JP2007008843A - Dentifrice composition and method for preventing discoloration of dentifrice composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice composition which has excellent anti-bacterial effects to intraoral bacteria, excellent effects for preventing dental caries and periodontal diseases, and good temporal color stability, and to provide a method for preventing the discoloration of the dentifrice composition by comprising compounding an antibacterial metal ion-carrying zeolite. <P>SOLUTION: This dentifrice composition is characterized by containing (a) the antibacterial metal ion-carrying zeolite and (b) polylysine or its salt, wherein the component (a) is compounded in an amount of 0.05 to 1.0 mass% based on the total amount of the composition, and the mass ratio of (b)/(a) is 1 to 5. In addition, one or more selected from isopropylmethylphenol, triclosan (2, 4, 4'-trichloro-2'-hydroxydiphenyl ether), benzalkonium chloride, and cetylpyridinium chloride as (c) a sterilizer are compounded with the dentifrice composition. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a dentifrice composition having excellent preventive effect against worm teeth and periodontal diseases and having good stability regarding discoloration, and a method for preventing discoloration of a dentifrice composition by blending zeolite loaded with antibacterial metal ions. .

  It is generally accepted that the primary cause of dental caries and periodontal disease is the accumulation of plaque. Streptococcus mutans, a resident bacteria in the oral cavity, produces water-insoluble glucan by the action of glucosyltransferase using sucrose as a substrate, and firmly adheres to the tooth surface to form plaque. Caries are a phenomenon in which teeth are decalcified by an organic acid such as lactic acid produced by the decomposition of sugar in the above process. In addition, when plaque accumulates and an anaerobic environment is prepared and periodontal pathogens such as Gram-negative bacteria settle and grow, gingivitis occurs due to toxins and inflammatory substances produced by the bacteria. To develop. As a technique for suppressing this plaque formation, it is conventionally known to use an antibacterial agent composed of an inorganic or organic substance in the oral composition.

  However, plaque, i.e. biofilm, is a fungicide that is effective against floating oral bacteria because of the poor penetration of antibacterial agents. Is not effective, and there is a problem that the plaque suppression effect as expected cannot be obtained.

  As means for solving this problem, the use of zeolite or the like in which an antibacterial metal ion is supported on zeolite is known (Patent Document 1, Japanese Patent Laid-Open No. 60-181002, Patent Document 2; Japanese Patent Laid-Open No. 3-2113). In particular, a synergistic effect can be expected when used in combination with a phenolic antibacterial agent, an etheric antibacterial agent, a quaternary ammonium antibacterial agent and a pyridinium antibacterial agent.

  However, the metals used in these antibacterial metal ion-carrying zeolites have high reactivity, and there is a problem that the composition reacts with the components in the dentifrice composition and the composition discolors with time.

JP 60-181002 A JP-A-3-2113 Japanese Patent Laid-Open No. 8-26955 Journal of Chemical Society, vol. 85, p2149-2154 (1963)

  The present invention has been made in view of the above circumstances, has an excellent antibacterial effect against bacteria in the oral cavity, has an excellent preventive effect on worms and periodontal diseases, and has good temporal stability with respect to discoloration, Another object of the present invention is to provide a method for preventing discoloration of a dentifrice composition due to the blending of zeolite loaded with antibacterial metal ions.

  As a result of intensive studies to achieve the above object, the inventor of the present invention uses (a) a zeolite carrying an antibacterial metal ion and (b) polylysine or a salt thereof in combination, and the blending of the component (a). When the amount is 0.05 to 1.0% by mass of the total composition and the mass ratio of component (b) / component (a) is in the range of 1 to 5, discoloration derived from the antibacterial metal ion-carrying zeolite is achieved. A dentifrice composition that can be suppressed, exhibits a high antibacterial effect against oral bacteria, has an excellent preventive effect against worms and periodontal diseases, and has excellent discoloration stability that hardly causes discoloration over time. Further, (c) selected from isopropylmethylphenol, triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether), benzalkonium chloride, and cetylpyridinium chloride as a fungicide. By blending one or two or more, a higher antibacterial effect is obtained, and finding that it is possible to exhibit more excellent characteristics, the present invention has been accomplished.

