JP5894792B2 - Solid bath agent - Google Patents

Description

  The present invention relates to a solid bath agent.

  Conventionally, a solid bath agent containing a liquid bath component such as a fragrance or a surfactant is known, and when the bath agent dissolves in the bath water, the liquid bath component diffuses into the bath water and has various functions. Bring. In such a solid bath agent, it is required that the liquid bath component does not have an adverse effect during molding, during transportation, or during storage until it is used. In addition, it is known that a bath agent containing a carbon dioxide gas generator can impart an excellent warm bath effect due to the generation of carbon dioxide gas, but if the content of a liquid bath component is increased while containing a carbon dioxide gas generator, it is preserved. There is a possibility that carbon dioxide gas is generated therein and the bag-shaped packaging material swells.

  On the other hand, carboxymethylcellulose or a salt thereof obtained by lightly carboxymethylating cellulose is a component that is harmless to the human body and excellent in water absorption and moisture retention, and is expected to be used in various fields such as food and medicine. (See Patent Document 1). For example, Patent Document 2 discloses a bath agent packaged in such a sheet using carboxymethyl cellulose having a substitution degree of carboxymethyl group per glucose unit of 0.1 to 1.0 or a salt thereof as a base material of the sheet. It is disclosed.

JP 2008-56889 A JP 2001-240124 A

  However, the degree of etherification of carboxymethylcellulose actually used in the examples of Patent Document 2 is as high as 0.65, and bath preparations containing carboxymethylcellulose having an etherification degree of 0.5 or less are known. Not.

  Therefore, the object of the present invention is to provide a solid bath agent that combines high storage stability, good moldability and excellent solubility while maintaining good non-aqueous liquid bath components such as surfactants and oily components. Is to provide.

  Therefore, the present inventor has made various investigations. As a result, when incorporating a non-aqueous liquid bath component into a solid bath agent containing a carbon dioxide gas generator, carboxymethyl cellulose having a specific degree of etherification or a salt thereof, and / or a specific surface. When the treated cellulose is contained, the non-aqueous liquid bath component is locally retained in the characteristic tertiary structure formed thereby to increase the content of the non-aqueous liquid bath component. It was found that a solid bath agent capable of being obtained was obtained.

That is, the present invention includes the following components (A), (B) and (C):
(A) Non-aqueous liquid bath component,
(B) Carboxymethyl cellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof (b-1) and / or cellulose (b-2) surface-treated with a water-soluble polymer, and (C) carbonic acid A solid bath agent containing a gas generant is provided.

  According to the present invention, the non-aqueous liquid bath component can be satisfactorily retained in the solid bath agent, and the non-aqueous liquid bath component oozes out during molding, or carbon dioxide gas is generated during storage, resulting in a bag-like shape. It can suppress that a packaging material expand | swells. In addition, when it is introduced into the bath water, it exhibits excellent solubility, and the non-aqueous liquid bath components can be diffused well into the bath water. Therefore, the added value can be sufficiently increased by increasing the content of the non-aqueous liquid bath component.

Hereinafter, the present invention will be described in detail.
The solid bath agent of the present invention contains a non-aqueous liquid bath component (A). The non-aqueous liquid bath component is liquid at room temperature (25 ° C.) and means a bath component other than water. Preferred non-aqueous liquid bath components (A) include oily components and surfactants. These may be used alone or in combination of two or more. These components (A) for non-aqueous liquid bath can bring about actions unique to each component, for example, actions such as warm bathing effect, imparting aroma, moisturizing effect and the like.

