JP2013056864A - Cationized glyceryl glucoside mixture and skin external preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substance capable of exhibiting an excellent effect as an additive for a skin external preparation.SOLUTION: There is provided a mixture of cationized glyceryl glucoside expressed by general formula (I). (In the formula, GG represents a glyceryl glucoside residue; R, Rand Reach represents a hdyrocarbyl group; X represents a counter anion; and n denotes an integer of 1 to 3.) The mixture of the above cationized glyceryl glucoside is used as an additive for a skin external preparation. There is also provided a skin external preparation which contains the cationized glyceryl glucoside expressed by general formula (I).

Description

  The present invention relates to a mixture of cationized glyceryl glucosides. The present invention further relates to the use of such a cationized glyceryl glucoside mixture, specifically to the use as an additive for a skin external preparation and the skin external preparation.

Conventionally, various kinds of substances have been blended into skin external preparations such as skin cosmetics and hair cosmetics to enhance the performance of the cosmetics. For example, a hair cleaning agent to which a cationized polymer is added to impart smoothness, flexibility, gloss, suppleness and the like to hair has been proposed (see, for example, Patent Document 1). By adding a cationized raw material to an external preparation for skin, an improvement in the ability to form a film on the surface of hair or skin and an antibacterial effect are expected. Natural product derivatives tend to be used as a cationized raw material in consideration of safety to the human body, and water-soluble polymers, hydrolyzed starches, trehalose and the like are used (for example, Patent Document 2). However, cationized water-soluble polymers do not have sufficient co-solubility with the co-existing solvent, and precipitation of precipitates occurs due to co-existing surfactants. In cationized hydrolyzed starch, the color changes due to heating or alkali treatment or changes over time. Coloring and cationized trehalose have respective problems as additives for external preparations for skin, such as a sticky feel due to sugar.
Under such circumstances, there is a demand for a substance that is highly safe as an additive for external preparations for skin and can exhibit even more excellent effects.

Japanese Patent Publication No. 47-20635 Japanese Patent Laid-Open No. 10-279591

  The present inventors have been searching for a substance that can exert an excellent effect as an additive for external preparations for skin. As a result, glucose, which is a natural product, becomes glycerin that has been used for many years as an additive for external preparations for skin. Focuses on glyceryl glucoside, which is a bonded compound and has an advantageous characteristic as a cosmetic raw material that there is no stickiness due to the binding of sugar, despite improved moisturizing performance compared to glycerin The inventors have found that a predetermined derivative of glyceryl glucoside is useful as an additive for external preparations for skin, and have completed the present invention. Specifically, the present inventors have found that a mixture of cationized glyceryl glucoside obtained by cationizing glyceryl glucoside is useful as an additive for external preparation for skin.

（式中、ＧＧはグリセリルグルコシド残基を表し、Ｒ₁、Ｒ₂、Ｒ₃は各々ヒドロカルビル基を表し、Ｘは対アニオンを表し、ｎは１〜３の整数を表す。）
本発明はまた、皮膚外用剤用添加剤である上記一般式（Ｉ）で示されるカチオン化グリセリルグルコシドの混合物に向けられている。
本発明はさらに、上記一般式（Ｉ）で示されるカチオン化グリセリルグルコシドを含有する皮膚外用剤である。 Accordingly, the present invention is first a mixture of cationized glyceryl glucosides represented by the following general formula (I).
(I)

(In the formula, GG represents a glyceryl glucoside residue, R ₁ , R ₂ , and R ₃ each represent a hydrocarbyl group, X represents a counter anion, and n represents an integer of 1 to 3)
The present invention is also directed to a mixture of the cationized glyceryl glucoside represented by the above general formula (I), which is an additive for external preparation for skin.
The present invention further provides a skin external preparation containing the cationized glyceryl glucoside represented by the above general formula (I).

  The mixture of cationized glyceryl glucoside of the present invention gives smoothness, flexibility, luster, suppleness, etc. to the hair, and also has excellent film properties, so that the skin and hair can be protected from dirt, Excellent as an additive to external preparations. The external preparation for skin containing the cationized glyceryl glucoside of the present invention has a good feeling of use and has a high function of protecting skin and hair.

The mixture of the cationized glyceryl glucoside of the present invention can be obtained by using a mixture containing at least two kinds of glyceryl glucosides shown below as a raw material and allowing a cationizing agent to act on the mixture. Such a mixture of glyceryl glucosides can be obtained by, for example, reacting glycerin and glucose in the presence of a catalyst and purifying the mixture through concentration or distillation. More specifically, for example, it can be obtained by reacting glycerin derived from palm oil and glucose derived from corn. Moreover, you may obtain the mixture of the mixture of glyceryl glucoside by another chemical synthesis method.

  As an example of the mixture of glyceryl glucoside as the raw material, COSARTE-2G (registered trademark, manufactured by Toyo Seika Co., Ltd.) can be mentioned. In the mixture of glyceryl glucoside as a raw material, the glyceryl glucoside content is suitably 60% by mass or more, and more preferably 65% by mass or more. The raw material may include glyceryl maltoside, glyceryl maltotrioside, glycerin and water. Moreover, it is preferable that content of glyceryl glucoside is 80 mass% or more in conversion of an anhydride in the mixture used as such a raw material.

