TECHNICAL FIELD

The present invention relates to a specific cation-modified galactomannan polysaccharide functioning as a cationic polymer which, when contained in a cosmetic composition, improves adhesion to hair and skin, exerts good conditioning effects, and achieves satisfactory finish free of rigidity after drying, and to a cosmetic composition, in particular, a hair treatment composition, containing the cation-modified galactomannan polysaccharide.

BACKGROUND TECHNOLOGY

A hair treatment composition for hair cleansing contains a conditioning agent for reducing damage on tangled hair during washing and rinsing and for improving the feeling of hair after washing. Substances that yield conditioning effects must adsorb onto hairs; thus, cationic polymers having ionic adsorption ability are typically used as such substances. Among these polymers, cation-modified cellulose derivatives, cation-modified guar gum, and dimethyldiallyl ammonium chloride derivatives have been widely used. For example, Patent Document discloses the use of a cation-modified cellulose derivative, which incorporates a quaternary nitrogen-containing group, in a shampoo or hair treatment composition. Patent Document 2 discloses cation-modified guar gum having a ratio of mannose (galactomannan polysaccharide) constituting the main chain to galactose constituting the side chain of 2:1, the cation modified guar gum being used as a cationic conditioning polymer in hair care products, such as shampoos, hair rinses, etc., together with insoluble, nonvolatile silicone to improve the appearance of hair. Patent Document 3 discloses a cation-modified galactomannan polysaccharide prepared by depolymerizing a galactomannan polysaccharide, i.e., guar gum or locust bean gum, by decomposition with an enzyme or the like, followed by cationic modification. Patent Document 4 discloses the use of a cation-modified galactomannan polysaccharide prepared by modifying a galactomannan polysaccharide, i.e., guar gum or locust bean gum, with a hydroxyalkyl group, followed by cation modification and depolymerization, in a hair treatment composition and a skin care composition.

However, these cation-modified polymers cause rigidity that is unsatisfactory for users after drying and insufficient conditioning effects during rinsing due to the ratio of the main chain to the side chain of the galactomannan polysaccharide, structural differences caused by the presence or absence of hydroxyalkyl groups, and the difference in viscosity caused depolymerization. In order to overcome these problems, cation-modified locust beam gum and cation-modified tara gum are used. Patent Document 5 discloses use of cation-modified locust beam gum in a hair care product, such as a shampoo or rinse, etc. and reports improved conditioning effects during rinsing and less frictional feel and rigidity after drying in comparison with a product with a cation-modified guar gum. Non-patent Document 1 discloses an example of a hair care product, such as a shampoo or conditioner, containing this cation-modified locust beam gum. Patent Document 6 discloses cation-modified tara gum is suitable as a component of a hair care product, such as a shampoo or rinse, or a skin care composition, such as body cleansing preparation, because it improves the foam quality and feeling.

Patent Document 1: Japanese Patent Publication No. Sho 47-20635 (p. 5)
Patent Document 2: Japanese Patent Application Laid-open No. Hei 4-364111 (pp.1-6)
Patent Document 3: Japanese Patent Application Laid-open No. Hei 7-173029 (pp.1-7)
Patent Document 4: Japanese Patent No. 3349219 (pp.1-6)
Patent Document 5: Japanese Patent Application Laid-open No. 2000-103724(pp. I to 6)
Patent Document 6: Japanese Patent Application Laid-open No. 2003-327603 (pp. 1-23)
Non-patent Document 1: FRAGRANCE JOURNAL 2003-10 (p. 34)

DISCLOSURE OF THE INVENTION

Problem to be Solved by the Invention

Diversified fashion trends have increased the frequency of using hair colors and hair dyes, which significantly damage hair and require conditioning agents to achieve greater conditioning effects, in particular, to render smoothness to hair during the use. For the purpose of improving lack of conditioning effects at use and worse of use feeling which were caused by cation-modified cellulose derivatives, depolymerized cation-modified galactomannan polysaccharides, cation-modified guar gum, and the like, cation-modified locust bean gum and cation-modified tara gum have been invented by, respectively, cation-modifying locust gum and tara gum. However, when they are used to treat damaged hair, hair becomes tangled at the fingers during the rinsing and the finish after drying is rarely satisfactory. Moreover, when they are incorporated in skin care compositions, satisfaction of users (use feeling) is low and appearance is poor due to the presence of water-insoluble substances.

Means to Solve the Invention

Under these circumstances, the inventors have conducted extensive investigations to search for a compound that can render improved smoothness to wet hair and improved finish after drying when the compound is contained in a hair treatment composition composed of the conventional cation-modified locust bean gum or a cation-modified tara gum and that can improve the foam quality and the feeling of skin after use when the compound is contained in a skin care composition. As a result, the inventors have found that a particular cation-modified galactomannan polysaccharide has excellent conditioning effects, improves the smoothness of wet hair, enhances foam formation (lathering) and foam quality, and ensures the improvement of feeling when the cation-modified purified galactomannan polysaccharide is contained in a cosmetic composition. This cation-modified purified galactomannan polysaccharide is prepared by introducing a particular amount of a quaternary nitrogen-containing group into a galactomannan polysaccharide (hereinafter also referred to as â€œpurified galactomannan polysaccharideâ€ ) which is obtained by purifying crude galactomannan polysaccharide, comprises a main chain composed of mannose units and a side chain composed of galactose units, and has a mannose to galactose ratio of 4:1 and/or 3:1 and contains 80 wt % or more of galactomannan, and aqueous solution of which can form a gel with an aqueous solution of xanthan gum and/or carrageenan. The cation charge density of this cation-modified galactomannan polysaccharide is within a particular range.

Means to Solve the Problem

Thus, the present invention relates to a cation-modified purified galactomannan polysaccharide prepared by partially substituting hydroxyl groups of a purified galactomannan polysaccharide with a quaternary nitrogen-containing group of Formula (1), the purified galactomannan polysaccharide being prepared by purifying a crude galactomannan polysaccharide, comprising a main chain composed of mannose units and a side chain composed of galactose units, and containing 80 wt % or more of galactomannan:
Chemical Formula (1) [Image Omitted]
(where R₁and R₂each independently represent an alkyl group having 1 to 3 carbon atoms; R₃represents an alkyl group having 1 to 24 carbon atoms; X^âˆ’ represents an anion; n is either 0 or 1 to 30; and, when n is 1 to 30, (R₄O)_nrepresents a polymer residue of an alkylene oxide having 2 to 4 carbon atoms and forms a polyalkylene glycol chain composed of a single alkylene oxide and/or a polyalkylene glycol chain composed of two or more types of alkylene oxide), wherein the cation charge density derived from the quaternary nitrogen-containing group is in the range of 0.1 to 3.0 meq/g. An aqueous solution of the purified galactomannan polysaccharide can form a gel with an aqueous solution of xanthan gum and/or carrageenan. The purified galactomannan polysaccharide has a mannose to galactose ratio of 4:1 and/or 3:1.

The inventive cation-modified purified galactomannan polysaccharide reduces water-insoluble matters in crude galactomannan polysaccharides, so that when the inventive cation-modified purified galactomannan polysaccharide is contained in a hair treatment composition, such as a shampoo or rinse, it can achieve conditioning effects superior to those achieved by hair treatment compositions containing the conventional cation-modified locust bean gum (hereinafter also referred to as â€œnonpurified cation-modified locust bean gumâ€ ) and cation-modified tara gum (hereinafter referred to as â€œnonpurified cation-modified tara gumâ€ ) prepared by cation-modifying locust bean gum and tara gum containing less than 80 wt % of galactomannan. Moreover, the hair treatment composition containing the inventive cation-modified purified galactomannan polysaccharide will yield excellent feeling after drying. When the inventive cation-modified purified galactomannan polysaccharide is contained in a skin care composition, foam formation and foam quality can be improved and good finish feel can be achieved. Thus, the present invention can provide a cosmetic composition that has excellent use feeling compared to conventional products.

One of galactomannan polysaccharides used in the present invention contains a main chain composed of mannose units and a side chain composed of galactose units and is a nonionic polysaccharide having a mannose to galactose ratio of 4:1. The galactomannan polysaccharide is a natural water-soluble gum obtained from albumens of seeds of locust bean (Ceratonia Siliqua), a perennial leguminous plant grown in Mediterranean regions and is commonly called â€œlocust bean gumâ€ or â€œcarob gumâ€ . The present invention uses a purified galactomannan polysaccharide prepared by purifying a crude galactomannan polysaccharide obtained from albumens of seeds of locust bean so that the galactomannan content is 80 wt % or more and preferably 83 wt % or more.

Another galactomannan polysaccharide used in the present invention contains a main chain composed of mannose units and a side chain composed of galactose units and is a nonionic polysaccharide having a mannose to galactose ratio of 3:1. This galactomannan polysaccharide is a natural water-soluble gum obtained from albumens of seeds of tara (Caesalpinia Spinosa), a leguminous plant native of the South American Andes, and is commonly called â€œtara gumâ€ . The present invention uses a purified galactomannan polysaccharide prepared by purifying a crude galactomannan polysaccharide obtained from albumens of seeds of tara so that the galactomannan content is 80 wt % or more and preferably 83 wt % or more.

An example process for purifying crude galactomannan polysaccharide to increase the galactomannan content to 80 wt % or more includes dissolving crude galactomannan polysaccharide (hereinafter also referred to as â€œnonpurified galactomannan polysaccharideâ€ ) containing less than 80 wt % of galactomannan in water to prepare an aqueous solution, filtering the aqueous solution to remove water-insoluble matters, precipitating the filtrate in an organic solvent, and drying the resulting precipitates. Alternatively, the purified galactomannan polysaccharide may be obtained by removing the shell portions of the seeds and milling only the cores of albumens left thereby. Although the crude galactomannan polysaccharide is purified by such conventional processes, the purifying process is not limited to these.

It is well known that locust bean gum having a mannose to galactose ratio of 4:1 and tara gum having a mannose to galactose ratio of 3:1 have different properties, such as rheological properties, from those of guar gum having a mannose to galactose ratio of 2:1.

A cation-modified purified galactomannan polysaccharide of the present invention can be produced by reacting a galactomannan polysaccharide with a glycidyltrialkyl ammonium salt having a quaternary nitrogen-containing group or a 3-halogeno-2-hydroxypropyltrialkyl ammonium salt having a quaternary nitrogen-containing group, the galactomannan polysaccharide being prepared by purifying a crude galactomannan polysaccharide and containing 80 wt % or more of galactomannan and having a mannose to galactose ratio of 4:1 (in such a case, the polysaccharide is referred to as â€œpurified locust bean gumâ€ ) or a mannose to galactose ratio of 3:1 (in such a case, the polysaccharide is referred as â€œpurified tara gumâ€ ). The galactomannan polysaccharide may be a mixture of the two gums. The reaction is conducted in a suitable solvent, preferably a hydrous alcohol, in the presence of an alkali. Such an introduction of a quaternary nitrogen-containing group can be conducted by known techniques, but the introduction process is not particularly limited. For example, the reaction between the galactomannan polysaccharide and the quaternary nitrogen-containing group of the glycidyltrialkyl ammonium salt or the 3-halogeno-2-hydroxypropyltrialkyl ammonium salt may be conducted after alkylene oxide having 2 to 4 carbon atoms are added to part of hydroxyl groups contained in a purified galactomannan polysaccharide having a mannose to galactose ratio of 4:1, thereby yielding the cation-modified purified galactomannan polysaccharide of the present invention (hereinafter, the cation-modified galactomannan polysaccharide having a mannose to galactose ratio of 4:1 is also referred to as â€œpurified cation-modified locust bean gum). Moreover, in order to prevent aggregation of the purified locust bean gum in the solvent during the reaction, an inorganic salt, preferably sodium chloride, may be added to the reaction system. Moreover, in order to prevent aggregation of the purified locust bean gum, to enhance the dispersibility of the solute and to increase the rate of reaction, an alkali or inorganic salt may be dissolved or dispersed in the reaction solvent, and subsequently the purified locust bean gum may be added and dissolved or dispersed to introduce the quaternary nitrogen-containing group.

A galactomannan polysaccharide having a mannose to galactose ratio of 3:1 and containing 80 wt % or more of galactomannan (hereinafter also referred to as â€œpurified tara gumâ€ ) can be modified with cation by the same process as that for producing the purified locust bean gum described above to produce an inventive cation-modified purified galactomannan polysaccharide (hereinafter, the inventive cation-modified galactomannan polysaccharide having a mannose to galactose ratio of 3:1 is also referred to as â€œpurified cation-modified tara gumâ€ ).

Alternatively, a cation-modified purified galactomannan polysaccharide containing 80 wt % more of galactomannan can be produced by removing water-insoluble matters, such as shells, by milling, classifying, or filtering a crude galactomannan polysaccharide containing less than 80 wt % of galactomannan after the crude galactomannan polysaccharide was cation-modified by a similar process of the above-described process.

Alternatively, an inventive cation-modified purified galactomannan polysaccharide can be produced by cation-modifying a mixture of a purified locust bean gum and a purified tara gum by the same process employed for the purified locust bean gum.

In the present invention, a quaternary nitrogen-containing group represented by general formula (1) is introduced to a purified locust bean gum, i.e., a galactomannan polysaccharide having a mannose to galactose ratio of 4:1, or a purified tara gum, i.e., a galactomannan polysaccharide having a mannose to galactose ratio of 3:1. Examples of R₁and R₂in the quaternary nitrogen-containing group include methyl, ethyl and propyl. Examples of R₃, which is an alkyl group having 1 to 24 carbon atoms, include methyl, ethyl, propyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and dococyl. Examples of R₄O include ethoxy, propoxy and butoxy. Examples of anion X^âˆ’ include halogen ions such as a chlorine ion, a bromine ion and an iodine ion, a methyl sulfate ion, an ethyl sulfate ion and an acetate ion.