  Specific examples of the oily component that can be used as the component (A) include cetyl octanoate, cetyl isooctanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, isocetyl myristate, and octyl myristate. Dodecyl, isopropyl palmitate, isostearyl palmitate, isopropyl adipate, butyl stearate, isocetyl stearate, isotridecyl isononanoate, decyl oleate, cholesterol isostearate, butyl laurate, isoamyl laurate, methyl myristate, ethyl myristate , Ethyl stearate, isononyl isononanoate, isopropyl linoleate, isostearyl isostearate, isopropyl isostearate, oleic acid Fatty acid esters such as oleyl, ethyl oleate and oleyl oleate; fatty acid glycerides such as tri (caprylic acid / capric acid) glycerin and glyceryl tricaprylate having a fatty acid ester structure in the molecule; soybean oil, nuka oil, jojoba oil Natural oils such as avocado oil, almond oil, olive oil, cocoa butter, sesame oil, persic oil, castor oil, coconut oil, mink oil, oils obtained by hydrogenating these natural oils and fats and myristic acid glycerides, 2-ethyl Glycerides such as hexanoic acid glyceride; hydrocarbon oils such as liquid paraffin, squalane, squalene, dioctylcyclohexane, bristan; higher fatty acids such as oleic acid, linoleic acid, linolenic acid, lanolinic acid, isostearic acid; ethanol, isopropyl alcohol, Glycerin, o Alcohols such as yl alcohol and 2-hexyldecanol; polyethers such as liquid polyethylene glycol having a number average molecular weight of less than 1500; silicone oils; peppermint oil, jasmine oil, pepper brain oil, cypress oil, spruce oil, ryu oil, Turpentine oil, cinnamon oil, bergamot oil, mandarin oil, ginger oil, pine oil, lavender oil, bay oil, clove oil, hiba oil, rose oil, eucalyptus oil, lemon oil, thyme oil, peppermint oil, rose oil, sage Essential oils such as oils; terpene hydrocarbon fragrances, sesquiterpene hydrocarbon fragrances such as menthol, cineol, eugenol, citral, citronellal, borneol, linalool, gerall, camphor, thymol, spirantol, pinene, limonene, etc. , Alcohol flavors, ethers Among fragrances such as fragrances, aldehyde fragrances, ketone fragrances, ester fragrances, lactone fragrances, synthetic musks, nitrogen-containing / sulfur compounds and the like, those which are liquid at room temperature (25 ° C.) can be mentioned.

  As the surfactant that can be used as the component (A), for example, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant may be used. Sucrose fatty acid ester, glycerin fatty acid ester, propylene glycol fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, polyoxyethylene polyoxypropylene Glycol, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene polyoxypropylene alkenyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene Ren hydrogenated castor oil, polyglycerol fatty acid esters, sorbitan fatty acid esters, of such nonionic surfactants polyoxypropylene alkyl ether include those liquid at room temperature (25 ° C.). Of these, polyoxyethylene sorbitol fatty acid esters are preferred in that they can increase the effect of the warm bath in combination with the carbon dioxide gas generation product of the component (C) described later and provide a sufficient warm feeling. The average added mole number of the ethyleneoxy group is preferably 20 to 70, more preferably 30 to 60, and most preferably 40 to 50. As for the type of fatty acid, lauric acid, myristic acid, palmitic acid and stearic acid are preferable, and stearic acid is most preferable.

  The content of the non-aqueous liquid bath component (A) is preferably 0.1 to 0.1 in the solid bath preparation of the present invention in terms of sufficiently exhibiting the unique action of the component, moldability, and storage stability. It is 30% by mass, preferably 1 to 20% by mass, and more preferably 3 to 10% by mass.

  The solid bath agent of the present invention contains carboxymethylcellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof, and / or cellulose (B) surface-treated with a water-soluble polymer. Hereinafter, carboxymethylcellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof is referred to as component (b-1), and cellulose surface-treated with a water-soluble polymer is referred to as component (b-2).

  Carboxymethylcellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof (b-1) used in the present invention generally has a degree of etherification of 1.0 or more of carboxymethylcellulose or a salt thereof blended in a bath agent. Since it is -1.5, it is carboxymethylcellulose or its salt with a very low degree of etherification. Such a component (b-1) can unexpectedly contain the non-aqueous liquid bath component of the component (A) in the solid bath agent in the solid bath agent during storage. On the other hand, if it is the solid bath agent of this invention which has this structure, the solid bath agent of this invention thrown into bath water can be dissolved rapidly.

