JP6715592B2 - Cosmetics containing low molecular weight cationized hyaluronic acid - Google Patents

Description

The present invention relates to cosmetics containing low molecular weight cationized hyaluronic acid and/or salts thereof.

Conventionally, hyaluronic acid, which is widely distributed in various tissues in the living body including humans, has excellent safety and has a high moisturizing effect, has been blended as a component of various skin cosmetics and hair cosmetics. (For example, Patent Documents 1 to 3).
Hyaluronic acid is a polysaccharide having at least one repeating constitutional unit composed of a disaccharide of glucuronic acid and N-acetylglucosamine, and has an anionic carboxyl group in its structure. Therefore, when hyaluronic acid is applied to the surface of skin or hair which is normally negatively charged, there is a problem that hyaluronic acid is difficult to be adsorbed to the skin due to repulsion of electric charge.
In order to solve such problems, cationized hyaluronic acid having a quaternary ammonium group-containing group introduced therein has been proposed in order to enhance the adsorptivity to living tissues such as skin (Patent Document 4).

JP 54-52733 A JP-A-61-167610 Japanese Patent Laid-Open No. 1-28121 International Publication No. 2008/133267 Pamphlet

The cationized hyaluronic acid of the previously proposed Patent Document 4 has been shown to have an increased amount of adsorbed hair and adsorbed on the skin, but has poor permeability to the inside of hair and skin, and is also washed. There is a problem that desorption of hyaluronic acid is likely to occur.
In addition, there is a problem that the compatibility with various components such as a solvent used in cosmetics is low and the formulation is limited.

The inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, low molecular weight cationized hyaluronic acid and/or a salt thereof has a high adsorptivity to living tissues as well as a high permeability to the inside of tissues. In addition to having the above-mentioned properties, the compound has high compatibility with various cosmetic ingredients such as solvents, and has been found to be useful as a cosmetic ingredient, and has completed the present invention.

That is, the present invention provides a low molecular weight cationized hyaluronic acid having a molecular weight of 2000 to 15,000 in which a part of hydroxy groups is substituted with a quaternary nitrogen-containing group represented by the following general formula <1> and/or The present invention relates to cosmetics containing the salt.
(In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to ₃ carbon atoms, R ₃ represents an alkyl group or an alkenyl group having 1 to 24 carbon atoms, and X ⁻ is a monovalent group. Represents an anion.)

The low molecular weight cationized hyaluronic acid and/or its salt preferably has a cationization degree of 0.30 to 1.00.
The low molecular weight cationized hyaluronic acid and/or its salt is preferably contained in 0.001 to 10% by mass based on the total mass of the cosmetic.

The cosmetics of the present invention are suitable for cosmetics for skin, hair, and nails.

The low molecular weight cationized hyaluronic acid used in the cosmetic of the present invention shows high adsorbability to these living tissues even after being applied to the living tissues such as skin and hair and after being washed. Further, the low molecular weight cationized hyaluronic acid has excellent permeability into the hair and the skin. Therefore, by blending the low-molecular-weight cationized hyaluronic acid, the cosmetic of the present invention can maintain a high moisturizing effect derived from hyaluronic acid and also realize a moisturizing effect inside the living tissue.
Further, the low molecular weight cationized hyaluronic acid shows excellent compatibility with various cosmetic ingredients such as solvents, and therefore, it can be applied to various formulation, and therefore can be applied to various dosage forms. Since it can be applied, it can be made into various cosmetic forms for hair, skin and nails and can exhibit its high moisturizing effect.

FIG. 1 is a fluorescence image showing the adsorptivity of hyaluronic acids to hair evaluated in Example 1, (a) purified water, (b) high molecular weight sodium hyaluronate (1% by mass aqueous solution), (c) low. Molecular weight hyaluronic acid (1% by weight aqueous solution), (d) low molecular weight sodium hyaluronate (1% by weight aqueous solution), (e) high molecular weight cationized hyaluronic acid (1% by weight aqueous solution), (f) low molecular weight cationized hyaluronic acid It is a figure which shows the image which applied (1 mass% aqueous solution) and (g) low molecular weight cationized hyaluronic acid (10 mass% aqueous solution) to the hair. FIG. 2 is a fluorescence image showing the adsorptivity of hyaluronans to skin dermal fibroblasts evaluated in Example 1, (a) purified water, (b) high molecular weight sodium hyaluronate (1% by mass aqueous solution), (C) Low molecular weight hyaluronic acid (1% by weight aqueous solution), (d) Low molecular weight sodium hyaluronate (1% by weight aqueous solution), (e) High molecular weight cationized hyaluronic acid (1% by weight aqueous solution), (f) Low molecular weight Images of cationized hyaluronic acid (1% by mass aqueous solution) and (g) low molecular weight cationized hyaluronic acid (10% by mass aqueous solution) applied to the cells ((1) fluorescently labeled cell nuclei, (2) fluorescently labeled hyaluronic acids) FIG. FIG. 3 is a fluorescence image showing the adsorptivity of hyaluronic acids to skin dermal fibroblasts evaluated in Example 1, (a) purified water, (f) low molecular weight cationized hyaluronic acid (1) of sample number 1. Mass% aqueous solution), (h) low molecular weight cationized hyaluronic acid of sample number 4 (1% by weight aqueous solution), (i) sample number 5 low molecular weight cationized hyaluronic acid (1% by weight aqueous solution) applied to the cells It is a figure which shows ((1) fluorescence-labeled cell nucleus, (2) fluorescence-labeled hyaluronic acid). FIG. 4 is a fluorescence image showing the adsorptivity of hyaluronans to skin epidermal keratinocytes evaluated in Example 1, (a) purified water, (b) high molecular weight sodium hyaluronate (1% by mass aqueous solution), (C) Low molecular weight hyaluronic acid (1% by mass aqueous solution), (d) Low molecular weight sodium hyaluronate (1% by mass aqueous solution), (e) High molecular weight cationized hyaluronic acid (1% by mass aqueous solution), (f) Low molecular weight Images of cationized hyaluronic acid (1% by mass aqueous solution) and (g) low molecular weight cationized hyaluronic acid (10% by mass aqueous solution) applied to the cells ((1) fluorescently labeled cell nuclei, (2) fluorescently labeled hyaluronic acids) FIG. FIG. 5 is a fluorescence image showing the adsorptivity of hyaluronic acid to skin epidermal keratinocytes evaluated in Example 1, (a) purified water, (f) sample number 1 low molecular weight cationized hyaluronic acid (1 Mass% aqueous solution), (h) low molecular weight cationized hyaluronic acid of sample number 4 (1 mass% aqueous solution), and (i) low molecular weight cationized hyaluronic acid of sample number 5 (1 mass% aqueous solution) were applied to the cells. It is a figure which shows an image ((1) fluorescence-labeled cell nucleus, (2) fluorescence-labeled hyaluronic acid). FIG. 6 is a fluorescence image showing the adsorptivity of hyaluronic acids evaluated in Example 1 on three-dimensional cultured skin, (a) purified water, (b) high molecular weight sodium hyaluronate (1% by mass aqueous solution), c) low molecular weight hyaluronic acid (1% by weight aqueous solution), (d) low molecular weight sodium hyaluronate (1% by weight aqueous solution), (e) high molecular weight cationized hyaluronic acid (1% by weight aqueous solution), (f) low molecular weight cation FIG. 3 is a view showing an image in which chlorinated hyaluronic acid (1% by mass aqueous solution) and (g) low molecular weight cationized hyaluronic acid (10% by mass aqueous solution) are applied to the cells (the arrow in the figure indicates the upper surface of the cultured skin). .. FIG. 7 is a photograph showing the compatibility of hyaluronic acids evaluated in Example 2, purified water, sodium lauryl sulfate (final concentration: 0.5% by mass, 10% by mass), glycerin (the same: 5% by mass, 20% by mass), sorbitol (the same: 5% by mass, 20% by mass), butylene glycol (the same: 5% by mass, 20% by mass) and hydrolyzed soybean protein (the same: 5% by mass), ( 1) 1:1 mixed solution with purified water, (2) sample (e) high molecular weight cationized 1:1 mixed solution with hyaluronic acid (1% by mass aqueous solution), (3) sample (f) low molecular weight cationized It is a figure which shows the 1:1 mixed liquid with hyaluronic acid (1 mass% aqueous solution) (all pH at the time of compounding: 5-6). FIG. 8 is a photograph showing the compatibility of the hyaluronic acids evaluated in Example 2, cationized cellulose (final concentration: 0.5% by mass), polyquaternium-7 (the same: 0.5% by mass), ethanol ( (4:) 1:1 mixture with purified water, (5) sample (f) 1:1 mixture with low molecular weight cationized hyaluronic acid (1% by weight aqueous solution) when using 20% by weight) FIG. 3 is a diagram showing a liquid, (6) sample (e), a 1:1 mixed liquid with a high molecular weight cationized hyaluronic acid (1% by mass aqueous solution) (each of which has a pH of 5-6 when compounded). FIG. 9 is a ToF-SIMS image showing the evaluation of permeability in hyaluronic acids evaluated in Example 3, in which sample (f) low molecular weight cationized hyaluronic acid (1% by mass aqueous solution, m/z=134), sample ( (e) High molecular weight cationized hyaluronic acid (1 mass% aqueous solution, m/z=274) and sample (c) low molecular weight hyaluronic acid (1 mass% aqueous solution, m/z=126). (1) Hair cross-section analysis area (portion surrounded by a frame), (2) Hair cross-section mapping result at specific m/z value).

