JP2017222584A - Dentifrice composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dentifrice composition capable of effectively suppressing an increase in viscosity over time and ensuring good shape retention even after storage.SOLUTION: According to the present invention, there is provided a dentifrice composition comprising the following components (A), (B), (C), and (D): (A) thickening silica having an oil absorption amount of 150 to 500 mL/100 g in amount of 2% by mass or more and 15% by mass or less; (B) a water-soluble calcium salt in amount of 0.002% by mass or more and 0.1% by mass or less in terms of calcium atoms; (C) a water-soluble polyvalent metal salt other than a calcium salt; and (D) water in amount of 10% by mass or more and 50% by mass or less. In the dentifrice composition, the molar ratio ((C) mol/(B) mol) of the component (C) to the component (B) is 0.2 or more and 10 or less, and the content of the abrasive silica having an oil absorption of 50 mL/100 g or more and less than 150 mL/100 g is 10% by mass or less.SELECTED DRAWING: None

Description

  The present invention relates to a dentifrice composition.

  It is desirable that the dentifrice has an appropriate shape-retaining property since it is desired to provide good dispersibility and feel when applied to the oral cavity in addition to giving ease to the toothbrush. It is. Under these circumstances, for example, Patent Document 1 discloses a dentifrice containing a specific amount and a specific mass ratio of thickening silica and calcium carbonate having an oil absorption of 150 to 500 mL / 100 g in the presence of a specific amount of water. It has been shown that it has a sufficient shape-retaining property while providing a light feeling of use, and also has good dispersibility in the oral cavity.

  On the other hand, in Patent Document 2, in order to improve that the calcium salt used in combination with the thickening silica is limited to calcium carbonate, the mechanism for improving the shape-retaining property of the thickening silica has been further studied, and sufficient retention is thus achieved. In order to ensure good taste and foaming, the present inventors have found a dentifrice in which a specific amount of thickening silica is combined with a water-soluble calcium compound having a specific amount of calcium atom equivalent. This is attributed to the fact that calcium ions released from the water-soluble calcium compound dissolved in water have a good effect on the gel formation of the three-dimensional structure of silica.

JP 2010-280616 A JP 2013-18710 A

  However, the dentifrices described in Patent Documents 1 and 2 all have good shape-retaining properties, but there is a risk that viscosity will increase after storage, and excellent performance will be maintained over time. Requires further improvement.

  Therefore, the present invention relates to a dentifrice composition that can effectively suppress the increase in viscosity over time and ensure good shape retention even after storage.

  Therefore, the present inventors have conducted various studies and found that the three-dimensional structure of the gel formed by the thickened silica and the water-soluble calcium compound in the presence of water is a major factor causing an increase in viscosity after storage. A dentifrice composition capable of effectively suppressing the increase in viscosity by obtaining knowledge, using a specific water-soluble polyvalent metal salt in a specific molar ratio, and limiting the content of abrasive silica. It was found that a product was obtained.

That is, the present invention includes the following components (A), (B), (C), and (D);
(A) Thickening silica having an oil absorption of 150 to 500 mL / 100 g 2% by mass to 15% by mass,
(B) Water-soluble calcium salt 0.002% by mass or more and 0.1% by mass or less in terms of calcium atom,
(C) A water-soluble polyvalent metal salt other than calcium salt, and (D) 10 to 50% by mass of water, and the molar ratio of component (C) to component (B) ((C) mol / ( B) It relates to a dentifrice composition having a content of abrasive silica having a mol) of 0.2 or more and 10 or less and an oil absorption of 50 mL / 100 g or more and less than 150 mL / 100 g of 10% by mass or less.

  According to the dentifrice composition of the present invention, it is possible to effectively suppress the increase in viscosity over time while favorably forming the three-dimensional structure of the gel by the thickening silica and the water-soluble calcium compound in the presence of water. Therefore, good shape retention can be maintained even after storage. Moreover, since a good foam quality is maintained after storage, it is possible to bring about a comfortable feeling of cleaning and use.