By cation-modifying a purified galactomannan polysaccharide containing 80 wt % or more of galactomannan, the inventive cation-modified purified galactomannan polysaccharide prepared exhibits adsorption to hair and skin, provides satisfactory smoothness, and is thus suitable as a component of cosmetic compositions. For example, when the inventive cation-modified purified galactomannan polysaccharide is contained in a hair treatment composition, finger-passing during hair-rinsing can be reduced and the finish feel after drying can be improved. If the inventive polysaccharide is contained in a skin care composition, e.g., a body cleansing preparation, the foam quality can be improved, and the feel of the skin to the feeling after use can be improved. Thus, the present invention is also directed to these cosmetic compositions containing the inventive cation-modified purified galactomannan polysaccharide.

The cation charge density derived from the quaternary nitrogen-containing group in the inventive cation-modified purified galactomannan polysaccharide is in the range of 0.1 to 3.0 meq/g, and preferably 0.5 to 2.5 meq/g. At a cation charge density of less than 0.1 meq/g, the adsorption of the cation-modified purified galactomannan polysaccharide to hair and skin will be insufficient; thus, a hair treatment composition or skin care composition, such as a shampoo, a conditioner, or a body cleansing preparation, containing this cation-modified purified galactomannan polysaccharide will exhibit no improvement. A hair treatment composition or a skin care composition containing a purified cation-modified galactomannan polysaccharide having a charge density exceeding 3.0 meq/g will obstruct formation of foam and give stickiness and sliminess feel disagreeable for users during the use. Moreover, skin or hair after the treatment will be undesirably rigid and sticky.

Here, the â€œcation charge densityâ€ derived from the quaternary nitrogen-containing group in the cation-modified purified galactomannan polysaccharide refers to the equivalent weight of the quaternary nitrogen-containing group of Formula (1) per gram of the cation-modified purified galactomannan polysaccharide. In general, the nitrogen content derived from the quaternary nitrogen-containing group is determined by Kjeldahl analysis (The Japanese Standards of Cosmetic Ingredients, old edition, General Test Methods, Nitrogen Determination, Method 2), and the equivalent weight can be calculated from the observed nitrogen content. However, the purified galactomannan polysaccharide having a mannose to galactose ratio of 4:1 or 3:1 used in the present invention contains nitrogen. The nitrogen content derived from the purified galactomannan polysaccharide must be subtracted from the observed nitrogen content of the inventive cation-modified purified galactomannan polysaccharide to determine the nitrogen content derived from the quaternary nitrogen-containing group. For example, suppose an inventive cation-modified purified galactomannan polysaccharide, in which the quaternary nitrogen-containing group represented by formula (1) contains R₁, R₂, and R₃each representing methyl, X^âˆ’ representing chlorine ion, and n being zero, is prepared by introducing a cation to a purified locust bean gum, and the nitrogen content of that inventive polysaccharide is determined to be 2.16% by Kjeldahl analysis. In such a case, the cation charge density can be determined by the following equation (the purified locust bean gum used in the present invention usually contains about 0.90% of nitrogen): $\begin{matrix} cation â ¢ â€ƒ â ¢ charge â ¢ â€ƒ â ¢ density â ¢ â€ƒ â ¢ (meq / g) = (nitrogen â ¢ â€ƒ â ¢ content â ¢ â€ƒ â ¢ (%) â ¢ â€ƒ â ¢ derived â ¢ â€ƒ â ¢ from â ¢ â€ƒ â ¢ quaternary â ¢ â€ƒ â ¢ nitrogen â ¢ - â ¢ containing â ¢ â€ƒ â ¢ group Ã— 1000) / (atomic â ¢ â€ƒ â ¢ weight â ¢ â€ƒ â ¢ of â ¢ â€ƒ â ¢ nitrogen â ¢ â€ƒ â ¢ (14.0) Ã— 100) = (2.16 - 0.90) / 1.40 = 0.90 & Equation â ¢ â€ƒ â ¢ 1 \end{matrix}$

The â€œgalactomannan contentâ€ in the crude galactomannan polysaccharide refers to the mass percent of galactomannan contained per gram of a crude galactomannan polysaccharide, i.e., a natural water-soluble gum from which the inventive cation-modified purified galactomannan polysaccharide is made, based on solid content. Although an example method of determining the galactomannan content by using absorbance after enzymic decomposition is given below, the method is not limited to this and may be a liquid chromatographic method, a thin-layer chromatographic method, or the like. A sample of about 20 mg is accurately weighted, placed in a centrifugal tube, and mixed with 5 mL of ethanol. The mixture is then incubated at 85Â° C. to 95Â° C. and separated by centrifugation into an upper phase and a lower phase. To the lower phase, 10.0 mL of a 50 mM acetic acid buffer solution (pH 4.5) is added, and the resulting mixture is heated and left to stand at 40Â° C. for 12 hours. Subsequently, 20 Î¼L of Î²-mannanase is added to the mixture, and the resulting mixture is cultured at 40Â° C. for 180 minutes. The mixture is then centrifuged and 0.1 mL of supernatant is sampled. The supernatant is mixed with 0.2 mL of a 50 mM acetic acid buffer solution (pH 4.5) and 20 Î¼L of Î±-galactosidase. The resulting solution is incubated at 40Â° C. and mixed with 2.5 mL of a 200 mM tris buffer solution and then with 0.1 mL of Î²-nicotineamide adeninedinucleotide (0.1 g/10 mL) and 8 Î¼L of galactose dehydrogenase. The resulting mixture is incubated at 40Â° C. for 60 minutes. Subsequently, the absorbance of the solution at 340 nm is measured. The galactose content is then determined by the following equation from the observed absorbance (the galactomannan content is determined from the galactose content using the mannose to galactose ratio of the sample):
galactose content (%)=(Eâˆ’E₀)Ã—(1/W)Ã—A*â€ƒâ€ƒEquation 2

- E: absorbance at 340 nm (sample solution)
- E₀: absorbance at 340 nm (blank)
- A*: conversion factor for determining galactose content
- W: sample-collecting amount (mg)

To be more specific, using a galactomannan assay kit produced by Biocon (Japan) Ltd., the galactomannan content in the purified locust bean gum used in the present invention is determined. Given that the conversion factor A* determined from the calibration curve is 1384.6, that the absorbance of the blank at 340 nm is 0.276, that 17.8 mg of the purified locust bean gum (based on solid content) is sampled, and that the absorbance of the sample solution at 340 nm is 0.502, the calculated galactose content is 17.6%. Since the locust bean gum has a mannose to galactose ratio of 4:1, the galactomannan content is 88.0%.

The inventive purified cation-modified galactomannan polysaccharide is particularly suitable as a component of a cosmetic composition. For example, a hair care composition containing the inventive cation-modified purified galactomannan polysaccharide will render improved smoothness to wet hair, achieve improved conditioning effect, and ensure a more satisfactory finish feel as compared with a hair treatment composition containing the conventional nonpurified cation-modified locust bean gum or the conventional nonpurified cation-modified tara gum prepared by cation-modifying an nonpurified locust gum or nonpurified tara gum containing less than 80 wt % of galactomannan. Because nonpurified cation-modified locust bean gum and nonpurified tara gum contain water-insoluble matters in addition to galactomannan polysaccharide which is a natural water-soluble gum, skin care compositions containing the conventional gums do not have satisfactory feeling due to the presence of water-insoluble matters. In contrast, skin care compositions containing inventive cation-modified purified galactomannan polysaccharide will not cause any lowering of feeling due to fewer water-insoluble matters by the purification and will produce satisfactory foaming. Thus, the present invention can provide a high quality skin care composition.

When the cation-modified purified galactomannan polysaccharide of the present invention is contained in a hair treatment composition or a skin care composition, the content thereof is preferably 0.05 to 5 wt % relative to 100 wt % of the entire composition. At a content less than 0.5 percent by mass, its conditioning effects tend to be insufficient. At a content exceeding 5 wt %, the composition will give the user sliminess and stickiness feeling and degrade the smoothness, thereby causing the use feeling worse.

To a hair treatment composition of the present invention, a cationic water-soluble polymer or amphoteric water-soluble polymer may be added, in addition to a cation-modified galactomannan polysaccharide, in order to further enhance the conditioning effect of the composition. However, the amount of the additional polymer added should be adjusted so as not to interfere with the emulsifiability and soft texture to hair of a cation-modified galactomannan polysaccharide used in combination. The amount in question added is preferably 5% by weight or lower, with respect to the weight (100% by weight) of the entire composition. If the amount added exceeded the above range, the membrane-forming activity and hair-setting performance of a cation-modified galactomannan polysaccharide used in combination would be impaired. Moreover, if the composition to which that additional polymer is added is for treating the skin, the skin would be so slimy as to displease the user.

Suitable cationic water-soluble polymers and amphoteric water-soluble polymers include the following compounds, but they are not necessarily limited to these compounds.

The cationic water-soluble polymer may include a quaternary nitrogen-based cationic polysaccharide (cation-modified hydroxyethyl cellulose, cation-modified guar gum, cation-modified locust-bean guar gum, cation-modified starch, cation-modified tara gum, cation-modified tamarind gum, etc.), dimethyldiallyl ammonium chloride derivatives (copolymers of dimethyidiallyl ammonium chloride and acrylamide, polychlorinated dimethylmethylenepiperidinium, etc.), vinylpyrrolidone derivatives (copolymers of vinylpyrrolidone and dimethylaminoethylmethacrylate, copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride, copolymers of vinylpyrrolidone and methylvinylimidazolium chloride, etc.), and methacrylate derivatives (copolymers of methacryloylethyidimethylbetaine, methacryloylethyltrimethylammonium chloride and methacrylic acid 2-hydroxyethyl, copolymers of methacryloylethyldimethylbetaine, methacryloylethyltrimethylammonium chloride, and methacrylic acid methoxypolyethylene glycol, etc.).

The amphoteric water-soluble polymer may include amphoterized starch, dimethyldiallylammonium chloride derivatives (copolymers of acrylamide, acrylic acid and dimethyldiallylammonium chloride, copolymers of acrylic acid and dimethyldiallylammonium chloride, etc.), and methacrylate derivatives (copolymers of polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N,N-dimethylammonium-a-methylcarboxybetaine and alkyl methacrylate, etc.)

A cosmetic preparation according to the present invention can be obtained by adding a cation-modified galactomannan polysaccharide of the present invention to a prescribed system at a specified amount by a commonly known method, and other components to be used in combination are not limited to specific ones, but any components generally used in such cosmetic preparations may be used. Such additives to be used in combination include followings.

The anionic surfactant may include C 8-24 alkyl sulfate, C 8-24 alkyl ether sulfate, C 8-24 alkyl benzene sulfonate, C 8-24 alkyl phosphate, C 8-24 polyoxyalkylenealkyl ether phosphate, C 8-24 alkyl sulfosuccinate, C 8-24 polyoxyalkylenealkyl ether sulfosuccinate, C 8-24 acyl alaninate, C 8-24 acyl N-methyl-Î²-alaninate, C 8-24 acyl glutamate, C 8-24 acyl isethionate, C 8-24 acyl sarcosinate, C 8-24 taurinate, C 8-24 acyl methyl taurinate, Î±-sulfofatty acid ester salt, ether carbonate, polyoxyalkylene fatty acid monoethanol amide sulfonate, C 8-24 long chain carboxylate, etc. (C 8-24 means 8 to 24 carbon atoms.)

The nonionic surfactant may include alkanol amide, glycerin fatty acid ester, polyoxyalkylenealkyl ether, polyoxyalkyleneglycol ether, polyoxyalkylenesorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylenesorbit fatty acid ester, sorbit fatty acid ester, polyoxyalkyleneglycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylenealkylphenyl ether, tetrapolyoxyalkylene ethylenediamine-condensed substances, sucrose fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkyleneglycol fatty acid ester, polyoxyalkylene castor oil derivatives, polyoxyalkylene-hardened castor oil derivatives, alkylpolyglycoside, polyglycerin fatty acid ester, etc.

The amphoteric surfactant may include alkyl (8-24 carbons) amidopropylbetaine, alkyl (8-24 carbons) carboxybetaine, alkyl (8-24 carbons) sulfobetaine, alkyl (8-24 carbons) sulfobetaine, alkyl (8-24 carbons) hydroxysulfobetaine, alkyl (8-24 carbons) amidopropylhydroxysulfobetaine, alkyl (8-24 carbons) hydroxyphosphobetaine, alkyl (8-24 carbons) aminocarboxylate, alkyl (8-24 carbons) imidazoliumbetaine, alkyl (8-24 carbons) amineoxide, alkyl (8-24 carbons) phosphate esters containing a tertiary or quaternary nitrogen group, etc.

In addition to the cationic or nonionic water-soluble polymers described above, an anionic or nonionic polymer may be added to a hair treatment composition or skin care composition of the present invention in order to adjust the viscosity of the composition or improve the performance of the composition in maintaining the finished style, so long as the addition of the polymer does not interfere with the expected effects of the composition of the present invention.

Such anionic polymers may include acrylate derivatives (polyacrylic acid and its salts, and copolymers of acrylic acid, acryl amide and ethyl acrylate, and their salts), methacrylate derivatives (polymethacrylic acid and its salts, copolymers of methacrylic acid, acryl amide, diacetone acrylamide, alkylesteracrylate and alkylestermethacrylate, and their salts), crotonate derivatives (copolymers of vinylacetate and crotonic acid, etc.), maleate derivatives (copolymers of anhydrous maleic acid and diisobutylene, copolymers of isobutylene and maleic acid, etc.), polyglutamic acid and its salts, hyaluronic acid and its salts, carboxymethyl cellulose, carboxyvinyl polymer, etc.

