JPWO2004099259A1 - Cation-modified alginic acid derivative and cosmetic composition containing the substance - Google Patents

Abstract

When blended in a cosmetic composition such as a hair treatment composition or skin cosmetic composition, it provides improved foaming and foamy feel, and when blended in a hair treatment composition, provides excellent conditioning. Provided is a cation-modified alginic acid derivative which gives an effect and a good feeling of finishing feeling and improves the feeling of use due to the conditioning effect when it is blended in a skin cosmetic composition such as a body cleaning agent. Specifically, it is a natural polysaccharide contained as a calcium salt of the cell wall of brown algae (scientific name: Phaeophyceae) such as kombu and wakame in seaweed, and uronic acid units of L-glucuronic acid and D-mannuronic acid are 1,4 glycosides. A cationically modified alginic acid derivative obtained by introducing a specific quaternary nitrogen-containing group into a part of hydroxyl groups contained in an alginic acid derivative which is a polymer bonded by a bond, and a cosmetic composition containing the cationically modified alginic acid derivative It is a thing.

Description

  When the present invention is blended in a cosmetic composition, it improves foam feel such as foaming and foam quality, and has a good conditioning effect with good adsorptivity to hair and skin. Relates to a cation-modified alginic acid derivative that provides a good finish without stickiness, and a cosmetic composition, in particular a hair treatment composition, containing the same.

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. For this reason, it is essential that the conditioning agent be adsorbed on the hair, and a cationic polymer having an adsorption action based on ionicity is mainly used as the substance that gives the conditioning effect. As the cationic polymer, water-soluble polymers obtained by introducing quaternary nitrogen-containing groups into polysaccharides such as cellulose derivatives, guar gum and starch, dialkyl diallyl ammonium salt polymers, and the like are used. For example, Patent Document 1 discloses that a cation-modified cellulose derivative having a quaternary nitrogen-containing group introduced therein is used for shampoos and hair cosmetics. Furthermore, Patent Document 2 discloses cation-modified starch introduced with a quaternary nitrogen-containing group, Patent Document 3 and Patent Document 4 include cation-modified guar gum introduced with a quaternary nitrogen-containing group, shampoo, rinse, etc. It has been shown for use in hair care products. Further, Patent Document 5 uses a cation-modified cellulose derivative that has good adhesion to hair and also functions as a set component, and can provide a moist feeling with high molecular weight dimethylsiloxane that can impart smoothness and glossiness. Hair cosmetics containing specific sugar alcohols and the like are shown.
On the other hand, in the composition for hair treatment which shows a set effect, when it mix | blends with shampoo, rinse, and a conditioner in patent document 6, when it mix | blends in hairdressing agents, such as a mousse, while showing a conditioning effect, polyglycerin which shows a set effect Patent Document 7 discloses a hair styling agent using a thermogelling polymer substance having a setting effect, which is a hair cosmetic characterized by containing a modified silicone compound. However, in the above-mentioned use examples, the cation-modified alginic acid derivative as in the present invention is used in the hair treatment composition to improve the feel of foam such as foaming foam quality, excellent conditioning effect and set effect after drying. There is no description.
On the other hand, in the case of a skin cosmetic composition, soaps and anionic surfactants are generally used, but during washing, oily and fat components of the skin are removed more than necessary, and the skin feels tight. There is also a problem that occurs. From the effect of eliminating such inconvenience and giving a moist feeling, skin cosmetic compositions such as body cleaning agents are also blended with conditioning agents such as cationic polymers, and humectants such as glycerin. Document 8 shows that cation-modified polygalactomannan obtained by cation modification of guar gum and locust bean gum having a similar structure is used in hair care products such as shampoos and rinses and body cleaning agents (body soaps).
Further, in Patent Document 9, a shampoo composition containing a copolymer of a dialkyl diallylammonium salt and a cellulose derivative having a quaternary nitrogen-containing group is introduced, which gives a smooth and smooth feel to the fingers when shampooing. In addition, it has been shown to give a smooth and smooth finger passage to the hair when rinsed, and to give a good gloss to the hair when finished. Also, by blending these cationic polymers, it is possible to obtain a creamy foam quality, to eliminate the feeling of tension on the skin, and to give a moist feeling to skin cosmetic compositions such as body cleaning agents. Is also blended.
On the other hand, Patent Document 10 discloses a detergent composition having an excellent feeling of use by blending an alginate and an alkyl glucoside fatty acid ester having a specific structure with a higher fatty acid as a cleaning main component. Is a lipid-lowering agent characterized by containing a polyelectrolyte complex of polyuronic acid such as alginic acid and pectinic acid and a cationized dextran derivative as an active ingredient. Patent Document 12 discloses a polysaccharide and L-arginine. An external skin preparation excellent in moisture retention and flexibility is shown, and alginic acid is included as a polysaccharide together with acidic heteropolysaccharide, xanthan gum, cationized cellulose and the like. However, there is no description in the above use examples that a cation-modified alginic acid derivative in which a quaternary nitrogen-containing group is introduced into the alginic acid derivative of the present invention gives an excellent effect as a conditioning agent.
Furthermore, Patent Document 13 discloses a water-soluble cationic polysaccharide substituted with a hydrophob (hydrophobic) for body care products and shampoo applications. As the polysaccharide, cellulose, starch, hydroxyethyl cellulose, carrageenan, chitosan, natural gum Alternatively, alginates (alginic acid) are included together with biologically derived polysaccharides, but a cation-modified alginic acid derivative having a quaternary nitrogen-containing group introduced into the alginic acid derivative of the present invention has an excellent effect as a conditioning agent, There is no description that it gives a feeling of foam improvement such as foaming and foam quality and a set effect by having film-forming properties, and gives a feeling improvement when blended into a skin cosmetic composition.
Furthermore, Patent Document 14 discloses a cationized derivative obtained by cationizing alginic acid together with guar gum, locust bean gum, agar, curdlan and the like as one of polysaccharides in a liquid detergent composition in a spray container as a dispersant. Patent Document 15 shows that this cationized derivative is used as a thickener in cleaning detergent-impregnated sheets. Patent Document 16 discloses the use of these as a dispersant in a solid particle dispersion cleaning composition. However, the cation-modified alginic acid derivative of the present invention is also used for the hair treatment composition and skin cosmetic composition in the above-mentioned use examples, and has excellent conditioning effects and film-forming properties, so that foaming and foaming are achieved. There is no description of improving the feel of foam such as quality and setting effect after drying.
On the other hand, a natural polysaccharide contained as a calcium salt or the like in the cell wall of brown algae such as kombu and seaweed in seaweed, and a polymer in which uronic acid units of L-guluronic acid and D-mannuronic acid are linked by 1,4 glycoside bonds As for the alginic acid derivative, a polymer of guluronic acid and mannuronic acid is disclosed in Non-Patent Document 1 as a thickener or gelling agent in the food or feed industry, and from a fixing agent or heat or fire in the biochemical field. It is used as a protective material, and in Non-Patent Document 2, it is used in the field of foods, cosmetics and medical materials because of its property of forming a gel in the presence of a cation, and further, seaweed belonging to brown algae, Laminaria diguitarta Algi obtained by enzymatic depolymerization of polysaccharides consisting of L-guluronic acid and D-mannuronic acid obtained from (Laminaria digita) The acid-based oligosaccharides and their chelate compounds have skin protective effects, sedative effects, anti-inflammatory effects, and immunoprotective effects, and are useful as cosmetic raw materials. In Non-Patent Document 3, sodium alginate is an anion. In addition to being well compatible with non-ions, blending with shampoo creates a thin film on the hair to give it a finish, and it is also used in shave creams to improve water retention and foam stability. It has properties such as emulsification stability and colloidal dispersibility, and has been shown to be used for applications such as a viscosity imparting agent, a dispersant, an emulsion stabilizer, and a film forming agent. In Non-Patent Document 4, since the spherical polymer of calcium alginate has water absorption, it has been improved in functionality by blending it into seasonal products such as deolant powder and summer foundation. It is shown that However, in any of the above-mentioned documents, the quaternary nitrogen-containing group is introduced into the alginic acid derivative of the present invention. There is no description that gives the improvement of the feeling of foam and the setting effect, and further improves the feeling when blended into the skin cosmetic composition.
Japanese Examined Patent Publication No. 47-20635 (5th tribute) Japanese Patent Publication No. 60-42761 (page 1-9) JP 55-164300 A (1-2 tribute) JP-A-4-364111 (No. 1-6 tribute) Japanese Patent Laid-Open No. 5-112437 (1-3 tribute) JP 10-316540 A (2-3 Mitsugu) JP 2001-342117 A (2-4 tribute) JP-A-7-238186 (2-3 Mitsugu, 5-6 Mitsugu) Japanese Unexamined Patent Publication No. 1-128914 (1-3 Mitigation) Japanese Patent Laid-Open No. 10-310798 (1-6 tribute) JP-A 61-64701 (No. 2-42) JP 7-33635 A (1-2 tribute) JP 61-181801 (No. 1-34) JP 10-121099 A (2-4 tribute) Japanese Patent Laid-Open No. 10-287900 (No. 3 and No. 6) Japanese Patent Application Laid-Open No. 10-88196 (second tribute, fifth tribute) Fragrance JOURNAL, April 1994 (71-73 tribute) Fragrance JOURNAL, May 2002 (74-83 tribute) FRAGRANANCE JOURNAL, April 1999 issue (No. 82-83) FRAGRANCE JOURNAL, April 1999 issue (65-67 tribute)

  The cation-modified cellulose derivative forms a complex salt with an anionic surfactant when blended with a hair treatment composition and adsorbs it to the hair. While it exhibits an excellent conditioning effect upon rinsing, it exhibits a feeling of stiffness after drying and a poor feel. There is a problem. In addition, the cation-modified guar gum has a problem that the amount of adsorption is small and the conditioning effect at the time of rinsing is weak although the feeling of stiffness after drying is small. Furthermore, even if the conditioning effect is sufficient, it does not show the setting effect, and even if it shows the conditioning effect and the setting effect depending on the application as in Patent Document 6, it is anionic because it is nonionic. Compared to conventional cationic polymers such as cellulose derivatives having a quaternary nitrogen-containing group introduced on the hair surface, much adsorption cannot be expected and the effect may not be fully satisfactory. In addition, when a conditioning agent such as a cationic polymer or a moisturizing agent such as glycerin is blended in the skin cosmetic composition, stickiness or sliminess may occur depending on the blending amount in the formulation. There is a problem that we cannot be satisfied. Furthermore, although these cationic polymers can obtain a smooth foam quality, there is a problem that, depending on the formulation, sufficient foaming cannot be obtained, and the feeling during use cannot be sufficiently satisfied. .

（式中Ｒ_１、Ｒ_２は各々炭素数１〜３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。ｎは、ｎ＝０又はｎ＝１〜３０を示し、ｎ＝１〜３０のとき、（Ｒ_４Ｏ）_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。）In such a situation, the present inventors can improve the conditioning effect at the time of rinsing when blended with the hair treatment composition of conventional cationic polymers and the finishing feeling after drying, and can impart a set effect to the hair. Furthermore, intensive studies on compounds that eliminate the feeling of firmness and bulkiness when added to skin cosmetic compositions, improve the feeling of stickiness and sliminess, and improve the foam feel such as foaming and foam quality. did. As a result, L-guluronic acid and D-mannuronic acid uronic acid units are composed of 1,4-glycosidic bonds, which are natural polysaccharides contained as calcium salts in the cell walls of brown algae (scientific name: Phaeophyceae) such as kombu and seaweed in seaweed. A cation-modified alginic acid derivative in which a specific amount of a quaternary nitrogen-containing group is introduced into a combined polymer alginate derivative and the cationic charge amount is adjusted to a specific range has excellent properties as a conditioning agent in a cosmetic composition. In particular, in the composition for treating hair, it has been found that since the film-forming property is good, it is possible to impart a set effect to the hair at the time of drying, and further, the foam feel can be improved by forming a uniform film. It came.
Therefore, the present invention is suitable for use in various hair treatment compositions such as shampoos, rinses, setting agents, hair styling agents, hair colors, etc., skin cosmetic compositions, and other cosmetic compositions such as makeup agents. A part of the hydroxyl group contained in the alginic acid derivative, which is a natural polysaccharide in which L-guluronic acid and D-mannuronic acid uronic acid units are linked by 1,4 glycoside bonds, is represented by the following chemical formula (1): A cation-modified alginic acid which is a cation-modified polysaccharide substituted with a quaternary nitrogen-containing group and has a cation charge amount derived from the quaternary nitrogen-containing group of 0.1 to 3.0 meq / g Relates to derivatives.

