JP7335758B2 - Effervescent solid bath agent - Google Patents

Description

TECHNICAL FIELD The present invention relates to an foaming solid bath agent.

Effervescent bath agents containing carbonates and organic acids are known to generate bubbles of carbon dioxide gas in the bath water, allowing you to enjoy the sensation of bubbling, as well as to obtain a warming sensation and blood circulation-promoting effect due to carbon dioxide gas. ing. In addition, studies have also been conducted to bring about additional effects and synergistic effects by further blending various components into such bath agents.
For example, Patent Document 1 discloses a solid tablet-type bath agent composition containing an organic acid such as carbonate and fumaric acid, and an aromatic ester such as ethyl benzoate, methyl salicylate, diethyl phthalate, dibutyl phthalate, or dioctyl phthalate. It is disclosed that by blending the same, the scent is mild and the dissolution time in water or hot water can be adjusted to be short.
In addition, menthol has been conventionally blended in bath agents so that a cool feeling can be obtained by taking a bath.
For example, in Patent Document 2, l- A cooling sensation composition containing at least one cooling sensation substance selected from menthol and the like, a salicylic acid ester such as 2-hydroxyethyl salicylate, and a liquid bath agent formulation containing the cooling sensation composition are disclosed. .
Patent Document 3 describes a powder bath agent composition containing l-menthol that has excellent stability, long lasting coolness, and little irritation to the eyes and nose. A powdered cooling agent is disclosed.

JP-A-8-319228 WO2003/074622 JP 2009-203177 A

In recent years, due to the growing health consciousness, there is a growing awareness of exercise such as sports.
When a large amount of a cooling agent such as l-menthol is added to a foaming bath agent such as that disclosed in Patent Document 1, a refreshing or cooling sensation can be felt, while the cooling agent is immediately bathed together with carbon dioxide gas bubbles. Since it spreads in the water, I sometimes felt pain due to cold stimulation when taking a bath.
In addition, the liquid bath agent and powdered bath agent composition containing l-menthol and the like disclosed in Patent Documents 2 and 3 do not foam, and the warming feeling and blood circulation promoting effect of carbon dioxide gas cannot be obtained.
Furthermore, bath agents containing l-menthol and other oily ingredients such as methyl salicylate, which is known as an anti-inflammatory agent, cause swelling of the packaging material when the bath agent is enclosed in the packaging material and stored, resulting in sufficient storage stability. There is a risk that it may not be possible to ensure the quality of the product, and further improvements are required.

The present invention provides an expandable solid that suppresses cold irritation while maintaining the cooling sensation of l-menthol and the like, and that is resistant to swelling of the packaging material and has excellent storage stability even when enclosed in a packaging material and stored. An object of the present invention is to provide a bath agent.

The present inventors have found that an foaming solid bath agent containing fumaric acid, carbonate, l-menthol or a derivative thereof (hereinafter also referred to as l-menthol etc.) further contains methyl salicylate and a water-soluble polymer. It was found that the above problems could be solved by blending in the range of
That is, the present invention
Components (A), (B), (C), (D), and (E) below:
(A) fumaric acid (B) carbonate (C) l-menthol or its derivative (D) methyl salicylate (E) containing a water-soluble polymer that is solid at 25° C. and containing component (C) relative to component (D) The mass ratio [(C)/(D)] is 0.2 or more and 10 or less, and the total mass ratio of the component (C) and the component (D) to the component (E) [{(C) + (D)} /(E)] is 0.01 or more and 1.0 or less.

According to the present invention, the cooling sensation due to l-menthol etc. is maintained while suppressing the cold stimulus, and even when enclosed in the packaging material and stored, the packaging material is less likely to swell and the foaming has excellent storage stability. It is possible to provide a non-toxic solid bath agent.

[Effervescent Solid Bath Agent]
The foamable solid bath agent of the present invention (hereinafter also simply referred to as "solid bath agent") comprises the following components (A), (B), (C), (D), and (E):
(A) fumaric acid (B) carbonate (C) l-menthol or its derivative (D) methyl salicylate (E) containing a water-soluble polymer that is solid at 25° C. and containing component (C) relative to component (D) The mass ratio [(C)/(D)] is 0.2 or more and 10 or less, and the total mass ratio of the component (C) and the component (D) to the component (E) [{(C) + (D)} /(E)] is 0.01 or more and 1.0 or less.