Hereinafter, the present invention will be described in detail.
The dentifrice composition of the present invention contains 2% by mass or more and 15% by mass or less of thickening silica having an oil absorption of 150 to 500 mL / 100 g as the component (A). Such thickening silica has a larger oil absorption than silica used in dentifrice compositions as ordinary abrasive silica. In this way, the component (A) and the water-soluble calcium compound of the component (B) described later having a specific amount of calcium atom equivalent are dispersed in the water of the component (D), so that the water solution dissolved in water is dissolved. Calcium ions released from functional calcium compounds act on the gel formation of the three-dimensional structure of silica, exhibiting excellent shape retention as a dentifrice composition, and exhibiting excellent dispersibility in the oral cavity and feeling of use can do.
The amount of oil absorption indicates the amount of oil that can be supported by silica, and the measurement method is specified by the method of JIS K5101-13-2 (established in 2004) according to the amount of oil absorbed in the boiled sea bream. Value.

The oil absorption amount of the component (A) is 150 to 500 mL / 100 g, preferably 200 to 400 mL / 100 g, more preferably 250 to 380 mL / 100 g, from the viewpoint of ensuring good shape retention. As this component (A), commercially available products such as SYLOPURE25 manufactured by Fuji Silysia Chemical Co., Ltd. and SORBOSILTC15 manufactured by CROSFIELD can be used.
Moreover, the average particle diameter of a component (A) becomes like this. Preferably it is 1-10 micrometers, More preferably, it is 1.5-9 micrometers, More preferably, it is 2-8 micrometers.

  The content of the component (A) is 2% by mass or more in the dentifrice composition of the present invention, and preferably 3 from the viewpoint of ensuring appropriate shape retention, dispersibility in the oral cavity, and usability. It is at least 4% by mass, more preferably at least 4% by mass. In addition, the content of the component (A) is 15% by mass or less in the dentifrice composition of the present invention from the viewpoint of effectively suppressing increase in viscosity over time while maintaining appropriate shape retention. Preferably, it is 12 mass% or less, More preferably, it is 10 mass% or less, More preferably, it is 8 mass% or less. And content of a component (A) is 2 to 15 mass% in the dentifrice composition of this invention, Preferably it is 3-12 mass%, More preferably, it is 4-10 mass%. And more preferably 4 to 8% by mass.

  The dentifrice composition of this invention contains 0.002 mass% or more and 0.1 mass% or less of water-soluble calcium salt in a calcium atom conversion amount as a component (B). When the component (B) is dissolved in the water of the component (D) described later, calcium ions are liberated, and the calcium ions and the component (A) can form a three-dimensional gel. In addition, a firm gel can be effectively formed with a very small amount of calcium ions, and the increase in viscosity over time can be effectively suppressed by the component (C) described later.

  In addition, the water-soluble calcium salt of a component (B) means the calcium salt whose solubility with respect to 100 mL of water in 20 degreeC is 2 g / 100 mL or more. Of these, water-soluble calcium salts that can be used in the oral cavity are preferred. In the present invention, since the content of the component (B) is a very small value, the water-soluble calcium salt is thrown into the water in an amount not exceeding the solubility in water. Releases calcium ions in an amount equivalent to the converted amount immediately.

  Specific examples of the component (B) include calcium chloride, calcium benzoate, calcium acetate, calcium formate, calcium propionate, calcium lactate, calcium gluconate, calcium bromide, calcium nitrate, and dihydrogen phosphate. Examples thereof include one or more selected from calcium, calcium glycerophosphate, and hydrates thereof. Among these, the water at 20 ° C. of the component (B) is used from the viewpoint of effectively suppressing the increase in viscosity over time in combination with the component (C) described later while forming a gel having a three-dimensional structure well with the component (A). The solubility with respect to 100 mL is preferably 3 g / 100 mL or more, and preferably 8 g / 100 mL or less. Specifically, for example, one or more selected from calcium gluconate, calcium chloride, calcium benzoate, calcium acetate, calcium formate, calcium propionate, calcium lactate, calcium glycerophosphate and hydrates thereof are preferable. One or more selected from calcium gluconate, calcium chloride, calcium lactate and calcium glycerophosphate are more preferred.