(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 a polyalkylene glycol chain composed of a single alkylene oxide and (Or a polyalkylene glycol chain composed of two or more alkylene oxides)

The alginic acid derivative used in the present invention is contained as a calcium salt or the like in the cell wall of brown algae (scientific name: Phaeophyceae) such as kombu and wakame, and is composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid. Three types of block polysaccharides: a block composed of a bond between L-guluronic acids, a block composed of a bond between D-mannuronic acids, and a block composed of a bond between L-guluronic acid and D-mannuronic acid Polyuronic acid. In addition, the carboxyl group of the uronic acid unit has ion exchange properties, so it forms salts with various metal ions contained in seawater in seaweed and is in a water-insoluble jelly state. In this step, it is converted into pure alginic acid and various salts or esters according to the purpose. Further, depending on the purpose, the polymer may be depolymerized and reduced in molecular weight by a biological treatment such as an enzyme and a chemical treatment such as hydrolysis with acid or alkali. Therefore, the “alginate derivative” used in the present specification means pure alginic acid, various alginates obtained from pure alginic acid, alginic acid esters, and these derivatives having a reduced molecular weight. These alginic acid derivatives are trade names “Duck Algin NSPH”, “Duck Algin NSPL”, “Duck Algin NSPL”, “Duck Assid” (manufactured by Kibun Food Chemifa Co., Ltd.), and “Kimiroid” (Kimitsu Chemical Co., Ltd.). Furthermore, it is easily available as “PHYCO ANTI-POLLU” and “PHYCO ANTI-INFLA” (manufactured by Kodif), which are seaweeds belonging to the order of brown algae and obtained from Laminaria diguita.
The cation-modified alginic acid derivative of the present invention can obtain a conditioning effect by improving the adsorptivity by cation-modifying the alginic acid derivative. In addition, when it is formulated into a coating-type cosmetic composition due to its film-forming properties, a strong setting effect is obtained, and when it is formulated into a wash-out cosmetic composition such as shampoo and rinse, it is elastic to the hair. Is added, and it gives firmness and firmness to the hair. Furthermore, when blended into shampoos, body cleaners, etc., it has a film-forming property to form a uniform film, improving foam feel such as foaming and foam quality during use.
The cation modification according to the present invention is carried out by adding a glycidyl trialkylammonium salt having a quaternary nitrogen-containing group to an alginic acid derivative composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid, or 3-halogeno-2. -It can be produced by reacting a hydroxypropyltrialkylammonium 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. For example, after adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, the quaternary glycidyl trialkylammonium salt or the 3-halogeno-2-hydroxypropyltrialkylammonium salt is added. The cation-modified algin derivative of the present invention can be produced by reacting with a nitrogen-containing group. Furthermore, in addition to using alginic acid and alginates that have been reduced in molecular weight as alginic acid derivatives, the product of the present invention can also be reacted with a quaternary nitrogen-containing group after hydrolyzing the alginic acid derivative with an acid or alkali to lower the molecular weight. Can be manufactured. Furthermore, it can also be produced by introducing a quaternary nitrogen-containing group into the alginic acid derivative and then hydrolyzing with an acid or alkali. Also, an inorganic salt, preferably sodium chloride, can be added to prevent aggregation of the alginic acid derivative in the solvent during the reaction. Furthermore, in order to prevent aggregation of the alginic acid derivative, improve dispersibility and increase the reaction rate, after adding or dissolving the alkali and inorganic salt in the reaction solvent, and then adding the alginic acid derivative and dissolving or dispersing It can also be produced by introducing the quaternary nitrogen-containing group.
In the quaternary nitrogen-containing group represented by the chemical formula (1) introduced into the alginic acid derivative in the present invention, specific examples of R ₁ and R ₂ include a methyl group, an ethyl group, and a propyl group, and carbon Specific examples of R ₃ as the alkyl group having 1 to 24 include the same as R ₁ and R ₂ above, and octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, docosyl group and the like. It is done. Specific examples of R ₄ O include an ethoxy group, a propoxy group, and a butoxy group. Further, the anion X ^- include Specific examples of other halogen ions such as chlorine ions, bromine ions and iodine ions, methyl sulfate ions, ethyl sulfate ion, an acetate ion.
The cation-modified alginic acid derivative of the present invention is excellent as a blending component of a cosmetic composition because it has a film-forming property and an ability to adsorb to hair and skin. For example, when formulated in a cosmetic composition, Improves foam feel such as foaming and foam quality due to film properties, and provides conditioning effect, elasticity imparting and setting effect when blended into a hair treatment composition, and a skin cosmetic composition such as a body cleanser When blended with, the oily and fat components of the skin are not removed more than necessary, and the touch is further improved. Therefore, the present invention also relates to these cosmetic compositions containing the cation-modified alginic acid derivative of the present invention.
The cation-modified alginic acid derivative of the present invention has a cation charge amount derived from a quaternary nitrogen-containing group of 0.1 to 3.0 meq / g, more preferably 0.5 to 2.5 meq / g. When the amount of cationic charge is less than 0.1 meq / g, the amount of adsorption to hair and skin becomes insufficient, and even if it is actually blended with a hair treatment composition such as a shampoo, rinse, body cleaning agent or skin cosmetic composition, it is effective. It is not allowed. Further, when the charge amount exceeds 3.0 meq / g, even if a hair treatment composition and a skin cosmetic composition containing such a cation-modified alginic acid derivative are used, deterioration of foaming and stickiness are felt at the time of use. Further, a feeling of stickiness is generated, the feeling of use is deteriorated, and a feeling of finish after use is also undesirable, such as a feeling of stickiness and stickiness, and further, imparting elasticity and setting effect cannot be obtained.
The cation charge amount derived from the quaternary nitrogen-containing group of the cation-modified alginic acid derivative is the number of equivalents of the quaternary nitrogen-containing group represented by the chemical formula (1) contained in 1 g of the cation-modified alginic acid derivative. Usually, the nitrogen content derived from the 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 calculated from the measured value. Since the alginic acid derivative composed of two types of uronic acids, guluronic acid and D-mannuronic acid, contains a nitrogen content, it is used in the present invention from the nitrogen content of the cation-modified alginic acid derivative of the present invention determined by the Kjeldahl method. The value obtained by subtracting the nitrogen content derived from the alginic acid derivative composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid, is the nitrogen content derived from the quaternary nitrogen-containing group. More specifically, in the quaternary nitrogen-containing group represented by the chemical formula (1), R ₁ , R ₂ and R ₃ are methyl groups, X ⁻ is a chlorine ion, and n is a quaternary nitrogen having n = 0. When the nitrogen content of the product of the present invention obtained by cation-modifying sodium alginate with a containing group was measured by the Kjeldahl method and was 1.00%, the cation charge amount of this substance was expressed by the following formula: Desired. The sodium alginate used in the present invention usually contains about 0.02% nitrogen.
Cationic charge (meq / g) = nitrogen content from quaternary nitrogen-containing group (%) × 1000
Atomic weight of nitrogen (14.0) × 100
= (1.00-0.02) /1.40
= 0.70
The blending amount of the cation-modified alginic acid derivative of the present invention with respect to the hair treatment composition or skin cosmetic composition 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 effect, imparting elasticity and setting effect tend not to be fully demonstrated. If it exceeds 5% by mass, it will become sticky and sticky when used, and the flexibility will deteriorate and the feeling of stickiness will be seen. Etc. tend to be worse.
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. The film-forming property and the setting effect are not impaired, and the total composition is 100% by mass, and is preferably 5% by mass or less. The film forming property and the setting effect exhibited by the derivative are not sufficiently exhibited. 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 locust bean gum, cation-modified starch, cation-modified tara gum, cation-modified tamarind 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 derivatives (methacryloylethyldimethylbenzene) IN chloride methacryloyloxyethyl 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 a required amount of the cation-modified alginic acid derivative of the present invention into the formulation system by a known formulation, but the other ingredients in the cosmetic are not particularly limited, 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 8-24). ) Phosphate, polyoxyalkylene alkyl (C8-24) ether phosphate, alkyl (C8-24) sulfosuccinate, polyoxyalkylene alkyl (C8-24) ether sulfosuccinate, acyl (C8-C24) alanine salt, acyl (C8-C24) N-methyl-β-alanine salt, acyl (C8-C24) glutamate, acyl (C8-24) Isethionate, acyl (carbon number 8-24) sarcosine salt, acyl (carbon number 8-24) taurine salt, acyl (carbon number 8-24) methyl taurate α- sulfofatty acid ester salts, ether carboxylates, polyoxyalkylene fatty acid monoethanolamide sulfates, long chain (8 to 24 carbon atoms) carboxylic acid salts, and the like.
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.
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) amidopropylhydroxysulfobetaine, alkyl (carbon number 8-24) hydroxyphosphobetaine, alkyl (carbon number 8-24) aminocarboxylate, alkyl (carbon number 8-24) Examples include imidazolinium betaine, alkyl (carbon number 8 to 24) amine oxide, alkyl (carbon number 8 to 24) phosphate ester containing tertiary nitrogen and quaternary nitrogen.
Examples of the oil include olive oil, jojoba oil, liquid paraffin, and fatty acid alkyl ester. Examples of the pearlizing agent include fatty acid ethylene glycol, and examples of the suspending agent include polystyrene emulsion.
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 for purposes such as improving viscosity and 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 salts thereof, 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 acid 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.) and the like.
In yet another embodiment, 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 are added to the hair treatment composition and skin cosmetic composition of the present invention. Thus, the conditioning effect can be improved. 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 it exceeds this, the feeling after use becomes heavy or it becomes slippery and the usability is deteriorated.
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, etc.), humectants (glycerin) , Trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, sodium hyaluronate, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristate) Myristyl acid, myristate-2-hexyldecyl, 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, trimethylo tri-2-ethylhexylate Propane, glyceryl tri-2-ethylhexylate, pentaerythritol tetra-2-ethylhexylate, cetyl-2-ethylhexanoate, diisobutyl adipate, 2-heptylundecyl adipate, 2-hexyldecyl adipate, di Pentaerythritol fatty acid ester, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, glyceride tri-2-heptylundecanoate, 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 ester Chill, etc.), antioxidants (tocopherol, BHT, etc.), silicones (methylpolysiloxane, methylphenylpolysiloxane, highly polymerized methylpolysiloxane, cyclic polysiloxane, etc.) and silicone derivatives (polyether-modified silicone, amino-modified silicone, (Meth) acrylic-silicone graft copolymers), higher alcohols, higher fatty acids (lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, oleic acid, undecylenic acid, tall oil fatty acid, coconut oil Fatty acids, palm fatty acids, palm kernel fatty acids, linoleic acid, linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, etc.), amino acids (arginine, glutamic acid, etc.), UV absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, Toxiccinnamic acid derivatives), UV scattering agents (inorganic compounds such as zinc oxide, zirconium oxide, titanium oxide), thickeners, metal sequestering agents (edetates, etc.), pH adjusters, bactericides, preservatives, hair growth Agents, vitamins, anti-inflammatory agents, dyes, pigments (inorganic white pigments such as titanium dioxide, iron oxide (bengala), inorganic red pigments such as iron titanate, inorganic green pigments such as cobalt titanate, iron oxide treatment) Mica titanium, carbon black-treated mica titanium, etc.), fragrances, foam enhancers and the like.
The dosage form of the cosmetic composition according to the present invention described above is not limited and can be any dosage form. Further, in addition to the above (essential) component, the dosage form may be used as long as the effects of the present invention are not impaired. 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 are set to improve foam feel such as foaming and foaming due to film-forming properties of the cation-modified alginic acid derivative of the present invention. It uses effects, imparting elasticity and conditioning effects. 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 alginic acid derivative]

After adding 5.9 g of 48 mass% sodium hydroxide aqueous solution and 1.0 g of sodium chloride to 600 ml of 50 volume% isopropanol aqueous solution, 99.5 g of sodium alginate was gradually added and dispersed. Next, 60.8 g of an 80% by mass glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) aqueous solution was added, and the mixture was heated and reacted at 50 ° C. for 3 hours. After completion of the reaction, 7.0 g of 35% hydrochloric acid was diluted with 800 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 500 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 cationic charge amount of the cation-modified alginic acid derivative thus obtained was 0.66 meq / g. The results are shown in Table 1 (Sample No. 1 in Table 1).
Similarly, cation-modified alginic acid derivatives 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 2 and 3 in Table 1).

  176 g of alginic acid (duck acid; manufactured by Kibun Food Chemifa Co., Ltd.) was dispersed in 1100 ml of 60% by volume isopropanol aqueous solution, and 6.0 g sodium chloride and 136.8 g 48% by weight sodium hydroxide aqueous solution were added. After the addition, the mixture was heated and hydrolyzed at 70 ° C. for 3 hours. Cool to 50 ° C after hydrolysis. After cooling, 514.5 g of 3-halogeno-2-hydroxypropyldimethylmonolauryl ammonium chloride was added and reacted at 50 ° C. for 3 hours. After completion of the reaction, 14.0 g of 35% hydrochloric acid was diluted with 1700 ml of 70% by volume isopropanol aqueous solution and used for neutralization. After neutralizing at room temperature for 1 hour, the reaction solution was poured into 1200 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 alginic acid derivative thus obtained had a cation charge of 0.71 meq / g. The results are shown in Table 1 (Sample No. 4 in Table 1).