（式中、Ｒ₁、Ｒ₂、Ｒ₃は各々ヒドロカルビル基を表し、Ｘは対アニオンを表し、Ｙはハロゲン原子を表す。）
上記一般式（Ａ）及び（Ｂ）において、具体的にＲ₁、Ｒ₂、Ｒ₃は各々、炭素原子数１〜１８のヒドロカルビル基が適当であり、直鎖、分岐鎖又は環式であってよく、また、飽和でも不飽和でもよく、脂肪族又は芳香族炭化水素基であってもよい。より具体的にはＲ₁、Ｒ₂、Ｒ₃はそれぞれ炭素原子数１〜１８のアルキル基が好ましく、中でも、Ｒ₁及びＲ₃が炭素原子数１〜３のアルキル基であって、Ｒ₂が炭素原子数１〜１８のアルキル基であるのが好ましい。対アニオンＸは無機アニオンでも有機アニオンでもよく、例えばハロゲンイオンであり、中でも塩素イオン（Ｃｌ^-）が挙げられる。上記一般式（Ｂ）中、Ｙはハロゲン原子であって、中でも塩素原子が好ましい。 Examples of the cationizing agent to be used include glycidyl trihydrocarbyl ammonium salt represented by the following general formula (A) and 3-halogeno-2-hydroxypropyl trihydrocarbyl ammonium salt represented by the following general formula (B). Such cationizing agents can be used alone or in combination of two or more.

(Wherein R ₁ , R ₂ and R ₃ each represents a hydrocarbyl group, X represents a counter anion, and Y represents a halogen atom.)
In the general formulas (A) and (B), specifically, R ₁ , R ₂ , and R ₃ are each suitably a hydrocarbyl group having 1 to 18 carbon atoms, and may be linear, branched, or cyclic. It may be saturated or unsaturated, and may be an aliphatic or aromatic hydrocarbon group. More specifically, R ₁ , R ₂ , and R ₃ are each preferably an alkyl group having 1 to 18 carbon atoms. Among them, R ₁ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, and R ₂ Is preferably an alkyl group having 1 to 18 carbon atoms. The counter anion X may be an inorganic anion or an organic anion, and is, for example, a halogen ion, including a chlorine ion (Cl ⁻ ). In the general formula (B), Y is a halogen atom, and a chlorine atom is particularly preferable.

  Examples of the cationizing agent represented by the general formula (A) include glycidyl trimethyl ammonium chloride, glycidyl triethyl ammonium chloride, glycidyl tripropyl ammonium chloride, glycidyl dimethyl octyl ammonium chloride, glycidyl dimethyl decyl ammonium chloride, glycidyl dimethyl lauryl ammonium chloride, Examples thereof include glycidyl dimethyl myristyl ammonium chloride, glycidyl dimethyl palmityl ammonium chloride, glycidyl dimethyl dodecyl ammonium chloride, and glycidyl dimethyl octadecyl ammonium chloride. Examples of the cationizing agent represented by the general formula (B) include 3-halogeno-2-hydroxytrimethylammonium chloride, 3-halogeno-2-hydroxytriethylammonium chloride, 3-halogeno-2-hydroxytripropylammonium chloride, 3-halogeno-2-hydroxydimethyloctylammonium chloride, 3-halogeno-2-hydroxydimethyllaurylammonium chloride, 3-halogeno-2-hydroxydimethylmyristylammonium chloride, 3-halogeno-2-hydroxydimethylpalmitylammonium chloride, 3 -Halogen-2-hydroxydimethyldodecylammonium chloride, 3-halogeno-2-hydroxydimethyloctadecylammonium chloride, etc. .

（式中、ＧＧはグリセリルグルコシド残基を表し、Ｒ₁、Ｒ₂、Ｒ₃は各々ヒドロカルビル基を表し、Ｘは対アニオンを表し、ｎは１〜３の整数を表す。）
ここで、グリセリルグルコシド残基はグリセリルグルコシドの一級水酸基、さらには、二級水酸基から水素原子が引き抜かれた構造を表し、ヒドロカルビル基は、上述の一般式（Ａ）及び一般式（Ｂ）で定義したものと同義であり、及び対アニオンもまた、上述の一般式（Ａ）及び一般式（Ｂ）で定義したものと同義である。上記式中、ｎは好ましくは１又は２であり、さらには１である。
具体的にはＲ₁、Ｒ₂、Ｒ₃はそれぞれアルキル基が好ましく、中でも、Ｒ₁及びＲ₃が炭素原子数１〜３のアルキル基であって、Ｒ₂が炭素原子数１〜１８のアルキル基であるのが好ましい。対アニオンＸは無機アニオンでも有機アニオンでもよく、例えばハロゲンイオンであり、中でも塩素イオン（Ｃｌ^-）が挙げられる。
本発明のカチオン化グリセリルグルコシドの混合物におけるカチオン化グリセリルグルコシドとして、特に上記一般式（Ｉ）中、ｎが１であるカチオン化グリセリルグルコシドが挙げられ、中でもｎが１であり、ＸがＣｌであるカチオン化グリセリルグルコシドが挙げられる。上記一般式（Ｉ）中、ｎが１であるとき、グリセリルグルコシドの一級水酸基水素原子が引き抜かれて、エーテル結合によってカチオン化剤の３位の炭素が結合した構造が特に挙げられる。 The reaction of the mixture of glyceryl glucoside as a raw material and the cationizing agent can be carried out in the presence of water and an alkaline substance. The reaction temperature is suitably 40-80 ° C. In the reaction between glyceryl glucoside and the cationizing agent, it is considered that a hydrogen atom is extracted from the primary hydroxyl group of the glyceryl glucoside and further from the secondary hydroxyl group, and the carbon at the 3-position of the cationizing agent is bonded by an ether bond.
Therefore, in the mixture of cationized glyceryl glucoside prepared by the reaction as described above, the cationized glyceryl glucoside can be represented by the following general formula (I).
(I)

