JP2011136956A - Dentifrice - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dentifrice suppressing adsorption of a nonionic bactericide on a container, making the nonionic bactericide sufficiently act in the oral cavity during use, and having a good feeling of use. <P>SOLUTION: The dentifrice includes following ingredients (A), (B), (C) and (D): (A) 0.005-2 mass% of the nonionic bactericide; (B) 0.3-2.5 mass% of a surfactant; (C) 0.5-10 mass% of γ-cyclodextrin; and (D) 15-60 mass% of water. In the dentifrice, the mass ratio (A:C) of the ingredients (A) to (C) is (1:15)-(1:300). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a dentifrice containing a nonionic fungicide.

Toothpaste contains a bactericidal agent for the purpose of suppressing plaque, which is a causative agent of periodontal diseases such as cavity, gingivitis, and alveolar pyorrhea, or suppressing various oral bacteria in plaque to a low level. Among them, nonionic fungicides represented by triclosan, isopropylmethylphenol and the like are often used because of their wide antibacterial spectrum and strong bactericidal action.
Nonionic fungicides are nonionic, so there is little interaction with various compounding ingredients, but they are adsorbed on the surface of filled containers and have a problem that the concentration in the dentifrice will decrease if stored for a long period of time. There is (for example, Patent Document 1).

  In order to solve this problem, a technique for improving the adsorption of the nonionic disinfectant to the container by using a special polymer in the innermost layer portion of the container has been proposed. For example, Patent Document 1 proposes using ethylene vinyl alcohol for the inner layer. However, when a special polymer is used, there are a manufacturing problem such as a decrease in the manufacturability of the container and an economic problem that the cost is increased.

  On the other hand, as a technique for suppressing the adsorption of nonionic fungicides to the container in terms of composition, dentifrice stabilized by blending polyoxyethylene hydrogenated castor oil (Patent Document 2), anionic surfactant and nonionic interface A composition for an oral cavity in which a phenolic fungicide is stably blended by blending an activator at a specific ratio and having a water content of 40% or less (patent document 3), a polyol such as glycerin is blended, and a ratio of moisture to the polyol The composition for oral cavity which mix | blends a water-insoluble active ingredient stably by making 0.4 or less by weight ratio is proposed (patent document 4).

JP-A-6-279248 Japanese Patent Laid-Open No. 2004-250381 JP-A-11-322554 JP 2001-199854 A JP 2005-179266 A

However, when the moisture content is made lower than 40% by mass by containing a large amount of glycerin or the like as in the dentifrices described in Patent Documents 3 and 4, the viscosity increases, and the dispersion of the dentifrice in the oral cavity May deteriorate and the feeling of use may be impaired. In addition, glycerin has a bitter taste and affects not only the feeling of use but also the taste. On the other hand, dentifrice containing polyoxyethylene hydrogenated castor oil was able to prevent the adsorption of nonionic fungicide to the container, but as a result of the stable solubilization of nonionic fungicide, the bactericidal effect decreased. (Patent Document 5).
Therefore, the problem of the present invention is to suppress the adsorption (dissolution or absorption) of the nonionic fungicide to the container, and to allow the nonionic fungicide to act in the oral cavity at the time of use, and has a good feeling of use. It is to provide a dentifrice.

  Accordingly, the present inventor has made various studies to obtain a dentifrice that can suppress adsorption of the nonionic fungicide to the container in the dentifrice containing the surfactant. As a result, α-cyclodextrin and β- Even if cyclodextrin is blended, the adsorption of nonionic fungicide to the container can hardly be suppressed, but when γ-cyclodextrin is blended with the nonionic fungicide at a certain ratio, it is surprisingly nonionic. It was found that the adsorption of the agent to the container can be remarkably suppressed. When a nonionic fungicide, γ-cyclodextrin, and a certain amount of surfactant are blended, a nonionic fungicide can be prevented from adsorbing to the container, and the toothpaste has good foaming and good usability. As a result, the present invention was completed.

