JP6973034B2 - Toothpaste products - Google Patents

Description

The present invention relates to a dentifrice product in which a dentifrice composition containing a fluorine-containing compound is filled in a tube container.

Fluoride ion is known as an important component for promoting remineralization for caries prevention, and sodium fluoride, sodium monofluorophosphate, etc. are blended in many dentifrices as fluorine-containing compounds that supply fluorine ions. ing. On the other hand, an abrasive-free composition results in a mild oral composition for the teeth and oral mucosa, and prefers an abrasive-free or low-abrasive dentifrice with such a mild abrasive feel. There are also users.

However, a composition containing or not containing a fluorine-containing compound and having a low or no abrasive content has usability such that the agent drips from the mouth of the container and the agent collects on the cap of the container when stored in the toothpaste tube. When the problem of badness arises and the content of the fluorine-containing compound becomes high, the problem becomes remarkable.

Japanese Unexamined Patent Publication No. 6-157258 Japanese Unexamined Patent Publication No. 4-210908

The present invention has been made in view of the above problems, and has good usability, stability in appearance storage at high temperature, dispersibility of the composition in the oral cavity, and fluorine retention effect, and has a low abrasive content or no compounding. It is an object of the present invention to provide a dentifrice product in which a dentifrice composition is filled in a tube container.

As a result of diligent studies to achieve the above object, the present inventors have mixed three binders (polyacrylic acid or a salt thereof, carrageenan, and xanthan gum) in a specific ratio and stored them in a specific toothpaste container. A dentifrice containing a fluorine-containing compound that does not easily drip, is easy to extrude, has excellent appearance storage stability at high temperatures, and has good dispersibility and fluorine retention effect of the composition in the oral cavity. It was discovered that the dentifrice product of the above can be obtained, and the present invention was made.

Therefore, the present invention provides the following dentifrice products.
[1]. (A) Fluorine-containing compound,
(B) Polyacrylic acid or a salt thereof,
It contains (C) carrageenan and (D) xanthan gum, and the content mass ratio of component (B) / component (C) is 1.4 to 10.
A dentifrice composition having a component (B) / component (D) content of 1.4 to 10 and an abrasive content of 10% by mass or less has a body deformation resistance of 0.3 to 1. A dentifrice product filled in a tube container having a tube diameter of 5N, a tube diameter of 27 to 40 mm, and a spout inner diameter of 1 to 3 mm.
[2]. (A) The dentifrice product according to [1], wherein the component is sodium fluoride.
[3]. (A) The dentifrice product according to [2], wherein the content of sodium fluoride is 0.02 to 0.66% by mass in the dentifrice composition.
[4]. The dentifrice product according to [1], [2] or [3], wherein the dentifrice composition further contains (E) the fatty acid amide propyl betaine.
[5]. The dentifrice product according to any one of [1] to [4], wherein the dentifrice composition does not contain an abrasive.

According to the present invention, a dentifrice composition having a low abrasive content or no compound, which has good usability, stability in appearance storage at high temperature, and good dispersibility and fluorine retention effect of the composition in the oral cavity, is a tube. It is possible to provide a dentifrice product filled in a container.

Hereinafter, the present invention will be described in detail.
(I) Toothpaste composition (hereinafter, may be abbreviated as composition)
[(A) component]
The component (A) is a fluorine-containing compound and has a fluorine retention effect on the tooth surface. Examples of the fluorine-containing compound include sodium fluoride, sodium monofluorophosphate, stannous fluoride, ammonium fluoride, strontium fluoride and the like, and these may be used alone or in combination of two or more. Can be used. Of these, sodium fluoride is preferable.

The content of the component (A) is preferably 100 to 3,000 ppm (mass, the same applies hereinafter), more preferably 500 to 3,000 ppm, and even more preferably 1,100 to 3,000 ppm as the fluorine ion concentration in the composition. In particular, when the component (A) is sodium fluoride, 0.02 to 0.66% by mass is preferable, 0.11 to 0.66% by mass is more preferable, and 0.24 to 0.66% by mass is more preferable. .. When it is 0.02% by mass or more, the retention of fluorine on the tooth surface is further improved, and when it is 0.66% by mass or less, the sagging of the composition can be further suppressed.

[(B) component]
The component (B) is polyacrylic acid or a salt thereof, and has an action of preventing the composition from dripping. The polyacrylic acid or a salt thereof is not particularly limited, and a crosslinked polyacrylic acid or a salt thereof can also be used. For example, Leosic 260H manufactured by Toagosei Co., Ltd. can be used.