The cosmetic of the present invention contains a low molecular weight cationized hyaluronic acid obtained by cationizing a low molecular weight hyaluronic acid.
Hereinafter, the low molecular weight cationized hyaluronic acid will be described first.

[Low molecular weight cationized hyaluronic acid]
The cationized hyaluronic acid and/or its salt (hereinafter also simply referred to as hyaluronic acid) used in the cosmetic of the present invention comprises reacting a low molecular weight hyaluronic acid having a molecular weight of about 2,000 to 15,000 with a cationizing agent. Can be prepared by

Hyaluronic acid is a mucopolysaccharide having at least one repeating constitutional unit composed of a disaccharide of glucuronic acid and N-acetylglucosamine, and is extracted from living tissues such as gooseberry of a chicken cob or cultivated by using a microorganism. Are produced industrially by and are commercially available, including their salts (such as sodium salts).

Since the molecular weight of naturally-occurring hyaluronic acid is usually 500,000 or more, in the present invention, it is hydrolyzed in the presence of acid or alkali, treated with an enzyme such as hyaluronidase, or ultrasonically or sheared. It is preferable to employ, as a raw material, hyaluronic acid whose molecular weight has been reduced by physically cutting it.
Further, the salt of hyaluronic acid is not particularly limited, and in addition to the above-mentioned sodium salt, potassium salt, calcium salt, zinc salt, magnesium salt, ammonium salt and the like can be mentioned, and it is preferably used if it is a pharmaceutically acceptable salt. You can

Hyaluronic acid is generally known to have a molecular weight of about 8 to 2.5 million. In the present invention, those having an average molecular weight of about 15,000 or less are low molecular weight hyaluronic acid, and those having a molecular weight of 1 million or more are high molecular weight. Hyaluronic acid, about 10,000 to 1,000,000 is called medium molecular weight hyaluronic acid.
In the present invention, the molecular weight of hyaluronic acid is a value measured by gel permeation chromatography (GPC). In general, the molecular weight of hyaluronic acid having a high molecular weight can be obtained by a method of determining the intrinsic viscosity from the kinematic viscosity and converting the intrinsic viscosity into the molecular weight.

The low molecular weight cationized hyaluronic acid used in the cosmetic of the present invention is obtained by partially replacing the hydroxy group of hyaluronic acid with a quaternary nitrogen-containing group represented by the following general formula <1>.
In the above formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to ₃ carbon atoms, R ₃ represents an alkyl group or alkenyl group having 1 to 24 carbon atoms, and X ⁻ is a monovalent group. Represents an anion.

In the quaternary nitrogen-containing group represented by the chemical formula <1>, specific examples of the alkyl group having 1 to 3 carbon atoms in R ₁ and R ₂ include a methyl group, an ethyl group and a propyl group.
Specific examples of the alkyl group having 1 to 24 carbon atoms in R ₃ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group and dodecyl group. Examples thereof include a group, a tetradecyl group, a hexadecyl group, an octadecyl group, an icosyl group, a docosyl group and a tetracosyl group, which may be linear, branched or cyclic. Further, the alkenyl group having 1 to 24 carbon atoms represents a group in which any one carbon-carbon single bond in the above alkyl group is substituted with a carbon-carbon double bond, and examples thereof include an oleyl group.
Specific examples of the anion X ⁻ include halogen ions such as chlorine ion, bromine ion and iodine ion, as well as methylsulfate ion, ethylsulfate ion and acetate ion.

The cationization of the low molecular weight hyaluronic acid can be carried out by reacting hyaluronic acid as a raw material with a cationizing agent having a quaternary nitrogen-containing group. More specifically, in the structure of hyaluronic acid, the OH moiety (hydroxy group) in the carboxyl group derived from glucuronic acid, and/or the hydroxy group other than the above present in the structure of hyaluronic acid, a quaternary nitrogen-containing group is included. Cationized hyaluronic acid can be obtained by reacting a cationizing agent having a group.
This reaction is carried out in the presence of alkali in a suitable solvent, preferably hydroalcoholic. The introduction of such a quaternary nitrogen-containing group can be carried out according to a conventionally known method, and is not necessarily limited thereto. Further, an inorganic salt, preferably sodium chloride, may be added to prevent aggregation of low molecular weight hyaluronic acid in the solvent during the reaction.

As the cationizing agent, a cationizing agent containing a quaternary ammonium group such as 2,3-epoxypropyltrialkylammonium halide (glycidyltrialkylammonium salt) or 3-halogeno-2-hydroxypropyltrialkylammonium halide Can be preferably used, and these may be used alone or in combination of two or more kinds.
Examples of the 2,3-epoxypropyltrialkylammonium halide (glycidyltrialkylammonium salt) include glycidyltrimethylammonium chloride, glycidyltriethylammonium chloride, glycidyltripropylammonium chloride, glycidyldimethyloctylammonium chloride, glycidyldimethyldecylammonium chloride. , Glycidyl dimethyl lauryl ammonium chloride, glycidyl dimethyl stearyl ammonium chloride and the like.
Examples of 3-halogeno-2-hydroxypropyltrialkylammonium halides include 3-chloro-2-hydroxypropyltrimethylammonium chloride, 3-chloro-2-hydroxypropyltriethylammonium chloride, 3-chloro-2-hydroxy. Propyltripropylammonium chloride, 3-chloro-2-hydroxypropyldimethyloctylammonium chloride, 3-chloro-2-hydroxypropyldimethyldecylammonium chloride, 3-chloro-2-hydroxypropyldimethyllaurylammonium chloride, 3-chloro-2 -Hydroxypropyl dimethyl stearyl ammonium chloride and the like can be mentioned.
Among these, it is preferable to use 3-chloro-2-hydroxypropyltrimethylammonium chloride and/or glycidyltrimethylammonium chloride as the cationizing agent.

