placed in a pear-shaped flask and stirred with a magnetic stirrer under reduced pressure (aspirator suction, 2 700 Pa), a solution prepared by dissolving 0.2 g of l-menthol in 1.4 g of ethanol was gradually dropped into a pear-shaped flask from a nozzle and impregnated. Thereafter, ethanol was volatilized and removed overnight using a vacuum dryer at a reduced pressure of 1 Pa to obtain l-menthol-encapsulated calcium carbonate capsules. The amount of l-menthol incorporated in the capsule was quantified using ¹ H-NMR.
That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were placed in an NMR tube, and about 0.4 mL of deuterated chloroform was added as a solvent. Further, 3 drops of 35% by mass deuterated hydrochloric acid was added to completely dissolve the calcium carbonate film, and l-menthol was extracted. When quantified using a peak area of 6.0 ppm of 1,1,2,2-tetrachloroethane and a peak area of 3.4 ppm of l-menthol, the amount of l-menthol incorporated into the capsule is It was 16 mass% with respect to.

(B) Evaluation of bad breath prevention effect The obtained l-menthol-encapsulated calcium carbonate capsule was added to a mouthwash solution having the following common composition in an amount of 0.8% by mass as a l-menthol compounding amount to prepare a sample. For comparison, l-menthol is obtained by impregnating 16 mass% of l-menthol into porous calcium carbonate (IK-3000 manufactured by Shiroishi Central Research Laboratory) instead of 16 mass% encapsulated calcium carbonate capsules. Prepared according to the preparation method of the encapsulated calcium carbonate capsules, and prepared a mouthwash (0.8% by mass as the amount of l-menthol) mixed in the common composition. Furthermore, as a comparison, a mouthwash containing l-menthol alone with a common composition of 0.8% by mass was prepared. 30 subjects were divided into 3 groups, and each mouth was rinsed with 1-menthol-containing calcium carbonate capsule mouthwash, 1-menthol-containing calcium carbonate capsule mouthwash, and l-menthol-containing mouthwash, 30 minutes Then, after 60 minutes and 90 minutes, the bad breath was self-evaluated. The results are shown in Table 2.
Mouthwash common composition:
Ethanol 10.0%
Saccharin sodium 0.05
Sodium lauryl sulfate 0.3
Sodium polyoxyethylene myristyl sulfate 0.3
Sodium benzoate 0.05
Water balance
100.0 mass% in total

  From the results shown in Table 2, when 1-menthol-containing mouthwash is used, the sustainability of the bad breath prevention effect is not felt so much, and when 1-menthol impregnated porous calcium carbonate is used, the initial bad breath prevention effect is obtained. However, it was found that sustainability was inferior. On the other hand, when 1-menthol-encapsulated calcium carbonate capsules were used, it was confirmed that there were many people who did not feel bad breath over time, and that the bad breath prevention effect was sustained.

[Experimental Example 4]
(A) Preparation of calcium carbonate hollow capsule According to the preparation method described in Non-Patent Document 1, a hollow capsule using calcium carbonate as a membrane material was prepared. The preparation process and reaction conditions are as follows.
Step 1: Surfactant (0.448 g sorbitan monooleate (Span 80) and 0.896 g polyoxyethylene sorbitan monooleate (Tween 80)) was added to the W / O emulsified solvent (64 mL of n-hexane) at room temperature. The oil phase was dissolved. This oil phase was stirred at 8,000 rpm using a homogenizer (ULTRA-TURRAX T25basic manufactured by TKA-WERKE), and 32 mL (4 mol / L) of an aqueous potassium carbonate solution was added in 3 seconds, and 1 at 8,000 rpm. Emulsification for a minute gave a W / O emulsion.
Step 2: W / O / W emulsification The obtained W / O emulsion was added to 512 mL (0.5 mol / L) of aqueous calcium chloride solution stirred at 400 rpm using three downward propeller blades in 3 seconds. , W / O / W emulsification was carried out, and the mixture was reacted at room temperature for 1 hour to form a calcium carbonate capsule membrane.