Therefore, the present invention
(I) (a) containing an antibacterial metal ion-supported zeolite and (b) polylysine or a salt thereof, and the blending amount of the component (a) is 0.05 to 1.0% by mass of the whole composition A dentifrice composition, wherein the mass ratio of (b) / (a) is 1 to 5,
(II) Further, (c) one or two kinds of fungicides selected from isopropylmethylphenol, triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether), benzalkonium chloride, and cetylpyridinium chloride The above dentifrice composition characterized by comprising the above,
(B) polylysine or a salt thereof as a discoloration preventing agent in a dentifrice composition comprising (III) (a) a zeolite carrying an antibacterial metal ion in an amount of 0.05 to 1.0% by mass, By using together in the mass ratio of said (b) / (a) in the range of 1-5, the method of preventing discoloration of the dentifrice composition by the mixing | blending of (a) the zeolite which carry | supported the antibacterial metal ion is provided.

  The dentifrice composition of the present invention has a high antibacterial effect against bacteria in the oral cavity, has an excellent preventive effect on worms and periodontal diseases, and has good temporal stability with respect to discoloration, according to the method of the present invention, It is possible to effectively prevent discoloration of the dentifrice composition due to the blending of the zeolite loaded with antibacterial metal ions.

  Hereinafter, the present invention will be described in more detail. The dentifrice composition of the present invention is suitably prepared as a toothpaste, liquid toothpaste, etc., particularly as a toothpaste, and (a) a zeolite carrying an antibacterial metal ion (B) Polylysine or a salt thereof is blended.

  In the zeolite carrying the antibacterial metal ion to be blended in the dentifrice composition of the present invention, examples of the antibacterial metal include silver, copper, zinc, lead, tin, bismuth, cadmium, chromium, nickel, cobalt and the like. . In particular, one or more antibacterial metals selected from silver, zinc, and copper are more preferably used from the viewpoints of antibacterial action, safety to the human body, and the like, and the combined use of silver and zinc is particularly preferable.

The antibacterial metal ion-supported zeolite is obtained by substituting ions capable of exchanging ions in the zeolite with ions of the antibacterial metal. Zeolite is generally an aluminosilicate having a three-dimensional framework structure and is represented by the following general formula (1).
_{XM 2 / n O · Al 2} O 3 · YSiO 2 · ZH 2 O (1)

  In the above formula (1), M represents an ion-exchangeable ion, and is usually a monovalent or divalent metal ion, such as sodium ion, calcium ion, potassium ion, magnesium ion, or iron ion. n is the valence of the metal ion. X is a coefficient of metal oxide, Y is a coefficient of silica, and Z represents the number of crystal water.

  Here, there are both natural and synthetic zeolites. About 40 kinds of natural ones and about 200 or more synthetic ones are already known. In the present invention, natural zeolite and synthetic ones are known. Any of zeolite may be sufficient. Specific examples of the zeolite are not particularly limited. For example, A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcite, clinopti Lolite, chabasite, erionite, etc. can be mentioned. Among these, natural zeolite contains impurities and lacks homogeneity, so synthetic zeolite is preferable, and A-type zeolite, X-type zeolite, Y-type zeolite, and mordenite are particularly preferable.

  The antibacterial metal ion-carrying zeolite according to the present invention is obtained by replacing the ion-exchangeable ion (M) in the zeolite represented by the above formula (1) with the metal ion of the antibacterial metal. The content of the antibacterial metal ion is preferably 0.1 to 25% (mass%, the same applies hereinafter) in the zeolite in terms of the antibacterial effect.

  As such an antibacterial metal ion-carrying zeolite, a commercially available product can be used, and its production method is not particularly defined. What was prepared by adopting the following method described in Japanese Patent No. 26955) can be suitably used.

  That is, the zeolite is brought into contact with a mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, and zinc ions prepared in advance to replace the ion-exchangeable ions in the zeolite with the antibacterial metal ions. The contact is suitably performed at 10 to 70 ° C., preferably 40 to 60 ° C. for 3 to 24 hours, preferably 10 to 24 hours. In addition, it is appropriate to adjust the pH of the mixed aqueous solution to 3 to 10, preferably 5 to 7. Such adjustment is preferable because precipitation of silver oxide or the like on the zeolite surface or in the pores can be prevented. In addition, each antibacterial metal ion in the mixed aqueous solution is usually supplied as a salt. For example, nitrate, sulfate, perchlorate, acetate, etc. can be used.

