JP2007031293A - Cosmetic composition comprising low-cationized galactomannan polysaccharide - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cosmetic composition that exhibits skin-protecting effects by a composite salt of a cationic polymer with a surfactant while exhibiting good stability and hardly suffering from deterioration in feelings caused by accumulation of the salt during repeated use. <P>SOLUTION: The cationized galactomannan polysaccharide is obtained by introducing a quaternary nitrogen-containing group represented by chemical formula (1) into a part of hydroxy groups contained in the galactomannan polysaccharide, where the cation charge quantity derived from the quaternary nitrogen-containing group is less than 0.1 meq/g. In chemical formula (1), R<SB>1</SB>and R<SB>2</SB>are each a 1-3C alkyl group; R<SB>3</SB>is a 1-24C alkyl group; X<SP>-</SP>is an anion; n is 0 or 1-30; and when n is 1-30, (R<SB>4</SB>O)<SB>n</SB>is a residue of a polymer of a 2-4C alkylene oxide and is a polyalkylene glycol chain composed of a single alkylene oxide and/or a polyalkylene glycol chain composed of at least two kinds of alkylene oxides. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

The present invention relates to a cosmetic composition having excellent usability and stability, and more specifically, by preventing aggregation of the composite salt, it has excellent dosage form stability, and prevents accumulation upon repeated use. The present invention relates to a skin cosmetic composition and a hair treatment composition containing a specific cation-modified galactomannan polysaccharide, which have a good feeling of use and an excellent conditioning effect.

Conventionally, the basic function of a skin and hair cleaning agent was to remove dirt on the body surface and clean the skin and hair. However, in recent years, due to changes in the environment surrounding skin care and hair care, such as the spread of showers, increased frequency of bathing and washing, and increased use of hair colors and hair dyes, these skin care and hair care products are simply cleaned. In addition to removal, a feeling during use and after use, a good finish, a mildness, and a conditioning effect have been required. As a result, conditioning agents such as cationic polymers, cationic surfactants, and silicone derivatives have been widely used for the purpose of protecting the skin and hair, adjusting the state thereof, and improving the touch.

Among these, cationic polymers are blended in hair treatment compositions such as shampoos for the purpose of damaging hair entangled during shampooing and rinsing and improving touch after shampooing. For example, Patent Document 1 uses a cation-modified cellulose derivative in which a quaternary nitrogen-containing group is introduced into shampoos and hair cosmetics, and Patent Document 2 describes a main chain mannose belonging to the galactomannan polysaccharide and a side chain. It has been shown that a guar gum cationic derivative with a 2: 1 chain galactose can be used as a cationic conditioning polymer in insoluble and non-volatile silicone for hair care products such as shampoos, rinses, etc. Has been.

Furthermore, in Patent Document 3, guar gum and locust bean gum are used as the galactomannan polysaccharide, and after the hydroxyalkyl modification, cation modification is performed so that the nitrogen content is 0.2 to 3% by weight, and the cation modified galacto is further reduced in molecular weight. Mannan polysaccharides have been shown to be used in skin cosmetic compositions as well as hair treatment compositions.

Furthermore, Patent Document 4 shows that cationized cellulose and cationized guar gum are used as thickeners for massage cosmetics. Patent Document 5 shows that cationized cellulose and cationized guar gum are used for the purpose of maintaining the imparted smoothness. Patent Document 6 discloses an emulsion type in which storage stability and feel are improved by blending carnitine having poor storage stability with a polysaccharide polymer containing a cationized polysaccharide and an acrylic polymer. A topical skin preparation is shown. Furthermore, Patent Document 7 discloses that cation-modified tara gum is excellent as a composition for skin cosmetics such as hair care products such as shampoos and rinses, and body cleaning agents for the purpose of improving foam quality and feel. It is shown. In particular, a complex salt composed of a cationic polymer and a surfactant is excellent in protecting the skin and hair, preparing the state thereof, and improving the touch. Patent Documents 8, 9, and 10 include a surfactant and A cosmetic composition having an improved skin protection effect by a complex salt of a cationic polymer is shown. However, the improvement of the skin protection effect by the complex salt of the cationic polymer and the surfactant may cause aggregation with the anionic surfactant when forming the complex salt, thereby obtaining a stable cosmetic composition. It was difficult.

In addition, the cationic polymer is blended for many purposes such as a feeling of use at the time of application and a moisturizing effect because of its good affinity for the skin. However, when these cation-modified polymers are used, the negatively charged skin is remarkably adsorbed and a conditioning effect can be obtained. However, there is a residual feeling such as sliminess, and problems such as accumulation when repeatedly used. have. The accumulation is the same in the hair treatment composition, and the aggregated complex salt accumulates on the hair surface, and has an adverse effect such as deterioration of fingering at the time of shampooing and stiff feeling of dry hair. In recent years, in particular, there has been an increase in the number of shampooing times and the use of hair colors and hair dyes due to diversified fashion, and the resulting damage to the hair has led to an increase in the accumulation of complex salts on the hair surface. Is a problem.

