JP2006131862A - Cation-modified, purified galactomannan polysaccharide and cosmetic composition containing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cation-modified galactomannan polysaccharide which, if blended to a hair treating composition, gives the excellent conditioning effect and the wettish good touch and softness after the drying, and which, if blended to a skin cosmetic composition such as a body detergent, gives the conditioning effect and the use touch improved by the emulsion performance. <P>SOLUTION: The cation-modified, purified galactomannan polysaccharide is obtained by introducing a specific, quaternary nitrogen-containing group to a part of hydroxy groups contained in the purified galactomannan that has a galactomannan content of 85% by mass or more and that is obtained by purifying a crude galactomannan which is obtained from the endosperm part in a seed of fenugreek of Trigonella foenum-graecum and which is constituted with the principal chain having the constitutional unit of mannose and with the side chain of a galactose unit, with the compositional ratio of mannose and galactose being 1:1; and the cosmetic composition contains this cation-modified, purified galactomannan polysaccharide. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention has a specific cationic modification as a cationic polymer that, when formulated in a cosmetic composition, has good adsorptivity to hair and skin, provides a good conditioning effect, and provides a good finish without any sensation after drying. The present invention relates to a galactomannan polysaccharide and a cosmetic composition containing the same, particularly a hair treatment composition.

  The hair treatment composition for the purpose of washing contains a conditioning agent for damaging hair entangled during washing and rinsing and for improving touch after washing. As a substance that imparts a conditioning effect, it is essential to adsorb to the hair, and therefore a cationic polymer having an adsorption action mainly based on ionicity is used. Among them, cation-modified cellulose derivatives, cation-modified guar gum, dimethyldiallyl chloride are used. Ammonium derivatives and the like are widely used. 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. A cationic derivative of guar gum having a chain galactose ratio of 2 to 1 can be used as a cationic conditioning polymer in an insoluble and non-volatile silicone for hair care products such as shampoos, rinses, etc. Further, Patent Document 3 uses guar gum and locust bean gum as galactomannan polysaccharides, cation-modified cation-modified galactomannan polysaccharides that have been decomposed and reduced in molecular weight by enzymes and the like, and Patent Document 4 discloses galactomannan polysaccharides. Guar gum and locust bean gum are used as polysaccharides. It has been shown that a cation-modified galactomannan polysaccharide, which is cation-modified after kill-modification and further reduced in molecular weight, is used in a hair treatment composition and a skin cosmetic composition.

However, when these cation-modified polymers are used, deterioration of the feeling of use due to dryness after drying and insufficient conditioning effect at the time of excessive, the composition ratio of main chain and side chain of galactomannan polysaccharide, presence or absence of hydroxyalkyl group, etc. This is caused by the difference in structure due to the difference in viscosity due to the presence or absence of low molecular weight. In order to improve these, cation-modified fenugreek gum is used. In Patent Documents 5 and 6, when cation-modified fenugreek gum is used in a cleaning composition such as a shampoo, the detergent composition has excellent foaming power and conditioning properties. Things are shown to be provided. Furthermore, Patent Document 7 shows that a detergent composition excellent in foaming power and conditioning properties is provided by blending cation-modified fenugreek gum, cation-modified cellulose, and cation-modified guar gum.

Japanese Patent Publication No.47-20635 (page 5) JP-A-4-364111 (page 1-6) JP-A-7-73029 (page 1-7) Japanese Patent No. 3349219 (pages 1-6) JP 2004-203799 A (pages 1-17) JP 2004-203800 A (pages 1-16) JP 2004-203803 A (Pages 1-16)

  In recent years, with the diversification of fashion, the use of hair colors and hair dyes has increased, and as a result, the hair has been significantly damaged, so that the conditioning effect of the conditioning agent, particularly the slipping property during use, has become important. Cationic modification of fenugreek gum, which was invented for the purpose of improving the deficiency of the conditioning effect during use and the deterioration of feeling of use, as seen in cationically modified cellulose derivatives, low molecular weight cationic modified galactomannan polysaccharides, and cationic modified guar gum When the cation-modified fenugreek gum is used for such damaged hair, the feeling of finish after rinsing and after drying is not fully satisfactory. In addition, the emulsification performance is affected. In addition, even when blended in a skin cosmetic composition, the feeling of use is not sufficiently satisfactory, and there are also problems in appearance.

  Under such circumstances, the present inventors have improved the slipperiness to wet hair when blended with a conventional cation-modified fenugreek gum hair treatment composition, and also improved the finished feeling after drying, and the skin makeup. The present inventors have intensively studied compounds that improve the foam quality when blended into the coating composition and the feeling after use. As a result, the galactomannan polysaccharide with a galactomannan content of 85% by mass or more and a mannose and galactose composed of mannose as a side chain in a main chain containing mannose as a constituent unit (hereinafter referred to as galactomannan polysaccharide) Purified galactomannan polysaccharide) is a cation-modified galactomannan polysaccharide introduced with a specific amount of quaternary nitrogen-containing groups and having a cationic charge amount adjusted to a specific range, and has excellent properties as a conditioning agent in cosmetic compositions. Thus, the present inventors have found that it is possible to improve slipperiness on wet hair, improve foaming and foam quality, and further improve the feel.

(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 is a mannose constituent unit obtained by purifying crude galactomannan polysaccharide, which is suitable for use in various hair treatment compositions, skin cosmetic compositions, and other cosmetic compositions such as makeup agents. A purified galactomannan polysaccharide having a galactose unit content of 85% by mass or more, wherein the main chain is composed of galactose units as side chains and the composition ratio of mannose and galactose is 1: 1. A part of the hydroxyl group of the mannan polysaccharide is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1), and the cation charge amount derived from the quaternary nitrogen-containing group is 0.1 to 3.0 meq / g. The present invention relates to a certain cation-modified purified galactomannan polysaccharide (hereinafter also referred to as cation-modified purified galactomannan polysaccharide).

(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.)

  The cation-modified galactomannan polysaccharide of the present invention is a conventional conditioning agent for hair when used in a hair treatment composition such as shampoo and rinse when the water-insoluble matter in the crude galactomannan polysaccharide is reduced. The galactomannan polysaccharide with a galactomannan content of less than 85% by mass is used as a cation-modified phenoglycam gum (hereinafter also referred to as unrefined cation-modified fenugreek gum), and is dried while giving a conditioning effect equivalent to or better than that. Later a good feel is obtained. Furthermore, when the cation-modified purified galactomannan polysaccharide of the present invention is blended in a skin cosmetic composition such as a body cleaning agent, the foaming is improved, the foam quality is improved, and a good finish is given. Therefore, it is possible to provide a cosmetic composition that is more comfortable to use than conventional products.

  The galactomannan polysaccharide used in the present invention is a nonionic polysaccharide having a mannose-containing main unit and a galactose unit as a side chain, and a composition ratio of mannose and galactose of 1: 1. It is a natural water-soluble gum obtained from the endosperm part of the seed of fenugreek (scientific name Trigonella foenum-graecum), which is an annual herbaceous plant grown in the Middle East, Africa and India. In the present invention, a galactomannan polysaccharide obtained by purifying a crude galactomannan polysaccharide obtained from the endosperm portion of fenugreek seed so as to have a galactomannan content of 85% by mass or more, preferably 87% by mass or more is used.