  The mixture obtained in step 2 was allowed to stand for 15 minutes to separate into a hexane layer and an aqueous layer, and then the hexane layer was removed by decantation. The remaining aqueous layer was suction filtered through a 1 μm pore filter paper. The solid content remaining on the filter paper was dispersed in 200 mL of water and stirred for 5 minutes with a stirrer, and then suction filtered through a 1 μm pore filter paper again. This water dispersion and filtration operation was repeated once more. The solid content remaining on the filter paper was dispersed in 200 mL of ethanol and stirred with a stirrer for 5 minutes, followed by suction filtration through a 1 μm pore filter paper. The remaining solid was allowed to stand at 100 ° C. overnight and dried to obtain a calcium carbonate hollow capsule. It was 1-6 micrometers when the particle size of the obtained capsule was measured by phase contrast microscope observation (average particle diameter of 4.8 micrometers). When the sliced surface of the capsule was observed with a transmission electron microscope, the thickness of the capsule film was 0.1 to 0.6 μm. As a result of calculating the hollowness of the capsule from the particle diameter observed with a transmission electron microscope and the capsule film thickness, it was 56%. When the capsules were measured for breaking strength using a micro compression tester manufactured by Shimadzu Corporation, the average was 30.3 MPa.

(B) Preparation of Calcium Carbonate Capsule Encapsulating Triclosan Subsequently, according to the method shown in Experimental Example 2, 2.0 g of an ethanol solution of triclosan (concentration 17% by mass) was dropped into 2 g of the calcium carbonate hollow capsule under reduced pressure. Impregnated. When the amount of triclosan taken into the capsule after the ethanol was volatilized and removed was quantified by ¹ H-NMR according to Experimental Example 2 (a), it was 14% by mass with respect to the total amount of the capsule.

[Experimental Example 5]
<Preparation of calcium carbonate capsules containing isopropylmethylphenol>
2 g of the calcium carbonate hollow capsule obtained in Experimental Example 1 was placed in a pear-shaped flask and stirred with a magnetic stirrer, and an ethanol solution of isopropylmethylphenol (concentration 17% by mass) under reduced pressure (aspirator suction, 2,700 Pa). 2.5 g was gradually dropped into a pear-shaped flask from a nozzle and impregnated. Thereafter, ethanol was volatilized and removed by using a vacuum dryer at a reduced pressure of 1 Pa overnight to obtain isopropylmethylphenol-encapsulated calcium carbonate capsules. The amount of isopropylmethylphenol incorporated into the capsule was quantified using ¹ H-NMR.

  That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were placed in an NMR tube, and about 0.4 mL of deuterated chloroform was added as a solvent. Further, 3 drops of 35% by mass deuterated hydrochloric acid was added to completely dissolve the calcium carbonate film, and isopropylmethylphenol was extracted. The content of isopropylmethylphenol was calculated from the peak area of 6.0 ppm of 1,1,2,2-tetrachloroethane and the peak area of 2.3 ppm of isopropylmethylphenol. It was included.

[Experimental Example 6]
<Preparation of calcium carbonate capsules containing cetylpyridinium chloride>
2 g of the calcium carbonate hollow capsule obtained in Experimental Example 4 (a) was placed in a pear-shaped flask and stirred with a magnetic stirrer, and cetylpyridinium chloride monohydrate was added under reduced pressure (aspirator suction, 2,700 Pa). Ethanol solution (concentration 17% by mass) 2.5 g was gradually dropped into a pear-shaped flask from a nozzle and impregnated. Thereafter, ethanol was volatilized and removed by using a vacuum dryer at a reduced pressure of 1 Pa overnight to obtain calcium carbonate capsules containing cetylpyridinium chloride monohydrate. The amount of cetylpyridinium chloride monohydrate incorporated into the capsule was quantified using ¹ H-NMR.

  That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were put into an NMR tube, about 0.4 mL of deuterated methanol was added as a solvent, Cetylpyridinium chloride was extracted by irradiation with sound waves for 5 minutes. The content of cetylpyridinium chloride monohydrate was calculated from the peak area of 6.5 ppm of 1,1,2,2-tetrachloroethane and the peak area of 4.7 ppm of cetylpyridinium chloride. In contrast, 13% by mass was contained.

