JP2013136541A - Solid bathing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a solid bathing agent having both appropriate hardness that can effectively maintain a liquid bathing component such as a fragrance or a surfactant with a high content by using carboxymethyl cellulose having a specific etherification degree or a salt thereof, and an excellent solubility.SOLUTION: The solid bathing agent contains the following components (A), (B) and (C): (A) a nonaqueous liquid bathing component; (B) carboxymethyl cellulose having 0.01-0.5 of an etherification degree or a salt thereof (b-1), and/or a cellulose (b-2) subjected to a surface treatment with a water-soluble polymer; and (C) a polyethylene glycol having 1,500-20,000 of number average molecular weight, wherein the mass ratio (B/C) of the component (B) with respect to the component (C) is 0.1-1.5.

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 has been 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. Some of these solid bath agents use polyethylene glycol. For example, Patent Document 1 discloses a bath composition containing a medicinal plant extract dissolved or dispersed in a large amount of polyethylene glycol together with a dissolution and dispersion aid.

  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 2). For example, Patent Document 3 discloses a bath agent packaged in such a sheet using carboxymethyl cellulose or a salt thereof having a substitution degree of carboxymethyl group per glucose unit of 0.1 to 1.0 as a base material of the sheet. It is disclosed.

JP 2005-336060 A JP 2008-56889 A JP 2001-240124 A

  However, in general, a large amount of polyethylene glycol is required in order to maintain a better hardness after enclosing a sufficient amount of liquid bath components in a solid. However, when a large amount of polyethylene glycol is contained in this manner, the solubility of the solid bath preparation tends to deteriorate, and further studies are required to improve the solubility while maintaining good hardness.

  Accordingly, an object of the present invention is to provide a solid bath agent that has appropriate hardness and excellent solubility while maintaining good non-aqueous liquid bath components such as surfactants and oily components. .

  Therefore, the present inventor has made various studies and found that when carboxymethyl cellulose having a specific degree of etherification or a salt thereof and / or cellulose having a specific surface treatment and a specific polyethylene glycol are used in combination, a non-aqueous liquid bath is used. It has been found that a solid bath agent having both high hardness and excellent solubility can be obtained while maintaining the components well.

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) number A solid bath agent containing polyethylene glycol having an average molecular weight of 1500 to 20000 and having a mass ratio (B / C) of component (B) to component (C) of 0.1 to 1.5 is provided.

  According to the present invention, the non-aqueous liquid bath component can be satisfactorily contained in the solid bath agent while having high hardness, and exhibits excellent solubility when introduced into bath water. The water-liquid bath component can be diffused well. Therefore, when molded into a solid bath agent that takes the form of a tablet, there is no risk of non-aqueous liquid bath components leaching out, exhibiting good moldability, and excellent dissolution when introduced into bath water Can demonstrate its sexuality.

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. The preferred non-aqueous liquid bath component (A) is a liquid bath component having a ClogP value of 4 to 18, and examples thereof include oily components and surfactants having a ClogP value of 4 to 18. 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 having a ClogP value of 4 to 18 that can be used as the component (A) include cetyl octanoate, cetyl isooctanoate, myristyl lactate, cetyl lactate, isopropyl myristate, myristyl myristate, Isocetyl myristate, octyldodecyl myristate, 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, isostearic acid Fatty acid esters such as propyl, methyl oleate, ethyl oleate, 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, avocado oil, almond oil, olive oil, cocoa butter, sesame oil, persic oil, castor oil, coconut oil, mink oil, and other natural fats and oils and myristic acid glycerides obtained by hydrogenating these natural fats and oils Glycerides such as 2-ethylhexanoic acid glycerides; hydrocarbon oils such as liquid paraffin, squalane, squalene, dioctylcyclohexane and bristan; higher fatty acids such as oleic acid, linoleic acid, linolenic acid, lanolinic acid and isostearic acid; ethanol , Isopropyl Alcohols such as coal, glycerin, oleyl alcohol, 2-hexyldecanol; polyethers such as liquid polyethylene glycol having a number average molecular weight of less than 1500; silicone oils; mint 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, Essential oils such as rose oil and sage oil; menthol, cineole, eugenol, citral, citronellal, borneol, linalool, gellarol, camphor, thymol, spirantol, pinene, limonene, terpene hydrocarbon fragrances, sesquiterpene Hydrocarbon fragrances, al Among fragrances such as coal fragrances, ether fragrances, aldehyde fragrances, ketone fragrances, ester fragrances, lactone fragrances, synthetic musks, nitrogen-containing / sulfur compounds, etc., the ClogP value is 4 to 18 and room temperature ( 25 ° C.).