  As one method for purifying a crude galactomannan polysaccharide to a galactomannan content of 85% by mass or more, a crude galactomannan polysaccharide having a galactomannan content of less than 85% by mass (hereinafter also referred to as an unpurified galactomannan polysaccharide) 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.

  Moreover, fenugreek gum, which is a galactomannan polysaccharide having a mannose / galactose composition ratio of 1: 1, is the same galactomannan polysaccharide, and a mannose / galactose composition ratio of 2: 1 to guar gum or 4: 1 locust bean gum. It is a known fact that the rheology of aqueous solutions is different. Furthermore, it is a known fact that the emulsion stability is better than that of guar gum or locust bean gum due to the composition ratio, the rheology of the aqueous solution, and the like.

The cation-modified galactomannan polysaccharide according to the present invention is a galactomannan polysaccharide having a galactomannan content of 85% by mass or more obtained by purifying a crude galactomannan polysaccharide, and the composition ratio of mannose and galactose is 1: 1. It can be produced by reacting a galactomannan polysaccharide (hereinafter also referred to as purified fenugreek gum) with a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. it can. 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 purified galactomannan polysaccharide having a composition ratio of mannose to galactose of 1: 1, the glycidyl trialkylammonium salt or 3-halogeno The cation-modified galactomannan polysaccharide of the present invention (hereinafter also referred to as cation-modified purified fenugreek gum) can also be produced by reacting with a quaternary nitrogen-containing group of 2-hydroxypropyltrialkylammonium salt. In addition, an inorganic salt, preferably sodium chloride, can be added to prevent aggregation of the purified fenugreek gum in the solvent during the reaction. Furthermore, in order to prevent agglomeration of purified fenugreek 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 purified fenugreek gum is added and dissolved or dispersed. Then, it can also be produced by introducing the quaternary nitrogen-containing group described above.

  Furthermore, after crude galactomannan polysaccharide having a galactomannan content of less than 85% by mass is cationized by the same method, water insoluble matters such as the outer skin are removed and purified by a method such as pulverization, classification, or filtration. Even so, it is possible to produce a cation-modified purified galactomannan polysaccharide having a galactomannan content of 85% by mass or more according to the present invention.

In the quaternary nitrogen-containing group represented by the above chemical formula (1) to be introduced into the purified fenugreek gum, which is a galactomannan polysaccharide having a composition ratio of mannose and galactose of 1: 1 in the present invention, R ₁ and R ₂ Specific examples include methyl, ethyl, and propyl. Specific examples of R ₃ as the alkyl group having 1 to 24 carbon atoms include the same as R ₁ and R ₂ above, as well as octyl, decyl, dodecyl, Examples include tetradecyl, hexadecyl, octadecyl, docosyl and the like. 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-modified purified galactomannan polysaccharide of the present invention has an ability to adsorb to the hair and skin by cation-modifying the purified galactomannan polysaccharide having a galactomannan content of 85% by mass or more, and has good sliding properties. It is excellent as a blending component of a cosmetic composition because it is applied. For example, when blended in a hair treatment composition, it improves the finger feeling during rinsing and the finished feeling after drying. When incorporated into a composition, such as a body cleaner, it improves foam quality and feel after use. Therefore, the present invention also relates to these cosmetic compositions containing the cation-modified galactomannan polysaccharide of the present invention.

  The cationic charge amount derived from the quaternary nitrogen-containing group of the cation-modified galactomannan polysaccharide of the present invention is 0.1 to 3.0 meq / g, more preferably 0.5 to 2.5 meq / g. If the amount of cationic charge is less than 0.1 meq / g, the amount adsorbed on the hair and skin will be insufficient, and in fact, even if it is added to hair treatment compositions such as shampoos, rinses, body cleaners, and skin cosmetic compositions, the effect is recognized. I can't. In addition, when a cation-modified purified galactomannan polysaccharide with a charge amount of more than 3.0 meq / g is blended with a hair treatment composition and a skin cosmetic composition, the foaming deteriorates during use, and a sticky feeling and a slimy feeling are exhibited. The resulting feeling of use is worsened, and the finished feeling after use is unfavorable because it causes a feeling of stickiness and stickiness.

The cation charge amount derived from the quaternary nitrogen-containing group of the cation-modified purified galactomannan polysaccharide is equivalent to the quaternary nitrogen-containing group represented by the chemical formula (1) contained in 1 g of the cation-modified purified 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 purified galactomannan polysaccharide with a mannose composition ratio of 1: 1 contains nitrogen, the nitrogen content in the cation-modified galactomannan polysaccharide of the present invention determined by the Kjeldahl method is used to determine the galactose and mannose used in the present invention. The value obtained by subtracting the nitrogen content derived from the galactomannan polysaccharide having a composition ratio of 1: 1 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 When the nitrogen content of the product of the present invention obtained by cation modification of purified fenugreek gum was measured by the Kjeldahl method and found to be 1.38%, the cation charge amount of this substance was determined by the following formula: It is done. The purified fenugreek gum used in the present invention usually contains about 0.35% nitrogen.

具体的に説明すると、日本バイオコン(株)社製ガラクトマンナン測定キットを用い、本発明品に使用する精製フェヌグリークガム中のガラクトマンナン含有量を測定した場合、検量線より求められたガラクトース含有量への換算係数A*が1384.6であり、ブランクの340nmにおける吸光度が0.276である時、精製フェヌグリークガムを固形分換算で12.1mg採集し、その試料溶液の340nmにおける吸光度が0.663である例では、ガラクトース含有量は44.3%となる。フェヌグリークガムはマンノースとガラクトースの組成比が1対1であるから、ガラクトマンナン含有量は88.6%となる。 The galactomannan content in the crude galactomannan polysaccharide is a mass percentage of galactomannan contained per 1 g of the crude galactomannan polysaccharide, which is a natural water-soluble gum, which is a raw material for the cation-modified purified galactomannan polysaccharide. The measurement method is as follows. In addition to the measurement based on the absorbance after enzymatic decomposition, the measurement can also be performed by liquid chromatography, thin layer chromatography, or the like. As a measurement method, about 20 mg of a sample is accurately weighed, put into a centrifuge tube, 5 mL of ethanol is added and incubated at 85 to 95 ° C., and then centrifuged. 10.0 mL of 50 mM acetate buffer (pH 4.5) was added to the lower phase separated into an upper phase and a lower phase, and the mixture was heated and then allowed to stand at 40 ° C. for 12 hours. Thereafter, 20 μL of β-mannanase is added and incubated at 40 ° C. for 180 minutes. After incubation, centrifuge, take 0.1 mL of the supernatant, and add 0.2 mL of 50 mM acetate buffer (pH 4.5) and 20 μL of α-galactosidase. Incubate this solution at 40 ° C, add 2.5 mL of 200 mM Tris buffer, add 0.1 mL of β-nicotinamide adenine dinucleotide (0.1 g / 10 mL) and 8 μL of galactose dehydrogenase, and incubate at 40 ° C for 60 minutes. Then, the absorbance at 340 nm of the solution is measured. The galactose content is determined from the obtained absorbance using the following formula. The galactomannan content is calculated from the amount of galactose using the composition ratio of mannose and galactose of the sample.
<a formula>

Specifically, using the galactomannan measurement kit manufactured by Nippon Biocon Co., Ltd., when measuring the galactomannan content in the purified fenugreek gum used in the present invention product, to the galactose content determined from the calibration curve When the conversion factor A * is 1384.6 and the blank absorbance at 340 nm is 0.276, 12.1 mg of purified fenugreek gum is collected in terms of solid content, and the sample solution has an absorbance at 340 nm of 0.663, which contains galactose The amount will be 44.3%. Since fenugreek gum has a one-to-one composition ratio of mannose and galactose, the galactomannan content is 88.6%.

