JP6700110B2 - Toothpaste composition - Google Patents

Description

  The present invention relates to a dentifrice composition.

  It is desired that the dentifrice has appropriate shape-retaining property, since it is desired to provide good dispersibility and feel when applied to the oral cavity, in addition to imparting ease of removal to a toothbrush. Be done. Among these, 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 amount 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 giving a light feeling of use, and has a 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 above-mentioned thickening silica is limited to calcium carbonate, after further studying the mechanism for improving the shape retention of the thickening silica, sufficient retention was obtained. In order to secure a good taste and foaming while having formability, a dentifrice has been found in which a specific amount of thickening silica is used in combination with a water-soluble calcium compound having a specific amount in terms of calcium atoms. This is attributed to the fact that the calcium ions liberated from the water-soluble calcium compound dissolved in water act well on the gel formation of the three-dimensional structure of silica.

JP, 2010-280616, A JP, 2013-18710, A

  However, all of the dentifrices described in Patent Documents 1 and 2 above have good shape-retaining properties, but viscosity may increase after storage, and excellent performance is retained over time. Requires further improvement.

  Therefore, the present invention relates to a dentifrice composition capable of effectively suppressing an increase in viscosity with time and ensuring good shape retention even after storage.

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

That is, the present invention provides 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 or more and 15% by mass or less,
(B) Water-soluble calcium salt 0.002 mass% or more and 0.1 mass% or less in terms of calcium atom,
(C) Water-soluble polyvalent metal salt other than calcium salt, and (D) Water 10 mass% or more and 50 mass% or less are contained, The molar ratio of component (C) with respect to component (B) ((C) mol/( B) mol) is 0.2 or more and 10 or less, and the content of 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.

  According to the dentifrice composition of the present invention, the viscosity increase silica and the water-soluble calcium compound in the presence of water can effectively suppress the increase in viscosity over time while favorably forming the three-dimensional structure of the gel. Therefore, good shape retention can be maintained even after storage. In addition, since it also retains a good foam quality after storage, it is possible to provide a comfortable cleaning feeling and a feeling of 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 amount of 150 to 500 mL/100 g as the component (A). Such thickening silica has a larger oil absorption amount than silica used in a dentifrice composition as ordinary polishing silica. As described above, the component (A) and the water-soluble calcium compound of the component (B) described below, which has a specific amount of calcium atoms, are dispersed in the water of the component (D) to dissolve in water. Calcium ions released from the water-soluble calcium compound act on the gel formation of the three-dimensional structure of silica, exhibiting good shape retention as a dentifrice composition, while exhibiting excellent dispersibility in the oral cavity and feeling of use. can do.
The oil absorption amount indicates the amount of oil that can be supported by silica, and the measuring method is specified by the method of JIS K5101-13-2 (established in 2004) and specified by the amount of boiled linseed oil absorbed. Means a value.

The oil absorption of the component (A) is 150 to 500 mL/100 g, preferably 200 to 400 mL/100 g, and more preferably 250 to 380 mL/100 g, from the viewpoint of ensuring good shape retention. As the component (A), commercially available products such as SYLOPURE25 manufactured by Fuji Silysia Chemical Ltd. and SORBOSILTC15 manufactured by CROSFIELD can be used.
The average particle size of the component (A) is preferably 1 to 10 μm, more preferably 1.5 to 9 μm, and further preferably 2 to 8 μm.

  The content of the component (A) is 2% by mass or more, preferably 3% by weight in the dentifrice composition of the present invention, from the viewpoint of ensuring appropriate shape retention, dispersibility in the oral cavity, and feeling of use. It is at least mass%, more preferably at least 4 mass%. Further, 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 an increase in viscosity over time while maintaining an appropriate shape retention property. , Preferably 12% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less. And content of a component (A) is 2 mass% or more and 15 mass% or less 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 the present invention contains, as the component (B), a water-soluble calcium salt in an amount of not less than 0.002 mass% and not more than 0.1 mass% in terms of calcium atom. By dissolving the component (B) in water of the component (D) described later, calcium ions are released, and the calcium ions and the component (A) can form a gel having a three-dimensional structure. Further, a very small amount of calcium ions can effectively form a firm gel, and the component (C) described later can effectively suppress the increase in viscosity over time.

  The water-soluble calcium salt of component (B) means a calcium salt having a solubility in 100 mL of water at 20° C. of 2 g/100 mL or more. Of these, water-soluble calcium salts that can be used in the oral cavity are preferable. In the present invention, since the content of the component (B) is a very small value, the water-soluble calcium salt is added to water in an amount within the range that does not exceed the solubility in water, and the input amount of calcium atom Immediately releases the equivalent amount of calcium ions.