  The content of antibacterial metal ions in the zeolite can be appropriately controlled by adjusting the concentration of each antibacterial metal ion in the mixed aqueous solution. For example, when the antibacterial metal ion-carrying zeolite contains silver ions, the silver ion content is suitably 0.1 to 5% by adjusting the silver ion concentration in the mixed aqueous solution to 0.002 to 0.15 mol / L. The antibacterial metal ion-carrying zeolite can be obtained. When the antibacterial metal ion-supported zeolite further contains copper ions and zinc ions, the copper ion concentration in the mixed aqueous solution is 0.1 to 0.85 mol / L, and the zinc ion concentration is 0.15 to 1.2 mol. By setting / L, an antibacterial metal ion-supported zeolite having a copper ion content of 0.1 to 8% and a zinc ion content of 0.1 to 8% can be obtained as appropriate. In addition to the above mixed aqueous solution, the antibacterial metal ion-carrying zeolite can be ion-exchanged by using an aqueous solution containing each antibacterial metal ion alone and sequentially contacting each aqueous solution with the zeolite. The concentration of each antibacterial metal ion in each aqueous solution can be determined according to the concentration of each antibacterial metal ion in the mixed aqueous solution.

  The zeolite after the ion exchange is sufficiently washed and then dried. Drying is preferably performed at 105 to 115 ° C. or 70 to 90 ° C. under reduced pressure (0.1 to 4 kPa). In addition, ion exchange of ions and organic ions without appropriate water-soluble salts such as tin and bismuth should be carried out by using an organic solvent solution such as alcohol or acetone so that a hardly soluble basic salt does not precipitate. Can do.

  The total amount of the antibacterial metal ion-supported zeolite in the present invention is 0.05 to 1.0%, preferably 0.1 to 0.5% in the composition. If the blending amount is less than 0.05%, the effect of the present invention cannot be sufficiently obtained, and if it exceeds 1.0%, it becomes difficult to prevent discoloration.

  Next, the polylysine as the component (b) used in the present invention is a polymer (peptide) of one kind of basic amino acid lysine. Polylysine can take two structures, α-polylysine and ε-polylysine, depending on the position of the amino group to be polymerized, but ε-polylysine is produced by Streptomyces albulus and listed in the existing additive dictionary. In the present invention, it is particularly preferable to use ε-polylysine from the viewpoint of safety.

  The peptide can be easily synthesized by not only a commercially available product but also a solid phase method commonly used for peptide synthesis. For example, it can be synthesized according to the method of Merifeed et al. Described in Journal of Chemical Society, Vol. 85, p2149-2154 (1963) (Non-patent Document 1). It can also be synthesized by a commercially available peptide synthesizer. In addition, by using a gene encoding the amino acid sequence of a lysine peptide, it can be produced in large quantities in microbial cells, plant cells, and animal cells using genetic engineering techniques.

  The obtained crude synthetic peptide can be further purified by means commonly used for purification of proteins and peptides, such as gel filtration, normal phase, reverse phase HPLC, and ion exchange column purification.

In the polylysine used in the present invention, the number average molecular weight is preferably 300 to 500,000, more preferably 1,000 to 50,000, and if it is less than 300, the discoloration preventing effect may be insufficient. If it exceeds 500,000, the appearance of dentifrice such as rough skin may be impaired. Here, the number average molecular weight is the number average molecular weight Mn given by Mn = ΣMiNi / ΣNi when Ni molecules having a molecular weight Mi exist, and the osmotic pressure method and the boiling point increase method are used as measurement methods. And a freezing point depression method and a GPC (Gel Permeation Chromatography) method. The GPC method measures the molecular weight distribution. The molecular weight is converted into a standard substance such as polystyrene, the low angle light scattering method (LALLS), and the multi angle light scattering method (MALLS). GPC-LALLS method and GPC-MALLS method. GPC is also called SEC (Size Exclusion Chromatography). The method for measuring the number average molecular weight is not particularly limited, but is measured, for example, under the following conditions.
GPC-LALLS method column: Tosoh Biosep G5000 PW _XL , 7.8 mm × 30 cm
Moving layer: 0.1 mol / L sodium phosphate buffer (pH 7.0)
Flow rate: 0.5 mL / min
Column temperature: 40 ° C

  In the present invention, polylysine can also be used in a free form or in the form of a salt. The salt form includes inorganic acid salts such as hydrochloride and sulfate, and organic acid salts such as citrate and malate. Is included.

