JP5625647B2 - Dentifrice composition - Google Patents

Description

  The present invention relates to a technique for effectively blending into a dentifrice composition without impairing the bactericidal effect of the cationic bactericidal agent. More specifically, the high bactericidal effect derived from the cationic bactericidal agent is exhibited, and the moldability of the preparation is improved. The present invention relates to a dentifrice composition having a good cleaning feeling during brushing and good use feeling.

  Cationic fungicides are known to have a positive effect on ecological tissues including oral bacteria due to their cationic charge, and have an excellent bactericidal effect, preventing caries and periodontal disease It is used as an active ingredient in many oral care products. However, since it is cationic, it has a high effect on unintended objects, and when formulated in a dentifrice composition, binding and adsorption occur due to electrostatic interaction with other dentifrice components, resulting in a decrease in work efficiency. It was happening. In addition, many of the cationic fungicides have a unique bitterness, and when blended in a dentifrice composition, the bitterness tends to be strong and the feeling of use tends to be poor.

  In response to these problems, compositions designed with dentifrice ingredients that do not exhibit anionic properties have been proposed. For example, since anhydrous silicic acid blended with an abrasive or the like has an anionic surface, a composition using calcium phosphate or calcium carbonate as an abrasive has been proposed in order to suppress adsorption of a cationic disinfectant. Further, for example, a composition stably blended by using a polyoxyethylene / polyoxypropylene block polymer together (see Patent Document 1), a composition ensuring moldability by using a cationic polymer together (see Patent Document 2), A composition (see Patent Document 3) that ensures good moldability by including surface-treated crystalline cellulose is known.

  However, silicic acid anhydride is used as a thickener by blending it in the form of fine particles in addition to the purpose of being used as an abrasive, and strengthens the caking state formed from abrasive particles and a water-soluble polymer substance. Therefore, it also has a function of enhancing the feeling of cleaning during toothbrushing and giving a good feeling of use (see Patent Document 4). From this, a composition that does not contain anhydrous silicic acid does not give a good cleaning feeling, but when anhydrous silicic acid is added to obtain a feeling of cleaning, there is a problem that the effect of the cationic sterilizing component cannot be obtained. For this reason, it has been difficult to achieve both a good cleaning feeling and a high bactericidal effect with a cationic fungicide-containing composition.

  As for bitterness, for example, masking action by stevia sweeteners (see Patent Document 5), resinoids extracted from resins and the like (see Patent Document 6), capsaicin which is a spicy component (see Patent Document 7), etc. Although the effect is known, the dentifrice composition does not necessarily satisfy both the bitterness suppression and the bactericidal effect.

  In addition, many commercially available dentifrice compositions contain anionic surfactants such as sodium lauryl sulfate to ensure foaming properties, but they reduce the action of cationic fungicides and thus anionic surfactants. A composition that does not contain an agent has been proposed. For example, a composition in which foaming is ensured with a polyoxyethylene / polyoxypropylene block polymer (see Patent Document 1), a composition in which foamability is secured with a glyceryl etherified polyhydric alcohol (see Patent Document 8), nonionic foaming Composition with excellent foamability obtained by blending an agent and cyclodextrin (see Patent Document 9), a composition using a polyoxyethylene alkyl ether having 20 or more carbon atoms of an alkyl group and 20 or more moles of ethylene oxide added A thing (refer patent document 10) etc. are proposed and the method of using together with a cationic disinfectant is known. However, these techniques are not always satisfactory in terms of moldability and feeling of cleaning, and techniques that sufficiently satisfy the moldability and feeling of cleaning of the dentifrice are required while having an excellent sterilizing effect.

  Regarding the oral composition containing a cationic bactericidal agent, in addition to the above-mentioned patent document, for example, an oral composition excellent in plaque removal effect and bactericidal effect (see Patent Document 11), tooth surface retention of the cationic bactericidal agent Oral composition (see Patent Document 12) with improved performance, dentifrice composition (see Patent Document 13) containing cetylpyridinium chloride and hydroxyethyl cellulose, amphoteric surfactant, and a positive active ingredient that is inactive to cationic active ingredients An oral composition containing ion-compatible inorganic particles (see Patent Document 14) has been proposed. Patent Document 13 discloses a dentifrice composition using calcium hydrogen phosphate dihydrate as an abrasive and blended with palm oil fatty acid amidopropyl betaine. However, from these conventional techniques, it is difficult to predict that the cationic bactericidal agent has an excellent bactericidal effect, a feeling of cleaning, and a moldability by appropriately using a thickened silicic acid anhydride together with a specific abrasive.

  In the dentifrice composition, the liquid separation stability related to the stability of the preparation over time and the ease of extrusion leading to the ease of collection from the toothpaste container to the toothbrush are also important factors. Cellulose derivatives such as hydroxyethyl cellulose and polyethylene glycol are well-known substances as ingredients of dentifrice compositions, and are used as nonionic binders. About the combination with a cationic disinfectant, for example, a liquid oral composition (see Patent Document 15) having a viscosity and thixotropy suitable for use on an interdental brush is proposed. 13.

JP-A-4-202121 Japanese Patent Laid-Open No. 06-239725 International Publication No. 2008/059881 Pamphlet JP 2010-111648 A JP 08-268855 A JP 2001-072562 A JP 2004-115382 A JP 05-229923 A Japanese Patent Laid-Open No. 08-259428 JP-A-10-175832 JP 2001-278758 A JP 2002-179541 A International Publication No. 2007/066497 Pamphlet Special table 2009-501225 JP 2002-234826 A

  The present invention was made in order to solve the above-mentioned problems, and has a high bactericidal effect derived from a cationic bactericidal agent, and has good general characteristics such as moldability, feeling of cleaning and feeling of use of a dentifrice formulation. An object is to provide a dentifrice composition containing an agent.

