JP2007119365A - Composition for hair treatment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composition for hair treatment having an excellent feeling of use such as reduction in squeakiness during rinsing, combability of dry hair and suppleness during repeated use and the excellent feeling of use especially for damaged hair. <P>SOLUTION: The composition for hair treatment is composed of 0.05-10 mass% of a specific rinse base, 0.5-15 mass% of a higher alcohol and a low-viscosity cationically modified galactomannan polysaccharide in which the viscosity of an aqueous solution is within a specific range and the amount of cationic charges is regulated within a specified range by introducing a specific amount of quaternary nitrogen-containing group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hair treatment composition having an excellent usability.

  Conventionally, in hair treatment cosmetics, shampoos and other hair cleaning agents have an anionic surfactant as the main component, removing excess sebum, sweat, dandruff, dust and other dirt attached to the scalp and hair, It keeps the scalp and hair clean, but it removes not only dirt but also the necessary oil that protects the hair surface, which may lose the flexibility and gloss of the hair and make it difficult to comb. . Therefore, for the purpose of preventing such harmful effects, hair treatment compositions such as hair rinses, hair conditioners, hair treatments and the like mainly composed of cationic surfactants such as alkyltrimethylammonium chloride salts have been widely used. . However, with cationic surfactants alone, it is difficult to obtain sufficient effects in terms of touch such as gloss, smoothness, and moist feeling, so attempts to combine various oil agents and attempts to use surfactants in place of cationic surfactants Has been made.

  Patent Document 1 discloses a hair composition containing a polyhydric alcohol fatty acid ester, an alkyl quaternary ammonium salt, glyceryl monostearate and cetyl ethylhexanoate, and Patent Document 2 includes a specific amidoamine compound, A hair cosmetic comprising a higher fatty acid, an organic acid, and a specific high-molecular-weight dimethylpolysiloxane is described in Patent Document 3, which satisfies not only the feeling after rinsing and drying, but also the rich feeling when put out in the hand. A hair treatment agent comprising a higher fatty acid having a hydroxyl group in the chain and a higher alcohol, an amidoamine derivative or a quaternary ammonium salt is disclosed in Patent Document 4 as a hair conditioning agent selected from hydrocarbons and silicones, Conditioning Composition Comprising Nonionic Nonionic Polymer Thickener and Quaternary Ammonium Salt or Fatty Amine Salt There, Patent Document 5, a particular cationic cellulose - scan, poly (alkyl dimethyl ammonium) polymer - and behenic amidopropyl dihydroxypropyl dimonium conditioning compositions comprising a ride is shown.

  In recent years, with increasing awareness of cleanliness and fashion, women's hair has increased in the number of shampooing, physical damage due to styling, dryers, etc., and chemical damage due to breach, permanents, hair coloring, etc. It is easy to receive. Examples of problems with damaged hair include fingering during rinsing, crispness after drying, deterioration in smoothness, and deterioration in combing. In order to improve these, attempts are made to add various oils such as hydrocarbon oils, ester oils, triglycerides, silicone oils, etc., and to use surfactants in place of cationic surfactants typified by amidoamine type surfactants. However, it is the present situation that no sufficient effect is found for hair with many bruises. For the purpose of improving the feel of damaged hair, Patent Document 6 discloses amino-modified silicone and ammonia. A cosmetic comprising a modified silicone, a dimethyl silicone, a cyclic silicone, a higher fatty acid, a higher alcohol, a cationic surfactant, a guanidino derivative, and an amidoamine type surfactant is disclosed in Patent Document 7 as a guar. Gum or derivative thereof, cationic surfactant, saturated monovalent higher fatty acid alcohol, ester oil solid at 25 ° C., oily component liquid at 25 ° C., silicone Derivatives, compositions comprising the amino acid derivatives are shown.

  Furthermore, Patent Document 8 and Patent Document 9 disclose cation-modified galactomannan polysaccharides that have been cation-modified after degrading with an enzyme or the like using gua-gum or locust bean gum as galactomannan polysaccharides. Reference 10 uses guar gum and locust bean gum as galactomannan polysaccharides, and cation-modified galactomannan polysaccharides, which have been reduced in molecular weight by cation modification after hydroxyalkyl modification, are used for shampoos and rinses. It has been shown.

JP-A-10-158128 (page 1-5) JP-A-9-71516 (page 1-9) JP 2002-226327 A (page 1-8) U.S. Pat. No. 4,374,825 US Pat. No. 5,288,484 JP 2004-131423 (page 1-34) JP 2003-160446 A (page 1-9) JP-A-7-173029 (page 1-7) JP-A-10-36403 (page 1-9) Japanese Patent No. 3349219 (pages 1-6)

  In the case of hair treatments containing cation-modified cellulose or cation-modified guar gum for the purpose of improving the feel of damaged hair, they generally have an aqueous solution viscosity of 100 mPa · s or more when the conventional aqueous solution concentration is 2% by mass. There are many blends of cationically modified polymers with a high viscosity of aqueous solution, and although some improvements such as fingering at the time of rinsing are seen, the deterioration of fingering at the time of shampooing due to accumulation of cationic polymer due to repeated use and It has become a problem to have adverse effects such as dry hair stiffness. In particular, with the recent increase in the number of shampoos, this tendency is remarkable. On the other hand, a hair treatment composition containing a cation-modified galactomannan polysaccharide having a low molecular weight is not sufficiently satisfactory in the feel during rinsing. Therefore, there has been a demand for the development of a hair treatment composition for damaged hair that is more excellent in finishing effect and does not deteriorate in touch even when used repeatedly.