(In the formula, GG represents a glyceryl glucoside residue, R ₁ , R ₂ , and R ₃ each represent a hydrocarbyl group, X represents a counter anion, and n represents an integer of 1 to 3)
Here, the glyceryl glucoside residue represents a primary hydroxyl group of glyceryl glucoside, and further represents a structure in which a hydrogen atom is extracted from a secondary hydroxyl group, and the hydrocarbyl group is defined by the above general formula (A) and general formula (B). The counter anion is also synonymous with those defined in the general formula (A) and the general formula (B). In the above formula, n is preferably 1 or 2, and more preferably 1.
Specifically, each of R ₁ , R ₂ and R ₃ is preferably an alkyl group. Among them, R ₁ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms. An alkyl group is preferred. The counter anion X may be an inorganic anion or an organic anion, and is, for example, a halogen ion, including a chlorine ion (Cl ⁻ ).
Examples of the cationized glyceryl glucoside in the mixture of the cationized glyceryl glucoside of the present invention include a cationized glyceryl glucoside in which n is 1 in the general formula (I), among which n is 1 and X is Cl. And cationized glyceryl glucoside. In the general formula (I), when n is 1, a structure in which the primary hydroxyl hydrogen atom of glyceryl glucoside is extracted and the carbon at the 3-position of the cationizing agent is bonded by an ether bond is particularly mentioned.

The amount of cationizing agent used for the glyceryl glucoside in the mixture of glyceryl glucoside as a raw material is generally 1 mol or more of cationizing agent per 1 mol of glyceryl glucoside. Suitably the cationizing agent is used so that at least one cationizing agent is bound per molecule of glyceryl glucoside. It is appropriate that up to two cationizing agents are bound per molecule of glyceryl glucoside, more preferably a cationizing agent is used so that one cationizing agent is bound per molecule of glyceryl glucoside. Is appropriate.
The mixture of the cationized glyceryl glucoside of the present invention may contain unreacted glyceryl glucoside in addition to the cationized glyceryl glucoside.

  The amount of water in the reaction and the amount of the alkaline substance to be used can be appropriately selected so that an appropriate reaction proceeds. In general, the amount of alkaline substance is suitably up to 1 mole per mole of glyceryl glucoside. Specific examples of alkaline substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ethylenediamine, diethylenetriamine, triethylamine, monoethanolamine, diethanolamine And organic amines such as triethanolamine. Ammonia, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and the like can also be used. Of these, sodium hydroxide is preferable.

  After the reaction between glyceryl glucoside and the cationizing agent is completed, the alkaline substance is neutralized with a mineral acid or an organic acid. In order to remove the unreacted cationizing agent from the neutralized reaction solution, it is a non-solvent of cationized glyceryl glucoside, such as alcohols such as 2-propanol, 2-butanol and isoamyl alcohol, dimethyl ether and diethyl ether. Separation of cationized glyceryl glucoside by an appropriate separation means such as centrifugation, liquid separation, vacuum distillation, etc. To do. For example, in the case of centrifugation, the supernatant portion where unreacted cationizing agent is present can be removed, and the same washing operation can be repeated to recover cationized glyceryl glucoside. Further, in order to sufficiently remove the solvent from the cationized glyceryl glucoside mixture thus recovered, the remaining solvent can be removed by an appropriate means, for example, by drying under reduced pressure. In addition, as a purification method of the cationized glyceryl glucoside mixture, a method of removing an unreacted cationizing agent by adding and mixing an adsorbent such as cellulose powder or activated carbon, or a method of passing a neutralized reaction solution through an electrodialysis membrane Can also be adopted.

As a typical example of the mixture of the cationized glyceryl glucoside thus obtained, a cationized glyceryl glucoside in which n is 1 and X is Cl in the above general formula (I) is included. Water, glycerin, unreacted glyceryl glucoside and the like may be included.
In the mixture of the cationized glyceryl glucoside of the present invention, the nitrogen content is suitably in the range of 0.5 to 5.0% by mass. Such measurement of the nitrogen content can be performed according to the nitrogen determination method (semi-micro Kjeldahl method) described in the 16th revision Japanese Pharmacopoeia.
In the mixture of the cationized glyceryl glucoside of the present invention, the content of the cationized glyceryl glucoside is preferably 1.0% by mass or more, and more preferably 3.0% by mass or more.

（式中、ＧＧはグリセリルグルコシド残基を表し、Ｒ₁、Ｒ₂、Ｒ₃は各々ヒドロカルビル基を表し、Ｘは対アニオンを表し、ｎは１〜３の整数を表す。）
式中、グリセリルグルコシド残基は上記に説明したとおりであり、またＲ₁、Ｒ₂、Ｒ₃が各々表すヒドロカルビル基、及びＸが表す対アニオンは上記のように定義したとおりである。
特にＲ₁、Ｒ₂、Ｒ₃はそれぞれアルキル基であり、中でも、Ｒ₁及びＲ₃が炭素原子数１〜３のアルキル基であって、Ｒ₂が炭素原子数１〜１８のアルキル基であり、対アニオンＸは無機アニオン又は有機アニオンであり、例えばハロゲンイオンであり、中でも塩素イオン（Ｃｌ^-）が挙げられる。典型的には、上記一般式（Ｉ）中、ｎが１であるカチオン化グリセリルグルコシドが挙げられる、中でも、ＸがＣｌであるカチオン化グリセリルグルコシドが挙げられる。 The mixture of the cationized glyceryl glucoside of the present invention can be used as a component of an external preparation for skin.
Therefore, the present invention is also directed to a skin external preparation containing a cationized glyceryl glucoside represented by the following general formula (I).
(I)

(In the formula, GG represents a glyceryl glucoside residue, R ₁ , R ₂ , and R ₃ each represent a hydrocarbyl group, X represents a counter anion, and n represents an integer of 1 to 3)
In the formula, the glyceryl glucoside residue is as described above, and the hydrocarbyl group represented by each of R ₁ , R ₂ and R ₃ and the counter anion represented by X are as defined above.
In particular, R ₁ , R ₂ and R ₃ are each an alkyl group, among which R ₁ and R ₃ are alkyl groups having 1 to ₃ carbon atoms, and R ₂ is an alkyl group having 1 to 18 carbon atoms. Yes, the counter anion X is an inorganic anion or an organic anion, for example, a halogen ion, among which a chlorine ion (Cl ⁻ ) is mentioned. Typically, in the above general formula (I), a cationized glyceryl glucoside in which n is 1 is mentioned. Among them, a cationized glyceryl glucoside in which X is Cl is mentioned.