  As a result of intensive studies to achieve the above object, the present inventor blended (A) a cationic fungicide, (B) calcium carbonate or calcium phosphate as an abrasive, and (C) thickened anhydrous silicic acid, When the content of the component C) is 0.5-2% by mass and the mass ratio of the component (C) / component (A) is 10-50, an excellent bactericidal effect derived from the cationic fungicide is exhibited. In addition, the present inventors have found that the formulation is excellent in moldability and cleanliness and has a good feeling in use, and thus the present invention has been completed.

  More specifically, cationic bactericides have a problem that the bactericidal effect is not sufficiently exhibited in the dentifrice composition. Conventionally, as a means for improving the bactericidal action of the bactericidal agent, the solubilized state with a surfactant has been studied. It has been. On the other hand, as a result of studying the elution property of the bactericidal component into the solution in the dispersion of the dentifrice preparation containing the solid component, the present inventor has found that the dentifrice composition containing the cationic bactericidal agent has an anhydrous silica composition. A significant decrease in the dissolution rate of the cationic fungicide was observed due to the presence of the acid, and it was found that reducing the amount of silicic anhydride was effective in increasing the dissolution concentration. Furthermore, in this case, if the blending amount of silicic anhydride is reduced, it is difficult to satisfactorily obtain moldability and cleanliness. However, 0.5 to 2% by mass of thickening silicic anhydride as the silicic anhydride is appropriate for the cationic fungicide. In combination with calcium carbonate or calcium phosphate as a polishing agent, it is surprisingly effective for cationic fungicides, such as caries-causing bacteria such as Streptococcus mutans. It has been found that it has an excellent bactericidal effect, a moldability of the preparation and a feeling of cleaning, and a good feeling in use. Furthermore, it discovered that the said bactericidal effect improved more by mix | blending a specific amphoteric surfactant.

According to the present invention, the bactericidal effect of the cationic bactericidal agent is effectively exhibited in the dentifrice composition, the bactericidal effect is excellent on oral bacteria, and the toothbrush is obtained by appropriately blending the thickening anhydrous silicic acid. The moldability and the feeling of cleaning, which are general characteristics of the agent, are obtained satisfactorily. In addition, cationic bactericides often have a strong bitter taste due to their high activity on the tongue surface, but according to the present invention, the bitter taste in toothbrushing brushing is suppressed, and the cleaning feeling felt on the tooth surface is good. It becomes.
Furthermore, by adding a specific amphoteric surfactant, the bactericidal effect can be further improved while suppressing the expression of bitterness.

  In addition, when the thickening silicic acid anhydride is limited to the above blending amount, the stability of liquid separation over time may not be sufficient, and when an abrasive that elutes calcium ions is used, the viscosity over time However, it may not be sufficient to extrude, but by adding a specific nonionic binder to the composition of the present invention, these can also be improved and stable liquid separation over time And good extrudability can be secured.

Accordingly, the present invention provides the following dentifrice composition.
Claim 1:
(A) a cationic disinfectant, (B) containing calcium carbonate or calcium phosphate as an abrasive, and (C) thickening anhydrous silicic acid, (A) the content of the component is 0.001 to 0.5 mass%, The content of (B) component is 15 to 60% by mass, the content of (C) component is 0.5 to 2% by mass, and the mass ratio of (C) component / (A) component is 10 to 37.5. A dentifrice composition characterized by the above.
Claim 2:
(A) a cationic disinfectant, (B) containing calcium carbonate or calcium phosphate as an abrasive, and (C) thickening anhydrous silicic acid, and (A) component content is 0.001 to 0.5 mass%, The content of the component (B) is 15 to 60% by mass, the content of the component (C) is 0.5 to 2% by mass, and the mass ratio of the component (C) / (A) is 10 to 50. A dentifrice composition characterized by not containing an anionic surfactant and a silica type abrasive | polishing agent.
Claim 3 :
(C) The dentifrice composition according to claim 1 or 2, wherein the thickening silicic acid anhydride has a liquid absorption of 2.0 to 3.0 ml / g.
Claim 4 :
Further, (D) 0.5 to 3% by mass of fatty acid amidopropyl betaine or 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine having a fatty acid carbon chain length of 12 to 14 is contained. 1 , 2 or 3 dentifrice composition.
Claim 5 :
Additionally, (E) hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, any average molecular weight of claims 1 to 4 containing 0.5 to 3 wt% of one or more selected from polyethylene glycols of 2,000 to 20,000 The dentifrice composition of Claim 1 .

  According to the present invention, an excellent bactericidal effect derived from a cationic bactericidal agent is exhibited, the moldability of the preparation is good, a sufficient cleaning feeling is obtained, and the bitterness is low and the feeling of use is good. Can provide. Furthermore, the liquid separation stability over time and the ease of extrusion from the container can be secured well. The composition of the present invention is useful for preventing or treating caries or periodontal disease.

  Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention is prepared as a dentifrice such as a toothpaste, a liquid dentifrice, and a moisturized dentifrice, particularly a paste or gel toothpaste. (A) Cationic disinfectant, (B) Calcium carbonate or calcium phosphate as an abrasive, and (C) 0.5 to 2% by mass of thickened anhydrous silicic acid, (C) component / (A) component mass The ratio is 10-50.

