JP2008222970A - Aqueous gel, skin care preparation, and cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous gel exhibiting a good feel of use, when used for cosmetics or the like. <P>SOLUTION: The aqueous gel contains a complex consisting of an amphoteric amphiphilic macromolecule compound expressed by general formula (1), having an average molecular weight as determined by GPC of 4,000-2,000,000 and containing 0.1-50.0% of an acyl group and an anionic macromolecule compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an aqueous gel, an external preparation for skin, and a cosmetic. More specifically, the present invention relates to an aqueous gel that can be used as a component of cosmetics, a skin external preparation containing the aqueous gel, and a cosmetic.

  Conventionally, a water-in-oil-in-water emulsion preparation is known as a cosmetic that undergoes phase inversion upon application to the skin and expresses a fresh feeling of use (see Patent Documents 1 and 2).

  However, the water-in-oil-in-water emulsion preparations described in Patent Documents 1 and 2 each have a drawback in that the production efficiency is low because an emulsification step is required twice during production. Further, the water-in-oil-in-water emulsion preparation has a drawback that its stability over time is insufficient. Furthermore, the water-in-oil-in-water emulsion preparation has a drawback that after application, the water-in-oil emulsion particles remain on the skin surface, resulting in stickiness.

  On the other hand, gel preparations using gelling agents typified by carboxyvinyl polymers that have been used in conventional skin external preparations or cosmetics are superior in production efficiency to water-in-oil-in-water emulsion preparations. ing.

However, such a gel preparation has a disadvantage that it is difficult to change it to a fresh feeling during application. In addition, the gel preparation has a disadvantage of low stability because the gel structure easily breaks in the presence of powders such as titanium oxide and iron oxide and in the presence of electrolytes such as ascorbic acid derivatives.
JP-A-11-33391 JP 2002-275029 A

  The present invention has been made in view of the above-mentioned conventional drawbacks, and can maintain a gel preparation stably even in the presence of an electrolyte, and is good for the cosmetic when used as a component such as cosmetic. One object is to provide an aqueous gel that achieves at least one of developing a feeling of use. Another object of the present invention is to provide an external preparation for skin that achieves at least one of expressing excellent stability and obtaining a good feeling during use. Furthermore, another object of the present invention is to provide a cosmetic that achieves at least one of expressing excellent stability and obtaining a good feeling during use.

  The present invention has been made in view of the above problems, and in one aspect, the general formula (1):

[Wherein, n represents an integer of 10 or more, n R ^{1 s} each independently represent a hydrogen atom or an acyl group having 8 to 18 carbon atoms, and n R ^{2 s} each independently represent Represents a carboxymethyl group or a hydrogen atom)
A zwitterionic compound having a weight average molecular weight of 4,000 to 2,000,000 as measured by gel permeation chromatography, wherein the acyl group content in the compound is 0.1 to 50.0% The present invention relates to an aqueous gel containing a complex of an amphiphilic polymer compound and an anionic polymer compound. In another aspect, the present invention relates to a skin external preparation containing the aqueous gel. Furthermore, in another aspect, the present invention relates to a cosmetic containing an aqueous gel.

  According to the aqueous gel of the present invention, there is an excellent effect that it can be stably maintained even in the presence of an electrolyte. Moreover, according to the aqueous gel of this invention, when this aqueous gel is used as components, such as cosmetics, there exists the outstanding effect that a favorable usability | use_condition can be expressed in the said cosmetics. Furthermore, according to the skin external preparation of this invention, there exists an outstanding effect that the outstanding stability is expressed. Moreover, according to the skin external preparation of this invention, there exists an outstanding effect that a favorable usability | use_condition is obtained at the time of use. Furthermore, according to the cosmetics of this invention, there exists the outstanding effect that the outstanding stability is expressed. Furthermore, according to the cosmetic of the present invention, there is an excellent effect that a good usability can be obtained during use.

  In one aspect, the aqueous gel of the present invention has the general formula (1):

[Wherein, n represents an integer of 10 or more, n R ^{1 s} each independently represent a hydrogen atom or an acyl group having 8 to 18 carbon atoms, and n R ^{2 s} each independently represent Represents a carboxymethyl group or a hydrogen atom)
A zwitterionic compound having a weight average molecular weight of 4,000 to 2,000,000 as measured by gel permeation chromatography, wherein the acyl group content in the compound is 0.1 to 50.0% The present invention relates to an aqueous gel containing a complex of an amphiphilic polymer compound and an anionic polymer compound.

  The aqueous gel of the present invention has one major feature in that it contains a complex of the amphoteric amphiphilic polymer compound and the anionic polymer compound.

  The complex is a complex in which the amphoteric amphiphilic polymer compound and the anionic polymer compound are interacted with each other. Therefore, the composite is in a gel state in the absence of stress, but due to the external force acting, part or all of the intermolecular force of the gel structure is reversibly destroyed to become a sol state, On the other hand, when the external force no longer acts, the thixotropic property that the gel structure is regenerated is exhibited.

  Therefore, since the aqueous gel of the present invention contains the complex, when the aqueous gel is used as a component of cosmetics, the cosmetics are used, for example, when applied to the skin. Exhibits a fresh feeling of use, and on the other hand, after use, for example, after application to the skin, exhibits an excellent effect of substantially not exhibiting stickiness and the like. In addition, the composite can maintain the gel state for a long period of time in the absence of stress even in the presence of an electrolyte and / or powder, and also exhibits the thixotropic property. Therefore, according to the aqueous gel of the present invention, an excellent effect of exhibiting long-term stability in the presence of electrolytes and / or powders such as titanium oxide and iron oxide, which has been difficult in the past, is exhibited. To do.

  In the present specification, “an aqueous gel containing a composite” intends that water or the like may be contained in the gel structure of the composite. In the present specification, when a component other than the complex is present in the aqueous gel, a product obtained by further complexing the component with the complex, or the component and the complex react with each other. Even if it contains a product produced as described above, it is intended to be included in the concept of “aqueous gel containing complex” as long as it does not interfere with the object of the present invention.

  In the amphoteric amphiphilic polymer compound represented by the general formula (1), n is preferably an integer of 10 or more, and preferably an integer of 50000 or less from the viewpoint of the ability to form an aqueous gel.

  From the viewpoint of enhancing water solubility, the carboxymethyl group of the amphoteric amphiphilic polymer compound represented by the general formula (1) preferably interacts with a cation such as sodium ion or potassium ion to form a salt. It is desirable to form.

In the amphoteric amphiphilic polymer compound represented by the general formula (1), R ¹ is a hydrogen atom or an acyl group having 8 to 18 carbon atoms. The number of carbon atoms of the acyl group is preferably 8 or more, more preferably 10 or more from the viewpoint of satisfactorily forming a stable gel state, and 18 or less is preferable from the viewpoint of obtaining sufficient water dispersibility of the gel. The acyl group is not particularly limited as long as it excludes the hydroxyl group of the carboxyl group in the carboxylic acid. Oleyl group, linoleyl group and the like. Among these, from the viewpoint of gel forming ability, decanoyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, oleyl group, and linoleyl group are preferable. In the general formula (1), n R ^{1 s} are each independently a hydrogen atom or an acyl group having 8 to 18 carbon atoms.