［カチオン変性アルギン酸誘導体の評価］
実施例４ 造膜性
カチオン変性したアルギン酸誘導体（表１の試料番号１、２、４及び５）の造膜性を以下の方法で確認した。２０ｍｌの試験液（０．２％水溶液）を角形のステンレス製の容器（縦×横×深さ＝１３５ｍｍ×１７０ｍｍ×３０ｍｍ）に流し、真空乾燥機にて発泡に注意しながら乾燥（７５℃）を行う。乾燥後、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置した後、ステンレス容器から乾燥物を取り出し、乾燥物の状態を目視にて観察した。比較のため、他のカチオン性ポリマーとしてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）及び窒素含有率１．９質量％のカチオン変性グアーガム（カチナールＣＧ−１００；東邦化学工業（株）社製）、さらには未変性のアルギン酸誘導体（アルギン酸ナトリウム、商品名：ダックアルギンＮＳＰＨ、（株）紀文フードケミファ社製）、各々について同様の造膜性試験を実施した。結果を表２に示す。

表２の結果から、アルギン酸誘導体をカチオン変性した本発明品のカチオン変性アルギン酸誘導体は、従来のコンディショニング剤に使用されているカチオン性ポリマーと比較し、造膜性に優れていることが確認された。
［カチオン変性アルギン酸誘導体を配合した各化粧料の製造とその評価］
実施例５ 毛髪に対する弾力性付与（その１）
カチオン変性したアルギン酸誘導体の毛髪に対する弾力性付与効果を洗い流し製品（ヘアシャンプー）で確認した。
（ヘアシャンプーの調製）
５−ａ
実施例１、２及び３で得た表１中の試料番号１、３、４及び５のカチオン変性アルギン酸誘導体を用いて表３の（Ａ）に示した組成のシャンプーを調製した。表３中の（Ａ）の成分（１２）を６０℃に加熱し、成分（１）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合した。こうして表３の（Ａ）に示した組成のシャンプーを各々調製し、表１中の試料番号１、３、４及び５に対応するカチオン変性アルギン酸誘導体から調製したシャンプーを順に、本発明品の処方Ｓ１〜Ｓ４とした。
５−ｂ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子としてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を含む、表３の（Ｂ）に示した組成のシャンプーを調製した。表３中の（Ｂ）の成分（１２）を６０℃に加熱し、成分（１）及び（３）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ５とした。
５−ｃ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらに両性水溶性高分子としてＮ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）を含む、表３の（Ｃ）に示した組成のシャンプーを調製した。表３中の（Ｃ）の成分（１２）を６０℃に加熱し、成分（１）及び（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ６とした。
５−ｄ
実施例１で得た試料番号１のカチオン変性アルギン酸誘導体を用い、さらにカチオン性水溶性高分子と両性水溶性高子の両方を含む、表３の（Ｄ）に示した組成のシャンプーを調製した。表３中の（Ｄ）の成分（１２）を６０℃に加熱し成分（１）及び（３）、（４）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーを本発明品の処方Ｓ７とした。

５−ｅ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体のシャンプーにおける効果を比較するため、例１で得た表１中の試料番号６、７のカチオン変性アルギン酸誘導体を用いて表３の比較品（Ｅ）に示した組成のシャンプーを調製した。表３中の比較品（Ｅ）の成分（１２）を６０℃に加熱し成分（２）を攪拌しながらゆっくり加え溶解させた。溶解を確認した後、加熱を止め成分（５）〜（７）を加えて攪拌して均一とし、３０〜４０℃で成分（８）〜（１１）を加え均一に混合し、得られたシャンプーをそれぞれ比較品Ｃ１及びＣ２とした。
５−ｆ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体のシャンプーにおける効果を比較するため、上記５−ｅで使用した試料番号６の代わりに、同じ配合割合の未変性アルギン酸誘導体（アルギン酸ナトリウム、商品名：ダックアルギンＮＳＰＨ、（株）紀文フードケミファ社製）を用い、表３の比較品（Ｅ）に示した組成のシャンプーを５−ｅと同様に調製し、これを比較品Ｃ３とした。
（評価）
先述の５−ａ〜５−ｆで調製した各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと比較品Ｃ１、Ｃ２及びＣ３のシャンプー、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーを、それぞれ１．０ｇ用いて１５ｇの毛髪ストランド（全長１８０ｍｍ）を洗髪した。その後流水中ですすぎ、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、自然乾燥を行った。その後毛髪のコシの強さを純曲げ試験機（カトーテック株式会社製、ＫＥＳ−ＦＢ２−Ｓ）にて測定した。その結果を表４に示した。尚、ブランクは表３のブランク（Ｆ）中の成分（１２）を６０℃に加熱した後、成分（５）〜（７）を加え攪拌して均一とした後、冷却し３０〜４０℃で成分（８）〜（１１）を加え均一に混合して調製した。
先述の５−ａ〜５−ｆで調製した、各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと比較品Ｃ１、Ｃ２及びＣ３のシャンプー、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーについて、１０名のテスターにより洗髪した後、ドライヤーにて乾燥した後の毛髪の弾力性（毛髪のコシ）を確認した。仕上がりの髪にコシがあると感じたテスターの人数により次の基準で評価し、その結果を表４中に示した。
・髪にコシが有ると感じたテスターが８名以上・・・◎
・髪にコシが有ると感じたテスターが６〜７名・・・○
・髪にコシが有ると感じたテスターが４〜５名・・・△
・髪にコシが有ると感じたテスターが４名未満・・・×

表４の結果から、アルギン酸誘導体をカチオン変性した試料番号１、３、４及び５のカチオン変性アルギン酸誘導体を含む本発明品のシャンプーＳ１〜Ｓ４はブランクと比較すると曲げ剛性（Ｂ値）及びヒステリシス幅（２ＨＢ）が共に向上している。同様の結果はカチオン電荷量値が本発明の範囲よりも高い試料番号７のカチオン変性アルギン酸誘導体を含む比較品Ｃ２にもみられるが、曲げ剛性が大きくなりすぎ、ごわつき感を示唆する結果となった。一方、カチオン電荷量値が本発明の範囲よりも低い、試料番号６のカチオン変性アルギン酸誘導体を含む比較品Ｃ１及び、未変性のアルギン酸誘導体を含む比較品Ｃ３は、ブランクと同じ結果となった。これは未変性のアルギン酸誘導体及びカチオン電荷量値が本発明の範囲よりも低いカチオン変性アルギン酸誘導体を洗い流し製品に用いた場合、毛髪に対しイオン性に基づく吸着能が得られず、該アルギン酸誘導体の毛髪への吸着が少ないので、その効果が得られなかったことを示したものと考えられる。これに対し、アルギン酸誘導体を特定の範囲でカチオン変性した本発明品は、毛髪へのイオン性に基づく吸着能を有するので、シャンプー、リンスのような洗い流し製品に於いて弾力性が付与され、毛髪のコシの強さが改善された。よって、本発明のカチオン変性アルギン酸誘導体はシャンプー、リンス等の洗い流し製品に配合した場合においても、その効果を十分発揮すると共に、ヘアスプレー、ヘアジェル等の塗布型の毛髪処理用組成物に配合した場合においても造膜性を有することによる弾力性の付与から、セット効果が期待できることが判った。
また、本発明のカチオン変性アルギン酸誘導体とエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）、Ｎ−メタクリロイルオキシエチルＮ，Ｎ−ジメチルアンモニウム−α−メチルカルボキシベタイン・メタクリル酸アルキル共重合体（Ｙｕｋａｆｏｒｍｅｒ ＳＭ；三菱化学株式会社製）等のコンディショニング効果を持つ水溶性高分子と併用した系に於いてもその効果は失われないことが確認された。
実施例６ 毛髪に対する弾力性付与（その２）
（評価）
実施例５で調製した各々の本発明品の処方Ｓ１〜Ｓ７のシャンプーと、比較品Ｃ１、Ｃ２及びＣ３のシャンプーを用い、本発明のカチオン変性アルギン酸誘導体の損傷した毛髪に対する弾力性付与効果を洗い流し製品で確認した。実施例５で使用したものと同様の毛髪ストランドを、６％Ｈ_２Ｏ_２と３％アンモニア水の２対１混合液（ｗ／ｗ）のブリーチ剤に、浴比１対１００（毛髪ストランド重量対ブリーチ剤溶液重量）、４０℃の条件下で６０分間浸漬した。温水で洗浄後、ドライヤーで乾燥した。このブリーチ処理により得られた損傷の著しい毛髪ストランドを、先述の５−ａ〜５−ｄで調製した本発明品の処方Ｓ１〜Ｓ７、５−ｅ及び５−ｆで調製した比較品Ｃ１〜Ｃ３、さらにブランクとして表３のブランク（Ｆ）に示す組成からなるシャンプーを、それぞれ１．０ｇ用いて１５ｇの毛髪ストランド（全長１８０ｍｍ）を洗髪した。その後流水中ですすぎ、恒温恒湿（２０℃、４０％ＲＨ）雰囲気中に２４時間放置し、自然乾燥を行った。その後毛髪のコシの強さを純曲げ試験機（カトーテック株式会社製、ＫＥＳ−ＦＢ２−Ｓ）にて測定した。その結果を表５に示した。尚、ブランクは実施例５同様に、表３のブランク（Ｆ）中の成分（１２）を６０℃に加熱した後、成分（５）〜（７）を加え攪拌して均一とした後、冷却し３０〜４０℃で成分（８）〜（１１）を加え均一に混合して調製した。

表５の結果から損傷毛髪で評価した場合、本発明品を含むシャンプーＳ１〜Ｓ４をブランクと比較すると、曲げ剛性（Ｂ値）とヒステリシス幅（２ＨＢ）がともに向上している。同様の結果は、カチオン電荷量値が本発明の範囲よりも高い試料番号７のカチオン変性アルギン酸誘導体を含む比較品Ｃ２にもみられるが、曲げ剛性が大きくなりすぎ、ごわつき感を示唆する結果となった。一方、カチオン電荷量値が本発明の範囲よりも低い試料番号６のカチオン変性アルギン酸誘導体を含む比較品Ｃ１では、曲げ剛性とヒステリシス幅が僅かに向上しているが、優位差を確認できる程度の向上は得られず、未変性のアルギン酸誘導体を含む比較品Ｃ３では、ブランクと同じ結果となった。更に、実施例５のブリーチ未処理の健常毛髪で評価した場合よりも、曲げ剛性、ヒステリシス幅ともにブランクとの差が大きくなっていることから、本発明品の損傷毛髪での有用性が確認された。
実施例７ 泡立ち試験
本発明のカチオン変性したアルギン酸誘導体（表１の試料番号１、２、４及び５）を表６の（Ａ）に示す組成で配合した化粧料組成物の泡立ちについて測定した。比較のため、他のカチオン性ポリマーとしてエチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）及び、未変性アルギン酸誘導体としてアルギン酸ナトリウム（ダックアルギンＮＳＰＨ；（株）紀文フードケミファ社製）を含む化粧料組成物をそれぞれ表６の（Ｂ）に示す組成で配合し、同様に泡立ちを測定した。
測定方法は、表６の処方の各化粧料組成物を、それぞれ実施例５に示した手順に準じた方法にて調製し、この調製した化粧料組成物の５％水溶液１５０ｍｌを市販のジューサーミキサーに入れ撹拌し泡立てる。撹拌時間と泡の量を測定し、その結果を表７に示した。

表７の結果から、本発明のカチオン変性したアルギン酸誘導体は、他のカチオン性ポリマー（カチナールＨＣ−１００：カチオン変性ヒドロキシエチルセルロース）と比較した場合、毛髪への弾力性の付与で見られた結果と同様、造膜性が優れる為、泡の膜が強固で、直後の泡立ち、速泡性に優れていることが確認された。よって、本発明品はシャンプー、ボディ用洗浄剤、洗顔料等の泡立ちを有する化粧料組成物に配合した場合、泡立ち、泡質などの泡の感触改善が期待できる。
以下、カチオン変性したアルギン酸誘導体により得られる造膜性、セット効果、弾力性の付与、コンディショニング効果及び泡立ち、泡質等の泡の感触改善を剤型の異なる化粧料組成物それぞれにおいて、官能評価及び機器測定によりさらに確認した。
ヘアシャンプー
（調製）199 g of sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.) was dispersed in 900 ml of 70% by volume isopropanol aqueous solution in a pressurized airtight container, and 11.8 g of 48% by mass sodium hydroxide aqueous solution was added. . Next, 66 g of ethylene oxide and 234 g of propylene oxide were added, and the mixture was heated and reacted at 70 ° C. for 3 hours under pressure and hermetic sealing. After completion of the reaction, the pressure is released and cooled to 50 ° C. After cooling, 242.4 g of 80% by 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 1000 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 alginic acid derivative thus obtained had a cation charge of 0.60 meq / g. The results are shown in Table 1 (Sample No. 5 in Table 1).
Example 1
According to the method of Example 1, cation-modified alginic acid derivatives having different charge amounts were synthesized by changing the amount of GTA to be added. The results are shown in Table 1 (Sample numbers 6 and 7 in Table 1).