The cationic fungicide of component (A) may be any that can be applied to a dentifrice composition, such as alkyl pyridinium salts, benzyl long chain alkyl short chain dialkyl ammonium salts and derivatives thereof, long chain alkyl short chain trialkyl ammonium salts, and the like. Is mentioned. Examples of such a cationic bactericidal agent include cetylpyridinium chloride, benzalkonium chloride, and benzethonium chloride. Among them, cetylpyridinium chloride is more preferable because of its excellent bactericidal activity.
These cationic fungicides can be used alone or in combination of two or more. Particularly, the combined use of cetylpyridinium chloride, benzalkonium chloride and benzethonium chloride is preferable because of its high bactericidal effect.
In addition, as these cationic fungicides, commercially available products available from Wako Pure Chemical Industries, Ltd., Nippon Oil & Fats Co., Ltd., Lonza Japan Co., Ltd. and the like can be used.

The compounding amount of the cationic bactericidal agent is 0.001 to 0.5% (mass%, the same applies hereinafter) of the entire composition (hereinafter, unless otherwise specified, all compounding amounts are based on the entire composition). In particular, 0.02 to 0.1% is preferable. If it is less than 0.001%, a sufficient bactericidal effect may not be obtained. If it exceeds 0.5%, the bitterness peculiar to cations may be strong and the feeling of use may be deteriorated.
When cetylpyridinium chloride is used in combination with benzalkonium chloride and benzethonium chloride, the blending amount of cetylpyridinium chloride is 0.01 to 0.05%, and the blending amounts of benzalkonium chloride and benzethonium chloride are each set to 0. The content may be 01 to 0.02%.

Component (B), calcium carbonate and calcium phosphate, is an abrasive and can be used as long as it can be applied to a dentifrice composition. In addition, since calcium carbonate and calcium phosphate may solidify when used together, it is desirable not to use them together. Good moldability and a feeling of cleaning can be obtained by appropriately using calcium carbonate or calcium phosphate together with the component (C).
Examples of calcium carbonate include light calcium carbonate and heavy calcium carbonate, both of which can be used. An average particle diameter of about 3 to 15 μm is preferably used.
Examples of calcium phosphate include dibasic calcium phosphate dihydrate, dibasic calcium phosphate anhydrate, calcium pyrophosphate, insoluble calcium metaphosphate, and tribasic calcium phosphate. An average particle diameter of about 10 to 20 μm is preferably used.

  In addition, the said average particle diameter is a median diameter (d50), and a median diameter is the value measured using the particle size distribution measuring apparatus (The Nikkiso Co., Ltd. make, Microtrac particle size distribution meter, dispersion medium; water). .

  The blending amount of the component (B) abrasive is preferably 15 to 60%, particularly preferably 20 to 50%. If it is less than 15%, the cleaning power and the feeling of cleaning may not be sufficiently obtained. When exceeding, the viscosity of a composition may become high and the extrusion ease from a container may worsen.

  The thickening anhydrous silicic acid of the component (C) may be any thickening anhydrous silicic acid that can be applied to the dentifrice composition. For example, ignitable silica, precipitated silica and the like obtained by a known production method. Can be used. In general, silicic acid anhydride is synthesized by neutralization reaction of sodium silicate and mineral acid, but in the wet method of preparing precipitated silica, the reaction conditions are appropriately adjusted such as neutral pH range, low temperature, high salt concentration, etc. Under the conditions, after the aggregation is performed while suppressing the growth of the primary particles, the primary particles are grown in the aggregated state, thereby increasing the specific surface area, the pore volume, and the oil absorption amount. Silica can be obtained.

Thickening anhydrous silicic acid having a liquid absorption of 2.0 to 3.0 ml / g, particularly 2.1 to 2.7 ml / g, is suitable for achieving the effects of the present invention. If the amount of liquid absorption is less than the above value, the moldability on the toothbrush is deteriorated and the feeling of cleaning may be lowered, and if it exceeds the above value, sufficient sterilizing power may not be obtained.
In addition, the liquid absorption amount measuring method is as follows.
A sample (1.0 g) was weighed on a clean glass plate, and the sample was mixed with a stainless spatula while adding 42.5% glycerin dropwise little by little using a microburette. The end point was when the sample became a lump and it came off cleanly from the glass plate with a spatula, and the amount of liquid required (ml) was taken as the liquid absorption amount.

Further, thickening silicic anhydride, specific surface area by BET method 250~450m ² / g, in particular those of 350~420m ² / g preferred. 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).

  Examples of the thickening silicic acid anhydride include Tokuyama Soda Co., Ltd. Tokusil, INEOS Co., Ltd. SORBOSIL TC15, Rhodia Co., Ltd. TIXOSIL 43, Huber Co., Ltd. Zeodent 113, DSL Japan Co., Ltd. Carplex. # 67Q and the like.

  The blending amount of the thickening silicic acid anhydride is 0.5 to 2%, particularly preferably 0.8 to 1.6%. If it is less than 0.5%, satisfactory shape retention cannot be obtained, the mold will be deformed on the toothbrush, and the feeling of cleaning during brushing will be reduced.

  The mass ratio of (C) thickening silicic anhydride / (A) cationic fungicide is 10-50, preferably 20-40. If the blending ratio is less than 10, sufficient moldability cannot be obtained or the bitterness of the cationic bactericidal agent becomes strong. Can not be compatible.

  In this invention, it is preferable to mix | blend amphoteric surfactant as (D) component further, and a bactericidal effect improves more by using amphoteric surfactant together. As the amphoteric surfactant, fatty acid amidopropyl betaine or 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine is suitable.