  The calcium atom equivalent amount of the component (B) is 0.002% by mass or more in the dentifrice composition of the present invention from the viewpoint of maintaining appropriate shape retention and ensuring dispersibility in the oral cavity. The content is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more. In addition, the calcium atom equivalent amount of the component (B) is from the viewpoint of ensuring good foaming while suppressing the increase in viscosity over time by the combined use of the component (C) described later, and suppressing the decrease in flavor due to saltiness. In the dentifrice composition of this invention, it is 0.1 mass% or less, Preferably it is 0.08 mass% or less, More preferably, it is 0.07 mass% or less. And the calcium atom conversion amount of a component (B) is 0.002 mass% or more and 0.1 mass% or less in the dentifrice composition of this invention, Preferably it is 0.01-0.08 mass%. Yes, more preferably 0.03 to 0.07% by mass.

The content of the component (B) may vary depending on the type of the component (B). However, when dissolved in water, the content of the component (B) is appropriately calculated based on the calcium atom equivalent so that the above amount of calcium ions can be released. do it. For example, the content of the component (B) is preferably 0.025 to 1.2% by mass, more preferably 0.1 to 1% by mass, and still more preferably in the dentifrice composition of the present invention. It is 0.35-0.8 mass%, More preferably, it is 0.3-0.75 mass%. Specifically, for example, when calcium gluconate is used as the component (B), the content of the calcium gluconate is preferably 0.022 to 1.1% by mass in the dentifrice composition of the present invention. More preferably, it is 0.1-1 mass%, More preferably, it is 0.3-0.8 mass%.
Further, the molar concentration of the component (B) may be appropriately calculated and prepared based on the above calcium atom equivalent amount. Specifically, for example, in the dentifrice composition of the present invention, preferably 0.0005 to It is 0.025 mol / L, More preferably, it is 0.0025-0.02 mol / L, More preferably, it is 0.0075-0.017 mol / L.

  The mass ratio ((B) / (A)) of the amount of component (B) converted to calcium atom and the content of component (A) effectively suppresses the increase in viscosity over time while maintaining appropriate shape retention. From this point of view, it is preferably 0.0002 or more, more preferably 0.001 or more, and still more preferably 0.003 or more. Further, the mass ratio ((B) / (A)) of the component (B) in terms of calcium atom and the content of the component (A) makes it possible to suppress the increase in viscosity over time by the combined use of the component (C). However, from the viewpoint of ensuring good foaming, it is preferably 0.05 or less, more preferably 0.02 or less, and still more preferably 0.015 or less. And the mass ratio ((B) / (A)) of the calcium atom conversion amount of component (B) and the content of component (A) is preferably 0.0002 to 0.05, more preferably 0. 0.001 to 0.02, more preferably 0.003 to 0.015.

  The dentifrice composition of this invention contains water-soluble polyvalent metal salt other than a calcium salt as a component (C). It has been found by the present inventors that the three-dimensional structure of the gel constructed by the component (A) and the component (B) in the presence of the component (D) is also a factor that increases the viscosity after storage, The present inventors have found that this is effectively suppressed by using the component (C) in combination. A polyvalent metal ion released from the water-soluble polyvalent metal salt of component (C) acts on the three-dimensional structure of the gel constructed by component (A) and component (B) to suppress an increase in viscosity. it is conceivable that.

  In addition, the water-soluble polyvalent metal salt of a component (C) means polyvalent metal salts other than a calcium salt whose solubility with respect to 100 mL of water at 20 degreeC is 2 g / 100 mL or more like a component (B). Among these, water-soluble polyvalent metal salts that can be used in the oral cavity are preferable. Specific examples of the polyvalent metal of component (C) include one or more selected from magnesium, zinc, copper, iron, and aluminum, and from the viewpoint of excellent viscosity increase inhibiting effect, One or more selected from magnesium, zinc, and aluminum are preferred. Examples of the salt of component (C) include sulfuric acid, gluconic acid, and nitric acid, and sulfuric acid and gluconic acid are preferable from the viewpoint of excellent viscosity increase inhibiting effect. Moreover, from the viewpoint of applicability to the oral cavity, one or more selected from magnesium sulfate, aluminum sulfate, and zinc gluconate are preferable.