[Experimental Example 7]
<Preparation of calcium carbonate capsule containing triclosan and isopropylmethylphenol (IPMP)>
2 g of the calcium carbonate hollow capsule obtained in Experimental Example 4 (a) was put in a pear-shaped flask and stirred with a magnetic stirrer, and 12% by mass of triclosan and isopropylmethylphenol 6 under reduced pressure (aspirator suction, 2,700 Pa). 1.95 g of ethanol solution in which mass% was dissolved was gradually dropped from a nozzle into a pear-shaped flask and impregnated. Thereafter, ethanol was volatilized and removed by using a vacuum dryer at a reduced pressure of 1 Pa overnight to obtain triclosan and isopropylmethylphenol-encapsulated calcium carbonate capsules. The amount of triclosan and isopropylmethylphenol incorporated into the capsule was quantified using ¹ H-NMR.
That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were placed in an NMR tube, and about 0.4 mL of deuterated chloroform was added as a solvent. Further, 3 drops of 35% by mass deuterated hydrochloric acid was added to completely dissolve the calcium carbonate film, and triclosan and isopropylmethylphenol were extracted. When quantified using a peak area of 6.0 ppm of 1,1,2,2-tetrachloroethane, a peak area of 6.7 ppm of triclosan and a peak area of 2.3 ppm of isopropylmethylphenol, it was incorporated into the capsule. The amounts of triclosan and isopropylmethylphenol were 10% by mass and 5% by mass, respectively, with respect to the total capsule.

[Experimental Example 8]
<Preparation of calcium carbonate capsules containing hinokitiol>
An ethanol solution in which 2 g of the calcium carbonate hollow capsule obtained in Experimental Example 4 (a) was placed in a pear-shaped flask and set in a rotary evaporator, and 18% by mass of hinokitiol was dissolved under reduced pressure (aspirator suction, 2,700 Pa). 25 g was gradually dropped from a nozzle into a pear-shaped flask and impregnated. Thereafter, ethanol was volatilized and removed overnight using a vacuum dryer at a reduced pressure of 1 Pa to obtain hinokitiol-encapsulated calcium carbonate capsules. The amount of hinokitiol incorporated into the capsule was quantified using ¹ H-NMR.
That is, 10.1 mg of capsule powder and 3.5 mg of internal standard 1,1,2,2-tetrachloroethane were placed in an NMR tube, and about 0.4 mL of deuterated chloroform was added as a solvent. Further, 3 drops of 35% by mass deuterated hydrochloric acid were added to completely dissolve the calcium carbonate film, and hinokitiol was extracted. When quantified using the peak area of 6.0 ppm of 1,1,2,2-tetrachloroethane and the peak area of 2.86 ppm of hinokitiol, the amount of hinokitiol incorporated into the capsule was 10 with respect to the total amount of capsule. It was mass%.

[Experimental Example 9]
<Preparation of calcium carbonate capsule containing bisabolol>
2 g of the calcium carbonate hollow capsule obtained in Experimental Example 4 (a) was placed in a pear-shaped flask and set in a rotary evaporator, and an ethanol solution in which 16% by mass of bisabolol was dissolved under reduced pressure (aspirator suction, 2,700 Pa) 7 g was gradually dropped from a nozzle into a pear-shaped flask and impregnated. Thereafter, ethanol was volatilized and removed by using a vacuum dryer at a reduced pressure of 1 Pa overnight to obtain a bisabolol-encapsulated calcium carbonate capsule. When the amount of bisabolol incorporated into the capsule was quantified by gas chromatography mass spectrometry, it was 12% by mass based on the total amount of the capsule.