The foaming solid bath agent of the present invention, having the above constitution, suppresses the cold stimulus while maintaining the refreshing feeling of l-menthol and the like, and has excellent storage stability. Although the reason is not necessarily clear, it is considered as follows.
That is, l-menthol or a derivative thereof as component (C) imparts a refreshing sensation as a cooling agent, and methyl salicylate as component (D) imparts a feeling of recovery from fatigue as an anti-inflammatory agent. On the other hand, 1-menthol and the like are irritating and may cause pain due to cold stimulation. , it is difficult to enjoy a refreshing feeling and a feeling of recovery from fatigue.
However, although the reason for this is not clear, by setting the mass ratio [(C)/(D)] of component (C) to component (D) within the above range, while suppressing the irritating properties of l-menthol and the like, , it was found that the refreshing scent of methyl salicylate can promote the cooling sensation during bathing. Therefore, even if a large amount of l-menthol or the like is contained to cause cold stimulation, it is possible to sufficiently feel the cooling sensation while suppressing the irritation.
Furthermore, when the effervescent solid bath agent is enclosed in a packaging material and stored, l-menthol and the like and methyl salicylate contribute to carbon dioxide gas from component (A), which is fumaric acid, and component (B), which is carbonate. Due to the generation reaction of , the packaging material may swell and sufficient storage stability may not be ensured. By setting the mass ratio of to within the above range, such a problem could be solved. Although the reason for this is not clear, component (C) and component (D) are stably supported on component (E), and component (A) and component (B) are formed in the presence of component (C) and component (D). It is considered that the generation of carbon dioxide was suppressed by suppressing the generation reaction of carbon dioxide by.

<Component (A): Fumaric acid>
The solid bath agent of the present invention contains fumaric acid as component (A). By containing the component (A), the solid bath agent of the present invention can generate carbon dioxide gas through the action of the component (B), which will be described later, and can provide a good warming speed as well as a blood circulation promoting effect. . Since fumaric acid has a low solubility in water, when it is used in combination with a carbonate among other organic acids in an effervescent solid bath agent, it has the advantage of preventing choking during bathing.

The content of component (A) in the solid bath agent of the present invention is preferably 25% by mass or more, more preferably 30% by mass or more, still more preferably 30% by mass or more, from the viewpoint of imparting good warming speed and foamability. is 35% by mass or more, more preferably 40% by mass or more. The content of component (A) in the solid bath agent of the present invention is preferably 70% by mass or less, more preferably 65% by mass, from the viewpoint of imparting good moldability, good warming speed and foamability. % or less, more preferably 60 mass % or less, still more preferably 55 mass % or less.
The content of component (A) in all the organic acids contained in the solid bath agent of the present invention is 85% by mass or more from the viewpoint of preventing choking during foaming and ensuring an appropriate amount of carbon dioxide gas generation. It is preferably 90% by mass or more, more preferably 95% by mass or more, and still more preferably 100% by mass.

The solid bath agent of the present invention may contain an organic acid other than fumaric acid (A) as long as the effects of the present invention are not impaired. Examples of such organic acids include carboxylic acid-based compounds, organic sulfonic acid-based compounds, and organic phosphoric acid-based compounds, and one or more of these can be used. Among these, carboxylic acid compounds are preferred from the viewpoint of imparting good solubility in bath water.
The carboxylic acid-based compound may be a compound having at least one carboxy group, and examples thereof include aliphatic carboxylic acids, aromatic carboxylic acids, and heterocyclic carboxylic acids. Aliphatic carboxylic acids include succinic acid, malic acid, citric acid, tartaric acid, maleic acid, glutaric acid, and adipic acid, and aromatic carboxylic acids include benzoic acid, phthalic acid, salicylic acid, and the like. Cyclic carboxylic acids include pyrrolidonecarboxylic acid and the like.
The content of organic acids other than fumaric acid (A) in all organic acids contained in the solid bath agent of the present invention is 15% by mass or less, preferably 10% by mass, from the viewpoint of preventing choking during foaming. Below, more preferably 5% by mass or less, still more preferably substantially 0% by mass.

<Component (B): Carbonate>
The solid bath agent of the present invention contains a carbonate as component (B). Component (B), when the solid bath agent of the present invention is added to bath water, generates carbon dioxide gas by its action with component (A), thereby promoting blood circulation and imparting a good warming speed. can be done.
Component (B) includes alkali metal carbonates such as sodium carbonate and potassium carbonate; alkaline earth metal carbonates such as calcium carbonate and magnesium carbonate; and alkali metal bicarbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; etc., and these may be contained singly or in combination of two or more. Among them, one or more selected from the group consisting of sodium carbonate, sodium hydrogen carbonate, and calcium carbonate is preferable from the viewpoint of imparting good moldability, warming speed, and foamability, and consists of sodium carbonate and sodium hydrogen carbonate. One or two selected from the group are more preferable.
Component (B) preferably contains an alkali metal carbonate from the viewpoint of imparting good moldability, and preferably contains an alkali metal bicarbonate from the viewpoint of imparting a warming speed and good foamability. . That is, component (B) preferably contains an alkali metal carbonate and an alkali metal bicarbonate, and more preferably contains sodium carbonate and sodium hydrogen carbonate.