The cosmetic of the present invention is a cationized hyaluronic acid having a molecular weight of 2,000 to 15,000 as described above, from the viewpoints of the effect of modifying hair and skin (moisture retaining effect, etc.) and the ease of incorporation into cosmetics. It is preferable that the molecular weight is 3,000 to 12,000, and more preferably the molecular weight is 5,000 to 10,000.
If the molecular weight of the cationized hyaluronic acid exceeds 15,000, the cationized hyaluronic acid can easily be detached from the hair or the skin surface by washing after applying the blended cosmetics, and penetrates into the hair or the skin. In addition to lowering the compatibility, the compatibility with other cosmetic ingredients may deteriorate. When the molecular weight is less than 2,000, the moisturizing effect possessed by hyaluronic acid becomes difficult to be exhibited.

In the cosmetic of the present invention, the degree of cationization of cationized hyaluronic acid is 0.30 to 1.00, preferably 0.55 to 0.90, and more preferably 0.65 to 0.80. ..
If the degree of cationization is less than 0.30, the amount adsorbed to hair and skin becomes insufficient, and in fact, a hair treatment composition such as shampoo, conditioner and body cleaner, and a skin cosmetic composition such as lotion and beauty essence. Even if it is blended with a product, a sufficient effect such as a moisturizing effect cannot be obtained. Further, when the degree of cationization exceeds 1.0, even when a hair treatment composition and a skin cosmetic composition containing such a cationized hyaluronic acid are used, foaming is deteriorated and stickiness is felt during use. A slimy feeling is caused, which deteriorates the feeling of use, and the finished feeling after use is not preferable, such as a feeling of stiffness and a feeling of stickiness.

In the present invention, the cationization degree of the cationized hyaluronic acid means a value derived from the quaternary nitrogen-containing group represented by the formula <1>, that is, the repeating constitutional unit constituting the cationized hyaluronic acid. The number (degree of substitution) of the quaternary nitrogen-containing group represented by the above chemical formula <1> bound per (disaccharide consisting of glucuronic acid and N-acetylglucosamine).

Generally, the degree of cationization of a cationized compound is determined by measuring the nitrogen content derived from a quaternary nitrogen-containing group by the Kjeldahl method [Quasi drug raw material standard 2006, general test method, nitrogen determination method, second method (Kjeldahl method) (37th method). Page right column to page 19 right column)), and is a value calculated from the measured value obtained. However, since there is a nitrogen atom derived from N-acetylglucosamine in the structure of hyaluronic acid used in the present invention, from the nitrogen component (measured value) in the cationized hyaluronic acid obtained by the Kjeldahl method, the hyaluronic acid as a raw material is obtained. The value obtained by subtracting the nitrogen content derived from the acid (N-acetylglucosamine) is the cationization degree of the cationized hyaluronic acid used in the present invention (nitrogen content derived from the quaternary nitrogen-containing group).
For example, in the above chemical formula <1>, R ₁ , R ₂ and R ₃ each represent a methyl group, and X ⁻ is a quaternary nitrogen-containing group in which a hyaluronic acid is cation-modified and is obtained. When the nitrogen content of the cation-modified hyaluronic acid was measured by the Kjeldahl method to be 5.6%, the degree of cationization is calculated by the following formula. The hyaluronic acid used in the present invention usually contains about 3.5% nitrogen. Further, the "molecular weight of the cationized substitution portion" in the formula means a portion of the quaternary nitrogen-containing group of the chemical formula <1> that substitutes with a hydroxy group, which is modified by the substitution (ie, the bonding end in the formula <1>). The part other than the oxygen atom) is a molecular weight.

In addition to the above methods, the degree of cationization is a colloid titration method in which an aqueous solution of toluidine blue is used as an indicator and titration is performed with an aqueous solution of potassium polyvinyl sulfate (compounding component standards according to makeup product type, chloride O-[2-hydroxy-3-(trimethylammonium chloride)). E) Propyl] hydroxyethyl cellulose, quantitative method).

[Cosmetic]
In the cosmetic of the present invention, the compounding amount of the low molecular weight cationized hyaluronic acid (solid content conversion) is 0.001 to 10% by mass, preferably 0.01 to 1% by mass, based on 100% by mass of the entire cosmetic. It is preferable that If the blending amount is less than 0.001% by mass, the conditioning effect and the setting property tend not to be sufficiently exhibited, and if the blending amount exceeds 10% by mass, a slimy feeling and a sticky feeling are generated at the time of use and the flexibility is deteriorated, and a stiff feeling is generated. Tend to occur and the usability tends to deteriorate, and it is not preferable from the viewpoint of economy. The blending amount is more preferably 0.1 to 0.5% by mass.

The cosmetic of the present invention can be any kind of cosmetics such as skin (skin) cosmetics, hair cosmetics, and nail cosmetics.
The dosage form of the cosmetic according to the present invention described above is not limited and can be any dosage form. Further, in addition to the above (essential) components, the dosage form is usually selected depending on the dosage form. It can be produced by a conventional method by adding various components to be mixed with the cosmetic.

Examples of skin (skin) cosmetics include facial cleanser, detergent, lotion (for example, whitening lotion), cream (for example, vanishing cream, cold cream), milky lotion, beauty essence, pack (for example, jelly form). Peel off type, paste wipe type, powder wash type, etc.), cleansing, foundation, lipstick, lip balm, lip gloss, lip liner, blusher, mascara, eyeliner, eyebrow, shaving lotion, after shaving lotion, sunscreen (cream) , Gel etc.), tanning agent (lotion, cream etc.), after-sun care product (lotion, gel etc.), deodorant lotion, body lotion (including hand care lotion, foot care lotion etc.), body cream (including hand cream etc.) Various cosmetics such as basic cosmetics, makeup cosmetics, body cosmetics such as body oil, soap, body soap (body shampoo) and bath salts.
Examples of hair cosmetics include shampoo, conditioner, conditioner-inclusive shampoo, hair conditioner, hair treatment, hair pack, hair cream, hair styling, hair wax, hair gel, hair foam (hair mousse), hair lotion, hair spray. , Hair oil, hair tonic, hair nourishing agent, permanent liquid, hair color, hair color pretreatment liquid, hair mascara, hair mascara cleansing agent and the like. These hair cosmetics may be either a type of cosmetic that is washed off in a short time after being applied to hair (such as shampoo) or a type of cosmetic that is not rinsed after application (such as hair cream).
Further, examples of the nail cosmetics include nail cream, nail treatment, nail oil, nail remover and the like.

