JP3946682B2 - Bath additive - Google Patents

Description

  The present invention relates to a bath agent having high dispersibility / emulsification ability and excellent usability.

  Bathing agent has various effects inherent to bathing, 1) promotes blood circulation to relieve fatigue, 2) various symptoms such as stiff shoulders / back pain / coldness / neuralgia, skin diseases such as skinnyness / moistness / redness, etc. 3) It is used to enhance the "healing" effect of relaxing mentally, etc. For this reason, bathing agents include various organic / inorganic salts, humectants such as glycerin and polyhydric alcohol, oils and fats and oils with high skin care effect (Patent Document 1, Patent Document 2 and Patent Document 3), crude drug extracts, Vitamins (Patent Document 4), carbonates and organic acids (Patent Document 5) that generate carbon dioxide gas to enhance the warm bath effect, proteins such as collagen, amino acids and enzymes (Patent Document 6), surfactants, high water-solubility A wide variety of drugs / bases such as molecular compounds, saccharides, various fragrances, vibrant pigments and dyes / inorganic pigments are blended, and many techniques are disclosed. Moreover, the form is also various, such as a powder or solid, a thick transparent liquid, a milky milky emulsion emulsified with an oil, a transparent liquid composition emulsified and cloudy after adding hot water (Patent Document 7), etc. is there.

The biggest problem of the bath preparation composition is the extremely dilute use concentration (the amount of use is 40 g, the amount of hot water in a general household bathtub; when it is added to 200 L or more, the total concentration of each component is 200 ppm or less. How) each drug / base can function, which has not been completely overcome so far. The main reason for this is that many of the main bases of bathing agents such as oils and fats, herbal extracts, organic acids, fragrances, and inorganic pigments are sparingly soluble in water. This is not so difficult if a large amount of surfactant is allowed, but with a very small amount of surfactant without foaming bath water, a dilute dispersion or emulsified state can be obtained at a high temperature of around 40 ° C. It is extremely difficult to maintain it stably. On the other hand, other easily soluble bathing agent components and sparingly soluble bathing agent components that have achieved stable dispersion or emulsification have inherently contradictory problems in that they are too dilute to act effectively on the human body. It was out.
Japanese Patent Publication No. 6-99297 Japanese Patent Laid-Open No. 63-190819 JP 52-64415 A JP 56-156210 A Japanese Patent Publication No. 7-72126 JP-A-60-215621 JP-A-8-25866

  An object of the present invention is to provide a bathing agent that can finely disperse or emulsify poorly soluble drugs / bases such as oils, fragrances, and inorganic pigments, and can stably maintain them even at bath temperature. .

  When the present inventors finely disperse or emulsify sparingly soluble bathing agent / base such as oils, fragrances, inorganic pigments, etc., and maintain them stably even at bath temperature, polyglycerol-modified silicone is extremely excellent. It was found that the effect was demonstrated.

  That is, the present invention relates to a bath agent containing polyglycerol-modified silicone, particularly polyglycerol composed of glycerol group or glycidol group represented by the following structural formula (1), (2), (3) or (4). Provided is a bath agent containing a polyglycerol-modified silicone in which the chain is bonded via a linking group to at least one silicon atom of the silicone.

(Here, the polyglycerol chain is bonded to the silicon atom of the silicone chain via a linking group at the methylene carbon atom end of any one of structural formulas (1), (2), (3) or (4), It can be bonded to the methylene carbon atom end of the adjacent structural formula (1), (2), (3) or (4) at the oxygen atom end of the structural formula (1), (2) or (3).
As described above, a polyglycerol chain in which glycerol groups or glycidol groups are bonded to each other via an ether bond has a very flexible skeletal structure. Particularly in a multi-branched polyglycerol chain having a branched structure, half of the hydroxy groups (+1) becomes a highly active primary hydroxy group and a large number of terminal hydroxy groups are confined in a narrow space area with free movement restricted, so chelate multi-element adsorption becomes possible. When bathed in the added bath water, various bathing agent bases can be immediately adsorbed onto the skin. As a result, a fragrance and other medicinal components can be fixed / acted on the skin very efficiently even from a dilute bath additive-added bath water, and an extremely high skin care effect can be exhibited even after the bath is finished. In addition, this polyglycerol-modified silicone has a low intermolecular interaction, low viscosity, and extremely low friction coefficient as its base skeleton, so it is not sticky or null on the skin and is extremely refreshing and refreshing. A feeling of hot water can be provided.

  The bathing agent of the present invention has high blending stability, and when used in a small amount, greatly improves the dispersibility / emulsifying properties of other bathing agent components in bath water, promoting blood circulation, fatigue recovery, skin care effect and relaxation. Various effects inherent to bathing such as effects can be greatly enhanced.