  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 include one or more selected from calcium, calcium glycerophosphate, and hydrates thereof. Among them, from the viewpoint of effectively forming a gel having a three-dimensional structure together with the component (A) and effectively suppressing an increase in viscosity with time in combination with the component (C) described later, water of the component (B) at 20° C. The solubility in 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. More preferably, one or more selected from calcium gluconate, calcium chloride, calcium lactate and calcium glycerophosphate.

  The amount of component (B) converted to calcium atoms 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. It is preferably 0.01% by mass or more, and more preferably 0.03% by mass or more. In addition, the equivalent amount of calcium of the component (B) is from the viewpoint of securing good foaming while suppressing the increase in viscosity with time by using the component (C) described later together and suppressing the deterioration of flavor due to salty taste. In the dentifrice composition of the present invention, it is 0.1% by mass or less, preferably 0.08% by mass or less, and more preferably 0.07% by 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, and more preferably 0.03 to 0.07 mass %.

The content of the component (B) may vary depending on its type, but when it is dissolved in water, it is prepared by appropriately calculating based on the calcium atom conversion amount so that the above-mentioned amount of calcium ion can be released. do it. For example, the content of the component (B) in the dentifrice composition of the present invention is preferably 0.025 to 1.2% by mass, more preferably 0.1 to 1% by mass, and further preferably It is 0.35 to 0.8% by mass, and further preferably 0.3 to 0.75% by mass. Further, specifically, when calcium gluconate is used as the component (B), the content of the calcium gluconate in the dentifrice composition of the present invention is preferably 0.022 to 1.1% by mass. %, more preferably 0.1 to 1% by mass, still more preferably 0.3 to 0.8% by mass.
Further, the molar concentration of the component (B) may be appropriately calculated and prepared based on the above calcium atom conversion amount. Specifically, for example, in the dentifrice composition of the present invention, preferably 0.0005 to 5 The amount is 0.025 mol/L, more preferably 0.0025 to 0.02 mol/L, and further preferably 0.0075 to 0.017 mol/L.

  The mass ratio ((B)/(A)) between the amount of component (B) converted to calcium atom and the content of component (A) effectively suppresses an increase in viscosity with time while maintaining an appropriate shape retention property. From this viewpoint, it is preferably 0.0002 or more, more preferably 0.001 or more, and further preferably 0.003 or more. In addition, the mass ratio ((B)/(A)) between the amount of calcium atom equivalent of the component (B) and the content of the component (A) makes it possible to suppress increase in viscosity with time by using the component (C) together. However, from the viewpoint of ensuring good foaming, it is preferably 0.05 or less, more preferably 0.02 or less, still more preferably 0.015 or less. The mass ratio ((B)/(A)) between the amount of component (B) converted to calcium atoms and the content of component (A) is preferably 0.0002 to 0.05, more preferably 0. 0.001 to 0.02, and more preferably 0.003 to 0.015.

  The dentifrice composition of the present invention contains a water-soluble polyvalent metal salt other than the calcium salt as the component (C). The present inventors have found 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 of increasing the viscosity after storage. The present inventors have found that the combined use of the component (C) effectively suppresses this. What suppresses an increase in viscosity due to the action of polyvalent metal ions released from the water-soluble polyvalent metal salt of component (C) on the three-dimensional structure of the gel constructed by component (A) and component (B) it is conceivable that.

  The water-soluble polyvalent metal salt of the component (C) means a polyvalent metal salt other than the calcium salt, which has a solubility in 100 mL of water at 20° C. of 2 g/100 mL or more, like the component (B). Of these, water-soluble polyvalent metal salts that can be used in the oral cavity are preferable. Specific examples of the polyvalent metal of the component (C) include one or more selected from magnesium, zinc, copper, iron, and aluminum, and from the viewpoint of excellent effect of suppressing viscosity increase, One or more selected from magnesium, zinc, and aluminum are preferable. Examples of the salt of the component (C) include sulfuric acid, gluconic acid, and nitric acid, and sulfuric acid and gluconic acid are preferable from the viewpoint of excellent effect of suppressing viscosity increase. From the viewpoint of applicability in 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) is 0.2 or more from the viewpoint of ensuring good foaming while suppressing an increase in viscosity over time. It 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 with time while maintaining an appropriate shape retention property. It is 10 or less, preferably 8 or less, and 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, and more preferably 0.5 to 7 and more preferably 1 to 7 when the component (C) is a magnesium salt.