  Examples of the surfactant having a ClogP value of 4 to 18 that can be used as the component (A) include any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant. Specifically, 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 Among nonionic surfactants such as castor oil, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxypropylene alkyl ether, etc., ClogP value is 4-18, and room temperature (25 ° C.) And liquid form.

  The content of the non-aqueous liquid bath component (A) is preferably in the solid bath preparation of the present invention in terms of sufficiently exhibiting the unique action of the component and achieving both high hardness and good solubility. It is 0.01-35 mass%, More preferably, it is 0.1-20 mass%, More preferably, it is 0.5-10 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).

  Carboxymethyl cellulose 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 carboxymethyl cellulose 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 exhibit unexpectedly high hardness in combination with polyethylene glycol (C) having a number average molecular weight of 1500 to 20000, which will be described later, in a solid bath agent during storage. The aqueous liquid bath component (A) can be effectively contained in the solid bath agent. On the other hand, if it is the solid bath agent of this invention which has this structure, it will melt | dissolve rapidly when thrown into bath water, and a component (A) can be spread | diffused immediately.

The more preferable degree of etherification of the component (b-1) carboxymethylcellulose or a salt thereof is 0.05 to 0.3, and more preferably 0.1 to 0.2. 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 the salt of carboxymethylcellulose include alkali metal salts such as sodium and potassium, ammonium salts, and the like, and sodium carboxymethylcellulose is preferable from the viewpoints of inexpensiveness, availability, and solubility in bath water.

  Moreover, the average particle diameter of the component (b-1) carboxymethylcellulose or a salt thereof is preferably 1 to 100 μm, more preferably 10 to 50 μm, from the viewpoint of achieving both high hardness and good solubility. .

  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), in combination with the polyethylene glycol (C) having a number average molecular weight of 1500 to 20000, which will be described later, expresses high hardness in the solid bath preparation of the present invention, the component (b-1) and the component The total content of (b-2) is preferably 0.01 to 35% by mass, more preferably 0.1 to 20% by mass, and still more preferably 0.7 to 10% by mass.

  The solid bath agent of the present invention contains polyethylene glycol (C) having a number average molecular weight of 1500 to 20000. Component (C), in combination with component (B), can keep component (A) better than expected. The number average molecular weight is preferably 2000 to 13000, and more preferably 3000 to 9000, from the viewpoint of imparting good solubility while expressing higher hardness. When measuring the number average molecular weight of polyethylene glycol, GPC method using water / ethanol as a solvent and polystyrene as a standard is used.

  The content of the polyethylene glycol as the component (C) is preferably 0.01 to 35% by mass, more preferably 0.00% in the solid bath preparation of the present invention from the viewpoint of achieving both high hardness and good solubility. It is 1-20 mass%, More preferably, it is 0.5-10 mass%.

  In the solid bath preparation of the present invention, the mass ratio (A / C) of the component (A) to the component (C) is preferably from 0.5 to more effectively achieving both high hardness and good solubility. 5, more preferably 0.8 to 2.0. In the case of the solid bath preparation of the present invention, even if the component (A) is highly contained in the component (C), good hardness and good solubility can be obtained by blending a specific amount of the component (B). It is possible to achieve both.