  The cation-modified purified galactomannan polysaccharide of the present invention is excellent as a blending component of a cosmetic composition. For example, when blended in a hair treatment composition, compared to blending a conventional unpurified cation-modified galactomannan polysaccharide, the slipperiness and conditioning effect on wet hair is improved, and the finished feeling after drying is also improved. The In addition, the unpurified cation-modified galactomannan polysaccharide contains many water-insoluble substances other than galactomannan polysaccharide, which is a natural water-soluble gum. When the cation-modified purified galactomannan polysaccharide of the invention is used, the water-insoluble matter is reduced by purification, so that the touch is not lowered. Moreover, since good foaming can be obtained, it is also excellent as a skin cosmetic composition.

  The blending amount of the cation-modified purified galactomannan polysaccharide of the present invention with respect to the hair treatment composition or the skin cosmetic composition is preferably 0.05 to 5% by mass, based on 100% by mass of the whole composition, and 0.05% by mass. If it is less than 5, the conditioning effect and the emulsification performance tend not to be sufficiently exhibited. If it exceeds 5% by mass, the feeling of stickiness and stickiness at the time of use is generated, and the slipping property is deteriorated and the feeling of use tends to be deteriorated.

  The hair treatment composition of the present invention may further contain various cationic water-soluble polymers and amphoteric water-soluble polymers in order to improve the conditioning effect. It is within the range that does not impair the slipperiness and conditioning effect of mannan polysaccharide on hair, and foam quality, etc., and the total composition is 100% by mass, preferably 5% by mass or less. There is a tendency for the feeling to deteriorate and the slipperiness to the hair to deteriorate. Furthermore, in the skin cosmetic composition, a feeling of sliminess is generated and the feeling of use becomes worse.

  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 guar gum, cation-modified starch, cation-modified tamarind gum, cation-modified locust bean gum, cation-modified tara gum, etc.), chloride Dimethyldiallylammonium derivatives (dimethyldiallylammonium chloride / acrylamide copolymer, polydimethylmethylenepiperidinium chloride, etc.), vinylpyrrolidone derivatives (vinylpyrrolidone / dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone / methacrylamidopropyltrimethylammonium salt) Chloride copolymer, vinylpyrrolidone / methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivative (methacryloylethyldimethylbetaine / salt) Methacryloyl ethyl trimethyl ammonium 2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine chloride methacryloyloxyethyl trimethyl ammonium methacrylate methoxy polyethylene glycol 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.).

  As described above, the cosmetic of the present invention can be obtained by blending the required amount of the cation-modified galactomannan polysaccharide of the present invention into the formulation system by a known formulation, but the other components in the cosmetic are not particularly limited. In addition, it is possible to mix components commonly used in cosmetics as optional components. 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 purposes such as adjusting viscosity and improving styling usability 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, alkylpyridium salt, alkyldimethylbenzylammonium salt, Benzethonium chloride, 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.) , Moisturizers (glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristate) Myristyl acid, 2-hexyldecyl myristate, glyceryl trimyristate, isopropyl palmitate, 2-heptylundecyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, 12-hydroxystearic acid Cholesteryl, cetostearyl alcohol, cetyl octanoate, hexyldecyl dimethyloctanoate, isocetyl isostearate, trimethylolpropane triisostearate, decyl oleate, oleic oil, cetyl lactate, myristyl lactate, ethyl acetate, amyl acetate butyl acetate, acetic acid Lanolin, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, ethylene glycol di-2-ethylhexylate, trimethylolpropane tri-2-ethylhexylate, tri-2-ethylhexyl Acid glycerin, tetra-2-ethylhexylate pentaerythritol, cetyl-2-ethylhexanoate, diisobutyl adipate, 2-heptylundecyl adipate, 2-hexyldecyl adipate, dipentaerythritol fatty acid ester, dicapric acid Neopentyl glycol, diisostearyl malate, di-2-heptylundecanoic acid glycerin, tri-2-heptylundecanoic acid glyceride, castor oil fatty acid methyl ester, acetoglyceride, N-lauroyl-L-glutamic acid-2-octyldodecyl ester , Di-2-ethylhexyl sebacate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, ethyl laurate, mink oil fatty acid ethyl, etc.), antioxidant (tocopherol, BHT, etc.), silicone (methyl polysiloxane) , Me Tilphenyl 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.) Ultraviolet absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc.), pearlizing agents (fatty acid ethylene glycol, etc.), suspending agents (polystyrene emulsions, etc.), thickeners, metal sequestering agents (edetic acid) Salt), pH adjuster, bactericidal agent, Preservative, hair restorer, 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. Usually, various components blended in the cosmetic composition can be added and produced by conventional methods, but among them, it can be preferably used as a hair treatment composition. Examples of the dosage form include shampoos, rinses, conditioners, hair waxes, hair lotions, hair mists, etc., all of which improve the slipperiness and conditioning effect of the cation-modified galactomannan polysaccharide of the present invention, and improve the finished feeling after use. , Utilizing the effect of improving the foam quality. In addition, it can be used in body cleaning agents, facial cleansers, lotions, and can be blended into acidic hair dyes, oxidative hair dyes, permanent agents, etc. due to the effect of improving the feeling of 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 cation-modified purified galactomannan polysaccharide]
Example 1
After adding 11.8 g of 48% by mass aqueous sodium hydroxide solution to 900 mL of 50% by volume isopropanol aqueous solution, 162 g of purified fenugreek gum having a galactomannan content of 88% by mass 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 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 cation-modified purified galactomannan polysaccharide thus obtained had a cation charge of 0.93 meq / g. The results are shown in Table 1 (Sample No. 1 in Table 1).

Similarly, cation-modified purified galactomannan polysaccharides 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).

Example 2
162 g of purified fenugreek gum having a galactomannan content of 90% by mass was dispersed in 900 mL of a 55% by volume isopropanol aqueous solution, and 48.3 g of a 48% by mass sodium hydroxide aqueous solution was added. Next, 142.8 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride 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 70% 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 cation-modified purified galactomannan polysaccharide thus obtained had a cationic charge amount of 0.76 meq / g. The results are shown in Table 1 (Sample No. 4 in Table 1).

Example 3
In a pressurized airtight container, 162 g of the purified fenugreek gum used in Example 1 was dispersed in 900 mL of an 80 volume% isopropanol aqueous solution, and 11.8 g of a 48 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, decompress the pressure and cool to 50 ° C. After cooling, 150 g of 80 mass% GTA aqueous solution is added 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 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-modified purified galactomannan polysaccharide thus obtained had a cation charge of 0.82 meq / g. The results are shown in Table 1 (Sample No. 5 in Table 1).