In the amphoteric amphiphilic polymer compound represented by the general formula (1), R ² is a carboxymethyl group or a hydrogen atom. R ² is preferably a lauroyl group, a myristoyl group, a palmitoyl group, or a stearoyl group from the viewpoint of exhibiting a gel-forming ability having excellent stability. In the general formula (1), n R ^{2 s} are each independently a carboxymethyl group or a hydrogen atom.

The acyl group content in the amphoteric amphiphilic polymer compound is preferably 0.1% or more, more preferably 1.0% or more, and 2.0% or more, from the viewpoint of forming a gel well. Is more preferable, and from the viewpoint of obtaining sufficient water dispersibility of the gel, it is preferably 50% or less, and more preferably 25.0% or less. In this specification, “acyl group content” means the number (ratio) of acyl groups contained in the amphoteric amphiphilic polymer compound represented by the general formula (1), and is 400 MHz. ¹ H-NMR analysis is performed, and the peak area of the methyl group proton of the acyl group detected at the peak position corresponding to 0.8 to 0.9 ppm and the peak position corresponding to 3.0 to 3.3 ppm are detected. This value is determined by the peak area of the proton at the C2 position of the constituent monosaccharide to be detected.

  From the viewpoint of forming a stable gel state, the weight average molecular weight of the zwitterionic amphiphilic polymer compound measured by gel permeation chromatography is 4000 or more, preferably 50000 or more and sufficient. From the viewpoint of obtaining the water dispersibility of the gel, it is 2000000 or less, preferably 1000000 or less. The weight average molecular weight is, for example, GPC-HPLC (gel filtration chromatography column: manufactured by Tosoh Corporation, trade name: TSK-gel-G3000PXL and trade name: TSK-gel-G2500PWXL) connected with a data module GPC cartridge. Solvent: 0.4 M acetic acid-sodium acetate buffer (pH 4.8)] Measured by revealing molecular weight distribution by analysis. As the molecular weight standard, chitosan oligosaccharide (molecular weight: 4131006), dextran sulfate (molecular weight: 5000, 8000), pullulan molecular weight standard and the like are used.

  The anionic polymer compound may be any compound that exhibits water solubility. The anionic polymer compound is preferably a compound that exhibits a thickening action. The “thickening action” is, for example, an action that increases the viscosity by adding it to a non-viscous aqueous solution and imparts a property having a function of giving a sol-like (viscosity but fluidity) viscosity. Say.

  The zeta potential of the anionic polymer compound is −5 mV or more, preferably −20 mV or more, from the viewpoint of exhibiting stable gel-forming ability when the pH is set to 5 to 7 at a 1% aqueous solution concentration. From the viewpoint of obtaining the water dispersibility of such a gel, it is −100 mV or less, preferably −80 mV or less. The zeta potential represents a surface potential that governs the electrostatic repulsion effect by the interfacial electric double layer.

  The anionic polymer compound may be a naturally derived polymer compound or a synthesized polymer compound. The anionic polymer compound is not particularly limited. For example, a compound derived from a polymer compound such as acrylic acid, methacrylic acid, or cellulose (specifically, for example, a poly (meth) acrylic polymer compound) , Anionic cellulose semisynthetic polymer compounds, synthetic polymer compounds derived from natural polymer compounds, etc.); polymer compounds such as homopolymers or copolymers mainly composed of vinyl alcohol; amino acid polymers; polysaccharides or the like A salt or a derivative thereof; collagen; a mixture thereof. More specifically, the anionic polymer compound is not particularly limited. For example, an alkyl-modified carboxyvinyl polymer (for example, manufactured by Goodrich, product name: pemlen, etc.), a carboxyvinyl polymer (for example, manufactured by Goodrich) , Trade name: Carbopol, manufactured by Wako Pure Chemical Industries, Ltd., trade name: Hibis Wako, etc.), carboxymethylcellulose, carboxymethylhydroxyethylcellulose, alkyl acrylate / methacrylic acid steareth-20 copolymer (for example, manufactured by Rohm and Haas) , Trade name: Aculin 22), acrylic copolymer (for example, manufactured by Rohm and Haas, trade name: Aculin 33), acrylates / steareth-20 methacrylate copolymer (for example, manufactured by Rohm and Haas, Product name: Acrine 88), acrylates / steares-20 itacolate copolymer, polyacrylic acid, acrylates / behenes methacrylate 25 copolymer, acrylates / laureth methacrylate 25 copolymer, acrylates / vinyl neodecanoate cross copolymer, alkyl acrylate / methacrylic Acid steareth-20 crosspolymer, acrylates / stearemethacrylate methacrylate cross copolymer, succinylated collagen, carboxymethyl chitin, succinylated chitosan, sodium cellulose sulfate, gelatin, pectic acid, gum arabic, mucin, carrageenan, dehydroxanthan gum, dextran, Xanthan gum, chondroitin sulfate, carrageenan, hyaluronic acid, γ-polyglutamic acid, alginic acid, etc. I can get lost. Among these, from the viewpoint of obtaining good gel-forming ability and gel stability, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, carboxymethylcellulose, alkyl acrylate / stealaceth methacrylate-20 copolymer, acrylic copolymer, acrylates / methacrylic are preferred. Acid steareth-20 copolymers, acrylates / vinyl neodecanoate cross-copolymers, polyacrylic acid, xanthan gum, chondroitin sulfate, hyaluronic acid, γ-polyglutamic acid, carboxymethyl chitin, succinyl chitosan are preferred. The “(meth) acryl” means “acryl” and / or “methacryl”.

  In the aqueous gel of the present invention, the composite is obtained by mixing a zwitterionic amphiphilic polymer compound and an anionic polymer compound in a mass ratio (amphoteric amphiphilic polymer compound / anionic polymer compound). ) Is preferably 1/100 to 100/1. Here, the mass ratio is preferably 1/100 or more, more preferably 1/10 or more, from the viewpoint of sufficiently exhibiting good gel-forming ability and function, and from the viewpoint of sufficiently exhibiting the function. The ratio is preferably 100/1 or less, more preferably 10/1 or less.

  The aqueous gel of the present invention may further contain an electrolyte. Since the aqueous gel of the present invention contains the composite, the gelling agent used alone in conventional aqueous gels (for example, homopolymer or copolymer mainly composed of acrylic acid, methacrylic acid, vinyl alcohol, etc.) Unlike the case of alkyl-modified carboxyvinyl polymer, carboxyvinyl polymer, polymer formed from carboxymethyl cellulose, which is a synthetic polymer compound such as, etc., even in the case of containing an electrolyte, the gel state in a stress-free state The excellent effect of being able to maintain good is exhibited. Therefore, the aqueous gel of the present invention is more excellent in stability when an electrolyte is contained than the conventional aqueous gel. Moreover, according to the aqueous gel of the present invention, even when an electrolyte is contained, cosmetics having higher viscosity than conventional gels (for example, oil-in-water creams, essence preparations, etc.) are obtained. Is possible. The content of the electrolyte in the aqueous gel is 0.01 to 10.00% by mass.

  The electrolyte may be any substance that can be used in cosmetics, and specific examples include ascorbic acid or a derivative thereof.