In order to improve the conditioning effect and the skin protection effect, the cosmetic of the present invention may further contain various cationic water-soluble polymers and amphoteric water-soluble polymers in addition to the low molecular weight cationized hyaluronic acid of the present invention. However, the blending amount thereof is within a range that does not impair the feel, stability, etc. during repeated use of the cosmetic composition containing the low molecular weight cationized hyaluronic acid of the present invention, and the total amount of the cosmetic composition is 5% by mass. % Or less is preferable, and if it exceeds this, a feeling of stiffness is generated at the time of use and the usability is deteriorated. Further, in skin cosmetics, the stability of the dosage form is deteriorated, and the feeling of touch causes a slimy feel, resulting in a poor feeling in use.

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

Examples of the cationic water-soluble polymer include quaternary nitrogen-modified polysaccharides (cation-modified fenugreek gum, cation-modified guar gum, cation-modified tara gum, cation-modified locust bean gum, cation-modified starch, cation-modified tamarind gum, cation-modified hydroxy). Ethyl cellulose, cation-modified dextran, cation-modified chitosan, cation-modified honey, etc.), dimethyldiallylammonium chloride derivative (dimethyldiallylammonium chloride/acrylamide copolymer, polydimethylmethylenepiperidinium chloride, polydimethyldiallylammonium halide type cationic polymer, etc.) ), vinylpyrrolidone derivatives (vinylpyrrolidone/dimethylaminoethylmethacrylic acid copolymer salt, vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloride copolymer, vinylpyrrolidone/methylvinylimidazolium chloride copolymer, etc.), methacrylic acid derivatives ( Examples thereof include methacryloylethyl dimethyl betaine/methacryloyl ethyl trimethyl ammonium chloride/2-hydroxyethyl methacrylate copolymer, methacryloyl ethyl dimethyl betaine/methacryloyl ethyl trimethyl ammonium chloride/methacrylic acid methoxy polyethylene glycol copolymer, and the like.

Examples of the amphoteric water-soluble polymer include amphoteric starch, dimethyldiallylammonium chloride derivative (acrylamide/acrylic acid/dimethyldiallylammonium chloride copolymer, acrylic acid/dimethyldiallylammonium chloride copolymer, etc.), methacrylic acid derivative ( Polymethacryloylethyl dimethyl betaine, N-methacryloyloxyethyl-N,N-dimethylammonium-α-methylcarboxybetaine/alkyl methacrylate copolymer, etc.) and the like.

Further, in the cosmetic of the present invention, in addition to the above-mentioned cationized hyaluronic acid having a low molecular weight, various components usually mixed in the cosmetic can be appropriately mixed. Other components that can be mixed are illustrated below, but the components are not limited to these components.

For example, as the surfactant, as the anionic surfactant, alkyl (8 to 24 carbon atoms) sulfate, alkyl (8 to 24 carbon atoms) ether sulfate, alkyl (8 to 24 carbon atoms) benzenesulfonic acid Salts, alkyl (8 to 24 carbon atoms) sulfosuccinates, polyoxyalkylene alkyl (8 to 24 carbon atoms) ether sulfosuccinates, alkyl (8 to 24 carbon atoms) phosphates, polyoxyalkylene alkyl ( C8-C24 ether phosphates, acyl (C8-24)-modified taurine salts, acyl (C8-24)-methyl taurine salts, acyl (C8-24)-alanine Salts, acyl (8 to 24 carbon atoms)-modified N-methyl-β-alanine salts, acyl (8 to 24 carbon atoms) glutamate, acyl (8 to 24 carbon atoms) isethionates, acyl ( Examples include sarcosinate having 8 to 24 carbon atoms, α-sulfofatty acid ester salt, ether carboxylate, long-chain (8 to 24 carbon atoms) carboxylate, polyoxyalkylene fatty acid monoethanolamide sulfate, and the like. To be
As the nonionic surfactant, alkanolamide, glycerin fatty acid ester, polyoxyalkylene alkyl ether, polyoxyalkylene glycol ether, polyoxyalkylene sorbitan fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene sorbit fatty acid ester, sorbit 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 Examples thereof include derivatives, polyoxyalkylene hydrogenated castor oil derivatives, alkyl polyglycosides, and polyglycerin fatty acid esters.
Examples of the amphoteric surfactant include alkyl (8 to 24 carbon atoms) betaine, alkyl (8 to 24 carbon atoms) amidopropyl betaine, alkyl (8 to 24 carbon atoms) carboxybetaine, alkyl (8 to 24 carbon atoms). 24) Sulfobetaine, alkyl (8 to 24 carbon atoms) hydroxysulfobetaine, alkyl (8 to 24 carbon atoms) amidopropyl hydroxysulfobetaine, alkyl (8 to 24 carbon atoms) hydroxyphosphobetaine, alkyl (carbon atoms Number 8 to 24) Aminocarboxylic acid salt, alkyl (C 8 to C 24) sodium amphoacetate, alkyl (C 8 to C 24) amine oxide, alkyl containing tertiary nitrogen, and quaternary nitrogen (number of carbon atoms) 8-24) Phosphate ester, imidazolinium betaine, egg yolk lecithin, soybean lecithin and the like.

In addition to the above cationic and amphoteric water-soluble polymers that can be blended in the cosmetics of the present invention, anionic and nonionic polymers are used for the purpose of adjusting viscosity and improving the usability during styling to some extent. It may be further compounded within a range that does not impair the effects of the invention, and examples thereof include the following.

Examples of the anionic polymer include acrylic acid derivatives (polyacrylic acid and salts thereof, acrylic acid/acrylamide/ethyl acrylate copolymers and salts thereof), methacrylic acid derivatives (polymethacrylic acid and salts thereof, methacrylic acid).・Acrylamido/diacetone acrylamide/alkyl acrylate/methacrylic acid alkyl ester copolymers and salts, etc., crotonic acid derivatives (vinyl acetate/crotonic acid copolymers etc.), maleic acid derivatives (maleic anhydride/diisobutylene) Copolymers, isobutylene/maleic acid copolymers, etc.), polyglutamic acid and its salts, hyaluronic acid and its salts, carboxymethylcellulose, carboxyvinyl polymers and the like.
Examples of nonionic polymers include acrylic acid derivatives (hydroxyethyl acrylate/methoxyethyl acrylate copolymer, polyacrylic acid amide, etc.), vinylpyrrolidone derivatives (polyvinylpyrrolidone, vinylpyrrolidone/vinyl acetate copolymer, etc.) , Polyoxyalkylene glycol derivatives (polyethylene glycol, polypropylene glycol, etc.), cellulose derivatives (methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.), polysaccharides and their derivatives (guar gum, locust bean gum, dextran, etc.) and the like.

In still another embodiment, the cosmetic of the present invention contains an organic acid salt and/or an inorganic acid salt of an amidoamine compound obtained by completely or partially neutralizing the amidoamine compound with a neutralizing agent such as an organic acid and/or an inorganic acid. Furthermore, the conditioning effect can be improved by adding a higher fatty acid and/or a higher alcohol. The amount of the compound 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 amount, the feeling after use becomes heavy or the product feels slimy and the usability deteriorates.