[Polyglycerol chain]
In the present invention, the polyglycerol chain is preferably a branched polyglycerol chain containing a branched glycerol group represented by the structural formula (1) (hereinafter referred to as group (1)). The polyglycerol chain is composed of a group (1), b glycidol groups represented by structural formula (2) (hereinafter referred to as group (2)), and c glycerol represented by structural formula (3). A group (hereinafter referred to as the group (3)) and d terminal glycerol groups represented by the structural formula (4) (hereinafter referred to as the group (4)) are bonded to each other.

  In the polyglycerol chain, the groups (1), (2) and (3) may be bonded to each other in any sequence. As the number of groups (1) increases, the branched structure develops, and the group (4) is present at the end of each branched chain.

When the polyglycerol-modified silicone of the present invention contains a branched structure of the group (1), the presence thereof is a peak peculiar to the group (1) at δ78.0-81.0 ppm in ¹³ C-NMR analysis as described later. Can be easily confirmed. Preferably, the average number of groups (1) per polyglycerol chain is 1 or more.

  In the present invention, the average total number of bonds (a + b + c + d) of the groups (1), (2), (3) and (4) in the polyglycerol chain can be easily determined by NMR analysis or molecular weight comparison with the precursor silicone. However, the number is 1 or more, preferably 3 or more. In order for the polyglycerol-modified silicone of the present invention to maintain appropriate silicone properties, it is more preferably 3 to 201, and more preferably 3 to 101. Is more preferable, it is especially preferable that it is 3-51, and it is most preferable that it is 3-21.

  In the present invention, the average branching ratio in all polyglycerol chains is preferably a / (a + b + c + d) of 1/20 to 1/2, and preferably 1/10 to 1/2 in order to have a sufficient adsorption effect. Is more preferable, and 1/5 to 1/2 is particularly preferable.

  In one polyglycerol chain, 1 to 100 groups (1) are preferably present, more preferably 2 to 100 groups, still more preferably 2 to 50 groups, and more preferably 2 to 25 groups. It is particularly preferred that 2 to 10 are present. 2 to 101 groups (4) are preferably present in one polyglycerol chain, more preferably 3 to 101 groups, and even more preferably 3 to 51 groups, and 3 to 26 groups (4). It is particularly preferred that 3 to 11 are present, and most preferably. The groups (2) and (3) are the same or different and are preferably 0 to 198, more preferably 0 to 196, and more preferably 0 to 96 in one polyglycerol chain. More preferably, it is particularly preferably 0 to 46, and most preferably 0 to 16.

[Linking group]
In the polyglycerol-modified silicone of the present invention, there are no particular limitations on the linking group that binds the silicon atom of the silicone and the polyglycerol chain described above, but a divalent or trivalent group having an ether group is preferred.

The divalent group having an ether group is preferably a group represented by the general formula (5) (hereinafter referred to as a linking group (5)). In the linking group (5), the R ¹ side is bonded to the silicon atom of the silicone chain, and the (A ¹ O) _p side is bonded to the polyglycerol chain.

—R ¹ —O— (A ¹ O) _p − (5)
(Wherein R ¹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group, or an arylene group having 6 to 28 carbon atoms, and A ¹ O is carbon. C1-4 alkyleneoxy group (also referred to as an oxyalkylene group) or arylene group having 6 to 10 carbon atoms (also referred to as oxy arylene group), p is a number of 0 to 30, p pieces of a ¹ O is They may be the same or different.)
In the linking group (5), the arylene group in R ¹ includes an alkylene arylene group, an arylene alkylene group, and an alkylene arylene alkylene group. The alkylene group or alkenylene group preferable as R ¹ is an alkylene group or alkenylene group having 1 to 16 carbon atoms, particularly preferably 1 to 12 methylene, ethylene, propylene, trimethylene, butylene, tetramethylene, pentamethylene, hexamethylene. , Heptamethylene, octamethylene, nonamethylene, decamethylene, undecamethylene, dodecamethylene, tridecamethylene, tetradecamethylene, pentadecamethylene, hexadecamethylene group, and the like. Preferred as the arylene group as R ¹ is an alkylene group And an alkylenephenylene group having 1 to 22 carbon atoms, and a trimethylenephenylene group is preferred. Among these R ¹ , an ethylene group, a propylene group, a trimethylene group, or a trimethylenephenylene group is more preferable, and an ethylene group, a trimethylene group, or a trimethylenephenylene group is particularly preferable from the viewpoint of easy synthesis of raw materials.

As a substituent in R ¹ , a hydroxy group, an amino group (1 to 22 carbon atoms), an imino group (1 to 22 carbon atoms), a carboxy group, an alkoxy group (1 to 22 carbon atoms), an acyl group (1 carbon atom) ~ 22) and the like.

In the linking group (5), A ¹ O is preferably an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, and more preferably an ethyleneoxy group or a phenyleneoxy group.