Here, the external preparation for skin means all external compositions applied externally to the skin and hair, such as cosmetics, quasi-drugs, and external medicines.
For example, hair shampoos, hair shampoos, hair rinses, emollients, hair treatments, conditioning hair treatments, hair tonics, hair lotions, etc., pomade, hair tics, hair set lotions, hair creams, hair sprays, hair liquids, etc. Hair dyes such as cosmetics, color sprays and color rinses, scalp, hair restorer, cream, milky lotion, basic cosmetics such as lotion, makeup base, foundation, lipstick, eye shadow, eyeliner, blusher, eyebrow, mascara, etc. Makeup cosmetics, body shampoos, body rinses, body lotions, sunscreens and the like.

The dosage form of the external preparation for skin of the present invention is arbitrary, ampoules, capsules, powders, granules, tablets, solids, liquids, gels, pastes, emulsions, creams, ointments, sheets , Mousse, powder dispersion, multilayer, etc.
Specifically, the external preparation for skin of the present invention can be made into a dosage form such as cream, milky lotion, cosmetic liquid, ointment, oil, pack agent, lotion, gel agent and the like.
In the external preparation for skin of the present invention, the blending amount of the cationized glyceryl glucoside is suitably 0.01 to 30% by mass, preferably 0.05 to 20% by mass, and preferably 0.1 to 10% by mass of the entire composition. Is more preferable.

The skin external preparation of the present invention includes components usually used in skin external preparations, such as oily components, surfactants (synthetic and natural), moisturizers, thickeners, antiseptic / disinfectants, powder components, ultraviolet rays. Absorbers, whitening agents, antioxidants, alcohols, colorants, aqueous components, water, physiologically active components and the like can be appropriately blended as necessary.
Here, for example, olive oil, jojoba oil, castor oil, soybean oil, rice oil, rice germ oil, palm oil, palm oil, cacao oil, meadow foam oil, sheer butter, tea tree oil, avocado oil, macadamia nut Oils, plant-derived oils and fats such as plant-derived squalane; animal-derived oils and fats such as mink oil and turtle oil; waxes such as beeswax, canauba wax, rice wax, lanolin; liquid paraffin, petrolatum, paraffin wax, squalane, etc. Hydrocarbons; fatty acids such as myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cis-11-eicosenoic acid; higher alcohols such as lauryl alcohol, cetanol, stearyl alcohol; isopropyl myristate, butyl oleate 2-ethylhexyl Ruguriseraido, higher fatty acid octyldodecyl (octyldodecyl stearate, etc.), and the synthetic esters and synthetic triglycerides, such as.

Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyethylene glycol fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Nonionic surfactants such as hydrogenated castor oil, polyoxyethylene sorbitol fatty acid ester, fatty acid alkanolamide; fatty acid salt, alkyl sulfate, alkyl benzene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene fatty amine sulfate, Polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene alkyl ether phosphate, sodium N-lauroyl sarcosine Anionic surfactants of: quaternary ammonium salts, primary to tertiary fatty amine salts, trialkylbenzylammonium salts, alkylpyridinium salts, 2-alkyl-1-hydroxyethylimidazolinium salts, N, N-dialkyl Cationic surfactants such as morpholinium salts and polyethylene polyamine fatty acid amide salts; N, N-dimethyl-N-alkyl-N-carboxymethylammoniobetaine, N, N, N-trialkyl-N-alkyleneammoniocarboxyl Amphoteric surfactants such as betaine, N-acidaminopropyl-N ′, N′-dimethyl-N′-β-hydroxypropylammoniosulfobetaine, and coconut oil fatty acid amidopropylbetaine can be used.
In addition, stevia derivatives such as enzyme-treated stevia, lecithin and derivatives thereof, lactic acid bacteria fermented rice, lactic acid bacteria fermented germinated rice, lactic acid bacteria fermented cereals (wheat, beans, millet, etc.), etc. You can also.

  Examples of humectants include glycerin, propylene glycol, dipropylene glycol, 1,3-butylene glycol, polyethylene glycol, sorbitol, xylitol, sodium pyrrolidonecarboxylate, and sugars such as trehalose, lactic acid bacteria fermented rice, and mucopolysaccharides. (For example, hyaluronic acid and its derivatives, chondroitin and its derivatives, heparin and its derivatives, etc.), elastin and its derivatives, collagen and its derivatives, NMF related substances, lactic acid, urea, higher fatty acid octyldodecyl, seaweed extract, seafood Examples include derived collagen and derivatives thereof, various amino acids and derivatives thereof.

  Thickeners include, for example, algaic acid, agar, carrageenan, fucoidan and other dry algae, green algae or red algae-derived components, beech extract, pectin, locust bean gum, polysaccharides such as aloe polysaccharide, xanthan gum, tragacanth gum, guar gum, etc. Synthetic polymers such as gums, cellulose derivatives such as carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic acid / methacrylic acid copolymer; hyaluronic acid and its derivatives, polyglutamic acid and its derivatives, etc. Is mentioned.