The content of the component (C) may vary depending on its type, but it may be appropriately calculated and prepared based on the above molar ratio. For example, the content of the component (C) in the dentifrice composition of the present invention is preferably 0.05 to 2.0% by mass, more preferably 0.1 to 1.5% by mass, and It is preferably 0.2 to 1.2% by mass.
Further, 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. 2 mol/L, more preferably 0.004 to 0.1 mol/L, further preferably 0.005 to 0.08 mol/L, and when the component (C) is a magnesium salt. Is more preferably 0.01 to 0.08 mol/L.

The dentifrice composition of this invention contains 10 mass% or more and 50 mass% or less of water as a component (D). As a result, a firm gel is formed together with the components (A) and (B) to maintain a good shape retention property, while suppressing a decrease in foaming, thereby providing a good dispersibility in the oral cavity and a feeling of use. Can be secured. From such a viewpoint, the content of the component (D) in the dentifrice composition of the present invention is 10% by mass or more, preferably 11% by mass or more, more preferably 12% by mass or more, 50 It is not more than 30% by mass, preferably not more than 40% by mass, more preferably not more than 30% by mass.
Here, the water of the component (D) in the present invention means not only purified water or the like mixed in the dentifrice composition, but also, for example, a 70% sorbitol liquid (aqueous solution), the component (B) and the component (C) used in the formulation. ), the total water content contained in the dentifrice composition, including the water content contained in each compounded component.

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

The dentifrice composition of the present invention has a viscosity over time due to component (C) in the presence of a gel having a three-dimensional structure consisting of water of component (D), calcium ions of component (B) and silica of component (A). From the viewpoint of maintaining good rise suppressing effect and ensuring the dispersibility of the toothpaste composition in the oral cavity, the content of 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. Restrict. The abrasive silica has a smaller oil absorption than the thickening silica of the component (A), and the oil absorption has a value specified by the same method as described above.
The oil absorption 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 the abrasive silica is a dentifrice composition of the present invention from the viewpoint of keeping good effect of suppressing viscosity increase over time, the dispersibility of the dentifrice composition in the oral cavity, and the viewpoint of ensuring a good feeling of use. The content 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 ensuring the tooth stain removal ability. 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 effectively suppressing an increase in viscosity with time and ensuring good foaming. Examples of the component (E) include acylamino acid salts such as sodium acylglutamate and sodium acylsarcosine, alkyl phosphate salts such as sodium alkyl phosphate, alkyl sulfate ester salts, higher fatty acid sulfonated monoglyceride salts, and isethionic acid fatty acids. One or more selected from ester salts, N-methyl long-chain acyl taurine sodium salt, polyoxyethylene monoalkyl phosphate and the like can be mentioned. Among them, an alkyl sulfate ester salt is preferable from the viewpoint of providing good foaming and the viewpoint of availability and the like, and an acylamino acid salt and sodium N-methyl long-chain acyltaurine salt from the viewpoint of having both good foaming and low irritation. Salts are preferable, and these may be used in combination.

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

  In addition to the above components, the dentifrice composition of the present invention effectively suppresses an 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. Further, it may further contain a binder (F). Examples of the component (F) include sodium alginate, sodium carboxymethyl cellulose, carrageenan, xanthan gum, sodium polyacrylate, hydroxyethyl cellulose, hydroxypropyl cellulose, pectin, tragacanth gum, gum arabic, guar gum, karaya gum, locust bean gum, gellan gum, One or more selected from tamarind gum, psyllium seed gum, polyvinyl alcohol, sodium chondroitin sulfate, methoxyethylene maleic anhydride copolymer and the like can be mentioned. Of these, one or more selected from sodium carboxymethyl cellulose, carrageenan, and xanthan gum are preferable.

  The content of the component (F) is to increase the viscosity more than necessary in the presence of water of the component (D), calcium ions of the component (B) and gel of three-dimensional structure of silica of the component (A). From the viewpoint of ensuring good shape retention while suppressing the above, 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 Is 0.1% by mass or more. In addition, the content of the component (F) is increased more than necessary in the presence of water of the component (D), calcium ions of the component (B), and gel of three-dimensional structure of silica of the component (A). From the viewpoint of suppressing the above, and from the viewpoint of ensuring a good feeling in use, 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 further preferably It is 0.6 mass% or less. The content of the component (F) in the dentifrice composition of the present invention is preferably 0.05 to 0.8% by mass, more preferably 0.07 to 0.7% by mass, and It is preferably 0.1 to 0.6% by mass.