  In such a situation, the present inventors have conducted extensive studies on deterioration of the feeling of use due to accumulation and improvement in touch when rinsing when a hair treatment composition containing a conventional cationic polymer is repeatedly used. -10% by mass of specific rinsing base, 0.5-15% by mass of higher alcohol and galactomannan polysaccharide, a specific amount of quaternary nitrogen-containing group is introduced, and the cation charge amount is in a specific range It has been found that a hair treatment composition containing a cation-modified galactomannan polysaccharide having an aqueous solution viscosity in a specific range as an essential component is good in improving the feel during rinsing and in the feeling of use after repeated use. The present invention has been completed.

（式中Ｒ_１、Ｒ_２は各々炭素数１〜３個のアルキル基、Ｒ_３は炭素数１〜２４のアルキル基を示し、Ｘ⁻は陰イオンを示す。）
Therefore, the present invention is suitable for use in hair treatment compositions such as hair rinses, hair conditioners, hair treatments, etc. (a) 0.05-10% by weight of rinse base, (b) 0.5- A hair treatment composition comprising 15% by mass of higher alcohol and (c) 0.05-5% by mass of a cationic polymer as an essential component, wherein the cationic polymer is a galactomannan polysaccharide. The viscosity of a 10% by mass aqueous solution in which part of the hydroxyl group is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) is 5 to 50 mPa · s, and the cation charge amount is 0.1 to 3 The present invention relates to a hair treatment composition which is a low-viscosity cation-modified galactomannan polysaccharide of 0.0 meq / g.

(In the formula, 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, and X ⁻ represents an anion.)

  The hair treatment composition of the present invention was particularly damaged while providing a conditioning effect equal to or higher than that of a hair treatment composition containing a conventional cation-modified guar gum or cation-modified cellulose derivative as a conditioning agent. When it is repeatedly used on the hair, it accumulates on the hair surface and gives a good feel. In addition, by using a cation-modified galactomannan polysaccharide with a cation charge amount adjusted to a specific range, a specific rinse base, and a higher alcohol in a specific blending amount, the conventional low-viscosity cation-modified galactomannan and cationization degradation Compared to hair treatment compositions containing guar gum, it has better touch feeling such as fingering during rinsing, combing after drying, and flexibility, and it is more comfortable to use than conventional products. A composition can be provided.

  Examples of the rinse base (a), which is one of the essential components of the present invention, include cationic surfactants and amidoamine type surfactants. As cationic surfactants, alkyl (carbon number 8-24) trimethylammonium salt, dialkyl (carbon number 8-24) dimethylammonium salt, alkyl (carbon number 8-24) pyridinium salt, alkyl (carbon number 8-24) Examples thereof include dimethylbenzylammonium salt, benzethonium chloride, benzalkonium chloride and the like. Amideamine type surfactants include stearic acid diethylaminoethylamide, stearic acid dimethylaminoethylamide, palmitic acid diethylaminoethylamide, palmitic acid dimethylaminoethylamide, myristic acid diethylaminoethylamide, myristic acid dimethylaminoethylamide, behenic acid diethylamino acid. Ethylamide, behenic acid dimethylaminoethylamide, isostearic acid diethylaminoethylamide, isostearic acid dimethylaminoethylamide, stearic acid diethylaminopropylamide, stearic acid dimethylaminopropylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminopropylamide, myristic Diethylaminopropylamide, dimyristate myristate Aminopropyl amide, behenic acid diethylaminopropylamide, behenic acid dimethylaminopropylamide, isostearic acid diethylaminopropylamide, isostearic acid dimethyl aminopropyl amide illustratively. Among these, amidoamine type surfactants are preferably used from the viewpoint of reducing irritation, and more preferably diethylaminopropylamide stearate, dimethylaminopropylamide stearate, diethylaminopropylamide behenate, dimethylaminopropylamide behenate. Is used. In the present invention, one or more of these rinse bases can be arbitrarily used.

  The compounding quantity of the rinse base contained in the composition for hair treatment of this invention is 0.05-10 mass% by making the whole composition 100 mass%, Preferably it is 0.5-5%. If it is less than 0.05% by mass, the conditioning effect is insufficient, and if it exceeds 10% by mass, there is a problem in the stability of the dosage form.

  Furthermore, the higher alcohol (b), which is one of the essential components of the present invention, is not particularly limited as long as it can be generally blended into cosmetics. For example, saturated linear monohydric alcohol And unsaturated monovalent alcohol. Examples of saturated linear monohydric alcohols include lauryl alcohol, tridecanol, myristyl alcohol, pentadecanol, cetyl alcohol, heptadecanol, stearyl alcohol, isostearyl alcohol, and nonadecanol. , Icosanol, henicosanol, behenyl alcohol, tricosanol, tetracosanol, pentacosanol, hexacosanol and the like. In the present invention, one kind or two or more kinds of these higher alcohols can be arbitrarily used.

  The compounding quantity of the higher alcohol contained in the composition for hair treatment of this invention is 0.5-15 mass% by making the whole composition 100 mass%, Preferably it is 2-10 mass%. If it is less than 0.5% by mass, the viscosity of the composition will be low and the usability will be impaired, and if it exceeds 15% by mass, the composition will have too high a viscosity and the elongation to the hair will be poor, and the conditioning effect will be reduced. It will be insufficient.