In the linking group (5), p is preferably 0 to 20, more preferably 0 to 15, further preferably 0 to 10, particularly preferably 0 to 5, and 0 or 1 from the viewpoint of easy availability of raw materials. Most preferably, particularly when R ¹ is an ethylene group or trimethylene group, ¹ is most preferable, and when R ¹ is an alkylene arylene group, 0 is most preferable.

The p A ¹ Os may be the same or different and may be alternating, random or block, or a periodic arrangement other than these, or may be of a random type.

  In the present invention, the most preferred linking group is a divalent linking group represented by the following general formula (7) (hereinafter referred to as linking group (7)). In the linking group (7), the trimethylene side is bonded to the silicon atom of the silicone chain, and the oxygen atom side is bonded to the polyglycerol chain.

  In the linking group (7), the bonding mode of the oxygen atom and trimethylene group bonded to the phenylene group of the oxyphenylene group may be any of the ortho, meta, and para positions, and a mixture thereof. However, the ortho position is desirable from the viewpoint of raw material availability.

Further, in the polyglycerol-modified silicone of the present invention, the linking group that bonds the silicon atom of the silicone chain and the above-mentioned polyglycerol chain may be a trivalent group. Among such linking groups, a group represented by the following general formula (6) (hereinafter referred to as linking group (6)) or a group represented by the following general formula (8) (hereinafter referred to as linking group (8)). Is preferred). In the linking group (6), the R ¹ side is bonded to the silicon atom of the silicone chain, the (A ² O) _q and (A ³ O) _r sides are bonded to the polyglycerol chain, and in the linking group (8), The trimethylene side is bonded to the silicon atom of the silicone chain, and the two oxygen atom sides are each bonded to the polyglycerol chain.

(In the formula, R ¹ represents the above meaning, A ² O and A ³ O each independently represents an alkyleneoxy group having 1 to 4 carbon atoms or an aryleneoxy group having 6 to 10 carbon atoms, and q represents 1 to (The number of 30 and r represents a number of 1 to 30, and q A ² O and r A ³ O may be the same or different.)

In the linking group (6), A ² O and A ³ O are the same or different and are preferably a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group or a phenyleneoxy group, more preferably a methyleneoxy group or It is an ethyleneoxy group.

  In the linking group (6), q and r each represent a number of 1 to 30, preferably 1 to 10, particularly preferably 1 to 5, and most preferably 1.

The q A ² Os and the r A ³ Os may be the same or different. In the case where they are different, the mutual bonding mode of the A ² O and A ³ O may be an alternating type, a block type, or other than these. It may be a periodic array or may be a random type.

  In the linking group (8), for any two of the two oxygen atoms and trimethylene groups bonded to the phenylene group of the oxyphenylene group, the bonding modes are the ortho, meta, and para positions relative to each other. Any of these may be used, or a mixture thereof may be used.

[Polyglycerol-modified silicone]
The silicone forming the polyglycerol-modified silicone of the present invention is derived from a polysiloxane having two or more silicon atoms, and the shape of the polysiloxane may be linear, branched, or cyclic. Good. Moreover, the number average molecular weight of polysiloxane becomes like this. Preferably it is 300-700,000, More preferably, it is 300-200,000, More preferably, it is 1000-20,000. The number average molecular weight can be determined by a gel permeation chromatograph (hereinafter referred to as GPC) method, a light scattering method, or the like.

  The polyglycerol-modified silicone of the present invention is preferably a linear silicone represented by the general formula (9) (hereinafter referred to as silicone (9)).

(In the formula, R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ are the same or different, and are a linking group or a substituent bonded to a polyglycerol chain. A linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkoxy group, or an aryl group having 6 to 22 carbon atoms, which may have a group, R ² , R ³ , R ⁴ , T ⁵ , t ⁶ R ⁶ , R ⁷ , R ⁸ , R ⁹ are at least one linking group to which a polyglycerol chain is bonded, where t is a number from 0 to 10,000. )
In silicone (9), R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ other than the linking group to which the polyglycerol chain is bonded are The same or different, which may have a substituent, is a linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkoxy group, or an aryl group having 6 to 22 carbon atoms, Examples of the alkyl group having 1 to 22 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl, trifluoropropyl group, etc., and alkenyl having 1 to 22 carbon atoms. Examples of the group include a vinyl group and an allyl group. Examples of the alkoxy group having 1 to 22 carbon atoms include methoxy, ethoxy, propoxy, butoxy, pentyloxy, and hexyloxy. Shi, heptyloxy, octyloxy, and a phenoxy group. Examples of the aryl group having 6 to 22 carbon atoms include a phenyl group. In these, a C1-C12 linear or branched alkyl group, a vinyl group, an allyl group, or a phenyl group is preferable, and a methyl group, an ethyl group, a propyl group, or a phenyl group is particularly preferable. Among these, a methyl group is more preferable from the viewpoint of versatility and price, but a phenyl group is more preferable from the viewpoint of heat resistance.