  According to the aqueous gel of the present invention, in the case of an aqueous gel containing a gelling agent used alone in conventional aqueous gels, the ascorbic acid or its derivative, for example, ascorbine, which has been difficult to maintain the gel structure. Acid phosphoric acid ester salts such as ascorbic acid phosphoric acid ester sodium salt, ascorbic acid phosphoric acid ester magnesium salt, and ascorbic acid glucoside can be used. According to the aqueous gel of the present invention containing such ascorbic acid or a derivative thereof, effects such as a whitening effect (melanin reducibility), an effect of promoting collagen production, an effect of removing active oxygen, an anti-acne effect based on sebum suppression, etc. Manufacture of the stable cosmetics etc. which express can be performed simply. Further, according to the aqueous gel of the present invention, for example, even in the pH range (pH 8 to 9) in which the ascorbic acid phosphate salt is stably maintained, the gel state in a stress-free state is stably maintained. Therefore, it is possible to stabilize an active ingredient that is stably maintained in the pH range used for cosmetics and the like.

  The aqueous gel of the present invention may further contain a polyhydric alcohol from the viewpoint of improving the temporal stability of physical properties such as viscosity. Examples of the polyhydric alcohol include 1,3-butylene glycol, dipropylene glycol, glycerin, diglycerin, pentadiol, polyethylene glycol, sorbitol, mannitol and the like. The content of the polyhydric alcohol in the aqueous gel is 0.1 to 80.0% by mass.

  The pH value of the aqueous gel of the present invention is 5.0 to 10.0. From the viewpoint of obtaining sufficient gel-forming ability and gel stability, the pH value is preferably 5.5 or more, more preferably 6.5 or more, and from the viewpoint of obtaining sufficient water dispersibility of the gel. Preferably, it is 9.5 or less, more preferably 8.5 or less.

  The viscosity of the aqueous gel of the present invention can be evaluated by measuring at 25 ° C. using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER) at a rotational speed of 6 rpm.

  Further, for the aqueous gel of the present invention, the viscosity at 25 ° C. was measured at a rotational speed of 6 rpm and a rotational speed of 60 rpm using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER). The thixotropy can be evaluated by determining the ratio of the viscosity at a rotational speed of 60 rpm to the viscosity when the rotational speed is 6 rpm. In the aqueous gel of the present invention, the ratio of the viscosity at a rotational speed of 60 rpm to the viscosity at the rotational speed of 6 rpm is, for example, about 2.0 to 7.0, and expresses high thixotropic properties.

  The aqueous gel of the present invention is, for example, 0.01 to 100 times as a mass ratio with respect to the amphoteric amphiphilic polymer compound while stirring the aqueous solution of the amphoteric amphiphilic polymer compound. The anionic polymer compound is gradually added so that the amount becomes an amount, and then the resulting mixture is stirred with a stirrer such as a homomixer, for example, at 1000 rpm for 1 minute, so that the amphoteric amphiphilic property is increased. It can be easily obtained by complexing a polymer compound and an anionic polymer compound. By such complexing, for example, the amino group present in the amphoteric amphiphilic polymer compound and the anion site of the anionic polymer compound interact electrostatically, and the amphoteric amphiphilic polymer compound is high. Hydrophobic interaction with the hydrophobic group of the molecular compound causes the ionic amphiphilic polymer compound and the anionic polymer compound to form a network structure that is a three-dimensional network structure. In addition, this complexing can cause a repulsive action between, for example, the carboxyl group of the amphoteric amphiphilic polymer compound and the anion site of the anionic polymer compound. It forms a gel that can be solated by the action. The compounding of the amphoteric amphiphilic polymer compound and the anionic polymer compound has an advantage that it can be carried out at room temperature.

  Since the aqueous gel of the present invention is also excellent in emulsification ability, according to the aqueous gel of the present invention, it is possible to produce an oil-in-water emulsion formulation without using a conventionally used low molecular surfactant. Become. That is, according to the aqueous gel of the present invention, a liquid oil agent can be stably emulsified without using a conventionally used low molecular surfactant. Therefore, the water-based gel of the present invention can be widely applied to emulsified cosmetics and external preparations that have a refreshing use feeling and a skin roughening-improving action that are not present in the past, and that are not sticky after application. In addition, the aqueous gel of the present invention exhibits excellent uniform dispersibility with respect to titanium oxide, zinc oxide, ultraviolet absorbers, pigments, and the like, and also exhibits excellent water resistance. It is also useful for UV-protective cosmetics, external preparations for skin, emulsified foundations and the like having a fresh and fresh feeling of use.

  Furthermore, the aqueous gel of the present invention can be widely applied to pharmaceuticals applied to the skin; quasi drugs applied to the skin, hair, oral cavity, etc .; cosmetics and the like. The aqueous gel of the present invention can be applied to a wide variety of preparations such as gel preparations, solubilized preparations, emulsion preparations, slightly viscous sol preparations, essence preparations, liquid preparations, water-oil two-layer preparations, and powder-containing preparations.

  In another aspect, the present invention relates to a skin external preparation containing the aqueous gel of the present invention. Since the skin external preparation of the present invention contains the aqueous gel of the present invention, it exhibits an excellent effect of exhibiting excellent stability. Moreover, according to the skin external preparation of this invention, since the aqueous gel of this invention is contained, the outstanding effect that a favorable usability is obtained at the time of use is exhibited.

  The external preparation for skin of the present invention may further contain components defined in the quasi-drug raw material standard, the cosmetic ingredient-specific formulation standard, the cosmetic raw material standard, the Japanese pharmacopoeia, the food additive official standard, and the like. Such ingredients include moisturizing softeners, antioxidants, astringents, whitening agents, antibacterial agents, anti-inflammatory agents, antibacterial agents, antiallergic agents, UV absorbers, UV scattering agents, stabilizers, vitamins, enzymes Etc.

  In addition, the external preparation for skin of the present invention includes, as an active ingredient, for example, a component having a whitening effect by inhibiting tyrosinase activity, a component having a whitening effect by melanin reduction, an anti-aging component that activates skin cells, a skin cell You may contain the component which suppresses oxidation.

  The “component having a whitening effect by inhibiting tyrosinase” is not particularly limited, and examples thereof include compounds contained in herbal extracts or plant extracts (eg, polyphenol compounds, isoflavan compounds, etc.), ellagic acid, arbutin, hydroquinone. And higher unsaturated fatty acids such as kojic acid linoleic acid, ethyl linoleate, and linolenic acid. The herbal extract is not particularly limited, and examples thereof include oil-soluble licorice extract and licorice flavonoids containing grabrizine, grabredin or lycochalcone. In addition, the compound contained in the herbal extract is not particularly limited, and examples thereof include lycochalcone, grabridine, grabredin, and licorice flavonoids. Examples of the plant extract include soy extract containing soy isoflavone, plant extract containing ferulic acid, plant containing Pycnogenol, Clara extract, Ammarok fruit extract, Sahakuhihi extract, Yukinoshita extract, rosemary extract; And plant extract Ogon extract containing hesperidin or quercetin. Specific examples of the compound contained in the plant extract include, but are not particularly limited to, for example, soybean isoflavone, ferulic acid, pycnogenol, rutin, hesperidin, quercetin; plant polyferol derived from grape, acerola, and the like. It is done.