  Further, (c) a low-viscosity cation-modified galactomannan polysaccharide having a viscosity of 5 to 50 mPa · s when the aqueous solution concentration is 10% by mass is an essential component of the present invention. It can be obtained by reducing the viscosity by a biochemical decomposition method using fungi or fungi, a chemical decomposition method using acid, alkali, or the like, or a physical decomposition method using high-speed stirring and a shearing machine. Furthermore, a low-viscosity galactomannan polysaccharide having a viscosity of 5 to 50 mPa · s when the aqueous solution concentration is 10% by mass by biochemical decomposition method, chemical decomposition method, physical decomposition method, etc. Although it can also be obtained by cation modification after being obtained, it is preferably cation modification of the galactomannan degradation product after degrading the galactomannan polysaccharide.

  Examples of the galactomannan polysaccharide used in the present invention include guar gum and cod (scientific name Caesalpinia), which are natural water-soluble gums obtained from the endosperm portion of the seeds of guar (scientific name Cyamopsis tetragonolobus), an annual legume plant. spinosa), a natural water-soluble gum made from the endosperm portion of spinosa seeds and a side chain galactose in a composition of about 1: 3, leguminous evergreen tree, carob Locust bean gum, which is a natural water-soluble gum obtained from the endosperm portion of the seeds of the scientific name Ceratonia siliqua, in which the main chain mannose and the side chain galactose are combined in a ratio of about 1: 4 A natural water-soluble gum obtained from the endosperm portion of the seed of fenugreek (scientific name Trigonella foenum-graecum), in which the main chain mannose and the side chain galactose are combined in a one-to-one composition. A fenugreek gum Etc. it includes, in the present invention, may be used in combination of one or more kinds of galactomannan polysaccharide, in particular guar - gum is preferred. This product is readily available under the trade name “Sun Fiber” (manufactured by Taiyo Kagaku Co., Ltd.). The viscosity of a 10% by mass aqueous solution is about 16 mPa · s, and the molecular weight is about 20,000. .

  The low-viscosity cation-modified galactomannan polysaccharide in the present invention is a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group or a 3-halogeno-2-hydroxypropyltrialkylammonium decomposed product obtained by decomposing a galactomannan polysaccharide. It can be produced by reacting a salt. 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. In addition, an inorganic salt, preferably sodium chloride can be added to prevent aggregation of the galactomannan polysaccharide in the solvent during the reaction. Furthermore, in order to prevent aggregation of the galactomannan polysaccharide, improve dispersibility and increase the reaction rate, the alkali and inorganic salt are added to the reaction solvent and then dissolved or dispersed, and then the galactomannan degradation product is added and dissolved or dispersed. Then, it can also be produced by introducing the quaternary nitrogen-containing group described above. Alternatively, after introducing a quaternary nitrogen-containing group into the galactomannan polysaccharide before decomposition in the same manner, biochemical decomposition methods using enzymes, fungi, fungi, chemical decomposition methods using acids, alkalis, etc. Alternatively, the low-viscosity cation-modified galactomannan polysaccharide of the present invention can also be obtained by reducing the viscosity by high-speed stirring and physical decomposition using a shearing machine. Preferably, a quaternary nitrogen-containing group is introduced into the galactomannan decomposition product.

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, 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, the anion X ^- include Specific examples of chlorine ion, bromine ion, and other halogen ions such as iodide ion, methyl sulfate ion, ethyl sulfate ion, an acetate ion.

  In the present invention, the cationic charge amount derived from the quaternary nitrogen-containing group of the low-viscosity cation-modified galactomannan polysaccharide is 0.1 to 3.0 meq / g, more preferably 0.5 to 2.5 meq / g. is there. If the amount of cationic charge is less than 0.1 meq / g, the amount of hair adsorbed becomes insufficient, and even if it is added to a hair treatment composition such as hair rinse, hair conditioner, hair treatment, etc., no effect is observed. In addition, when the charge amount exceeds 3.0 meq / g, even when using a hair treatment composition containing such a cation-modified galactomannan polysaccharide, a sticky feeling, a slimy feeling is produced, and the feeling of use is deteriorated. The finished feeling after use is also unfavorable because it causes a feeling of stickiness and stickiness.

The cation charge amount derived from the quaternary nitrogen-containing group of the low-viscosity cation-modified galactomannan polysaccharide is the quaternary nitrogen-containing group represented by the chemical formula (1) contained in 1 g of the low-viscosity cation-modified galactomannan polysaccharide. The number of equivalents. Usually, the nitrogen content derived from the quaternary nitrogen-containing group can be obtained by the Kjeldahl method (former cosmetic raw material standard, general test method, nitrogen determination method, second method) and calculated from the measured value. Specifically, the quaternary nitrogen-containing groups represented by the chemical formula (1), R ₁ , R ₂ and R ₃ are methyl, X ⁻ is a quaternary nitrogen-containing group of chloride ion, and galactomannan polysaccharide As a result of measuring the nitrogen content of the product of the present invention obtained by cation-modifying low viscosity guar gum (trade name: Sunfiber (made by Taiyo Kagaku Co., Ltd.)) by the Kjeldahl method, 0.93% In this case, the cation charge amount of this substance can be obtained by the following formula. The sun fiber used in the present invention usually contains about 0.06% nitrogen.