Japanese Examined Patent Publication No. 47-20635 (Page 5) Japanese Patent Laid-Open No. 4-364111 (page 1-6) Japanese Patent No. 3349219 (pages 1-6) JP 11-139954 A (page 1-3) JP 2003-183119 A (page 1-4) JP 2005-53835 A (page 1-11) JP 2003-327603 A (pages 1-23) JP-A-54-127882 JP-A-61-22005 JP 2002-37711 A (pages 1-7)

Therefore, the problem to be solved by the present invention is that it has a skin protection effect due to a complex salt of a cationic polymer and a surfactant, has a good stability, has little accumulation due to repeated use, and has little deterioration in feel. The object is to provide a cosmetic composition.

In such a situation, the present inventors have intensively studied, and as a result, introduced a specific amount of a quaternary nitrogen-containing group into a galactomannan polysaccharide having a galactose unit as a side chain in the main chain having mannose as a structural unit. In addition, a cosmetic composition containing a cation-modified galactomannan polysaccharide with a cation charge adjusted to a specific range can improve the cohesiveness of a complex salt of a cationic polymer and a surfactant, and has excellent dosage form stability. The present inventors have found that the feeling of use when used repeatedly is good and have completed the product of the present invention.

(式中R₁、R₂は各々炭素数1〜3個のアルキル基、R₃は炭素数1〜24のアルキル基を示し、X^-は陰イオンを示す。nは、n
= 0又はn = 1〜30を示し、n = 1〜30の時、(R₄O)_nは炭素数2〜4のアルキレンオキサイドの重合体残基であって、単一のアルキレンオキサイドからなるポリアルキレングリコール鎖及び／又は2種類以上のアルキレンオキサイドからなるポリアルキレングリコール鎖を示す。) Accordingly, the present invention provides a quaternary nitrogen-containing quaternary nitrogen represented by the following chemical formula (1) in the main chain having mannose as a structural unit, a part of the hydroxyl group contained in the galactomannan polysaccharide having a galactose unit as a side chain. A cation-modified galactomannan polysaccharide substituted with a group, the cation-modified galactomannan polysaccharide having a cation charge derived from the quaternary nitrogen-containing group of less than 0.1 meq / g (hereinafter also referred to as a low cation-modified galactomannan polysaccharide) ).

(Wherein R ₁ and R ₂ each represent an alkyl group having 1 to ₃ carbon atoms, R ₃ represents an alkyl group having 1 to 24 carbon atoms, X ⁻ represents an anion, and n represents n
= 0 or n = 1 to 30, and when n = 1 to 30, (R ₄ O) _n is a polymer residue of alkylene oxide having 2 to 4 carbon atoms, and consists of a single alkylene oxide The polyalkylene glycol chain which consists of a polyalkylene glycol chain and / or 2 or more types of alkylene oxide is shown. )

The low cation-modified galactomannan polysaccharide of the present invention has a conditioning effect equivalent to or higher than that of a cationic polymer used as a conventional conditioning agent for hair when used in a hair treatment composition such as shampoo and rinse. When it is used repeatedly while being applied, there is little accumulation on the hair surface and a good feel can be obtained. Furthermore, when blended into a skin cosmetic composition, the amount of surfactant added is less than the amount blended into the hair treatment composition, so that conventional cationic polymers have agglomerated complex salts and deteriorated stability. However, a stable cosmetic composition can be obtained by blending the low cation-modified galactomannan polysaccharide of the present invention. In addition, it solves problems such as residual feeling such as luster and accumulation when repeatedly used, and gives a good finish. Therefore, it is possible to provide a cosmetic composition that is more comfortable to use than conventional products, and can also be suitably used for other cosmetic compositions such as makeup agents.

The galactomannan polysaccharide used in the present invention is a nonionic polysaccharide in which a galactose unit is formed as a side chain in a main chain having mannose as a structural unit, and the composition ratio of mannose and galactose has an arbitrary value. Preferably, it is a polysaccharide having a composition ratio of 1: 1 to 4: 1. A preferred galactomannan polysaccharide used in the present invention is specifically described. One of them is a main chain having mannose as a constituent unit and a galactose unit as a side chain, and the composition ratio of mannose and galactose is 1: 1. Fenugreek (scientific name Trigonella)
foenum-graecum) is a natural water-soluble gum obtained from the endosperm portion of seeds and is generally called fenugreek gum.

Furthermore, one of the preferred galactomannan polysaccharides used in the present invention is a legume plant having a main chain containing mannose as a constituent unit and a galactose unit as a side chain, and the composition ratio of mannose and galactose is 2: 1. A guar (scientific name Cyamopsis), which is an annual herbaceous plant grown mainly in India and Pakistan.
Tetragonolobus) is a natural water-soluble gum obtained from the endosperm portion of seeds and is generally called guar gum.

Furthermore, one of the preferred galactomannan polysaccharides used in the present invention is a legume plant having a mannose-containing main unit and a galactose unit as a side chain, and the composition ratio of mannose and galactose is 3: 1. It is a natural water-soluble gum obtained from the endosperm portion of seeds of a certain cod (scientific name Caesalpinia Spinosa), and is generally called cod gum.