As the fatty acid amidopropyl betaine, fatty acid having a carbon chain length of 12 to 14 is preferable, and examples thereof include lauric acid amidopropyl betaine and coconut oil fatty acid amidopropyl betaine.
Further, as 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium, N-lauroyl-N-carboxymethyl- Examples include sodium N-hydroxyethylethylenediamine.
Among these amphoteric surfactants, fatty acid amidopropyl betaine, particularly coconut oil fatty acid amidopropyl betaine, is preferable from the point of no bitterness, and the bactericidal effect can be more effectively improved while suppressing the expression of bitterness.

As lauric acid amidopropyl betaine, for example, Amphithol 20AB (30% aqueous solution, Kao Corporation), Softazolin LPB (30% aqueous solution, Kawaken Fine Chemical Co., Ltd.), etc. 55AB (30% aqueous solution, Kao Co., Ltd.), TEGO BETAIN CK (30% aqueous solution, Goldschmidt), NIKKOL AM-3130N (30% aqueous solution, Nikko Chemicals Co., Ltd.) are used.
Examples of N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium include enadicol C-40H (40% aqueous solution (solid content), Lion Co., Ltd.), Amphital 20Y-B (Kao Co., Ltd.) )), Softazoline CH (30% aqueous solution, Kawaken Fine Chemical Co., Ltd.), softazoline CL-R (30% aqueous solution, Kawaken Fine Chemical Co., Ltd.) and the like are N-lauroyl-N-carboxymethyl-N-hydroxyethyl. As ethylenediamine sodium, for example, softazolin LHL (27% aqueous solution, Kawaken Fine Chemicals Co., Ltd.) is used, but in any case, it is not limited to the above.

  When these amphoteric surfactants are blended, the blending amount is preferably 0.5 to 3%, particularly 1.0 to 2.0%. If it is less than 0.5%, the effect of improving the bactericidal effect may not be observed, and if it exceeds 3%, the bitterness may become strong.

  In the present invention, it is preferable to further blend a nonionic binder as the component (E). (E) By mix | blending a component, the liquid separation stability of a formulation and the ease of extrusion from a storage container can be improved. As a nonionic binder, cellulose derivatives such as hydroxyethylcellulose, hydroxypropylmethylcellulose, methylcellulose, polyethylene glycol and the like can be used.

Hydroxyethylcellulose, hydroxypropylmethylcellulose and methylcellulose are all nonionic cellulose derivatives.
As hydroxyethyl cellulose, those having a viscosity in a 1% aqueous solution of 50 to 10,000 mPa · s (B-type viscometer, rotor No. 4, 30 rpm, 20 ° C., measured value after 2 minutes) can be preferably used. In particular, those having a moldability of 500 mPa · s or more are preferred, and those having a solubility of 8,000 mPa · s or less are preferred.
Specific examples of hydroxyethyl cellulose include those sold by Daicel Chemical Industries, Ltd. under product names such as SE600, SE850, and SE900.

As the hydroxypropyl methylcellulose, those having a viscosity of 100 to 12,000 mPa · s (20 ° C., 2% aqueous solution, measured value by a rotational viscometer method of the Japanese Pharmacopoeia) can be used. In particular, those having a moldability of 1,000 mPa · s or more are preferred, and those having a solubility of 10,000 mPa · s or less are preferred.
As such hydroxypropyl methylcellulose, those sold by Shin-Etsu Chemical Co., Ltd. under the product names such as METOLOSE 60SH 4000, METOLOSE 60SH 10000, and METOLOSE 65SH 4000 can be used.

As the methyl cellulose, those having a viscosity of 100 to 10,000 mPa · s (20 ° C., 2% aqueous solution, measured value by rotational viscosity method of Japanese Pharmacopoeia) can be used. In particular, those having a moldability of 1,000 mPa · s or more are preferred, and those having a solubility of 5,000 mPa · s or less are preferred.
As such methylcellulose, those sold by Shin-Etsu Chemical Co., Ltd. under the product names such as METOLOSE SM 1500 and METOLOSE SM 4000 can be used.

The polyethylene glycol preferably has an average molecular weight of 2,000 to 20,000, particularly 3,000 to 10,000 in view of solubility and effect. In the present invention, the average molecular weight of polyethylene glycol is a value determined by the measurement method listed in Gabara (a quasi-drug raw material standard). Specifically, a predetermined amount of polyethylene glycol is anhydrous in a pyridine solution. It was reacted with phthalic acid when heated to obtain a phthalate ester, titration of polyethylene glycol phthalate and excess phthalic acid with a sodium hydroxide solution using a phenolphthalein pyridine solution as an indicator, and the average molecular weight was determined from the consumption of alkali.
Examples of polyethylene glycol having an average molecular weight of 2,000 to 20,000 include polyethylene glycol 2000, polyethylene glycol 4000, polyethylene glycol 6000, and polyethylene glycol 20000. These polyethylene glycols are obtained from, for example, Sanyo Chemical Industries, Ltd. Commercial products that can be used can be used.
In addition, the average molecular weight of the commercially available polyethylene glycol indicates the average molecular weight described in the Quasi-drug Raw Material Standard 2006, polyethylene glycol 2000 (average molecular weight 1,850 to 2,150), polyethylene glycol 4000 (average molecular weight 2,600 to 3,800), polyethylene glycol 6000 (average molecular weight 7,480-10,200), polyethylene glycol 20000 (average molecular weight 15,500-25,000), and the like. In the present invention, the average molecular weight is 2,000- What is 20,000 can be used conveniently. A commercially available product of polyethylene glycol may have a # between the polyethylene glycol and the numerical value, such as polyethylene glycol # 4000, depending on the product.