  Further, in addition to the above-mentioned method as a method for obtaining the cation charge amount, a colloid titration method using a toluidine blu-water solution as an indicator and titrating with a potassium polyvinyl sulfate aqueous solution (specifying component specifications according to cosmetic varieties, chloride O- [2-hydroxy-3- (Trimethylammonio) propyl] hydroxyethyl cellulose, quantitative method).

  The aqueous solution viscosity of the low-viscosity cation-modified galactomannan polysaccharide in the present invention is preferably 5 to 50 mPa · s (measurement temperature 25 ° C.) at a concentration of 10% by mass. Even if it is blended in a hair treatment composition such as hair rinse, hair conditioner, hair treatment, etc., no effect is observed. On the other hand, when the viscosity of the aqueous solution exceeds 50 mPa · s, although a conditioning effect can be obtained, it is not preferable because a feeling of use is deteriorated due to deterioration of a finished feeling or accumulation due to repeated use.

  The blending amount of the low-viscosity cation-modified galactomannan polysaccharide contained in the hair treatment composition of the present invention is preferably 0.05 to 5% by mass, based on 100% by mass of the entire composition, and less than 0.05% by mass. Conditioning effects such as fingering tend not to be fully exhibited, and if it exceeds 5% by mass, the feeling of use tends to be poor, such as the stickiness and stickiness during use, and the feeling of stiffness after use.

  In addition to the low-viscosity cation-modified galactomannan polysaccharide of the present invention, various cationic water-soluble polymers and amphoteric water-soluble polymers are used in combination for improving the conditioning effect of the hair treatment composition of the present invention. However, the blending amount of the hair treatment composition containing the rinse base, the higher alcohol, and the low-viscosity cation-modified galactomannan polysaccharide of the specific blending amount in the present invention as essential components is as follows. If the total composition is 100% by mass, the content is preferably 5% by mass or less, and if it exceeds this, a feeling of stiffness will occur during use and the usability will deteriorate.

  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 cellulose derivatives, cation-modified phenol gum, cation-modified guar gum, cation-modified tara gum, cation-modified locust bean gum, Cation-modified starch, cation-modified tamarind gum, etc.), dimethyldiallylammonium chloride derivative (dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivative (vinylpyrrolidone / dimethylaminoethyl methacrylate) Polymer salt, vinyl pyrrolidone / methacrylamide propyl trimethyl ammonium chloride copolymer, vinyl pyrrolidone / methyl vinyl imidazolium chloride copolymer, etc.), methacrylic acid derivative (methacryloyl ethyl) Dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium-2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol - alcohol copolymer, etc.) and the like.

  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.).

  When preparing a hair treatment composition containing the rinse base, the higher alcohol, and the low viscosity cation-modified galactomannan polysaccharide as essential components in the present invention, other components in the composition are particularly limited. First, it is possible to mix | blend the component generally used for cosmetics as an arbitrary component. Other ingredients that can be blended are exemplified below.

  Examples of the anionic surfactant include alkyl (carbon number 8-24) sulfate, alkyl (carbon number 8-24) ether sulfate, alkyl (carbon number 8-24) benzenesulfonate, alkyl (carbon number 8). To 24) sulfosuccinate, polyoxyalkylene alkyl (carbon number 8 to 24) ether sulfosuccinate, alkyl (carbon number 8 to 24) phosphate, polyoxyalkylene alkyl (carbon number 8 to 24) d Telluric acid salt, acyl (carbon number 8-24) taurine salt, acyl (carbon number 8-24) methyl taurine salt, acyl (carbon number 8-24) alanine salt, acyl (carbon number 8-24) N-methyl-β-alanine salt, acyl (carbon number 8-24) glutamate, acyl (carbon number 24-24) isethionate, acyl (carbon number 8-24) sarcosine salt, -Sulfo fatty acid ester salt, ether carboxylate, long chain (carbon number 8-24) carboxylate, polyoxyalkylene fatty acid monoethanolamide sulfate and the like, preferably alkyl (carbon number 8-24) Sulfate, alkyl (carbon number 8-24) ether sulfate alkyl (carbon number 8-24) sulfosuccinate, polyoxyalkylene alkyl (carbon number 8-24) ether sulfosuccinate, alkyl (carbon number) 8-24) phosphate, polyoxyalkylene alkyl (carbon number 8-24) ether phosphate, acyl (carbon number 8-24) taurine salt, acyl (carbon number 8-24) methyl taurate, Examples include acyl (carbon number 8 to 24) sarcosine salt, polyoxyalkylene fatty acid monoethanolamide sulfate, and the like.

  Examples of amphoteric surfactants include alkyl (carbon number 8-24) amidopropyl betaine, alkyl (carbon number 8-24) carboxybetaine, alkyl (carbon number 8-24) sulfobetaine, alkyl (carbon number 8-24) 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 to 24) amine oxide, tertiary nitrogen, and alkyl (carbon number 8 to 24) phosphate ester containing quaternary nitrogen.

  Nonionic surfactants include alkanolamides, glycerin fatty acid esters, polyoxyalkylene alkyl ethers, polyoxyalkylene glycol ethers, polyoxyalkylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyoxyalkylene sorbit fatty acid esters, Sorbit fatty acid ester, polyoxyalkylene glycerin fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene alkyl phenyl ether, tetrapolyoxyalkylene ethylenediamine condensate, sucrose fatty acid ester, polyoxyalkylene fatty acid amide, polyoxyalkylene glyco -Fatty acid ester, polyoxyalkylene castor oil derivative, polyoxyalkylene hydrogenated castor oil derivative, alkyl poly Glycosidic, polyglycerol fatty acid esters, and the like.