[Example 1] Dentifrice calcium carbonate hollow capsule ^* 5.0%
Precipitated silica 15.0
Propylene glycol 3.0
Sorbit 20.0
Sodium carboxymethylcellulose 1.4
Saccharin sodium 0.1
Sodium lauryl sulfate 1.0
Tranexamic acid 0.05
α-Alumina Anhydride 3.0
Methylparaben 0.05
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 1 Average particle diameter 6.2 μm, film thickness 0.1-0.9 μm,
Fracture strength Average 31.4MPa, Hollow ratio 47%

[Example 2] Dentifrice triclosan-encapsulated calcium carbonate capsule ^* 2.0%
(Triclosan content is 17% by mass based on the total capsule)
Silica anhydride 10.0
Titanium oxide 0.5
Sodium carboxymethylcellulose 1.1
Carrageenan 0.2
Sodium lauryl sulfate 0.9
Sorbit 20.0
Glycerin 20.0
Propylene glycol 3.0
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 2

As a result of conducting a sterilization test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 5 mL of a dispersion obtained by diluting the toothpaste of Example 2 with water three times, 120 minutes later The number of viable bacteria was 4.5 × 10 ⁶ . The number of viable bacteria after 120 minutes of dentifrice excluding only the capsule from the dentifrice composition of Example 2 was 36.2 × 10 ⁶ , and therefore the dentifrice of Example 2 has high bactericidal activity. Admitted.

[Example 3] Liquid dentifrice triclosan-encapsulated calcium carbonate capsule ^* 0.5%
(Triclosan content is 17% by mass based on the total capsule)
60% sorbite solution 25.0
Glycerin 25.0
Propylene glycol 5.0
Xanthan gum 0.2
Sodium lauryl sulfate 0.5
Carrageenan 0.5
Sodium alginate 1.0
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 2

As a result of a bactericidal test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of the liquid toothpaste of Example 3, the number of viable bacteria after 120 minutes was 3.4 × 10 ⁶ . Since the number of viable bacteria after 120 minutes of the liquid dentifrice excluding only the capsule from the liquid dentifrice composition of Example 3 was 29.1 × 10 ⁶ , the liquid dentifrice of Example 3 has high bactericidal activity. It was recognized that there was.

[Example 4] Mouthwash l-menthol-encapsulated calcium carbonate capsule ^* 5.0%
(1-Menthol content 16% by mass based on the total capsule)
Ethanol 10.0
Saccharin sodium 0.05
Sodium lauryl sulfate 0.3
Sodium polyoxyethylene myristyl sulfate 0.3
Sodium benzoate 0.05
Sodium monofluorophosphate 0.05
Perfume 0.3
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 3

[Example 5] Chewing gum triclosan-encapsulated calcium carbonate capsule ^{* 1} 0.24%
(Triclosan content is 17% by mass based on the total capsule)
l-Menthol-encapsulated calcium carbonate capsule ^{* 2} 2.8
(1-Menthol content 16% by mass based on the total capsule)
Gum base 40.0
Xylitol 10.0
Perfume 0.5
Sorbitol balance
100.0 mass% in total
* 1: Obtained in Experimental Example 2 * 2: Obtained in Experimental Example 3

[Comparative Example 1] Chewing gum triclosan 0.04%
l-Menthol 0.45
Gum base 40.0
Xylitol 10.0
Perfume 0.5
Sorbitol balance
100.0 mass% in total

  Using the chewing gum of Example 5, the actual sensitivity of bad breath prevention was evaluated. That is, 20 subjects were divided into 2 groups of 10 subjects, and one group was chewed with the chewing gum of Example 5 for 30 minutes, and the other group was blended with only the active ingredient instead of blending the calcium carbonate capsule containing the active ingredient. The chewing gum of Comparative Example 1 was chewed for 30 minutes. After 90 minutes, the presence of bad breath was self-evaluated. In the group in which the chewing gum of Example 5 was evaluated, 7 out of 10 people did not feel bad breath, 3 people answered that bad breath was felt slightly, and no one answered that bad breath was felt. On the other hand, in the group in which the chewing gum of Comparative Example 1 was evaluated, 4 persons out of 10 felt bad breath, 6 persons felt bad breath, and none answered that bad breath was not felt. From this result, it was confirmed that the chewing gum of Example 5 had a bad breath prevention effect.