Example 4
After 11.8 g of 48% by mass aqueous sodium hydroxide solution was added to 900 mL of 50% by volume isopropanol aqueous solution, 162 g of purified fenugreek gum having a galactomannan content of 97% by mass was gradually added and dispersed. Next, 77.2 g of an 80 mass% 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 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 cation-modified purified galactomannan polysaccharide thus obtained had a cation charge of 1.07 meq / g. The results are shown in Table 1 (Sample No. 6 in Table 1).

Example 1
In order to compare with the cation-modified galactomannan polysaccharide of the present invention, according to the method of Example 1, cation-modified purified galactomannan polysaccharides having different cation charge amounts were synthesized by changing the amount of GTA to be added. The results are shown in Table 1 (Sample numbers 7 and 8 in Table 1).

Comparative Example 1
In order to compare with the cation-modified galactomannan polysaccharide of the present invention, a cation-modified unpurified galactomannan polysaccharide was synthesized using unpurified fenugreek gum having a galactomannan content of less than 85% by mass in the galactomannan polysaccharide. Unrefined fenugreek gum having a galactomannan content of 79% by mass in the galactomannan polysaccharide was cation-modified according to the method of Example 1. The cation charge amount of the obtained unpurified cation-modified galactomannan polysaccharide was 0.91 meq / g. The results are shown in Table 1 (Sample No. 9 in Table 1).

[Production and evaluation of cosmetics containing cation-modified purified galactomannan polysaccharide]
Example 5 Sliding property against hair (part 1)
The slip property of the cation-modified purified galactomannan polysaccharide on the hair was washed away and confirmed with the product.
<Adjustment of rinse-off products>
5-a
A shampoo having the composition shown in (A) of Table 2 was prepared using the cation-modified purified galactomannan polysaccharide obtained in Examples 1, 2, and 4. Ingredient (12) of (A) in Table 2 was heated to 80 ° C, and component (1) was slowly added and dissolved with stirring. After confirming dissolution, heating was stopped and ingredients (5) to (7) Were added and stirred to make it uniform, and then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C. In this way, each shampoo having the composition shown in (A) of Table 2 was prepared, and the cation-modified purified galactomannan polysaccharide of sample number 1 was blended with the cation-modified purified galactomannan polysaccharide of the product of the present invention. Was blended with the prescription S2 of the product of the present invention and the cation-modified purified galactomannan polysaccharide of sample number 6 was blended with the prescription S3 of the product of the present invention.

5-b
Using the cation-modified purified galactomannan polysaccharide of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal HC−) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass. 100; manufactured by Toho Chemical Co., Ltd.) and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; Mitsubishi Chemical Corporation) A shampoo having the composition shown in Table 2 (B) was prepared. Ingredient (B) in Table 2 (12) was heated to 80 ° C and ingredients (1), (3) and (4) were slowly added and dissolved with stirring. Add (5) to (7) and stir to homogenize, add components (8) to (11) at 30 to 40 ° C and mix uniformly, and thus shampoo with the composition shown in Table 2 (B) Was adjusted to be a formulation S4 of the present invention.

5-c (Comparison product adjustment)
In order to compare the effect of the cation-modified galactomannan polysaccharide of the product of the present invention on the shampoo, a comparative product shampoo having the composition shown in (C) of Table 2 was prepared using the unpurified cation-modified galactomannan polysaccharide obtained in Comparative Example 1. Each was prepared. Ingredient (12) of comparative product (C) in Table 2 was heated to 80 ° C, and component (2) was slowly added and dissolved while stirring.After confirming dissolution, heating was stopped and ingredients (5) to ( 7) was added and stirred to make it uniform, and components (8) to (11) were added and mixed uniformly at 30 to 40 ° C. Sample No. 12 blended with unpurified cation-modified galactomannan polysaccharide was designated as comparative product C1.

(Evaluation)
To each of the 5% aqueous solutions of the shampoos of the present invention products S1 to S4 prepared in the above 5-a to 5-b, hair strands (manufactured by Beaulux Co., Ltd., root aligned human hair, length 60 mm, After washing the shampoo thoroughly, measure the coefficient of dynamic friction of this wet hair with a friction tester (KES-SE, KES-SE) to evaluate the slipperiness. did. The evaluation results are shown in Table 3. In addition, for the shampoo of Comparative Product C1 prepared in 5-c, after dipping the hair strand in the same manner and thoroughly washing out the shampoo, the dynamic friction coefficient of the hair strand that was still wet was measured with a friction tester, and the shampoo was slipped. Evaluation of sex was made. The results are shown in Table 3.

Regarding the shampoos of the formulations S1 to S4 of the present invention prepared in the aforementioned 5-a to 5-c and the shampoo of the comparative product C1, a finger test after shampooing by 10 testers was performed as follows. I went. Washing and rinsing were performed using the shampoos of formulations S1 to S4 of the present invention and the shampoo of comparative product C1, and fingering during rinsing was confirmed. The test was evaluated according to the following criteria based on the number of testers who had good fingering, and the results are shown in Table 3.
・ 8 or more testers felt that fingering was good ... ◎
・ 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 ... ×

From the results in Table 3, it was confirmed that the shampoo containing the cation-modified galactomannan polysaccharide of the product of the present invention lowers the dynamic friction coefficient of wet hair than that containing the unpurified cation-modified galactomannan polysaccharide. . This also appeared in sensory evaluation, and it was confirmed that what was blended with the product of the present invention was superior to the shampoo blended with unpurified cation-modified galactomannan polysaccharide. Further, it was confirmed that the effect was not lost even in a system in which a cationic water-soluble polymer and an amphoteric water-soluble polymer were used in combination. Therefore, it was confirmed that the slip property was improved by cationically modifying a galactomannan polysaccharide having a galactomannan content of 85% by mass or more in the crude galactomannan polysaccharide. Moreover, since the improvement of the slipperiness with respect to hair is recognized, the touch improvement with respect to skin cosmetics, such as a body washing | cleaning agent and face wash, can also be anticipated.

Example 6 Slip on hair (Part 2)
(Evaluation)
Using the shampoos of the formulations S1 to S4 of the products of the present invention and the shampoo of the comparative product C1 prepared in Example 5, the effect of imparting the slipperiness to the damaged hair of the cation-modified purified galactomannan polysaccharide of the present invention was washed away. Confirmed with. A hair strand similar to that used in the test of Example 5 was added to a bleaching agent of 2: 1 mixture (w / w) of 6% H ₂ O ₂ and 3% ammonia water, and a bath ratio of 1: 100 (hair strand). : Solution weight), and immersed for 60 minutes at 40 ° C. After washing with warm water, the dryer was dried. The hair strands with remarkable damage obtained by this bleaching treatment are each immersed in a 5% aqueous solution of the shampoo of the present invention formulations S1 to S4 prepared in 5-a to 5-b, and the shampoo is thoroughly washed off. After that, the dynamic friction coefficient of the wet hair strand was measured with a friction tester to evaluate slipperiness. The evaluation results are shown in Table 4. Furthermore, for the shampoo of comparative product C1 prepared in 5-c, the hair strand that had been bleached was dipped in the same manner, and after the shampoo was thoroughly washed out, the hair strand that remained wet was slippery by a friction tester. Evaluation was performed and the results are shown in Table 4.