  As the component (E), it is preferable to use one kind selected from hydroxyethylcellulose, hydroxypropylmethylcellulose, methylcellulose, and polyethylene glycol having an average molecular weight of 2,000 to 20,000 alone or in combination of two or more kinds. .

  (E) When mix | blending a component, the compounding quantity is 0.5 to 3%, Especially 1.0 to 2.5% is suitable. If it is less than 0.5%, the liquid separation stability may be inferior. If it exceeds 3%, the viscosity of the preparation increases and the extrudability may deteriorate.

  The dentifrice composition of the present invention, in addition to the above-described components, is usually an optional component that is usually added to the dentifrice composition, for example, abrasives other than the component (B), surfactants, and thickeners. , Binders, medicinal components other than the component (A), sweeteners, colorants, preservatives, pH adjusters, fragrances, and other appropriate components can be blended as necessary within the range not impairing the effects of the present invention. .

Examples of the abrasive include aluminum hydroxide, alumina, titanium dioxide, polymethyl methacrylate, insoluble calcium metaphosphate, magnesium carbonate, tertiary magnesium phosphate, zeolite hydroxyapatite, fluoroapatite, and calcium deficient apatite. In addition, it is preferable not to mix | blend the silica type abrasive | polishing agent which may produce an interaction with a cationic disinfectant.
The blending amount of these abrasives is preferably 0 to 20%, particularly 0 to 5% of the whole composition other than the component (B) calcium carbonate or calcium phosphate.

As the surfactant, in addition to the amphoteric surfactant of component (D), other surfactants may be blended. Nonionic surface activity such as polyoxyethylene alkyl ether, alkyl glycoside, sucrose fatty acid ester, alkylol amide, polyoxyethylene sorbitan monostearate, polyoxyethylene polyoxypropylene glycol, fatty acid polyglyceryl, polyoxyethylene hydrogenated castor oil Agents. In addition, anionic surfactants such as alkyl sulfates such as sodium lauryl sulfate, polyoxyethylene alkyl sulfates, N-lauroyl taurine salts, lauroyl sarcosine salts, α-olefin sulfonates, and the like are added to cationic sterilizers. Since it may interact with the agent and impair the bactericidal effect, it is preferably not blended.
The blending amount of these surfactants is preferably 0 to 10%, particularly 0 to 3%.

  Thickeners include sorbitol, glycerin, ethylene glycol, propylene glycol, 1,3-butylene glycol, sugar glycols such as polyethylene glycols other than the above molecular weight, polypropylene glycol, xylitol, maltitol, erythritol, and polyhydric alcohols. May be. The blending amount of the thickener is usually 10 to 50%, particularly 15 to 40%.

  As the binder, other than the cellulose derivative of component (E) and polyethylene glycol, for example, sodium polyacrylate, carrageenan, sodium carboxymethylcellulose, sodium alginate, xanthan gum and the like can be blended. The blending amount of these binders is preferably 0 to 1.5%.

  Medicinal ingredients (active ingredients) include those other than cationic fungicides, such as fluorides such as sodium fluoride, potassium fluoride, stannous fluoride, strontium fluoride, sodium monofluorophosphate, chlorhexidine, triclosan, Bactericidal substances such as isopropylmethylphenol, sorbate, hinokitiol, azulene sulfonate, glucanase enzymes such as dextranase and mutanase, proteases such as protease and lysozyme, tranexamic acid, epsilon aminocaproic acid, allantoin, glycyrrhizic acid, Anti-inflammatory substances such as glycyrrhetinic acid, inorganic salts such as sodium chloride, potassium nitrate, aluminum lactate, zinc chloride, zinc citrate, strontium chloride, sodium tripolyphosphate, sodium pyrophosphate, zeolite Chelating compounds such as copper chlorophyllin sodium, chlorophyll, glycerophosphate, various vitamins such as ascorbic acid, tocopherol acetate, pyridoxine, natural extracts such as toki soft extract, duckweed extract, chamomile, clove, rosemary, ogon, safflower, etc. Is mentioned. The compounding quantity of these active ingredients can be made into an effective quantity in the range which does not prevent the effect of this invention.

  As the sweetener, saccharin sodium, stevioside, neohesperidyl dihydrochalcone, perilartin, p-methoxycinnamic aldehyde, aspartame, sucralose, acesulfame K and the like can be blended.

As coloring agents, Red No. 2, Red No. 3, Red No. 225, Red No. 226, Yellow No. 4, Yellow No. 5, Yellow No. 205, Blue No. 1, Blue No. 2, Blue No. 201, Blue No. 204, Green No. 3, mica titanium, titanium oxide and the like.
Examples of the preservative include paraoxybenzoic acid ester and sodium benzoate.

  Examples of the pH adjuster include citric acid, malic acid, lactic acid, tartaric acid, acetic acid, phosphoric acid, glycerophosphoric acid, various salts thereof, sodium hydroxide, and the like, which are appropriately selected according to a desired pH. Can be used. It is preferable that the dentifrice composition of this invention is adjusted to pH 6-10, especially 7-9.