  (B) Polylysine or a salt thereof is blended as an anti-discoloring agent. In the present invention, (b) polylysine or an anti-discoloring agent is added to a dentifrice composition containing (a) an antibacterial metal ion-carrying zeolite. By using the salt in combination at a specific ratio, discoloration of the dentifrice composition due to the blending of the (a) antibacterial metal ion-carrying zeolite can be effectively prevented. In this case, the blending amount of (b) polylysine or a salt thereof is (b) / (a) having a mass ratio of 1 to 5 with respect to (a) the antibacterial metal ion-carrying zeolite from the viewpoint of preventing discoloration. In particular, the mass ratio of (b) / (a) is preferably in the range of 2-5. If the blending amount of polylysine or a salt thereof is less than the blending amount of the antibacterial metal ion-carrying zeolite, that is, if (b) / (a) is less than 1, the effect of suppressing discoloration derived from the antibacterial metal ion-carrying zeolite is insufficient. When the mass ratio of (b) / (a) exceeds 5, coloring by polylysine itself is recognized. Further, the blending amount of polylysine or a salt thereof is preferably 0.05 to 5.0%, particularly preferably 0.1 to 0.5% of the whole composition, and if it exceeds 5.0%, coloring derived from polylysine is recognized. There is a case.

In the present invention, these components (a) and (b) are preferably combined and further combined with (c) an antibacterial agent, whereby the antibacterial activity can be synergistically improved.
(C) As an antibacterial agent having a synergistic effect as a component, one type selected from a phenolic antibacterial agent, an etheric antibacterial agent, a quaternary ammonium antibacterial agent and a pyridinium antibacterial agent alone, or two or more types It can mix | blend in combination.

  Here, as the phenolic antibacterial agent, the general names biosol, thymol, carvacrol known as isomers of isopropylmethylphenol, and as the etheric antibacterial agent, triclosan (2,4,4′-trichloro-2 ′) -Hydroxydiphenyl ether), quaternary ammonium antibacterial agents include, but are not limited to, benzalkonium chloride, benzethonium chloride, and pyridinium antibacterial agents such as cetylpyridinium chloride. Of these fungicides, isopropylmethylphenol, triclosan, and cetylpyridinium chloride are particularly preferably used.

  When the above-mentioned (c) bactericidal agent is blended, the blending amount is preferably 0.0001 to 5%, particularly 0.0005 to 2%, especially 0.001 to 1% of the entire composition. If the blending amount is less than 0.0001%, a sufficient blending effect may not be obtained, and an excellent bactericidal effect may not be exhibited. If the blending amount exceeds 5%, it is disadvantageous in terms of stability, usability, cost, etc. of the preparation. It may become.

  In addition, among these bactericides, when blending an antibacterial agent such as triclosan with low water solubility, or a phenolic antibacterial agent such as isopropylmethylphenol, the disinfectant should be previously solubilized with a solvent such as alcohol. It is preferable to mix | blend with an aqueous formulation or to mix | blend with surfactant formulation.

  The dentifrice composition of the present invention can contain other additives as optional components in addition to the above essential components. In the case of toothpaste, for example, abrasives, wetting agents, binders, surfactants, fragrances, sweeteners, preservatives, various active ingredients, colorants, etc. can be blended, and these ingredients are mixed with water. can do.

  As abrasives, anhydrous silicic acid, amorphous anhydrous silicic acid, dentifrice calcium hydrogen phosphate, aluminum hydroxide can be blended, calcium pyrophosphate, calcium carbonate, alumina, magnesium carbonate, tertiary magnesium phosphate, insoluble Examples thereof include inorganic abrasives such as sodium metaphosphate, insoluble potassium metaphosphate, and titanium oxide, and organic abrasives such as polymethyl methacrylate and crystalline cellulose. 5-60% of the whole composition is suitable for the compounding quantity of an abrasive | polishing agent, Preferably it is 10-50%.

  Examples of the wetting agent include sorbit, glycerin, propylene glycol, xylit, maltite, lactit and the like, and sorbit and xylit are particularly preferable. The blending amount of these wetting agents is preferably 10 to 60%, particularly 20 to 50% of the entire composition.

  As binder, cellulose derivatives such as carrageenan, sodium carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, gums such as xanthan gum, tragacanth gum, karaya gum, arabic gum, polyvinyl alcohol, crosslinked sodium polyacrylate, uncrosslinked sodium polyacrylate And organic binders such as carboxyvinyl polymer such as polyvinyl pyrrolidone, and inorganic binders such as silica gel, aluminum silica gel, bee gum, and laponite. The blending amount of the binder is preferably 0.1 to 5%, more preferably 0.5 to 3% of the entire composition.