[Example 6] Dentifrice triclosan-encapsulated calcium carbonate capsule ^* 1.5%
(Triclosan content 14% by mass with respect to capsule total)
Silica anhydride 10.0
Titanium oxide 0.5
Sodium carboxymethylcellulose 1.0
Carrageenan 0.2
Sodium lauryl sulfate 0.9
Sorbit 22.0
Glycerin 18.0
Propylene glycol 3.0
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 4

As a result of conducting a sterilization test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 6 with water three times, 120 minutes later The number of viable bacteria was 3.9 × 10 ⁶ . Since the viable count after 120 minutes of the toothpaste excluding only the capsule from the toothpaste composition of Example 6 was 39.4 × 10 ⁶ , the toothpaste of Example 6 has high bactericidal activity. Admitted.

[Example 7] Dentifrice isopropylmethylphenol-encapsulated calcium carbonate capsule ^* 1.0%
(Isopropylmethylphenol content 17% by mass based on the total capsule)
Silica anhydride 16.0
Titanium oxide 0.4
Sodium alginate 0.4
Xanthan gum 0.6
Sodium lauryl sulfate 1.0
Sorbit 25.0
Propylene glycol 3.0
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 5

As a result of conducting a sterilization test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 7 with water three times, 120 minutes later The number of viable bacteria was 6.4 × 10 ⁶ . Since the viable count after 120 minutes of the toothpaste excluding only the capsule from the toothpaste composition of Example 7 was 38.3 × 10 ⁶ , the toothpaste of Example 7 has high bactericidal activity. Admitted.

[Example 8] Dentifrice cetylpyridinium chloride-encapsulated calcium carbonate capsule ^* 1.2%
(Cetylpyridinium chloride monohydrate content 13% by mass with respect to the total capsule content)
Silicic anhydride 18.0
Titanium oxide 0.5
Sodium carboxymethylcellulose 1.2
Sodium lauryl sulfate 1.0
Sorbit 30.0
Propylene glycol 3.0
Methylparaben 0.05
Saccharin sodium 0.12
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 6

As a result of conducting a sterilization test of Streptococcus mutans, a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 8 with water three times, 120 minutes later The viable cell count was 7.3 × 10 ⁶ . Since the viable count after 120 minutes of dentifrice excluding only the capsule from the dentifrice composition of Example 8 was 41.0 × 10 ⁶ , the dentifrice of Example 8 has high bactericidal activity. Admitted.

[Example 9] Dentifrice triclosan and isopropylmethylphenol-encapsulated calcium carbonate capsules ^* 2.0%
(Triclosan content 10% by mass with respect to the total capsule,
Isopropyl methylphenol content 5% by mass with respect to the total capsule)
Silicic anhydride 20.0
Titanium oxide 0.5
Sodium alginate 0.4
Xanthan gum 0.6
Sodium lauryl sulfate 1.0
Sorbit 22.0
Glycerin 5.0
Propylene glycol 3.0
Sodium monofluorophosphate 0.7
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 7

As a result of conducting a sterilization test of Streptococcus mutans, a caries-causing bacterium, according to Experimental Example 2 (c) using 5 mL of a dispersion obtained by diluting the toothpaste of Example 9 with water three times, 120 minutes later The number of viable bacteria was 4.9 × 10 ⁶ . Since the viable count after 120 minutes of dentifrice excluding only the capsule from the dentifrice composition of Example 9 was 37.7 × 10 ⁶ , the dentifrice of Example 9 has high bactericidal activity. Admitted.

[Example 10] Dentifrice hinokitiol-encapsulated calcium carbonate capsule ^* 1.0%
(Hinokitiol content 10% by mass with respect to the total capsule)
Silicic anhydride 18.0
Titanium oxide 0.5
Sodium carboxymethylcellulose 1.0
Carrageenan 0.2
Sodium lauryl sulfate 0.9
Sorbit 22.0
Glycerin 3.0
Propylene glycol 3.0
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 8

As a result of performing a sterilization test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 10 three times with water, 120 minutes later The viable cell count was 8.1 × 10 ⁶ . Since the viable count after 120 minutes of dentifrice excluding only capsules from the dentifrice composition of Example 10 was 40.2 × 10 ⁶ , the dentifrice of Example 10 has high bactericidal activity. Admitted.