In the silicone (9), R ^{2 to} R ⁹ may have a phenyl group, phenoxy group, hydroxy group, carboxy group, amino group (0 to 14 carbon atoms), imino group, (aminoethyl) ) Amino group, (dimethylaminoethyl) amino group, polyoxyalkylene group, mercapto group, epoxy group, and polysiloxysilyl group. Of these, hydroxy, amino, (aminoethyl) amino, (dimethylaminoethyl) amino, polyoxyalkylene, and polysiloxysilyl groups are particularly preferred. Moreover, when it has these substituents, as R < ² > -R < ⁹ >, an ethyl group or a propyl group is especially preferable.

In the silicone (9), at least one, preferably 1 to 10, more preferably R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ^9. 1 to 5, particularly preferably 1 to 2, are a linking group to which a polyglycerol chain is bonded. This linking group may be located at any of the side chain, one end and / or both ends of the silicone (9), or may be a mixture thereof.

One selected from the group consisting of R ^{2 to} R ⁴ and one selected from the group consisting of R ^{7 to} R ⁹ represent a linking group to which a polyglycerol chain is bonded, and the remaining R ^{2 to} R ⁴ and R ^{When 7 to} R ⁹ , t R ⁵ , and t R ⁶ represent other groups, the polyglycerol-modified silicone of the present invention becomes a polyglycerol-modified silicone having a both-end substitution type, and is higher in water. It is easy to adopt a structure and can exhibit the dispersion / emulsification / adsorption ability more effectively with a small amount of use, and is very preferable as a polyglycerol-modified silicone to be blended in the bathing agent of the present invention. In that case, it is particularly preferable that the remaining R ^{2 to} R ⁴ and R ^{7 to} R ⁹ , t R ⁵ , and t R ⁶ are methyl groups.

When the linking group to which the polyglycerol chain is bonded is present in three or more selected from t R ⁵ and t R ⁶ , the polyglycerol-modified silicone of the present invention is a side chain polysubstituted poly It becomes a glycerol-modified silicone and exhibits a high effect even on a bath base that is more difficult to disperse / emulsify, and is preferred as a polyglycerol-modified silicone to be blended in the bath of the present invention.

  T in the silicone (9) represents a number of 0 to 10,000, preferably a number of 1 to 3,000, more preferably a number of 5 to 500, and particularly preferably a number of 10 to 150. .

  The number average molecular weight of the polyglycerol-modified silicone of the present invention is preferably 500 to 500,000, more preferably 750 to 200,000, and particularly preferably 1,000 to 100,000. The measuring method of this number average molecular weight is based on GPC (in terms of polystyrene or polyethylene glycol).

  The polyglycerol-modified silicone of the present invention has a total number of silicon atoms (Si) in the silicone and groups (1), (2), (3) and (4) in the polyglycerol chain (hereinafter referred to as the number of glycerol groups) ( The ratio (G / Si) of G) is preferably 0.001 to 50, more preferably 0.05 to 10, still more preferably 0.07 to 3, and particularly preferably 0.1 to 1. Within this range, in general, the dispersion / emulsification ability and the base fixing / adsorption ability to the skin are particularly high.

  In the polyglycerol-modified silicone of the present invention, as long as the characteristics of the polyglycerol-modified silicone of the present invention do not significantly inhibit the ability to disperse / emulsify the bath agent / base and the ability to fix / adsorb to the skin. A small amount of ethyleneoxy group and / or propyleneoxy group may be present in the polyglycerol chain. The ethyleneoxy group and / or propyleneoxy group may be present randomly in the polyglycerol chain, or a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in a block form in the polyglycerol chain. It may be. In this case, the block composed of a plurality of ethyleneoxy groups and / or propyleneoxy groups may be present in the vicinity of the linking group of the polyglycerol chain, may be present at the terminal, or may be present in the middle. It may be. When the ethyleneoxy group and / or propyleneoxy group is present, the ethyleneoxy group and / or propyleneoxy group is preferably present in an amount of 0.001 to 0.5 molar equivalents relative to 1 molar equivalent of the glycerol group. More preferably, it is present at 0.02 to 0.2 molar equivalent.

  Such polyglycerol-modified silicone includes, for example, a hydropolysiloxane having a hydrogen atom bonded to a part of a silicon atom in a silicone chain and a polyglycerol compound having an aliphatic unsaturated group in the presence of a platinum-based catalyst. Or by polycyclic siloxane having an epoxy group or a hydroxyl group as a reactive group and ring-opening graft polymerization of glycidol in the presence of an alkali metal catalyst such as potassium.