[Evaluation of cation-modified alginic acid derivatives]
Example 4 Film-forming property The film-forming property of a cation-modified alginic acid derivative (sample numbers 1, 2, 4 and 5 in Table 1) was confirmed by the following method. Pour 20 ml of the test solution (0.2% aqueous solution) into a rectangular stainless steel container (length x width x depth = 135 mm x 170 mm x 30 mm), and dry (75 ° C) while paying attention to foaming in a vacuum dryer. I do. After drying, the substrate was left in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 24 hours, and then the dried product was taken out from the stainless steel container and the state of the dried product was visually observed. For comparison, as other cationic polymers, 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.) and nitrogen Cation-modified guar gum (Catinal CG-100; manufactured by Toho Chemical Industry Co., Ltd.) having a content of 1.9% by mass, and an unmodified alginic acid derivative (sodium alginate, trade name: Duck Algin NSPH, Kibun Food Co., Ltd.) Chemifa Co., Ltd.) and the same film-forming property test were carried out for each. The results are shown in Table 2.

From the results in Table 2, it was confirmed that the cation-modified alginic acid derivative of the present invention obtained by cation-modifying an alginic acid derivative is superior in film-forming properties as compared with the cationic polymer used in the conventional conditioning agent. .
[Production and Evaluation of Cosmetics Containing Cation-Modified Alginic Acid Derivatives]
Example 5 Giving elasticity to hair (part 1)
The effect of imparting elasticity to the hair of the cation-modified alginic acid derivative was confirmed by washing with a product (hair shampoo).
(Preparation of hair shampoo)
5-a
Using the cation-modified alginic acid derivatives of Sample Nos. 1, 3, 4, and 5 in Table 1 obtained in Examples 1, 2, and 3, shampoos having the compositions shown in Table 3 (A) were prepared. Ingredient (12) (A) in Table 3 was heated to 60 ° C., and component (1) was slowly added and dissolved while stirring. After dissolution was confirmed, heating was stopped and ingredients (5) to (7) were added. In addition, the mixture was stirred to make it uniform, and components (8) to (11) were added and mixed uniformly at 30 to 40 ° C. Thus, shampoos having the compositions shown in (A) of Table 3 were prepared, and the shampoos prepared from the cation-modified alginic acid derivatives corresponding to Sample Nos. 1, 3, 4, and 5 in Table 1 were sequentially prepared. S1 to S4.
5-b
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass A shampoo having the composition shown in Table 3 (B) was prepared, including HC-100 (manufactured by Toho Chemical Co., Ltd.). The component (12) of (B) in Table 3 was heated to 60 ° C., and the components (1) and (3) were slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and the components (5) to (5) to (7) was added and stirred to make it uniform, then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as prescription S5 of the product of the present invention.
5-c
The cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1 was used, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) was used as an amphoteric water-soluble polymer. A shampoo having the composition shown in (C) of Table 3 was prepared, including SM; manufactured by Mitsubishi Chemical Corporation. Ingredient (12) of (C) in Table 3 was heated to 60 ° C. and components (1) and (4) were slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and ingredients (5) to (5) to (7) was added and stirred to be uniform, then components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as formulation S6 of the present invention.
5-d
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further containing both a cationic water-soluble polymer and an amphoteric water-soluble high molecule, a shampoo having the composition shown in (D) of Table 3 was prepared. . The component (12) of (D) in Table 3 was heated to 60 ° C. and components (1), (3) and (4) were slowly added and dissolved while stirring. After confirming dissolution, heating was stopped and the component ( 5) to (7) were added and stirred to be uniform, and components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was designated as S7 of the present invention.

5-e (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the shampoo, the cation-modified alginic acid derivatives of Sample Nos. 6 and 7 in Table 1 obtained in Example 1 were used and shown in the comparative product (E) of Table 3. A shampoo of composition was prepared. The component (12) of the comparative product (E) in Table 3 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming dissolution, heating was stopped, components (5) to (7) were added and stirred to make uniform, components (8) to (11) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo Were designated as comparative products C1 and C2, respectively.
5-f (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the shampoo, an unmodified alginic acid derivative (sodium alginate, trade name: Duck Algin NSPH, A shampoo having the composition shown in Comparative Product (E) in Table 3 was prepared in the same manner as 5-e, and this was designated as Comparative Product C3.
(Evaluation)
The shampoos of the formulations S1 to S7 of the products of the present invention prepared in the above-mentioned 5-a to 5-f and the shampoos of comparative products C1, C2 and C3, and further, the composition shown in the blank (F) of Table 3 as a blank Each 1.0 g of shampoo was used to wash 15 g of hair strands (total length: 180 mm). 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 4. In addition, after heating the component (12) in the blank (F) of Table 3 to 60 degreeC, adding a component (5)-(7), stirring a blank, and cooling, it is 30-40 degreeC after cooling. Components (8) to (11) were added and mixed uniformly.
From the composition shown in the blank (F) of Table 3 as shampoos of the formulations S1 to S7 and comparative products C1, C2 and C3 of the present invention products prepared in the above-mentioned 5-a to 5-f. About the shampoo which becomes, after wash | cleaning hair by 10 testers, the elasticity (hair stiffness) of the hair after drying with a dryer was confirmed. The number of testers who felt that the finished hair was stiff was evaluated according to the following criteria, and the results are shown in Table 4.
・ There are more than 8 testers who feel that the hair is stiff ... ◎
・ 6-7 testers who felt that their hair was stiff ... ○
・ 4 to 5 testers who feel that their hair is stiff ... △
・ There are less than 4 testers who feel that hair is stiff ... ×

From the results of Table 4, the shampoos S1 to S4 of the present invention containing the cation-modified alginic acid derivatives of Sample Nos. 1, 3, 4 and 5 in which the alginic acid derivative was cation-modified are compared with the blank in terms of bending rigidity (B value) and hysteresis width. Both (2HB) are improved. Similar results are also seen in comparative product C2 containing the cation-modified alginic acid derivative of Sample No. 7 whose cation charge value is higher than the range of the present invention, but the bending rigidity was too large, suggesting a sense of stiffness. . On the other hand, Comparative Product C1 containing a cation-modified alginic acid derivative of Sample No. 6 and Comparative Product C3 containing an unmodified alginic acid derivative, which had a cation charge value lower than the range of the present invention, had the same results as the blank. This is because when an unmodified alginic acid derivative and a cation-modified alginic acid derivative having a cation charge value lower than the range of the present invention are washed out and used as a product, the adsorptive capacity based on ionicity cannot be obtained with respect to the hair. It is considered that the effect was not obtained because of less adsorption to the hair. On the other hand, the product of the present invention in which the alginic acid derivative is cation-modified within a specific range has an adsorption ability based on the ionicity to the hair, so that elasticity is imparted in a washing product such as shampoo and rinse. The strength of the body has been improved. Therefore, when the cation-modified alginic acid derivative of the present invention is blended in a shampoo, rinse, or other wash-out product, the effect is sufficiently exerted, and when blended in an application-type hair treatment composition such as a hair spray or hair gel. It was also found that a set effect can be expected from the provision of elasticity by having film-forming properties.
In addition, the cation-modified alginic acid derivative of the present invention, cation-modified hydroxyethyl cellulose having an average ethylene oxide addition number of 1.8 and a nitrogen content of 1.8% by mass (Katinal HC-100; manufactured by Toho Chemical Co., Ltd.), N In a system used in combination with a water-soluble polymer having a conditioning effect such as methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer SM; manufactured by Mitsubishi Chemical Corporation) It was confirmed that the effect was not lost.
Example 6 Giving elasticity to hair (part 2)
(Evaluation)
Using the shampoos of formulations S1 to S7 of each of the present invention products prepared in Example 5 and the shampoos of comparative products C1, C2 and C3, the elasticity-imparting effect of the cation-modified alginic acid derivative of the present invention on damaged hair was washed away. Confirmed with the product. A hair strand similar to that used in Example 5 was added to a bleaching agent in a 2: 1 mixture (w / w) of 6% H ₂ O ₂ and 3% aqueous ammonia with a bath ratio of 1 to 100 (hair strand weight). It was immersed for 60 minutes under the condition of 40 ° C. After washing with warm water, it was dried with a dryer. Comparatively damaged products C1 to C3 prepared according to the formulations S1 to S7, 5-e and 5-f of the products of the present invention prepared according to the aforementioned 5-a to 5-d, were obtained by the bleaching treatment. Furthermore, 1.0 g of a shampoo having the composition shown in the blank (F) of Table 3 was used as a blank to wash 15 g of hair strands (total length: 180 mm). 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 5. In addition, after heating the component (12) in the blank (F) of Table 3 to 60 degreeC similarly to Example 5, adding a component (5)-(7) and stirring and making it uniform, cooling The ingredients (8) to (11) were added at 30 to 40 ° C. and mixed uniformly.

When evaluated with damaged hair from the results in Table 5, when the shampoos S1 to S4 including the product of the present invention are compared with the blank, both the bending rigidity (B value) and the hysteresis width (2HB) are improved. Similar results can be seen in Comparative Product C2 containing the cation-modified alginic acid derivative of Sample No. 7 whose cation charge value is higher than the range of the present invention, but the bending rigidity becomes too large, suggesting a sense of stiffness. It was. On the other hand, in the comparative product C1 containing the cation-modified alginic acid derivative of Sample No. 6 whose cation charge amount value is lower than the range of the present invention, the bending rigidity and the hysteresis width are slightly improved. No improvement was obtained, and Comparative Product C3 containing the unmodified alginic acid derivative gave the same result as the blank. Furthermore, since the difference between the bending rigidity and the hysteresis width from the blank is larger than that in the case of the unbleached untreated healthy hair of Example 5, the usefulness of the product of the present invention on the damaged hair was confirmed. It was.
Example 7 Foaming Test The foaming of a cosmetic composition in which the cation-modified alginic acid derivative of the present invention (Sample Nos. 1, 2, 4, and 5 in Table 1) was blended with the composition shown in Table 6 (A) was measured. For comparison, as other cationic polymer, an average addition mole number of ethylene oxide of 1.8, a cation-modified hydroxyethyl cellulose having a nitrogen content of 1.8% by mass (Kachinal HC-100; manufactured by Toho Chemical Co., Ltd.), and A cosmetic composition containing sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.) as an unmodified alginate derivative was blended in the composition shown in Table 6 (B), and foaming was measured in the same manner.
For the measurement, each cosmetic composition having the formulation shown in Table 6 was prepared according to the procedure shown in Example 5, and 150 ml of a 5% aqueous solution of the prepared cosmetic composition was commercially available as a juicer mixer. Stir and whisk. The stirring time and the amount of foam were measured, and the results are shown in Table 7.

From the results in Table 7, the cation-modified alginic acid derivative of the present invention was found to give elasticity to hair when compared with other cationic polymers (Catinal HC-100: cation-modified hydroxyethyl cellulose). Similarly, it was confirmed that since the film forming property was excellent, the foam film was strong, and the foaming immediately thereafter and the rapid foaming property were excellent. Therefore, when the product of the present invention is blended in a foamed cosmetic composition such as a shampoo, a body cleaner, or a facial cleanser, improvement in foam feel such as foaming and foam quality can be expected.
Hereinafter, in each cosmetic composition having a different dosage form, the sensory evaluation and the film forming property obtained by the cation-modified alginic acid derivative, setting effect, imparting elasticity, conditioning effect and improvement of foaming feeling such as foaming, foam quality, etc. Further confirmation by instrument measurements.
Hair shampoo (preparation)

８−ｇ（比較品の調製）
さらに他のカチオン性ポリマーと効果を比較する為、上記８−ｆにおける例１で得たカチオン変性アルギン酸誘導体の代わりに、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を用い、表８の比較品（Ｇ）に示した組成のシャンプーを８−ｆと同様に調製し、これを比較品３とした。
（評価）8-a
Shampoos having the compositions shown in Table 8 (A) were prepared using the cation-modified alginic acid derivatives of Sample Nos. 1 to 5 of the present invention obtained in Examples 1, 2 and 3. The component (14) of (A) in Table 8 was heated to 65 ° C. and the component (1) was slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and (5) to (10) were added. The mixture was stirred to make it uniform, and components (11) to (13) were further added at 30 to 40 ° C. and mixed uniformly. In this way, each shampoo having the composition shown in Table 8 (A) in which the cation-modified alginic acid derivative corresponding to the sample numbers 1 to 5 in Table 1 was blended was prepared, and the shampoo containing the sample numbers 1 to 5 in Table 1 was prepared. It was set as prescription 1-5 of this invention product in order.
8-b
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as the cationic water-soluble polymer A, a cation-modified hydroxyethyl cellulose having an average added mole number of ethylene oxide of 1.8 and a nitrogen content of 1.8% by mass ( A shampoo having the composition shown in Table 8 (B) was prepared, including Kachinal HC-100 (manufactured by Toho Chemical Co., Ltd.). The component (14) of (B) in Table 8 is heated to 65 ° C., components (1) and (3) are slowly added and dissolved while stirring, and after confirming dissolution, the heating is stopped and components (5) to (5) (10) was added and stirred to make it uniform, and then components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as formulation 6 of the product of the present invention.
8-c
A shampoo having the composition shown in Table 8 (C) 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 7 of the present invention.
8-d
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) as an amphoteric water-soluble polymer. A shampoo having a composition shown in (D) of Table 8 was prepared, including SM (manufactured by Mitsubishi Chemical Corporation). The component (14) of (D) in Table 8 was heated to 65 ° C., and the components (1) and (4) were slowly added and dissolved while stirring. After confirming the dissolution, the heating was stopped and the components (5) to (5)-( 10) was added and stirred to make it uniform, and components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo was used as the formulation 8 of the present invention product.
8-e
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, a shampoo having a composition shown in (E) of Table 8 containing a cationic water-soluble polymer and an amphoteric water-soluble polymer was prepared. The component (14) of (E) in Table 8 was heated to 65 ° C. and components (1), (3) and (4) were slowly added and dissolved while stirring. After confirming dissolution, the heating was stopped and the component ( 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., and the resulting shampoo was used as the formulation 9 of the product of the present invention.
8-f (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the shampoo, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (G) shown in Table 8. A shampoo of the same composition 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, components (5) to (10) were added and stirred to make uniform, components (11) to (13) were added and mixed uniformly at 30 to 40 ° C., and the resulting shampoo Were comparative products 1 and 2, respectively.