Other components to be added to the cosmetic of the present invention include cationic surfactants (alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt, alkyl pyridinium salt, alkyl dimethyl benzyl ammonium salt, benzethonium chloride, benzalkonium chloride, stearyl chloride). Trimethylammonium, etc.), solubilizers (ethanol, ethylene glycol, propylene glycol, etc.), waxes (beeswax, carnauba wax, candelilla wax, etc.), hydrocarbon oils (liquid paraffin, squalane, olive oil, jojoba oil, avocado oil, camellia) Oil, horse oil, etc., moisturizer (glycerin, trehalose, sorbitol, maltitol, dipropylene glycol, 1,3-butylene glycol, atelocollagen, sodium hyaluronate, hydrolyzed hyaluronic acid, acetylated hyaluronic acid, dimethylsilanol hyaluronate , Ceramide, phytoglycogen, hydrolyzed egg shell membrane, etc.), esters (hexyl laurate, isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, glyceryl trimyristate, isopropyl palmitate) , 2-heptylundecyl palmitate, 2-hexyldecyl palmitate, butyl stearate, isocetyl stearate, cholesteryl 12-hydroxystearate, cetostearyl alcohol, cetyl octanoate, hexyldecyl dimethyloctanoate, isocetyl isostearate. , Trimethylolpropane triisostearate, decyl oleate, oil oleate, cetyl lactate, myristyl lactate, ethyl acetate, butyl acetate amyl acetate, lanolin acetate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, di-2- Ethylene glycol ethylhexylate, trimethylolpropane tri-2-ethylhexylate, glycerin tri-2-ethylhexylate, pentaerythritol tetra-2-ethylhexylate, cetyl-2-ethylhexanoate, diisobutyl adipate, adipic acid-2- Heptylundecyl, 2-hexyldecyl adipate, dipentaerythritol fatty acid ester, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, glyceride tri-2-heptylundecanoate, castor oil Fatty acid methyl ester, acetog Lyceride, N-lauroyl-L-glutamic acid-2-octyldodecyl ester, di-2-ethylhexyl sebacate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, ethyl laurate, mink oil fatty acid ethyl etc.), Antioxidants (tocopherol, BHT, etc.), silicones (methyl polysiloxane, methylphenyl polysiloxane, high degree of polymerization methyl polysiloxane, cyclic polysiloxane, etc.) and silicone derivatives (polyether-modified silicone, amino-modified silicone, etc.), higher alcohols (Cetyl alcohol, stearyl alcohol, behenyl alcohol, isostearyl alcohol, batyl alcohol, etc.), polyhydric alcohol (glycerin, diglycerin, propylene glycol, polyethylene glycol, pentylene glycol, etc.), higher fatty acid (lauric acid, myristic acid, palmitic acid) , Stearic acid, behenic acid, isostearic acid, oleic acid, undecylenic acid, tall oil fatty acid, coconut oil fatty acid, palm fatty acid, palm kernel fatty acid, linoleic acid, linoleic acid, eicosapentaenoic acid, docosahexaenoic acid, etc., amino acids (arginine) , Glutamic acid, glycine, alanine, hydroxyproline, cysteine, serine, L-theanine, etc.), UV absorbers (benzophenone derivatives, paraaminobenzoic acid derivatives, methoxycinnamic acid derivatives, etc.), UV reflectors (titanium oxide, zinc oxide, etc.) , Pearlizing agent (fatty acid ethylene glycol etc.), suspension agent (polystyrene emulsion etc.), thickener (cellulose ether, carboxyvinyl polymer, xanthan gum, dextrin palmitate etc.), sequestering agent (edetate salt, etidronic acid) Salts, etc.), pH adjusters, bactericides, preservatives (methylparaben, ethylparaben, butylparaben, propylparaben, phenoxyethanol, etc.), hair restorers, foam boosters, protein hydrolysates (eg, keratin peptides, collagen peptides, Soybean peptide, wheat peptide, milk peptide, silk peptide, egg white peptide, etc.), natural product extracts (kujin extract, kasil extract, tenchika extract, seaweed extract, eucalyptus extract, royal jelly extract, rosemary extract, beech tree extract, etc.), and other functions Sex ingredients (Coenzyme Q10, arbutin, polyquaternium-51, elastin, platinum nanocolloid, retinol palmitate, panthenol, Allantoin, sodium lysine dilauroylglutamate, etc.), phospholipid polymers, vitamins, anti-inflammatory agents, pigments, fragrances and the like.

The present invention will be described below with reference to examples. However, the present invention is not limited to these Examples and Comparative Examples.

[Synthesis Example 1: Preparation of cationized hyaluronic acid (1)]
After adding 29.3 g of 48 mass% sodium hydroxide aqueous solution to 733 mL of 60 vol% isopropanol aqueous solution, 100 g of low molecular weight hyaluronic acid (molecular weight 5000 Da) was gradually added and dispersed therein to obtain a dispersion liquid.
Next, 66.8 g of an 80% by mass glycidyltrimethylammonium chloride (hereinafter also referred to as GTA) aqueous solution was added to the above dispersion liquid, heated, and reacted at 50° C. for 3 hours. After the reaction was completed, 36.7 g of 35% hydrochloric acid was added to neutralize the reaction system. After mixing at room temperature for 1 hour, the reaction solution was poured into 5000 mL of methanol to precipitate a reaction product, which was separated by filtration. The obtained precipitate was washed with a methanol aqueous solution, and then the reaction product was dried under reduced pressure. The cationized hyaluronic acid (Sample No. 1) thus obtained had a cationization degree of 0.70 and a molecular weight measured by GPC of 6600 (number average molecular weight). The results are shown in Table 1.
[Synthesis Examples 2 to 5: Preparation of Cationized Hyaluronic Acid (2)]
By the same procedure as in Synthesis Example 1 above, but by changing the amount of GTA to be added or using hyaluronic acid having a different molecular weight as a raw material, a cationized hyaluronic acid having a different cationization degree and a different molecular weight (Sample No. 2 to sample number 5) were prepared.

A list of prepared cationized hyaluronic acid is shown below.

In this example, the conditions for measuring the molecular weight (number average molecular weight) of cationized hyaluronic acid by GPC are as follows.
-Device used: LC-10ADvp [Shimadzu Corporation]
-Use column: Shodex (registered trademark) OHpak SB-802.5 HQ + OHpak SB-803 HQ [manufactured by Showa Denko KK]
・Eluent: 0.1 M sodium nitrate ・Flow rate: 1 mL/min ・Oven temperature: 40°C
-Measurement time: 60 minutes-Calibration curve Tosoh Corporation TSK gel standard polyethylene oxide SE-8 Molecular weight: 101000
SE-2 27700
GL Science Co., Ltd. polyethylene glycol 2070-9 molecular weight: 8650
2070-8 6450
2070-7 4250
2070-6 1470