When an alkali metal carbonate and an alkali metal bicarbonate are contained as component (B), the ratio is not particularly limited. The mass ratio of the bicarbonate [alkali metal bicarbonate/alkali metal carbonate] is preferably 0.2 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and preferably 4.5. It is 0 or less, more preferably 2.0 or less, and still more preferably 1.5 or less.

The content of component (B) in the solid bath agent of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass, from the viewpoint of imparting good warming speed and foamability. % by mass or more, more preferably 25% by mass or more, still more preferably 30% by mass or more, and preferably 65% by mass or less, more preferably 60% by mass or less, still more preferably 55% by mass or less, and more More preferably, it is 50% by mass or less.

The mass ratio [(B)/(A)] of component (B) to component (A) in the solid bath agent of the present invention is preferably 0.5 from the viewpoint of imparting good warming speed and foamability. above, more preferably 0.6 or more, still more preferably 0.8 or more. In addition, the mass ratio [(B)/(A)] is preferably 1.3 or less, more preferably 1.1 or less, and still more preferably 1.0, from the viewpoint of imparting good warming speed and foamability. 0.95 or less, and more preferably 0.95 or less.

<Component (C): l-menthol or derivative thereof>
The solid bath agent of the present invention contains l-menthol or a derivative thereof as component (C). By containing such a component (C), it is possible to impart good cooling sensation and refreshing sensation. Derivatives of l-menthol include, for example, menthyl lactate, menthyl acetate, and menthone. One or more of these component (C) l-menthol or derivatives thereof may be contained, with l-menthol being preferred.
The content of component (C) in the solid bath agent of the present invention is preferably 0.1% by mass or more, more preferably 0, from the viewpoint of providing and sustaining good cooling and refreshing sensations. 0.15% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.25% by mass or more. In addition, the content of component (C) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.7% by mass or less, from the viewpoint of suppressing cold irritation. and more preferably 0.5% by mass or less.

<Component (D): Methyl Salicylate>
The solid bath agent of the present invention contains methyl salicylate as component (D). By containing the component (D), it is possible to provide a refreshing feeling due to the unique scent derived from the component (D), and the sedative and anti-inflammatory effects can provide an effect of recovering from fatigue after exercise such as sports. can be expected. Furthermore, by containing the component (D) and the component (C) in a specific ratio, it is possible to suppress the cold irritation caused by the component (C) while ensuring a cool feeling.
The content of component (D) in the solid bath agent of the present invention is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, from the viewpoint of providing a good refreshing feeling. It is preferably 0.1% by mass or more, and more preferably 0.12% by mass or more. In addition, the content of component (D) is preferably 1% by mass or less, more preferably 0.8% by mass or less, and still more preferably 0.7% by mass, from the viewpoint of suppressing excessive cooling sensation. or less, and more preferably 0.6% by mass or less.

In the solid bath agent of the present invention, the mass ratio [(C)/(D)] of component (C) to component (D) is preferably 0.2 or more, from the viewpoint of enhancement and sustainability of refreshing sensation. is 0.3 or more, more preferably 0.5 or more, and still more preferably 0.7 or more. In addition, the mass ratio of component (C) to component (D) [(C)/(D)] is 10 or less from the viewpoint of suppressing cold irritation caused by component (C) while ensuring a cool feeling. It is preferably 8 or less, more preferably 6.5 or less, and still more preferably 4.5 or less.

<Component (E): Solid water-soluble polymer at 25°C>
The solid bath agent of the present invention contains a water-soluble polymer that is solid at 25°C as component (E) from the viewpoint of imparting good storage stability. In the present invention, the water-soluble polymer refers to a polymer compound that dissolves in 100 g of pure water at 25° C. in an amount of 0.5% by mass or more. It is synonymous with showing 30°C or higher.