Perfumes are peppermint oil, spearmint oil, anise oil, eucalyptus oil, wintergreen oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamom oil, coriander oil, mandarin oil, lime Oil, lavender oil, rosemary oil, laurel oil, camomil oil, caraway oil, marjoram oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete, absolute peppermint Natural fragrances such as absolute rose and orange flower, and fragrances processed by these natural fragrances (total reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder fragrance, etc.), and , Menthol, carvone, anethole, cineol, salicylic acid , Cinnamic aldehyde, eugenol, 3-1-menthoxypropane-1,2-diol, thymol, linalool, linalyl acetate, limonene, menthone, menthyl acetate, N-substituted-paramentane-3-carboxamide, pinene, octyl Acetaldehyde, citral, pregon, calbeetoacetate, anisaldehyde, ethyl acetate, ethyl butyrate, allylcyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, hexanal, ethyl alcohol, propyl Alcohol, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, methyl lactate Toothpaste composition such as strawberry flavor, apple flavor, banana flavor, pineapple flavor, grape flavor, mango flavor, butter flavor, milk flavor, fruit mix flavor, tropical fruit flavor, etc. The well-known fragrance | flavor raw material used for a thing can be used, It is not limited to the fragrance | flavor of an Example.
Moreover, although a compounding quantity is not specifically limited, It is preferable to use said fragrance | flavor raw material 0.000001 to 1% in a formulation composition. Moreover, as a fragrance | flavor for fragrance | flavor using the said fragrance | flavor raw material, it is preferable to use 0.1 to 2.0% in a formulation composition.

The material in particular of a container is not restrict | limited, Usually, the container used for a dentifrice composition can be used. Specifically, plastic containers such as polyethylene, polypropylene, polyethylene terephthalate, and nylon can be used. For example, a laminate tube having a diameter of 26 mm and a mouth inner diameter of 8 to 12 mm (LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / AL10 / EMAA30 / LDPE20 / LLDPE30 from the outermost layer) can be preferably used. The above abbreviations are as follows, and the number at the end indicates the thickness (μm).
LDPE: Low density polyethylene White LDPE: White low density polyethylene LLDPE: Linear low density polyethylene AL: Aluminum PET: Polyethylene terephthalate EMAA: Copolymer resin of ethylene / methacrylic acid

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In the following examples, the blending amount is mass%. Moreover, about the component whose form is aqueous solution, all showed the compounding quantity of pure content also including the table | surface. The average particle diameter, liquid absorption amount, BET specific surface area and the like are measured values by the above-described methods.

Examples and comparative examples
Toothpaste compositions (toothpaste) having the compositions shown in Tables 1 to 4 were prepared by the following method and filled into a laminate tube having a diameter of 26 mm and a mouth inner diameter of 8 mm. About the obtained dentifrice composition, the following method evaluated bactericidal power, the moldability on a toothbrush, a bitter taste, a feeling of cleaning, the liquid separation stability of a formulation, and the easiness of extrusion over time. The results are shown in Tables 1-4.

Preparation of test dentifrice composition:
After dissolving water-soluble substances such as sodium saccharin, sodium fluoride, and polyethylene glycol of component (E) in purified water, and adding thickened anhydrous silicic acid and sorbit of component (C), separately added to polyethylene glycol # 400 ( A solution in which the cationic fungicide of component A), hydroxyethylcellulose, hydroxypropylmethylcellulose, methylcellulose, binder, and the like of component (E) were dispersed was added and stirred. Thereafter, a flavoring agent, a polishing agent such as calcium carbonate as the component (B), and a surfactant such as fatty acid amidopropyl betaine as the component (D) are sequentially added, and further stirred under reduced pressure (5.3 kPa) to obtain a dentifrice composition. Obtained. A unimixer (FM-SR-25, manufactured by POWEX CORPORATION) was used for the production.

The detail of each component used for preparation of these dentifrice compositions is as follows.
The raw materials used include cetylpyridinium chloride (Wako Pure Chemical Industries, Ltd.), benzalkonium chloride (Nippon Yushi Co., Ltd.), benzethonium chloride (Lonza Japan Co., Ltd.), heavy calcium carbonate (average particle size 5 μm, Calfine Co.), dicalcium phosphate dihydrate (average particle size 20 μm, Tosoh Akzo Co., Ltd.), thickened anhydrous silicic acid (precipitate silica by wet method, liquid absorption 2.5 ml / g) , Specific surface area value by BET method 405 m ² / g, trade name Carplex # 67Q, DSL Japan Co., Ltd., hydroxyethyl cellulose (SE900, 1% aqueous solution 5,000 mPa · s, manufactured by Daicel Chemical Industries, Ltd.), hydroxypropyl Methylcellulose (METOLOSE 60SH 4000, 2% aqueous solution 4,000 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd.), Methylcellulose (METOLOSE SM 4000, 2% aqueous solution 4,000 mPa · s, manufactured by Shin-Etsu Chemical Co., Ltd.), polyethylene glycol 4000 (average molecular weight 3,390, PEG-4000S, Sanyo Chemical Industries, Ltd.), polyethylene glycol 20000 ( An average molecular weight of 19,800, PEG-20000, Sanyo Chemical Industries, Ltd., and coconut oil fatty acid amidopropyl betaine solution (30% aqueous solution product, TEGO BETAIN CK, manufactured by Goldschmidt) were used. Polyoxyethylene (60) hydrogenated castor oil, sorbite (70% aqueous solution), xanthan gum, polyethylene glycol # 400, sodium polyacrylate, sodium alginate, xanthan gum, sodium saccharin, sodium monofluorophosphate, water A material conforming to the external material standard 2006 was used.
As the fragrance, fragrance A to fragrance I shown in Table 5 were prepared and blended using the flavor compositions shown in Tables 6 to 11.