  In the solid bath preparation of the present invention, the mass ratio (A / B) of the component (A) to the component (B) is preferably from 0.1 to more effectively achieving both high hardness and good solubility. It is 10, More preferably, it is 0.5-5.0, More preferably, it is 0.8-2.0.

  In the solid bath preparation of the present invention, the mass ratio (B / C) of the component (B) to the component (C) is 0.1 to 1.5. The mass ratio (B / C) is preferably 0.3 to 1.4, more preferably 0.4 to 1.3 from the viewpoint of more effectively achieving both high hardness and good solubility. is there.

  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 increasing the hardness. By containing the cellulose of the component (D), the component (B) and the component (C) can be combined to increase the hardness and improve the solubility while maintaining the component (A) in a good condition. . As such a component (D), for example, crystalline cellulose or powdered cellulose can be used, and preferably crystalline 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 0.2 to 5, more preferably 0.8. 3 to 3.

  The content of the cellulose having a degree of etherification of component (D) of 0 is preferably 0.01 to 20% 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 0.1-18 mass%, More preferably, it is 0.3-10 mass%.

  The hardness which the agent for solid baths of this invention has can use the penetration hardness measured by using FUDOH RHEOMETER NRM-2010J-CW as a parameter | index, for example. Specifically, a solid bath agent sample to be measured is dissolved in a glass bottle and immersed in an 80 ° C. hot water bath, and then stirred, and the test sample is injected into a cylindrical container having a diameter of 3 cm and a depth of 1 cm. Then, cover with a slide glass, soak the entire container in water at room temperature (25 ° C) to half height, cool and harden. Next, the slide glass is removed, and a 1 mm diameter needle (tip is flat) is lowered vertically at 2.0 cm / min as a measurement probe while being placed in a container, and the maximum stress until it enters 1.0 mm is measured. B), relative value to the maximum stress when the component (C) and the component (D) were similarly measured with a control sample mixed at a ratio of 1.0: 2.0: 1.0 (maximum of the test sample) Stress / maximum stress of control sample) is defined as penetration hardness. In this case, the penetration hardness is preferably 0.5 or more, and more preferably 0.7 or more.

  The solid bath agent of the present invention is used in the form of a granular or granular form by appropriately mixing each component while using a granulating means such as an extruding granulator, a rolling granulator, or dropping. To the granular or granular solid bath agent thus prepared, a desired bath component may be added and mixed to prepare a solid bath agent exhibiting a granular or granular form, such as tableting. You may produce the agent for solid baths which show the form of a tablet with a compression molding method.

  In the case of a solid bath agent prepared by adding and mixing a desired bath component, the content of the non-aqueous liquid bath component (A) in the total amount of the solid bath agent sufficiently exerts the unique action of the component, In terms of achieving both high hardness and good solubility, it is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and further preferably 0.5 to 3% by mass. It is. In addition, the cellulose content of the component (B) in the total amount of the solid bath agent prepared by adding and mixing desired bath components is preferably from the point of expressing high hardness in combination with the component (C). It is 01-10 mass%, More preferably, it is 0.1-6 mass%, More preferably, it is 0.7-4 mass%. Further, the content of the polyethylene glycol of the component (C) in the total amount of the solid bath agent prepared by adding and mixing desired bath components is preferably 0 from the viewpoint of achieving both high hardness and good solubility. 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and still more preferably 0.5 to 3% by mass.

  Even in the case of a solid bath agent that takes the form of a tablet, the once-prepared granular or granular solid bath agent retains high hardness and has good solubility while maintaining stable component (A). In tableting, etc., it effectively prevents the component (A) from oozing out and exhibits excellent moldability, and when it is poured into bath water, the tablet dissolves quickly and the component immediately (A) can be diffused in the bath water.