The viscosity of polyacrylic acid or a salt thereof at 25 ° C. is preferably 7,000 to 10,000 mPa · s. If the viscosity is less than 7,000 mPa · s, the composition may easily drip, and if it exceeds 10,000 mPa · s, the dispersibility may be deteriorated. The method for measuring the viscosity is as follows.

Weigh 10 g of propylene glycol into a 500 mL poly beaker, add 2.50 g of sample, and disperse well. Add 487.5 g of purified water to the obtained dispersion at a time, and stir well by hand until uniform. Cover with a dry prevention lid and leave it for a whole day and night. Next, the mixture is placed in a constant temperature water bath at 25 ° C. and left for 1 hour, and then measured with a B-type viscometer (No. 5 rotor, measurement time 2 minutes, 20 rpm).

The content of the component (B) is preferably 0.2 to 3% by mass, more preferably 0.45 to 2% by mass, still more preferably 0.6 to 1.5% by mass in the composition. When the content is 0.2% by mass or more, the composition can be further suppressed from dripping, and the appearance preservation stability at high temperature is further improved. Further, when the content is 3% by mass or less, the extrudability is good, the dispersibility in the oral cavity, and the appearance preservation stability at high temperature are further improved.

[(C) component]
The component (C) is carrageenan, which has a fluorine retention effect and an action of preventing the composition from dripping. Examples of the type of carrageenan include κ (kappa) -carrageenan, ι (iota) -carrageenan, and λ (lambda) -carrageenan. These can be used alone or in combination of two or more, and ι (iota) -carrageenan is preferable.

Examples of ι (iota) -carrageenan include carrageenan CF02 manufactured by Sansho Co., Ltd., GENUVISCO type PJ-JPE manufactured by CP Kelco, GENUGEL type CJ, and GENUGEL type WR-78-J, GENUGEL type as κ-type. WG-115 and the like can be used.

The content of the component (C) is preferably 0.1 to 0.6% by mass, more preferably 0.1 to 0.5% by mass, still more preferably 0.2 to 0.4% by mass in the composition. When the content is 0.1% by mass or more, the fluorine retention effect is further improved, the composition can be further suppressed from dripping, and the appearance storage stability at high temperatures is further improved. Further, when the content is 0.6% by mass or less, the extrudability is good, the dispersibility in the oral cavity, and the appearance storage stability at high temperatures are further improved.

[(D) component]
The component (D) is xanthan gum, which has an action of preventing the composition from dripping. As the xanthan gum, for example, Monato gum DA manufactured by CP Kelco Co., Ltd. can be used. When the viscosity is measured by the method specified in the section of Pharmaceutical Additive Standard 2013 "Xanthan Gum", it is preferably 1,000 to 2,000 mPa · s. By setting the viscosity to 1,000 mPa · s or more, dripping of the composition can be further suppressed. Further, if the viscosity is too high, the spinnability may deteriorate.

The content of the component (D) is preferably 0.1 to 0.6% by mass, more preferably 0.1 to 0.5% by mass, still more preferably 0.2 to 0.4% by mass in the composition. By setting the content to 0.1% by mass or more, dripping of the composition can be further suppressed. Further, when the content is 0.6% by mass or less, the extrudability is good, the dispersibility in the oral cavity, and the appearance storage stability at high temperatures are further improved.

The content mass ratio represented by the component (B) / the component (C) is 1.4 to 10, preferably 1.5 to 7, and more preferably 1.7 to 5. If the above ratio is less than 1.4, the agent tends to drip, and if it exceeds 10, the appearance stability at high temperatures deteriorates.

The content mass ratio of the component (B) / the component (D) is 1.4 to 10, preferably 1.5 to 7, preferably 1.7 to 5. If the above ratio is less than 1.4, the agent tends to drip, and if it exceeds 10, the appearance stability at high temperatures deteriorates.

[(E) component]
From the viewpoint of improving the dispersibility in the oral cavity, the composition of the present invention preferably contains (E) fatty acid amide propyl betaine. Examples of the fatty acid amide propyl betaine include coconut oil fatty acid amide propyl betaine and lauric acid amide propyl betaine, and one type alone or two or more types can be appropriately selected and used. Examples of the coconut oil fatty acid amide propyl betaine include TEGO BETAIN CK manufactured by EVONIK.

The content of the component (E) is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass in the composition. When it is 0.1% by mass or more, the dispersibility in the oral cavity is further improved, and when it exceeds 3% by mass, bitterness may occur.