[Bath additive]
In the bath agent of the present invention, the content of the polyglycerol-modified silicone can be appropriately selected according to the form of the bath agent and the expected effect, and is not particularly limited, but is 0.0001 to 50 mass. % Is preferable, 0.001 to 30% by mass is more preferable, 0.05 to 15% by mass is further preferable, 0.1 to 12% by mass is particularly preferable, and 0.2 to 10% by mass is most preferable.

  The form of the bath agent of the present invention is not particularly limited, and may be a powder form or a powder compressed solid form, or may be a transparent liquid, an emulsion liquid, a transparent form that becomes milky after being added to bath water, or a jelly form. , Pasty or other forms.

  In the bathing agent of the present invention, there are no restrictions on the kind of compounding agents or bases other than polyglycerol-modified silicone and the amount of the compounding agent, and the known bathing agent components as well as other compounds can be used as bathing agents. Any compound that exhibits some effect can be appropriately blended. For example, the following drugs / bases can be exemplified.

  1) Inorganic salts: sodium chloride, potassium nitrate, sodium nitrate, calcium nitrate, aluminum nitrate, sodium polyphosphate, ammonium chloride, sodium nitrate iron phosphate, sodium thiosulfate, sodium carbonate, boric acid, metasilicic acid, anhydrous silicic acid and the like.

  2) Organic acids: benzoic acid, citric acid, fumaric acid, tartaric acid, pyrrolidone carboxylic acid, succinic acid, malic acid and salts thereof.

  3) Herbal medicines / extracts / vitamins: sardines, peanuts, valerian, oysters, kokuboku, senkyu, orange peel, ginger, powdered ginseng, carrots, keihi, peonies, mint leaves, oxon, sanshin, bukuro, dokukatsu, shobu, gaiyou , Pine beetle, peony, jujube, rhinoceros, saffron, acorn extract, chimpi, fennel, campy powder, chamomile, melissa, rosemary, maronier, sorghum grass, rice bran extract, onion extract and garlic extract, arnica, vitamin A, B, C, D, E, F, K, etc.

  4) Oils / fats: cetyl octoate, isopropyl adipate, isopropyl palmitate, isopropyl myristate, glyceryl myristate, butyl stearate, cholesteryl isostearate, coconut oil, olive oil, jojoba oil, soybean oil, almond oil, olive oil, Cypress oil, cinnamon oil, castor oil, coconut oil, lavender oil, eucalyptus oil, rose oil, sage oil, liquid paraffin, white petrolatum, squalane, carnauba wax, beeswax, lanolin, etc.

  5) Dye / pigment / pigments: Ministry of Health and Welfare Ordinance of Red No. 2, Yellow No. 4, Green No. 3, Blue No. 1, Red No. 213, Orange No. 205, Yellow No. 1, Green No. 204, Blue No. 2, etc. Tar pigments I and II pigments, chlorophyll, riboflavin, annatto, canthaxanthin, crocin, cochineal, Benibana, anthraquinone and other natural pigments recognized as food additives, titanium oxide, zinc oxide, calcium carbonate, magnesium carbonate Inorganic pigments such as yellow iron oxide, red iron oxide (Bengara), black iron oxide, ultramarine.

  6) Alcohols: ethanol, stearyl alcohol, isopropyl alcohol, lauryl alcohol, cetyl alcohol, (iso) stearyl alcohol, oleyl alcohol, cholesterol and the like.

  7) Polyhydric alcohol: glycerin, propylene glycol, sorbitol, etc.

  8) Surfactant: Anionic surfactant such as sodium alkyl sulfate, polyoxyethylene alkyl ether sulfate, glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, tetraoleic acid poly Oxyethylene sorbit, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxypropylene alkyl ether, polyethylene glycol fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyglycerin fatty acid ester, etc. Nonionic surfactants, as well as various cationic surfactants and amphoteric surfactants.

  9) Water-soluble polymers: polyacrylic acid, polyvinyl pyrrolidone, polyvinyl alcohol, polyethylene oxide and the like.

  10) Fragrance: Various essential oils (Hacka, Eucalyptus, Lemon, Perpena, Citronella, Kayapte, Salpia, Thyme, Crop, Rosemary, Hysop, Pagele, etc.), formic acid, acetic acid, ethyl formate, propyl formate, acetate ester, amyl nitrite , Scents such as trimethylcyclohexanol, allyl sulfide, essential oils such as jasmine, camomil, neroli, hypnotic scents such as nonyl alcohol, decyl alcohol, phenylethyl alcohol, methyl carbonate, ethyl carbonate, wormwood oil, rosemary Oil, eucalyptus oil, mill oil, phenylacetate, guaiacol, indole, cresol, thiophenol, p-dichlorobenzene, p-methylquinoline, isoquinoline, pyridine, organic amines, camphor, mercaptan, ammonia, hydrogen sulfide Fragrances for appetite suppression, essential oils such as pegle, perilla, marjoram, thyme, laurel, juniper berry, lemon, nutmeg, ginger, onion, garlic, appetite promoting fragrances such as carvone, estragole, elemol, lavender, bergamot , Lemon, Marjoram, Rosemary, Clary Sage, Peppermint, Basil, Rose, Jasmine, Petit Glen, Nuts Meg, Cinnamon, Clove, Mace, Ginger, etc.・ Antidepressant and other fragrances include orange, lemon, bergamot, lavender, rosemary, basil, peppermint, camphor, eucalyptus, clove, cinnamon, nutmeg Essential oils such as mace, ginger, sunflower carrot, artemisia, camphor, salvia, menthol, cineole, eugenol, citral, hydroxycitronellal, absynthic acetic acid, acetate ester, sandalwood oil, costas oil, labdanum oil, amber , Musk, α-pinene, limonene, methyl salicylate, terpene compounds, and the like.