  As the surfactant, an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant can be blended. Examples of anionic surfactants include sodium alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate, sodium N-acyl sarcosinate such as sodium N-lauroyl sarcosinate, sodium N-myristoyl sarcosinate, sodium dodecylbenzenesulfonate, hydrogen Added coconut fatty acid monoglyceride sodium monosulfate, sodium lauryl sulfoacetate, N-acyl glutamate such as sodium N-palmitoyl glutamate, N-methyl-N-acyl taurine sodium, N-methyl-N-acylalanine sodium, α-olefin sulfone Sodium acid or the like can be used. Examples of the cationic surfactant include alkylammonium and alkylbenzylammonium salts. Examples of amphoteric surfactants include betaine acetate, imidazolinium betaine, and lecithin. The blending amount of the surfactant is preferably 0 to 8% of the whole composition, more preferably 0.1 to 5%.

  As sweeteners, saccharin sodium, stevioside, neohesperidyl dihydrochalcone, glycyrrhizin, perilartin, aspartame, xylitol and the like can be blended in a usual blending amount.

  Perfumes include peppermint oil, spearmint oil, anise oil, eucalyptus oil, winter green 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, grapefruit oil, sweetie Natural fragrances such as oil, coconut oil, Iris concrete, absolute peppermint, absolute rose, orange flower, and processing of these natural fragrances (front reservoir cut, rear reservoir cut, fractional distillation, liquid-liquid extraction, essence, powder Perfumes, etc.) and menthol, Rubon, Anethole, Cineol, Methyl salicylate, Synamic aldehyde, Eugenol, 3-l-Mentoxypropane-1,2-diol, Thymol, Linalol, Linarel acetate, Limonene, Menthone, Menthyl acetate, N-Substituted-paramenthane 3-carboxamide, pinene, octylaldehyde, citral, pulegone, carbyl acetate, anisaldehyde, ethyl acetate, ethyl butyrate, allyl cyclohexane propionate, methyl anthranilate, ethyl methyl phenyl glycidate, vanillin, undecalactone, Hexanal, butanol, isoamyl alcohol, hexenol, dimethyl sulfide, cycloten, furfural, trimethylpyrazine, ethyl lactate, ethyl Oral compositions such as single flavors such as o-acetate, and other flavors 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. It can be used in combination with known perfume materials used in the above.

  Moreover, although the compounding quantity of a fragrance | flavor is not specifically limited, As a fragrance | flavor for perfume using the said fragrance | flavor raw material, it is preferable to use 0.1 to 2.0% in a formulation composition.

  As colorants, 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. As preservatives, various parabens, sodium benzoate, essential oil components and the like can be blended in effective amounts.

  Furthermore, as active ingredients, enzymes such as dextranase, mutanase, amylase, lysozyme, protease, lytic enzyme, superoxide dismutase, fluorides such as sodium monofluorophosphate, sodium fluoride, polyethylene glycol, polyvinylpyrrolidone, allantoin, Dihydrocholesterol, glycyrrhizic acid, glycyrrhetinic acid, epsilon aminocaproic acid, tranexamic acid, ascorbic acid and its salts, tocopherol, herbal extracts such as ugone, peonies, rosemary, clove, thyme, etc. can be blended. In addition, the said active ingredient can be mix | blended in an effective amount in the range which does not prevent the effect of this invention.

  The material in particular of the container which accommodates the dentifrice composition of this invention is not restrict | limited, The container normally used for a dentifrice composition can be used. Specifically, an aluminum tube, a laminated tube obtained by laminating both surfaces of aluminum with plastic, a plastic tube, a container such as a bottle-shaped container or an aerosol container can be used.

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.
Also, in any of the following Examples and Comparative Examples, (a) antibacterial metal ion-supported zeolite is Zeonic AJ10N (silver ion content 2.5 mass%, zinc ion content 14 mass%) manufactured by Sinanen Zeomic Co., Ltd. (B) Polylysine is a Sankee No. 381 (polylysine 50 mass% powder, number average molecular weight 4,000 measured by low angle light scattering method (GPC-LALLS method)) was used. In the following examples, the blending amounts are all by mass%, and the blending amount converted purely only for polylysine is shown.