Examples of the antiseptic / bactericidal agent include urea; paraoxybenzoates such as methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and butyl paraoxybenzoate; dibutylhydroxytoluene, phenoxyethanol, dichlorophene, chlorhexidine hydrochloride, chloride Examples include benzalkonium, salicylic acid, ethanol, undecylenic acid, phenols, isopropylmethylphenol, jamal (imidazodenyl urea), 1,2-pentanediol, various essential oils, and bark distillate.
Examples of powder components include sericite, titanium oxide, talc, kaolin, bentonite, zinc oxide, magnesium carbonate, magnesium oxide, zirconium oxide, barium sulfate, silicic anhydride, mica, nylon powder, polyethylene powder, silk powder, and cellulose. System powder, grains (rice, wheat, corn, millet, etc.) powder, beans (soybean, red beans, etc.) powder, etc.

  Examples of the ultraviolet absorber include ethyl paraaminobenzoate, ethylhexyl paradimethylaminobenzoate, amyl salicylate and derivatives thereof, 2-ethylhexyl paramethoxycinnamate, octyl cinnamate, oxybenzone, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -Methoxybenzophenone-5-sulfonate, 4-tertiarybutyl-4-methoxybenzoylmethane, 2- (2-hydroxy-5-methylphenyl) benzotriazole, urocanic acid, ethyl urocanate, aloe extract, etc. .

Examples of physiologically active ingredients include whitening ingredients such as t-cycloamino acid derivatives, kojic acid and its derivatives, ascorbic acid and its derivatives, hydroquinone derivatives, ellagic acid and its derivatives, resorcinol derivatives, pine bark extract, etc. -Dihydroxybenzoic acid derivatives, nicotine derivatives, vitamin E and its derivatives, α-hydroxy acids and the like.
Examples of the kojic acid derivatives include kojic acid esters such as kojic acid monobutyrate, kojic acid monocaprate, kojic acid monopalmitate, kojic acid butyrate, kojic acid ethers, kojic acid sugar derivatives such as kojic acid glucoside, etc. Examples of the acid derivative include L-ascorbic acid-2-phosphate sodium, L-ascorbic acid-2-phosphate magnesium, L-ascorbic acid-2-sulfate sodium, L-ascorbic acid-2-sulfate ester. Ascorbic acid ester salts such as lunamagnesium, L-ascorbic acid-2-glucoside (2-O-α-D-glucopyranosyl-L-ascorbic acid), L-ascorbic acid-5-glucoside (5-O-α-D) Ascorbic acid sugars such as (glucopyranosyl-L-ascorbic acid) Conductors, 6-position acylated products of these ascorbic acid sugar derivatives (acyl groups are hexanoyl, octanoyl, decanoyl, etc.), L-ascorbic acid tetraisopalmitate, L-ascorbic acid tetralaurate, etc. Ascorbic acid tetra fatty acid esters, 3-O-ethylascorbic acid, L-ascorbic acid-2-phosphate-6-O-palmitate sodium, etc., as hydroquinone derivatives, arbutin (hydroquinone-β-D-glucopyranoside) , Α-arbutin (hydroquinone-α-D-glucopyranoside) and the like, and as the resorcinol derivative, for example, 4-n-butylresorcinol, 4-n-butylresorcinol, 4-isoamylresorcinol and the like are 2,5-dihydroxybenzoic acid. Examples of derivatives include 2,5-diacetoxybenzoic acid, 2-acetoxy-5-dihydroxybenzoic acid, 2-hydroxy-5-propionyloxybenzoic acid, etc., and nicotinic acid derivatives include, for example, nicotinamide, benzyl nicotinate, and the like. Examples of the E derivative include vitamin E nicotinate and vitamin E linoleate, and examples of the α-hydroxy acid include lactic acid, malic acid, succinic acid, citric acid, and α-hydroxyoctanoic acid.

  Other salts such as sodium chloride, disodium edetate, trisodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, sequestering agents, caffeine, tannin, verapamil, tranexamic acid and its derivatives Licorice extract, hornon extract, aloe extract, various herbal medicines, drugs such as tocopherol acetate, glycyrrhizic acid and its derivatives or salts thereof, sugars such as glucose, fructose, mannose, sucrose, trehalose, potassium hydroxide, A pH adjusting agent such as an acid, and ethanol or water as a solvent can be appropriately mixed.

  The external preparation for skin of the present invention can be produced according to a conventional method depending on its form and shape, and the mixture of the above-mentioned cationized glyceryl glucoside may be blended in an appropriate production process.

  Hereinafter, the present invention will be specifically described by way of examples.

[Example 1]
[Preparation example 1 of cationized glyceryl glucoside mixture]
A glycidyltrimethylammonium chloride aqueous solution (purity 90%, trade name SY-GTA80; Sakamoto Yakuhin Kogyo Co., Ltd.) is used as a cationizing agent for 200 g of a glyceryl glucoside aqueous solution (purity 75%, trade name Cosarte-2G; manufactured by Toyo Seika Co., Ltd.). 50 g and 50 g sodium hydroxide aqueous solution (concentration 3%) were added and sufficiently stirred, and then left in a constant temperature bath at 60 ° C. for 24 hours. Thereafter, the heat was removed to room temperature and neutralized with 1N hydrochloric acid. In order to remove the unreacted cationizing agent from the neutralized reaction solution, ion-exchanged water was added to 2-propanol (purity 99.7%, special grade reagent; manufactured by Kanto Chemical Co., Inc.), and 95% 2- Propanol aqueous solution (cleaning solution) was prepared, and the same amount of the above cleaning solution was added to the reaction solution and stirred. Then, using a centrifuge (H-108M2; Kokusan Co., Ltd.), rotating at 3000 rpm for 15 minutes at room temperature. Centrifuged. After removing the supernatant with an aspirator, the reaction solution after centrifugation is again filled with an equal amount of washing solution. Repeat the same operation three times until the remaining cationizing agent is removed. It was. Thereafter, the remaining 2-propanol was sufficiently removed by drying under reduced pressure, and then 145 g of cationized glyceryl glucoside was obtained as a final purified product. In this way, a cationized glyceryl glucoside mixture which was a light yellow transparent liquid was obtained. The nitrogen content of this cationized glyceryl glucoside mixture was subjected to elemental analysis using SUMIGRAPH NCH-22F manufactured by Sumika Chemical Analysis Center, and it was 1.72% by mass.