  11) Polysaccharide / protein / amino acid / enzymes: polysaccharides such as starch, carrageenan, hydroxyethylcellulose, methylcellulose, chitin, chitosan, mucopolysaccharides such as sodium carboxymethylcellulose, chondroitin sulfate, hyaluronic acid, collagen, elastin, keratin, hybroin Casein and its derivatives, amino acids such as alanine, glycine, aspartic acid, glutamic acid and threonine, enzymes such as cellulase, protease and lipase, ceramide and nucleic acid (DNA, RNA) and the like.

  The bath agent of the present invention may contain other silicone compounds. Other silicone compounds include dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, alkyl modified silicone, amino modified silicone, alkyl / amino modified silicone, amide modified silicone, alkyl / amide modified silicone, polyether modified silicone, alkyl / Polyether-modified silicone, amino / polyether-modified silicone, amide / polyether-modified silicone, epoxy-modified silicone, fluorine-modified silicone, oxazoline-modified silicone, and their cross-linked products and cyclic silicone, among others, dimethylpolysiloxane , Methylphenyl polysiloxane, amino-modified silicone, polyether-modified silicone, oxazoline-modified silicone, and cyclic silicone are preferred. There.

  In addition to the above, the bathing agent of the present invention includes sulfur, mineral sand, hot spring flower, neutral clay, sodium salicylate, egg yolk powder, iri rice cake, mica powder, kaolin, talc, skim milk powder, l-menthol, camphor, menthol derivative. A cooling sensation agent such as humectant, vasodilator, anti-inflammatory agent, antipruritic agent, bactericidal preservative, chelating agent, thickener and the like may be added.

  In the bathing agent of the present invention, it is desirable to use a suitable combination of polyglycerol-modified silicone and a plurality of the above-mentioned various drugs / bases.

  When the bathing agent of the present invention is poured into bath water, it will spontaneously become cloudy emulsified, and if it is a transparent liquid self-emulsifying bath agent, the moist feeling, smooth feeling and relaxation effect given at the time of bathing will be much higher, bathing The subsequent moisturizing effect and skin care effect are further enhanced, which is preferable. Such a self-emulsifying system may be composed of any drug / base, but for example, a mixture of an oily component and a nonionic surfactant at a high concentration is preferable. The oil component is preferably insoluble or sparingly soluble in bath water, and is preferably liquid or solid at room temperature, and the above-described oil / oil and fat, higher fatty acids, higher alcohols, essential oils, silicones and the like are preferable. . These oil components can be used alone or in combination of two or more. The blending amount of these oily components in the self-emulsifying bath of the present invention is such that the total concentration of oily components is preferably 0.5 to 500 ppm, more preferably 10 to 100 ppm when charged into bath water. As a compounding quantity in the self-emulsification type bath agent of invention, 0.5-50 mass parts is preferable in 100 mass parts of bath agents, and it is more preferable to set it as 10-30 mass parts. Examples of the nonionic surfactant include the nonionic surfactants described above, and any nonionic surfactant may be used as long as it can stably emulsify the oil component in the bath water. These nonionic surfactants can be used alone or in combination of two or more. The blending amount of these nonionic surfactants in the self-emulsifying bath of the present invention is preferably 5 to 200 parts by weight, more preferably 10 to 100 parts by weight, particularly preferably 100 parts by weight of the oily component. Is 15-60 parts by mass.

  If the bath agent of the present invention is an effervescent bath agent, the blood circulation promoting effect is further enhanced, which is preferable. Any foaming agent can be used as long as it is a substance that generates a gas when poured into bath water. For example, a substance that generates carbon dioxide by the reaction of an acid and a carbonate in water; The thing which generate | occur | produces oxygen gas like sodium carbonate can be mention | raise | lifted. As the acid used for the substance that generates carbon dioxide gas by the reaction of an acid and a carbonate in water, either an organic acid or an inorganic acid can be used, and these are preferably water-soluble and solid. Examples of the organic acid include the organic acids and acidic salts thereof, and examples of the inorganic acid include phosphoric acid and acidic sodium hexametaphosphate. Among these, succinic acid, tartaric acid, citric acid, fumaric acid, malic acid, and phosphoric acid are particularly preferable from the viewpoints of price and formulation stability. Examples of the carbonate include sodium hydrogen carbonate, sodium sesquicarbonate, potassium hydrogen carbonate, potassium carbonate, potassium sesquicarbonate, ammonium hydrogen carbonate, ammonium carbonate, and the like. Can be used in combination.