The more preferable degree of etherification of the component (b-1) carboxymethylcellulose or a salt thereof is preferably 0.05 to 0.3 from the viewpoint of achieving both moldability and storage stability and good solubility. More preferably, it is 0.1-0.15. Here, the degree of etherification refers to the degree of substitution of carboxymethyl groups per glucose unit. The degree of etherification can be obtained, for example, according to the CMC industry association analysis method (ashing method). Weigh precisely 1 g of sodium carboxymethylcellulose, put it in a magnetic crucible, incinerate at 600 ° C., titrate sodium oxide produced by incineration with N / 10 sulfuric acid using phenolphthalein as an indicator, and titrate per 1 g of sodium carboxymethylcellulose. YmL can be calculated by putting it in the following formula and the obtained degree of etherification can be shown.
Degree of etherification = (162 × Y) / (10,000-80 × Y)

  Examples of salts of carboxymethyl cellulose include alkali metal salts such as sodium and potassium, ammonium salts, etc. In addition to inexpensive points and easy availability, both moldability and storage stability and good solubility are compatible. In view of the above, sodium carboxymethylcellulose is preferred.

  In addition, the median diameter of the component (b-1) carboxymethyl cellulose or a salt thereof is preferably 1 to 100 μm, more preferably 20 to 20 m from the viewpoint of achieving both moldability and storage stability and good solubility. 50 μm. The median diameter of carboxymethyl cellulose or a salt thereof is a value calculated from a weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve (mesh 2000 to 45 μm) of JIS Z 8801. means.

  Cellulose (b-2) surface-treated with a water-soluble polymer used in the present invention is a cellulose that has been subjected to a treatment such as coating the surface of cellulose with a water-soluble polymer and has increased affinity with water. is there. Such a component (b-2) is a component which exhibits the same effect as a component (b-1) in the agent for solid baths of this invention.

  Examples of the water-soluble polymer for surface-treating the component (b-2) cellulose include carboxymethylcellulose salt, methylcellulose, hydroxycellulose, xanthan gum, karaya gum, dextrin, carrageenan, and alginates. These may be used alone or in combination of two or more. Further, as the cellulose to be surface-treated, normal cellulose, that is, crystalline cellulose or powdered cellulose can be used, and preferably crystalline cellulose can be used.

  The component (b-2) cellulose has a mass ratio of cellulose to water-soluble polymer (cellulose: water-soluble polymer) of 1: 1 to 50 in order to achieve both high hardness and good solubility. : 1 is preferred, 3: 1 to 30: 1 is more preferred, and 4: 1 to 20: 1 is even more preferred.

  In the solid bath agent of the present invention, as the component (B), one of the components (b-1) and (b-2) may be used alone, or both components may be used in combination. . Especially, it is preferable to use a component (b-1) at least from the point which makes high hardness and favorable solubility compatible.

  The content of the component (B) is preferably 0.1 to 20% by mass, more preferably as the total content of the component (b-1) and the component (b-2) in the solid bath preparation of the present invention. 1-15 mass%, More preferably, it is 3-10 mass%.

  The agent for solid baths of the present invention contains a carbon dioxide gas generation product (C). When the solid bath preparation of the present invention is introduced into the bath water, carbon dioxide gas is generated by the component (C), and blood circulation is promoted by the action of this carbon dioxide gas, and the warm bath effect can be enhanced. The carbon dioxide generator is preferably a combination of acid and carbonate. The acid is preferably a solid at room temperature (25 ° C.) from the viewpoint of achieving both moldability and storage stability and good solubility, and either an organic acid or an inorganic acid can be used.

  As the organic acid, for example, fumaric acid, malic acid, tartaric acid, citric acid, maleic acid, succinic acid, phthalic acid, glutaric acid, adipic acid, benzoic acid, salicylic acid, oxalic acid and the like are preferable. Among them, from the viewpoint of storage stability, the solubility is 1 g / 100 g (60 ° C./water) or more, that is, 1 g or more of organic acid is dissolved in 100 g of aqueous solution at 60 ° C., and 10 g / 100 g or less (20 ° C. · More preferably, 10 g or less of the organic acid is dissolved in 100 g of an aqueous solution at 20 ° C. Specifically, fumaric acid, succinic acid, adipic acid and oxalic acid are preferable, and fumaric acid is more preferable. In addition, the median diameter of the organic acid is preferably 10 to 3000 μm, more preferably 60 in terms of providing an effect of sufficiently incorporating the component (A) for the non-aqueous liquid bath component and improving moldability and storage stability. ˜1000 μm. The median diameter of the organic acid means a value calculated from a weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve (mesh 2000 to 45 μm) of JIS Z 8801.