[Example 1: Evaluation of adsorption of cationized hyaluronic acid]
[Procedure of test]
Regarding cationized hyaluronic acid with various degrees of cationization and molecular weight, it is adsorbable to hair, dermal fibroblasts, skin epidermal keratinocytes, and three-dimensional cultured skin. Was evaluated according to the following procedures.
The hyaluronic acid and the like used in the above various evaluations are shown in (a) to (i) below. Further, (b) to (f), (h) and (i) of hyaluronic acid (hereinafter, hyaluronic acid used in the examples regardless of the presence or absence of cationization is generically referred to as hyaluronic acid) is added to purified water. Was subjected to an actual test as a 1% by mass aqueous solution. Further, (g) was made into a 10 mass% aqueous solution by adding purified water and subjected to an actual test.
(A) Purified water (b) High molecular weight sodium hyaluronate [commercial product, hyaluronic acid molecular weight: 1.37 to 1.53×10 ⁶ Da, tested with 1 mass% aqueous solution]
(C) Low molecular weight hyaluronic acid [commercial product, hyaluronic acid molecular weight: 10,000 or less, test with 1% by mass aqueous solution]
(D) Low molecular weight sodium hyaluronate [commercial product, hyaluronic acid molecular weight: 7,000, tested with 1% by mass aqueous solution]
(E) High-molecular-weight cationized hyaluronic acid [commercial product, hyaluronic acid molecular weight: 500,000 to 800,000, tested with 1% by mass aqueous solution]
(F) Low molecular weight cationized hyaluronic acid [Tested with 1% by weight aqueous solution of low molecular weight cationized hyaluronic acid of Sample No. 1 above]
(G) Low molecular weight cationized hyaluronic acid [Tested with low molecular weight cationized hyaluronic acid of Sample No. 1 above, 10% by mass aqueous solution]
(H) Low-molecular-weight cationized hyaluronic acid [Tested with low-molecular-weight cationized hyaluronic acid of Sample No. 4 above, 1% by mass aqueous solution]
(I) Low-molecular-weight cationized hyaluronic acid [Tested with low-molecular-weight cationized hyaluronic acid of Sample No. 5 above, 1% by mass aqueous solution]

[1] Adhesion test on hair Human black hair (obtained from Vyrax Co., Ltd.) was dipped in a 2% aqueous ammonia solution containing 2% hydrogen peroxide for 30 minutes and washed with water to prepare damaged hair.
The prepared damaged hair was dipped in the samples (a) to (g) for 10 minutes. After 10 minutes, the hair was washed with running water, and the hair was pinched in Kim Towel (registered trademark) to remove excess water. After fixing the hair to the slide glass with cellophane tape, blocking was performed with a phosphate buffer containing 3 mass% bovine serum albumin (BSA) (hereinafter also referred to as PBS containing 3% BSA). After blocking, hyaluronic acid adsorbed on hair was fluorescently labeled with biotin-labeled hyaluronan-binding protein (HABP) and streptavidin-labeled TRITC (tetramethylrhodamine isothiocyanate). After the labeling, a fluorescent discoloration preventing agent was dropped and a cover glass was put on and sealed, and then fluorescence observation was performed.

[2] Adhesion test to skin dermal fibroblasts Skin dermal fibroblasts were seeded in a 96-well plate at a density of 5×10 ⁴ cells/cm ² and cultured for 3 days. After 3 days, the sample was rinsed with purified water and the samples (a) to (i) were allowed to act for 10 minutes. After 10 minutes, the product was rinsed three times with purified water, and a 4 mass% paraformaldehyde/phosphate buffer solution (hereinafter also referred to as 4% PFA/PBS) was allowed to act thereon to fix hyaluronic acid. After that, blocking was performed with PBS containing 3% BSA. After blocking, the nuclei of fibroblasts were fluorescently labeled with Hoechst 33342, and hyaluronic acid adsorbed to the fibroblasts was fluorescently labeled with biotin-labeled HABP and streptavidin-labeled TRITC. After the labeling, a fluorescent discoloration preventing agent was dropped, and fluorescence was observed.

[3] Adhesion test to skin epidermal keratinocytes Skin epidermal keratinocytes were seeded in a 96-well plate at a density of 5×10 ⁴ cells/cm ² and cultured for 3 days. After 3 days, the sample was rinsed with purified water and the samples (a) to (i) were allowed to act for 10 minutes. After 10 minutes, rinsing with purified water was performed three times, and 4% PFA/PBS was allowed to act thereon to fix hyaluronic acids. After that, blocking was performed with PBS containing 3% BSA. After blocking, the nucleus of keratinocytes was fluorescently labeled with Hoechst 33342, and hyaluronic acid adsorbed to the keratinocytes was fluorescently labeled with biotin-labeled HABP and streptavidin-labeled TRITC. After the labeling, a fluorescent discoloration preventing agent was dropped, and fluorescence was observed.

[4] Adsorption test to three-dimensional cultured skin Three-dimensional cultured skin having dermis composed of type I collagen and fibroblasts and epidermis composed of keratinocytes was prepared, and the surface of the cultured skin was rinsed with purified water. .. After rinsing, the samples (a) to (g) were allowed to act for 10 minutes. After 10 minutes, rinsing with purified water was performed 3 times, 4% PFS/PBS was allowed to act, and hyaluronic acid was immobilized on the three-dimensional cultured skin for 1 day at 4°C. After fixation, 4% PFS/PBS was replaced with 30% sucrose and allowed to stand at 4°C for 1 day, then replaced with 30% sucrose again and allowed to stand at 4°C for 1 day (total 2 times sucrose replacement). Carried out). After the replacement, a cryosection of the three-dimensional cultured skin was prepared using Cryostat (CryoStar NX70, Thermo Fisher Scientific Co., Ltd.). After that, blocking was performed with PBS containing 3% BSA. After blocking, the fibroblast and keratinocyte nuclei were fluorescently labeled with Hoechst 33342, and hyaluronic acid adsorbed on the skin surface was fluorescently labeled with biotin-labeled HABP and streptavidin-labeled TRITC. After the labeling, a fluorescent discoloration preventing agent was dropped and a cover glass was put on and sealed, and then fluorescence observation was performed.

[Image analysis of fluorescence observation]
Using the fluorescence observation images (fluorescence micrographs) obtained in [1] to [4] above, the amount of hyaluronic acid adsorbed on hair and cells was evaluated by image analysis.
Image analysis software "NIS-Elements BR 3.1" (manufactured by Nikon Corporation) was used for image analysis, and the adsorption amount (rate) was determined by unifying and analyzing the brightness threshold value [threshold]. Was quantified as
<Evaluation of hair>
One hair is cut out from the acquired image, the threshold of the brightness of the hair itself and the threshold of the brightness of the part where the hyaluronic acid is adsorbed are set, and the comparison of these intensities shows that the amount of adsorbed (residual) hyaluronic acid on the hair is determined. The percentage was analyzed.
Adsorption amount on hair (%)=luminance of adsorbed hyaluronic acid (threshold value: 900 to 4078)/luminance of entire hair (threshold value: 350 to 4078)
<Evaluation of cells>
Considering that the cells were distributed in the entire image, it was evaluated that the entire acquired image represents the entire cell. That is, the threshold value of the brightness of the portion where the hyaluronic acid was adsorbed in the entire image was set, and the intensity of the portion where the hyaluronic acid was adsorbed to the entire image was analyzed as the ratio of the amount of adsorbed (residual) hyaluronic acid to the cells.
Adsorption amount to cell (%) = Adsorption amount of hyaluronic acid (threshold value: 1200-4078)

[Evaluation results]
[1] Results of Adhesion Test on Hair The results of observation (photograph) by a fluorescence microscope are shown in FIG. 1, and the results of calculation of the adsorption rate on hair by image analysis are shown in Table 2 below.
As can be seen from FIG. 1, the brightness of the samples (f) and (g) is higher than that of the other samples (a) to (e), and as shown in Table 2, the low molecular weight cationized hyalurone of the present invention is used. It was confirmed that Samples (f) and (g), which are aqueous solutions of acids, had the highest adsorptivity to hair.