8-g (preparation of comparative product)
Furthermore, in order to compare the effect with other cationic polymers, instead of the cation-modified alginic acid derivative obtained in Example 1 in 8-f, an ethylene oxide average added mole number of 1.8 and a nitrogen content of 1.8% by mass were obtained. Using cation-modified hydroxyethyl cellulose (Kachinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.), a shampoo having the composition shown in Comparative Product (G) in Table 8 was prepared in the same manner as 8-f, and this was compared product. It was set to 3.
(Evaluation)

比較例１
先述の８−ｆ及び８−ｇで調製した各々のシャンプー、比較品１〜３について、実施例９と同様に性能評価を実施し、その結果を表１１中に示した。

表１１の結果から、カチオン変性アルギン酸誘導体のカチオン電荷量が０．１〜３．０ｍｅｑ／ｇにある本発明のカチオン変性アルギン酸誘導体は、シャンプーに用いた場合、洗髪時の泡立と、使用時の指通り、手触りなどのコンディショニング効果に優れ、使用後ではしっとり感、櫛通りなどのコンディショニング効果と、造膜性による弾力性の付与から、毛髪のコシの強さが得られることが確認された。
また、本発明品を含むシャンプーの性能は、従来よりコンディショニング剤として用いられるカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００）のみを含む比較品３と比較すると、泡立ちに優れ、使用時のコンディショニング効果は同等以上であり、使用後においては、従来のコンディショニング剤には無い、本発明のカチオン変性アルギン酸誘導体のもつ造膜性による弾力性の付与から、毛髪のコシの強さが得られた。また、配合成分に、カチオン性水溶性高分子（カチナールＨＣ−１００、Ｍｅｒｑｕａｔ ５５０）及び／又は両性水溶性高分子（Ｙｕｋａｆｏｒｍｅｒ ＳＭ）を併用することにより、本発明のカチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例１〜３）
以下に、シャンプーへの本発明の好適な配合例を示す。

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。

精製水を７０℃に加熱し、他成分を加え均一に溶解した後、冷却した。
ヘアリンス
（調製）For each shampoo prepared in the above-mentioned 8-a to 8-e, that is, formulations 1 to 9 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 as a component, and a shampoo to be evaluated, and the feeling of use at the time of shampooing, depending on the dryer The feeling of use after drying is based on the standard product (F).
・ Bubbling at the time of hair washing ・ Presence / absence of conditioning effect when using (finger and hair touch),
・ Presence or absence of conditioning effect after use (dry hair) (comb feeling, feel of hair) and strength of hair
Were compared and digitized by the methods shown in Tables 9 and 10 below, and the evaluation values of 10 testers for each item were summed. The evaluation results are shown in Table 11. In addition, after heating the component (14) in the standard product (F) in Table 8 to 65 ° C., adding the components (5) to (10), stirring and homogenizing the standard product (F), cooling The components (11) to (13) were added at 30 to 40 ° C. and mixed uniformly.

Comparative Example 1
For each shampoo and comparative products 1-3 prepared in 8-f and 8-g described above, performance evaluation was performed in the same manner as in Example 9, and the results are shown in Table 11.

From the results of Table 11, the cation-modified alginic acid derivative of the present invention in which the cation-modified alginic acid derivative has a cation charge amount of 0.1 to 3.0 meq / g, when used in shampoo, It has been confirmed that it has excellent conditioning effects such as touching and touching, and after use it provides moist feeling, combing and other conditioning effects, and elasticity due to film-forming properties, giving it firmness. .
Moreover, the performance of the shampoo containing the product of the present invention is superior to that of Comparative Product 3 containing only cation-modified hydroxyethyl cellulose (Catinal HC-100), which is conventionally used as a conditioning agent, and has the same conditioning effect when used. As described above, after use, the firmness of the hair was obtained from the elasticity imparted by the film-forming property of the cation-modified alginic acid derivative of the present invention, which is not found in conventional conditioning agents. In addition, by using a cationic water-soluble polymer (Catinal HC-100, Merquat 550) and / or an amphoteric water-soluble polymer (Yukaformer SM) in combination, the performance of the cation-modified alginic acid derivative of the present invention can be obtained. It was confirmed that the conditioning effect was improved without loss.
(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, followed by cooling.

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.

Purified water was heated to 70 ° C., and other components were added and dissolved uniformly, followed by cooling.
Hair rinse (preparation)

１０−ｄ（比較品の調製）
本発明によるカチオン変性アルギン酸誘導体のリンスにおけるその効果を比較するため、例１で得たカチオン変性アルギン酸誘導体、すなわち表１中の試料番号６及び７を用いて表１５の比較品（Ｄ）に示した組成のリンスを調製した。表１５中の比較品（Ｄ）の成分（５）〜（１０）を８０℃に加熱し、攪拌して均一にした溶液に、予め成分（１２）に成分（２）を攪拌しながら加え溶解させた溶液を８０℃に加熱したものを攪拌しながら加えた後、冷却しながら成分（１１）を加えて均一に混合し、表１中の試料番号６及び７を含むリンスをそれぞれ比較品４及び５とした。
１０−ｅ（比較品の調製）
さらに他のカチオン性水溶性高分子と効果を比較する為、上記１０−ｄにおける例１で得たカチオン変性アルギン酸誘導体の代わりに、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００；東邦化学工業（株）社製）を用い、表１５の比較品（Ｄ）に示した組成のリンスを１０−ｄと同様に調製し、これを比較品６とした。
（評価）10-a
Behenic acid neutralized with citric acid as the neutralizing agent and the amidoamine compound shown in Table 15 (A) below using the cation-modified alginic acid derivatives of Sample Nos. 1-4 obtained in Examples 1 and 2 A rinse having a composition containing dimethylaminopropylamide citrate and further a higher alcohol (cetanol) was prepared. The components (5) to (10) of (A) in Table 15 were heated to 80 ° C. and stirred, and the component (1) was previously added to the component (12) with stirring and dissolved. A solution heated to 80 ° C. was added with stirring, and then component (11) was added while cooling and mixed uniformly. Thus, the rinses having the compositions shown in Table 15 (A) were prepared, and the rinses containing the cation-modified alginic acid derivatives of Sample Nos. 1 to 4 in Table 1 were used as the formulations 10 to 13 in this order.
10-b
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an ethylene oxide average addition mole number of 1.8 and a nitrogen content of 1.8% by mass The rinse of the composition shown to (B) of Table 15 containing HC-100; Toho Chemical Industries Co., Ltd.) was prepared. While stirring the components (1) and (3) in the component (12) in advance, the components (5) to (10) of (B) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution that was added and dissolved was heated to 80 ° C. and added with stirring, and then component (11) was added and mixed uniformly while cooling. The resulting rinse was designated as formulation 14 of the present invention.
10-c
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) as an amphoteric water-soluble polymer. A rinse having the composition shown in (C) of Table 15 including SM (manufactured by Mitsubishi Chemical Corporation) was prepared. While stirring the components (1) and (4) in the component (12) in advance, the components (5) to (10) of (C) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution dissolved and heated to 80 ° C. was added with stirring, and then component (11) was added and mixed uniformly while cooling, and the resulting rinse was designated as formulation 15 of the product of the present invention.

10-d (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on rinsing, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (D) shown in Table 15. A rinse of the same composition was prepared. Ingredients (5) to (10) of comparative product (D) in Table 15 were heated to 80 ° C. and stirred to make a uniform solution. The solution heated to 80 ° C. was added with stirring, and then the component (11) was added while cooling and mixed uniformly. The rinses containing the sample numbers 6 and 7 in Table 1 were compared with the comparative product 4 respectively. And 5.
10-e (Preparation of comparative product)
Furthermore, in order to compare the effect with other cationic water-soluble polymers, instead of the cation-modified alginic acid derivative obtained in Example 1 in 10-d above, ethylene oxide average added mole number 1.8, nitrogen content 1.8 Using 10% by mass of cation-modified hydroxyethyl cellulose (Catinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.), a rinse having the composition shown in Comparative Product (D) in Table 15 was prepared in the same manner as 10-d. Was designated as comparative product 6.
(Evaluation)

表１７の結果から、カチオン電荷量が０．１〜３．０ｍｅｑ／ｇにある本発明のカチオン変性アルギン酸誘導体を含み、さらにアミドアミン化合物、中和剤及び高級アルコール（セタノール）を含むリンスでは、組成物の毛髪へのコンディショニング効果が優れるとともに、弾力性の付与による毛髪のコシの強さが得られることが確認された。
またアミドアミン化合物、中和剤及び高級アルコールを含むリンスにおける本発明品の性能を、他のカチオン性ポリマーと比較すると、コンディショニング効果は使用時及び使用後で同等以上であり、かつ使用後には弾力性の付与によるによる毛髪のコシの強さが得られた。またさらに、カチオン性水溶性高分子及び／又は両性水溶性高分子を併用することにより、カチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例４〜６）
以下に、リンス、コンディショナー等のコンディショニング効果を必要とする毛髪処理用組成物への、本発明の好適な配合例を示す。

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、１，３−ブチレングリコール、アルキル（Ｃ１２、１４）オキシヒドロキシプロピルアルギニン塩酸塩、ヒドロキシプロピルトリモニウム加水分解ケラチン、色素を加え７５℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、７５℃に保つ（油相）。水相と油相を加えた後、イソプロパノールを加えホモミキサーで乳化後、撹拌しながら冷却した。

表１９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、ステアリ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、フェノキシエタノール、色素を加え８０℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、８０℃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。

表２０の精製水に、本発明品、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、加水分解シルクを加え７０℃に保つ（水相）。残りの他の成分を混合、加熱溶解し、７０℃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。
ヘアジェル
（調製）For each of the rinses prepared in the above-mentioned 10-a to 10-c, that is, the formulations 10 to 15 of the product of the present invention, the performance evaluation of the following items was performed by 10 testers.
The performance evaluation method uses the rinse of the composition shown in the standard product (E) of Table 15 that does not contain a cationic polymer as a component, and the rinse of the object to be evaluated, and the feeling of use after drying with a dryer. Based on the standard product (E),
-The presence or absence of dry hair condition effect (comb street, squeak, etc.)
・ The strength of the hair
Were compared with each other, digitized by the method of Table 16 below, and the values of 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 17. The standard product (E) was prepared by heating the components (5) to (10) in the standard product (E) in Table 15 to 80 ° C. and stirring them to make a uniform solution. 12) was added with stirring, and then component (11) was added while cooling to prepare a uniform mixture.
Comparative Example 2
For each of the rinses prepared in 10-d and 10-e described above, that is, comparative products 4, 5 and 6, performance evaluation was performed in the same manner as in Example 11, and the results are shown in Table 17.

From the results shown in Table 17, in the rinse containing the cation-modified alginic acid derivative of the present invention having a cation charge amount of 0.1 to 3.0 meq / g and further containing an amidoamine compound, a neutralizing agent and a higher alcohol (cetanol), the composition It was confirmed that the effect of conditioning the hair on the hair was excellent and the firmness of the hair was obtained by imparting elasticity.
In addition, the performance of the product of the present invention in rinsing containing an amidoamine compound, a neutralizing agent and a higher alcohol is compared with other cationic polymers, and the conditioning effect is equivalent or better after use and after use. The firmness of the hair due to the application of was obtained. Furthermore, it has been confirmed that the use of a cationic water-soluble polymer and / or an amphoteric water-soluble polymer improves the conditioning effect without impairing the performance of the cation-modified alginic acid derivative.
(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.

To the purified water shown in Table 18, the product of the present invention, stearyltrimethylammonium chloride, 1,3-butylene glycol, alkyl (C12, 14) oxyhydroxypropylarginine hydrochloride, hydroxypropyltrimonium hydrolyzed keratin, and dye are added to 75 ° C. Keep (water phase). The remaining other components are mixed, dissolved by heating and kept at 75 ° C. (oil phase). After adding an aqueous phase and an oil phase, isopropanol was added and emulsified with a homomixer, followed by cooling with stirring.