[Examples 1 to 12, Comparative Examples 1 to 6]
Toothpaste compositions having the compositions shown in Tables 1 to 3 were prepared by a conventional method and filled into a laminate tube having a diameter of 8 mm. The antibacterial effect and discoloration of the obtained toothpaste composition on oral bacteria in the biofilm were evaluated by the following methods. The results are shown in Tables 1-3.

[Evaluation method]
Antibacterial effect on oral bacteria in biofilm:
Biofilms using Aquidite Hydroxy on the Biofilm using 5 types of oral bacteria, Streptococcus mutans ATCC 25175 strain, Streptococcus sanguinis ATCC 10556 strain, Actinomyces naesrandi ATCC 51655 strain, Fusobacterium nucleatum ATCC 10953 strain and Bayonella parbra ATCC 17745 strain Formed. Specifically, the above bacteria were inoculated to 10 ⁷ cells / ml in 700 ml of BMM medium (see the composition below) in a continuous culture vessel with hydroxyapatite on a rotating plate, and anaerobic at 37 ° C. overnight. Cultured. Thereafter, the BMM medium was continuously supplied to the continuous culture vessel by a pump so as to be 70 ml / hour, and the same amount of the culture solution was discharged by another pump for continuous culture. After continuous supply of the medium, the medium was discharged 11 hours and 30 minutes later, and replaced with Todd Hewitt medium (hereinafter abbreviated as THB (manufactured by Becton Dickinson)) containing 1% sucrose for 30 minutes at 37 ° C. Cultured. The medium was discharged, replaced with 700 ml of BMM medium again, and continuously cultured for 11 hours and 30 minutes. A cycle of 30 minutes of incubation with 1% sucrose-added THB was performed four times to form a biofilm on the hydroxyapatite surface. Hydroxyapatite after biofilm formation was taken out and washed with physiological saline, and then the centrifugal supernatant of the dentifrice composition diluted 4-fold with 10 mM phosphate buffer, pH 6 was allowed to act at 37 ° C. for 1 minute. The treated hydroxyapatite was washed twice with physiological saline, and then anaerobically cultured overnight at 37 ° C. in a 24-well plate with 1.5 ml of heart infusion medium (Becton Dickinson). This was washed twice with physiological saline, then 2 ml of physiological saline was added, the biofilm was dispersed with an ultrasonic homogenizer, diluted as appropriate, smeared on a THB agar dish, and anaerobically cultured at 37 ° C. for 5 days. The number of viable bacteria in the biofilm was measured by measuring the number of colonies after culturing, and the ratio of the viable count of those treated with each dentifrice composition when the one treated with the buffer was taken as 100 was measured according to the following criteria: Indicated.

Evaluation criteria;
◎: Number of remaining viable bacteria less than 1% ○: Number of remaining viable bacteria 1% to less than 10% △: Number of remaining viable bacteria 10% to less than 50% ×: Number of remaining viable bacteria more than 50%

BMM (Basal Medium Mucin) medium composition Proteose peptone ^{* 1} 0.2%
East Extract ^{* 1} 0.1
Tripty case peptone ^{* 1} 0.1
Porcine stomach mucin ^{* 2} 0.25
KCl ^{* 3} 0.05
L-cysteine hydrochloride ^{* 3} 0.01
Ion exchange water remaining
Total 100%
* 1: Nippon Becton Dickinson Co., Ltd. * 2: Sigma-Aldrich Japan Co., Ltd. * 3: Wako Pure Chemical Industries, Ltd.

discoloration:
The dentifrice composition filled in the laminate tube was stored in a constant temperature bath at 40 ° C. for 1 month, then extruded onto paper and visually observed, and the dentifrice composition stored for 1 month in a −5 ° C. constant temperature bath was compared as a control product. Evaluation was made according to the criteria.
Evaluation criteria;
(Double-circle): A color change is not recognized compared with a control product.
○: Almost no change in color compared to the control product.
Δ: Some change in color is observed compared to the control product.
X: A color change is recognized compared with a control product.

  As is clear from the results of Tables 1 to 3, discoloration of the toothpaste composition was observed with the antibacterial metal ion-supported zeolite alone, but the antibacterial metal ion-supported zeolite was mixed in an amount of 0.05 to 1.0%, In addition, the dentifrice composition containing polylysine blended in an equal amount to 5 times the mass ratio of the antibacterial metal ion-carrying zeolite showed antibacterial activity and almost no discoloration. In addition, since the antibacterial activity of the discolored toothpaste composition was generally low, it is presumed that the antibacterial activity of the antibacterial metal was reduced by the discoloration.