  The container used in the following evaluation was a laminated tube (Dai Nippon Printing Co., Ltd.) having a diameter of 26 mm and a mouth inner diameter of 8 mm, and the layer structure was LDPE55 / PET12 / LDPE20 / white LDPE60 / EMAA20 / from the outermost layer. AL10 / EMAA30 / LDPE20 / LLDPE30, and thickness is 257 μm. The abbreviations are as described above, and the numerical values indicate the thickness (μm) of each layer.

(1) Evaluation method of bactericidal power Dentifrice composition is artificial saliva (final concentrations are 50 mM KCl, 1 mM KH ₂ PO ₄ , 1 mM CaCl ₂ , 0.1 mM MgCl _2), and the pH is adjusted to 7.0 with KOH. To 1 L with distilled water) to obtain a centrifugal supernatant (12,000 g × 10 minutes, 20 ° C.) diluted 4-fold. A TSB medium (Becton, manufactured by Dickinson company) culture solution was added to the supernatant, and 2 ml of each dentifrice dilution culture solution was prepared by doubling dilution to obtain a dentifrice dilution ratio of 100 to 6,400 times.
Separately, Streptococcus mutans (S. mutans 10449) bacterium was added to 4 mL of TSB medium culture solution and anaerobically cultured overnight at 37 ° C. (80 vol% nitrogen, 10 vol% carbon dioxide, 10 vol% hydrogen) to obtain a bacterial solution. 50 μL of this bacterial solution was added to each of the above-prepared toothpaste diluted cultures, and after anaerobic culture at 37 ° C. for 2 days, the presence or absence of bacterial growth was visually determined. The bactericidal power was shown as the maximum dilution rate at which no growth of bacteria was observed.

The sterilizing power was evaluated according to the following criteria, and it was determined that the sterilizing power was excellent when it was excellent.
(Evaluation criteria)
◎: Maximum dilution ratio is 3,200 times or more ○: Maximum dilution ratio is 1,600 times or more and less than 3,200 times △: Maximum dilution ratio is 400 times or more and less than 1,600 times ×: Maximum dilution ratio is less than 400 times

(2) Method for evaluating formability on toothbrush The shape change on the toothbrush when the dentifrice composition was filled in the laminate tube and 1.5 g was placed on the toothbrush was evaluated according to the following criteria.
(Evaluation criteria)
4 points: No deformation on the toothbrush is observed 3 points: A slight deformation on the toothbrush is observed, but there is no problem in use 2 points: The mold gradually loses its shape on the toothbrush 1 point: Immediately loses its shape on the toothbrush

The five evaluation results were averaged, and the formability on the toothbrush was determined in the following four stages. The samples with ◎ and 歯 were judged to be dentifrice compositions that ensure moldability on a toothbrush.
(Evaluation criteria)
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

(3) Evaluation method of feeling of use (no bitterness) Using 10 subjects, about 1 g of the dentifrice composition was placed on a commercial toothbrush and brushed for 3 minutes. Responses were obtained in three stages, “somewhat” and “some”. Of these answers, “No” was 3 points, “Somewhat” was 2 points, and “Are” was 1 point, and the usability was evaluated from the average score of 10 people according to the following criteria.
(Evaluation criteria)
◎: Average point 2.5 points or more and 3.0 points or less ○: Average point 2.0 points or more and less than 2.5 points △: Average point 1.5 points or more and less than 2.0 points ×: Less than 1.5 points

(4) Evaluation method of a feeling of cleaning A sensory test was conducted using 10 expert panelists. About 1g of dentifrice composition is put on a commercial product toothbrush and brushed for 3 minutes by the method of brushing normal teeth, and the feeling of cleaning of the tooth surface (actual feeling to remove dirt) is evaluated as follows for the feeling of cleaning felt during use. Evaluated according to. An average value of the evaluation results of 10 people was obtained, and those for which evaluations of ◎ and ○ were ensured based on the following criteria were judged to be a dentifrice composition with a good feeling of cleaning.
(Score)
4 points: feels a strong feeling of brushing 3 points: feels a feeling of brushing 2 points: feels a slight feeling of brushing 1 point: hardly feels a feeling of brushing

Evaluation results of 10 professional panelists were averaged and judged according to the following criteria (evaluation criteria)
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

(5) Evaluation of liquid separation stability of the preparation 50 g of the dentifrice composition was filled in the above laminate tube, each composition was stored at 50 ° C. for 1 month, and then the dentifrice composition was extruded 10 cm on the straw half paper, and the straw half paper was The length of the oozed liquid was measured, and the degree of liquid separation was evaluated in the following four stages. The liquid separation stability of the preparation tended to promote liquid separation depending on the temperature, and 50 ° C. was selected as a storage temperature that can be evaluated in a storage period of one month.
(Score)
4 points: No liquid separation is observed at all 3 points: When extruded, liquid separation is slightly observed at the mouth, but there is no problem in use 2 points: When extruded, 1 to 3 cm of liquid separation is observed at the mouth 1 point : When extruding, liquid separation is recognized over 3cm at the mouth

The average value of the three evaluation points was determined, and the degree of liquid separation was determined in the following four stages. The samples with も の and ○ were judged to be dentifrice compositions with excellent liquid separation stability when stored at 50 ° C.
(Evaluation criteria)
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