To the purified water shown in Table 19, the product of the present invention, hydroxypropyltrimonium chloride, dimethylaminopropylamide stearate, hydrolyzed wheat, L-glutamic acid, glycerin, phenoxyethanol, and pigment are added 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.

To the purified water of Table 20, the product of the present invention, dimethylaminopropylamide stearate, 50% lactic acid, glycerin, phenoxyethanol, sodium benzoate and hydrolyzed silk are added and kept 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.
Hair gel (preparation)

（評価）12-a
The effect of the product of the present invention on the coating-type hair cosmetic was confirmed by the following method. Using the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 3 obtained in Example 1, hair gels having the composition shown in Table 21 (A) were prepared. Add component (1) and components (5) to (9) in Table 21 to the stirring component (11), dissolve uniformly, then add component (10) and mix until clear did. Thus, hair gels having the composition shown in (A) of Table 21 were prepared, and hair gels containing the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 3 in Table 1 were respectively formulated with the formulations 16, 17 and 18 of the present invention. did.
12-b
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and further, as a cationic water-soluble polymer, cation-modified hydroxyethyl cellulose (Catinal) having an ethylene oxide average addition mole number of 1.8 and a nitrogen content of 1.8% by mass The hair gel of the composition shown to (B) of Table 21 containing HC-100; Toho Chemical Industry Co., Ltd. product) was prepared. Add the components (1), (3) and (5) to (9) shown in (B) of Table 21 to the stirring component (11) and uniformly dissolve, then add the component (10) Mix until clear. In this way, a hair gel having the composition shown in (B) of Table 21 was prepared and used as the formulation 19 of the present invention.
12-c
Using the cation-modified alginic acid derivative of Sample No. 1 obtained in Example 1, and N-methacryloyloxyethyl N, N-dimethylammonium-α-methylcarboxybetaine / alkyl methacrylate copolymer (Yukaformer) as an amphoteric water-soluble polymer. A hair gel having the composition shown in Table 21 (C) was prepared, including SM (manufactured by Mitsubishi Chemical Corporation). Add components (1), (4) and (5) to (9) shown in (C) of Table 21 to the stirring component (11), and after uniformly dissolving, add (10) to make it transparent Mix until. Thus, 12-d (preparation of comparative product) was prepared by preparing a hair gel having the composition shown in (C) of Table 21 as the formulation 20 of the present invention.
In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the hair gel, the cation-modified alginic acid derivative obtained in Example 1, ie, sample Nos. 6 and 7 in Table 1, was used as a comparative product (E) in Table 21. A hair gel having the composition described above was prepared. Components (2) and (5) to (9) in Table 21 were added to the stirring component (11), and after uniform dissolution, the component (10) was added and mixed until it became transparent. Thus, hair gels having the compositions shown in Table 21 (E) were prepared, and the hair gels containing the sample numbers 6 and 7 in Table 1 were designated as comparative products 7 and 8, respectively.
12-e (Preparation of comparative product)
In order to compare the effect with other cationic polymers, the average number of moles of ethylene oxide added was 1.8 instead of the cation-modified alginic acid derivative obtained in Example 1 used in 12-d above, and the nitrogen content was 1.8% by mass. The hair gel of the composition shown in the comparative product (E) of Table 21 containing the cation-modified hydroxyethyl cellulose (Katinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.) was prepared in the same manner as 12-d, and this was compared. Product 9.

(Evaluation)

For each of the hair gels prepared in the above-mentioned 12-a to 12-c, that is, the formulations 16, 17, 18, 19 and 20 of the present invention, performance evaluation of the following items was performed by 10 testers.
The performance evaluation method uses a hair gel having a composition shown in the standard product (D) of Table 21 that does not contain cationic water-soluble polymer or amphoteric water-soluble polymer as a component, and a hair gel to be evaluated. The feeling of use is based on the standard product (D).
・ Easy to apply,
-The feeling after use was compared, it digitized by the method shown in the following Table 22, and the value of the 10 testers who evaluated was totaled. The results are shown in Table 24. In addition, in the standard product, the components (5) to (9) in Table 21 (D) are added to the stirring component (11), and after uniform dissolution, the component (10) is added and mixed until it becomes transparent. Prepared.
Comparative Example 3
For each of the hair gels prepared in 12-d and 12-e described above and comparative products 7, 8 and 9, performance evaluation was performed in the same manner as in Example 13, and the results are shown in Table 24.

比較例４
先述の１２−ｄ及び１２−ｅで調製したヘアジェル、すなわち比較品７、８及び９について実施例１４と同様に性能評価を実施し、その結果を表２４中に示した。

表２４の結果から、塗布型の毛髪処理用組成物においても本発明のカチオン変性アルギン酸誘導体は造膜性を有することから、乾燥時に毛髪に対してセット効果を付与できるとともに、カチオン変性することで得られるコンディショニング効果により感触も良好であることが確認された。一方、カチオン電荷量が本発明に規定する０．１〜３．０ｍｅｑ／ｇの範囲外にある、試料番号６及び７では、塗布のしやすさや、使用後の感触において本発明のような評価は得られなかった。
また、従来のコンディショニング剤としてのカチオン性ポリマー（カチオン変性ヒドロキシエチルセルロース、カチナールＨＣ−１００）と比較すると、セット保持力に差が認められ、本発明品の有する造膜性によりセット効果が得られることが確認された。さらに、本発明のカチオン変性アルギン酸誘導体と、他のカチオン性水溶性高分子及び／又は両性水溶性高分子を併用することにより、本発明のカチオン変性アルギン酸誘導体のもつ性能を損なうこと無く、コンディショニング効果が向上することが確認された。
（配合例７〜１０）
以下に、ヘアジェル及びヘアジェル以外のセット効果及びコンディショニング効果を必要とするヘアミスト、ヘアムース等の塗布型の毛髪処理組成物への本発明の好適な配合例を示す。

本発明品とポリビニルピロリドン、グリセリン、ポリエチレングリコール、パラオキシ安息香酸メチルに一部の精製水を加え７０℃で加熱溶解した。他の成分を残部の精製水に溶解し、撹拌しながら添加した。

ヘアカラー
（調製）The set holding force was evaluated by the following method. A hair bundle having a length of 18 cm and a weight of 15 g is wetted with water, and the hair gel prepared in the above-mentioned 12-a to 12-c, that is, the formulations 16, 17, 18, 19, and 20 of the present invention are applied, and the rod ( It was wound around an outer diameter of 2 cm), and in that state, it was dried with a dryer (80 ° C.) and curled. After drying, the curled hair bundle was removed from the rod. The hair bundle was suspended in a constant temperature and humidity (20 ° C., 40% RH) atmosphere for 30 minutes, and the curl elongation was observed. Based on the degree of curl elongation, the set holding force was evaluated according to the evaluation criteria shown in Table 23 below. The results are shown in Table 24.
The evaluation scale is as follows. The length immediately after removing the rod of the hair bundle wound around the rod and dried with a drier (80 ° C.) in the same manner as described above except that the hair gel was not applied was defined as a holding power of 100%. Further, the rod was removed and left in an atmosphere of constant temperature and humidity (20 ° C., 40% RH) for 24 hours, and the length of the hair bundle in this state was set to 0% holding force.

Comparative Example 4
The hair gel prepared in the above 12-d and 12-e, that is, comparative products 7, 8 and 9, were subjected to performance evaluation in the same manner as in Example 14, and the results are shown in Table 24.

From the results shown in Table 24, the cation-modified alginic acid derivative of the present invention also has a film-forming property even in a coating-type hair treatment composition. It was confirmed that the feel was good due to the resulting conditioning effect. On the other hand, in sample numbers 6 and 7, in which the cation charge amount is outside the range of 0.1 to 3.0 meq / g specified in the present invention, the evaluation as in the present invention in terms of ease of application and feel after use. Was not obtained.
Moreover, when compared with a cationic polymer (cation-modified hydroxyethyl cellulose, kachinal HC-100) as a conventional conditioning agent, there is a difference in the set holding power, and the setting effect is obtained by the film forming property of the product of the present invention. Was confirmed. Furthermore, by using the cation-modified alginic acid derivative of the present invention in combination with another cationic water-soluble polymer and / or an amphoteric water-soluble polymer, the conditioning effect can be obtained without impairing the performance of the cation-modified alginic acid derivative of the present invention. Has been confirmed to improve.
(Formulation examples 7 to 10)
Below, the suitable compounding example of this invention to application type hair treatment compositions, such as hair mist and hair mousse which require the setting effect and conditioning effect other than hair gel and a hair gel, is shown.

A part of purified water was added to the product of the present invention and polyvinylpyrrolidone, glycerin, polyethylene glycol, and methyl paraoxybenzoate, and the mixture was heated and dissolved at 70 ° C. The other ingredients were dissolved in the remaining purified water and added with stirring.

Hair color (preparation)

（評価）15-a
Using the cation-modified alginic acid derivatives of Sample Nos. 1 and 4 obtained in Examples 1 and 2, two-part oxidative hair dyes shown in (A) of Table 29 below were prepared. Two-component oxidative hair dyes containing 1 and 4 cation-modified alginic acid derivatives were designated as formulations 21 and 22 of the present invention. At the time of use, the first agent and the second agent of this two-component oxidative hair dye were mixed at a weight ratio of 1: 1 and applied to the hair.
15-b (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative according to the present invention on the hair color with other cationic polymers, the average number of moles of ethylene oxide added is 1 instead of the cation-modified alginic acid derivative of the present invention used in 15-a above. 2.8, cation-modified hydroxyethyl cellulose having a nitrogen content of 1.8% by mass (Katinal HC-100; manufactured by Toho Chemical Industry Co., Ltd.), shown in the comparative product (C) in Table 29 above. An oxidative hair dye was prepared. In this way, a two-part oxidative hair dye containing cation-modified hydroxyethyl cellulose was used as Comparative Product 10. At the time of use, the first agent and the second agent of this two-component oxidative hair dye were mixed at a weight ratio of 1: 1 and applied to the hair.

(Evaluation)

表３１の結果より、本発明のカチオン変性アルギン酸誘導体を染毛剤に配合した場合、損傷毛髪に対するコンディショニング効果により、すすぎ時におけるすべり性が向上し、良好な指通り感が得られ、乾燥後の仕上がり感もしっとり感が得られ改善された。さらに本発明品の有する損傷毛髪に対する弾力性の付与から毛髪のコシの改善が認められた。よって、染毛剤等の組成物として優れていることが確認された。
さらに、他のカチオン性ポリマーを含む比較品１０と比べて、本発明品の処方２１及び２２はともに、乾燥後の感触が向上してわり、損傷毛髪においても、本発明のカチオン変性アルギン酸誘導体が優れていることが確認された。
（配合例１１、１２）
以下に本発明のカチオン変性アルギン酸誘導体の損傷毛髪に対するコンディショニング効果及び弾力性付与効果を利用した、好適な配合例を示す。

ボディ用洗浄剤
（調製）With respect to each of the two-part oxidative hair dyes prepared in the above 15-a, that is, the formulations 21 and 22 of the present invention, the performance evaluation of the following items was performed by 10 testers. The performance evaluation method uses a two-component oxidative hair dye having a composition shown in a standard product (B) in Table 29 that does not contain a cationic polymer as a component, and an oxidative hair dye to be evaluated. An equal volume mixture of the first and second agents was applied to the hair, allowed to stand at room temperature for 30 minutes, rinsed with running water at 40 ° C. for 3 minutes, and dried with a drier. The sliding property at the time of rinsing and the feeling after drying with a dryer, based on the standard product (B),
・ Slipperiness when rinsing ・ Feel after drying (moist feeling, elasticity (hair stiffness))
Were compared with each other, digitized by the method shown in Table 30 below, and the values of the ten testers who performed the evaluation were totaled. The evaluation results are shown in Table 31. The standard product (B) was prepared according to 15-a, and the first agent and the second agent were mixed at a weight ratio of 1: 1 and applied to the hair.
Comparative Example 5
Performance evaluation was carried out in the same manner as in Example 16 for the two-component oxidative hair dye of Comparative Product 10 prepared in 15-b above, and the results are shown in Table 31.

From the results of Table 31, when the cation-modified alginic acid derivative of the present invention is blended in a hair dye, the conditioning effect on damaged hair improves slipperiness at the time of rinsing, and a good feeling of fingering is obtained. The feeling of finish is also moist and improved. Furthermore, the improvement of the stiffness of hair was recognized from the elasticity imparted to the damaged hair of the product of the present invention. Therefore, it was confirmed that it is excellent as a composition such as a hair dye.
Furthermore, compared with the comparative product 10 containing other cationic polymers, both the formulations 21 and 22 of the present invention have improved feeling after drying, and the cation-modified alginic acid derivative of the present invention is also applied to damaged hair. It was confirmed to be excellent.
(Formulation examples 11 and 12)
Below, the suitable compounding example using the conditioning effect with respect to the damaged hair of the cation modified | denatured alginic acid derivative of this invention and the elasticity provision effect is shown.