From the results of Table 4, even in damaged hair, in a formulation containing a cation-modified purified galactomannan polysaccharide obtained by cationically modifying a purified galactomannan polysaccharide having a galactomannan content of 85% by mass or more, unrefined cation-modified galacto It was confirmed that the improvement effect of the slipperiness on wet damaged hair was superior to the one containing the mannan polysaccharide, and moreover, the dynamic friction was higher than that evaluated in the unbleached healthy hair in Example 5. Since the difference in coefficient was large, the usefulness of the product of the present invention on damaged hair was confirmed.

Example 7 Foaming Test Foaming was measured using each of the shampoos of formulations S1 to S4 of the present invention prepared in 5-a to 5-b of Example 5. For comparison, foaming was also measured for the shampoo of Comparative Product C1 prepared in 5-c.
The measuring method is that the shampoos of the formulations S1 to S4 of the present invention and the shampoo of the comparative product C1 are diluted with water of hardness 4 to 1.5% by mass, and 145 mL of each prepared aqueous solution is commercially available. The mixture was stirred and foamed, and the amount of foam at this time was measured. The results are shown in Table 5.

  From the results in Table 5, it was proved that the cation-modified purified galactomannan polysaccharide of the product of the present invention was superior in foaming compared with the conventional unpurified cation-modified galactomannan polysaccharide. Therefore, when this invention product is mix | blended with cosmetics compositions which have foaming, such as a shampoo, a body washing | cleaning agent, and a face wash, improvement of foaming can be anticipated.

Example 8 Softness to hair The softness of the cation-modified purified galactomannan polysaccharide to hair was washed away and confirmed with a product (hair shampoo).

(Evaluation)
Using 1.0 g each of the shampoos of the formulations S1 to S4 of the present invention and the shampoo of the comparative product C1 prepared in 5-a to 5-b of Example 5, 15 g of hair strands (180 mm in total length) were used. I washed my hair. Thereafter, it was rinsed with running water, left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours, and then naturally dried. Thereafter, the firmness of the hair was measured with a pure bending tester (KES-FB2-S, manufactured by Kato Tech Co., Ltd.). The results are shown in Table 6.

For each of the shampoos of formulations S1 to S4 of the present invention prepared in 5-a to 5-b of Example 5 and the shampoo of comparative product C1, the hair was washed with 10 testers and then dried with a dryer. The softness of the hair was confirmed. The number of testers who felt that the finished hair quality was soft was evaluated according to the following criteria, and the results are shown in Table 6.
・ 8 or more testers who felt that their hair quality was soft ... ◎
・ 6-7 testers who felt that their hair quality was soft ... ○
・ 4-5 testers who felt that their hair quality was soft ... △
・ There are less than 4 testers who feel that their hair quality is soft ... ×

  From the results of Table 5, the shampoos S1 to S4 of the present invention containing the cation-modified purified galactomannan polysaccharides of Sample Nos. 1, 3, 4, and 5 obtained by cation-denaturing the purified galactomannan polysaccharides were obtained from the conventional unpurified galactomannan polysaccharides. Bending rigidity (B value) and hysteresis width (2HB) are both improved as compared with the shampoo of the comparative product C1 including the sample number 9 which is cation-modified. Furthermore, this result was confirmed by the effect of giving a soft touch to the hair with the hand-sensitive surface. Therefore, it was found that the cation-modified purified galactomannan polysaccharide of the present invention exerts its effect sufficiently even when it is blended in a shampoo, rinse or the like.

  In addition, the cation-modified purified galactomannan polysaccharide of the present invention and cation-modified hydroxyethyl cellulose having an average addition mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.) , N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation), etc. There was no difference in the hysteresis width (2HB), and it was confirmed that not only the effect was not lost by the combined use but also the bending rigidity was moderately improved and the hair was firm.

Example 9 Emulsification Performance The emulsification performance of the cation-modified purified galactomannan polysaccharide of the present invention (sample numbers 1, 2, 4 and 5 in Table 1) was confirmed by the following method. At room temperature (25 ° C.), add 10 ml of n-butanol as an oil to 40 ml of test solution (0.125% aqueous solution) in a measuring cylinder with a cap of 100 ml and emulsify n-butanol by shaking for 30 seconds. After that, the volume of n-butanol separated after 30 minutes and 24 hours was measured. The results are shown in Table 7. The smaller the numerical value in Table 7, the greater the emulsification performance. For comparison, the same emulsification performance test was performed on the unpurified cation-modified galactomannan polysaccharide of Sample No. 9 obtained in Comparative Example 1. The results are shown in Table 7.

  From the results of Table 7, it was proved that the cation-modified purified galactomannan polysaccharide of the present invention has an increased emulsifying performance as compared with the unpurified cation-modified galactomannan polysaccharide. This is considered to be because the emulsification performance was improved by removing or reducing the deposits derived from the outer shell, proteins, and water-insoluble substances contained in the raw fenugreek gum. Therefore, when the cation-modified purified galactomannan polysaccharide of the present invention is blended in a hair treatment composition or a skin cosmetic composition, an improvement in feel associated with emulsification performance can be expected.

  Hereinafter, the improvement in slipperiness, good foaming performance, and improvement in feel obtained by the cation-modified purified galactomannan polysaccharide for healthy hair and damaged hair were further confirmed in each cosmetic composition having different dosage forms.

Hair shampoo
(Preparation)
Example 10
10-a
Using the cation-modified purified galactomannan polysaccharide of Sample Nos. 1 to 6 of the present invention obtained in Examples 1 to 4, shampoos having the compositions shown in Table 8 (A) were prepared. Heat component (14) of (A) in Table 8 to 65 ° C and slowly add and dissolve component (1) with stirring. After confirming dissolution, stop heating and add (5) to (10). The components (11) to (13) were further added and mixed uniformly at 30 to 40 ° C. In this way, shampoos having the compositions shown in Table 8 (A) were prepared, each containing the cation-modified purified galactomannan polysaccharide corresponding to the sample numbers 1 to 6 in Table 1, and the sample numbers 1 to 6 in Table 1 were included. The shampoos were used as prescriptions 1 to 6 of the present invention.

10-b
Using the cation-modified purified galactomannan polysaccharide of sample number 1 obtained in Example 1, and further, as cationic water-soluble polymer A, cation-modified hydroxyethyl cellulose (Catinal HC) having an average ethylene oxide addition mole number of 1.8 and a nitrogen content of 1.8% by mass -100; manufactured by Toho Chemical Industry Co., Ltd.), a shampoo having the composition shown in Table 8 (B) was prepared. Ingredient (14) (B) in Table 8 was heated to 65 ° C, ingredients (1) and (3) were slowly added and dissolved with stirring. After confirming dissolution, heating was stopped and ingredients (5 ) To (10) were added and stirred to be uniform, and components (11) to (13) were further added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as the formulation 7 of the product of the present invention.

10-c
A shampoo having the composition shown in (C) of Table 8 containing diallyldimethylammonium chloride / acrylamide copolymer (Merquat 550; manufactured by NALCO) as the cationic water-soluble polymer B instead of the cationic water-soluble polymer A Was prepared in the same manner, and this was designated as the formulation 8 of the present invention.