  Examples of the inorganic acid include boric acid, metasilicic acid, and silicic anhydride.

  Examples of the carbonate include sodium carbonate, sodium hydrogen carbonate, magnesium carbonate, potassium carbonate, calcium carbonate and the like. Of these, sodium carbonate and sodium hydrogen carbonate are preferable from the viewpoint of moldability and storage stability. Further, the median diameter of the carbonate is preferably 10 to 3000 μm, more preferably 50 to 1000 μm, from the viewpoint of improving moldability and storage stability. The median diameter of the carbonate means a value calculated from a weight fraction according to the size of the mesh after vibrating for 5 minutes using a standard sieve (mesh 2000 to 45 μm) of JIS Z 8801.

  These acids and carbonates used as the carbon dioxide gas product of component (C) may be used alone or in combination of two or more. Among these, it is preferable to use a combination of a solid organic acid and carbonate at room temperature (25 ° C.).

  The content of the carbon dioxide gas generation product of the component (C) is preferably 30 to 95% by mass in the solid bath agent of the present invention from the viewpoint of securing an appropriate amount of carbon dioxide gas generation and storage stability. 93 mass% is more preferable, and 60-90 mass% is especially preferable.

  The solid bath agent of the present invention preferably further contains cellulose (D) having a degree of etherification of 0 from the viewpoint of more effectively enhancing moldability and storage stability. Component (D) means a component that is not surface-treated with a water-soluble polymer, unlike cellulose (b-2) surface-treated with a water-soluble polymer (B). By containing the cellulose of the component (D), the action of effectively retaining the component (A) by the component (B) can be further enhanced, and as a result, the moldability and storage stability and good solubility can be obtained. Both can be achieved. As such a component (D), for example, crystalline cellulose or powdered cellulose can be used, and preferably powdered cellulose can be used. When the solid bath preparation of the present invention contains the component (D), the mass ratio (B / D) of the component (B) to the component (D) is preferably 0.1 to 5.0, more preferably. It is 0.2-3.0, More preferably, it is 0.5-2.0.

  The content of the cellulose having a degree of etherification of component (D) of 0 is preferably 0.05 to 10% by mass in the solid bath preparation of the present invention, from the viewpoint of achieving both high hardness and good solubility. More preferably, it is 0.1-5 mass%, More preferably, it is 1.5-2.5 mass%.

  In the solid bath agent of the present invention, other bath components can be appropriately blended. In addition to inorganic salts such as magnesium oxide, calcium silicate, sodium metaphosphate, sodium chloride, calcium chloride, magnesium chloride, glucose, antifoaming agents, antioxidants, antibacterial / antifungal agents, Examples include pigments and crude drugs.

  The solid bath preparation of the present invention may be used as a bath preparation that exhibits a granular or granular form by appropriately mixing each component while using a granulating means such as an extrusion granulator or a rolling granulator. It is good also as a bathing agent which exhibits the form of a compression mold, specifically, a tablet by compression molding methods. Even in the case of a solid bath preparation that takes the form of a tablet, it has good solubility while stably holding the component (A), so that the component (A) oozes out during tableting. While effectively preventing and exhibiting excellent moldability, the tablet can be dissolved quickly and the component (A) can be immediately diffused into the bath water when introduced into the bath water.

The solid bath preparation of the present invention is preferably packaged with a packaging material from the viewpoint of more effectively increasing the storage stability, and the water vapor permeability of the packaging material is 0.5 g / m ² · day or less (40 ° C. 75 % RH). When the water vapor permeability is the above value, the solid bath agent absorbs moisture to generate carbon dioxide gas, thereby preventing the packaging material from being swollen or ruptured. Preferred examples of the packaging material include an aluminum film, alumina vapor deposition, or glass vapor deposition polyethylene terephthalate film.

  EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples.

[Examples 1 to 11 and Comparative Examples 1 to 4]
Each component was mixed according to the prescription shown in Tables 1-2, and compressed into a cylindrical shape having a diameter of 5 cm at a pressure of about 10 MPa to produce a tablet (weight: 40 g). Each evaluation was performed according to the following method using the obtained tablet. The results are shown in Tables 1-2.

<< Solubility >>
The obtained tablets were put into a bath water of 40 ° C. and 150 L, and the time (minutes) from the time of charging until the whole amount of the tablets was dissolved was measured.

<Moldability>
The presence or absence of the component (A) at the time of compression molding and the presence or absence of breakage or collapse of the tablet were visually confirmed, and evaluation as moldability was performed according to the following evaluation criteria.
◎: Component (A) did not exude at all, and no breakage or collapse of the tablet was observed. ○: Component (A) did not exude, and damage or collapse of the tablet was hardly observed. At least one of the exudation of component (A) or breakage or collapse of the tablet was observed.

<Storage stability>
The tablet was packaged with an aluminum film (0.5 g / m ² · day or less (40 ° C., 75% RH)). After stacking five of them and measuring their height, they were allowed to stand at 50 ° C. for 10 days to confirm the degree of swelling of the packaging material due to the generation of carbon dioxide gas. Specifically, the height of the five packed tablets after standing was measured, and the ratio (%) was determined as the degree of swelling of the packaging material based on the height before standing, The storage stability was evaluated according to the evaluation criteria.
A: The height of the tablet after standing was less than 105%, and no swelling of the packaging material due to the generation of carbon dioxide gas was confirmed. ○: The height of the tablet in the bag after standing was 105 to 115%. Swelling of packaging material due to carbon dioxide gas generation was slightly confirmed. X: The height of the tablet in the bag after standing exceeded 115%, and the swelling of the packaging material due to carbon dioxide gas generation was remarkable.

  According to Table 1, (B) carboxymethylcellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof (b-1) and / or cellulose (b-2) surface-treated with a water-soluble polymer It can be seen that Examples 1 to 11 containing succinate have both a good moldability and a high storage stability while the dissolution time is shortened. Especially, Examples 6-9 and 11 which contain the carboxymethylcellulose whose etherification degree of a component (D) is 0 exhibit the further outstanding effect.

  On the other hand, Comparative Example 1 containing no component (B) has a long dissolution time, the component (A) oozes out during molding, and the packaging bulges due to the generation of carbon dioxide during storage. On the other hand, even in Comparative Example 2 containing carboxymethylcellulose or a salt thereof having a high degree of etherification instead of component (B) in Example 1, the dissolution time cannot be shortened and the moldability is reduced. It was also found that the storage stability could not be sufficiently improved. Further, even in Comparative Examples 3 to 4 containing dextrin and powdered cellulose instead of component (B), the dissolution time is still long, or the component (A) is oozed out at the time of molding, and storage stability is maintained. It turns out that it falls.

Claims (8)

The following components (A), (B) and (C):
(A) Non-aqueous liquid bath component 3 to 30% by mass ,
(B) Carboxymethyl cellulose having a degree of etherification of 0.01 to 0.5 or a salt thereof (b-1) , and (C) a solid bath agent containing a carbon dioxide gas generation product.   The solid bath preparation according to claim 1, wherein the content of the component (B) is 0.1 to 20% by mass. The solid bath agent according to claim 1 or 2 , wherein the component (A) is liquid at room temperature (25 ° C) and is a bath component other than water. The agent for solid baths according to any one of claims 1 to 3 , wherein the component (C) is a combination of an acid and a carbonate. The solid bath preparation according to any one of claims 1 to 4 , further comprising (D) cellulose having a degree of etherification of 0. The solid bath agent according to any one of claims 1 to 5, wherein the component (A) comprises a polyoxyethylene sorbitol fatty acid ester.   The mass ratio (B / D) of the component (B) to the component (D) is 0.1 to 5.0, The solid bath preparation according to any one of claims 1 to 6. The solid bath agent according to any one of claims 1 to 7 , wherein the solid bath agent is a compression mold.