  The molar ratio of the component (C) to the component (B) ((C) mol / (B) mol) was 0.2 or more from the viewpoint of securing good foaming while suppressing the increase in viscosity over time. The ratio is preferably 0.3 or more, more preferably 0.5 or more, and even more preferably 1 or more when the component (C) is a magnesium salt. Further, the molar ratio of the component (C) to the component (B) ((C) mol / (B) mol) is from the viewpoint of effectively suppressing the increase in viscosity over time while maintaining appropriate shape retention. 10 or less, preferably 8 or less, more preferably 7 or less. The molar ratio of the component (C) to the component (B) ((C) mol / (B) mol) is 0.2 or more and 10 or less, preferably 0.3 to 8, more preferably When it is 0.5-7 and a component (C) is a magnesium salt, More preferably, it is 1-7.

In addition, although content of a component (C) may fluctuate also with the kind, what is necessary is just to calculate and prepare suitably based on the said molar ratio. For example, the content of the component (C) is preferably 0.05 to 2.0 mass%, more preferably 0.1 to 1.5 mass% in the dentifrice composition of the present invention, Preferably it is 0.2-1.2 mass%.
In addition, the molar concentration of the component (C) may be appropriately calculated and prepared based on the above molar ratio. Specifically, for example, in the dentifrice composition of the present invention, preferably 0.002 to 0.00. 2 mol / L, more preferably 0.004 to 0.1 mol / L, even more preferably 0.005 to 0.08 mol / L, and when component (C) is a magnesium salt Is more preferably 0.01 to 0.08 mol / L.

The dentifrice composition of this invention contains 10 to 50 mass% of water as a component (D). Thereby, while forming a firm gel with the component (A) and the component (B) and maintaining good shape retention, the foaming is also suppressed from being lowered, and good dispersibility and usability in the oral cavity can be obtained. Can be secured. From this viewpoint, the content of the component (D) is 10% by mass or more, preferably 11% by mass or more, more preferably 12% by mass or more, in the dentifrice composition of the present invention. It is at most mass%, preferably at most 40 mass%, more preferably at most 30 mass%.
Here, the water of the component (D) in the present invention is not only purified water blended in the dentifrice composition, but also, for example, a 70% sorbitol solution (aqueous solution), a component (B) and a component (C) used in the formulation. The total moisture contained in the dentifrice composition, including the moisture contained in each of the blended components, such as the hydrate of

  The water content in the dentifrice composition of the present invention can be calculated from the blended moisture content and the moisture content in the blended component, but can also be measured, for example, with a Karl Fischer moisture meter. . Examples of the Karl Fischer moisture meter include a trace moisture measuring device (Hiranuma Sangyo). In this device, 2 g of the dentifrice composition can be taken and suspended in 100 mL of anhydrous methanol, and 5 mL of this suspension can be collected to measure the amount of water.

The dentifrice composition of the present invention has a three-dimensional structure gel composed of water of component (D), calcium ions of component (B) and silica of component (A), and viscosity with time of component (C). The content of abrasive silica having an oil absorption of 50 mL / 100 g or more and less than 150 mL / 100 g is set to 10% by mass or less from the viewpoint of satisfactorily maintaining the rise suppressing effect and ensuring the dispersibility of the dentifrice composition in the oral cavity. Restrict. Such abrasive silica means that the oil absorption is smaller than that of the thickening silica of component (A), and this oil absorption means a value specified by the same method as above.
The oil absorption amount of the abrasive silica is preferably 70 mL / 100 g or more, more preferably 80 mL / 100 g or more, and preferably 120 mL / 100 g or less from the viewpoint of abrasiveness.