In addition to the above components, the following components can be arbitrarily added to the composition of the present invention as long as the effects of the present invention are not impaired. For example, a binder, a thickener, a surfactant, a sweetener, a pigment, a preservative, a fragrance, a pH adjuster, various active ingredients and the like can be mentioned.

As the binder, components other than (B) polyacrylic acid or a salt thereof, (C) carrageenan, and (D) xanthan gum can be blended as long as the effects of the present invention are not impaired. Specifically, cellulosic binders such as sodium carboxymethyl cellulose, sodium hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, hydroxymethyl ethyl cellulose, methyl cellulose, and cationized cellulose, guagam, montmorillonite, tragant gum, karaya gum, arabia gum, and locust beans. Gum, polyvinyl alcohol, carboxyvinyl polymer, carbopol, silica gel, aluminum silica gel, bee gum, laponite and the like can be mentioned. One or more of these can be blended.

Examples of the viscous agent include sugar alcohols such as sorbitol, xylitol, martitol, and lactitol, polyhydric alcohols such as glycerin, propylene glycol, polyethylene glycol, 1,3-butylene glycol, and polypropylene glycol, and sugar alcohol-reduced starch saccharified products. Can be mentioned. One or more of these can be blended. When the thickener is blended, the content thereof is preferably 5 to 60% by mass in the composition.

As the surfactant, a surfactant usually blended in a dentifrice composition can be blended, and (E) an amphoteric surfactant other than the fatty acid amide propyl betaine, an anionic surfactant, and a nonionic surfactant. Can be blended, and one type alone or two or more types can be appropriately selected and used. When a surfactant is blended, its content is appropriately selected from 0.1 to 4% by mass in the composition.

Examples of the sweetener include saccharin sodium, aspartame, stebioside, stevia extract, paramethoxycinnamic aldehyde, neohesperidyl hydrocalcon, perraltin, thaumatin, aspartylphenylalanine methyl ester and the like.

As pigments, 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 No., titanium oxide and the like.

Examples of the preservative include parabens (paraoxybenzoic acid ester) such as butylparaben, methylparaben and ethylparaben, sodium benzoate and the like.

As fragrances, peppermint oil, sparemint oil, anis oil, eucalyptus oil, winter green oil, cassia oil, clove oil, thyme oil, sage oil, lemon oil, orange oil, peppermint oil, cardamon oil, coriander oil, mandarin oil, Lime oil, lavender oil, rosemary oil, laurel oil, camomill oil, caraway oil, majorum oil, bay oil, lemongrass oil, origanum oil, pine needle oil, neroli oil, rose oil, jasmine oil, iris concrete, absolute Natural fragrances such as peppermint, absolute rose, and orange flower, and fragrances that have been processed (pre-reservoir cut, rear-reservoir cut, distilling, liquid extraction, essence, powder fragrance, etc.) of these natural fragrances. And menthol, carboxylic, anator, cineole, methyl salicylate, cinnamic aldehyde, eugenol, 3-1-mentoxypropane-1,2-diol, timole, linalol, linalyl acetate, limonene, menton, mentyl acetate, N- Substitution-paramentan-3-carboxamide, pinen, octylacedehide, citral, pregon, calbeet acetate, anisaldehyde, ethylacetate, ethylbutyrate, allylcyclohexanepropionate, methylanthranilate, ethylmethylphenylglycidate, vanillin , Undecalactone, hexanal, ethyl alcohol, propyl alcohol, butanol, isoamyl alcohol, hexenol, dimethylsulfide, cycloten, furfural, trimethylpyrazine, ethyllactate, methyllactate, ethylthioacetate and other single fragrances, as well as strawberry flavor and apple. Known fragrance materials used in dentifrice compositions can be used, such as flavors, banana flavors, pineapple flavors, grape flavors, mango flavors, butter flavors, milk flavors, fruit mix flavors, tropical fruit flavors and the like. ..

Examples of the pH adjuster include citric acid and sodium citrate.

The content of the sweetener, the pigment, the preservative, the fragrance, and the pH adjuster can be set to a normal amount as long as the effect of the present invention is not impaired.