Furthermore, one of the preferred galactomannan polysaccharides used in the present invention is a nonionic polysaccharide having a composition ratio of mannose and galactose of 4 to 1, and is a perennial legume plant cultivated on the Mediterranean coast. It is a natural water-soluble gum obtained from the endosperm portion of the seed of locust bean (scientific name Caratonia Silica) and is generally called locust bean gum.

In addition, the galactomannan polysaccharide used in the present invention is a galactomannan polysaccharide obtained from the endosperm portion of the seed, and has a galactomannan content of 90% by mass or more, preferably 96% by mass or more, and a 1% by mass aqueous solution. Galactomannan polysaccharide purified to have a turbidity of 15% or less, preferably 8% or less (hereinafter also referred to as purified galactomannan polysaccharide. Each galacto having a composition ratio of mannose to galactose of 1: 1 to 4: 1 Mannan polysaccharide can also be used as purified fenugreek gum, purified guar gum, purified tara gum, and purified locust bean gum).

As one of the purification methods so that the galactomannan content is 90% by mass or more and the turbidity of a 1% by mass aqueous solution is 15% or less, a crude galactomannan polysaccharide having a galactomannan content of less than 90% by mass is used. It is obtained by dissolving in water to form an aqueous solution, removing impurities by filtration, reprecipitating the filtrate in an organic solvent, and drying the precipitate. Alternatively, it can also be obtained by grinding only the central part of the endosperm obtained by removing the outer part including the seed coat.

The low cation-modified galactomannan polysaccharide of the present invention is produced by reacting a galactomannan polysaccharide with a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. be able to. In this case, the reaction is carried out in a suitable solvent, preferably a hydrous alcohol, in the presence of alkali. The introduction of such a quaternary nitrogen-containing group can be performed according to a conventionally known method, but is not necessarily limited thereto. For example, after adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the galactomannan polysaccharide having a composition ratio of mannose and galactose of 4 to 1, the glycidyl trialkylammonium salt or 3-halogeno- The low cation modified galactomannan polysaccharide of the present invention by reacting with 2-hydroxypropyltrialkylammonium salt (hereinafter, the low cation modified galactomannan polysaccharide of the present invention having a composition ratio of mannose and galactose of 4 to 1, Locust bean gum). In addition, an inorganic salt, preferably sodium chloride, can be added to prevent aggregation of locust bean gum in the solvent during the reaction. Furthermore, in order to prevent aggregation of locust bean gum, improve dispersibility and increase the reaction rate, the alkali and inorganic salts are added to the reaction solvent and then dissolved or dispersed, and then the locust bean gum is added and dissolved or dispersed. Thereafter, it can also be produced by introducing the quaternary nitrogen-containing group described above.

Similarly, a galactomannan polysaccharide (hereinafter also referred to as tara gum, guar gum, or fenugreek gum) having a composition ratio of mannose to galactose of 3 to 1, 2 to 1, and 1 to 1 is cationized in the same manner as the aforementioned locust bean gum. The low cation modified galactomannan polysaccharide of the present invention (hereinafter referred to as the low cation modified galactomannan polysaccharide of the present invention having a composition ratio of mannose and galactose of 3: 1, 2: 1, 1: 1) Modified tara gum, low cation modified guar gum, and low cation modified fenugreek gum) can be produced.

In the quaternary nitrogen-containing group represented by the chemical formula (1) introduced into the galactomannan polysaccharide in the present invention, specific examples of R ₁ and R ₂ include methyl, ethyl, and propyl, and carbon Specific examples of R ₃ as the alkyl group having 1 to 24 include octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl and the like in addition to the same as R ₁ and R ₂ described above. Specific examples of R ₄ O include ethoxy, propoxy, and butoxy. Further, specific examples of the anion X ⁻ include methyl sulfate ion, ethyl sulfate ion, acetate ion, etc. in addition to halogen ions such as chlorine ion, bromine ion and iodine ion.

The cation charge amount derived from the quaternary nitrogen-containing group of the low cation-modified galactomannan polysaccharide of the present invention is less than 0.1 meq / g. However, from the viewpoint of the stability of the dosage form and the accumulation property when repeatedly used. More preferably, the lower limit of the cation charge amount is 0.001 meq / g or more, more preferably 0.01 meq / g or more, and most preferably 0.05 meq / g or more. When a cation-modified galactomannan polysaccharide with a cationic charge amount of 0.1 meq / g or more is blended with a hair treatment composition and a skin cosmetic composition, a conditioning effect is obtained, but the feeling of use deteriorates due to accumulation by repeated use. Further, it is not preferable because it causes a residual feeling on the skin, and further deteriorates the stability of the dosage form due to aggregation of the composite salt.