  The content of such abrasive silica is the dentifrice composition of the present invention from the viewpoint of favorably maintaining the effect of suppressing the increase in viscosity over time, the dispersibility of the dentifrice composition in the oral cavity, and the viewpoint of securing a good feeling of use. In the product, it is 10% by mass or less, preferably 9% by mass or less, more preferably 8% by mass or less, and 2% by mass or more from the viewpoint of securing the dirt removal ability of teeth. Is preferred.

  In addition to the above components, the dentifrice composition of the present invention preferably contains an anionic surfactant (E) from the viewpoint of ensuring good foaming while effectively suppressing an increase in viscosity over time. Examples of the component (E) include acylamino acid salts such as sodium acylglutamate and sodium acylsarcosine, alkylphosphates such as sodium alkylphosphate, alkylsulfuric acid ester salts, higher fatty acid sulfonated monoglyceride salts, and fatty acids of isethionic acid. One type or two or more types selected from ester salts, N-methyl long-chain acyl taurine sodium salts, polyoxyethylene monoalkyl phosphates and the like can be mentioned. Of these, alkyl sulfate salts are preferable from the viewpoint of providing good foaming and availability, and acylamino acid salts and N-methyl long-chain acyl taurine sodium are preferable from the viewpoint of combining good foaming and low irritation. Salts are preferred, and these may be used in combination.

  The content of the component (E) is preferably 0 to 5% by mass, more preferably in the dentifrice composition of the present invention, from the viewpoint of achieving both good foaming and a comfortable feeling such as low irritation. Is 0.1-3 mass%, More preferably, it is 0.2-1.5 mass%.

  In addition to the above components, the dentifrice composition of the present invention effectively suppresses the increase in viscosity over time while ensuring good shape retention, and from the viewpoint of ensuring a comfortable feeling of use that brings freshness and good flavor. Furthermore, a binder (F) can be contained. Examples of such component (F) include sodium alginate, sodium carboxymethyl cellulose, carrageenan, xanthan gum, sodium polyacrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, pectin, tragacanth gum, gum arabic, guar gum, caraya gum, locust bean gum, gellan gum, One type or two or more types selected from tamarind gum, psyllium seed gum, polyvinyl alcohol, chondroitin sodium sulfate, methoxyethylene maleic anhydride copolymer and the like can be mentioned. Especially, the 1 type (s) or 2 or more types chosen from sodium carboxymethylcellulose, a carrageenan, and a xanthan gum are preferable.

  The content of component (F) is to increase the viscosity more than necessary in the presence of a three-dimensional gel of component (D) water, component (B) calcium ions and component (A) silica. In the dentifrice composition of the present invention, it is preferably 0.05% by mass or more, more preferably 0.07% by mass or more, and further preferably, from the viewpoint of ensuring good shape retention while suppressing Is 0.1% by mass or more. Further, the content of the component (F) is such that the viscosity increases more than necessary in the presence of a three-dimensional gel of water of the component (D), calcium ions of the component (B) and silica of the component (A). In the dentifrice composition of the present invention, it is preferably 0.8% by mass or less, more preferably 0.7% by mass or less, and still more preferably from the viewpoint of securing a good usability. 0.6% by mass or less. The content of the component (F) is preferably 0.05 to 0.8% by mass, more preferably 0.07 to 0.7% by mass in the dentifrice composition of the present invention, Preferably it is 0.1-0.6 mass%.

  In addition to the above components, the dentifrice composition of the present invention includes polyethylene glycol, propylene glycol, sorbitol, glycerin, 1,3-butylene glycol, maltitol, lactitol, xylitol, trehalose, etc. Wetting agents: Nonionic surfactants, cationic surfactants, amphoteric surfactants and other surfactants other than the above anionic surfactants; fragrances; sweeteners; bactericides; preservatives; pH adjusters; β-glycyrrhetinic acid And various medicinal components such as tocopherol, various dentifrice granules and the like can be appropriately contained.

  The helipath viscosity at 25 ° C. of the dentifrice composition of the present invention is preferably 1000 to 5000 dPa · s from the point of view of combining good shape retention, dispersibility in the oral cavity, feeling of use, etc., from immediately after production to storage. s, more preferably in the range of 1500 to 4500 dPa · s. In addition, for example, the helipath viscosity at 25 ° C. of the dentifrice composition of the present invention after storage is the value when the helipath viscosity at 25 ° C. of the dentifrice composition of the present invention after storage for one day immediately after production is defined as 100% as a reference The ratio (%) of the increased viscosity is preferably 250% or less, more preferably 200% or less, and still more preferably 180% or less.