  In addition to the cationic and amphoteric water-soluble polymers blended in the hair treatment composition of the present invention, anionic and nonionic polymers may be used for the purpose of adjusting viscosity and improving usability during styling to some extent. Further, it 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, carboxymethyl cellulose, 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.) 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.).

  Other components to be blended in the hair treatment composition of the present invention include solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (carnauba wax, candelilla wax, etc.), carbonization Hydrogen oil (liquid paraffin, squalane, olive oil, jojoba oil, etc.), humectant (glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, Hyaluronic acid Na, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, glyceryl trimyristate, isopropyl palmitate, 2-heptylunpalmitate) Decyl, 2-hexyldecyl palmitate, butyl stearate, isostearate Cetyl, cholesteryl 12-hydroxystearate, cetostearyl alcohol, cetyl octoate, hexyl decyl dimethyloctanoate, isocetyl isostearate, trimethylolpropane triisostearate, decyl oleate, oil oleate, cetyl lactate, myristyl lactate, Ethyl acetate, butyl acetate amyl acetate, lanolin acetate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, ethylene glycol di-2-ethylhexylate, trimethylolpropane tri-2-ethylhexylate, tri-2 -Glyceryl ethylhexylate, pentaerythritol tetra-2-ethylhexylate, cetyl-2-ethylhexanoate, diisobutyl adipate, 2-heptylundecyl adipate, adipic acid-2- Xyldecyl, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, aceto Glyceride, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-ethylhexyl sebacate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, ethyl laurate, ethyl mink oil fatty acid, etc.) Antioxidants (tocopherol, BHT, etc.), silicones (methylpolysiloxane, methylphenylpolysiloxane, high polymerization degree methylpolysiloxane, cyclic polysiloxane, etc.) and silicone derivatives (polyether-modified silicone) , Mino-modified silicone, etc.), higher fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, isostearic acid, oleic acid, undecylenic acid, toll oil fatty acid, palm oil fatty acid, palm fatty acid, Palm nuclear fatty acid, linoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, etc.), amino acids (arginine, glutamic acid, etc.) UV absorbers, (benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc.) , Palletizing agent (fatty acid ethylene glycol, etc.), suspending agent (polystyrene emulsion, etc.), thickener, metal sequestering agent (edetate, etc.), pH adjuster, disinfectant, antiseptic, hair growth Agents, vitamins, anti-inflammatory agents, pigments, fragrances, foaming agents and the like.

  The hair treatment composition of the present invention is suitably used, for example, as a rinse, hair conditioner, hair treatment, etc., all of which are the specific rinse base, higher alcohol and low viscosity cation-modified galacto of the present invention. The hair treatment composition comprising a mannan polysaccharide utilizes effects such as improvement in touch when rinsing and improvement in touch when repeatedly used.

  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 viscosity cationic modified galactomannan polysaccharide]
Example 1
After adding 11.8 g of a 48% by mass aqueous sodium hydroxide solution to 900 mL of a 90% by volume isopropanol aqueous solution, a guar gum decomposition product having a 10% by mass aqueous solution viscosity of 17 mPa · s (Sunfiber: Taiyo Chemical Co., Ltd.) 162 g (manufactured by company) was gradually added and dispersed. Next, 65.5 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, 14.0 g of 35% hydrochloric acid was diluted with 1500 mL of a 90% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 1800 mL of acetone to precipitate the reaction product, which was filtered off. The resulting precipitate was washed with an aqueous acetone solution, and then the reaction product was dried under reduced pressure. The cation charge amount of the low molecular weight cation modified cellulose thus obtained is 0.91 meq / g, and the aqueous solution viscosity of 10% by mass is 25 ° C. using a Brookfield viscometer. -No. It was 13 mPa · s when measured at 1, 30 rpm. The results are shown in Table 1 (Sample No. 1 in Table 1). In addition, when the molecular weight of the gum gum decomposition product at this time and the low viscosity cation modification | denaturation galactomannan polysaccharide of this invention were calculated | required by GPC molecular weight measurement, the weight average molecular weight was 20,000 each.

  Similarly, low-viscosity cation-modified galactomannan polysaccharides having 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). Furthermore, a low-viscosity cation-modified galactomannan polysaccharide having a different aqueous solution viscosity was synthesized in the same manner as in Example 1 using guar gum decomposition products having different viscosities instead of sunfiber. The results are shown in Table 1 (Sample numbers 4 and 5 in Table 1).

Example 2
After adding 11.8 g of 48% by weight aqueous sodium hydroxide solution to 900 mL of 90% by volume isopropanol aqueous solution, gradually adding 162 g of conventional guar gum having a 1% by weight aqueous solution viscosity of 5,000 mPa · s. Dispersed. Next, 65.5 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, 14.0 g of 35% hydrochloric acid was diluted with 1500 mL of a 90% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 1800 mL of acetone to precipitate the reaction product, which was filtered off. The resulting precipitate was washed with an aqueous acetone solution, and then the reaction product was dried under reduced pressure. The aqueous solution was added with 50 mM acetate buffer (pH 4.5) and heated, and then allowed to stand at 40 ° C. for 12 hours. Thereafter, β-mannanase is added as a galactomannan-degrading enzyme and kept at 40 ° C. for 60 minutes. The obtained decomposition product was poured into acetone, and the resulting precipitate was collected and washed with an aqueous acetone solution, and then the reaction product was dried under reduced pressure. The cation charge amount of the low viscosity cation-modified galactomannan polysaccharide thus obtained is 0.78 meq / g, and the aqueous solution viscosity of 10% by mass is 25 ° C. using a Brookfield viscometer. -No. It was 8 mPa · s when measured at 1, 30 rpm. The results are shown in Table 1 (Sample No. 6 in Table 1). The molecular weight of the low viscosity cation-modified galactomannan polysaccharide of the present invention at this time was determined by GPC molecular weight measurement, and the weight average molecular weight was 15,000 each.