The nonionic polymer may include acrylate derivatives (copolymers of hydroxyethyl acrylate and methoxyethyl acrylate, amide polyacrylate, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, copolymers of vinylpyrrolidone and vinyl acetate, etc.), polyoxyalkylene glycol derivatives (polyethylene glycol, polypropylene glycol, etc.), cellulose derivatives (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polysaccharides and their derivatives (guar gum, locust-bean gum, dextran, etc.), etc.

In another embodiment to a hair treatment composition or skin care composition of the present invention, an amideamine compound and a neutralizing agent such as an organic and/or inorganic acid may be added together with a higher fatty acid and/or higher alcohol, so as to enhance the conditioning effect of the composition. The amount of an amideamine compound added is preferably 5% by weight or lower with respect to the weight (100% by weight) of the entire composition. If the amount in question added exceeded the above range, the skin treated with the resulting composition would become so mat and slimy as to displease the user.

Moreover, the conditioning effect may be enhanced by adding silicone (methylpolysiloxane, methylphenylsiloxane, high polymeric methylpolysiloxane, cyclic polysiloxane, polyether-modified silicone, amino-modified silicone, etd.) to a hair treatment composition or skin care composition of the present invention. The amount of a silicone added is preferably 5% by weight or lower with respect to the weight (100% by weight) of the entire composition. If the amount in question added exceeds the above range, the hairs or the skin treated with the resulting composition would become so mat and slimy as to displease the user, and moreover, the stability of the composition becomes deteriorated.

Other suitable components to be added to a hair treatment composition or to a skin care composition of the present invention may include cationic surfactants (alkyltrimethyl ammonium salts, dialkyldimethyl ammonium salts, alkylpyridium salts, alkyldimethylbenzyl ammonium salts, benzethonium chloride, benzalkonium chloride, etc.), solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (carnauba wax, candelilla wax, etc.), hydrocarbon oils (liquid paraffin, squalane, etc.), moisture retainers (glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristic acid myristate, myristic acid-2-hexyldecyl, glycerin trimyristate, isopropyl palmitate, palmitic acid-2-heptylundecyl, palmitic acid-2-hexyldecyl, butyl stearate, isocetyl stearate, 12-hydroxystearic acid cholesteryl, cetostearylalcohol, cetyl octanate, hexyldecyldimethyl octanate, isocetyl isostearate, trimethylolpropane triisostearate, decyl oleate, oleic acid oil, cetyl lactate, myristyl lactate, ethyl acetate, butyl acetate/amyl acetate, acetic acid lanolin, 2-ethylhexanoic acid cetyl, 2-ethylhexyl palmitate, di-2-ethylhexylic acid ethylene glycol, tri-2-ethylhexylic acid trimethylol propane, tri-2-ethylhexylic acid glycerin, tetra-2-ethylhexylic acid pentaerythritol, cetyl-2-ethyl hexanoate, diisobutyl adipate, adipic acid-2-heptylundecyl, adipic acid-2-hexyldecyl, dipentaerythritol fatty acid ester, neopentyl glycol dicaprylate, diisostearyl malate, di-2-heptylundecanoic acid glycerin, tri-2-heptylundecanoic acid glyceride, caster oil fatty acid methyl ester, acetoglyceride, N-lauryl-L-glutamic acid-2-octyldodecyl ester, di-2-ethylhexyl sebacate, diisopropyl sebacate, succinic acid-2-ethylhexyl, triethyl citrate, ethyl laurate, mink oil fatty acid ester, etc.), antioxidants (tocopherol, BHT, etc.), higher alcohols, higher fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, undecylenic acid, tall oil fatty acid, coconut oil fatty acid, palm oil fatty acid, palm kernel fatty acid, linolic acid, linoleic acid, eicosapentaenoic acid, docosahexanoic acid, etc.), amino acids (alginin, glutamic acid, etc.), UV absorbants (benzophenon derivatives, paraamino benzoate derivatives, methoxy cinnamate derivatives, etc.), UV-scattering agents (inorganic compounds such as zinc oxide, zirconium oxide, titanium oxide, etc.), thickeners, metal chelating agents (edetic acid salts, etc.), pH-adjusting agents, bactericides, preserving agents, hair growth stimulants, vitamins, anti-inflammatory agents, dyes, pigments (inorganic white pigments such as titanium dioxide, inorganic red pigments such as iron oxide (Indian red), iron titanate, etc., inorganic green pigments such as cobalt titanate, etc., iron oxide-treated mica titanium, carbon black-treated mica titanium, etc.), perfumes, foaming-promoting agents, etc.

A cosmetic composition prepared according to the present invention as described above is not limited in prescription to any specific one, but may take any desired prescription. Furthermore, any appropriate additive usually used in a common cosmetic composition other than those derived above may be added to a cosmetic composition of the present invention, so long as it does not interfere with the effects originally expected from the composition, and the resulting composition may be processed by conventional techniques into appropriate products. Particularly, such an additive may be added with profit to a hair treatment composition of the present invention. Suitable prescriptions a hair treatment composition of the present invention can take include shampoos, hair rinses, hair conditioners, hair waxes, hair lotions, hair mists, etc. All these prescriptions are based on smoothness of a cation-modified purified galactomannan polysaccharide of the present invention added to the composition, the improvements of conditioning effects and finish feeling after use, and improvement of foaming quality. Since the cation-modified purified galactomannan polysaccharide of the present invention, when applied to the skin, can improve the texture of the skin, it is possible to use a skin care composition supplemented with the catrion-modified purified galactomannan polysaccharide of the present invention as a body cleanser, facial cleanser, or facial lotion. Furthermore, it may be added to acidic hair dye, oxidized hair dye or perm-setting agent. Many formulation such as solid, dust, gel, cream, earzol, form may be used in accordance with portion or place to which the present invention is applied.

EXAMPLE

The present invention will be detailed below by means of the preferred embodiments. However, the present invention is not limited to those embodiments. In the following description, the content of constituents in compositions expressed by â€œwt %â€ and â€œvol %â€ mean â€œpercent by weightâ€ and â€œpercent by volumeâ€ , respectively unless otherwise specified.

Manufacture of Cation-Modified Purified Galactomannan Polysaccharide

Example 1

11.8 g of an aqueous 48 wt % sodium hydroxide solution was added to 900 ml of an aqueous 50 vol % isopropanol solution. 162 g of purified locust-bean gum containing 83 wt % of galactomannan was added and gradually dispersed to the mixture. 65.5 g of an aqueous 80 wt % glycidyltrimethyl ammonium chloride (GTA) solution was added to the mixture, and heated and reacted at 50Â° C. for three hours. After completion of the reaction, the reaction mixture was neutralized with 14.0 g of 50 vol % hydrochloric acid which was diluted with 1500 ml of an aqueous 50 vol % isopropanol solution. After neutralizing at room temperature for one hour, the reaction solution was poured into 1800 ml of methanol, and reaction product was precipitated and separated by filtration. The obtained precipitate was washed with an aqueous methanol solution, and the reaction product was dried under reduced pressure. Cationic charge density of the cation-modified purified galactomannan polysaccharide thus obtained was 0.95 meq/g. The result is shown in Table 1 (under Sample 1 in Table 1).

Similarly, cation-modified purified galactomannan polysaccharides having different cationic charge density were synthesized by changing the amount of GTA to be added. The result is shown in Table 1 (under Samples 2 and 3 in Table 1).

Example 2

162 g of galactomannan-containing 88 wt % purified locust-bean gum was dispersed in 900 ml of an aqueous 55 vol % isopropanol solution and added with 48.3 g of an aqueous 48 wt % sodium hydroxide solution. Then, 142.8 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added to the mixture, heated and reacted at 50Â° C. for three hours. After completion of the reaction, the reaction mixture was neutralized with 14.0 g of 35% hydrochloric acid which was diluted with 1500 ml of an aqueous 70 vol % isopropanol solution. After neutralizing at room temperature for one hour, the reaction solution was poured into 1800 ml of methanol, and reaction product was precipitated and separated by filtration. The obtained precipitate was washed with an aqueous methanol solution, and the reaction product was dried under reduced pressure. Cationic charge density of the cation-modified purified galactomannan polysaccharide thus obtained was 0.75 meq/g. The result is shown in Table 1 (under Sample 4 in Table 1).

Example 3

In an autoclave, 162 g of the purified locust-bean gum obtained in Example 1 was dispersed in 900 ml of an aqueous 80 vol % isopropanol solution and added with 11.8 g of an aqueous 48 wt % sodium hydroxide solution. 66 g of ethylene oxide and 240 g of propylene oxide were added to the mixture and heated and reacted at 70Â° C. for three hours under pressurization and sealing. After completion of the reaction, pressurization was released and the reaction mixture was cooled to 50Â° C. After cooling, 150 g of an aqueous 80 wt % GTA solution was added to the reaction mixture and reacted at 50Â° C. for three hours. After completion of the reaction, the reaction mixture was neutralized with 14.0 g of 35% hydrochloric acid which was diluted with 1500 ml of an aqueous 70 vol % isopropanol solution. After neutralizing at room temperature for one hour, the reaction solution was poured into 800 ml of methanol, and reaction product was precipitated and separated by filtration. The obtained precipitate was washed with an aqueous methanol solution, and the reaction product was dried under reduced pressure. Cationic charge density of the cation-modified purified galactomannan polysaccharide thus obtained was 0.83 meq/g. The result is shown in Table 1 (under Sample 5 in Table 1).

Example 4

11.8 g of an aqueous 48 wt % sodium hydroxide solution was added to 900 ml of an aqueous 50 vol % isopropanol solution. 162 g of purified locust-bean gum containing 97 wt % of galactomannan was gradually dispersed to the mixture. 77.2 g of an aqueous 80 wt % GTA solution was added to the mixture, and heated and reacted at 50Â° C. for three hours. After completion of the reaction, the reaction mixture was neutralized with 14.0 g of 35% hydrochloric acid which was diluted with 1500 ml of an aqueous 50 vol % isopropanol solution. After neutralizing at room temperature for one hour, the reaction solution was poured into 1800 ml of methanol, and reaction product was precipitated and separated by filtration. The obtained precipitate was washed with an aqueous methanol solution, and the reaction product was dried under reduced pressure. Cationic charge density of the cation-modified purified galactomannan polysaccharide thus obtained was 1.06 meq/g. The result is shown in Table 1 (under Sample 6 in Table 1).

Example 5

8.8 g of an aqueous 48 wt % sodium hydroxide solution and 3.0 g of sodium chloride was added to 900 ml of an aqueous 70 vol % isopropanol solution. 162 g of purified tara gum containing 84 wt % of galactomannan was gradually dispersed to the mixture. 44.1 g of an aqueous 80 wt % GTA solution was added to the mixture, and heated and reacted at 50Â° C. for three hours. After completion of the reaction, the reaction mixture was neutralized with 14.0 g of 35% hydrochloric acid which was diluted with 1500 ml of an aqueous 60 vol % isopropanol solution. After neutralizing at room temperature for one hour, the reaction solution was poured into 1800 ml of methanol, and reaction product was precipitated and separated by filtration. The obtained precipitate was washed with an aqueous methanol solution, and the reaction product was dried under reduced pressure. Cationic charge density of the cation-modified purified galactomannan polysaccharide thus obtained was 0.80 meq/g. The result is shown in Table 1 (under Sample 7 in Table 1).

Supplement 1

The same experimental procedures were repeated except that the added amount of GTA was varied, to produce some additional cation-modified purified galactomannan polysaccharides having different cationic charge densities. These results are also shown in Table 1 (under Samples 10 and 11 in Table 1).

Comparative Example 1

For the comparison with the cation-modified purified galactomannan polysaccharide of the present invention, cation-modified nonpurified galactomannan polysaccharide was synthesized by using galactomannan polysaccharide containing less than 80 wt % of galactomannan polysaccharides in crude galactomannan polysaccharides. Nonpurified locust-bean gum containing 74 wt % of galactomannan in crude galactomannan polysaccharides was cation-modified according to the method of Example 1. The cationic charge density of the obtained cation-modified nonpurified galactomannan polysaccharide was 0.91 meq/g. On the other hand, nonpurified tara gum containing 76 wt % of galactomannan in crude galactomannan polysaccharides was cation-modified according to the method of Example 5. The cationic charge density of the obtained cation-modified nonpurified galactomannan polyshaccaride was 0.88 meq/g. The result is shown in Table 1 (Samples 12 and 13 in Table 1).

TABLE 1Cation Charge DensityChargeSampledensityGalactomannanSynthesisSorts ofNo.(meq/g)contentmethodpolysaccharide10.9583 wt %Example 1purified locust beangum20.4283 wt %Example 1purified locust beangum32.4883 wt %Example 1purified locust beangum40.7588 wt %Example 2purified locust beangum50.8383 wt %Example 3purified locust beangum61.0697 wt %Example 4purified locust beangum70.8084 wt %Example 5purified tara gum81.2584 wt %Example 5purified tara gum92.6184 wt %Example 5purified tara gum100.0583 wt %Supplement 1purified locust beangum114.1083 wt %Supplement 1purified locust beangum120.9174 wt %ComparativenonpurifiedExample 1purified locast beangum130.8876 wt %ComparativenonpurifiedExample 1tara gum

[Production of Cosmetic Preparations Supplemented with Cation-modified Purified Galactomannan Polysaccharides, and their Evaluation]

Example 6 Enhancement of the Smoothness to Hairs (Part 1)

Enhancement of the smoothness to hairs due to a cation-modified purified galactomannan polysaccharide was evaluated by means of a water-rinse hair cleansing preparation supplemented with the cation-modified purified galactomannan polysaccharide.