[Example 2]
[Preparation Example 2 of Cationized Glyceryl Glucoside Mixture]
A glycidyltrimethylammonium chloride aqueous solution (purity 90%, trade name SY-GTA80; Sakamoto Yakuhin Kogyo Co., Ltd.) is used as a cationizing agent for 200 g of a glyceryl glucoside aqueous solution (purity 75%, trade name Cosarte-2G; manufactured by Toyo Seika Co., Ltd.). 25 g and 50 g of a sodium hydroxide aqueous solution (concentration 3%) were added and sufficiently stirred, and then left in a constant temperature bath at 60 ° C. for 24 hours. Thereafter, in order to adsorb unreacted cationizing agent, 20 g of cellulose powder (manufactured by Nippon Paper Industries; W-100) and 20 g of activated carbon (Nippon Envirochemicals Inc .; granular white birch KL) are added, The mixture was further stirred for 10 hours. Then, after removing heat to room temperature and removing cellulose powder and activated carbon by filtration, the filtrate was neutralized with 1N hydrochloric acid. The desalting after neutralization was performed using a microacylizer (Astom Corp .; S3), the applied voltage was 4.5 V, and the current value was changed from 0.06 A to 0.01 A. In the solution after desalting, water was left under reduced pressure in a rotary evaporator to obtain 125 g of cationized glyceryl glucoside as a final purified product. In this way, a cationized glyceryl glucoside mixture which was a light yellow transparent liquid was obtained. The nitrogen content of this cationized glyceryl glucoside mixture was subjected to elemental analysis using SUMIGRAPH NCH-22F manufactured by Sumika Chemical Analysis Center. It was 0.68% by mass.

本実施例で合成したカチオン化グリセリルグルコシドは、添加量１０ｗｔ％にも関わらず、グリセリルグルコシドの粘度を大幅に上昇させ、グリセリルグルコシドのカチオン化が確認された。 [Example 3]
[Increased viscosity due to addition of cationized glyceryl glucoside mixture]
A Brookfield viscometer was prepared by adding 10 wt% of the cationized glyceryl glucoside synthesized in Example 1 to a glyceryl glucoside aqueous solution (purity 75%, trade name Cosarte-2G; manufactured by Toyo Seika Co., Ltd.). (Made in Brookfield, USA; RVT), viscosity was measured (room temperature 25 ° C.). Moreover, the viscosity measurement of glyceryl glucoside aqueous solution and glycerol (purity 99.0%; made by Kanto Chemical Co., Inc.) was also performed as a control.
Table 1 Viscosity comparison

Although the cationized glyceryl glucoside synthesized in this example greatly increased the viscosity of glyceryl glucoside despite the addition amount of 10 wt%, cationization of glyceryl glucoside was confirmed.

Hereinafter, the present invention will be described in detail with specific examples of external preparations for skin, but the present invention is not limited thereto. In addition, all compounding quantities are the mass% (actual part).
[Examples 4 to 8 and Comparative Examples 1 to 5]
A hair shampoo having the composition shown in Table 1 below was prepared using the cationized glyceryl glucoside mixture obtained in Example 1 (hereinafter referred to as cationized GG). In addition, all compounding quantities are the mass% (actual part).
Based on the following evaluation criteria using these various hair shampoos, sensory evaluation was performed by 20 panelists on the foam quality at the time of shampooing, the feeling of use at the time of rinsing, the gloss of the hair after drying, and the effect of improving the roughness. The results are shown in the lower part of Table 2.

[Sensory evaluation for washing hair]
Evaluation standard about foaming (double-circle): Out of 20 people, 18 or more evaluated that it was excellent in foaming.
(Circle): It evaluated that 11-17 persons were excellent in foaming among 20 persons.
(Triangle | delta): It evaluated that 5-10 persons were excellent in foaming among 20 persons.
X: It evaluated that 4 or less out of 20 persons were excellent in foaming.
Evaluation criteria for foam texture and stiffness ◎: Out of 20 people, 18 or more were evaluated to be excellent in foam texture and stiffness.
(Circle): It evaluated that 11-17 persons were excellent in the texture of a foam and a firmness among 20 persons.
(Triangle | delta): Five to ten persons evaluated that it was excellent in the texture of a foam and a firmness among 20 persons.
X: It was evaluated that 4 or less out of 20 people were excellent in foam texture and stiffness.
Evaluation Criteria for Fingering ◎: Out of 20 people, 18 or more people evaluated that they were good for fingering.
(Circle): It evaluated that 11-17 persons were excellent according to a finger among 20 persons.
(Triangle | delta): It evaluated that 5-10 people were excellent according to a finger among 20 people.
X: Evaluated that 4 out of 20 people were excellent according to the finger.