Example 3
The amount of the 48 mass% sodium hydroxide aqueous solution used in Example 1 was changed to 48.3 g, and 132.8 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added in place of GTA to synthesize in the same manner. The cation charge amount of the low viscosity cation-modified galactomannan polysaccharide thus obtained is 0.76 meq / g, and the aqueous solution viscosity of 10% by mass is 25 ° C. using a Brookfield viscometer. -No. It was 10 mPa · s when measured at 1, 30 rpm. The results are shown in Table 1 (Sample No. 7 in Table 1).

Example 4
In place of the guar gum decomposition product used in Example 1, a locust bean gum degradation product having a 10% by mass aqueous solution viscosity of 30 mPa · s obtained by decomposing locust bean gum with a galactomannan degrading enzyme was used in the same manner. Was synthesized. Furthermore, it synthesized similarly using fenugreek gum instead of locust bin gum. The results are shown in Table 1 (Sample numbers 8 and 9 in Table 1).

Comparative Example 1
In order to compare with the low-viscosity cation-modified galactomannan polysaccharide of the present invention, low-viscosity cation-modified galactomannan polysaccharides having different cationic charges were synthesized by changing the amount of GTA to be 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 Hair Treatment Composition]
Example 5 Feeling of Repeated Use on Damaged Hair Regarding a hair treatment composition comprising the specific rinse base of the present invention, a higher alcohol and a low viscosity cation-modified galactomannan polysaccharide, use on damaged hair when used repeatedly The feeling was confirmed by slipperiness and sensory evaluation on the hair.
<Preparation of hair treatment composition>
5-a
The behendimethylaminopropylamide citrate neutralized with citric acid as the neutralizing agent and the amidoamine type surfactant as the rinsing base shown in (A) of Table 2 was used as a higher alcohol cetano. Further, a hair treatment composition (hair rinse) containing the low viscosity cation-modified galactomannan polysaccharide obtained in Examples 1, 2, 3 and 4 was prepared. Components (3) and (5) to (9) in Table 2 are heated to 80 ° C. and stirred to obtain a uniform solution. The solution which was added and dissolved while heating to 80 ° C. was added with stirring, and then component (10) was added and mixed uniformly while cooling. Thus, hair rinses having the compositions shown in (A) of Table 2 were prepared, and hair rinses containing sample numbers 1 to 9 in Table 1 were used as prescriptions 1 to 9 of the present invention in order.

5-b
The low-viscosity cation-modified galacto obtained in Example 1 was obtained by using stearyltrimonium chloride as the rinse base, cetanol as the higher alcohol, and the higher alcohol as shown in (B) of Table 2. A hair treatment composition (hair rinse) containing mannan polysaccharide was prepared. The components (4) to (9) of (B) in Table 2 were heated to 80 ° C. and stirred, and the components (1) were previously added to the components (11) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (10) was added while cooling and mixed uniformly. Thus, a hair rinse having the composition shown in (B) of Table 2 was prepared, and the hair rinse containing Sample No. 1 in Table 1 was used as the formulation 10 of the present invention product.

5-c
As shown in (C) of Table 2, behendimethylaminopropylamide citrate and stearyltrimonium chloride neutralized by using citric acid as a neutralizing agent as an amide amine type surfactant as a rinsing base, -A composition for hair treatment (hair rinse) containing cetanol as the rule and further containing the low viscosity cation-modified galactomannan polysaccharide obtained in Example 1 was prepared. The components (3) to (9) of (C) in Table 2 were heated to 80 ° C. and stirred, and the component (1) was previously added to the component (11) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (10) was added while cooling and mixed uniformly. Thus, a hair rinse having the composition shown in (C) of Table 2 was prepared, and the hair rinse containing Sample No. 1 in Table 1 was used as the formulation 11 of the present invention.

5-d (Preparation of comparative product)
In order to compare the feeling of use when the hair treatment composition of the present invention is repeatedly used, a comparison of the compositions shown in (D) of Table 2 using the low-viscosity cation-modified galactomannan polysaccharide obtained in Comparative Example 1 Each product for hair treatment (hair rinse) was prepared. Ingredients (3) to (9) of comparative product (D) in Table 2 were heated to 80 ° C. and stirred, and then added to ingredient (11) while stirring ingredient (2). After the dissolved solution heated to 80 ° C. was added with stirring, the component (10) was added while cooling and mixed uniformly. Thus, hair rinses having the compositions shown in (D) of Table 2 were prepared, and the hair rinses including sample numbers 10 to 11 in Table 1 were sequentially designated as comparative products 1 and 2.