(Preparation of Water-Rinse Hair Cleansing Preparation)

6-a

The cation-modified purified galactomannan polysaccharides prepared in Examples 1, 2 and 5 were used to prepare shampoo samples whose composition is as shown in column (A) of Table 2. The shampoo sample was prepared as follows. Distilled water (ingredient (12)) was heated to 80Â° C. to which one of the test Samples 1, 2 and 5 (ingredient (1)) as described above was slowly added with stirring and the mixture was stirred until it was dissolved. After recognizing the dissolution, heating was discontinued, and polyoxyethylene(3)lauryl ether sulfuric acid sodium (ingredient (5)), coconut oil fatty acid amide propylbetaine (ingredient (6)), and coconut oil fatty acid monoethanol amide (ingredient (7)) were added to the mixture with stirring at the weight ratios specified in Table 2. The mixture was stirred until it became a uniform liquid, to which sodium editate (ingredient (8)), sodium benzoate (ingredient (10)) and an aqueous solution of citric acid (for pH adjustment, pH 5.5-6.0)(ingredient (11)) were added at the weight ratios specified in Table 2 at 30 to 40Â° C., and the mixture was stirred to homogeneity. Thus, three kinds of shampoo samples with compositions as shown under column (A) of Table 2 were obtained. The shampoo sample prepared from the cation-modified purified galactomannan polysaccharides represented by test sample 1 was named test prescription Si. The shampoo sample prepared from the cation-modified purified galactomannan polysaccharides represented by test Sample 4 was named test prescription S2. The shampoo sample prepared from the cation-modified purified galactomannan polysaccharides represented by test Sample 7 was named test prescription S3.

6-b

The cation-modified purified galactomannan polysaccharide obtained in Example 1 and named test Sample 1 and a cation-modified hydroxyethyl cellulose containing nitrogen at 1.8 wt % to which an average of 1.8 mol of ethylene oxide was introduced (Catinal HC-100, Toho Chemical Industry Co. Ltd.) and a copolymer of N-methacryloyloxyethyl N,N-dimethyl ammonium-Î±-methylcarboxylbetaine and alkyl methacrylate (Yukaformer SM, Mitsubishi Chemicals Co.) as an amphoteric water-soluble polymer were combined at the weight ratio specified in (B) in Table 2, and used as a test sample. To this test sample, ingredients shown under column (B) of Table 2 were added and the resulting product was used as a test shampoo sample. Specifically, distilled water (ingredient (12)) was heated to 80Â° C. to which one of the test Samples 1, 4 and 7 (ingredient (1)), the cationic water soluble polymer (ingredient (3)) and the amphoteric water-soluble polymer (ingredient (4)) were slowly added with stirring at the weight ratios specified in column (B) of Table 2. The stirring was continued until the substances added were dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (7) were added to the mixture with stirring at the weight ratios specified in Table 2. The mixture was stirred until it became a uniform liquid, to which ingredients (8), (10) and (11) were added at the weight ratios specified in Table 2 at 30 to 40Â° C., and the mixture was stirred to homogeneity. A shampoo sample with a composition shown under column (B) of Table 2 was obtained. This was named a test prescription S4 of the present invention.

6-c (Preparation of Comparative Prescriptions)

To compare the effects of test shampoo preparations containing a cation-modified purified galactomannan polysaccharide of the present invention, comparative shampoo samples were prepared by using the cation-modified nonpurified galactomannan polysaccharides prepared in Comparative Example 1. The composition of the comparative shampoo samples was as shown under column (C) of Table 2. Specifically, distilled water (ingredient (12)) of the comparative shampoo sample in Table 2 was heated to 80Â° C. to which comparative Sample 12 or 13 (ingredient (2)) was slowly added with stirring. The stirring was continued until the substance added was dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (7) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid. Ingredients (8), (10) and (11) were added to the mixture at 30 to 40Â° C., and the mixture was stirred to homogeneity. The shampoo sample compounded with cation-modified nonpurified galactomannan polysaccharide of the test Sample 12 were named comparative prescription C1. The shampoo sample compounded with cation-modified nonpurified galactomannan polysaccharide of the test Sample 13 were named comparative prescription C2.

TABLE 2Shampoo PrescriptionsWeight ratio(%, in terms of solids)ComparativeIngredients(A)(B)sample (C)(1)Present invention0.30(test Samples 1, 4, 7)(2)Comparative samples00.3(comparative Sample 12, 13)(3)Cationic water-soluble polymer00.30(Catinal HC-100)(4)Amphoteric water-soluble polymer00.20(Yukaformer SM)(5)Polyoxyethylene (3)lauryl9.09.0ether sulfuric acid sodium(6)Coconut oil fatty acid amide4.54.5propylbetaine(7)Coconut oil fatty acid2.52.5monoethanol amide(8)Sodium edetate0.10.1(10)Sodium benzoate0.10.1(11)Aqueous solution of citric acidasas(for pH adjustment, pH 5.5-6.0)appropriateappropriate(12)Distilled waterrestrest

(Evaluation)

Strands of hairs (manufactured by BEAULAX CO., LTD.; artificial hairs the roots of which were arranged uniformly; 60 mm in length and 40 mm in width) were immersed in 5% aqueous solutions of shampoo of the test prescriptions S1 to S4 prepared in the above sections 6-a to 6-b (present invention). After the shampoo was fully wahsed away, coefficient of dynamic friction was measured with respect to the hairs which were in wet-state as they were, by using a friction-sensing tester (KES-SE manufactured by KATO TECH CO., LTD.) to evaluate smoothness. The evaluation result is shown in Table 3. Strands of hairs were similarly immpersed in shampoo of the comparative prescriptions C1 and C2 prepared in the above section 6-c. After the shampoo was fully wahsed away, coefficient of dynamic friction of the strands of hairs was measured with respect to the hairs which were in wet-state of hairs as they were, by the friction-sensing tester to evaluate smoothness. The result is shown in Table 3.

With respect to the shampoo of test prescriptions S1 to S4 prepared in the above sections 6-a to 6-c and the shampoo of the comparative prescriptions C1 and C2, ten testers carried out finger-passing text after hair-washing. After they washed and rinsed their hairs by using the shampoo of test prescriptions S1 to S4 and the shampoo of the comparative prescriptions C1 and C2 so as to determine finger-passing at rinsing time. Each of the prescriptions tested was ranked depending on the numbers of testers who gave good finger-passing according to the following four rank scale. The result is shown in Table 3.

âŠšâ€”The number of positive testers who felt good finger-passing is eight or more.
â—¯â€”The number of positive testers who felt good finger-passing is six to seven.
Î”â€”The number of positive testers who felt good finger-passing is four to five.

Ã—â€”The number of positive testers who felt good finger-passing is three or less.

TABLE 3Comparison of smoothness inwater-rinse hair cleansing preparation (shampoo)Test prescriptionsof the present inventionS4Sample 1 +ComparativeCatinalprescriptionsCationicS1S2HC-100 +C1C2polymersSam-Sam-S3YukaformerSampleSampleusedple 1ple 4Sample 7SM1213Coefficent0.390.380.350.350.460.47ofdynamicpropertyFinger-âŠšâŠšâŠšâŠšâ—¯Î”passing

From the result shown in Table 3, it was confirmed that the shampoos containing the cation-modified purified galactomannan polysaccharide of the present invention descended coefficient of dynamic friction in wet hairs in comparison with the shampoos containing the conventional cation-modified nonpurified galactomannan polysaccharides. This appears in organoleptic evaluation and it was confirmed that the shampoos of the cation-modified purified galactomannan polysaccharide of the present invention indicated excellent finger-passing after hair-washing in comparison with the shampoos containing the conventional cation-modified nonpurified galactomannan polysaccharides. Moreover, it is recognized that the above-mentioned effects were not lost even in the shampoos used in combination of cation-modified water-soluble polymer or amphoteric water-soluble polymer. It was confirmed that smoothness was improved by cation-modifying purified galactomannan polysccharide containing 80 wt % or more of galactomannan. Furthermore, since the improvement of smoothness to hairs was recognized, improvement of feeling to skin cosmetic compositions such as body cleansing agent, facial cleanser, etc.

Example 7 Smoothness to Hairs (Part 2)

The smoothness affording effect on the damaged hairs by the cation-modified galactomannan purified polysaccharide of the present invention was tested in water-rinse hair cleansing preparations using shampoos containing the test prescriptions Si to S4 of the present invention and comparative prescriptions C1 to C2 prepared in Example 6. The same strands of hairs as the one used in Example 6 were immersed in a bleaching solution which comprised a 6% H₂O₂and 3% aqueous ammonium at 2:1 (w/w): the hair strand was immersed for 60 minutes in the bleaching solution whose weight against that of the hair strand was adjusted to 100:1 and whose temperature was kept at 40Â° C. The hair strand was rinsed with warm water, and dried with a dryer. The strands of hairs which had been seriously damaged by being immersed in the bleaching solution were immersed in aqueous 5% solution of shampoo containing the test prescriptions S1 to S4 of the present invention prepared in the above sections 6-a to 6-b. After shampoo was fully washed away, coefficient of dynamic friction was measured with respect to the hairs which were in wet-state as they are by using a friction-sensing tester to evaluate smoothness. The evaluation result is shown in Table 4. Strands of hairs were similarly immpersed in shampoo of the comparative prescriptions C1 and C2 prepared in the above section 6-c. After the shampoo was fully wahsed away, coefficient of dynamic friction was measured with respect to the hairs which were in wet-state of hairs as they were by the friction-sensing tester to evaluate smoothness. The result is shown in Table 4.

TABLE 4Smoothness affording effect to damaged hairs inwater-rinse hair cleansing preparationTest prescriptionsof the present inventionS4Sample 1 +ComparativeCatinalprescriptionsCationicS1S2HC-100 +C1C2polymersSam-Sam-S3YukaformerSampleSampleusedple 1ple 4Sample 7SM1213Coefficent0.420.410.380.390.580.57ofdynamicproperty

From the result shown in Table 4, it was confirmed that even in the damaged hairs, the prescriptions containing cation-modified purified galactomannan polysaccharide obtained by cation-modifying purified galactomannan polysacchaide containing 80 wt % or more of galactomannan were excellent in effect of improving smoothness to damaged hairs in wet in comparison with prescriptions containing nonpurified cation-modified galactomannan polysaccharide. Moreover, the difference of coefficient of dynamic friction was become greater than the case evaluated in normal hairs which were not treated by bleaching solution in Example 6, and accordingly, it was confirmed that the present invention was useful to damaged hairs.

Example 8 Foaming Test

Foaming activities were tested by using shampoos containing the test prescriptions SI to S4 of the present invention prepared in the above sections 6-a to 6b of Example 6. For the comparison, foaming activities were similarly tested by using the comparative prescriptions C1 to C2 prepared in the above section 6-c of Example 6.

Testing procedures were as follows. A 175-ml sample of a 1.5% aqueous solution of each preparation shampoo of the prescriptions S1 to S4 of the present invention and of the comparative prescriptions C1 and C2. They were transferred to a commercially available juice-mixer where it was spun to develop bubbles. The foam amount was plotted as a function of spun time. The results are shown in Table 5.

TABLE 5Foaming test result (mL)Test prescriptionsof the present inventionS4Sample 1 +ComparativeCatinalprescriptionsCationicS1S2HC-100 +C1C2polymersSam-Sam-S3YukaformerSampleSampleusedple 1ple 4Sample 7SM12131.5%118011701190119011401150aqueoussolution

From the result shown in Table 5, it was proved that the cation-modified purified galactomannan polysaccharides of the present invention were excellent in foaming activity in comparison with the conventional nonpurified cation-modified galactomannan polysaccharide. Accordingly, when the present invention is contained in a cosmetic composition having foam formation (lathering) such as a shampoo, body cleansers, facial cleansers, etc., foaming improvement can be expected.

In the following, improvement of smoothness, good foam-forming performance and feeling improvement which were obtained by the cation-modified purified galactomannan polysaccharide applied to normal hairs and damaged hairs were confirmed in various cosmetic compositions having different formulations.

Hair Shampoo

(Preparation)

Example 9

9-a

The cation-modified galactomannan purified polysaccharides prepared in Examples 1 to 5 and named Samples 1-9 were used to prepare shampoo samples with compositions as shown in column (A) of Table 6. The shampoo sample was prepared as follows. Distilled water (ingredient (14)) in column (A) of Table 6 was heated to 65Â° C. to which one of the test Samples (ingredient (1)) was slowly added with stirring, and mixture was stirred until it was dissolved. After recognizing the dissolution, heating was discontinued, and polyoxyethylene(1,5)lauryl ether sulfuric acid triethanol amine (ingredient (5)), polyoxyethylene(3)lauryl ether sulfuric acid sodium (ingredient (6)), coconut oil fatty acid amide propylbetaine (ingredient (7)), coconut oil fatty acid monoethanol amide (ingredient (8)), dipropylene glycol (ingredient (9)) and ethylene glycol distearate (ingredient (10)) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid, to which sodium edetate (ingredient (11)), sodium benzoate (ingredient (12)), and an aqueous solution of citric acid (for pH adjustment, pH 5.5-6.0)(ingredient (13)) were added, and the mixture was stirred to homogeneity. Thus, five kinds of shampoo samples with compositions as shown under column (A) of Table 6 were obtained. The five shampoo samples containing the cation-modified purified galactomannan polysaccharides represented by Samples 1-9 were named test prescriptions 1-9 of the present invention, respectively.