[Sensory evaluation for rinsing]
Evaluation Criteria for Fingering ◎: Out of 20 people, 18 or more people evaluated that they were good for fingering.
(Circle): It evaluated that 11-17 persons were excellent according to a finger among 20 persons.
(Triangle | delta): It evaluated that 5-10 people were excellent according to a finger among 20 people.
X: Evaluated that 4 out of 20 people were excellent according to the finger.
Evaluation criteria for feeling of squeezing A: 18 or more of 20 people evaluated that there was no squeaking feeling when rinsing.
◯: Among 20 people, 11 to 17 people evaluated that there was no squeaky feeling when rinsing.
Δ: Among 20 people, 5 to 10 people evaluated that there was no squeaky feeling when rinsing.
X: Of 20 people, 4 or less evaluated that there was no squeaky feeling when rinsing.

[Sensory evaluation after drying]
Evaluation Criteria for Fingering ◎: Out of 20 people, 18 or more people evaluated that they were good for fingering.
(Circle): It evaluated that 11-17 persons were excellent according to a finger among 20 persons.
(Triangle | delta): It evaluated that 5-10 people were excellent according to a finger among 20 people.
X: Evaluated that 4 out of 20 people were excellent according to the finger.
Evaluation Criteria for Comb Street A: Out of 20 people, 18 or more were evaluated as being superior in comb street.
(Circle): It evaluated that 11-17 persons were excellent in comb street among 20 persons.
(Triangle | delta): It evaluated that 5-10 persons were excellent in combing out of 20 persons.
X: It evaluated that 4 or less out of 20 people were excellent in comb street.
Evaluation criteria for suppleness A: Evaluated that 18 or more out of 20 felt supple.
A: It was evaluated that 11 to 17 of 20 people felt supple.
(Triangle | delta): It evaluated that 5-10 persons felt suppleness among 20 persons.
X: Evaluated that 4 or less out of 20 felt supple.

Evaluation Criteria for Good Condition ◎: Out of 20 people, 18 or more evaluated the good condition.
○: Among 20 people, 11 to 17 people evaluated that the condition was good.
Δ: Among 20 people, 5 to 10 people evaluated that the condition was good.
X: Among 20 people, 4 or less people evaluated that the condition was good.
Evaluation criteria for a feeling of tightness ◎: Of 20 people, 18 or more were evaluated to have a finished feeling.
○: Out of 20 people, 11 to 17 people evaluated it as a finished finish.
(Triangle | delta): It evaluated that the finish which made 5-10 persons feel the perfect feeling among 20 persons.
X: It was evaluated that, among 20 people, 4 or less people finished with a tight feeling.
Evaluation Criteria for Shine A: Out of 20 people, 18 or more people evaluated that the hair was shiny.
○: Among 20 people, 11 to 17 people evaluated that the hair had gloss.
(Triangle | delta): 5-10 people evaluated that there was glossiness in hair among 20 people.
X: Of 20 people, 4 or less evaluated that the hair had gloss.

＜作り方・使用感＞
(1)〜(13)の各成分を加熱して均一溶解した後、室温まで冷却して適当な容器に充填した。
得られたシャンプーは、洗髪中においては、豊かな泡立ち、滑らかさ及び指通りの良さを与え、更にすすぎ後においても指通り及び櫛通りは滑らかで、ブローがしやすいものであった。また、乾燥後においても、指通り及び櫛通りは滑らかで、しなやかなでこしのある仕上がり感が得られた。 Furthermore, the following skin external preparations were prepared.
[Example 9] Hair shampoo

<How to make and feel>
The components (1) to (13) were heated and uniformly dissolved, then cooled to room temperature and filled into a suitable container.
The obtained shampoo gave rich foaming, smoothness and good fingering during shampooing, and even after rinsing, the fingering and combing were smooth and easy to blow. In addition, even after drying, the fingers and combs were smooth, and a supple finish feeling was obtained.

＜作り方・使用感＞
(1)〜(18)の各成分を加熱して均一溶解した後、室温まで冷却して適当な容器に充填した。
得られたシャンプーは、洗髪中においては、豊かな泡立ち、滑らかさ及び指通りの良さを与え、更にすすぎ後においても指通り及び櫛通りは滑らかで、ブローがしやすいものであった。また、乾燥後においても、指通り及び櫛通りは滑らかで、しなやかなでこしのある仕上がり感が得られた。 [Example 10] Mild shampoo

<How to make and feel>
The components (1) to (18) were heated and uniformly dissolved, and then cooled to room temperature and filled in a suitable container.
The obtained shampoo gave rich foaming, smoothness and good fingering during shampooing, and even after rinsing, the fingering and combing were smooth and easy to blow. In addition, even after drying, the fingers and combs were smooth, and a supple finish feeling was obtained.

＜作り方・使用感＞
加熱して均一溶解させた(1)〜(4)に均一溶解させた(5)〜(7)を加えてケン化した後、(8)〜(13)の成分を加えて十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたボディシャンプーは、クリーミィな豊かな泡立ちにも拘らず、洗浄時の泡切れに優れていた。また、サッパリとした洗いあがり感にも関わらず、しっとりと潤いのある肌が得られた。 [Example 11] Body shampoo

<How to make and feel>
After saponification by adding (5) to (7) uniformly dissolved in (1) to (4), which was uniformly dissolved by heating, after adding the components (8) to (13) and stirring sufficiently Cooled to room temperature and filled into a suitable container.
The obtained body shampoo was excellent in defoaming at the time of washing despite the creamy rich foaming. In addition, moist and moisturized skin was obtained despite the refreshing feeling.

＜作り方・使用感＞
加熱して均一溶解させた(9)〜(15)に均一溶解させた(1)〜(8)を加えて乳化した後、十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたリンスはすすぎ時において、滑らかな指通りを与え、乾燥後においては、良好なつやを与え、しなやかでしっとりとした感触を与えるものであった。 [Example 12] Hair rinse

<How to make and feel>
After heating and uniformly dissolving (1) to (8) in (9) to (15), the mixture was emulsified and sufficiently stirred, then cooled to room temperature and filled into a suitable container.
The rinse obtained gave a smooth fingering during rinsing, good gloss after drying, and a supple and moist feel.