The cation charge amount derived from the quaternary nitrogen-containing group of the low cation-modified galactomannan polysaccharide is equivalent to the quaternary nitrogen-containing group represented by the chemical formula (1) contained in 1 g of the low cation-modified galactomannan polysaccharide. Is a number. Usually, the nitrogen content derived from a quaternary nitrogen-containing group can be calculated by the Kjeldahl method (former cosmetic raw material standard, general test method, nitrogen determination method, second method), and can be calculated from the measured value, but the galactose used in the present invention Since the galactomannan polysaccharide having a mannose composition ratio of 4: 1, 3: 1, 2: 1 and 1: 1 contains nitrogen, the low cation modified galactomannan polysaccharide of the present invention obtained by the Kjeldahl method The value obtained by subtracting the nitrogen content derived from the galactomannan polysaccharide used in the present invention from the nitrogen content is the nitrogen content derived from the quaternary nitrogen-containing group. Specifically, in the quaternary nitrogen-containing group represented by the chemical formula (1), R ₁ , R ₂ and R ₃ are methyl, X ⁻ is a chlorine ion, n is a quaternary nitrogen containing n = 0 As a result of measuring the nitrogen content of the product of the present invention obtained by cation-modifying purified locust bean gum by the Kjeldahl method and found to be 0.18%, the cation charge amount of this substance is expressed by the following formula: Desired. The refined locust bean gum used in the present invention usually contains about 0.07% nitrogen.

Further, in addition to the above method, the colloid titration method in which toluidine blue aqueous solution is used as an indicator and titration with polyvinyl potassium sulfate aqueous solution is used as a method for obtaining the cation charge amount (specifying component specifications according to cosmetic varieties, O- [2-hydroxy-3- (chloride) Trimethylammonio) propyl] hydroxyethylcellulose, quantitative method).

The blending amount of the low cation-modified galactomannan polysaccharide contained in the cosmetic composition of the present invention is preferably 0.05 to 5% by mass based on 100% by mass of the whole composition, and if it is less than 0.05% by mass, the conditioning effect In addition, the performance tends to be insufficient, such as improvement of skin protection effect and feeling of use, and if it exceeds 5% by mass, the feeling of use tends to be poor, such as a feeling of stickiness and stickiness when used.

Further, the cosmetic composition of the present invention can be combined with two or more of the low cation-modified galactomannan polysaccharides of the present invention in order to improve the conditioning effect and skin protection effect, and various cationic water-soluble Although a polymer and an amphoteric water-soluble polymer can be used in combination, the blending amount thereof is a range that does not impair the feel, stability, etc. during repeated use of a cosmetic composition containing a low cation-modified galactomannan polysaccharide, The total composition is 100% by mass, preferably 5% by mass or less, and if it exceeds this, a feeling of stiffness will occur at the time of use, and the usability will deteriorate. Furthermore, in the skin cosmetic composition, the stability of the dosage form is deteriorated, and a feeling of stickiness is produced on the touch surface, and the feeling of use is deteriorated.

Examples of the cationic water-soluble polymer and the amphoteric water-soluble polymer to be blended include the following, but are not necessarily limited thereto.

Examples of cationic water-soluble polymers include quaternary nitrogen-modified polysaccharides (cation-modified hydroxyethyl cellulose, cation-modified starch, cation-modified tamarind gum, etc.), dimethyldiallylammonium chloride derivatives (dimethyldiallylammonium chloride / acrylamide copolymer) Poly (dimethylmethylenepiperidinium chloride), vinylpyrrolidone derivatives (vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone / methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone / methylvinylimidazolium chloride) Polymers), methacrylic acid derivatives (methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride / 2-hydroxyethyl methacrylate copolymer) And methacryloylethyldimethylbetaine / methacryloylethyltrimethylammonium chloride / methacrylic acid methoxypolyethylene glycol copolymer).

Examples of amphoteric water-soluble polymers include amphoteric starch, dimethyldiallylammonium chloride derivatives (acrylamide / acrylic acid / dimethyldiallylammonium chloride copolymer, acrylic acid / dimethyldiallylammonium chloride copolymer, etc.), methacrylic acid derivatives ( Polymethacryloylethyldimethylbetaine, N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer, etc.).

As described above, a cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention can be obtained, but other components in the cosmetic composition are not particularly limited, and components generally used in cosmetics are optional components. It is possible to mix | blend in the range which does not impair the effect of this invention. Other ingredients that can be blended are exemplified below.

As an anionic surfactant, alkyl (carbon number 8-24) sulfate, alkyl (carbon number 8-24) ether sulfate, alkyl (carbon number 8-24) benzenesulfonate, alkyl (carbon number 8-24) ) Phosphate, polyoxyalkylene alkyl (carbon number 8-24) ether phosphate, alkyl (carbon number 8-24) sulfosuccinate, polyoxyalkylene alkyl (carbon number 8-24) ether sulfosuccinate, acyl (C8-C24) alanine salt, acyl (C8-C24) N-methyl-β-alanine salt, acyl (C8-C24) glutamate, acyl (C8-C24) Isethionate, acyl (carbon number 8-24) sarcosine salt, acyl (carbon number 8-24) taurine salt, acyl (carbon number 8-24) methyl taurate, α-sulfo fatty acid ester salt, ether Carboxylate, polyoxyalkylene fatty acid monoethanolamide sulfate Examples thereof include a salt and a long chain (carbon number 8 to 24) carboxylate.

Nonionic surfactants include alkanolamide, glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbite fatty acid ester, sorbite fatty acid ester, polyoxy Alkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl phenyl ether, tetrapolyoxyalkylene ethylene diamine condensate, sucrose fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkylene glycol fatty acid ester, polyoxyalkylene castor oil Derivatives, polyoxyalkylene hydrogenated castor oil derivatives, alkyl poly Glycosidic, polyglycerol fatty acid esters, and the like.