That is, the present invention includes the following components (A), (B), (C) and (D):
(A) Nonionic fungicide 0.005-2 mass%,
(B) Surfactant 0.3-2.5% by mass,
(C) γ-cyclodextrin 0.5 to 10% by mass,
(D) Water 15-60 mass%
And a dentifrice having a mass ratio (A: C) of components (A) and (C) of 1:15 to 1: 300.

  The dentifrice of the present invention suppresses the adsorption of the nonionic fungicide to the container, can be stored in the container while maintaining the content of the nonionic fungicide in the dentifrice, and the nonionic fungicide While suppressing diffusion, it does not affect the viscosity of the dentifrice, is excellent in dispersibility in the oral cavity, does not affect the taste, and has a good feeling of use.

The NMR spectrum of a triclosan (TC) containing surfactant (sodium lauryl sulfate: AS) aqueous solution is shown. “No additive” means no cyclodextrin. “Α-CD” is α-cyclodextrin added. “Β-CD” is β-cyclodextrin added. “Γ-CD” is γ-cyclodextrin added.

The dentifrice of the present invention contains component (A) nonionic fungicide, component (B) surfactant, component (C) γ-cyclodextrin, and component (D) water.
(A) Examples of nonionic fungicides include triclosan, isopropylmethylphenol, hinokitiol, phenol, etc. Triclosan and isopropylmethylphenol are effective in terms of bactericidal activity, plaque suppression effect, adsorption suppression effect on the container, and feeling of use. Triclosan is preferable, and triclosan is more preferable.

  Triclosan is a halogenated diphenyl ether type bactericide having a broad antibacterial spectrum, and its chemical name is 2 ', 4,4'-trichloro-2-hydroxydiphenyl ether, for example, from Ciba Specialty Chemicals Co., Ltd. It is sold under the trade name of Irugacare MP. Isopropyl methylphenol is a bactericide having a broad antibacterial spectrum, and its chemical name is 1-hydroxy-4-isopropyl-3-methylphenol. For example, it is sold by Osaka Kasei Co., Ltd. under the trade name Biosome.

  The content of the (A) nonionic fungicide in the dentifrice of the present invention is 0.005 to 2% by mass, preferably 0.01 to 1% by mass, and further 0 from the viewpoint of plaque suppression effect. 0.01 to 0.5 mass% is preferable.

As the surfactant (B) used in the dentifrice of the present invention, an anionic surfactant, a nonionic surfactant and an amphoteric surfactant are used.
Anionic surfactants include alkyl sulfates such as sodium lauryl sulfate and sodium myristyl sulfate; N-acyl sarcosine salts such as sodium N-lauroyl sarcosinate and sodium N-myristoyl sarcosate; sodium N-palmitoyl glutamate and the like N-acyl glutamate, sodium N-methyl-N-acyl taurate, sodium N-methyl-N-acylalanine, sodium α-olefin sulfonate, sodium dioctyl sulfosuccinate and the like.

Nonionic surfactants include sugar fatty acid esters such as sucrose fatty acid esters; sugar alcohol fatty acid esters such as maltitol fatty acid esters and lactitol fatty acid esters; polyoxyethylene sorbitan monolaurate and polyoxyethylene sorbitan monostearate. Polyoxyethylene sorbitan fatty acid ester such as; fatty acid diethanolamide such as lauric acid mono- or diethanolamide, myristic acid mono- or diethanolamide; sorbitan fatty acid ester, fatty acid monoglyceride, polyoxyethylene higher alcohol ether, polyoxyethylene polyoxypropylene copolymer Coalescence etc. are used.
Examples of zwitterionic surfactants include N-alkyldiaminoethylglycine such as N-lauryldiaminoethylglycine and N-myristyldiaminoethylglycine, N-alkyl-N-carboxymethylammonium betaine, and 2-alkyl-1-hydroxyethylimidazoline. Betaine sodium and the like are used.
Among these, as the surfactant, anionic surfactants are more preferable from the viewpoint of foaming and feeling of use, and alkyl sulfates such as sodium lauryl sulfate are more preferable.