9 -b

The cation-modified purified galactomannan polysaccharide prepared in Example 1 and named Sample 1 and a cation-modified hydroxyethyl cellulose containing nitrogen at 1.8 wt % to which an average of 1.8 mol of ethylene oxide was introduced (Catinal HC-100, Toho Chemical Industry Co., Ltd.) represented as a cation-modified water-soluble polymer A in Table 6 were combined at the weight ratios specified in Table 6, and used as a test sample. To this test sample, ingredients shown under column (B) of Table 6 were added and the resulting product was used as a test shampoo sample. Specifically, distilled water (ingredient (14)) was heated to 65Â° C. to which Sample 1 (ingredient (1)) and cationic water-soluble polymer A or B (ingredient (3)) were slowly added with stirring at the weight ratios specified in column (B) of Table 6. The stirring was continued until the substances added were dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (10) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid, to which ingredients (11) to (13) were further added at 30 to 40Â° C., and the mixture was stirred to homogeneity. A shampoo sample with a composition as shown under column (B) of Table 6 was obtained. This was named test prescription 10.

9-c

The same procedures as in the above section 9-b were employed except that a copolymer of dialkyldimethyl ammonium chloride and acryl amide (Merquat 550, Nalco) was used instead of the cation-modified water-soluble polymer A, to provide a shampoo sample with a composition as shown under column (C) of Table 6. This was named test prescription 11.

9-d

The cation-modified purified galactomannan polysaccharide prepared in Example 1 and named Sample 1 and a copolymer of N-methacryloyloxyethyl N,N-dimethyl ammonium-a-methylcarboxylbetaine and alkyl methacrylate (Yukaformer SM, Mitsubishi Chemicals Co.) as an amphoteric water-soluble polymer were combined at the weight ratio specified in Table 6, and used as a test sample. To this test sample, ingredients shown under column (D) of Table 6 were added and the resulting product was used as a test shampoo sample. Specifically, distilled water (ingredient (14)) was heated to 65Â° C. to which one of Samples I to 5 (ingredient (1)) and the amphoteric water-soluble polymer (ingredient (4)) were slowly added with stirring at the weight ratios specified in column (D) of Table 6. The stirring was continued until the substances added were completely dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (10) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid. Ingredients (11) to (13) were added to the mixture kept at 30 to 40Â° C., and the mixture was stirred to homogeneity. A shampoo sample with a composition as shown under column (D) of Table 6 was obtained. This was named test prescription 12.

9-e

The cation-modified galactomannan polysaccharide prepared in Example 1 and named Sample 1, the cationic water-soluble polymer and the amphoteric water-soluble polymer were combined at the weight ratios specified under (E) in Table 6, and used as a test sample. To this test sample, ingredients shown under column (E) of Table 6 were added and the resulting product was used as a test shampoo sample. Specifically, distilled water (ingredient (14)) under (E) of Table 6 was heated to 65Â° C. to which one of Samples 1 to 5 (ingredient (1)), the cationic water-soluble polymer A or B (ingredient (3)), and the amphoteric water-soluble polymer (ingredient (4)) were slowly added with stirring at the weight ratios specified in column (E) of Table 6. The stirring was continued until the substances added were dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (10) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid. Ingredients (11) to (13) were added to the mixture at 30-40Â° C., and the mixture was stirred to homogeneity. A shampoo sample with a composition as shown under column (E) of Table 6 was obtained. This was named test prescription 13.

9-f (Preparation of Comparative Prescriptions)

To compare the effects of the test shampoo preparations containing the cation-modified purified galactomannan polysaccharide of the present invention, comparative shampoo samples were prepared by using the cation-modified purified galactomannan polysaccharides prepared in Supplement 1 and listed in Table 1 under the names Samples 10 and 11. The composition of the comparative shampoo samples was as shown under column (G) of Table 6. Specifically, distilled water (ingredient (14)) was heated to 65Â° C. to which Samples 10, 11, 12 or 13 (ingredient (2) in column (G) of Table 6) was slowly added with stirring. The stirring was continued until the substance added was dissolved. After recognizing the dissolution, heating was discontinued, and the ingredients (5) to (10) were added to the mixture with stirring. The mixture was stirred until it became a uniform liquid. Ingredients (11) to (13) were added to the mixture at 30 to 40Â° C., and the mixture was stirred to homogeneity. The shampoo samples thus obtained were named comparative prescriptions 1 and 2.

9-g (Preparation of Comparative Prescriptions)

To further compare effects, shampoos having the composition shown under comparative prescription (G) in Table 6 were prepared in similarity with the above section 9-f by using, instead of cation-modified purified galactomannan polysaccharide in the above section 9-f, cation-modified nonpurified galactomannan polysaccharide in which cation-modifying nonpurified galactomannan polysaccharide containing less than 80 wt % of galactomannan was cation-modified, i.e., Samples 12 and 13 in Table 1 which were obtained in Comparative Example 1. The obtained products were named as comparative prescriptions 3 and 4.

TABLE 6Prescription of Shampoo PreparationsWeight ratio (%,in terms of solids)ReferenceComparativeprescriptionprescriptionsIngredients(A)(B)(C)(D)(E)(F)(G)(1)Present invention0.600(samples 1-5)(2)Comparative samples (sample000.610-13)(3)Cationic water-soluble polymer00.4000.200A (Catinal HC-100)Cationic water-soluble polymer000.40000B (Merquat 550)(4)Amphoteric water-soluble polymer0000.40.200(Yukaformer SM)(5)Polyoxylethylene(1,5)laurylether6.06.06.0sulfuric acid triethanol amine(6)Polyoxyethylene(3)laurylether3.03.03.0sulfuric acid sodium(7)Coconut oil fatty acid amide4.54.54.5propylbetaine(8)Coconut oil fatty acid2.52.52.5monoethanol amide(9)Dipropylene glycol3.03.03.0(10)Ethylene glycol distearate1.01.01.0(11)Sodium edetate0.10.10.1(12)Sodium benzoate0.10.10.1(13)Aqueous solution of citric acidas appropriateasas(for pH adjustment, pH 5.5-6.0)appropriateappropriate(14)Distilled waterrestrestrest

9-h (Preparation of Comparative Prescription)

To further compare the effects with other cationic, a comparative shampoo sample was prepared by using, instead of the cation-modified nonpurified galactomannan polysaccharide in the above section 9-f, a cation-modified guar gum, in which the composition ratio of mannose and galactose is 2:1 though it is the same galactomannan polysaccharide, containing nitrogen at 1.9 wt % (Catinal CG-100, Toho Chemical Industry Co., Ltd.). The ingredients shown under column (G) of Table 6 were treated in the same manner as described in the above section 9-f to provide the comparative shampoo preparation which was named comparative prescription 5.

(Evaluation)

Example 10

In this test, test prescriptions 1 to 13 prepared as described in the above sections 9-a to 9-e, and a reference prescription were used. The reference prescription with a composition as shown under column (F) of Table 6 was obtained by using ingredients similar to those used for the production of test and comparative prescriptions and treating them similarly, except that they did not contain any cationic polymer.

Of test prescriptions 1 to 13, and the reference prescription, ten testers washed their hair using each of the prescriptions, and dried the hair with a dryer. The testers compared the conditioning effects of the respective test prescriptions as described below during and after use with those of the reference prescription. The conditioning effects compared consisted of:

- foam-formation (lathering) at washing
- smoothness during use (finger-passing and feeling of hair)
- comb-passing feeling after use (dried hairs).
  The tester's evaluation was scored according to the following five rank scale. For each of the test prescriptions, the scores of the ten testers were summed as in shown in Table 7, and the sum of ten testers' evaluation was taken as its overall evaluation result. The evaluation results of the test prescriptions are shown in Table 8. The reference prescription (F) was prepared in such a manner that distilled water (ingredient (14)) was heated to 65Â° C. to which the ingredients (5) to (10) were added. The mixture was stirred until it became a uniform liquid. To the mixture which was cooled to 30 to 40Â° C., ingredients (11) to (13) were added, and the mixture was stirred to homogeneity.

Comparative Example 2

With regard to comparative prescriptions 1 to 5 prepared as described in 9-f to 9-h, their conditioning effects were compared with those of the reference prescription in the same manner as in Example 10. The thus obtained evaluation results of comparative prescriptions 1 to 5 are shown in Table 8.

TABLE 7Ranking Scale for Evaluating Test PrescriptionsTest propertiesDuring useFoamEasy finger-After useformationpassingFeelingEasy comb-Score(Lathering)at washingof wet hairpassing+2HigherBetterSmootherBetter+1Slightly higherSighlty betterSlightlySlightlysmootherbetter0SameSameSameSameâˆ’1Slightly lowerSlightly worseSlightly moreSlightlystickyrigidityâˆ’2LowerWorseMore stickyRigidity

TABLE 8Evaluation Results of Shampoo PreparationsDuring useAfter useFoam-Easy fingerEasyCationicformationpassingFeeling ofcomb-polymer used(Lathering)at wasingwet hairspassingTest1Sample 116171615presciption2Sample 2161515153Sample 3161615144Sample 4151717165Sample 5161616146Sample 6171717157Sample 7171616168Sample 8171716159Sample 91516161510Sample 1CatinalHC-1001717171611Merquat 5501716161712Yukaformer16161616SM13Catinal17171616HC-100 andYukaformerSMComparative1Sample 105âˆ’10âˆ’81prescription2Sample 11âˆ’2âˆ’7âˆ’6âˆ’63Sample 1291010104Sample 131011995Catinal CG-10081195

From the results of Table 8, it was confirmed that when the cation-modified purified galactomannan polysaccharides of the present invention prepared by cation-modifying purified galactomannan polysaccharide were added to a shampoo preparation, foam-formation (lathering) at washing hairs was improved and conditioning effects such as finger-passing and feeling during use were superior, and conditioning effects of comb-passing after hair-dried were superior.

On the other hand, the comparative prescriptions 3 and 4 containing samples 12 and 13 prepared by cation-modifying nonpurified galactomannan polysaccharide were worse in conditioning effects such as â€œfinger-passing at washingâ€ , etc. in comparison with the cation-modified purified galactomannan polysaccharides of the present invention, and were poor in smoothness and finish-feeling after use. From these facts, it was shown that the performance was improved by the cation-modified purified galactomannan polysaccharides of the present invention prepared by cation-modifying purified galactomannan polysaccharide containing 80 wt % or more of galacttomannan. Moreover, by using, together, a cationic water-soluble polymer (Catinal HC-100, Merquat 550) and/or an amphoretic water-soluble polymer (Yukaformer SM) as the compounding ingredients, the conditioning effects of the test prescriptions were found to be enhanced without disturbing the performance possessed by the cation-modified purified galactomannan polysaccharide of the present invention. It was confirmed that when the test prescriptions are compared with the comparative prescription 5 which contains a cationic polymer (cation-modified guar gum: Catinal CG-100) prepared by cation-modifying galactomannan polysaccharide in which composite ratio of mannose and galactose is 2: 1, the present invention surpassed in both â€œduring useâ€ and â€œafter useâ€ and conferred smoothness at washing hairs and finish-feeling after hair dry which the cation-modified purified galactomannan polysaccharide of the present invention has, in comparison with the conventional conditioning agents which have not such smoothness and finish-feeling.

(Exemplary Shampoo Compositions 1-5)

Preferred shampoo compositions according to the present invention will be described below.

TABLE 9Composition 1. Shampoo (1)IngredientWeight ratio (%)Plyoxyethylene(3)lauryl ether sulfonic acid sodium6.0Coconut oil fatty acid amide methyl taurine sodium3.0Sodium Lauroamphoacetate3.0Lauric acid propylene glycol0.9Coconut oil fatty acid diethanol amide1.0Polyoxyethylene(4)alkyl(C12-14)sulfosuccinic2.0acid disodiumCationic cellulose0.5Present invention (Sample 2)0.2Propylene glycol0.3Sodium chloride0.5Sodium benzoate0.3Disodium 2 edetateâ€‚0.05Purified waterrestPerfume0.3

Purified water was heated to 70Â° C., to which other ingredients were added and dissolved to homogeneity. The mixture was then cooled.

TABLE 10Composition 2. Shampoo (2)IngredientWeight ratio (%)Distearic acid ethylene glycol2.0Coconut oil fatty acid amide methyl taurine sodium8.0Perm kernel fatty acid amide propylbetaine5.0Present invention (Sample 1)0.5Laurylhydroxysulfobetaine1.5Coconut oil fatty acid amide monoethanolamide3.0Stearic acid dimethylaminoproply amide0.3Citric acid0.55Sodium chloride1.2Phenoxyethanol0.1Perfume, pigment, preservativeas appropriateMetal ion sealant, pH adjusteras appropriatePurified waterrest

Purified water was heated to 70Â° C., to which other ingredients were added and dissolved to homogeneity. The mixture was then cooled.

TABLE 11Composition 3. Shampoo (3)IngredientsWeight ratio ((%)Polyoxyethylene(2)laurylether sulfuric acid sodium10.0Polyoxyethylene coconut oil fatty acid2.0monoethanolamide sulfuric acid sodiumDistearic acid ethylene glycol1.8Lauric acid propylene glycol2.0Coconut oil fatty acid amide propylbetaine4.0Methylpolysiloxane micro-emulsion1.0Present invention (Sample 6)0.3Polyquaternium-70.1Propylene glycol2.0Coconut oil fatty acid amide diethanolamide0.5Glyceryl oleate0.2Citric acid0.8Alginine0.1Sodium chloride0.4Phenoxyethanol0.1Sodium benzoate0.3Disodium edetate0.05Purified waterrestPerfumeas appropriate

Purified water was heated to 70Â° C., to which other ingredients were added and dissolved to homogeneity. The mixture was then cooled.