Amphoteric surfactants include alkyl (8 to 24 carbon) amidopropyl betaine, alkyl (8 to 24 carbon) carboxybetaine, alkyl (8 to 24 carbon) sulfobetaine, alkyl (8 to 24 carbon) hydroxy Sulfobetaine, alkyl (carbon number 8-24) amidopropyl hydroxysulfobetaine, alkyl (carbon number 8-24) hydroxyphosphobetaine, alkyl (carbon number 8-24) aminocarboxylate, alkyl (carbon number 8-24) Examples include sodium amphoacetate, alkyl (carbon number 8-24) amine oxide, tertiary nitrogen, and alkyl (carbon number 8-24) phosphate ester containing quaternary nitrogen.

In addition to the cationic and amphoteric water-soluble polymers blended in the hair treatment composition and skin cosmetic composition of the present invention, anionic properties can be used for the purpose of adjusting viscosity and improving the feeling during styling to some extent. The nonionic polymer can be further blended within a range not impairing the effects of the present invention, and examples thereof include the following.

Examples of anionic polymers include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid / acrylamide / ethyl acrylate copolymers and salts thereof), and methacrylic acid derivatives (polymethacrylic acid and salts thereof, methacrylic acid).・ Acrylamide, diacetone acrylamide, acrylic acid alkyl ester, methacrylic acid alkyl ester copolymers and their salts, etc.), crotonic acid derivatives (vinyl acetate, crotonic acid copolymers, etc.), maleic acid derivatives (maleic anhydride, diisobutylene, etc.) Copolymer, isobutylene / maleic acid copolymer, etc.), polyglutamic acid and its salt, hyaluronic acid and its salt, carboxymethylcellulose, carboxyvinyl polymer and the like.

Examples of nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate / methoxyethyl acrylate copolymer, polyacrylic amide, etc.), vinyl pyrrolidone derivatives (polyvinyl pyrrolidone, vinyl pyrrolidone / vinyl acetate copolymer, etc.) And polyoxyalkylene glycol derivatives (polyethylene glycol, polypropylene glycol, etc.), cellulose derivatives (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polysaccharides and derivatives thereof (guar gum, locust bean gum, dextran, etc.) and the like.

In still another embodiment, the hair treatment composition and the skin cosmetic composition of the present invention include an organic amidoamine compound obtained by completely or partially neutralizing an amidoamine compound with a neutralizing agent such as an organic acid and / or an inorganic acid. The conditioning effect can be improved by adding an acid salt and / or an inorganic acid salt and a higher fatty acid and / or higher alcohol. The blending amount thereof is preferably 5% by mass or less based on 100% by mass of the entire composition as an amidoamine compound, and if the amount exceeds this, the feeling after use becomes poor or the feeling of use becomes poor.

Other components to be blended in the hair treatment composition and skin cosmetic composition of the present invention include cationic surfactants (alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkylpyridinium salt, alkyldimethylbenzylammonium salt, chloride) Benzethonium, benzalkonium chloride, etc.), solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (carnauba wax, candelilla wax, etc.), hydrocarbon oils (liquid paraffin, squalane, olive oil, jojoba oil, etc.), Moisturizer (glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myris Myristylate, 2-hexyldecyl myristate, glyceryl trimyristate, isopropyl palmitate, 2-heptylundecyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, 12-hydroxystearate Cholesteryl acid, cetostearyl alcohol, cetyl octanoate, hexyl decyl dimethyloctanoate, isocetyl isostearate, trimethylolpropane triisostearate, decyl oleate, oil oleate, cetyl lactate, myristyl lactate, ethyl acetate, amyl acetate butyl acetate, Lanolin acetate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, ethylene glycol di-2-ethylhexylate, trimethylolpropane tri-2-ethylhexylate, tri-2-ethylhexyl Glyceryl phosphate, pentaerythritol tetra-2-ethylhexylate, cetyl-2-ethylhexanoate, diisobutyl adipate, 2-heptylundecyl adipate, 2-hexyldecyl adipate, dipentaerythritol fatty acid ester, dicaprin Acid neopentyl glycol, diisostearyl malate, glycerin di-2-heptylundecanoate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, acetoglyceride, N-lauroyl-L-glutamic acid-2-octyldodecyl Esters, di-2-ethylhexyl sebacate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, ethyl laurate, ethyl mink oil fatty acid, etc.), antioxidants (tocopherol, BHT, etc.), silicone (methyl poly Siloxane, Methyl phenyl polysiloxane, high polymerization degree methyl polysiloxane, cyclic polysiloxane, etc.) and silicone derivatives (polyether-modified silicone, amino-modified silicone, 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, palm oil fatty acid, palm fatty acid, palm kernel fatty acid, linoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, etc.), amino acids (arginine, glutamic acid, etc.) UV absorber, (benzophenone derivative, paraaminobenzoic acid derivative, methoxycinnamic acid derivative, etc.), pearlizing agent (fatty acid ethylene glycol, etc.), suspending agent (polystyrene emulsion, etc.), thickener, metal sequestering agent (edetic acid) Salt), pH adjuster, bactericidal agent Preservatives, hair growth agents, vitamins, anti-inflammatory agents, dyes, fragrances, foam boosters and the like.