Body cleaner (preparation)

１７−ｂ（比較品の調製）
本発明で用いるカチオン変性アルギン酸誘導体の、ボディ用洗浄剤におけるその効果を比較するため、未変性のアルギン酸誘導体であるアルギン酸ナトリウム（ダックアルギンＮＳＰＨ；（株）紀文フードケミファ社製）について表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製した。表３４中の（Ｃ）の成分（１１）を６０℃に加熱し、成分（２）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、更に３０〜４０℃で成分（８）〜（１０）を同様に撹拌しながら加え、均一に混合した。こうして表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製し、これを比較品１１とした。
１７−ｃ（比較品の調製）
同様に、本発明で用いるカチオン変性アルギン酸誘導体の、ボディ洗浄剤における効果を比較するため、エチレンオキサイド平均付加モル数１．８、窒素含有率１．８質量％のカチオン変性ヒドロキシエチルセルロース（カチナールＨＣ−１００：東邦化学工業（株）社製）について表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製した。表３４中の（Ｃ）の成分（１１）を６０℃に加熱し、成分（２）を攪拌しながらゆっくり加え溶解させ、溶解を確認した後、５０〜６０℃で成分（３）〜（７）を撹拌しながら加えて均一とし、更に３０〜４０℃で成分（８）〜（１０）を同様に撹拌しながら加え、均一に混合した。こうして表３４の（Ｃ）に示した組成のボディ用洗浄剤を調製し、これを比較品１２とした。
（評価）17-a
Using the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 4 obtained in Examples 1 and 2, body detergents (body soaps) having the compositions shown in Table 34 (A) were prepared. The component (11) of (A) in Table 34 was heated to 60 ° C., and the component (1) was added and dissolved while stirring. After confirming the dissolution, the components (3) to (7) at 50 to 60 ° C. Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, body cleaners having the compositions shown in (A) of Table 34 were prepared, and the body cleaners containing the cation-modified alginic acid derivatives of Sample Nos. 1, 2 and 4 in Table 1 were sequentially prepared. Formulations 23, 24 and 25 were used.

17-b (Preparation of comparative product)
In order to compare the effect of the cation-modified alginic acid derivative used in the present invention on a body cleaning agent, sodium alginate (Duck Algin NSPH; manufactured by Kibun Food Chemifa Co., Ltd.), which is an unmodified alginic acid derivative, is shown in Table 34. A body cleaning agent having the composition shown in C) was prepared. The component (11) of (C) in Table 34 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, components (3) to (7 ) Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, a body cleaner having the composition shown in (C) of Table 34 was prepared, and this was designated as Comparative Product 11.
17-c (Preparation of comparative product)
Similarly, in order to compare the effect of the cation-modified alginic acid derivative used in the present invention on the body cleaning agent, cation-modified hydroxyethyl cellulose (Catinal HC- 100: manufactured by Toho Chemical Co., Ltd.), a body cleaning agent having the composition shown in Table 34 (C) was prepared. The component (11) of (C) in Table 34 was heated to 60 ° C., and the component (2) was slowly added and dissolved while stirring. After confirming the dissolution, components (3) to (7 ) Was added with stirring to make it uniform, and components (8) to (10) were similarly added at 30 to 40 ° C. with stirring and mixed uniformly. Thus, a body cleaner having the composition shown in (C) of Table 34 was prepared, and this was designated as Comparative Product 12.
(Evaluation)

表３７の結果から、本発明のカチオン変性アルギン酸誘導体は、ボディ用洗浄剤に用いた場合、ボディ用洗浄剤の泡立ち、泡質及び使用感が改善されるとともに、使用後には、つっぱり感を解消し、しっとり感を与えることが確認された。
また、未変性のアルギン酸誘導体（アルギン酸ナトリウム）を含む比較品１１と比較すると、カチオン変性したことにより、皮膚への吸着が増し、使用時及び使用後の感触が改善されることが確認された。さらに、従来のコンディション剤としてのカチオン変性ヒドロキシエチルセルロース（比較品１２）と比較すると、造膜性の差から泡立ち、泡質が改善されると共にべたつき感、かさつき感、つっぱり感を解消し、しっとり感を得ることが確認された。

（配合例１３〜１７）
以下に、本発明のカチオン変性アルギン酸誘導体の造膜性を有することによる泡質の感触改善及び、コンディショニング効果による感触改善を利用した、ボディ用洗浄剤、洗顔料等の皮膚化粧料組成物の配合例を示す。

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。

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。

常法に基づき、洗顔料を製造する。

表４１の精製水に、本発明品、グリセリン、ソルビトール、アルギニン、香料を加え溶解し７０℃に保つ（水相）。真空乳化釜にヤシ油脂肪酸グルタミン酸カリウム２５％液、ヤシ油脂肪酸タウリンナトリウム３０％液、モノオレイン酸グリセリル、セテアレス−６０ミリスチルグリコール、エデト酸２ナトリウム、フェノキシエタノールを順次添加混合し、７０℃まで加熱し溶解する。溶解確認後、ヤシ油脂肪酸アミドプロピルベタイン３０％液、７０℃に保持した水相、ジステアリン酸エチレングリコールを順次添加し、均一に溶解する。溶解後、３５℃まで冷却し、精製水、１０％クエン酸水溶液で水分、ｐＨを調整する。

常法に基づき、洗顔料を製造する。
（配合例１８〜２１）
以下に、本発明のカチオン変性アルギン酸誘導体の皮膚化粧料組成物に対する感触改善を利用する他の適用例としてアフターシェーブローション等の配合例を示す。

表４４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。

常法に基づき、ファンデーションを製造する。

常法に基づき、入浴剤を製造する。
本発明のカチオン変性アルギン酸誘導体は、毛髪処理用組成物や皮膚化粧料組成物等の化粧料組成物に配合した場合、造膜性が良好なことから均一な膜が形成され、泡立ち、泡質などの泡の感触改善が得られる。また、シャンプー・リンスなど洗い流しの毛髪処理用組成物に配合した場合、使用時、使用後には毛髪に対し、従来のコンディショニング剤として用いられるカチオン性ポリマーと同等以上のコンディショニング効果を与えつつ、乾燥後には造膜性を有することで得られる弾力性の付与により、毛髪のコシの強さが得られ、ヘアジェル等の塗布型の毛髪処理用組成物に配合した場合には、従来のコンディショニング剤として用いられるカチオン性ポリマーと同等以上のコンディショニング効果と、造膜性を有することで得られるセット効果を与える。さらに、本発明のカチオン変性アルギン酸誘導体をボディ用洗浄剤等の皮膚化粧料組成物に配合した場合、べたつき感、つっぱり感を解消し、しっとり感を与える。従って、従来品よりもより使い心地の優れた化粧料組成物を提供することが出来る。The performance evaluation of the following items was carried out by 10 testers for each of the body cleansing agents 23, 24 and 25 of the product of the present invention obtained in the aforementioned 17-a.
The performance evaluation method uses a body cleaning agent having a composition shown in the standard product (B) of Table 34 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
・ The amount and quality of foam during use
・ Usage feeling during use (ease of rinsing, feeling of squeezing and slimming after rinsing),
・ 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 35 and 36 below, and the values of the 10 testers who performed the evaluation were totaled. The evaluation results are shown in Table 37. In addition, after heating the component (11) of the standard product (B) in Table 34 to 60 ° C., the standard product was added to the components (3) to (7) with stirring at 50 to 60 ° C. to make it uniform, and further 30 Add components (8) to (10) in the same manner at -40 ° C. with stirring, and mix evenly to prepare a body cleaner having the composition shown in Table 34 (B). did.
Comparative Example 6
The performance evaluation similar to Example 18 was performed about the cleaning agent for bodies of the comparative products 11 and 12 obtained by 17-b and 17-c mentioned above. These results are shown in Table 37.

From the results shown in Table 37, when the cation-modified alginic acid derivative of the present invention is used for a body cleaning agent, the foaming, foam quality and feeling of use of the body cleaning agent are improved, and after use, the feeling of tension is eliminated. And it was confirmed to give a moist feeling.
Moreover, compared with the comparative product 11 containing an unmodified alginic acid derivative (sodium alginate), it was confirmed that adsorption to the skin increased due to cation modification, and the feeling during and after use was improved. Furthermore, compared with the conventional cation-modified hydroxyethyl cellulose (Comparative product 12) as a conditioning agent, foaming and foam quality are improved due to the difference in film-forming properties, and stickiness, bulkiness, and feeling of stickiness are eliminated. It was confirmed that a feeling was obtained.

(Formulation examples 13-17)
The following is a formulation of a skin cosmetic composition such as a body cleanser and a facial cleanser using the improvement in feel of foam due to the film-forming property of the cation-modified alginic acid derivative of the present invention and the improvement in feel due to the conditioning effect. An example is shown.

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

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

A face wash is manufactured based on a conventional method.

The product of the present invention, glycerin, sorbitol, arginine, and fragrance are added to the purified water of Table 41 and dissolved and maintained at 70 ° C. (aqueous phase). In a vacuum emulsification pot, coconut oil fatty acid potassium glutamate 25% solution, coconut oil fatty acid taurine sodium 30% solution, glyceryl monooleate, ceteares-60 myristyl glycol, disodium edetate, and phenoxyethanol are sequentially added and heated to 70 ° C. Dissolve. After dissolution is confirmed, a 30% solution of coconut oil fatty acid amidopropyl betaine, an aqueous phase maintained at 70 ° C., and ethylene glycol distearate are sequentially added and dissolved uniformly. After dissolution, the solution is cooled to 35 ° C., and water and pH are adjusted with purified water and a 10% aqueous citric acid solution.

A face wash is manufactured based on a conventional method.
(Formulation examples 18-21)
Hereinafter, formulation examples such as after shave lotion will be shown as other application examples utilizing the improvement in feel of the cation-modified alginic acid derivative of the present invention to the skin cosmetic composition.

The product of the present invention was dissolved in purified water shown in Table 44, 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.

A foundation is manufactured based on a conventional method.

A bath preparation is produced based on a conventional method.
When the cation-modified alginic acid derivative of the present invention is blended in a cosmetic composition such as a hair treatment composition or a skin cosmetic composition, a uniform film is formed due to good film-forming properties, and foaming, foam quality It is possible to improve the feel of bubbles. In addition, when blended into a rinse-off hair treatment composition such as shampoo and rinse, after use, after use, it gives a conditioning effect equivalent to or better than the cationic polymer used as a conventional conditioning agent for the hair after use. Gives elasticity of hair obtained by having a film-forming property, and gives firmness to the hair. When blended in an application-type hair treatment composition such as a hair gel, it is used as a conventional conditioning agent. A conditioning effect equal to or better than that of the cationic polymer to be obtained and a set effect obtained by having a film-forming property. Furthermore, when the cation-modified alginic acid derivative of the present invention is blended in a skin cosmetic composition such as a body cleanser, it eliminates the sticky and sticky feeling and gives a moist feeling. Therefore, it is possible to provide a cosmetic composition that is more comfortable to use than conventional products.

（式中Ｒ_１Ｒ_２は各々炭素数１〜３のアルキル基、Ｒ_３は炭素数１〜２４のアル[0006]
DISCLOSURE OF THE INVENTION
In such a situation, the present inventors can improve the conditioning effect at the time of rinsing when blended with the hair treatment composition of conventional cationic polymers and the finishing feeling after drying, and can impart a set effect to the hair. Furthermore, intensive studies on compounds that eliminate the feeling of firmness and bulkiness when added to skin cosmetic compositions, improve the feeling of stickiness and sliminess, and improve the foam feel such as foaming and foam quality. did. As a result, L-guluronic acid and D-mannuronic acid uronic acid units are composed of 1,4-glycosidic bonds, which are natural polysaccharides contained as calcium salts in the cell walls of brown algae (scientific name: Phaeophyceae) such as kombu and seaweed in seaweed. A cation-modified alginic acid derivative in which a specific amount of a quaternary nitrogen-containing group is introduced into a combined polymer alginate derivative and the cationic charge amount is adjusted to a specific range has excellent properties as a conditioning agent in a cosmetic composition. In particular, in the composition for treating hair, it has been found that since the film-forming property is good, it is possible to impart a set effect to the hair at the time of drying, and further, the foam feel can be improved by forming a uniform film. It came.
Therefore, the first aspect of the present invention is used for cosmetic compositions such as various hair treatment compositions such as shampoos, rinses, set agents, hair styling agents, hair color, and other cosmetic compositions, and other makeup agents. A part of the hydroxyl group contained in the alginic acid derivative which is a natural polysaccharide contained in seaweed and is a polymer in which uronic acid units of L-guluronic acid and D-mannuronic acid are linked by 1,4 glycoside bonds, A cation-modified polysaccharide substituted with a quaternary nitrogen-containing group represented by the 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 cation-modified alginic acid derivative.