The content of the surfactant (B) in the dentifrice of the present invention is 0.3 to 2.5% by mass from the balance between the effect of preventing the nonionic disinfectant from adsorbing to the container, foaming, and feeling of use. (B) The content of the surfactant is preferably 0.5% by mass or more, more preferably 0.7% by mass or more from the viewpoint of obtaining foaming, and further improves the effect of preventing the adsorption of the nonionic disinfectant to the container. From the viewpoint, it is preferably 2.2% by mass or less, and more preferably 2.0% by mass or less.
The mass ratio of the anionic surfactant in the surfactant is preferably from 50 to 100%, more preferably from 80 to 100%, more preferably from nonionic surfactant to amphoteric interface from the viewpoint of foaming and feeling of use. The content of the activator is preferably less than 0.1% by mass, and more preferably 0.05% by mass or less.

  In the dentifrice of the present invention, by containing (C) γ-cyclodextrin, adsorption of the nonionic fungicide to the container can be prevented. Among cyclodextrins, α-cyclodextrin and β-cyclodextrin do not provide sufficient anti-nonionic antibacterial effect on the container, but excellent nonionic properties when γ-cyclodextrin is added. The effect of preventing the disinfectant from adsorbing to the container can be obtained. γ-cyclodextrin is available from Cyclochem Co., Ltd. under the trade name Cabamax W8 Food.

The content of (C) γ-cyclodextrin in the dentifrice of the present invention is 0.5 to 10% by mass, and further 1 to 7% by mass from the viewpoint of the effect of preventing adsorption of the nonionic fungicide to the container. Particularly preferred is 1.5 to 5% by mass. Furthermore, in the present invention, the mass ratio (A: C) of the components (A) and (C) is from 1:15 to preventing adsorption of the nonionic fungicide to the container and obtaining a good feeling of use. 1: 300, preferably 1:20 to 1: 200, more preferably 1:30 to 1: 180.
The mass ratio (C: B) of (C) γ-cyclodextrin of the dentifrice of the present invention and the anionic surfactant in the surfactant (B) is the prevention of adsorption of nonionic fungicides to the container and the feeling of use. From this point, 1: 0.01 to 1: 3 is preferable, and 1: 0.3 to 1: 2.5 is more preferable.

The dentifrice of the present invention contains (D) 15 to 60% by mass of water. By containing water in this range, it is possible to obtain a dentifrice with excellent usability and good shape retention, dispersibility in the mouth and ease of taking out from the container when placed on a toothbrush. . (D) The content of water is preferably 20 to 60% by mass, and more preferably 30 to 50% by mass, from the viewpoint of usability.
The content of (D) water in the dentifrice can also be calculated by calculation from the amount of purified water blended and the amount of water in the blended components, but can be measured, for example, with a Karl Fischer moisture meter. . As the Karl Fischer moisture meter, for example, a trace moisture measuring device (Hiranuma Sangyo) can be used. In this apparatus, 5 g of the dentifrice is taken and suspended in 25 g of anhydrous methanol, and 0.02 g of this suspension is taken and the amount of water can be measured.

  In addition to the above-mentioned components, for example, abrasives, wetting agents, binders, sweeteners, preservatives, bactericides other than nonionic bactericides, pigments, fragrances and the like can be added to the dentifrice of the present invention. Here, as the abrasive, silica-based abrasive such as precipitated silica, silica gel, aluminosilicate, zirconosilicate, dicalcium phosphate dihydrate and anhydrous, calcium pyrophosphate, calcium carbonate, aluminum hydroxide, alumina, Examples include magnesium carbonate, tribasic magnesium phosphate, zeolite, zirconium silicate, synthetic resin abrasives, and silica-based abrasives are preferred. The content of these abrasives is preferably 2 to 30%, particularly preferably 5 to 15%.

  Examples of the wetting agent include glycerin, sorbit, propylene glycol, polyethylene glycol, erythritol, xylitol, maltitol, lactitol and the like. Examples of the binder include sodium carboxymethyl cellulose, hydroxyethyl cellulose, carrageenan, carboxyvinyl polymer, guar gum, montmorillonite, gelatin, xanthan gum, gellan gum, starch and the like. The content of these binders is preferably 0.1 to 10%, particularly preferably 0.5 to 5%.