Examples of various active ingredients include (A) other than fluorine-containing compounds, specifically, water-soluble phosphoric acid compounds such as potassium salt of orthophosphoric acid and sodium salt, tranexamic acid, epsilon-aminocaproic acid, and allantinchlorhydroxyaluminum. Hinokithiol, ascorbic acid, sodium chloride, dl-tocopherol acetate, dihydrocholesterol, α-bisabolol, chlorhexidine salts, azulene, glycyrrhetin, glycyrrhetinic acid, copper chlorophyllin sodium, chlorophyll, glycerophosphate and other chelating phosphate compounds, copper gluconate, etc. Copper compound, aluminum lactate, strontium chloride, potassium nitrate, hydroxamic acid and its derivatives, sodium tripolyphosphate, zeolite, methoxyethylene, epidihydrocholesterin, benzethonium chloride, dihydrocholesterol, trichlorocarbanilide, zinc citrate, soft extract of Toki , Oubaku extract, chamomile, chouji, rosemary, ogong, benibana and other extracts. The blending amount of these active ingredients can be an effective amount within a range that does not interfere with the effects of the present invention.

The dentifrice composition of the present invention has a low abrasive content of 10% by mass or less in the composition, and when an abrasive is blended, it is preferably 5% by mass or less, and is not blended. Is more preferable. Examples of the abrasive include silica-based abrasives such as silicic acid anhydride, calcium carbonate and the like.

The water content in the dentifrice composition of the present invention is not particularly limited, but is preferably 35% by mass or more, more preferably 35 to 60% by mass.

The viscosity of the dentifrice composition of the present invention at 25 ° C. is not particularly limited, but is preferably in the range of 5 to 20 Pa · s in a B-type viscometer (No. 6 rotor, measurement time 3 minutes, 20 rpm). The present invention can obtain the effect that the combination of the above components and the container are easy to extrude and the composition does not easily drip, and the effect of the present invention cannot be obtained by keeping the viscosity within the above range.

(II) Tube container The material of the container filled with the dentifrice composition of the present invention is not particularly limited, and specifically, a single-layer or multi-layer container such as polyethylene, polypropylene, polyethylene terephthalate, nylon, or aluminum can be used. Can be used.

The deformation resistance of the body of the container is 0.3 to 1.5 N, preferably 0.6 to 1.2 N. If the body deformation resistance is less than 0.3N, the dentifrice composition may easily drip, and if it exceeds 1.5N, it may be difficult to extrude. The deformation resistance of the body is measured using a Tensilon universal material testing machine (for example, RTC-1250A manufactured by A & D Co., Ltd.) using a cylindrical sleeve in which the container is cut to a width of 15 mm as a sample. .. The measurement conditions are compression speed: 40 mm / min, compression jig: φ10 rod, pushing amount: 70% of tube diameter, load cell: 500N.

The tube diameter is 27 to 40 mm, preferably 30 to 37 mm. If the tube diameter is less than 27 mm, it may be difficult to extrude, and if it exceeds 40 mm, the dentifrice composition may easily drip.

The inner diameter of the spout is 1 to 3 mm, preferably 1.5 to 2.5 mm. If the inner diameter of the spout is less than 1 mm, it may be difficult to extrude, and if it exceeds 3 mm, the dentifrice composition may easily drip.

(III) Toothpaste Product The present invention is a dentifrice product having a dentifrice composition and a tube container for filling the dentifrice composition, and the dentifrice composition is filled in the specific tube container. Therefore, by combining such a dentifrice composition and a container, a dentifrice product having good usability, stability of appearance storage at high temperature, dispersibility of the composition in the oral cavity, and fluorine retention effect can be obtained. Can be done. The filling method is not particularly limited, and a normal method can be selected.

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. Unless otherwise specified in the following examples, "%" of the composition is mass% and the ratio is mass ratio.

[Examples, comparative examples]
The dentifrice composition having the composition shown in the table below was prepared by a conventional method. The sodium polyacrylate used in the examples has a viscosity of 8,690 mPa · s (B-type viscometer: No. 5 rotor, measurement time 2 minutes, 20 rpm). The detailed measurement method is as described in the above-mentioned method for measuring the component (B).
The following evaluation was performed on the dentifrice product obtained by filling the container (tube container) shown in the table with the dentifrice composition. The results are also shown in the table.

<Difficult to hang down>
A container was filled with 60 g of the dentifrice composition, and the cap was allowed to stand for 24 hours with the cap half-opened. The amount of the composition accumulated in the cap was measured and evaluated as the ease of dripping of the composition.
[Evaluation criteria]
⊚: <1.0 g
◯: 1.0 to 1.5 g
×:> 1.5 g

<Easy to extrude>
It was evaluated by a sensory test using 10 specialized panelists. The dentifrice composition filled in the container in the same manner as described above was evaluated for ease of extrusion when it was put out on a toothbrush (0.5 g) according to the following evaluation criteria. The results are shown by the following criteria from the average score of the results of 10 people.
[Evaluation criteria]
3: Easy to extrude 2: Slightly difficult to extrude 1: Difficult to extrude [Criteria]
⊚: Average score is 2.5 points or more and 3.0 or less ○: Average score is 1.5 points or more and less than 2.5 points ×: Average score is 1.0 points or more and less than 1.5 points