TABLE 12Composition 4. Shampoo (4)IngredientWeight ratio (%)Present invention (Sample 1)0.3Polyquaternium-70.1Cation-modified fenugreek gum (*1)0.2Distearic acid ethylene glycol2.0Coconut oil fatty acid amide methyl taurine sodium5.0Coconut oil fatty acid amide sarcosine sodium3.0Perm kernel fatty acid amide propylbetaine5.0Laurylhydroxysulfobetaine1.5Coconut oil fatty amide monoethanolamide3.0Octenylsuccinic acid dextrin ester0.5Stearic acid dimethylaminopropyl amide0.3Citric acid0.55Sodium chloride1.2Phenoxyethanol0.1Perfume, pigment, preservativeas appropriateMetal ion sealant, pH adjusteras appropriatePurified waterrest
Purified water was heated to 70Â° C., to which other ingredients were added and dissolved to homogeneity. The mixture was then cooled.

(*1) Cation-modified fenugreen gum (INCI name: Trigonella Foenum-Graecum Hydroxypropyltrimonium Chloride)

(INCI name: International Nomenclature Cosmetic Ingredient name)

TABLE 13Composition 5. Shampoo (5)IngredientWeight ratio (%)Present invention (Sample 2)0.1Present invention (Sample 8)0.3Cation-modified guar gum *20.2Distearic acid ethylene glycol2.0Coconut oil fatty acid amide methyl taurine sodium6.0Polyoxyethylene coconut oil fatty acid3.0monoethanolamide sulfuric acid sodiumCoconut oil fatty acid amide propylbetaine5.0Lauryl dimethylamino acetic acid betaine1.5Coconut oil fatty acid diethanolamide3.0Highly polymerized methyl polysiloxane0.2Polyoxyethylene(4)laurylether0.2Sodium chloride1.2Phenoxyethanol0.1Perfume, pigment, preservativeas appropriateMetal ion sealant, pH adjusteras appropriatePurified waterrest
Purified water was heated to 70Â° C., to which other ingredients were added and dissolved to homogeneity. The mixture was then cooled.

*2 Cation-modified guar gum (INCI name: Guar Hydroxypropyltrimonium Chloride)

As a result that effects in the costmetic compositions prepared according to composition examples 1 to 5 were confirmed, foam-formation (lathering) and foam quality during washing hairs were improved, conditioning effects such as finger-passing during hair-washing and during rinsing and feeling were excellent, and further, conditioning effects such as comb-passing and feeling after hair-drying.

Hair Rinse

(Preparation)

Example 11

11-a

The cation-modified purified galactomannan polysaccharides prepared in Examples 1, 2, 3 and 5 and named Samples 1, 4, 5 and 7 were used to prepare hair rinse samples whose composition is as shown in column (A) of Table 14 below. The hair rinse sample contained an amideamine compound, a behenic acid methylaminopropylamide citric acid salt which had been neutralized by citric acid as a neutralizer, and a higher alcohol (cetanol). The hair rinse sample was prepared as follows. Ingredients (5) to (9) and (11) specified in column (A) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. One of the test Samples 1, 4, 5 and 7 (ingredient (1)) was previously added with stirring to distilled water (ingredient (13)), and the mixture was stirred until it was dissolved. The solution, after being heated to 80Â° C., was poured into the above liquid with stirring, and an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled, and the mixture was stirred until it became a uniform solution. Thus, hair rinse sample with compositions as shown under column (A) of Table 14 were obtained. The hair rinse samples containing the cation-modified purified galactomannan polysaccharides of the present invention represented by samples 1, 4, 5 and 7 were named test prescriptions 14 to 17.

11-b

The cation-modified purified galactomannan polysaccharides prepared in Example 1 and named Sample 1 and a cation-modified hydroxyethyl cellulose containing nitrogen at 1.8 wt % into which an average of 1.8 mol of ethylene oxide was introduced (Catinal HC-100, Toho Chemical Industry Co., Ltd.) were combined at the weight ratios specified in Table 14 to give a mixture to which ingredients shown under column (B) of Table 14 were added, and the resulting product was used as a test hair rinse sample. Specifically, ingredients (5) to (9) and (11) specified in column (B) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. Ingredient (1) and Catinal HC-100 (ingredient (3)) were previously added with stirring to distilled water (ingredient (13)), and the mixture was stirred until it was dissolved. The solution, after being heated to 80Â° C., was poured into the above liquid with stirring, and the mixture was stirred until it became a uniform solution. Then, an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled. The obtained sample was named test prescription 18.

11-c

The cation-modified purified galactomannan polysaccharides prepared in Example 1 and named Sample 1 and a copolymer of N-methacryloyloxyethyl N,N-dimethyl ammonium-a-methylcarboxylbetaine and alkyl methacrylate (Yukaformer SM, Mitsubishi Chemicals Co.) as an amphoteric water-soluble polymer were combined into a mixture to which ingredients shown under column (C) of Table 14 were added and the resulting product was used as a test hair rinse sample. Ingredients (5) to (9) and (11) specified in column (C) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. Ingredient (1) and Yukaformer SM (ingredient (4)) were previously added with stirring to distilled water (ingredient (13)), and the mixture was stirred until it was dissolved. The solution, after being heated to 80Â° C., was poured into the above liquid with stirring, and the mixture was stirred until it became a uniform solution. Then, an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled. The mixture was stirred until it became a uniform solution. The obtained sample was named test prescription 19.

11-d

The cation-modified purified galactomannan polysaccharides prepared in Example 1 and named Sample 1 were used to prepare hair rinse samples whose composition is as shown in column (D) of Table 14 below. The hair rinse sample contained an amideamine compound, a behenic acid dimethylaminopropylamide citric acid salt which had been neutralized by citric acid as a neutralizer, a higher alcohol (cetanol) and a silicone (methylpolysiloxane). The hair rinse sample was prepared as follows. Ingredients (5) to (11) specified in column (D) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. Ingredient (1) was previously added with stirring to distilled water (ingredient (13)), and the mixture was stirred until it was dissolved. The solution, after being heated to 80Â° C., was poured into the above liquid with stirring, and the mixture was stirred until it became a uniform solution. Then, an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled. The obtained sample was named test prescription 20.

11-e (Preparation of Comparative Prescriptions)

To compare the effects of the test hair rinse preparations containing the cation-modified purified galactomannan polysaccharide of the present invention, comparative shampoo samples were prepared by using the cation-modified purified galactomannan polysaccharides prepared in Supplement 1 and listed in Table 1 under the names samples 10 and 11. The composition of the comparative hair rinse samples was as shown under column (F) of Table 14. Specifically, ingredients (5) to (9) and (11) specified in column (F) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. Ingredient (2) was previously added with stirring to distilled water (ingredient (13)), and the mixture was stirred until it was completely dissolved. The solution, after being heated to 80Â° C., was poured into the above liquid with stirring, and the mixture was stirred until it became a uniform solution. Then, an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled. The mixture was stirred until it became a uniform solution. Thus, hair rinse samples containing Samples 10 and 11 in Table 1 were obtained. These samples were named comparative prescriptions 6 and 7, respectively.

11-f (Preparation of Comparative Prescription)

To further compare effects, rinses having the composition shown under comparative prescription (F) in Table 14 were prepared in similarity with the above section1 -e by using, instead of the Samples 10 and 11, cation-modified nonpurified galactomannan polysaccharide in which nonpurified galactomannan polysaccharide was cation-modified, i.e., Samples 12 and 13 in Table 1 which were obtained in Comparative Example 1. The obtained rinses were named as comparative prescriptions 8 and 9.

TABLE 14Prescription of Rinse PreparationsWeight ratio (%) in termsof solids)ReferenceComparativeprescriptionprescriptionIngredient(A)(B)(C)(D)(E)(F)(1)Present invention1.000(Samples 1, 4, 5 and 7)(2)Comparative samples001.0(Samples 10, 11, 12, 13)(3)Cationic water-soluble00.50000polymer (Catinal HC-100)(4)Amphoeric water-soluble000.5000polymer (Yukafomer SM)(5)Behenic acid dimethyamino-2.02.02.0propylamide citric acid salt(6)Cetyl lactate2.02.02.0(7)Polyoxyethylene(4)-1.01.01.0stearylether(8)Isopropyl palmitate1.01.01.0(9)Cetanol6.06.06.0(10)Methylpolysiloxane0000.800(11)Paraoxybenzoic acid methyl0.10.10.1(12)Aqueous solution of citric acidas appropriateasas(for pH adjustment,appropriateappropriatepH 4.0-4.5)(13)Distilled waterrestrestrest

(Evaluation)

Example 12

In this test, performance evaluation shown in the following items was conducted with respect to the test prescriptions 14 to 20 prepared as described in the above sections 11-a to 11-d (rinse) by using ten testers. Performance evaluation system used rinse having composition shown under a reference prescription (E) in Table 14 containing no cationic polymer in its ingredient and rinses to be evaluated.

Of test prescriptions 10 to 15, and the reference prescription having no cationic polymer, ten testers washed their hair using each of the prescriptions, and dried the hair with a dryer. The testers compared use feeling of finger-passing during rinsing and of drying by use of a dryer with respect to the respective test prescriptions with those of the reference prescription (E).

- smoothness during rinsing (finger-passing)
- existence of conditioning effects of dried hairs (comb-passing and frictional feel)

The tester's evaluation was scored according to the following five rank scale in Table 15. For each of the test prescriptions, the scores of the ten testers were summed. The evaluation results of the test prescriptions are shown in Table 15. Ingredients (5) to (11) specified in column (E) of Table 14 were heated to 80Â° C. and stirred until the mixture became a uniform liquid. Distilled water (ingredient (13)), after being heated to 80Â° C., was poured into the above liquid with stirring, and the mixture was stirred until it became a uniform solution. Then, an aqueous solution of citric acid (ingredient (12)) was added to the mixture while the mixture was being cooled. The mixture was stirred until it became a uniform solution.

Comparative Example 3

With regard to comparative prescriptions 6 to 9 prepared as described in 11-e and 11-f, their conditioning effects were compared with those of the reference prescription in the same manner as in Example 12. The thus obtained evaluation results of comparative prescriptions 6 to 9 are shown in Table 16.

TABLE 15Ranking Scale for Evaluating Test PrescriptionsTest propertiesScoreFinger-passingComb-passingFrictional feel+2BetterBetterSmaller+1Slightly betterSlightly betterSlightly smaller0SameSameSameâˆ’1Slightly worseSlightly worseSlightly largerâˆ’2WorseWorseSlightly larger

TABLE 16Evaluation Results of Rinse PreparationsTest prescriptions1819Comparative14151617Sample 1PrescriptionsTest cationicSam-Sam-Sam-Sam-CatinalYukaformer206789polymersple 1ple 4ple 5ple 7HC-100SMSample 1Sample 10Sample 11Sample 12Sample 13Finger-passing161716161717160âˆ’2109at rinsingAt driedComb-16161617151516âˆ’4âˆ’3910passingFrictional131413131413150299feel

From the results of Table 16, it was confirmed that the hair rinse preparations which contained, in addition to the cation-modified purified galactomannan polysaccharide of the present invention which was prepared by cation-modifying purified galactomannan polysaccharide containing 80 wt % or more of galactomannan, an amideamine compound, neutralizer and higher alcohol (cetanol) were excellent in smoothness of the compositions at rinsing. Moreover, since comb-passing after drying hairs was improved and conditioning effects such as less frictional feel enabled to be obtained, it was confirmed good finish feel by the present invention in the systems containing an amideamine compound, neutralizer and higher alcohol.

Furthermore, when the performance of the test hair rinse preparations (Test prescriptions 14 to 20) containing the amideamine compound, neutralizer and higher alcohol were compared with nonpurified cation-modified galactomannan polysaccharides prepared by cation-modifying nonpurified galactomannan polysaccharide containing less than 80 wt % of galactomannan (Comparative prescriptions 8 to 9) of the Samples 12 and 13, it was confirmed that the present compositions were excellent in both conditioning effects during use and finish feel after use. This means that the cation-modified purified galactomannan polysaccharide of the present invention reduces precipitates derived from outer cover, proteins and water-unsoluble substances in comparison with the conventional nonpurified cation-modified galactomannan polysaccharide prepared by cation-modifying nonpurified galactomannan polysaccharide containing less than 80 wt % of galactomannan, whereby good smoothness during rinse treatment was obtained and at the same time, finish feel after use enabled to be improved. Moreover, it was confirmed that by using, together, cationic water-soluble polymer and/or amphoeric water-soluble polymer, the conditioning effects of the test prescriptions were found to be enhanced without disturbing the performance possessed by the cation-modified purified galactomannan polysaccharide of the present invention. Furthermore, it was confirmed that by containing silicone such as methylpolysiloxane, etc., conditioning effects enabled to be improved without disturbing the performance possessed by the cation-modified purified galactomannan polysaccharide of the present invention.

(Exemplary Hair Rinse Compositions 6-9)

Preferred hair treatment compositions such as hair rinses, hair conditioners, etc., according to the invention which require conditioning effects will be described below.

TABLE 17Composition 6. Rinse (1)IngredientsWeight ratio (%)Olive oil0.3Stearyl alcohol2.5Cetyl alcohol2.7Glycerin4.01,3-butylene glycol5.0Hydrolyzed wheat0.2Hydroxystearic acid0.52-ethylhexanoic acid cetyl1.0Distearyldimethylammonium chloride0.2Hydroxypropyltrimonium chloride starch0.3Behenic acid dimethylaminopropylamide0.5Present invention (Sample 4)1.0L-glutamic acid0.5Silicone oil2.0Perfume, Pigment, Preservativeas appropriatePurified waterrest

To purified water in Table 17, the cation-modified purified galactomannan polysaccharide of the present invention, hydroxypropyltrimonium chloride starch, behenic acid dimethylaminopropylamide, hydrolyzed wheat, L-glutamic acid, glycerin, 1,3-butylene glycol, and the mixture was maintained at 80Â° C. (water phase). The remaining ingredients in Table 17 were combined and heated so that they were dissolved, and the mixture was maintained at 80Â° C. (oil phase). The water phase was combined with the oil phase, and the mixture was spun with a homogenizer to be emulsified. Then, the emulsion was cooled with stirring.