Examples of water-soluble polymers include synthetic water-soluble polymers such as polyethylene glycol, polyvinylpyrrolidone, sodium polyacrylate, polyethyleneimine, and polyvinyl alcohol; glue, gelatin, collagen protein, casein, sodium alginate, carrageenan, furcelleran, Natural water-soluble polymers such as tamarind gum, pectin, gum arabic, guar gum, xanthan gum, tragacanth gum, locust bean gum, dextrin, dextran, agar, starch; carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, cellulose acetate phthalate, semi-synthetic water-soluble polymers such as propylene glycol alginate, oxidized starch, esterified starch, etherified starch, cationic starch; can contain. Among them, from the viewpoint of imparting excellent storage stability, one or two selected from the group consisting of polyethylene glycol and dextrin are preferable, and polyethylene glycol is more preferable. The molecular weight of polyethylene glycol is preferably 4,000 or more and 10,000 or less, more preferably 5,000 or more and 9,000 or less.

The content of component (E) in the solid bath agent of the present invention is preferably 1% by mass or more, more preferably 1.5% by mass or more, and still more preferably 3% by mass, from the viewpoint of imparting good storage stability. % or more. In addition, from the viewpoint of securing the amount of carbon dioxide gas generated and providing good warming speed and foamability, the content is preferably 20% by mass or less, more preferably 18% by mass or less, and further preferably 16% by mass or less. is.

The mass ratio [{(C)+(D)}/(E)] of the sum of components (C) and (D) to component (E) enhances the cooling sensation while maintaining sufficient foamability during bathing. From the viewpoint, it is 0.01 or more, preferably 0.02 or more, more preferably 0.03 or more, and still more preferably 0.065 or more. Further, the total mass ratio of component (C) and component (D) to component (E) [{(C) + (D)}/(E)] is the component (C) and component ( From the viewpoint of ensuring excellent storage stability by stably supporting D), it is 1.0 or less, preferably 0.8 or less, more preferably 0.5 or less, and still more preferably 0 .3 or less, and more preferably 0.2 or less.

The solid bath agent of the present invention can appropriately contain, as other components, components commonly used in bath agents. Such components include, for example, sucrose fatty acid esters, polyethylene glycol fatty acid esters, polyoxyethylene alkyl ethers, nonionic surfactants such as polyoxyethylene hydrogenated castor oil, and other surfactants; sodium sulfate, magnesium sulfate, chloride Inorganic salts other than the above components, such as potassium, sodium chloride, potassium nitrate, sodium nitrate, sodium polyphosphate, ammonium chloride, iron sulfate, sodium phosphate, sodium thiosulfate; excipients such as calcium silicate and glucose; medicinal ingredients such as herbal medicines; pigments; fragrances (excluding the above-mentioned components (C) and (D)); oils; and the like.

Perfumes (excluding the above components (C) and (D)) are not particularly limited as long as they can be used in bath agents, and can contain various perfume components.
Such perfumes include, for example, the perfumes described in "Synthetic Perfume Chemistry and Product Knowledge" (Genichi Indo, Kagaku Kogyo Nippo, 2005 revised edition), namely, myrcene, ocimene, camphene, terpinolene, and alpha-terpinene. , phellandrene, alpha-phellandrene, paracymene, farnesene, cedrene, longifolene, copaene, guayene, patchoulene, glujunene, limonene, citral, terpinene and other terpene hydrocarbons or sesquiterpene hydrocarbon fragrances;
One or more selected from alcohol fragrances, aldehyde fragrances, ketone fragrances, ether fragrances, oxide fragrances, ester fragrances, lactone fragrances and the like can be used.
They can also be contained as various perfume preparations according to the desired scent.

(dosage form)
The dosage form (product form) for use of the solid bath agent of the present invention is preferably a tablet. Tablets include compressed tablets and briquette-type preparations, and compressed tablets are more preferable from the viewpoint of sustained foaming.
When the solid bath agent of the present invention is in the form of tablets or briquettes, it can be produced by conventional methods such as compression molding using a press tableting machine or a briquetting machine.
In the production of tablets or briquettes, for example, a powder obtained by dry-blending all the components constituting the solid bath agent of the present invention may be subjected to compression molding. Alternatively, after molding, the mixture obtained by mixing with the remaining ingredients may be subjected to compression molding.

[Effervescent Solid Bath Agent Products]
The present invention can provide a foaming solid bath agent product in which the solid bath agent of the present invention is enclosed in a packaging material. Even when the solid bath agent of the present invention is enclosed in a packaging material and stored, swelling of the packaging material due to generation of carbon dioxide hardly occurs. .
The shape of the packaging material is not particularly limited as long as it has a structure capable of enclosing the bath agent, and examples thereof include bag-like, bottle-like, tray-like, and cup-like shapes. Among these, a bag-shaped packaging material is preferable.
There are no particular restrictions on the material that constitutes the packaging material, as long as it can enclose the bathing agent. For example, in the case of a bag-like packaging material, a resin film, or a laminated film obtained by laminating an inorganic thin film made of metal or metal oxide on a resin film, or the like can be used.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to the scope of the examples.