10-d
N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer as an amphoteric water-soluble polymer, using the cation-modified purified galactomannan polysaccharide of sample number 1 obtained in Example 1 A shampoo having the composition shown in (D) of Table 8 was prepared, including (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation). Ingredient (D) (14) in Table 8 was heated to 65 ° C and ingredients (1) and (4) were slowly added and dissolved with stirring. After confirming dissolution, heating was stopped and ingredient (5) ~ (10) was added and stirred to make it uniform, and then components (11) to (13) were added and mixed uniformly at 30 ~ 40 ° C, and the resulting shampoo was used as prescription 9 for the product of the present invention.

10-e
Using the cation-modified purified galactomannan polysaccharide of Sample No. 1 obtained in Example 1, a shampoo having the composition shown in (E) of Table 8 containing a cationic water-soluble polymer and an amphoteric water-soluble polymer was prepared. In Table 8, component (14) (E) is heated to 65 ° C and components (1), (3) and (4) are slowly added and dissolved with stirring. After confirming dissolution, heating is stopped. Add components (5) to (10) and stir to homogenize, add components (11) to (13) and mix uniformly at 30 to 40 ° C., and mix the resulting shampoo with prescription 10 of the product of the present invention. did.

10-f (preparation of comparative product)
In order to compare the effect of the cation-modified purified galactomannan polysaccharide according to the present invention on the shampoo, the cation-modified purified galactomannan polysaccharide obtained in Example 1 (namely, samples Nos. 7 and 8 in Table 1 were used as comparative products in Table 8). A shampoo having the composition shown in G) was prepared. The component (14) of the comparative product (G) in Table 8 was heated to 65 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and components (5) to (10) were added and stirred to be uniform, and components (11) to (13) were added and mixed uniformly at 30 to 40 ° C. The shampoos were comparative products 1 and 2, respectively.

10-g (preparation of comparative product)
In order to further compare the effect, instead of the cation-modified purified galactomannan polysaccharide in 10-f, an unpurified galactomannan polysaccharide having a galactomannan content in the galactomannan polysaccharide obtained in Comparative Example 1 of less than 85% by mass. Using cation-modified unpurified cation-modified galactomannan polysaccharide, that is, sample No. 9 in Table 1, a shampoo having the composition shown in Comparative Product (G) in Table 8 was prepared in the same manner as 10-f, and compared. Product 3.

(Evaluation)
Example 11
For each shampoo prepared in the above 10-a to 10-e, that is, the formulations 1 to 10 of the present invention, performance evaluation of the following items was performed by 10 testers. The performance evaluation method uses a shampoo having the composition shown in the standard product (F) in Table 8 that does not contain a cationic polymer or the like in the components and a shampoo to be evaluated, and a feeling of use at the time of shampooing, after drying Based on the standard product (F),
・ Bubbling at the time of washing hair ・ Slipperiness at the time of use (as per finger and touch of hair)
-Comb feeling after use (dry hair) was compared and digitized by the method shown in Table 9 below, and the evaluation values of 10 testers for each item were summed. The evaluation results are shown in Table 10. In addition, after heating the component (14) in the standard product (F) in Table 8 to 65 ° C., adding the components (5) to (10) and stirring to make the standard product (F) uniform, It was prepared by cooling and adding components (11) to (13) at 30 to 40 ° C. and mixing uniformly.

Comparative Example 2
Each shampoo prepared in 10-f to 10-h and comparative products 1 to 3 were subjected to performance evaluation in the same manner as in Example 11, and the results are shown in Table 10.

  From the results shown in Table 10, when the cation-modified galactomannan polysaccharide of the present invention, which is a cation-modified purified galactomannan polysaccharide, is used in a shampoo, it is excellent in conditioning effects such as foaming at the time of washing hair, fingering and touching at the time of use. After drying, it was confirmed that the combing and other conditioning effects were excellent.

  Further, Comparative Product 3 including trial number 9 obtained by cationic modification of unpurified galactomannan polysaccharide was inferior to the cation-modified purified galactomannan polysaccharide of the present invention in terms of conditioning effects such as finger washing, and slipping after drying. Therefore, it was shown that the performance was improved by the cation-modified purified galactomannan polysaccharide of the present invention obtained by cationically modifying a purified galactomannan polysaccharide having a high galactomannan content in the galactomannan polysaccharide. Furthermore, the performance of the cation-modified purified galactomannan polysaccharide of the present invention by using a cationic water-soluble polymer (Kachinal HC-100, Merquat 550) and / or an amphoteric water-soluble polymer (Yukaformer SM) as a blending component It was confirmed that the conditioning effect was improved without impairing the condition.

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。 (Formulation examples 1 to 3)
Below, the suitable compounding example of this invention to a shampoo is shown.

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.

Hair rinse
(Preparation)
Example 12
12-a
Using the cation-modified purified galactomannan polysaccharides of Sample Nos. 1, 4 and 5 obtained in Examples 1, 2 and 3, using amidoamine compound and citric acid as neutralizing agent shown in (A) of Table 14 below A neutralized rinse with a composition containing behenic acid dimethylaminopropylamide citrate and further a higher alcohol (cetanol) was prepared. Ingredients (5) to (11) in Table 14 (A) were heated to 80 ° C. and stirred into a uniform solution, and the ingredient (1) was added to the ingredient (13) while stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (12) was added while cooling and mixed uniformly. Thus, a rinse having the composition shown in (A) of Table 14 was prepared, and the rinses containing the cation-modified purified galactomannan polysaccharides of Sample Nos. 1, 4 and 5 in Table 1 of the present invention were sequentially prepared. It was set to ~ 13.

12-b
Using the cation-modified purified galactomannan polysaccharide of sample number 4 obtained in Example 2, the amide amino acid compound and neutralized with citric acid as a neutralizing agent shown in (B) of Table 14 below, dimethylamino behenate A rinse having a composition containing propylamide citrate, higher alcohol (cetanol), and silicone was prepared. Ingredients (5) to (11) in Table 14 (A) were heated to 80 ° C. and stirred, and the ingredients (1) were added to the ingredients (13) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (12) was added while cooling and mixed uniformly. Thus, a rinse having the composition shown in (A) of Table 14 was prepared, and the rinse containing the cation-modified purified galactomannan polysaccharide of Sample No. 4 in Table 1 was used as Formulation 13 of the product of the present invention.

12-b
Using the cation-modified purified galactomannan polysaccharide of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal HC−) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass. 100; manufactured by Toho Chemical Industry Co., Ltd.), a rinse having the composition shown in Table 14 (B) was prepared. Ingredients (5) to (10) in Table 14 (B) were heated to 80 ° C. and stirred to obtain a uniform solution. Ingredients (1) and (3) were agitated in advance in ingredient (12). Then, the solution dissolved at 80 ° C. was added while stirring, and then the component (11) was added and mixed uniformly while cooling, and the resulting rinse was used as the formulation 14 of the present invention product. .