  The dentifrice of the present invention has a helipath viscosity of 500 to 10,000 dPa · s at 25 ° C. in terms of shape retention when placed on a toothbrush, dispersibility in the mouth, and ease of removal from the container. It is preferable that it is 1000-5000dPa * s. In addition, said viscosity is 25 degreeC and says what was measured on the measurement conditions of a helipath viscometer (TVB-10R by Toki Sangyo Co., Ltd.), rotor C, and rotation speed 2.5rpm for 1 minute.

  The dentifrice of the present invention can be produced by mixing the above ingredients and filling the container. The container is preferably a synthetic resin container or at least an innermost synthetic resin container. Specifically, the container is a synthetic resin in addition to various types of containers usually used for dentifrices, such as a blow tube made of synthetic resin, a tube container formed of a synthetic resin single layer or a laminated film including a synthetic resin layer. Examples include a pump container in which a pump-type discharge device or a foam discharge device is attached to a conductive container, a foam discharge container, and the like, and a tube container is preferable in terms of manufacturability and the like. The material of the container is preferably a synthetic resin, and when a laminated film is used, a metal layer such as paper or aluminum can be included in the intermediate layer. The dentifrice of the present invention is suitable for filling into a synthetic resin container, and further suitable for filling into a polyethylene container, and when filling into a tube container having at least the innermost layer made of polyethylene. Is preferable, and adsorption of the nonionic bactericide to the inner layer of the container is suppressed.

  In the dentifrice of the present invention, the mechanism by which the adsorption of the nonionic fungicide to the container is not clear, but is considered as follows. That is, when γ-cyclodextrin is not added, the surfactant added to the dentifrice solubilizes the water-insoluble nonionic fungicide, and the nonionic fungicide dissolved in water diffuses over time in the dentifrice. Then, it is considered that it reaches the inner surface of the container and is absorbed (dissolved or absorbed) into the container. Without adding a surfactant, nonionic fungicides are difficult to dissolve in water and stabilize without diffusing in the dentifrice, but since it does not foam, it cannot be polished for a long time due to dripping from the mouth, etc. . On the other hand, when γ-cyclodextrin is blended, it is considered that γ-cyclodextrin extremely reduces the mobility of the nonionic fungicide in water and effectively suppresses adsorption to the container.

  EXAMPLES Next, an Example is given and this invention is demonstrated in detail. In addition, the unit of content in a table | surface is the mass% except the thing with special mention.

(Preservation test)
The dentifrice shown in Table 1 is manufactured, and the discharge port on one end side is filled from the opening on the other end side of the tube container, and the opening is fused and sealed after filling. It was stored in a sealed state at 50 ° C. for one month (30 days). The container body of the tube container used for the storage test has a linear low density polyethylene (LLDPE) as the innermost layer, and has a printed layer (including varnish) on the outside, and a printed layer / low density polyethylene (LDPE). / Adhesive / high density polyethylene (HDPE) / adhesive / aluminum / adhesive / polyethylene terephthalate (PET) / adhesive / LLDPE. The discharge port of this tube container and the shoulder part continuing from the discharge port to the container body are formed of polyethylene resin, and the filled dentifrice comes in contact with polyethylene.

(Measurement of triclosan after storage)
The amount of triclosan after storage was measured by squeezing the dentifrice from the tube and using the following method. The obtained values are shown in Table 1. The value in the table is the detected amount of triclosan after storage when the value before storage is 100. The method for measuring the triclosan content is shown below. Take 2.0g of each dentifrice after storage from a tube container, add 0.1w / v% phosphoric acid-containing methanol water mixture (methanol: water = 7: 3) as a mobile phase to make 100ml, which is enough The triclosan was extracted by stirring. A part of this liquid was filtered, and the absorbance of triclosan was measured by high performance liquid chromatography (HPLC) using the filtrate as a test solution. Triclosan standard solution was prepared by adding methanol to 0.05 g of triclosan to make 100 ml. In the measurement, a solution further diluted 10 times by volume with methanol was added to a 0.1 w / v% aqueous solution of phosphoric acid containing phosphoric acid ( Methanol: water = 7: 3) was used that was diluted 10 times by volume.