5-e (Adjustment of comparative product)
Further, in place of the low-viscosity cation-modified galactomannan polysaccharide in 5-d, as a conventional cationic polymer, CG-100 (aqueous solution viscosity: 1 mass%, 3,000 mPa · s (concentration of 10 mass%) Cation charge amount: 1.3 meq / g, manufactured by Toho Chemical Industry Co., Ltd.), cation charge amount: 1.3 meq / g, weight average molecular weight: 2,000,000, manufactured by Toho Chemical Industry Co., Ltd.) Then, a rinse having the composition shown in Comparative Product (D) in Table 2 was prepared in the same manner as 5-c, and used as Comparative Product 3.

5-f (Adjustment of comparative product)
Furthermore, a hair treatment composition (hair rinse) comprising a higher alcohol (setanol) not containing a rinse base and a low viscosity cation-modified galactomannan polysaccharide shown in (F) of Table 2 was prepared. . The components (5) to (9) of (F) in Table 2 were heated to 80 ° C. and stirred to make a uniform solution, and the component (1) was previously added to the component (11) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (10) was added while cooling and mixed uniformly. Thus, a hair rinse having the composition shown in Comparative Product (F) in Table 2 was prepared, and the hair rinse containing Sample No. 1 in Table 1 was used as Comparative Product 4.

5-g (Comparison product adjustment)
Further, a rinse base containing no low viscosity cation-modified galactomannan polysaccharide shown in (G) of Table 2 (behendimethylaminopropylamide neutralized with citric acid as a neutralizing agent for an amidoamine type surfactant) -A hair treatment composition (hair rinse) comprising citrate) and higher alcohol (cetanol) was prepared. Components (3) and (5) to (9) of (G) in Table 2 were heated to 80 ° C. and stirred to make a uniform solution, and component (11) was heated to 80 ° C. in advance. Was added with stirring, and then component (10) was added while cooling and mixed uniformly. Thus, a hair rinse having the composition shown in Comparative Product (G) in Table 2 was prepared and used as Comparative Product 5.

(Evaluation)
The slip property when the hair treatment composition of the present invention was repeatedly used on damaged hair was confirmed by the following method. Hair was bleached into a 2: 1 mixture (w / w) of 6% H ₂ O ₂ and 3% aqueous ammonia in a bath ratio of 1: 100 (hair: solution weight) at 40 ° C. It was immersed for 60 minutes, washed with warm water, and then dried with a dryer. A hair test piece was prepared using the damaged hair obtained by the bleaching treatment. The hair test pieces were obtained by attaching 13 damaged hairs having a length of 50 mm on a glass plate at a regular interval of 12 mm in width. The hair test piece thus obtained was immersed and washed in a 5% aqueous solution of a commercial shampoo. Then, after immersing in 5% aqueous solution of hair rinse (formulation 1-11) which is the hair treatment composition of the present invention prepared in the above-mentioned 5-a to 5-c, the hair rinse is thoroughly washed away, and is kept at constant temperature and humidity. (20 ° C., 40% RH) It was left overnight in an atmosphere and air dried. Similarly, after immersing and washing in a 5% aqueous solution of a commercial shampoo on the next day, after immersing in a 5% aqueous solution of the hair rinse of the present invention, the hair rinse was thoroughly washed out and further air-dried overnight in a constant temperature and humidity. A series of operations of this commercial shampoo soaking, washing, hair rinse soaking, washing, and natural drying was carried out 30 times. -SE) was used to measure the coefficient of dynamic friction and evaluate slipperiness. The evaluation results are shown in Table 3. Furthermore, for the hair rinses of comparative products 1 to 5 prepared in 5-d to 5-g, the hair test pieces were similarly immersed and washed in a commercial shampoo, immersed and washed in a comparative hair rinse, and kept at constant temperature and humidity. Natural drying was performed 30 times overnight, and the dynamic friction coefficient of the dried hair test piece after the measurement was measured with a friction tester to evaluate slipperiness. The results are shown in Table 4.

10 hair testers (damaged hair (breached hair)) for the hair rinses of the formulations 1 to 11 and the comparative products 1 to 5 prepared in the above-mentioned 5-a to 5-c. Was used continuously for 10 days, and the usability on the 10th day was evaluated by the following method. After the shampooing and washing, the hair rinses of the formulations 1 to 11 of the present invention and the hair rinses of the comparative products 1 to 5 were used, and the touches such as finger passage during rinsing, combing after drying, and softness were confirmed. Evaluation was made according to the following criteria according to the number of testers who felt that the touch was good and the touch was good, and the results are shown in Tables 3 and 4.
<As per finger when rinsing>
・ Eight or more testers felt good fingering ... ◎
・ 6-7 testers who felt that fingering was good ... ○
・ 4 to 5 testers who felt that fingering was good ... △
・ Less than 4 testers felt good fingering
<Comb street after drying>
・ 8 or more testers feel that combing is good ... ◎
・ 6-7 testers who feel that combing is good ... ○
・ 4-5 testers who felt that combing was good ... △
・ There are less than 4 testers who feel that combing is good ... ×
<Feel after drying>
・ Eight or more testers felt to feel good ... ◎
・ 6-7 testers who feel that the feel is good ... ○
・ 4 to 5 testers felt to feel good ... △
・ Less than 4 testers felt to feel good.

  In the results of Tables 3 and 4, it was confirmed that when the formulation of the product of the present invention was repeatedly used, the feeling of touch due to accumulation could be prevented because the coefficient of dynamic friction of dry hair was small. This can also be judged from the touch and feeling during drying in sensory evaluation. Furthermore, it was confirmed that the hair treatment composition comprising the specific rinse base of the present invention, the higher alcohol, and the low-viscosity cation-modified galactomannan polysaccharide was excellent in terms of fingering during rinsing.