The assignment of each peak in the ¹ H-NMR spectrum of the polyglycerol-modified silicone obtained in the following examples is somewhat shifted depending on the solvent, but is generally as follows.

0.0-0.2 ppm: Si—C H ₃
0.6-0.7 ppm: Si—C H ₂ —CH ₂ — (4H)
_{1.5-1.7ppm: Si-CH 2 -C H} 2 - (4H)
_{2.4-2.7ppm: Si-CH 2 -CH 2} -C H 2 - (4H)
3.3-4.0 ppm: H of polyglycerol chain (excluding terminal hydroxy groups, 5H × number of glycerol groups)
6.7-7.2 ppm: phenol (8H)
In addition, in the ¹³ C-NMR spectrum, the assignment of each carbon-derived peak of the groups (1) to (4) forming the polyglycerol chain was referred to the values described in Macromolecules, 1999, 32, 4240.

The average number of glycerol chains can be determined from the number of H of polyglycerol chains / (5 × number of linking groups) by ¹ H-NMR spectrum.

Synthesis Example 1: Synthesis Example of Branched Polyglycerol-modified Silicone A (Linking Group: —CH ₂ CH ₂ CH ₂ —C ₆ H ₄ —O—) Phenol-modified silicone (trade name; BY16 manufactured by Toray Dow Corning Co., Ltd.) -752 [both ends modified, specific gravity = 0.99 g / mL, viscosity = 110 cSt, hydroxy group equivalent = 1500 (average molecular weight = 3000 equivalent), GPC (column: G4000HXL + G2000HXL (manufactured by Tosoh Corporation)), THF solution (50 mmol / L acetic acid addition), 40 ° C., polystyrene conversion) Measured value; number average molecular weight (Mn) = 2340, weight average molecular weight (Mw) = 4780]) was taken in a flask, and 15 mL of 1M potassium hydroxide ethanol solution was added and stirred. While heating to 95 ° C under reduced pressure, the potassium-modified phenol-modified silane was treated as a pale orange oil. To obtain a cone. Under vigorous stirring, 77.8 g (3.5 equivalents) of glycidol was added over 5 hours using a quantitative feed pump. After further heating and stirring for 20 minutes and cooling to room temperature, a pale yellow viscous oily product was obtained. Ethanol (500 mL) was added to the obtained branched polyglycerol-modified silicone, and potassium was removed and concentrated using a cation exchange resin to obtain a branched polyglycerol-modified silicone A as a slightly yellow oil (yield 99.5%). By analysis of ¹³ C-NMR spectrum, it was confirmed from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) that it was a branched polyglycerol-modified silicone having the group (1). Further, by analysis of the ¹ H-NMR spectrum, the average number of glycerol groups (G) = 7.0 (3.5 on one side), the average number of silicon atoms (Si) = 33.5, and the G / Si ratio is 0.21. According to GPC analysis, the number average molecular weight (Mn) was 2850.

Synthesis Example 2: Synthesis Example of Branched Polyglycerol-modified Silicone B (Linking Group; —CH ₂ CH ₂ CH ₂ —C ₆ H ₄ —O—) Phenol-modified silicone (X-22-1821 manufactured by Shin-Etsu Chemical Co., Ltd.) 200 g of both ends modified, specific gravity = 0.99 g / mL, viscosity = 110 cSt, hydroxy group equivalent = 32 mg KOH / g (average molecular weight = 3500 equivalent)]) was added to the flask, and 8.01 g of 30% potassium methoxide methanol solution was added. While stirring, the mixture was heated to 60 ° C. under reduced pressure, and all the methanol was distilled off to obtain a potassium-modified phenol-modified silicone as a yellow oil. The temperature was raised to 95 ° C., and 21.2 g (2.5 equivalents) of glycidol was added over 4 hours under a stream of argon with vigorous stirring using a metered liquid feed pump. After further heating and stirring for 15 minutes, the mixture was allowed to cool to room temperature to obtain a transparent slightly yellow pasty product. The obtained branched polyglycerol-modified silicone was concentrated after desalting by cation exchange treatment to obtain branched polyglycerol-modified silicone B (213 g) as a high-viscosity slightly yellow oily substance. Yield 96.2%. By analysis of ¹³ C-NMR spectrum, it was confirmed from the presence of a signal (78.0 to 81.0 ppm) derived from the methine carbon of the group (1) that it was a branched polyglycerol-modified silicone having the group (1). Moreover, by analysis of ¹ H-NMR spectrum, the average number of glycerol groups (G) = 5.2 (one side 2.6), the average number of silicon atoms (Si) = 38.5, and the G / Si ratio was 0.14. .