TABLE 18Composition 7. Rinse (2)IngredientsWeight ratio (%)Isopropyl palmitate3.0Cetyl lactate3.0Behenyl alcohol2.0Stearyl alcohol2.0Hydroxypropyltrimonium hydrolyzed keratin0.3Stearyltrimethylammonium chloride0.7Glycerin0.45Isocetyl myristate0.1Mink fat fatty acid ethyl0.2Self-emulsified monostearic acid glycerin0.2Present invention (Sample 3)1.2Copolymer of aminoethylaminopropylsiloxane and2.0dimethylsiloxaneDimethylpolysiloxane0.5Phenoxyethanol0.5Pigmentas appropriatePerfumeas appropriatePurified waterrest

To purified water in Table 18, the cation-modified purified galactomannan polysaccharide of the present invention, stearyltrimethylammonium chloride, glycerin, hydroxypropyltrimonium hydrolyzed keratin, phenoxyethanol and pigment were added, and the mixture was maintained at 75Â° C. (water phase). The remaining ingredients in Table 18 were combined and heated so that they were dissolved, and the mixture was maintained at 75Â° C. (oil phase). The water phase was combined with the oil phase, to which isopropanol was added, and the mixture was spun with a homogenizer to be emulsified. Then, the emulsion was cooled with stirring.

TABLE 19Composition 8. Rinse (3)IngredientsWeight ratio (%)Present invention (Sample 3)0.3Present invention (Sample 7)0.4Polyquaternium-70.2Polyquaternium-220.1Octyl palmitate3.0Cetyl lactate3.0Behenyl alcohol2.0Cetanol1.5Stearyltrimethylammonium chloride1.0Glycerin0.45Isocetyl myristate0.1Mink fat fatty acid ethyl0.2Polyoxyethylene(4)stearylether0.5Dimethylpolysiloxane2.0Glyceryl stearate1.0Phenoxyethanol0.5Pigment, Perfumeas appropriatePurified waterrest

Rinse was prepared by a conventional method.

TABLE 20Composition 9. ConditionerIngredientsWeight ratio (%)Cetanol1.5Behenyl alcohol4.01,3-butylene glycol1.0Glycerin2.02-ethylhexanoic acid cetyl2.0Isocetyl myristate0.4Mink fat fatty acid ethyl0.1Polyoxyethylene(4)stearylether1.0N-(3-alkyl(12,14)oxy-2-hydroxypropyl)-L-0.6alginic hydrochloridePresent invention (Sample 8)0.6Stearic acid dimethylaminopropylamide1.550% lactic acid0.9Phenoxyethanol0.3Sodium benzoate0.3Perfume0.5Purified waterrest

To purified water in Table 20 cation-modified purified galactomannan polysaccharide of the present invention, N-(3-alkyl(12, 14)oxy-2-hydroxypropyl)-L-alginic hydrochloride, Stearic acid dimethylaminopropylamide, 50% lactic acid, glycerin, phenoxyethanol and sodium benzoate were added, and the mixture was maintained at 70Â° C. (water phase). The remaining ingredients were combined and heated so that they were dissolved, and the mixture was maintained at 70Â° C. (oil phase). The water phase was combined with the oil phase, and the mixture was spun with a homogenizer to be emulsified. Then, the emulsion was cooled with stirring.

As a result that effects in the costmetic compositions prepared according to composition examples 6 to 9 were confirmed, smoothness during rinse treatment was excellent, comb-passing after hair-dry was improved glating feeling was less and accordingly, conditioning effects were excellent.

Hair Color

(Preparation)

Example 13

13-a

The cation-modified purified galactomannan polysaccharide prepared in Example 1 and 5 and named Samples 1 and 7 were used to prepare two-component oxidation hair color samples whose composition was as shown in column (A) of Table 21 below. The two-component oxidation hair color samples containing the cation-modified purified galactomannan polysaccharides of the Samples 1 and 7 were named test prescriptions 21 and 22, respectively. At the time of use, the first and second components of each hair color sample was mixed at 1:1 weight ratio, and the mixture was applied to the hair.

13-b (Preparation of Comparative Prescriptions)

To compare the effects of the cation-modified purified galactomannan polysaccharide of the present invention in hair color preparations, a comparative hair color sample was prepared by using the nonpurified cation-modified galactomannan polysaccharide obtained in Comparative Example 1 in which nonpurified galactomannan polysaccharide containing less than 80 wt % of galactomannan content, i.e., Sample 13 in Table 1, to which ingredients specified under column (C) of Table 21 were added to provide a two-component oxidation hair color sample. The two-component oxidation hair color sample which contained nonpurified cation-modified tara gum of Sample 13 in Table 1 was named comparative prescription 10. At the time of use, the first and second components of the hair color sample was mixed at 1:1 weight ratio, and the mixture was applied to the hair.

TABLE 21Prescription of Combinational Oxidation Hair ColorWeight ratio (%,in terms of solids)ReferenceComparativeprescriptionprescriptionIngredients(A)(B)(C)1st component(1)Test prescriptions (Samples 1, 7)0.500(2)Comparative preparation (Sample 13)000.5(3)Cetostearylalcohol5.0(4)POE(5)behenylether2.0(5)POE(20)stearylether2.0(6)Highly polymerized silicone0.2(7)Propylene glycol2.0(8)Liquid paraffin5.0(9)28% aqueous ammonium solution2.0(10)Toluene-2,5-diamine1.5(11)Resorcin1.0(12)Disodium edetate0.2(13)Purified waterrest2nd component(1)Aqueous hydrogenperoxide solution (35%)17.0(2)Cetanol2.0(3)POE(30)cetylether3.0(4)POE(2)laurylether sulfuric acid sodium0.3(5)Methylparaben0.1(6)Citric acid (pH 3.5)as appropriate(7)Disodium hydrogenphosphate0.1(8)Disodium edetate0.2(9)Purified waterThe rest

(Evaluation)

Example 14

In this test, performance evaluation shown in the following items was conduced with respect to the test prescriptions 21 and 22 prepared as described in the above section 13-a, and a reference prescription were used. The reference prescription had a composition as shown under column (B) of Table 21.

Preparation of the reference prescription occurred as in the test prescriptions, except that it did not contain any cationic polymer.

For each of the test prescriptions, the first and second components were combined in equal amounts prior to use, and the mixture was applied to the hair. The hair was left at room temperature for 30 minutes, rinsed for 3 minutes with running water kept at 40Â° C., and dried with a drier.

Ten testers participated to evaluate the performance of the test prescriptions as compared with the reference prescription (B) with special attention being paid to:

- smoothness of the hairs during rinsing, and
- feeling after hair-dry.
  The tester's evaluation was scored according to the following five rank scale in Table 22.

For each of the test prescriptions, the scores of the ten testers were summed and the sum was taken as its overall evaluation result (in Table 22). The evaluation results of the test prescriptions are shown in Table 23. In that time, first and second components of each of hair color samples were mixed at 1:1 weight ratio, and the mixture was applied to hair.

Comparative Example 4

With regard to comparative prescription 10 prepared as described in the above section 13-b, its performance was compared with that of the reference prescription in the same manner as in Example 14. The thus obtained evaluation results are shown in Table 23.

TABLE 22Ranking Scale for Evaluating Test PrescriptionsTest propertiesSmoothnessFinish feel afterScoreduring rinsingdrying hairs+2BetterBetter+1Slightly betterSlightly better0SameSameâˆ’1Slightly worseSlightly worseâˆ’2WorseWorse

TABLE 23Evaluation Results of Combinational Hair Color PrescriptionsComparativeTest prescriptionsprescriptions212210Test cationic polymersSample 1Sample 7Sample 13Smoothness during rinsing14135Finish feel after drying hairs12114

The results of Table 23 indicate that the cation-modified purified galactomannan polysaccharide of the present invention, when added to a hair color preparation, enhances the smoothness of the hairs during rinsing which contributed to the treatment of damaged hairs, and enabled easy finger-passing. It also improved finish feel after drying hairs. Thus, it was confirmed the cation-modified purified galactomannan polysaccharide of the invention brought about beneficial effects when added to a hair color composition.

Further, it was confirmed that when the test prescriptions are compared with comparative prescription 10, the former preparations 21 and 22 of the present invention ensured more improved smoothness during rinsing treatment finish feel after drying of hairs in comparison with the comparative prescription 10 which contained the nonpurified cation-modified galactomannan polysaccharide, and they treated more effectively damaged hairs in comparison with the conventional nonpurified cation-modified galactomannan polysacchardies.

(Exemplary Two-Component Hair Color Compositions 10 and 1 1)

The following shows preferred hair color compositions which utilize the conditioning effects by the cation-modified purified galactomannan polysaccharide of the present invention on damaged hairs.

TABLE 24Composition 10. Prescription of CombinationalOxidation Hair ColorWeightIngredientsratio (%)1stâ€‚(1)Test prescriptions (Samples 2)0.3componentâ€‚(2)Polyquaternium-60.15â€‚(3)Polyquaternium-100.15â€‚(4)Stearyltrimethylammonium1.0chlorideâ€‚(5)POE(20)oleylether5.0â€‚(6)POE(10)hexyldecilether10.0â€‚(7)Liquid amidopropylbetaine laurate5.0â€‚(8)Cetanol5.0â€‚(9)Propylene glycol15.0(10)Polyethylene glycol5.0(11)Sodium thioglycolate0.5(12)Aminopropyldimethicone0.4(13)Toluene 2,5-diamine3.0(14)Resorcin0.8(15)2,4-diaminophenoxyethanol0.2hydrogen chloride(16)Paraphenylene diamine0.2(17)Metha-aminophenol0.2(18)28% aqueous ammonium solution5.0(19)Sodium sulfite0.5(20)Perfumeas appropriate(21)Preservativeas appropriate(22)Purified waterrest2ndâ€‚(1)Aqueous hydrogenperoxide17.0componentsolution (35%)â€‚(2)Cetanol1.0â€‚(3)Sodium laurylsulfate0.3â€‚(4)Phenacetin0.1â€‚(5)Disodium edetate0.2â€‚(6)Purified waterrest

Prescription of combinational oxidation hair color was prepared by a conventional method.

TABLE 25Compositon 11. Prescription of CombinationalHair-DecoloringWeightIngredientsratio (%)1stâ€‚(1)Test prescription (Samples 7)1.5componentâ€‚(2)Aqueous solution of3.0hydrolyzed collagen (36.5%)â€‚(3)Coconut oil fatty acid amidopropyl30.0betaineâ€‚(4)POE(2)dodecilether15.0â€‚(5)POE(10)cetylether15.0â€‚(6)Aminopropyldimethicone0.3â€‚(7)2-octyldecanol4.5â€‚(8)Polyethylene glycol5.0â€‚(9)Trimethylbehenylammonium1.0chloride(10)28% aqueous ammonium solution2.0(11)Ascorbic acid0.5(12)Anhydrous sodium sulfite0.2(13)Perfumeas appropriate(14)Preservativeas appropriate(15)Purified waterrest2ndâ€‚(1)Aqueous hydrogenperoxide15.0componentsolution (35%)â€‚(2)Cetanol2.0â€‚(3)POE(20)cetylether3.0â€‚(4)Sodium larylsulfate0.5â€‚(5)Preservative0.1â€‚(6)glycolic acidas appropriateâ€‚(7)Disodium hydrogenphosphate0.1â€‚(8)Disodium edetate0.2â€‚(9)Purified waterrest

Prescription of combinational hair-decoloring color was prepared by a conventional method.

As a result that effects in the costmetic compositions prepared according to composition examples 10 to 11 were confirmed, smoothness during rinse treatment was excellent and finish feel after drying hairs were excellent, and conditioning effects were excellent.

(Compositions 12 to 13)

Preferable composition examples of the present invention which are applied to other hair-treatment compositions which require conditioning effects are shown in the following.

TABLE 26Composition 12. Hair WaxIngredientsWeight ratio (%)Present invention (Sample 1)0.3Cation-modified guar gum (*3)0.1Polyquaternium-60.1Polyquaternium-280.3Liquid paraffin10.0Micro-crystalline wax10.0Methylpolysiloxane5.0Stearyl alcohol3.0Propylene glycol10.0Carnauba wax3.0Isostearic acid1.0Stearic acid5.0Tetra 2-ethylenehexanic acid pentaelisulit2.0Polyoxyethylene hardened castor oil3.0Polyoxyethylenelaurylether phosphoric acid2.0Self-emulsified monostearic acid glyceryl2.0Triethanolamine1.0D-Î´-tocophenol0.05Oat extract0.1Paraoxybenzoic acid ester0.2Polyacrylic acid sodium0.05Purified waterrestPerfume0.08
Hair wax was prepared by a conventional method.

(*3) Cation-modified guar gum (INCI name: Guar Hydroxyproplytrimonium Chloride)

TABLE 27Composition 13. Hair GelIngredientsWeight ratio (%)Present invention (Sample 3)0.8Polyquaternium-70.2Polyquaternium-111.0Glycerin5.0Ethanol20.0Polyoxyethyleneoctyldodecylether1.0Perfume, Chelating agentas appropriatePurified waterrest

Hair gel was prepared by a conventional method.