[2] Adhesion test results to skin dermal fibroblasts Observation results (photographs) of the samples (a) to (g) by a fluorescence microscope are shown in FIG. 2, and the samples (a), (f), (h) and ( FIG. 3 shows the observation result (photograph) of the i) by the fluorescence microscope, and Table 3 below shows the calculation results of the adsorption rate to the skin dermal fibroblasts by the image analysis of the samples (a) to (i). 2 and 3, (1) represents an image of fluorescently labeled cell nuclei, and (2) represents an image of fluorescently labeled hyaluronic acids. Note that the difference in FIGS. 2 and 3 and Table 3 (Table 3-1 and Table 3-2) is due to the change of the threshold value of the luminance in the image analysis.
As shown in FIG. 2, in the samples (a) to (e), the cell nuclei can be clearly confirmed in the image (1), but in the image (2), the fluorescence indicating hyaluronan has low brightness and is unclear. It was confirmed that it was scarcely adsorbed to the skin dermal fibroblasts.
On the other hand, in the samples (f) and (g), the fluorescence showing the adsorption of the cationized hyaluronic acid to the skin dermal fibroblasts is clear in the image (2) so that the cell nucleus shown in the image (1) can be confirmed as a guide. Was confirmed.
Further, as shown in FIG. 3, in any of Samples (f), (h) and (i), the adsorbability of these cationized hyaluronic acid to the skin dermal fibroblasts was confirmed.
Further, as shown in Table 3, the samples (f), (g), (h), and (i), which are the aqueous solution of the low molecular weight cationized hyaluronic acid of the present invention, have high adsorptivity to skin dermal fibroblasts. It was confirmed that the samples (f), (g) and (i) were particularly high.

[3] Results of Adhesion Test on Skin Epidermal Keratinocytes The observation results (photographs) of the samples (a) to (g) by a fluorescence microscope are shown in FIG. 4, and the samples (a), (f), (h) and ( FIG. 5 shows the observation result (photograph) of the i) by the fluorescence microscope, and Table 4 below shows the calculation results of the adsorption rate to the skin epidermal keratinocytes by the image analysis of the samples (a) to (i). 4 and 5, (1) represents an image of fluorescently labeled cell nuclei, and (2) represents an image of fluorescently labeled hyaluronic acid. The difference in FIGS. 4 and 5 and Table 4 (Table 4-1 and Table 4-2) is due to the change of the threshold value of the luminance in the image analysis.
Similar to the skin dermal fibroblasts described above, in the samples (a) to (e) in FIG. 4, the cell nuclei can be clearly confirmed in the image (1), but the fluorescence showing hyaluronic acid is low in the image (2). It was unclear and it was confirmed that these samples hardly adsorbed on the skin epidermal keratinocytes.
On the other hand, in the samples (f) and (g), the fluorescence indicating the adsorption of the cationized hyaluronic acid to the skin epidermal keratinocytes is clear in the image (2) so that the cell nucleus shown in the image (1) can be confirmed as a guide. Was confirmed.
Further, as shown in FIG. 5, in any of Samples (f), (h), and (i), the adsorbability of these cationized hyaluronic acid to skin epidermal keratinocytes was confirmed.
Further, as shown in Table 4, the samples (f), (g), (h) and (i), which are the aqueous solution of the low molecular weight cationized hyaluronic acid of the present invention, have the highest adsorptivity to skin epidermal keratinocytes. It was confirmed to be high.

[4] Adsorption test result to three-dimensional cultured skin The observation result (photograph) with a fluorescence microscope is shown in FIG. In FIG. 6, the arrow in each figure indicates the upper surface of the cultured skin, the fluorescence above this indicates the adsorbed portion of the hyaluronic acid of the sample, and the fluorescence below this indicates hyaluronic acid inside the skin (produced).
As shown in FIG. 6, in samples (a) to (e), fluorescence due to adsorption of hyaluronic acid on the upper surface of the cultured skin was hardly observed, while in samples (f) and (g), cationized hyaluronic acid was clearly detected. Fluorescence due to adsorption was confirmed.

[Example 2: Compatibility evaluation of cationized hyaluronic acid]
Using the sample (e) high molecular weight cationized hyaluronic acid (1% by mass aqueous solution) and the sample (f) low molecular weight cationized hyaluronic acid (1% by mass aqueous solution), compatibility with various cosmetic raw materials was evaluated.
An aqueous solution of cosmetic raw material shown in Table 5 below was prepared at a concentration twice the final concentration shown in the same table, and this and the solution of the sample (e) or (f) were mixed at a mass ratio of 1:1. The mixture was stirred, mixed and allowed to stand still, the appearance of the mixed solution was visually confirmed, and evaluated according to the following criteria. The obtained results are shown in Table 5 (in the table,% indicates mass %).
The concentrations shown in Table 5 indicate the final concentration of the cosmetic raw material. For example, when the concentration of the aqueous solution of the cosmetic raw material during mixing is 1% by mass and the concentration of the solution of hyaluronic acid is 1% by mass, the final concentration is 0.5% by mass. % (In this example, the final concentration of hyaluronic acid is 0.5% by mass).
The pH at the time of compounding is the pH of each of the aqueous cosmetic raw material solution and the hyaluronic acid solution adjusted with citric acid and an aqueous sodium hydroxide solution.
<Judgment criteria>
○: transparent ×: haze to semitransparent × ×: insoluble matter precipitation

Also, purified water, and sodium lauryl sulfate (final concentration: 0.5% by mass, 10% by mass), glycerin (the same: 5% by mass, 20% by mass), sorbitol (the same: 5% by mass, 20% by mass) as a raw material for cosmetics. %), butylene glycol (the same: 5% by mass, 20% by mass) and the hydrolyzed soybean protein (the same: 5% by mass), the appearance of the mixed solution with the above hyaluronic acid is shown in FIG. (In the figure,% indicates mass %). In FIG. 7, each photograph is a 1:1 mixture of the cosmetic raw material (concentration is the final concentration) shown in the upper part of the photograph and (1) purified water from the left, and (2) sample (e) 1: 1 mixture, (3) 1:1 mixture with the sample (f) (all pH at the time of compounding: 5-6).
Furthermore, the appearance of a mixed liquid with the above hyaluronic acid when cationized cellulose (final concentration: 0.5% by mass), polyquaternium-7 (same: 0.5% by mass), and ethanol (same: 20% by mass) are used. 8 shows a photograph after standing (in the figure,% indicates mass %). In Fig. 8, each photograph is a 1:1 mixture of cosmetic raw materials (concentration is final concentration) shown in the upper part of each photograph and (4) purified water from the left, (5) sample (f) low molecular weight cationization 1:1 mixture with hyaluronic acid (1% by weight aqueous solution), (6) sample (e) 1:1 mixture with high molecular weight cationized hyaluronic acid (1% by weight aqueous solution) -6) is shown.

As shown in Table 5, the sample (f) low molecular weight cationized hyaluronic acid targeted by the present invention resulted in compatibility with various cosmetic raw materials in a wide pH range (FIGS. 7 and 8). reference). On the other hand, it is assumed that the sample (e) high molecular cationized hyaluronic acid becomes semi-transparent in the cationic water-soluble polymer and lacks compatibility, and in ethanol, insoluble matter precipitates depending on pH and concentration, resulting in large incompatibility. Results were obtained (see especially FIG. 8).