Example 1 and Comparative Example 1
The present invention and comparative bathing agents having the compositions shown in Table 1 were prepared, and blending stability and bathing evaluation were performed by the following methods. The results are shown in Table 1.

<Compounding stability evaluation method>
The bath was stored at 50 ° C. for 3 months, visually observed for changes in appearance, and evaluated according to the following criteria.
◎: Very uniformly emulsified after storage ○: Slight concentration difference is observed, but almost uniformly emulsified ×: Poor emulsification <Bathing evaluation method>
Two bathtubs filled with 200 L of ion-exchanged water at 40 ° C. were prepared, 40 g of the bathing agent of the present invention was added to one side and 40 g of the comparative bathing agent was added to the other side (concentration: 200 ppm), respectively, and uniformly dissolved. After 5 minutes, a specialized panelist evaluated dispersibility, and further performed sensory evaluation on the feeling of use at the time of bathing and after bathing. Sensory evaluation was performed according to the following criteria.

・ Solubility / dispersion stability of components in bath water (visual confirmation)
◎: Dissolve or disperse very uniformly ○: Dissolve or disperse almost uniformly ×: Insoluble matter or precipitates ・ Slip feeling during bathing ◎: Very comfortable slipperiness ○: Slightly slippery × : There is a squeaky feeling.-Blood circulation promotion effect ◎: Blood circulation promotion effect is high. ○: Blood circulation promotion effect is high.-Relaxation effect ◎: Overall, very comfortable. ○: Overall, it is comfortable. Feeling ◎: No stickiness, smooth ○: No stickiness ×: Unpleasant stickiness ・ Moist feeling after 1 hour after bathing ◎: Very moist and moisturizing ○: Moisturized ×: Skin is soft -Residual fragrance after 1 hour after hot water ◎: Refreshing fragrance continues ○: A faint fragrance is felt ×: No residual fragrance

Example 2 and Comparative Example 2
The present invention and comparative bathing agents having the compositions shown in Table 2 were prepared, and bathing evaluation was performed in the same manner as in Example 1. The results are shown in Table 2.

Example 3 and Comparative Example 3
The present invention and comparative bathing agents having the compositions shown in Table 3 were prepared, and bathing evaluation was performed in the same manner as in Example 1. The results are shown in Table 3.

As shown in the results of Tables 1 to 3, the bathing agent of the present invention blended with polyglycerol-modified silicone has improved blending stability and emulsification / dispersibility, and the efficacy of each oil inherent to the bathing agent is greatly improved. It was confirmed.

Claims (3)

It is composed of a glycerol group or a glycidol group represented by the following structural formula (1), (2), (3) or (4) and contains at least one branched glycerol group represented by the structural formula (1). The branched polyglycerol chain is selected from a divalent group represented by the general formula (5), a trivalent group represented by the general formula (6), and a trivalent group represented by the general formula (8). A bath agent containing a branched polyglycerol-modified silicone bonded to at least one silicon atom of silicone through a linking group .

—R ¹ —O— (A ¹ O) _p − (5)
(Wherein R ¹ may have a substituent, a linear or branched alkylene group having 1 to 22 carbon atoms, an alkenylene group or an arylene group having 6 to 28 carbon atoms, and A ¹ O is carbon. C1-4 alkyleneoxy group (also referred to as an oxyalkylene group) or arylene group having 6 to 10 carbon atoms (also referred to as oxy arylene group), p is a number of 0 to 30, p pieces of a ^{1 O} is They may be the same or different.)

(In the formula, R ¹ represents the above meaning, A ² O and A ³ O each independently represents an alkyleneoxy group having 1 to 4 carbon atoms or an aryleneoxy group having 6 to 10 carbon atoms; (The number of 30 and r represents the number of 1 to 30, and q A ² O and r A ³ O may be the same or different.)

Linking group is a group represented by the general formula (7), bath agent according to claim 1.

The bath agent according to claim 1 or 2 , wherein the branched polyglycerol-modified silicone is a silicone represented by the following structural formula (9).

(Wherein R ² , R ³ , R ⁴ , t R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ are the same or different, and a linking group to which a branched polyglycerol chain is bonded, A linear or branched alkyl group having 1 to 22 carbon atoms, an alkenyl group or an alkoxy group, or an aryl group having 6 to 22 carbon atoms, which may have a substituent, R ² , R ³ , R ⁴ , at least one of R ⁵ , t R ⁶ , R ⁷ , R ⁸ , R ⁹ is a linking group to which a branched polyglycerol chain is bonded, and t is a number from 0 to 10,000. Show.)