  Next, a dentifrice composition having the following composition was prepared by a conventional method and evaluated in the same manner as described above. As a result, all of them showed excellent antibacterial effects against oral bacteria in plaque and were stable in terms of discoloration. It was.

[Example 13] Toothpaste, propylene glycol 3%
Sodium alginate 0.6
Xanthan gum 0.7
Sorbitol (70%) 45
Silicic anhydride 20
Titanium oxide 0.4
Sodium fluoride 0.21
Saccharin sodium 0.15
Sodium lauryl sulfate 1.2
(A) Antibacterial metal ion-carrying zeolite 0.3
(B) Polylysine 0.9
Isopropyl methylphenol 0.05
Fragrance 1.2
100% pure water balance <br/>
(B) / (a) mass ratio: 3

[Example 14] Toothpaste, propylene glycol 3%
Sodium alginate 0.6
Xanthan gum 0.7
Sorbitol (70%) 45
Silicic anhydride 20
Titanium oxide 0.4
Sodium fluoride 0.21
Saccharin sodium 0.15
Sodium lauryl sulfate 1.2
(A) Antibacterial metal ion-carrying zeolite 0.5
(B) Polylysine 2.5
Triclosan 0.3
Fragrance 1.2
100% pure water balance <br/>
(B) / (a) mass ratio: 5

[Example 15] Toothpaste, propylene glycol 3%
Sodium alginate 0.6
Xanthan gum 0.7
Sorbitol (70%) 45
Silicic anhydride 20
Titanium oxide 0.4
Sodium fluoride 0.21
Saccharin sodium 0.15
Sodium lauryl sulfate 1.2
(A) Antibacterial metal ion-carrying zeolite 0.05
(B) Polylysine 0.1
Benzalkonium chloride 0.01
Fragrance 0.98
100% pure water balance <br/>
Mass ratio of (b) / (a): 2

[Example 16] Toothpaste, propylene glycol 3%
Sodium alginate 0.6
Xanthan gum 0.7
Sorbitol (70%) 45
Silicic anhydride 20
Titanium oxide 0.4
Sodium fluoride 0.21
Saccharin sodium 0.15
Sodium lauryl sulfate 1.2
(A) Antibacterial metal ion supported zeolite 0.1
(B) Polylysine 0.5
Isopropylmethylphenol 0.02
Cetylpyridinium chloride 0.03
Fragrance 1.1
100% pure water balance <br/>
(B) / (a) mass ratio: 5

[Example 17] Toothpaste, propylene glycol 3%
Sodium alginate 0.6
Xanthan gum 0.7
Sorbitol (70%) 45
Silicic anhydride 20
Titanium oxide 0.4
Sodium fluoride 0.21
Saccharin sodium 0.15
Sodium lauryl sulfate 1.2
(A) Antibacterial metal ion supported zeolite 0.1
(B) Polylysine 0.3
Isopropylmethylphenol 0.02
Triclosan 0.02
Fragrance 0.98
100% pure water balance <br/>
(B) / (a) mass ratio: 3

Claims (4)

  (A) containing an antibacterial metal ion-supported zeolite and (b) polylysine or a salt thereof, and the blending amount of the component (a) is 0.05 to 1.0% by mass of the total composition; ) / (A) mass ratio is 1 to 5, dentifrice composition characterized by the above-mentioned.   The dentifrice composition according to claim 1, wherein the antibacterial metal is at least one selected from silver, zinc, and copper.   Furthermore, (c) As a fungicide, one or more selected from isopropylmethylphenol, triclosan (2,4,4′-trichloro-2′-hydroxydiphenyl ether), benzalkonium chloride, and cetylpyridinium chloride are blended The dentifrice composition of Claim 1 or 2 characterized by the above-mentioned.   (B) Polylysine or a salt thereof as a discoloration inhibitor (b) in a dentifrice composition comprising 0.05 to 1.0% by mass of a zeolite carrying antibacterial metal ions in the composition; ) / (A) is used in a mass ratio of 1 to 5 to prevent discoloration of the dentifrice composition due to the blending of (a) zeolite carrying antibacterial metal ions.