[Example 3: Evaluation of permeability of cationized hyaluronic acid into hair]
Sample (c) low molecular weight hyaluronic acid (1% by weight aqueous solution), sample (e) high molecular weight cationized hyaluronic acid (1% by weight aqueous solution) and sample (f) low molecular weight cationized hyaluronic acid (1% by weight aqueous solution) to 200 mL The damaged hair (length 10 cm) prepared in the above Example 1 [1] Hair adsorption test was immersed at 40° C. for 60 minutes. Then, the hair was taken out and dried for 12 hours in a thermo-hygrostat at a humidity of 50% and a temperature of 25°C. The obtained hair is cut, the cross section is analyzed by ToF-SIMS, the m/z value of hyaluronic acid detected by the qualitative spectrum is specified, and the m/z value is mapped to the inside of the hair. The permeability of hyaluronic acids was evaluated.

From qualitative spectrum analysis, sample (c) low molecular weight hyaluronic acid at m/z=126,128, sample (e) high molecular weight cationized hyaluronic acid at m/z=274, and sample (f) low molecular weight cationized Characteristic peaks of hyaluronic acid were observed at m/z=134.

FIG. 9(2) shows the mapping result of the hair cross section at the characteristic m/z value derived from hyaluronic acid of each sample. In FIG. 9(2), the high-brightness portion reflects the distribution of hyaluronic acids, and FIG. 9(1) shows the analysis area (the portion surrounded by a frame) of the hair cross section.
As shown in FIG. 9, it was confirmed that the sample (f) low molecular weight cationized hyaluronic acid targeted by the present invention was distributed (penetrated) to the inside of the hair cross section, while sample (e) high molecular weight cation It was confirmed that the modified hyaluronic acid remained in the distribution on the hair surface (outer periphery of the hair). It should be noted that (c) low molecular weight hyaluronic acid seems to be detected on the entire surface of the image, but it can be said that the result is due to the strong influence of the background. The results seem to have not reached the surface adsorption and the permeation into the hair.

[Example 4: Sensory evaluation of cosmetic preparation containing cationized hyaluronic acid]
Sample (g) 0.1% by mass of low molecular weight cationized hyaluronic acid (10% by mass aqueous solution) was added to a beauty essence having the following composition (final concentration of low molecular weight cationized hyaluronic acid: 0.01%). , Was subjected to a sensory evaluation with an unblended beauty essence.

Female subjects in their 20's to 70's: The same amount of the sample (g)-containing cosmetic liquid and the unmixed cosmetic liquid were separately applied to the 333 persons on the backs of the left and right hands and made to spread.
Then, the change in the feel was compared between the feel (A) of the back of the hand coated with the sample (g) unmixed beauty essence and the feel of the back of the hand coated with the sample (g) blended beauty essence.
327 (98%) of the subjects evaluated that the feel (B) was superior to the feel (A) in terms of moisturizing effect and skin conditioning effect, and 6 subjects evaluated that these feelings did not change ( 2%).

Hereinafter, prescription examples of various cosmetics using the above sample numbers 1 to 4 are shown as Examples 5 to 19. Not only the low molecular weight cationized hyaluronic acid of the sample number described here, but also the low molecular weight cationized hyaluronic acid of the other sample numbers shown in the above Table 1 are similarly excellent in the moisturizing property. Various cosmetics were obtained.

[Example 5: Lotion]
Based on a conventional method, the components shown in Table 7 were blended to produce a lotion.
The lotion of the following formulation was extremely excellent in the moist feeling (moisture retention) of the skin after use.

[Example 6: Body care lotion]
Based on a conventional method, the ingredients shown in Table 8 were blended to produce a body care lotion.
The body care lotion having the following composition was extremely excellent in the moist feeling (moisturizing property) of the skin after use.

[Example 7: beauty essence]
Based on a conventional method, the ingredients shown in Table 9 were blended to produce a beauty essence.
The beauty essence of the following formulation was extremely excellent in the moist feeling (moisturizing property) of the skin after use.

[Example 8: Body soap (body shampoo) (1)]
Based on a conventional method, the ingredients shown in Table 10 were blended to produce a body soap.
The body soap having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the skin after washing.

[Example 9: Body soap (body shampoo) (2)]
Based on a conventional method, the ingredients shown in Table 11 were blended to produce a body soap.
The body soap having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the skin after washing.

[Example 10: Face wash (1)]
Based on a conventional method, the components shown in Table 12 were blended to produce a face wash.
The facial cleansers of the following formulations were extremely excellent in moisturizing feeling (moisturizing property) after washing.

[Example 11: Face wash (2)]
Based on a conventional method, the components shown in Table 13 were blended to produce a face wash.
The facial cleansers of the following formulations were extremely excellent in moisturizing feeling (moisturizing property) after washing.

[Example 12: After-shave lotion]
Based on a conventional method, the components shown in Table 14 were blended to produce an aftershave lotion.
The after shave lotion having the following composition was extremely excellent in the moist feeling (moisture retention) of the skin after use.

[Example 13: Bath salt]
Based on a conventional method, the components shown in Table 15 were blended to produce a bath salt.
The bath agents having the following formulations were extremely excellent in the moist feeling (moisturizing property) of the skin after bathing.

[Example 14: Shampoo (1)]
Based on a conventional method, the ingredients shown in Table 16 were blended to produce a shampoo.
The shampoo having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of hair after washing.

[Example 15: Shampoo (2)]
Based on a conventional method, the ingredients shown in Table 17 were blended to produce a shampoo.
The shampoo having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of hair after washing.

[Example 16: Rinse (1)]
Based on a conventional method, the ingredients shown in Table 18 were blended to produce a rinse.
The rinse having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the hair after application and washing.

[Example 17: Rinse (2)]
Based on a conventional method, the ingredients in Table 19 were blended to produce a rinse.
The rinse having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the hair after application and washing.

[Example 18: Hair gel]
Based on a conventional method, the ingredients shown in Table 20 were blended to produce a hair gel.
The hair gel having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the applied hair.

[Example 19: Hair wax]
Based on a conventional method, the components shown in Table 21 were blended to produce a hair wax.
The hair wax having the following composition was extremely excellent in moisturizing feeling (moisturizing property) of the applied hair.

Claims (4)

A low molecular weight cationized hyaluronic acid having a molecular weight of 3,800 to 6,600 and/or a salt thereof, in which a part of the hydroxy group is substituted with a quaternary nitrogen-containing group represented by the following general formula <1>. a cosmetic comprising,
The low molecular weight cationized hyaluronic acid and/or its salt has a cationization degree represented by the following formula of 0.60 to 0.70.
(In the formula, R ₁ and R ₂ each independently represent an alkyl group having 1 to ₃ carbon atoms, R ₃ represents an alkyl group or an alkenyl group having 1 to 24 carbon atoms, and X ⁻ is a monovalent group. Represents an anion.)
(In the formula, the nitrogen content (%) derived from the quaternary nitrogen-containing group means the hyaluronic acid (N-acetylglucosamine) as a raw material from the nitrogen content (measured value) in the cationized hyaluronic acid obtained by the Kjeldahl method. It represents the value obtained by subtracting the nitrogen content from the source.) The cosmetic according to claim 1 , wherein the low molecular weight cationized hyaluronic acid and/or its salt is contained in an amount of 0.001 to 10 mass% with respect to the total mass of the cosmetic. The cosmetic according to claim 1 or 2 , which is a skin cosmetic. The cosmetic according to claim 1 or 2 , which is a cosmetic for hair.