  Examples of the “component having a whitening effect by melanin reducing action” include SH compounds such as glutathione, acetylcysteine, and cysteine; ascorbic acid, derivatives thereof, and salts thereof. Examples of the derivatives of ascorbic acid and salts thereof include water-soluble ascorbic acid such as sodium ascorbate phosphate, magnesium ascorbate phosphate magnesium, palmitoylated ascorbic acid phosphate and salts thereof, and the like. Derivatives: Ascorbyl tetraisopalmitate (for example, product name: VCIP, manufactured by Nikko Chemicals), ascorbyl palmitate, ascorbyl isopalmitate, ascorbyl stearate, ascorbyl diisopalmitate, alkyl ascorbate, alkyl ascorbate Examples also include hydrophobic ascorbic acid derivatives such as esters (oil-soluble vitamin C derivatives); ascorbic acid polypeptides.

  Examples of the “anti-aging component that activates skin cells” include retinol and retinol derivatives. Examples of the retinol derivative include retinol acetate and retinol palmitate.

  Examples of the “component that suppresses oxidation of skin cells” include vitamin E, vitamin E derivatives, and the like. Examples of the vitamin E derivative include tocopherol nicotinate, tocopherol linoleate, and tocopherol succinate.

  In the external preparation for skin of the present invention, as long as it does not interfere with the purpose of the present invention, ingredients generally used in the external preparation for skin are widely blended within a range that does not impair the effects and functionality of the aqueous gel of the present invention. sell. The components generally used in the above-mentioned external preparation for skin are not particularly limited. For example, higher alcohols such as cetanol and behenyl alcohol; nonpolar oils such as liquid paraffin and squalane; ester systems such as isopropyl palmitate and isopropyl myristate Oils; vegetable oils such as wheat germ oil and olive oil; silicone compounds such as trimethylsiloxysilicic acid and methylphenylpolysiloxane; fluorine compounds such as perfluoropolyether.

  The external preparation for skin of the present invention may appropriately contain a surfactant that can be usually used for external preparations for skin. The surfactant is not particularly limited as long as it is a low molecular surfactant, and examples thereof include nonionic surfactants such as fatty acid monoglycerides, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, and polyglycerin fatty acid esters. A cationic surfactant such as benzalkonium chloride; an amphoteric surfactant; an anionic surfactant;

  Since the external preparation for skin of the present invention contains the aqueous gel of the present invention, even if the external preparation for skin contains powders, pigments, etc., stability and effectiveness superior to those of the prior art. And can be provided as a gel-like external preparation and a gel-form emulsified external preparation exhibiting high viscosity and high thixotropic properties.

  In another aspect, the present invention relates to a cosmetic containing the aqueous gel of the present invention. Furthermore, according to the cosmetics of this invention, there exists the outstanding effect that the outstanding stability is expressed. Furthermore, according to the cosmetic of the present invention, an excellent effect is obtained in that a good feeling during use can be obtained.

  The cosmetic of the present invention can be made into an oil-in-water emulsion by further adding a liquid oil agent. The present invention also includes a cosmetic that is an oil-in-water emulsion and further contains a liquid oil.

  The liquid oil is not particularly limited, and examples thereof include liquid paraffin, squalane, isononyl isononanoate, isotridecyl isononanoate, cetyl ethylhexanoate, glyceryl tri-ethylhexanoate, glycerin tri (capryl / capric acid), cetyl palmitate Ester liquid oils such as 2-hexyldecyl isostearate, stearyl stearate, isostearyl myristate, neopentyl glycol di-2-ethylhexanoate, neopentyl glycol dicaprate, glyceryl diisostearate, propylene glycol distearate; Plant liquid oils such as oil, rice bran oil, evening primrose oil, wheat germ oil, olive oil, jojoba oil, grape seed oil, chamomile oil, grape seed oil, rosemary oil, fennel oil And animal-based liquid oils, such as egg yolk oil. Content of the said liquid oil agent in cosmetics is 0.1-60.0 mass%.

  The cosmetic of the present invention may further contain an ultraviolet absorber or an ultraviolet scattering agent. When the cosmetic of the present invention further contains an ultraviolet absorber or an ultraviolet scattering agent, the cosmetic exhibits an excellent effect that it is not re-emulsified on the skin. Therefore, according to the present invention, Cosmetics can also be provided as an oil-in-water emulsion containing an ultraviolet absorber or ultraviolet scattering agent that is excellent in water resistance.

  Examples of the ultraviolet absorber include, but are not limited to, cinnamic acid derivatives such as ethylhexyl paramethoxycinnamate; salicylic acid derivatives such as octyl salicylate; dibenzoylmethane derivatives such as butylmethoxydibenzoylmethane, and the like.

  The ultraviolet scattering agent is not particularly limited. For example, titanium oxide or zinc oxide hydrophilized with titanium oxide, zinc oxide, zirconium oxide, cerium oxide, alumina or the like (alumina-coated titanium oxide, alumina-coated zinc oxide). ), Titanium oxide and zirconium oxide (for example, silicone-coated titanium oxide, stearic acid-coated titanium oxide, and silicone-coated zirconium oxide) that have been subjected to a hydrophobizing treatment with silicone or fatty acid.

  As long as the cosmetic of the present invention does not interfere with the object of the present invention, ingredients generally used in cosmetics are appropriately blended within a range that does not impair the effects and functionality of the aqueous gel of the present invention. Also good. Ingredients generally used in the cosmetic are not particularly limited. For example, higher alcohols such as cetanol and behenyl alcohol; nonpolar oils such as liquid paraffin and squalane; ester oils such as isopropyl palmitate and isopropyl myristate Vegetable oils such as wheat germ oil and olive oil; silicone compounds such as trimethylsiloxysilicic acid and methylphenylpolysiloxane; fluorine compounds such as perfluoropolyether;

  Moreover, the cosmetics of this invention may contain the surfactant normally used for cosmetics suitably. Examples of the surfactant include, but are not limited to, nonionic surfactants such as fatty acid monoglycerides, polyoxyethylene fatty acid esters, polyoxyethylene alkyl ethers, and polyglycerin fatty acid esters; cationic interfaces such as benzalkonium chloride Activators; amphoteric surfactants; anionic surfactants and the like.

  Furthermore, the cosmetics of the present invention may appropriately contain ingredients defined in the quasi-drug raw material standard, the composition standard for each cosmetic variety, the cosmetic raw material standard, the Japanese Pharmacopoeia, the official standard for food additives, and the like. . Such ingredients include moisturizing softeners, antioxidants, astringents, whitening agents, antibacterial agents, anti-inflammatory agents, antibacterial agents, antiallergic agents, UV scattering agents, stabilizers, vitamins, enzymes and the like. .

  The cosmetic of the present invention can be provided as a preparation such as a creamy skin care agent, an emulsion makeup base, an emulsified mascara, or a foundation. Among them, since the cosmetic of the present invention contains the aqueous gel of the present invention, even when it contains powder, pigment, etc., it shows stability, effectiveness, etc. superior to conventional ones, It can be provided as a gel-like cosmetic or a gel-like emulsified cosmetic showing high viscosity and high thixotropic properties.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to this Example.