The dosage form of the above-described cosmetic composition according to the present invention is not limited and can take any dosage form. Further, in addition to the above (essential) component, the dosage form does not impair the effects of the present invention. Various components that are usually blended in the cosmetic composition can be added and manufactured by conventional methods. Examples of the dosage form include shampoo, rinse, conditioner, hair wax, hair lotion, hair mist, acid hair dye, oxidative hair dye, permanent agent, body cleaner, face wash, lotion, foundation, bath agent, etc. The present invention utilizes the effects of the cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention, such as the stability and the feeling improvement during repeated use.

The present invention will be described below in more detail based on examples, but the present invention is not limited thereto. Unless otherwise specified, the amount is shown in mass%.

[Production of low cation-modified galactomannan polysaccharide]
Example 1
After adding 6.7 g of 48% by mass aqueous sodium hydroxide solution to 900 mL of 50% by volume isopropanol aqueous solution, 162 g of purified locust bean gum having a galactomannan content of 98% by mass was gradually added and dispersed. Next, 4.4 g of an 80% by mass glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) aqueous solution was added, and the mixture was heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 7.9 g of 35% hydrochloric acid was diluted with 1500 mL of a 50% by volume isopropanol aqueous solution and used for neutralization. After neutralization at room temperature for 1 hour, the reaction solution was poured into 1800 mL of methanol to precipitate the reaction product, which was filtered off. The obtained precipitate was washed with an aqueous methanol solution, and then the reaction product was dried under reduced pressure. The low cation modified locust bean gum thus obtained had a cation charge of 0.08 meq / g. The results are shown in Table 1 (Sample No. 1 in Table 1).

Similarly, low cation modified locust bean gums with different cation charge amounts were synthesized by changing the amount of GTA added. The results are shown in Table 1 (Sample numbers 2 and 3 in Table 1).

In place of the purified locust bean gum of Example 1, another galactomannan polysaccharide was used to synthesize a low cation-modified galactomannan polysaccharide. The results are shown in Table 1 (Sample numbers 4, 5, 6, 7 in Table 1).

Example 2
Instead of GTA used in Example 1, 6.5 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added and synthesized in the same manner. The low cation-modified locust bean gum thus obtained had a cation charge of 0.06 meq / g. The results are shown in Table 1 (Sample No. 8 in Table 1).

Example 3
162 g of the purified guar gum used in Example 1 was dispersed in 900 mL of an 80% by volume isopropanol aqueous solution in a pressure sealed container, and 6.7 g of a 48% by mass sodium hydroxide aqueous solution was added. Next, 66 g of ethylene oxide and 240 g of propylene oxide were added, and the mixture was heated and reacted at 70 ° C. for 3 hours under pressure and hermetic sealing. After completion of the reaction, the pressure is released and cooled to 50 ° C. After cooling, 8.5 g of 80 mass% GTA aqueous solution is added and reacted at 50 ° C. for 3 hours. After completion of the reaction, 7.9 g of 35% hydrochloric acid was diluted with 1500 mL of a 70% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 800 mL of methanol to precipitate the reaction product, which was filtered off. The obtained precipitate was washed with an aqueous methanol solution, and then the reaction product was dried under reduced pressure. The cation charge amount of the low cation-modified galactomannan polysaccharide thus obtained was 0.05 meq / g. The results are shown in Table 1 (Sample No. 9 in Table 1).

Comparative Example 1
In order to compare with the low cation-modified galactomannan polysaccharide of the present invention, cation-modified galactomannan polysaccharides having different cation charge amounts were synthesized by changing the amount of GTA added according to the method of Example 1. The results are shown in Table 1 (Sample numbers 10 and 11 in Table 1).

[Production and evaluation of cosmetics containing low cation-modified galactomannan polysaccharide]
Example 4 Stability of Complex Salt The stability of a cosmetic composition containing a low cationic galactomannan polysaccharide was confirmed.
<Adjustment of cosmetic composition>
4-a
A cosmetic composition having the composition shown in (A) of Table 2 was prepared using the low cation-modified galactomannan polysaccharide obtained in Examples 1, 2, and 3. Ingredient (8) of (A) in Table 2 was heated to 80 ° C, and component (1) was slowly added and dissolved while stirring.After confirming dissolution, heating was stopped and ingredients (3) and (4) Was added and stirred to make it uniform, and components (5) to (7) were added and mixed uniformly at 30 to 40 ° C. In this way, the cosmetic compositions having the compositions shown in Table 2 (A) were prepared, and the cosmetic compositions containing the sample numbers 1 to 9 in Table 1 were used as the formulations 1 to 9 of the present invention in order.