Examples 1 to 10, Comparative Examples 1 to 4 (production and evaluation of solid bath agents)
Using the powder obtained by mixing each component shown in Table 1, with a rotary tableting machine, the weight is 69 to 71 g, the tablet height is 19.3 to 19.5 mm, and the tableting speed is 20 tablets / The mixture was tableted in minutes to produce a tablet (tablet) type solid bath agent. In addition, the following methods were used to evaluate the cooling sensation, cold irritation, and storage stability. Table 1 shows the results. All of the compounding amounts shown in Table 1 are amounts of active ingredients (% by mass).

<Evaluation of refreshing feeling>
150 L of bath water at 40°C was poured into a bathtub, 70 g (1 tablet) of the solid bath agent of each example was added, and after sufficiently stirring, one expert panelist was allowed to take a bath for 10 minutes, and the cooling sensation was evaluated according to the following criteria. .
A: Extremely cool feeling B: Very cool feeling C: Slightly cool feeling D: No cool feeling at all

<Evaluation of cold irritation>
Pour 150 L of bath water at 40°C into a bathtub, add 70 g (1 tablet) of the solid bathing agent of each example, stir thoroughly, and let one expert panelist take a bath for 10 minutes to evaluate cold irritation according to the following criteria. did.
A: No cold stimulus is felt at all B: Cold stimulus is slightly felt C: Cold stimulus is very much felt D: Cold stimulus is very strongly felt

<Evaluation of storage stability>
After putting 70 g (1 tablet) of the solid bath agent of each example in an aluminum pillow (manufactured by Dai Nippon Printing Co., Ltd., 9 cm x 11 cm) and enclosing it, it was placed in an incubator set at 50°C. The appearance of the aluminum pillow after lapse of months was visually observed and evaluated according to the following criteria.
A: No change in the appearance of the aluminum pillow B: A slight bulge in the appearance of the aluminum pillow C: A clear bulge in the appearance of the aluminum pillow

In Table 1, *1 to *6 are as follows.
* 1: l-menthol, "Menthol JP COS" manufactured by Takasago Perfumery Co., Ltd., active ingredient 100%
*2: Methyl salicylate, "Methyl Salicylate" manufactured by Inoue Perfumery Co., Ltd., active ingredient 100%
*3: Polyethylene glycol, "K-PEG6000 LA" manufactured by Kao Corporation (molecular weight 6,000)
* 4: Dextrin, "Dextrin CZRM-X" manufactured by Nichiden Chemical Co., Ltd.
*5: Fragrance ingredients, fragrance ingredients other than the above components (C) and (D) (mixed fragrance)
*6: Glucose, “Anhydrous crystalline glucose” manufactured by Nihon Shokuhin Kako Co., Ltd.

From Table 1, it can be seen that the solid bath additive of the present invention suppresses cold irritation while maintaining the cooling sensation of l-menthol and the like. It can be seen that the characteristics are excellent.

Table 2 shows formulation examples of the foaming solid bath agent of the present invention.

表２中、＊１～＊６は前記と同じである。

In Table 2, *1 to *6 are the same as above.

According to the present invention, the cooling sensation of l-menthol or the like is maintained while suppressing the cold stimulus, and even when enclosed in the packaging material and stored, the packaging material is less likely to swell and the foaming property is excellent in storage stability. A solid bath agent can be provided.

Claims (4)

Components (A), (B), (C), (D), and (E) below:
(A) fumaric acid (B) carbonate (C) l-menthol , menthyl lactate, menthyl acetate, and one or more selected from the group consisting of menthone
(D) Methyl salicylate (E) containing a water-soluble polymer that is solid at 25°C, and the mass ratio [(C)/(D)] of component (C) to component (D) is 0.2 or more and 10 or less; and the total mass ratio of component (C) and component (D) to component (E) [{(C) + (D)}/(E)] is 0.01 or more and 1.0 or less, foaming Solid bath agent. 2. The solid foaming bath agent according to claim 1, wherein the content of said component (C) in said foaming solid bath agent is 0.1% by mass or more and 1% by mass or less. 3. The solid foaming bath agent according to claim 1, wherein the content of said component (D) in said foaming solid bath agent is 0.01% by mass or more and 1% by mass or less. The foamable solid bath agent according to any one of claims 1 to 3, wherein said component (E) is one or two selected from the group consisting of polyethylene glycol and dextrin.