(Experimental example 1)
Carboxymethyl chitosan was prepared according to the method described in “Chitin / Chitosan Handbook” (edited by Chitin / Chitosan Study Group, page 241, Gihodo Publishing, 1995). 20 g of carboxymethyl chitosan was dissolved in 400 mL of a 10% by mass acetic acid aqueous solution. To the obtained solution, 1 L of ethanol and 1 L of methanol were added and stirred sufficiently to obtain a carboxymethyl chitosan solution.

  Thereafter, myristic anhydride was gradually added to the obtained carboxymethyl chitosan solution so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was maintained at 45 ° C. under reflux for 8 hours, thereby reacting the myristic anhydride with the carboxymethyl chitosan.

The product after the reaction was subjected to a dialysis membrane (Millipore, fractional molecular weight: 10,000) to remove unbound fatty acid (myristic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was then washed in turn with ether, acetone and ether and dried to give N-myristoylated carboxymethyl chitosan in the form of a white powder. Thereafter, the obtained N-myristoylated carboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of myristoylation of the obtained N-myristoylated carboxymethyl chitosan was 8.7%.

  The weight average molecular weight of the obtained N-myristoylated carboxymethylchitosan was determined by GPC-HPLC [gel filtration chromatography column: manufactured by Tosoh Corporation, trade name: TSK-gel-G3000WXL Name: TSK-gel-G2500PWXL, solvent: 0.4 M acetic acid-sodium acetate buffer (pH 4.8)] analysis (GPC analysis) was determined by determining the molecular weight distribution. As molecular weight standards, chitosan oligosaccharide (molecular weight: 413 to 1006), dextran sulfate (molecular weight: 5000, 8000), pullulan molecular weight standard, protein molecular weight standard, and the like were used. As a result, it was suggested that the weight average molecular weight was about 600,000.

(Experimental Examples 2-9)
In the carboxymethyl chitosan solution in Experimental Example 1, myristic anhydride was added to 0.001 molar equivalent, 0.015 molar equivalent, 0.06 molar equivalent, 0.13 molar equivalent, 0.25 molar equivalent of the carboxymethyl chitosan. The degree of acylation (degree of myristoylation) is 0.1 by the same method as in Example 1 except that 0.52 molar equivalent, 0.58 molar equivalent, and 0.1 molar equivalent are added. % (Experimental Example 3), 1.2% (Experimental Example 4), 5.5% (Experimental Example 5), 10.5% (Experimental Example 6), 22.5% (Experimental Example 7), 48.6 % (Experimental Example 8) and 55.8% (Experimental Example 9) of N-myristoylated carboxymethyl chitosan were obtained. Carboxymethyl chitosan was used as carboxymethyl chitosan having a degree of myristoyl formation of 0% (Experimental Example 2).

(Experimental example 10)
Acetic anhydride was gradually added to the carboxymethyl chitosan solution in Experimental Example 1 so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was maintained at 45 ° C. under reflux for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, fractional molecular weight: 10,000) to remove unbound fatty acid (acetic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-acetylcarboxymethylchitosan. The obtained N-acetylcarboxymethyl chitosan was subjected to 500 MHz ¹ H-NMR analysis. As a result, it was shown that the acetylation degree of the obtained N-acetylcarboxymethylchitosan was 9.2%. GPC analysis suggested that the weight average molecular weight was about 450,000.

(Experimental example 11)
To the carboxymethyl chitosan solution in Experimental Example 1, malonic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was maintained at 45 ° C. under reflux for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (malonic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-malonylcarboxymethyl chitosan. The obtained N-malonylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the malonylation degree of the obtained N-malonylcarboxymethyl chitosan was 8.5%. GPC analysis suggested that the weight average molecular weight was about 550000.

(Experimental example 12)
To the carboxymethyl chitosan solution in Experimental Example 1, succinic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was maintained at 45 ° C. under reflux for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, fractional molecular weight: 10,000) to remove unbound fatty acid (succinic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-succinylcarboxymethyl chitosan. The obtained N-succinylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of succinylation of the obtained N-succinylcarboxymethyl chitosan was 8.3% of N-succinylcarboxymethyl chitosan. GPC analysis suggested that the weight average molecular weight was about 500,000.

(Experimental example 13)
Butyric anhydride was gradually added to the carboxymethyl chitosan solution in Experimental Example 1 so as to be 0.1 molar equivalent of the carboxymethylated chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (butyric acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried to give N-butylcarboxymethyl chitosan. The obtained N-butylcarboxymethylchitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of butyrylation of the obtained N-butylcarboxymethylchitosan was 7.9%. GPC analysis suggested that the weight average molecular weight was about 600000.

(Experimental example 14)
To the carboxymethyl chitosan solution in Experimental Example 1, octanoic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, fractional molecular weight: 10,000) to remove unbound fatty acid (octanoic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-octanoylcarboxymethyl chitosan. The obtained N-octanoylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the obtained N-octanoylcarboxymethylchitosan had a degree of octanoylation of 9.2%. GPC analysis suggested that the weight average molecular weight was about 400,000.

(Experimental example 15)
Phthalic anhydride was gradually added to the carboxymethyl chitosan solution in Experimental Example 1 so as to be 0.1 molar equivalent of the carboxymethylated chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (phthalic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-phthaloylcarboxymethyl chitosan. The obtained N-phthaloylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of phthaloylation of the obtained N-phthaloylcarboxymethyl chitosan was 8.5%. GPC analysis suggested that the weight average molecular weight was about 500,000.

(Experimental example 16)
To the carboxymethyl chitosan solution in Experimental Example 1, decanoic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, fractional molecular weight: 10,000) to remove unbound fatty acid (decanoic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-decanoylcarboxymethyl chitosan. The obtained N-decanoylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the decanoylation degree of the obtained N-decanoyl carboxymethyl chitosan was 8.8%. GPC analysis suggested that the weight average molecular weight was about 550000.

(Experimental example 17)
To the carboxymethyl chitosan solution in Experimental Example 1, lauric anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was applied to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (lauric acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-lauroylcarboxymethyl chitosan. The obtained N-lauroylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of lauroylation of the obtained N-lauroylcarboxymethylchitosan was 9.5%. GPC analysis suggested that the weight average molecular weight was about 650000.

(Experiment 18)
To the carboxymethyl chitosan solution in Experimental Example 1, palmitic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was kept at reflux at 45 ° C. for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (palmitic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-palmitoylcarboxymethylchitosan. The obtained N-palmitoyl carboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the degree of palmitoylation of the obtained N-palmitoyl carboxymethyl chitosan was 8.5%. GPC analysis suggested that the weight average molecular weight was about 700,000.

(Experimental example 19)
Stearic anhydride was gradually added to the carboxymethyl chitosan solution in Experimental Example 1 so as to be 0.1 molar equivalent of the carboxymethyl chitosan. The resulting mixture was maintained at reflux at 45 ° C. for 8 hours. GPC analysis suggested that the weight average molecular weight was about 700,000.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (stearic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-stearoylcarboxymethyl chitosan. The obtained N-stearoyl carboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the obtained N-stearoyl carboxymethyl chitosan had a stearoylation degree of 8.1%. GPC analysis suggested that the weight average molecular weight was about 700,000.

(Experiment 20)
To the carboxymethyl chitosan solution in Experimental Example 1, oleic anhydride was gradually added so as to be 0.1 molar equivalent of the carboxymethylated chitosan. The resulting mixture was maintained at 45 ° C. under reflux for 8 hours.