＜作り方・使用感＞
加熱して均一溶解させた(9)〜(16)に均一溶解させた(1)〜(8)を加えて乳化した後、十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたエモリエントリンスはすすぎ時において、滑らかな指通りを与え、乾燥後においては、良好なつやを与え、しなやかでしっとりとした感触を与えるものであった。 [Example 13] Emollience

<How to make and feel>
(1) to (8) uniformly dissolved in (9) to (16) that had been uniformly dissolved by heating were added and emulsified, and after sufficient stirring, cooled to room temperature and filled into a suitable container.
The obtained emollients gave a smooth finger passage during rinsing, gave a good gloss after drying, and gave a supple and moist feel.

＜作り方・使用感＞
加熱して均一溶解させた(8)〜(14)に均一溶解させた(1)〜(7)を加えて乳化した後、十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたヘアトリートメントスはすすぎ時において、滑らかな指通りを与え、乾燥後においては、良好なつやを与え、しなやかでしっとりとした感触を与えるものであった。 [Example 14] Hair treatment

<How to make and feel>
(1) to (7) uniformly dissolved in (8) to (14) that had been heated and uniformly dissolved were added and emulsified, and after sufficient stirring, cooled to room temperature and filled into a suitable container.
The obtained hair treatments gave a smooth finger passage when rinsing, gave a good gloss after drying, and gave a supple and moist feel.

＜作り方・使用感＞
加熱して均一溶解させた(8)〜(11)に均一溶解させた(1)〜(7)を加えて乳化した後、十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたコンディショニングヘアトリートメントはすすぎ時において、滑らかな指通りを与え、乾燥後においては、良好なつやを与え、しなやかでしっとりとした感触を与えるものであった。 [Example 15] Conditioning hair treatment

<How to make and feel>
After adding (1) to (7) uniformly dissolved in (8) to (11) heated and uniformly dissolved, the mixture was emulsified, sufficiently stirred, cooled to room temperature, and filled into a suitable container.
The resulting conditioning hair treatment gave a smooth fingering during rinsing and a good gloss after drying, giving a supple and moist feel.

＜作り方・使用感＞
(1)〜(9)を加熱して均一溶解させた後、室温まで冷却して(10)の成分を添加して十分に攪拌した後、適当な容器に充填した。
得られたヘアセットローションは毛髪に良好なつやを与え、ベタツキ感も少なくと、滑らかな指通りで、しなやかでしっとりとした感触を与えるものであった。 [Example 16] Hair set lotion

<How to make and feel>
(1) to (9) were heated and uniformly dissolved, then cooled to room temperature, the component (10) was added, and the mixture was sufficiently stirred, and then filled into a suitable container.
The obtained hair set lotion gave the hair good gloss, less stickiness, smooth finger touch, and gave it a soft and moist feel.

＜作り方・使用感＞
加熱して均一溶解させた(11)〜(16)に均一溶解させた(1)〜(10)を加えて乳化した後、十分攪拌した後、室温まで冷却して適当な容器に充填した。
得られたヘアクリームは毛髪に良好なつやを与え、ベタツキ感も少なくと、滑らかな指通りで、しなやかでしっとりとした感触を与えるものであった。 [Example 17] Hair cream

<How to make and feel>
(1) to (10) uniformly dissolved by heating (11) to (16) were added and emulsified, and after sufficient stirring, cooled to room temperature and filled into a suitable container.
The obtained hair cream gave a good gloss to the hair, had a less sticky feeling, gave a smooth and smooth touch, and a soft and moist feel.

※１：微粒子酸化チタン分散体（大日本化成（株）製）
※２：微粒子酸化亜鉛分散体（大日本化成（株）製）
＜作り方・使用感＞
均一溶解させた(11)〜(15)に均一分散させた(1)〜(10)を加えて十分攪拌して乳化した後、適当な容器に充填した。
得られたサンスクリーンは、滑らかに塗布でき、ベタツキ感も少なくと、しなやかでしっとりとした感触を与えるものであった。 [Example 18] Sunscreen

* 1: Fine titanium oxide dispersion (Dainippon Kasei Co., Ltd.)
* 2: Fine zinc oxide dispersion (Dainippon Kasei Co., Ltd.)
<How to make and feel>
(1) to (10) uniformly dispersed in (11) to (15), which were uniformly dissolved, were added, sufficiently stirred and emulsified, and then filled into a suitable container.
The obtained sunscreen was able to be applied smoothly and had a less sticky feeling, giving it a supple and moist feel.

Claims (5)

A mixture of cationized glyceryl glucosides represented by the following general formula (I).
(I)

(In the formula, GG represents a glyceryl glucoside residue, R ₁ , R ₂ , and R ₃ each represent a hydrocarbyl group, X represents a counter anion, and n represents an integer of 1 to 3)   The mixture of cationized glyceryl glucoside according to claim 1, which is an additive for external preparation for skin. A skin external preparation containing a cationized glyceryl glucoside represented by the following general formula (I).
(I)

(In the formula, GG represents a glyceryl glucoside residue, R ₁ , R ₂ , and R ₃ each represent a hydrocarbyl group, X represents a counter anion, and n represents an integer of 1 to 3)   The skin external preparation of Claim 3 containing the cationized glyceryl glucoside which is n = 1 in general formula (I).   The skin external preparation of Claim 3 containing the cationized glyceryl glucoside which is n = 1 and is X = Cl in general formula (I).