The measurement conditions for HPLC are shown below.
Apparatus: Hitachi High-Performance Liquid Chromatogram La chroma Elite
Column: LiChroCART 125-4 Supersphere100 RP-8 Endcapped (Merck)
Column temperature: 40 ° C
Moving bed: 0.1 w / v% phosphoric acid-containing methanol aqueous solution (methanol: water = 7: 3)
Flow rate: 1.0 ml / min
Sample injection volume: 20 μl
Measurement wavelength: 254 nm
The triclosan content of the test solution is determined from the peak area of triclosan absorbance measured by HPLC according to the following formula, and is shown in Table 1.
Triclosan content = (Y1 × X2) / (X1 × Y2)
X1: Triclosan peak area obtained from the absorbance of the standard solution Y1: Triclosan peak area obtained from the test solution.
X2: Collection amount of standard triclosan (g)
Y2: Dentifrice collection amount (g)

  From Table 1, by adding 15 times or more of γ-cyclodextrin to triclosan, adsorption of triclosan to the tube was suppressed, and an appropriate amount of triclosan was detected in the squeezed dentifrice. On the other hand, this effect was not obtained with α-cyclodextrin and β-cyclodextrin.

  The dentifrices of Examples 5 to 9 and Comparative Examples 4 and 5 shown in Table 2 were produced, and the triclosan content after storage for 1 month was measured in the same manner as in Examples 1 to 5. In addition, the feeling of use of the dentifrice (foaming, dripping during polishing, etc.) and taste were evaluated by 10 panelists, and the evaluation with the largest number of people was adopted in the evaluation of 10 persons. The evaluation criteria are shown in the lower part of Table 2.

  As shown in Table 2, when the surfactant was less than 0.3% by mass, the foam was difficult to stand and the liquid dripped from the mouth when brushing the teeth, and the usability was significantly impaired. On the other hand, if the amount exceeds 2.5% by mass, bubbles will rise too much and dripping from the mouth, the feeling when polishing will be bad, taste will also occur, and the detected amount of triclosan after storage will be low, adsorbing to the tube It is recognized that On the other hand, in the examples, the detected amount of triclosan after storage was high, and sufficient evaluation as a dentifrice was obtained even with a feeling of use.

(Test example)
Using a test solution in which the solvent shown in Table 3 was used as heavy water, the mobility of triclosan in water in the presence of sodium lauryl sulfate was compared by NMR measurement. The NMR measurement conditions are shown below.
Measuring instrument: Bruke Avance 500 (Bruker)
Probe: 5 mm BBO probe Observation nucleus: 1H nucleus Measurement method: Single pulse method with flip angle of 30 degrees (pulse width 4.3 μs) Measurement range: 10330 Hz
Total number of times: 16 times Relaxation waiting time: 30 seconds

  The result is shown in FIG. As is clear from the results in FIG. 1, the triclosan peak was observed in the cyclodextrin-free solution, the α-cyclodextrin-added solution, and the β-cyclodextrin-added solution, whereas in the γ-cyclodextrin-added solution, the triclosan peak was observed. It was recognized that the peak was very small. From this result, when γ-cyclodextrin is contained, it is judged that the dissolution of triclosan in the aqueous surfactant solution is suppressed, and the dissolution of triclosan in the composition is suppressed, and its mobility is reduced. By suppressing, it is thought that the contact to a container is suppressed and as a result, the adsorption | suction to a container is suppressed.

Claims (5)

The following components (A), (B), (C) and (D):
(A) Nonionic fungicide 0.005-2 mass%,
(B) Surfactant 0.3-2.5% by mass,
(C) γ-cyclodextrin 0.5 to 10% by mass,
(D) Water 15-60 mass%
A dentifrice containing the ingredients (A) and (C) in a mass ratio (A: C) of 1:15 to 1: 300. (A) The dentifrice according to claim 1, wherein the nonionic fungicide is selected from isopropylmethylphenol and triclosan. (B) The dentifrice according to claim 1 or 2, wherein the surfactant is an anionic surfactant.   The dentifrice according to any one of claims 1 to 3, wherein the dentifrice is filled in a synthetic resin container or a container in which at least the innermost layer is a synthetic resin.   The dentifrice according to claim 4, wherein the synthetic resin is polyethylene.

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