The obtained product was subjected to a dialysis membrane (Millipore, molecular weight cut off: 10,000) to remove unbound fatty acid (oleic acid). The obtained product was subjected to acetone precipitation to obtain a precipitate. The resulting precipitate was washed in turn with ether, acetone and ether and dried, thereby obtaining N-oleylcarboxymethyl chitosan. The obtained N-oleylcarboxymethyl chitosan was subjected to ¹ H-NMR analysis at 500 MHz. As a result, it was shown that the oleylation degree of the obtained N-oleyl carboxymethyl chitosan was 7.8%. GPC analysis suggested that the weight average molecular weight was about 650000.

(Test Example 1)
1 g of carboxymethyl chitosan or N-myristoyl carboxymethyl chitosan of Experimental Examples 2 to 9 was dispersed in 100 mL of purified water to obtain a carboxymethyl chitosan dispersion or N-myristoyl carboxymethyl chitosan dispersion. Moreover, 0.3 g of carbovinyl vinyl polymer which is an anionic polymer compound was dispersed with 47 mL of purified water to obtain an anionic polymer compound dispersion.

  To the carboxymethyl chitosan dispersion or N-myristoylcarboxymethyl chitosan, the anionic polymer compound dispersion was gradually added at room temperature while stirring with a stirrer. 3 g of butylene glycol, which is a polyhydric alcohol, was added to the resulting mixture. Then, it was made to stir at room temperature for 2 minutes at 5000 rpm with the homomixer. Subsequently, the obtained product was allowed to stand at room temperature for 24 hours.

  About the obtained product, the gel forming ability was evaluated by measuring the viscosity at a rotational speed of 6 rpm using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER). In addition, the gel forming ability, when the viscosity is remarkably increased before and after standing for 24 hours to form a gel, and the viscosity is 10000 mPa · s or more, “good”, the viscosity increases to form a gel, The case where the viscosity was less than 10,000 mPa · s was evaluated as “good”, and the case where no gel was formed due to an increase in viscosity was evaluated as “bad”. The results are shown in Table 1.

  As a result, as shown in Table 1, it is understood that a gel is formed when the acylation degree is 0.1 to 48.6%.

(Test Example 2)
In the same manner as in Test Example 1, the gel-forming ability of the gel obtained by complexing the N-acylated carboxymethyl chitosan of Experimental Example 1 and Experimental Examples 10 to 20 with the carboxyl vinyl polymer that is an anionic polymer compound was evaluated. did.

  About the obtained product, the gel forming ability was evaluated by measuring the viscosity at a rotational speed of 6 rpm using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER). In addition, the gel forming ability, when the viscosity is remarkably increased before and after standing for 24 hours to form a gel, and the viscosity is 10000 mPa · s or more, “good”, the viscosity increases to form a gel, The case where the viscosity was less than 10,000 mPa · s was evaluated as “good”, and the case where no gel was formed due to an increase in viscosity was evaluated as “bad”. The results are shown in Table 2.

  As a result, as shown in Table 2, in the case of N-acylated carboxymethyl chitosan having 8 to 18 carbon atoms, a gel is formed.

  Furthermore, the N-acylated carboxymethyl chitosan was evaluated for emulsifying ability with respect to squalane which is a liquid oil agent. 1 g of carboxymethyl chitosan or N-acylated carboxymethyl chitosan of Experimental Examples 10 to 20 was dispersed in 100 mL of purified water to obtain a carboxymethyl chitosan dispersion or an N-acylated carboxymethyl chitosan dispersion. While gradually adding 50 g of squalane as a liquid oil to these dispersions, the mixture was stirred at 7000 rpm for 2 minutes at 60 ° C. with a homomixer. Subsequently, the obtained product was allowed to stand at room temperature for 48 hours.

  The squalane emulsification ability is “good” when the emulsion is formed and left to stand for 48 hours without separation, and “good” when the emulsion is formed but left to stand for 48 hours. The case where it was not formed was evaluated as “bad”. The results are shown in Table 3.

  As a result, as shown in Table 3, it can be seen that carboxymethylated-N-acylated chitosan having 8 to 18 carbon atoms exhibits squalane emulsifying ability.

(Test Example 3)
1 g of N-myristoylcarboxymethylchitosan (degree of myristoylation: 8.7%) obtained in Experimental Example 1 was dispersed in 100 mL of purified water to obtain a N-myristoylcarboxymethylchitosan dispersion.

  Also, 0.3 g of anionic polymer compound, amphoteric polymer compound, nonionic polymer compound or cationic polymer compound was dispersed in 47 mL of purified water to obtain an anionic polymer compound dispersion.

  The polymer compound dispersion was gradually added to the N-myristoylcarboxymethylchitosan dispersion at room temperature while stirring with a stirrer. 3 g of butylene glycol, which is a polyhydric alcohol, was added to the resulting mixture. Then, it was made to stir at room temperature for 2 minutes at 5000 rpm with the homomixer. Subsequently, the obtained product was allowed to stand at room temperature for 24 hours. The viscosity of the resulting product was measured at 25 ° C. at 6.0 rpm using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER).

  The gel-forming ability of the resulting product is “good” when the viscosity is remarkably increased before and after standing for 24 hours, and the viscosity is 10000 mPa · s or more. However, the case where the viscosity was less than 10,000 mPa · s was evaluated as “Poor”, and the case where no gel was formed due to the increase in viscosity was evaluated as “Poor”.

  The viscosity of the product was measured using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER) at 25 ° C. when the rotational speed was 6.0 rpm.

  Further, the obtained product was maintained at 40 ° C. for 2 months, and the viscosity was measured in the same manner as described above. Subsequently, the viscosity reduction rate of the gel before and after the maintenance after 2 months at 40 ° C. was determined. The stability of the gel indicates that the viscosity reduction rate is less than 20%, “good”, the viscosity reduction rate is 20-50%, “good”, the viscosity reduction rate exceeds 50%. , Evaluated as “bad”.

  The viscosity of the product was measured using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER) at 25 ° C. at 6.0 rpm and 60.0 rpm. . The ratio of the viscosity at 60.0 rpm to the viscosity at 6.0 rpm was calculated. The thixotropic property of the gel is “good” when the ratio is 3.0 or more, “good” when the ratio is less than 2.0 to 3.0, and the ratio is less than 2.0. The case was evaluated as “bad”.

  These results are shown in Tables 4-7.

  As a result, as shown in Table 4, when N-myristoylcarboxymethyl chitosan of Experimental Example 1 and an anionic polymer compound are used, a colorless translucent gel having a high viscosity of 10,000 mPa · s is obtained. I understand that. In addition, as shown in Table 4, this gel is excellent in stability and exhibits high thixotropic properties. Therefore, when the gel obtained by using N-myristoylcarboxymethyl chitosan of Experimental Example 1 and an anionic polymer compound is applied to the skin, the gel is solated and instantaneously phase-inverted and changed, It is suggested that a fresh feeling is obtained. On the other hand, as shown in Tables 5 to 7, when N-myristoylcarboxymethylchitosan of Experimental Example 1 and an amphoteric polymer compound, nonionic polymer compound or cationic polymer compound were used, It can be seen that a gel having inferior gel forming ability, stability and thixotropy is produced as compared with the case of using 1 N-myristoylcarboxymethyl chitosan and an anionic polymer compound.