4-b (Adjustment of comparative product)
In order to compare the stability of the cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention, comparison of the composition shown in (B) of Table 2 using the cation-modified galactomannan polysaccharide obtained in Comparative Example 1 Each cosmetic composition was prepared. Ingredient (8) of comparative product (B) in Table 2 was heated to 80 ° C, and component (2) was slowly added and dissolved with stirring.After confirming dissolution, heating was stopped and components (3), ( 4) was added and stirred to make it uniform, and then components (5) to (7) were added and mixed uniformly at 30 to 40 ° C. Thus, the cosmetic compositions having the compositions shown in Table 2 (B) were prepared, and the cosmetic compositions containing the sample numbers 10 to 11 in Table 1 were sequentially designated as Comparative products 1 and 2.

(Evaluation)
Each cosmetic composition of Formulations 1 to 9 of the product of the present invention prepared in 4-a above was allowed to stand at room temperature for 7 days, and its appearance was observed to evaluate stability. The evaluation results are shown in Table 3. Furthermore, the cosmetic compositions of Comparative Products 1 and 2 prepared in 4-b were also allowed to stand at room temperature for 7 days, and their appearance was observed to evaluate stability. The results are shown in Table 3.
-Aggregation of complex salt is not observed ...
・ Condensation of complex salt is observed ・ ・ ・ ・ ×

From the results in Table 3, it was confirmed that the cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention has excellent stability.

Example 5 Feeling of Repeated Use A feeling of use when a cosmetic composition containing a low cationic galactomannan polysaccharide was used repeatedly was confirmed by slipperiness on hair and sensory evaluation.
<Adjustment of cosmetic composition>
5-a
A shampoo having the composition shown in (A) of Table 4 was prepared using the low cation-modified galactomannan polysaccharide obtained in Examples 1, 2 and 3. Ingredient (9) (A) in Table 4 was heated to 80 ° C, and component (1) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and ingredients (3) to (5) Were added and stirred to make it uniform, and components (6) to (8) were added and mixed uniformly at 30 to 40 ° C. Thus, shampoos having the compositions shown in (A) of Table 4 were prepared, and the cosmetic compositions containing Sample Nos. 1 to 9 in Table 1 were sequentially used as the formulations 10 to 18 of the present invention.

5-b (Preparation of comparative product)
In order to compare the feeling of use when the cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention was repeatedly used, the cation-modified galactomannan polysaccharide obtained in Comparative Example 1 was used in (B) of Table 4. Comparative cosmetic compositions having the indicated compositions were each prepared. Ingredient (9) of comparative product (B) in Table 4 was heated to 80 ° C., and component (2) was slowly added and dissolved while stirring. 5) is added and stirred to make it uniform, and components (6) to (8) are added and mixed uniformly at 30 to 40 ° C., thus preparing a shampoo having the composition shown in Table 4 (B). The cosmetic compositions containing document numbers 10 to 11 in 1 were designated as comparative products 3 and 4, respectively.

5-c (Adjustment of comparative product)
Furthermore, instead of the cation-modified galactomannan polysaccharide in 5-b, a conventional cation-modified guar gum having a turbidity of 1% by weight of 70%, a nitrogen content of 1.7% by weight, and a cation charge of 0.79 meq / g (colloidal titration method) A shampoo having the composition shown in comparative product (B) in Table 4 was prepared in the same manner as 5-b using (Jaguar C-13S; manufactured by Rhodia), and used as comparative product 5.

(Evaluation)
The hair strands (manufactured by Beaulux Co., Ltd., root-aligned human hair, length 60) were added to the 5% aqueous solution of each shampoo of the present invention product 10-18 prepared in 5-a above.
mm, width 40 mm) and thoroughly washed off the shampoo, and then air dried overnight at room temperature. This series of shampoo soaking, washing, and air drying is performed 29 times (ie 29 days), and after the final 30th time, the shampoo is thoroughly washed out and then the hair remains wet without being naturally dried. The friction coefficient was measured by a friction tester (KES-SE, manufactured by Kato Tech Co., Ltd.), and this was evaluated as slip property. The evaluation results are shown in Table 5. Further, for the shampoos of Comparative products 3 to 5 prepared in 5-b and 5-c, similarly, the hair strands were immersed in the shampoo, washed thoroughly, and air dried overnight at room temperature for a total of 29 times. In the final 30th time, the shampoo was thoroughly washed out, and then the dynamic friction coefficient of the wet hair strand that was not allowed to dry naturally was measured with a friction tester, and the slipperiness was evaluated. The results are shown in Table 5. .

10 testers of 10 to 18 shampoos of the formulations of the present invention prepared in the above-mentioned 5-a to 5-c and shampoos of comparative products 3 to 5 were used continuously for 10 days (1 Times / day), a finger test after shampooing on the 10th day was carried out by the following method. Washing and rinsing were carried out using the shampoos of prescriptions 10 to 18 of the present invention and the shampoos of comparative products 3 to 5, and fingering during rinsing was confirmed. Furthermore, the touch after drying was also confirmed. Evaluation was made according to the following criteria based on the number of testers who felt that the touch after fingering or after drying was good, and the results are shown in Table 5.
・ 8 or more testers who feel that they are good to touch or feel ... ◎
・ Six to seven testers who feel that they are good to touch or feel ...
・ 4-5 testers who feel that they are good to touch or feel ・ ・ ・ △
-Less than 4 testers feel good by touching or touching ×

  From the results of Table 5, it was confirmed that when the cosmetic composition containing the low cation-modified galactomannan polysaccharide of the present invention was repeatedly used, the deterioration of touch due to accumulation could be prevented.