12-c
N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer as an amphoteric water-soluble polymer, using the cation-modified purified galactomannan polysaccharide of sample number 1 obtained in Example 1 A rinse having the composition shown in Table 14 (C) was prepared, including (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation). Ingredients (5) to (10) in Table 14 (C) were heated to 80 ° C. and stirred to obtain a uniform solution. Ingredients (1) and (4) were agitated in advance in ingredient (12). Then, the solution dissolved at 80 ° C. was added with stirring, and then the component (11) was added and mixed uniformly while cooling, and the resulting rinse was used as the formulation 15 of the present invention. .

12-d (Preparation of comparative product)
In order to compare the effect of the cation-modified purified galactomannan polysaccharide on rinsing according to the present invention, the cation-modified purified galactomannan polysaccharide obtained in Example 1 (namely, sample Nos. 7 and 8 in Table 1) was used as a comparative product in Table 14 ( A rinse having the composition shown in E) was prepared. Ingredients (5) to (10) of comparative product (E) in Table 14 were heated to 80 ° C. and stirred to make a uniform solution. After stirring the dissolved solution heated to 80 ° C, add component (11) while cooling and mix uniformly, and rinse each containing sample numbers 7 and 8 in Table 1, respectively. Comparative products 4 and 5 were designated.

12-e (Preparation of comparative product)
In order to further compare the effect, an unpurified cation-modified galactomannan polysaccharide obtained by cation-modifying the unpurified galactomannan polysaccharide of Comparative Example 1 instead of the sample numbers 7 and 8, ie, sample number 9 in Table 1 was used. A rinse having the composition shown in Comparative Product (E) in Table 14 was prepared in the same manner as 12-d, and the resulting rinse was designated as Comparative Product 6.

(Evaluation)
Example 13
For each of the rinses prepared in the above-mentioned 12-a to 12-c, that is, the formulations 11 to 15 of the present invention, the performance evaluation of the following items was performed by 10 testers. The performance evaluation method uses a rinse of the composition shown in the standard product (D) in Table 14 that does not contain a cationic polymer as a component, and a rinse of the object to be evaluated, respectively. The feeling after use is based on the standard product (D).
・ Sliding property when rinsing (as per finger)
・ Presence or absence of dry hair condition effect (comb street, squeaky feeling, etc.)
Were compared and numerically expressed by the method shown in Table 15 below, and the values of the 10 testers who performed the evaluation were summed. The evaluation results are shown in Table 16. The standard product (D) was heated to 80 ° C. in a solution obtained by heating the components (5) to (10) in the standard product (D) in Table 14 to 80 ° C. and stirring them uniformly. The component (12) was added while stirring, and then the component (11) was added while cooling to prepare a uniform mixture.

Comparative Example 3
For each of the rinses prepared in 12-d and 12-e described above, that is, comparative products 4 to 6, performance evaluation was performed in the same manner as in Example 13, and the results are shown in Table 16.

  From the results of Table 16, the purified galactomannan polysaccharide in which the galactomannan content in the crude galactomannan polysaccharide is 85% by mass or more includes the cation-modified purified galactomannan polysaccharide of the present invention, which is cation-modified, and further contains an amidoamine compound, neutralization In the case of the rinse containing the agent and the higher alcohol (cetanol), it was confirmed that the slipping property at the time of rinsing of the composition was excellent. Furthermore, since the conditioning effects such as improvement of combing after drying and less squeaky feeling can be obtained, even in a system containing an amidoamine compound, a neutralizing agent, and a higher alcohol, a good finish feeling by the product of the present invention. Was confirmed.

  In addition, the performance of the product of the present invention in the rinse containing the amidoamine compound, the neutralizing agent, and the higher alcohol (formulations 11 to 15 of the product of the present invention) is unpurified in which the galactomannan content in the galactomannan polysaccharide is less than 85% by mass. Compared with the unpurified cation-modified galactomannan polysaccharide of Sample No. 9 (comparison product formulation 6) obtained by cationically modifying the galactomannan polysaccharide, it was confirmed that both the conditioning effect during use and the finished feeling after use were excellent. . This is because the cation-modified purified galactomannan polysaccharide of the present invention has fewer precipitates, proteins, and water-insoluble substances than the conventional unpurified cation-modified galactomannan polysaccharide. It is considered that the finish feeling after use is improved at the same time that the properties are obtained. Furthermore, it was confirmed that by using a cationic water-soluble polymer and / or an amphoteric water-soluble polymer in combination, the conditioning effect is improved without impairing the performance of the cation-modified galactomannan polysaccharide. Furthermore, it was confirmed that the conditioning effect was improved by blending silicone without impairing the performance of the cation-modified galactomannan polysaccharide.

表１７の精製水に、本発明品、塩化ヒドロキシプロピルトリモニウムデンプン、ベヘン酸ジメチルアミノプロピルアミド、加水分解コムギ、L-グルタミン酸、グリセリン、1,3-ブチレングリコール、色素を加え80°Cに保つ(水相)。残りの他の成分を混合、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ーで乳化後、撹拌しながら冷却した。 (Formulation examples 4 to 6)
Below, the suitable example of a mixing | blending of this invention to the composition for hair treatment which requires conditioning effects, such as a rinse and a conditioner, is shown.

The purified water shown in Table 17 is added with the product of the present invention, hydroxypropyltrimonium chloride, dimethylaminopropylamide behenate, hydrolyzed wheat, L-glutamic acid, glycerin, 1,3-butylene glycol, and dye, and kept at 80 ° C. (Aqueous phase). The remaining other components 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.

表１８の精製水に、本発明品、塩化ステアリルトリメチルアンモニウム、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、フェノキシエタノール、色素を加え75°Cに保つ(水相)。残りの他の成分を混合、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ーで乳化後、撹拌しながら冷却した。

To the purified water shown in Table 18, the product of the present invention, stearyltrimethylammonium chloride, glycerin, hydroxypropyltrimonium hydrolyzed keratin, phenoxyethanol, and dye are added and kept at 75 ° C (aqueous phase). The remaining other ingredients 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.

表１９の精製水に、本発明品、N-(3-アルキル(12,14)オキシ-2-ヒドロキシプロピル)-L-アルギニン塩酸塩、ステアリン酸ジメチルアミノプロピルアミド、50%乳酸、グリセリン、フェノキシエタノール、安息香酸ナトリウム、を加え70°Cに保つ(水相)。残りの他の成分を混合、加熱溶解し、70°Cに保つ(油相)。水相と油相を加えホモミキサーで乳化後、撹拌しながら冷却した。

In the purified water of Table 19, the product of the present invention, N- (3-alkyl (12,14) oxy-2-hydroxypropyl) -L-arginine hydrochloride, dimethylaminopropylamide stearate, 50% lactic acid, glycerin, phenoxyethanol , Sodium benzoate, and maintain at 70 ° C (aqueous phase). The remaining other components are mixed, dissolved by heating and kept at 70 ° C (oil phase). The aqueous phase and the oil phase were added and emulsified with a homomixer, and then cooled with stirring.