(Example 1)
Gelled preparations having the compositions shown in Table 8 were prepared.

  Glycerin, dipropylene glycol, sodium ascorbate phosphate, ethanol, methyl parahydroxybenzoate, sodium hydroxide, and purified water were mixed and heated to 60 ° C. Gel was added and dispersed in the resulting mixture. The obtained dispersion was left to gel for 24 hours to obtain a gelled preparation (pH: 6.8).

  For the obtained gelled preparation, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation when the rotational speed was 6 rpm was 25000 mPa · s. Moreover, the ratio of the viscosity value at the rotational speed of 60 rpm to the viscosity value at the rotational speed of 6 rpm was 5.1, indicating that the gelled preparation exhibits high thixotropic properties.

(Example 2)
Gelled preparations having the compositions shown in Table 9 were prepared.

  Glycerin, dipropylene glycol, sodium ascorbate phosphate, ethanol, methyl parahydroxybenzoate, sodium hydroxide, and purified water were mixed and heated to 60 ° C. Gel was added and dispersed in the resulting mixture. The obtained dispersion was left to gel for 24 hours to obtain a gelled preparation (pH: 7.2).

  For the obtained gelled preparation, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 31000 mPa · s. Moreover, the ratio of the viscosity value at the rotational speed of 60 rpm to the viscosity value at the rotational speed of 6 rpm was 5.4, and it was shown that the gelled preparation exhibits high thixotropic properties.

(Example 3)
Gelled preparations having the compositions shown in Table 10 were prepared.

  Glycerin, dipropylene glycol, sodium ascorbate phosphate, ethanol, methyl parahydroxybenzoate, sodium hydroxide, and purified water were mixed and dissolved by heating at 50 ° C. Gel was added and dispersed in the resulting mixture. The obtained dispersion was left to gel for 24 hours to obtain a gelled preparation (pH: 7.5).

  For the obtained gelled preparation, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotation speed of 6.0 rpm was 22000 mPa · s. Moreover, the ratio of the viscosity value when the rotational speed was 60 rpm to the viscosity value when the rotational speed was 6 rpm was 3.1, and it was shown that the gelled preparation exhibited high thixotropic properties.

(Comparative Example 1)
Gelled preparations having the compositions shown in Table 11 were prepared.

  Carboxyvinyl polymer (manufactured by Goodrich, trade name: Carbopol), glycerin, dipropylene glycol, sodium ascorbate phosphate, ethanol, methyl parahydroxybenzoate, and purified water are mixed at 50 ° C. And dissolved by heating. Sodium hydroxide was added to the resulting mixture and dispersed. The obtained dispersion was left to gel for 24 hours to obtain a gelled preparation (pH: 7.1).

  For the resulting gelled preparation, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 3.0 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6.0 rpm was 9200 mPa · s. Moreover, the ratio of the viscosity value at the rotational speed of 60 rpm to the viscosity value at the rotational speed of 6 rpm is 1.7, and the gelled preparation is lower than the gelled preparations of Examples 1 to 3. It showed thixotropy.

(Comparative Example 2)
Gelled preparations having the compositions shown in Table 12 were prepared.

  An alkyl-modified carboxyvinyl polymer (manufactured by Goodrich, trade name: Pemlen), glycerin, dipropylene glycol, sodium ascorbate phosphate, ethanol, methyl parahydroxybenzoate, and purified water are mixed, and 50 Heated to ° C. Sodium hydroxide was added to the resulting mixture and dispersed. The obtained dispersion was left to gel for 24 hours to obtain a gelled preparation (pH: 7.2).

  For the obtained gelled preparation, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 8500 mPa · s. Further, the ratio of the viscosity value at the rotation speed of 60 rpm to the viscosity value at the rotation speed of 6 rpm is 1.5, and the gelled preparation is lower than the gelled preparations of Examples 1 to 3. It showed thixotropy. Further, it can be seen that the viscosity of the gelled preparation of Comparative Example 2 is lowered by sodium ascorbate phosphate despite the high blending amount of the alkyl-modified carboxy polymer compared to the gelled preparation of Example 2. .

(Test Example 4)
About "phase inversion feeling at the time of application", "freshness after application", "no stickiness after application", and "moist feeling after application" of the gelled preparations of Examples 1 to 3 and Comparative Examples 1 and 2 Evaluation by 50 female monitors. The results are shown in Table 13. In the table, “Excellent” indicates that “feeling of phase inversion during application”, “freshness after application”, “no stickiness after application” or “moist feeling after application”. Is 70% or more, “good” means that the response rate is 50% or more and less than 70%, “good” means that the response rate is 30% or more and less than 50%, “bad” "Indicates a case where the response rate is less than 30%.

  As a result, as shown in Table 13, all of the gelled preparations of Examples 1 to 3 were “phase inversion during application”, “freshness after application”, “no stickiness after application”. It can also be seen that it is excellent in “moist feeling after application”. On the other hand, the gelled preparations of Comparative Examples 1 and 2 were compared with the gelled preparations of Examples 1 to 3, "phase change feeling during application", "freshness after application", and "no stickiness after application". It can also be seen that the “moist feeling after application” is inferior.

Example 4
A gel cream having the composition shown in Table 14 was prepared.

  The gel of Experimental Example 26, sodium ascorbate phosphate, glycerin, dipropylene glycol, methyl paraoxybenzoic acid, and purified water were mixed and dissolved to obtain mixture 1. Further, stearyl alcohol, retinol, and isononyl isononanoate were mixed and heated to 60 ° C. to obtain a mixture 2. Thereafter, the mixture 1 and the mixture 2 were mixed. The obtained product was subjected to a homomixer and treated at 4500 rpm for 1 minute to emulsify to obtain a gel-like oil-in-water emulsion cream (pH: 6.5).

  About the obtained oil-in-water emulsified cream, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 35000 mPa · s. Further, the ratio of the viscosity value at the rotational speed of 60 rpm to the viscosity value at the rotational speed of 6 rpm was 4.2, and it was shown that the oil-in-water emulsified cream exhibits high thixotropic properties. .

(Example 5)
A water-based gel-like foundation having the composition shown in Table 15 was prepared.

  The gel of Experimental Example 39, fine particle titanium oxide, iron oxide, talc, bengara, glycerin, citrulline, theanine, ascorbic acid glucoside, and purified water were mixed to obtain a mixture 1. Further, cetanol and polymethylsiloxane were mixed, heated to 70 ° C. and dissolved to obtain a mixture 2. Thereafter, the mixture 1 and the mixture 2 were mixed. The obtained product was subjected to a homomixer and treated at 7000 rpm for 1 minute to be emulsified to obtain a gel-like oil-in-water emulsion foundation (pH: 6.9).

  About the obtained gel-like oil-in-water emulsified foundation, the viscosity at 25 ° C. was measured in the case of the rotational speed of 6 rpm and the rotational speed of 60 rpm in the same manner as in Test Example 3. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 27000 mPa · s. Further, the ratio of the viscosity value at the rotational speed of 60 rpm to the viscosity value at the rotational speed of 6 rpm was 4.1, and it was shown that the oil-in-water emulsified foundation expresses high thixotropic properties. .