常法に基づき、ヘアジェルを製造する。 Hereinafter, a hair treatment composition obtained by the cosmetic composition of the present invention, utilizing the conditioning effect, skin protection effect, improvement in use feeling when repeatedly used, and further improvement in dosage form stability. In addition, skin cosmetic compositions and the like were produced in a conventional manner and in different dosage forms, and further confirmed in each.

A hair gel is manufactured based on a conventional method.

常法に基づき、ヘアワックスを製造する。

A hair wax is produced based on a conventional method.

精製水を70°Cに加熱し、他成分を加え均一に溶解した後、冷却した。

Purified water was heated to 70 ° C, and other components were added and dissolved uniformly, and then cooled.

精製水を70°Cに加熱し、他成分を加え均一に溶解した後、冷却した。

Purified water was heated to 70 ° C, and other components were added and dissolved uniformly, and then cooled.

精製水を70°Cに加熱し、他成分を加え均一に溶解した後、冷却した。

Purified water was heated to 70 ° C, and other components were added and dissolved uniformly, and then cooled.

常法に基づき、リンスを製造する。

A rinse is manufactured based on a conventional method.

常法に基づき、リンスを製造する。

A rinse is manufactured based on a conventional method.

常法に基づき、液体状ボディ用洗浄剤(ボディソープ)を製造する。

A liquid body cleaning agent (body soap) is manufactured based on a conventional method.

常法に基づき、液体状ボディ用洗浄剤(ボディソープ)を製造する。

A liquid body cleaning agent (body soap) is manufactured based on a conventional method.

常法に基づき、洗顔料を製造する。

A face wash is manufactured based on a conventional method.

常法に基づき、アフターシェーブローションを製造する。

After-shave lotion is manufactured based on conventional methods.

常法に基づき、ファンデーションを製造する。

A foundation is manufactured based on a conventional method.

常法に基づき、ローションを製造する。

Manufacture lotions based on conventional methods.

常法に基づき、美容液を製造する。

Manufactures serums based on conventional methods.

常法に基づき、入浴剤を製造する。

A bath preparation is produced based on a conventional method.

As a result of further confirmation in each cosmetic composition having different dosage forms produced in Examples 6 to 22, the stability of the dosage form and repetition were obtained while having the same effect as the conditioning effect of the conventional cationic polymer. It was excellent in usability when used.

Claims (8)

Part of the hydroxyl group contained in the galactomannan polysaccharide having a galactose unit as a side chain was substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) in the main chain having mannose as a structural unit. A cosmetic composition comprising a cationically modified galactomannan polysaccharide, wherein the cationic charge amount derived from the quaternary nitrogen-containing group is less than 0.1 meq / g.

(Wherein R ₁ and R ₂ are each an alkyl group having 1 to ₃ carbon atoms, R ₃ is an alkyl group having 1 to 24 carbon atoms, X ⁻ represents an anion, and n is n = 0 or n = 1 to 30 and when n = 1 to 30, (R ₄ O) _n is a polymer residue of alkylene oxide having 2 to 4 carbon atoms, and is a polyalkylene glycol chain composed of a single alkylene oxide And / or a polyalkylene glycol chain composed of two or more alkylene oxides.) 2. The low cation-modified galactomannan polysaccharide according to claim 1, wherein the composition ratio of mannose and galactose constituting the galactomannan polysaccharide is at least one of 1: 1, 2: 1, 3: 1, and 4: 1. Cosmetic composition. The galactomannan polysaccharides with a composition ratio of mannose and galactose of 1: 1, 2: 1, 3: 1, 4: 1 are leguminous plants, fenugreek (scientific name Trigonella)
foenum-graecum), a natural water-soluble gum obtained from the endosperm portion of the seeds, Guar (scientific name Cyamopsis), an annual legume plant cultivated mainly in India and Pakistan
tetragonolobus) natural water-soluble gum obtained from the endosperm portion of the seed, leguminous plant cod (Caesalpinia Spinosa) natural water-soluble gum obtained from the endosperm portion of the seed, the perennial legume plant locust bean (scientific name) Caratonia
3. A cosmetic composition comprising a low cation-modified galactomannan polysaccharide according to claim 1, which is a natural water-soluble gum obtained from the endosperm portion of Silica) seeds. The cation modification of the galactomannan polysaccharide is made using a glycidyl trialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. A cosmetic composition comprising a cation-modified galactomannan polysaccharide. A cosmetic composition in which the content of the low cation-modified galactomannan polysaccharide according to claim 1 is 0.05 to 5% by mass, based on 100% by mass of the entire composition. The cosmetic composition according to any one of claims 1 to 5, wherein other cationic water-soluble polymer and / or amphoteric water-soluble polymer is contained in an amount of 5% by mass or less based on 100% by mass of the entire composition. The cosmetic composition. The cosmetic composition according to claim 1, wherein the cosmetic composition is a skin cosmetic composition. The cosmetic composition according to claim 1, wherein the cosmetic composition is a hair treatment composition.