Body Cleansing Preparation

(Preparation)

Example 15

15-a

The cation-modified cation-modified purified galactomannan polysacchardie prepared in Examples 1, 2 and 5, and named Samples 1, 4 and 7 were used to prepare body cleansing samples (body soaps) whose composition was as shown in column (A) of Table 28 below. Specifically, distilled water (ingredient (11)) was heated to 60Â° C., to which one of the test Samples 1, 4 and 7 (ingredient (1)) was added with stirring, and the mixture was further stirred until it became a uniform solution. Then, ingredients (3) to (7) were added to the solution at 50 to 60Â° C. with stirring and the mixture was further stirred until it was completely dissolved. Similarly, ingredients (8) to (10) were added to the mixture at 30-40Â° C. with stirring and dissolved to homogeneity. Thus, three kinds of body cleansing samples with compositions as shown under column (A) of Table 28 were obtained. The three body cleansing samples containing the cation-modified purified galactomannan polysaccharide represented by Samples 1, 4 and 7 were named test prescriptions 23, 24 and 25, respectively.

TABLE 28Prescription of Body Cleansers (Body Soaps)Weight ratio (%, in terms of solids)ReferenceComparativeprescriptionprescriptionsIngredients(A)(B)(C)â€‚(1)Test prescriptions (Sample 1, 4, 7)0.400â€‚(2)Comparative samples (Sample 12,000.4Cational HC-100)â€‚(3)Lauryl sulfuric acid ammonium9.59.59.5â€‚(4)Polyoxyethylene(3)laurylether sulfuric acid222sodiumâ€‚(5)Polyoxyethylene(2)laurylether phosphoric444acid sodiumâ€‚(6)Coconut oil fatty acid amide propylbetaine333â€‚(7)Coconut oil monoethanol amide2.72.72.7â€‚(8)Disodium edetate0.20.20.2â€‚(9)Sodium benzoate0.20.20.2(10)Aqueous solution of citric acidappropriateappropriateappropriate(for pH adjustment, pH 5.7-6.2)(11)Distilled waterrestrestrest

15-b (Preparation of Comparative Prescription)

To compare the effects of the cation-modified purified galactomannan polysaccharide of the present invention with those of a conventional cationic polymer in body cleansing preparations, the Sample 12 obtained in the Comparative Example 1 and another comparative body cleansing samples as other cationic polymer were prepared by using a cation-modified hydroxyethyl cellulose containing nitrogen at 1.8 wt % into which an average of 1.8 mol of ethylene oxide was introduced (Catinal HC-100, Toho Chemical Industry Co., Ltd.), and adding thereto ingredients specified under column (C) of Table 28. Specifically, distilled water (ingredient (11)) was heated to 60Â° C., to which Catinal HC-100 (ingredient (2)) was slowly added with stirring and dissolved. After recognizing the dissolution, ingredients (3) to (7) were added to the solution at 50 to 60Â° C. with stirring and the mixture was further stirred until it was dissolved to homogeneity. Then, ingredients (8) to (10) were added to the solution at 30 to 40Â° C. with stirring in the same manner as above, until they were dissolved to homogeneity. Thus, body cleansing samples with a composition as shown under column (C) of Table 28 were obtained. The samples were named comparative prescriptions 11 and 12.

(Evaluation)

Example 16

In this test, test prescriptions 23, 24 and 25 prepared as described in the above section 15-a and a reference prescription were used. The reference prescription had a composition as shown under column (B) of Table 28, the reference prescription containing no high polyer such as cationic polymer, etc. in this ingredients.

Each of the test prescriptions was used by ten testers to wash their body. The testers evaluated the performance of the test prescriptions as compared with the reference prescription with special attention being paid to:

*foam amount and foam quality during use,

- use feeling during use (easy rinsing, no tautness and sliminess after rinsing), and
- use feeling after use (after dried) (no tautness, smoothness, and moist feeling).
  The tester's evaluation was scored according to the following five rank scale.

For each of the test prescriptions, the scores of the ten testers were summed in Tables 29 and 30 and the sum was taken as its overall evaluation result by the system sthon in Table 31.

Distilled water (ingredient (11)) was heated to 60Â° C., to which ingredients (3) to (7) were added at 50 to 60Â° C. with stirring and dissolved to homogeneity. To the resulting solution at 30 to 40Â° C. ingredients (8) to (10) were added with stirring and the mixture was further stirred until it was completely dissolved. Thus, a body cleansing sample with a composition as shown under column (B) of Table 28 was obtained. The sample was used as a reference in this test.

TABLE 29Ranking Scale for Evaluating Test Prescriptions (During Use)Test propertiesScoreFoam amountFoam quality+2HigherBetter+1Slightly higherSlightly betterâ€‰â€‰0SameSameâˆ’1Slightly lowerSlightly worseâˆ’2lowerWorseTest propertiesTautness afterSliminess afterScoreRinsing easinessrinsingrinsing+2EasierLess tautLess slimy+1Slightly easierSlightly less tautSlightly less slimyâ€‰â€‰0SameSameSameâˆ’1Slightly harderSlightly more tautSlightly moreâˆ’2HarderMore tautMore slimy

TABLE 30Ranking Scale for Evaluating Test Prescriptions (After Use)Test propertiesTautnessSmoothnessMoist feelingScoreafter driedafter driedafter dried+2Less tautSmootherMore moisture-rich+1Slightly less tautSlightly smootherSlightly more moisture-rich0SameSameSameâˆ’1Slightly more tautSlightly moreSlightly more chappingstickyâˆ’2More tautMore stickyMore chapping

Comparative Example 5

With regard to comparative prescriptions 11 and 12 prepared as described in the above section1 5-b, their performance was compared with that of the reference prescription in the same manner as in Example 16. The thus obtained evaluation results are shown in Table 31.

TABLE 31Evaluation Results of Body Wash PrescriptionsComparativeprescriptionsTest12prescriptionsCation-modified23242511hydroxyethylSampleSampleSampleSamplecelluloseTest cationic polymers12412(Cational HC-100)During useFoam amount1615171310Foam quality151615128Rinsing easiness1213128âˆ’2Tautness after rinsing11101075Sliminess after rinsing109107âˆ’6AfterTautness after dry1112115âˆ’1useSmoothness after dry99116âˆ’3Moist feeling after dry10111175

From the results of Table 31, it was confirmed that when the inventive cation-modified purified galactomannan polysaccharide was added to a body cleansing preparation, use feeling at using time was improved and the foam amount and foam quality were improved, and finis feeling after use was improved. Moreover, when the present invention was compared with the comparative prescription 12 containing the conventional nonpurified cation-modified galactomannan polysaccharide, the present invention was excellent in use feeling, foam quality, foam amount and feeling after use. From these facts, it was shown that the performance of the body cleansing preparation was improved by the cation-modified purified galactomannan polysaccharide of the present invention obtained by cation-modifying purified galactomanna polysaccharide containing 80 wt % or more of galactomann. Moreover, when the present invention was compared with another cationic polymer (comparative prescription 12) with respect to performance during use and after use, it was confirmed that the cation-modified purified galactomann polysaccharide of the present invention was excellent.

(Compositions 14 to 18)

Preferable composition examples of cosmetic compositions such as body cleansers in which conditioning effects and improvement of feeling by removing water-unsoluble substances in the cation-modified purified galactomannan polysaccharide of the present invention were utilized are shown below.

TABLE 32Composition 14. Body Cleanser (1)IngredientsWeight ratio (%)Dipropylene glycol2.5Disodium sulfosuccinic laurylate2.0Polyoxypropylene glycerylether1.0Isostearic acid1.0Lauric acid2.0Palm fatty acid9.0Myristic acid10.0Ethylene glycol distearate1.0Coconut oil fatty acid diethanolamide1.0Polyoxyethylene(2)laurylether sulfuric acid sodium3.0Coconut oil fatty acid sarcosine sodium2.0Aqueous solution of potassium hydroxide (47%)10.0Present invention (Sample 7)0.4Disodium edetate0.1Sodium benzoate0.1Purified waterrestPerfumeas appropriate

Liquid body cleansing preparation (body soap) were prepared by a conventional method.

TABLE 33Composition 15. Body Cleanser (2)IngredientsWeight ratio (%)Polyoxyethylene(2)laurylether phosphate12.0Polyoxyethylene(3)laurylether sulfuric acid sodium3.0Coconut oil fatty acid taurine sodium2.0Coconut oil fatty acid diethanolamide1.0Ethyleneglycol distearate1.5Coconut oil fatty acid amide propylbetaine3.0Propylene glycol3.51,3-butylene glycol0.5Triethanolamine4.3Present invention (Sample 1)0.2Polyquaternium-100.05Glycerin0.1Disodium edetateas appropriatePreservative, Perfumeas appropriatePurified waterrest

Liquid body cleansing preparation (body soap) were prepared by a conventional method.

TABLE 34Composition 16. Body Cleanser (3)IngredientsWeight ratio (%)POE alky(12-14) sulfosuccinic acid disodium6.0Coconut oil fatty acid methyl taurine sodium9.0Laurylhydroxy sulfobetaine2.3Coconut oil fatty acid amide propylbetaine1.7Coconut oil fatty acid diethanolamide3.1Ethyleneglycol distearate3.0Present invention (Sample 6)0.2Cetanol0.5Disodium edetate0.2Paraoxybenzoic acid ester0.2Citric acid, perfumeas appropriatePurified waterrest

Liquid body cleansing preparation (body soap) were prepared by a conventional method.

TABLE 35Composition 17. Facial Cleanser (1)IngredientsWeight ratio (%)Present invention (Sample 4)0.14Present invention (Sample 8)0.06Polyquaternium-70.2Polyquaternium-100.55Glycerin4.0Squalane1.025% aqueous solution of coconut oil fatty acid17.0taurine sodiumMyristic acid7.2Palmitic acid10.8Polyoxyethylene(8)laurylether2.0Ethyleneglycol distearate3.0Polyoxyethylene(2)laurylether phosphate9.030% aqueous solution of coconut oil fatty acid5.0amide propylbetaineAqueous solution of potassium hydroxide (47%)15.3Crystalline cellulose0.1Menthol0.2Disodium edetate0.2Paraoxybenzoic acid methyl0.2Purified waterrestPerfumeas appropriate

A facial cleansing preparation was prepared by a conventional method.

TABLE 36Composition 18. Facial Cleanser (2)IngredientsWeight ratio (%)Present invention (Sample 1)0.4Polyquaternium-60.16Polyquaternium-390.2Glycerin2.2Sorbitol0.825% aqueous solution of coconut oil fatty acid10.0glutamic acid potassium30% aqueous solution of coconut oil fatty acid taurine20.0sodiumEthyleneglycol distearate3.030% aqueous solution of coconut oil fatty acid amide15.0propylbetaineGlyceryl mono-oleate2.0Ceteares-60 myristyl glycol2.010% aqueous solution of citric acid20.0Alginine3.0Disodium edetate15.0Phenoxyethanol2.0Purified water2.0Perfumeas appropriate

A facial cleansing preparation was prepared by a conventional method.

As a result that effects in the costmetic compositions prepared according to the composition examples 14 to 18 were confirmed, improved effect of use feeling and foam quality were confirmed and improvement of finish feel after use was confirmed.

(Exemplary Skin Treatment Compositions 19-22)

As other preferred examples which utilize the feeling improvement by the cation-modified purified galactomannan polysaccharide of the present invention, compositions such as after-shave lotions, etc. will be described below.

TABLE 37Composition 19. After-shave lotionWeightIngredientsratio (%)Carboxyvinyl polymer0.3Isodecil oleate8.02-hexyldecil palmitate3.0Polyoxyethylenecetylether(18)3.0Octyl dodecanol4.0Glycerin3.0Cetanol1.0Ethanol3.0Present invention (Sample 9)1.0Paraoxybenzoic acid methyl0.2Squalane0.2Hydrolyzed silk0.2Mentholas appropriatePigmentas appropriatePerfumeas appropriate25% sodium hydroxide (for pH adjustment, pH 5.7-6.2)as appropriateDistilled waterrest

Liquid after-shave lotion was prepared by a conventional method.

TABLE 38Composition 20. Make-up lotionIngredientsWeight ratio (%)Present invention (Sample 6)0.05Present invention (Sample 7)0.05Nonpurified cation-modified tara gum (*4)0.1Polyquaternium-70.4Glycerin0.7Squalane0.31,3-butanediol2.0Ethyl alcohol6.0Polyoxyethylene(60) hardened castor oil0.5Polyoxyethylene(8)cetylether0.2Octyldodecanol0.2Vitamin E acetate0.05Methylparaben0.2Talc0.9Pyrite0.05Ferric oxide0.02Ferrous oxide0.01Perfumeas appropriatePurified waterrest
Make-up lotion was prepared by a conventional method.

(*4) Nonpurified cation-modified tara gum (INCI name: Caesalpinia Spinosa Hydroxypropyltrimonium Chloride

TABLE 39Composition 21. FoundationIngredientsWeight ratio (%)Present invention (Sample 4)0.2Polyquaternium-70.1Polyquaternium-390.1Methylphenylpolysiloxane18.0Dimethylpolysiloxane7.0Squalane2.0Cetylisooctanoate2.0Organic modified mentonite1.8Diglycerildiisostearate1.61,3-butanediol4.0Silicone-treated talc10.0Silicone treated sericite12.0Silicone-treated titanium oxide8.0Silicone-treated pyrite2.2Silicone-treated ferric oxide0.7Monoglyceride stearate1.0Methylparaben0.2Perfumeas appropriatePurified waterrest

Foundation was prepared by a conventional method.

TABLE 40Composition 22. Bath preparationWeightIngredientsratio (%)Present invention (Sample 7)0.15Nonpurified cation-modified locust-bean gum (*5)0.15Magnesium palmitate2.0Calcium stearate3.0Liquid paraffin9.0Cetanol2.0Carboxyvinyl polymer0.15Triethanolamine0.13Squalane2.0Perfumeas appropriateParaoxybenzoic acid methyl0.2Distilled waterrest
Bath preparation was prepared by a conventional method.

(*5) Nonpurified cation-modified locustbean gum (INCI name: Locust Bean Hydroxypropyltrimonium Chloride)