(6) Evaluation of easiness of extrusion over time After 50 g of the dentifrice composition was filled into the above laminate tube and each of the three compositions was stored at 50 ° C. for 1 month, the dentifrice composition was extruded onto a straw half paper with a fingertip and kneaded. The ease of extrusion of the dentifrice composition was evaluated in the following four stages.
(Score)
4 points: Kneading out at a length of 10 cm or more after extruding 3 points: Kneading out at a length of 5 cm or more and less than 10 cm after extruding 2 points: Kneading out at a length of 2 cm or more and less than 5 cm 1 Point: Extrude at a stretch and knead out with a length of less than 2 cm

The average value of the three evaluation points was determined, and the degree of ease of extrusion was determined in the following four stages. The samples with ◎ and ○ were judged to be dentifrice compositions having excellent extrudability of the formulation when stored at 50 ° C.
(Evaluation criteria)
◎: 3.5 points or more and 4.0 points or less ○: 3.0 points or more and less than 3.5 points △: 2.0 points or more and less than 3.0 points ×: Less than 2.0 points

＊：純分換算した値を示した（以下同様）。

*: Indicates a value converted into a pure content (the same applies hereinafter).

  From the results of Tables 1 to 4, the dentifrice composition of the present invention exhibits an excellent bactericidal effect on oral bacteria such as Streptococcus mutans bacteria, has good moldability on a toothbrush, and has less bitterness. , Found to have a good feeling of cleaning. Furthermore, the antibacterial effect is further improved by blending the amphoteric surfactant of the component (D), and the liquid separation stability over time can be achieved by blending the nonionic binder of the component (E). It was found that the property and the ease of extrusion from the container were improved.

  The following dentifrice composition was prepared in the same manner using the same raw materials as described above, and 50 g was filled in a laminate tube (manufactured by Dai Nippon Printing Co., Ltd.) having a diameter of 26 mm and a mouth inner diameter of 8 mm. All of the dentifrice compositions had high bactericidal power and were good in moldability on a toothbrush, little bitterness, and a feeling of cleaning.

[Prescription Example 1] Toothpaste composition (A) Cetylpyridinium chloride 0.05%
(B) Heavy calcium carbonate 45
(C) Thickening anhydrous silicic acid 2.0
(D) N-coconut oil fatty acid acyl-N-carboxymethyl-N-
Hydroxyethylethylenediamine sodium ^** 1.0
Polyoxyethylene (60) hydrogenated castor oil 1.0
Polyethylene glycol 400 3.0
Sorbit ^* 21
Saccharin sodium 0.2
Isopropyl methylphenol 0.05
Sodium alginate 0.5
Xanthan gum 0.7
Fragrance A 1.3
Water remaining
Total 100.0%
(C) / (A) = 40
**: N-coconut oil fatty acid acyl-N-carboxymethyl-N-hydroxyethylethylenediamine sodium was enenacol C-40H (Lion Co., Ltd.), and the value obtained by pure conversion was shown.

[Prescription Example 2] Toothpaste composition (A) Cetylpyridinium chloride 0.05%
(B) Heavy calcium carbonate 25
(C) Thickening anhydrous silicic acid 1.5
Aluminum hydroxide 20
(D) Amidopropyl betaine laurate ^*** 1.5
Polyethylene glycol 400 3.0
Sorbit ^* 21
Saccharin sodium 0.2
Sodium polyacrylate 0.3
Sodium alginate 0.6
Xanthan gum 0.3
Fragrance A 1.3
Water remaining
Total 100.0%
(C) / (A) = 30
***: Amitol 20AB (30% aqueous solution, Kao Co., Ltd.) was used as lauric acid amidopropyl betaine.

[Prescription Example 3] Toothpaste composition (A) Cetylpyridinium chloride 0.05%
(B) Heavy calcium carbonate 45
(C) Thickening anhydrous silicic acid 2.0
(D) Amidopropyl betaine laurate ^*** 1.0
Polyoxyethylene (100) hydrogenated castor oil 1.5
Polyethylene glycol 400 3.0
Sorbit ^* 14
Glycerin 10
Saccharin sodium 0.2
Sodium alginate 0.3
Xanthan gum 0.6
Fragrance A 1.3
Water remaining
Total 100.0%
(C) / (A) = 40

Claims (5)

(A) a cationic disinfectant, (B) containing calcium carbonate or calcium phosphate as an abrasive, and (C) thickening anhydrous silicic acid, (A) the content of the component is 0.001 to 0.5 mass%, The content of (B) component is 15 to 60% by mass, the content of (C) component is 0.5 to 2% by mass, and the mass ratio of (C) component / (A) component is 10 to 37.5. A dentifrice composition characterized by the above. (A) a cationic disinfectant, (B) containing calcium carbonate or calcium phosphate as an abrasive, and (C) thickening anhydrous silicic acid, and (A) component content is 0.001 to 0.5 mass%, The content of the component (B) is 15 to 60% by mass, the content of the component (C) is 0.5 to 2% by mass, and the mass ratio of the component (C) / (A) is 10 to 50. A dentifrice composition characterized by not containing an anionic surfactant and a silica type abrasive | polishing agent. (C) The dentifrice composition according to claim 1 or 2, wherein the thickening silicic acid anhydride has a liquid absorption of 2.0 to 3.0 ml / g. Further, (D) 0.5 to 3% by mass of fatty acid amidopropyl betaine or 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine having a fatty acid carbon chain length of 12 to 14 is contained. 1 , 2 or 3 dentifrice composition. Additionally, (E) hydroxyethyl cellulose, hydroxypropyl cellulose, methylcellulose, any average molecular weight of claims 1 to 4 containing 0.5 to 3 wt% of one or more selected from polyethylene glycols of 2,000 to 20,000 The dentifrice composition of Claim 1 .