<High temperature appearance storage stability>
The appearance of the dentifrice composition when the dentifrice composition is filled in a container in the same manner as above, stored at 60 ° C. for 1 month, and then put out on a toothbrush is compared with the appearance of the dentifrice composition immediately after production. , Evaluated according to the following evaluation criteria. Of the three tubes evaluated, the worst sample was evaluated.
[Evaluation criteria]
⊚: No change in appearance ○: Almost no change in appearance ×: There is a clear precipitate and the appearance is inferior.

<Evaluation method of intraoral dispersibility>
It was evaluated by a sensory test using 10 specialized panelists. About 0.5 g of the dentifrice composition filled in the container in the same manner as above was put out on a toothbrush and brushed for 3 minutes, and the dispersibility in the oral cavity during the use of the composition was evaluated according to the following evaluation criteria. The results are shown by the following criteria from the average score of the results of 10 people.
[Evaluation criteria]
4 points: very good 3 points: good 2 points: neither 1 point: bad [judgment criteria]
⊚: Average score is 3.5 points or more and 4.0 points or less ○: Average score is 2.5 points or more and less than 3.5 points ●: Average score is 1.5 points or more and less than 2.5 points ×: Average score is 1.0 points or more and less than 1.5 points

<Fluorine retention effect>
A solution obtained by diluting the dentifrice composition 4-fold with purified water was allowed to act on a hydroxyapatite (HA) disc (diameter Φ7 mm, thickness 3.5 mm, manufactured by PENTAX) for 3 minutes, and immediately washed with purified water. After the HA disk was dried, the upper surface of the HA disk was decalcified with an acid (0.1N HCl: 0.1N NaCl = 1: 1 (volume ratio) mixed solution 50 μL) for 2 minutes to extract fluoride ions. The amount of fluoride ions contained in the solution was measured with a fluorine ion meter (Orion 1115000 4-Star: manufactured by Thermo Fisher Scientific Co., Ltd.). The results are shown by the following criteria based on the average value of N = 6.
[criterion]
⊚:> 0.12 ppm
◯: 0.06 to 0.12 ppm
×: <0.06 ppm

<Viscosity of dentifrice composition>
Measurement was performed using a B-type viscometer (No. 6 rotor, measurement time 3 minutes, 20 rpm).
Example 4: 8.86 Pa · s
Example 1: 11.75 Pa · s
Example 2: 10.66 Pa · s

[Prescription example 1]
A dentifrice composition having the following composition was prepared and filled in a tube container having a body deformation resistance of 0.9 N, a tube diameter of 37 mm, and a spout inner diameter of 2 mm.
composition(%)
(A) Sodium monofluorophosphate 1.1
(B) Sodium polyacrylate 0.7
(C) ι-Carrageenan 0.3
(D) Kintan gum 0.3
(E) Coconut oil fatty acid amide propyl betaine 0.3
Sorbitol (70% aqueous solution) 55
Propylene glycol 3
Xirit 7
Citric acid 0.02
Sodium citrate 0.3
Fragrance 0.5
Purified water balance
100.0 in total
(B) / (C) = 2.3
(B) / (D) = 2.3

Claims (5)

(A) Fluorine-containing compound Fluorine ion concentration of 100 to 3,000 ppm ,
(B) Polyacrylic acid or a salt thereof 0.2 to 3% by mass,
(C) Carrageenan 0.1-0.6% by mass, and (D) Xanthan gum 0.1-0.6% by mass
The content mass ratio of the component (B) / component (C) is 1.4 to 10, the content mass ratio of the component (B) / component (D) is 1.4 to 10, and the content of the dentifrice is A dentifrice composition having a mass ratio of 10% by mass or less is filled in a tube container having a body deformation resistance of 0.3 to 1.5 N, a tube diameter of 27 to 40 mm, and a spout inner diameter of 1 to 3 mm. Agent product. (A) The dentifrice product according to claim 1, wherein the component is sodium fluoride. (A) The dentifrice product according to claim 2, wherein the content of sodium fluoride is 0.02 to 0.66% by mass in the dentifrice composition. The dentifrice product according to claim 1, 2 or 3, wherein the dentifrice composition further contains (E) the fatty acid amide propyl betaine. Dentifrice composition, dentifrice product of any one of claims 1 to 4 which is abrasive-free formulation.