  In addition to the above components, the dentifrice composition of the present invention contains polyethylene glycol, propylene glycol, sorbitol, glycerin, 1,3-butylene glycol, maltitol, lactitol, xylitol, trehalose, etc. within a range that does not impair the effects of the present invention. 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 Various medicinal components such as and tocopherol, various granules for dentifrice and the like can be appropriately contained.

  The helipass viscosity of the dentifrice composition of the present invention at 25° C. is preferably 1000 to 5000 dPa from immediately after production until storage, from the viewpoint of having good shape retention, dispersibility in the oral cavity, and feeling of use. s, more preferably 1500 to 4500 dPa·s. Further, for example, the helipass viscosity of the toothpaste composition of the present invention after storage at 25° C. is based on the helipass viscosity of the toothpaste composition of the present invention after storage for one day immediately after production at 100° C. The ratio (%) of the viscosity of the increase is preferably 250% or less, more preferably 200% or less, and further preferably 180% or less.

  The helipass viscosity is a value measured by using a T-shaped spindle for the rotor, and the toothpaste composition is packed in a container for viscosity measurement and stored in a thermostat at 25° C. for 24 hours. A viscometer (TOKI SANGYO VISCOMETER TVB-10) can be used to measure at 25° C. under the conditions of rotor C, rotation speed 2.5 rpm, and 1 minute.

  Hereinafter, the present invention will be specifically described based on Examples. Unless otherwise specified in the table, the content of each component is% by mass.

[Examples 1 to 7, Comparative Examples 1 to 3]
Each dentifrice was prepared according to the prescription shown in Tables 1-2. Using the obtained dentifrice, measurement and evaluation were performed according to the following methods.

《Helipas viscosity》
The toothpaste composition immediately after preparation was packed in a container for measuring viscosity and stored in a thermostat at 25°C for 1 day, and then a helipath type viscometer (TOKI SANGYO VISCOMETER TVB-10) was used at 25°C to measure the rotor T- The helipass viscosity after storage for 1 day was measured under the conditions of C, rotation speed 2.5 rpm, and 1 minute.
Then, the mixture was stored in a thermostat at 25° C. immediately after the preparation for a period of 2 weeks, and the helipass viscosity after storage for 2 weeks was measured by the same method.
The results are shown in Table 1.

<<Comprehensive evaluation of viscosity increase suppression effect>>
From the value of the helipass viscosity, the ratio (%) of the viscosity of the helipass viscosity after storage for 2 weeks based on 100% of the helipass viscosity after storage for 1 day was calculated and used as an index of the viscosity increase suppressing effect.
The results are shown in Table 1.

<<Evaluation of foaming and flavor>>
Three specialist panelists brushed 1 g of each dentifrice obtained in Examples 1 and 5 and Comparative Examples 1 to 3 on a toothbrush (Check Standard, Normal, Kao Corporation) for 3 minutes, and then oral cavity of the dentifrice. The goodness of foaming and the taste in the oral cavity were evaluated according to the following criteria from the speed of foam spreading inside. The results of the consultation are shown in Table 2.
The results are shown in Table 2.
<<Evaluation criteria for foaming>>
A: Very good spread of bubbles in the oral cavity B: Good spread of bubbles in the oral cavity C: Slow spread of bubbles in the oral cavity <Evaluation criteria for flavor>
A: Good B: Generally good C: Salty and uncomfortable

  According to the results of Tables 1 and 2 above, the dentifrices of Examples effectively suppress the increase in viscosity over time, bring about good foaming, and have a good flavor, as compared with the dentifrices of Comparative Examples. 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 or more and 15% by mass or less,
(B) Water-soluble calcium salt 0.002% by mass or more and 0.1% by mass or less in terms of calcium atom,
(C) Water-soluble polyvalent metal salt other than calcium salt, and (D) Water 10 mass% or more and 50 mass% or less are contained, The molar ratio of component (C) with respect to component (B) ((C) mol/( (B) mol) is 0.2 or more and 10 or less, and the content of abrasive silica having an oil absorption of 50 mL/100 g or more and less than 150 mL/100 g is 2% by mass or more and 10% by mass or less.   The toothpaste composition according to claim 1, wherein a mass ratio ((B)/(A)) between the amount of component (B) converted to calcium atom and the content of component (A) is 0.0002 or more and 0.05 or less. object.   The dentifrice composition according to claim 1 or 2, further comprising an anionic surfactant (E).   Furthermore, the dentifrice composition according to any one of claims 1 to 3, which contains 0.05% by mass or more and 0.8% by mass or less of a 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.