[Example 11] Dentifrice bisabolol-encapsulated calcium carbonate capsule ^* 1.0%
(Bisabolol content 12% by mass based on total capsule)
Silicic anhydride 15.0
Titanium oxide 0.5
Sodium carboxymethylcellulose 1.0
Carrageenan 0.2
Sodium lauryl sulfate 0.9
Sorbit 22.0
Glycerin 8.0
Propylene glycol 3.0
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 9

As a result of conducting a sterilization test of Streptococcus mutans, which is a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 11 three times with water, 120 minutes later The number of viable bacteria was 7.9 × 10 ⁶ . Since the viable count after 120 minutes of dentifrice excluding only the capsule from the dentifrice composition of Example 11 was 38.6 × 10 ⁶ , the dentifrice of Example 11 has high bactericidal activity. Admitted.

[Example 12] Dentifrice triclosan and isopropylmethylphenol-encapsulated calcium carbonate capsule ^* 2.0%
(Triclosan content 10% by mass with respect to the total capsule,
Isopropyl methylphenol content 5% by mass with respect to the total capsule)
Aluminum hydroxide 35.0
Silica anhydride 2.0
Sodium alginate 0.6
Xanthan gum 0.4
Sodium lauryl sulfate 1.0
Sorbit 20.0
Propylene glycol 3.0
Sodium monofluorophosphate 0.7
Methylparaben 0.05
Saccharin sodium 0.15
Perfume 1.0
Water balance
100.0 mass% in total
*: Obtained in Experimental Example 7

As a result of conducting a sterilization test of Streptococcus mutans, a caries-causing bacterium, according to Experimental Example 2 (c) using 10 mL of a dispersion obtained by diluting the toothpaste of Example 12 with water three times, 120 minutes later The number of viable bacteria was 2.4 × 10 ⁶ . Since the viable count after 120 minutes of dentifrice excluding only capsules from the dentifrice composition of Example 12 was 39.4 × 10 ⁶ , the dentifrice of Example 12 has high bactericidal activity. Admitted.

  The oral composition of the present invention is an effective oral composition for preventing or ameliorating oral troubles such as caries, periodontal disease, bad breath, and pigmentation on the tooth surface. It can be prepared and used in liquids, coating agents, dental floss, tablets, chewing gum, gummi, candy, troches and the like.

It is the photograph which embedded the calcium carbonate capsule obtained in Experimental Example 1 in resin, and observed the sliced surface with the transmission electron microscope. It is the photograph which embedded the other calcium carbonate capsule obtained in Experimental Example 1 in resin, and observed the sliced surface with the transmission electron microscope. In Experimental example 1, it is a graph which shows the evaluation result (influence on the pH fall using a calcium carbonate capsule) of acid neutralization ability. It is a graph which shows the release | release behavior of the encapsulated triclosan by the acid (oral demineralization model liquid) addition of the triclosan encapsulated calcium carbonate capsule obtained in Experimental Example 2.

Claims (5)

An oral composition comprising a calcium carbonate capsule in which an active ingredient for oral cavity is encapsulated in a film made only of calcium carbonate . The oral composition according to claim 1 , wherein the oral active ingredient contained in the film is a bactericidal or antibacterial substance. The composition for oral cavity according to claim 2 , wherein the sterilizing or antibacterial substance is nonionic or cationic. The oral composition according to claim 3, wherein the nonionic bactericidal or antibacterial substance is triclosan, isopropylmethylphenol, hinokitiol or bisabolol. The oral composition according to claim 3, wherein the cationic bactericidal or antibacterial substance is chlorhexidine, chlorhexidine salt, benzethonium chloride, benzalkonium chloride, cetylpyridinium chloride or decalinium chloride.