  As the bath component, it is preferable to add a carbon dioxide gas generator from the viewpoint of obtaining a bath agent to which a warm bath effect or the like is imparted by the generation of carbon dioxide gas. The carbon dioxide generator is preferably a combination of acid and carbonate. As the acid, either an organic acid or an inorganic acid can be used, and those that are solid at room temperature (25 ° C.) are preferable. For example, fumaric acid, malic acid, tartaric acid, citric acid, maleic acid, succinic acid, phthalic acid, Organic acids such as glutaric acid, adipic acid, benzoic acid, salicylic acid and oxalic acid are more preferred. Examples of the inorganic acid include boric acid, metasilicic acid, and silicic anhydride. Moreover, as carbonate, sodium carbonate, sodium hydrogencarbonate, magnesium carbonate, potassium carbonate, calcium carbonate, etc. are preferable. These acids and carbonates may be used alone or in combination of two or more.

  The content of the carbon dioxide generator is preferably 10 to 95% by mass, more preferably 30 to 93% by mass, and still more preferably 50 to 90% by mass in the solid bath preparation of the present invention.

  Furthermore, other bath components can be appropriately blended. In addition to inorganic salts such as magnesium oxide, calcium silicate, sodium metaphosphate, sodium chloride, calcium chloride, and magnesium chloride, such ingredients include sugars such as glucose, antifoaming agents, antioxidants, antibacterial and antibacterial properties. Examples include glazes, pigments, and crude drugs.

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

[Examples 1-6, Comparative Examples 1-5]
In accordance with the formulation shown in Table 1, granules containing a fragrance as a non-aqueous liquid bath component are prepared in advance, and then the granules and each component are mixed and compressed into a cylindrical shape having a diameter of 5 cm at a pressure of about 10 MPa. 40 g) was produced. Each evaluation was performed according to the following method using the obtained granule or tablet. The results are shown in Table 1.

《Penetration hardness》
According to the above-mentioned method, the penetration hardness of granules containing a fragrance as a non-aqueous liquid bath component prepared in advance 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.

<< 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.

  According to Table 1, granules containing 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. It can be seen that in Examples 1 to 6 using the above, the hardness of the granules is high and the moldability and solubility of the resulting tablets are excellent. Especially, Examples 3-4 using the granule which used together the carboxymethylcellulose whose etherification degree of a component (D) is 0, or its salt show the further outstanding effect.

  On the other hand, Comparative Example 1 using granules containing carboxymethyl cellulose having a high degree of etherification or a salt thereof in the same amount as the component (b-1) of Example 1, and granules containing crystalline cellulose or powdered cellulose were used. In Comparative Examples 3 and 5, it can be seen that the hardness of the granules is lower than that in Example 1, and the moldability and solubility of the resulting tablets are also lowered. Further, in Comparative Examples 2 and 4 in which granules in which carboxymethyl cellulose having a degree of etherification of component (D) or a salt thereof was used in combination with carboxymethyl cellulose having a degree of etherification higher than 0.5 or a salt thereof were used in Example 3 It can be seen that the effect cannot be increased as in ˜4, and the solubility of the resulting tablet deteriorates as undissolved residue occurs.

Claims (6)

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) number A solid bath agent comprising polyethylene glycol having an average molecular weight of 1500 to 20000, wherein the mass ratio (B / C) of component (B) to component (C) is 0.1 to 1.5.   The solid bath agent according to claim 1, wherein the content of the component (B) is 0.01 to 35% by mass.   Furthermore, (D) the cellulose of 0 degree of etherification is contained, and mass ratio (B / D) of the component (B) with respect to a component (D) is 0.2-5.0. A solid bath preparation.   The solid bath agent according to any one of claims 1 to 3, wherein the component (A) is liquid at room temperature (25 ° C) and is a bath component other than water.   The water-soluble polymer for surface-treating the cellulose component (b-2) is one or more selected from carboxymethylcellulose salt, methylcellulose, hydroxycellulose, xanthan gum, karaya gum, dextrin, carrageenan and alginates Item 5. The solid bath preparation according to any one of Items 1 to 4.   The cellulose of a component (b-2) contains a cellulose and a water-soluble polymer by the mass ratio of cellulose: water-soluble polymer = 1: 1 to 50: 1. Solid bath agent.