  The helipath viscosity is a value measured using a T-shaped spindle as a rotor. After filling the dentifrice composition in a container for viscosity measurement and storing it in a thermostat at 25 ° C. for 24 hours, Using a viscometer (Toki Sangyo VISCOMETER TVB-10), it can be measured at 25 ° C. under conditions of rotor C, rotation speed 2.5 rpm, and 1 minute.

  Hereinafter, the present invention will be specifically described based on examples. In addition, unless otherwise indicated in a table | surface, content of each component shows the mass%.

[Examples 1-7, Comparative Examples 1-3]
Each dentifrice was prepared according to the formulation shown in Tables 1-2. Using the obtained dentifrice, it measured and evaluated according to the following method.

《Helipath viscosity》
The prepared dentifrice composition is packed in a container for viscosity measurement and stored in a thermostatic chamber at 25 ° C. for one day. C, Helipath viscosity after storage for 1 day was measured under the conditions of 2.5 rpm for 1 minute.
Next, the sample was stored in a 25 ° C. incubator immediately after the preparation until 2 weeks later, and the helipath viscosity after storage for 2 weeks was measured by the same method.
The results are shown in Table 1.

<Comprehensive evaluation of viscosity increase inhibiting effect>
From the value of the helicopter viscosity, the ratio (%) of the viscosity of the helipath viscosity after storage for 2 weeks, with the helipath viscosity after storage for 1 day being 100% as a reference, was obtained and used as an index of the effect of suppressing the increase in viscosity.
The results are shown in Table 1.

<< Evaluation of foaming and flavor >>
Three professional panelists brushed 1 g of each dentifrice obtained in Examples 1 and 5 and Comparative Examples 1 to 3 for a toothbrush (Check Standard, Ordinary, Kao Co., Ltd.) for 3 minutes. From the speed of spreading of bubbles in the inside, good foaming and flavor in the oral cavity were evaluated according to the following criteria. The results of the discussion are shown in Table 2.
The results are shown in Table 2.
<Evaluation criteria for foaming>
A: The spread of foam in the oral cavity is very good. B: The spread of foam in the oral cavity is good. C: The foam spread in the oral cavity is slow. << Evaluation criteria for flavor >>
A: Good B: Almost good C: Salty and uncomfortable

  According to the results of Tables 1 and 2 above, the dentifrice of the example effectively suppresses the increase in viscosity over time and brings about good foaming and good flavor as compared with the dentifrice of the comparative example. It can be seen that it is.

Claims (5)

The following components (A), (B), (C), and (D);
(A) Thickening silica having an oil absorption of 150 to 500 mL / 100 g 2% by mass to 15% by mass,
(B) Water-soluble calcium salt 0.002% by mass or more and 0.1% by mass or less in terms of calcium atom,
(C) A water-soluble polyvalent metal salt other than calcium salt, and (D) 10 to 50% by mass of water, and the molar ratio of component (C) to component (B) ((C) mol / ( B) A dentifrice composition having a mol) of 0.2 or more and 10 or less and an oil absorption of 50 mL / 100 g or more and less than 150 mL / 100 g of abrasive silica content of 10% by mass or less.   The dentifrice composition according to claim 1, wherein a mass ratio ((B) / (A)) of the component (B) in terms of calcium atom and the content of the component (A) is 0.0002 or more and 0.05 or less. object.   Furthermore, the dentifrice composition of Claim 1 or 2 containing an anionic surfactant (E).   Furthermore, dentifrice composition of any one of Claims 1-3 which contains 0.05 mass% or more and 0.8 mass% or less of binder (F).   The dentifrice composition according to any one of claims 1 to 4, wherein the polyvalent metal of component (C) is one or more selected from magnesium, zinc, copper, iron, and aluminum.