(Wherein R ₁ R ₂ are each an alkyl group having 1 to ₃ carbon atoms, and R ₃ is an alkyl group having 1 to 24 carbon atoms.

（式中Ｒ_１、Ｒ_２は各々炭素数１〜３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。ｎは、ｎ＝０又はｎ＝１〜３０を示し、ｎ＝１〜３０のとき、（Ｒ_４Ｏ）_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。）
本発明の第七の態様は、前記ウロン酸ユニットが１，４グリコシド結合で結合した重合体であるアルギン酸誘導体が、海藻中の褐藻類（学名Ｐｈａｅｏｐｈｙｃｅａｅ）に含まれるＬ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成される天然多糖類の誘導体である第六の態様記載の化粧料組成物に関する。
本発明の第八の態様は、前記カチオン変性アルギン酸誘導体のカチオン変性が、グリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩を用いてなされたものである第六又は第七の態様記載の化粧料組成物に関する。
本発明の第九の態様は、前記カチオン変性アルギン酸誘導体のカチオン変性が、アルギン酸誘導体に含まれる水酸基の一部に、炭素数２〜４のアルキレンオキサイドを付加し、続いてカチオン化剤としてグリシジルトリアルキルアンモニウム塩または、３−ハロゲノ−２−ヒドロキシプロピルトリアルキルアンモニウム塩を用いてなされたものである第六又は第七の態様記載の化粧料組成物に関する。
本発明の第十の態様は、前記カチオン変性アルギン酸誘導体がナトリウム塩、カリウム塩、カルシウム塩、マグネシウム塩等のアルギン酸塩である第六ないし第九の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十一の態様は、前記カチオン変性アルギン酸誘導体の含有量が組成物全体を１００質量％として、０．０５〜５質量％である第六ないし第十の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十二の態様は、さらに、他のカチオン性水溶性高分子及び／又は両性水溶性高分子を、組成物全体を１００質量％として、５質量％以下含有することを特徴とする第六ないし第十一の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十三の態様は、さらに、アミドアミン化合物と有機酸及び／又は無機酸等の中和剤とさらに、高級脂肪酸及び／又は高級アルコールを含むことを特徴とする第六ないし第十二の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十四の態様は、さらに、シリコーン及び／又はシリコーン誘導体を含むことを特徴とする第六ないし第十三の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
本発明の第十五の態様は、前記化粧料組成物が毛髪処理用組成物であることを特徴とする第六ないし第十四の態様のうちいずれか一の態様に記載の化粧料組成物に関する。
【発明を実施するための最良の形態】
本発明で用いられるアルギン酸誘導体は、コンブやワカメなどの褐藻類（学名Ｐｈａｅｏｐｈｙｃｅａｅ）の細胞壁にカルシウム塩等として含まれ、Ｌ−グルロン酸とＤ−マンヌロン酸の２種類のウロン酸から構成される直鎖状多糖で、Ｌ−グルロン酸同士の結合からなるブロックと、Ｄ−マンヌロン酸同士の結合からなるブロックと、Ｌ−グルロン酸とＤ−マンヌロン酸の結合からなるブロックの３種類のブロックが共存するポリウロン酸である。また、ウロン酸ユニットが有するカルボキシル基はイオン交換性をもち、そのため海藻中では海水中に含まれる様々な金属イオンと塩を形成し、水に不溶性のゼリー状態になっているが、抽出・精製する工程で、純アルギン酸及び、目的に応じた各種の塩或いはエステルへと変換される。さらに目的に応じ、酵素などの生物学的処理及び、酸、アルカリによる加水分解等の化学的処理により解重合し、低分子化されることもある。よって、本明細書で用いられる「アルギン酸誘導体」とは、純アルギン酸及び純アルギン酸から得られる各種のアルギン酸塩、アルギン酸エステル、さらに低分子化されたこれらの誘導体の意味である。これらのアルギン酸誘導体は、商品名「ダックアルギンＮＳＰＨ」、「ダックアルギンＮＳＰＬ」「ダックアルギンＮＳＰＬＬ」「ダックアッシド」（（株）紀文フードケミファ社製）として、また「キミロイド」（君津化学工業（株）社製）として、さらに、褐藻類コンブ目に属する海藻でラミナリアディギタータより得られる「ＰＨＹＣＯ ＡＮＴＩ−ＰＯＬＬＵ」、「ＰＨＹＣＯ ＡＮＴＩ−ＩＮＦＬＡ」（コディフ社製）として容易に入手可能である。
本発明のカチオン変性アルギン酸誘導体は、アルギン酸誘導体をカチオン変性することによる吸着性向上によって、コンディショニング効果が得られる。また、造膜性を有することにより塗布型の化粧料組成物へ配合したした場合、強力なセ[0007]
Represents a kill group, and X ⁻ represents an anion. n represents n = 0 or n = 1 to 30, and when n = 1 to 30, (R ₄ O) _n is a polymer residue of alkylene oxide having 2 to 4 carbon atoms, The polyalkylene glycol chain which consists of alkylene oxide and / or the polyalkylene glycol chain which consists of 2 or more types of alkylene oxide is shown. However, the case where n = 0, R ₁ , R ₂ and R _{3 all} represent a methyl group and X represents a chlorine ion is excluded. )
According to a second aspect of the present invention, the alginic acid derivative, which is a polymer in which the uronic acid units are linked by 1,4 glycosidic bonds, is L-guluronic acid and D-mannuron contained in brown algae (scientific name Phaeophyceae) in seaweed. The cation-modified alginic acid derivative according to the first aspect, which is a derivative of a natural polysaccharide composed of two types of uronic acids.
In a third aspect of the present invention, the cation modification of the cation-modified alginic acid derivative is performed by glycidyltrialkylammonium salt (excluding glycidyltrimethylammonium chloride) or 3-halogeno-2-hydroxypropyltrialkylammonium salt ( However, it relates to the cation-modified alginic acid derivative according to the first or second embodiment, which is made using N- (3-chloro-2-hydroxypropyl) trimethylammonium salt.
According to a fourth aspect of the present invention, the cation modification of the cation-modified alginic acid derivative is performed by adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, and subsequently glycidyl trimethyl as a cationizing agent. The present invention relates to the cation-modified alginic acid derivative according to the first or second aspect, which is made using an alkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt.
A fifth aspect of the present invention is the cation-modified alginic acid according to any one of the first to fourth aspects, wherein the cation-modified alginic acid derivative is an alginate such as sodium salt, potassium salt, calcium salt, magnesium salt and the like. Relates to derivatives.
In a sixth aspect of the present invention, a part of the hydroxyl group contained in the alginic acid derivative, which is a polymer in which uronic acid units are linked by 1,4 glycosidic bonds, contains a quaternary nitrogen represented by the following chemical formula (1). Cosmetic composition containing a cation-modified alginic acid derivative which is a cation-modified polysaccharide substituted with a group and has a cation charge amount derived from the quaternary nitrogen-containing group of 0.1 to 3.0 meq / g Also related.

(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 a polyalkylene glycol chain composed of a single alkylene oxide and (Or a polyalkylene glycol chain composed of two or more alkylene oxides)
In a seventh aspect of the present invention, the alginic acid derivative, which is a polymer in which the uronic acid units are linked by 1,4 glycosidic bonds, includes L-guluronic acid and D-mannuron contained in brown algae (scientific name: Phaeophyceae) in seaweeds. The cosmetic composition according to the sixth aspect, which is a derivative of a natural polysaccharide composed of two types of uronic acids.
In an eighth aspect of the present invention, the cation-modified alginic acid derivative is modified by cation modification using a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. The present invention relates to a cosmetic composition according to the seventh aspect.
According to a ninth aspect of the present invention, in the cation modification of the cation-modified alginic acid derivative, an alkylene oxide having 2 to 4 carbon atoms is added to a part of the hydroxyl group contained in the alginic acid derivative, and subsequently glycidyl trimethyl as a cationizing agent. The present invention relates to the cosmetic composition according to the sixth or seventh aspect, which is made using an alkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt.
A tenth aspect of the present invention is the cosmetic composition according to any one of the sixth to ninth aspects, wherein the cation-modified alginic acid derivative is an alginate such as a sodium salt, a potassium salt, a calcium salt, or a magnesium salt. The present invention relates to a material composition.
An eleventh aspect of the present invention is the process according to any one of the sixth to tenth aspects, wherein the content of the cation-modified alginic acid derivative is 0.05 to 5% by mass based on 100% by mass of the entire composition. The cosmetic composition according to the aspect.
The twelfth aspect of the present invention is characterized by further containing 5% by mass or less of another cationic water-soluble polymer and / or an amphoteric water-soluble polymer based on 100% by mass of the entire composition. The cosmetic composition according to any one of the sixth to eleventh aspects.
A thirteenth aspect of the present invention further includes an amidoamine compound, a neutralizing agent such as an organic acid and / or an inorganic acid, and further a higher fatty acid and / or a higher alcohol. The cosmetic composition according to any one of the embodiments.
A fourteenth aspect of the present invention relates to the cosmetic composition according to any one of the sixth to thirteenth aspects, further comprising silicone and / or a silicone derivative.
A fifteenth aspect of the present invention is the cosmetic composition according to any one of the sixth to fourteenth aspects, wherein the cosmetic composition is a hair treatment composition. About.
BEST MODE FOR CARRYING OUT THE INVENTION
The alginic acid derivative used in the present invention is contained as a calcium salt or the like in the cell wall of brown algae (scientific name: Phaeophyceae) such as kombu and wakame, and is composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid. Three types of block polysaccharides: a block composed of a bond between L-guluronic acids, a block composed of a bond between D-mannuronic acids, and a block composed of a bond between L-guluronic acid and D-mannuronic acid Polyuronic acid. In addition, the carboxyl group of the uronic acid unit has ion exchange properties, so it forms salts with various metal ions contained in seawater in seaweed and is in a water-insoluble jelly state. In this step, it is converted into pure alginic acid and various salts or esters according to the purpose. Further, depending on the purpose, the polymer may be depolymerized and reduced in molecular weight by a biological treatment such as an enzyme and a chemical treatment such as hydrolysis with acid or alkali. Therefore, the “alginate derivative” used in the present specification means pure alginic acid, various alginates obtained from pure alginic acid, alginic acid esters, and these derivatives having a reduced molecular weight. These alginic acid derivatives are trade names “Duck Algin NSPH”, “Duck Algin NSPL”, “Duck Algin NSPL”, “Duck Assid” (manufactured by Kibun Food Chemifa Co., Ltd.), and “Kimiroid” (Kimitsu Chemical Co., Ltd.). Furthermore, it is easily available as “PHYCO ANTI-POLLU” and “PHYCO ANTI-INFLA” (manufactured by Kodif), which are seaweeds belonging to the order of brown algae and obtained from Laminaria diguita.
The cation-modified alginic acid derivative of the present invention can obtain a conditioning effect by improving the adsorptivity by cation-modifying the alginic acid derivative. In addition, when it is formulated into a coating-type cosmetic composition due to its film-forming properties, it has a strong security.

Claims (10)

Cation-modified polysaccharide in which a part of the hydroxyl group contained in the alginic acid derivative which is a polymer in which uronic acid units are bonded by 1,4 glycosidic bonds is substituted with a quaternary nitrogen-containing group represented by the following chemical formula (1) And a cation-modified alginic acid derivative having a cation charge amount derived from the quaternary 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 a polyalkylene glycol chain composed of a single alkylene oxide and (Or a polyalkylene glycol chain composed of two or more alkylene oxides) The alginic acid derivative, which is a polymer in which the uronic acid units are linked by 1,4 glycosidic bonds, is composed of two types of uronic acids, L-guluronic acid and D-mannuronic acid, contained in brown algae (scientific name: Phaeophyceae) in seaweeds. The cation-modified alginic acid derivative according to claim 1, which is a derivative of a natural polysaccharide. 3. The cation-modified alginic acid derivative according to claim 1, wherein the cation-modified alginic acid derivative is cation-modified using a glycidyltrialkylammonium salt or a 3-halogeno-2-hydroxypropyltrialkylammonium salt. The cation modification of the cation-modified alginic acid derivative is carried out by adding an alkylene oxide having 2 to 4 carbon atoms to a part of the hydroxyl group contained in the alginic acid derivative, followed by glycidyl trialkylammonium salt or 3-halogeno- The cation-modified alginic acid derivative according to claim 1, which is formed using a 2-hydroxypropyltrialkylammonium salt. The cation-modified alginic acid derivative according to claim 1, wherein the cation-modified alginic acid derivative is an alginate such as sodium salt, potassium salt, calcium salt, magnesium salt. A cosmetic composition containing the cation-modified alginic acid derivative according to claim 1. The cosmetic composition according to claim 6, wherein the content of the cation-modified alginic acid derivative according to any one of claims 1 to 5 is 0.05 to 5% by mass based on 100% by mass of the entire composition. The cosmetic composition according to claim 6 or 7, 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. Cosmetic composition. A cosmetic composition comprising the cosmetic composition according to any one of claims 6 to 8, 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. A cosmetic composition according to claim 6, wherein the cosmetic composition is a hair treatment composition.