Body cleaner
(Preparation)
Example 14
14-a
Using the cation-modified purified galactomannan polysaccharides of sample numbers 1, 4 and 6 obtained in Examples 1, 2 and 4, body detergents (body soaps) having the compositions shown in Table 20 (A) were prepared. . The component (11) of (A) in Table 20 was heated to 60 ° C., and the component (1) was added and dissolved while stirring. After confirming the dissolution, the components (3) to ( 7) was added with stirring to make it uniform, and components (8) to (10) were further added with stirring at 30 to 40 ° C. and mixed uniformly. Thus, body cleaners having the compositions shown in Table 20 (A) were prepared, and the body cleaners containing the cation-modified galactomannan polysaccharides of Sample Nos. 1, 4 and 6 in Table 1 of the present invention were sequentially prepared. The formulations of the present invention were 16, 17, and 18.

14-b (Preparation of comparative product)
In order to compare the effect of the cation-modified purified galactomannan polysaccharide used in the present invention on the body cleaning agent, the sample number 9 obtained in Comparative Example 1 and other cationic polymers as ethylene oxide average addition mole number 1.8, containing nitrogen A body cleaning agent having a composition shown in Table 20 (C) was prepared for cation-modified hydroxyethyl cellulose (Catinal HC-100: manufactured by Toho Chemical Industry Co., Ltd.) having a rate of 1.8% by mass. Ingredient (11) of (C) in Table 20 was heated to 60 ° C., and component (2) was slowly added and dissolved while stirring. After confirming dissolution, components (3) to (7) was added with stirring to make it uniform, and components (8) to (10) were further added with stirring at 30 to 40 ° C. and mixed uniformly. Thus, body cleaners having the compositions shown in Table 20 (C) were prepared and used as comparative products 7 and 8, respectively.

(Evaluation)
Example 15
The performance evaluation of the following items was carried out by 10 testers on the body cleaning agents of the formulations 16, 17 and 18 of the present invention obtained in 14-a above. The performance evaluation method uses a body cleaning agent having a composition shown in the standard product (B) in Table 20 that does not contain a high molecular compound such as a cationic polymer as a component, and a body cleaning agent to be evaluated. And
・ Amount of foam and foam quality during use ・ Usability during use (ease of rinsing, feeling of tension after rinsing, and feeling of sliminess)
・ Usage after use (after drying) (tiffness, smoothness, moistness)
In comparison with the comfort of the standard product (B), it was quantified by the methods shown in Tables 21 and 22 below, and the values of 10 testers who were evaluated were totaled. The evaluation results are shown in Table 23. In addition, after heating the component (11) of the standard product (B) in Table 20 to 60 ° C, add the components (3) to (7) with stirring at 50 to 60 ° C to make the standard product uniform. Further, components (8) to (10) were similarly added with stirring at 30 to 40 ° C., and mixed uniformly to prepare a body cleaning agent having the composition shown in Table 20 (B). A standard product was used.

Comparative Example 5
The same performance evaluation as in Example 15 was performed on the cleaning agents for body of Comparative products 7 and 8 obtained in 14-b above. These results are shown in Table 23.

  From the results shown in Table 23, when the cation-modified purified galactomannan polysaccharide of the present invention was used as a body cleaning agent, the cation-modified purified galactomannan polysaccharide contained in the cation-modified galactomannan polysaccharide even when compared with Comparative Product 7 containing unpurified cation-modified galactomannan polysaccharide. Since there are few water-insoluble matter, the feeling at the time of use becomes favorable, and also the improvement effect of the foam quality was confirmed, and it was confirmed that the finished feeling after use was also improved. In addition, it was confirmed that even when compared with other cationic polymers (Comparative Product 8), a good feeling during use and after drying derived from the cation-modified galactomannan polysaccharide was given.

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。 (Formulation examples 9-12)
The following is a preferred formulation example for a skin cosmetic composition such as a body cleaning agent, which utilizes the conditioning effect of the cation-modified galactomannan polysaccharide of the present invention and the improvement of feel by removing water insoluble matter.

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、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.

(Composition example 12 ~)
Hereinafter, as other application examples utilizing the improvement in feel of the cation-modified purified galactomannan polysaccharide of the present invention with respect to the skin cosmetic composition, formulation examples such as after-shoe lotion are shown.

表２８の精製水に本発明品を溶解した後、グリセリン、スクワラン及び１，３−ブタンジオールを添加して水相部とした。次に、エチルアルコールにポリオキシエチレン（６０）硬化ヒマシ油、ポリオキシエチレン（８）セチルエーテル、オクチルドデカノール、ビタミンアセテート、メチルパラベン及び香料を添加して調整したアルコール相部を水相部に添加し混合した。この混合物に、タルク、黄酸化鉄、赤酸化鉄、黒酸化鉄を添加して分散処理し、メーキャップローションを製造する。

The product of the present invention was dissolved in purified water shown in Table 28, and glycerin, squalane and 1,3-butanediol were added to form an aqueous phase part. Next, the alcohol phase part prepared by adding polyoxyethylene (60) hydrogenated castor oil, polyoxyethylene (8) cetyl ether, octyldodecanol, vitamin acetate, methyl paraben and fragrance to ethyl alcohol is added to the aqueous phase part. And mixed. To this mixture, talc, yellow iron oxide, red iron oxide, and black iron oxide are added and dispersed to produce a makeup lotion.

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、入浴剤を製造する。

A bath preparation is produced based on a conventional method.

Claims (10)

The content of galactomannan, which is obtained by purifying crude galactomannan polysaccharide, is composed of 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. A purified galactomannan polysaccharide having a mass% or more, wherein a part of the hydroxyl groups of the purified galactomannan polysaccharide is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1), and the quaternary A cation-modified purified galactomannan polysaccharide having a cation charge derived from a nitrogen-containing group of 0.1 to 3.0 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 cation-modified protein according to claim 1, wherein the galactomannan polysaccharide having a composition ratio of mannose to galactose of 1: 1 is a natural water-soluble gum obtained from the endosperm portion of the seed of the legume plant Trigonella foenum-graecum. Galactomannan polysaccharide. When replacing the hydroxyl group in the purified galactomannan polysaccharide with a quaternary nitrogen-containing group, it can be produced by reacting glycidyltrialkylammonium salt or 3-halogeno-2-hydroxypropyltrialkylammonium salt with galactomannan polysaccharide. The cation-modified purified galactomannan polysaccharide according to claim 1 or 2, which can be produced. In the cation modification of the purified galactomannan polysaccharide, an alkylene oxide having 2 to 4 carbon atoms is added to a part of the hydroxyl group contained in the purified galactomannan polysaccharide, and then a glycidyl trialkylammonium salt or 3-halogeno- The cation-modified purified galactomannan polysaccharide according to claims 1 to 3, which is made using a 2-hydroxypropyltrialkylammonium salt. A cosmetic composition containing the cation-modified purified galactomannan polysaccharide according to claim 1. The cosmetic composition according to claim 5, wherein the content of the cation-modified purified galactomannan polysaccharide according to claims 1 to 4 is 0.05 to 5% by mass, based on 100% by mass of the whole composition. The cosmetic composition according to claim 5 or 6, characterized in that it contains other cationic water-soluble polymer and / or amphoteric water-soluble polymer 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 5, comprising an amidoamine compound, a neutralizing agent such as an organic acid and / or an inorganic acid, and a higher fatty acid and / or a higher alcohol. . Silicone is mix | blended with the cosmetic composition of Claims 5-8, The said cosmetic composition characterized by the above-mentioned. A composition in which the cosmetic composition according to claim 5 is a hair treatment composition.