Example 6
“Composition”
The feel of the hair treatment composition of the present invention comprising the specific amount of rinse base, higher alcohol and low viscosity cation-modified galactomannan polysaccharide was further confirmed during repeated use on damaged hair.

(Evaluation) The touch evaluation method for repeated use on damaged hair was carried out in the same manner as in Example 5. Table 5 shows the composition of the hair treatment composition used for the evaluation and the evaluation result at that time.

(Evaluation) Appearance of the product of the present invention Further, the appearance of the hair treatment composition used for the evaluation was visually observed. The evaluation results are shown in Table 5.
・ Suitable viscosity and excellent handling.
-Gelation or viscosity is too low and handling is inferior

  Hereinafter, the conditioning effect obtained by the hair treatment composition of the present invention and the improvement in the feeling of use when repeatedly used were further confirmed.

表６の精製水に、低粘度カチオン変性ガラクトマンナン多糖、塩化ヒドロキシプロピルトリモニウムデンプン、加水分解コムギ、L−グルタミン酸、グリセリン、１，３−ブチレングリコ−ルを加え８０°Cに保つ（水相）。残りの他の成分（シリコ−ン油、香料、色素、防腐剤を除く）を混合、加熱溶解し、８０°Cに保つ（油相）。水相と油相を加えホモミキサ−で乳化後、撹拌しながら冷却した。冷却後、シリコ−ン油、香料、色素、防腐剤を加え溶解した。

Add low viscosity cation-modified galactomannan polysaccharide, hydroxypropyltrimonium chloride, hydrolyzed wheat, L-glutamic acid, glycerin, 1,3-butylene glycol to purified water of Table 6 and keep at 80 ° C (aqueous phase) ). The remaining other components (excluding silicone oil, fragrance, coloring matter and preservative) are mixed, dissolved by heating and kept at 80 ° C. (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring. After cooling, silicone oil, fragrance, pigment and preservative were added and dissolved.

表７の精製水に、低粘度カチオン変性ガラクトマンナン多糖、トレハロ−ス、グリセリン、ヒドロキシプロピルトリモニウム加水分解ケラチンを加え７５°Cに保つ（水相）。残りの他の成分（フェノキシエタノ−ル、色素、香料、ｐＨ調整剤を除く）を混合、加熱溶解し、７５°Cに保つ（油相）。水相と油相を加えホモミキサ−で乳化後、撹拌しながら冷却した。冷却後、フェノキシエタノ−ル、色素、香料、ｐＨ調整剤を加え溶解した。

Low viscosity cation-modified galactomannan polysaccharide, trehalose, glycerin, hydroxypropyltrimonium hydrolyzed keratin are added to the purified water of Table 7 and kept at 75 ° C. (aqueous phase). The remaining other components (excluding phenoxyethanol, dye, fragrance, and pH adjuster) are mixed, dissolved by heating, and kept at 75 ° C. (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring. After cooling, phenoxyethanol, a dye, a fragrance, and a pH adjuster were added and dissolved.

常法に基づき、ヘアリンスを製造する。

A hair rinse is manufactured based on a conventional method.

常法に基づき、ヘアリンスを製造する。

A hair rinse is manufactured based on a conventional method.

常法に基づき、ヘアリンスを製造する。

A hair rinse is manufactured based on a conventional method.

常法に基づき、コンディショナ−を製造する。

A conditioner is manufactured based on a conventional method.

常法に基づき、コンディショナ−を製造する。

A conditioner is manufactured based on a conventional method.

As a result of further confirmation in each of the hair treatment compositions produced in Examples 7 to 13, feelings such as finger passage upon rinsing, comb passage after drying, flexibility, etc. when used repeatedly in healthy hair and damaged hair In addition, the usability during use was also good.

Claims (7)

(A) 0.05-10 mass% rinse base, (b) 0.5-15 mass% higher alcohol, (c) 0.05-5 mass% cationic polymer as essential components A hair treatment composition containing 10%, wherein a part of hydroxyl groups in the galactomannan polysaccharide is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) as the cationic polymer: 10% A composition for treating hair, which is a low-viscosity cation-modified galactomannan polysaccharide having an aqueous solution viscosity of 5 to 50 mPa · s and a cationic charge amount of 0.1 to 3.0 meq / g.

(In the formula, 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, and X ⁻ represents an anion.) The hair treatment composition according to claim 1, wherein the rinse base of (a) is a cationic surfactant. The hair treatment composition according to claim 2, wherein the cationic surfactant is a quaternary ammonium salt. The hair treatment composition according to claim 1, wherein the rinse base of (a) is an amidoamine type surfactant. The hair according to any one of claims 1 to 4, wherein the cation modification of the galactomannan polysaccharide is performed using a glycidyl trialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. Treatment composition. The hair according to any one of claims 1 to 5, wherein the galactomannan polysaccharide is one or more polysaccharides selected from locust bean gum, guar gum, tara gum, and fenugreek gum. Treatment composition. The hair treatment composition according to any one of claims 1 to 6, wherein 5% by mass of another cationic water-soluble polymer and / or an amphoteric water-soluble polymer is 100% by mass of the entire composition. The said hair treatment composition characterized by containing below.