(Example 6)
Sunscreen cosmetics having the compositions shown in Table 16 were prepared.

  Sodium ascorbate phosphate, glycerin, dipropylene glycol, fine particle titanium oxide, and purified water were mixed and heated to 60 ° C. The gel of Experimental Example 27 was added to the obtained mixture to obtain a mixture 1. Also, stearyl alcohol, ethylhexyl paramethoxycinnamate, and isononyl isononanoate were mixed, heated to 60 ° C., and dissolved to obtain mixture 2. Thereafter, the mixture 1 and the mixture 2 were mixed. The obtained product was subjected to a homomixer and treated at 4500 rpm for 1 minute to emulsify, and a sunscreen cream (pH: 6.9) was obtained as a gel-like oil-in-water emulsion.

  For the obtained sunscreen cream (pH: 6.9), the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotation speed was 6 rpm and when the rotation speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 41000 mPa · s. In addition, the ratio of the viscosity value at the rotation speed of 60 rpm to the viscosity value at the rotation speed of 6 rpm was 5.2, indicating that the sunscreen exhibited high thixotropy.

(Comparative Example 3)
Sunscreen cosmetics having the compositions shown in Table 17 were prepared.

  Sodium ascorbate phosphate, glycerin, dipropylene glycol, fine particle titanium oxide, hyaluronic acid, alkyl acrylate / stearic methacrylic acid steareth-20 copolymer (Rohm and Haas, trade name: Aculin 22) And purified water were mixed and heated to 60 ° C. to obtain a mixture 1. In addition, isononyl isononanoate, sorbitan oleate, polyoxyethylene (40) cetyl ether, and polyoxyethylene (20) sorbitan stearate were mixed, heated to 70 ° C., and dissolved to obtain mixture 2. . Thereafter, the mixture 1 and the mixture 2 were mixed. The obtained product was subjected to a homomixer and treated at 4500 rpm for 1 minute to emulsify and obtain a sunscreen cream (pH: 6.6) as a gel-like oil-in-water emulsion.

  About the obtained sunscreen, the viscosity at 25 degreeC in the case of rotational speed 6rpm and the case of rotational speed 60rpm was measured similarly to the said Test example 3. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 27000 mPa · s. Moreover, the ratio of the viscosity value at the rotation speed of 6.0 rpm to the viscosity value at the rotation speed of 3.0 rpm is 1.2, and the sunscreen cream is compared with the sunscreen cream of Example 6. It showed low thixotropy.

(Test Example 5)
By measuring SPF (Sun Protection Factor) for each of the sunscreen cream of Example 6 and the sunscreen cream of Comparative Example 3 by a method according to the US Food and Drug Administration (FDA), A sex test was performed. In addition, SPF value shows the minimum erythema amount of a sample application part / the minimum erythema amount of a sample non-application part, and it shows that an ultraviolet-ray protective effect is so high that a numerical value is high. Further, the minimum erythema dose indicates the minimum dose that causes erythema after 24 hours when the skin is irradiated with ultraviolet rays in a healthy person.

In part of the range of 20 cm ² of the subject's back of male and female adults each 10 people each sunblock sunscreen and Comparative Example 3 Example 6 was coated to a 2 mg / cm ² of. Immediately after application, the minimum amount of erythema was measured.

Furthermore, each of the sunscreen cream of Example 6 and the sunscreen cream of Comparative Example 3 was applied to a portion adjacent to the application site of the sunscreen cream so as to be ² mg / cm ² and sufficiently dried. .

  Next, in order, the subject was allowed to perform a 20-minute underwater exercise in the indoor pool, a 20-minute break, and a 20-minute underwater exercise in the indoor pool. Next, the sunscreen cream applied part was dried without using a towel. Thereafter, the minimum amount of erythema was measured. Table 18 shows the results of examining the SPF before and after underwater exercise. In the table, SPF uses a xenon arc solar simulator (manufactured by Solar Light Co., Ltd., trade name: Model 600) as a light source for the unapplied part and the applied part of sunscreen cream in 10 adult male and female subjects. Irradiate ultraviolet rays, measure the minimum erythema amount of the unapplied part and the minimum erythema amount of the sample application part, calculate the value of the minimum erythema amount of the unapplied part relative to the minimum erythema amount of the sample application part, and then subject It is the value calculated | required by calculating the average value of.

  As shown in Table 18, according to the sunscreen cream of Example 6, it can be seen from the SPF value that it exhibits excellent water resistance of 96.6% remaining before and after exercise in water. . On the other hand, it can be seen that the conventional sunscreen cream (Comparative Example 3) is significantly inferior in water resistance to the sunscreen cream of Example 6.

  Thus, an oil-in-water emulsion containing a gel containing a complex of a predetermined amphoteric amphiphilic polymer compound and an anionic polymer compound, sunscreen cream, etc. are excellent in use. It can be seen that it exhibits a sense of compatibility, a refreshing feeling and the like, and its cosmetic effect, durability of effectiveness, water resistance, etc. are remarkably improved.

(Example 7)
A gel hair treatment, which is a cosmetic for hair having the composition shown in Table 19, was prepared.

  Hydrogenated phospholipid, stearyl alcohol, butylene glycol, and purified water were mixed and heated to 70 ° C. to obtain a mixture. The gel of Experimental Example 27 was added to the obtained mixture to obtain a mixture 1. Further, ceramide 3, high-viscosity polymethylsiloxane, and polyglycerin fatty acid ester were mixed, heated to 70 ° C., and dissolved to obtain mixture 2. Thereafter, the mixture 1 and the mixture 2 were mixed. The obtained product was subjected to a homomixer and treated at 4500 rpm for 1 minute to emulsify and obtain a hair treatment (pH: 6.2) as a gel-like oil-in-water emulsion.

  For the obtained hair treatment, the viscosity at 25 ° C. was measured in the same manner as in Test Example 3 when the rotational speed was 6 rpm and when the rotational speed was 60 rpm. As a result, the viscosity of the gelled preparation at a rotational speed of 6 rpm was 39000 mPa · s. Further, the ratio of the viscosity value at the rotation speed of 60 rpm to the viscosity value at the rotation speed of 6 rpm was 4.9, and it was shown that the hair treatment expresses high thixotropic properties.

(Test Example 6)
Using carboxymethyl chitosan having a different weight average molecular weight, in the same manner as in Example 1, N-myristoyl carboxymethyl chitosan having a myristoylation degree of 6 to 9% and a different weight average molecular weight was prepared. The weight average molecular weight is a value measured by GPC analysis.

  Subsequently, 1 g of each N-myristoyl carboxymethyl chitosan obtained was dispersed in 100 mL of purified water to obtain an N-myristoyl carboxymethyl chitosan dispersion. Moreover, 0.3 g of carbovinyl vinyl polymer which is an anionic polymer compound was dispersed with 47 mL of purified water to obtain an anionic polymer compound dispersion.

  An anionic polymer compound dispersion was gradually added to N-myristoylcarboxymethylchitosan at room temperature while stirring with a stirrer. 3 g of butylene glycol, which is a polyhydric alcohol, was added to the resulting mixture. Then, it was made to stir at room temperature for 2 minutes at 5000 rpm with the homomixer. Subsequently, the obtained product was allowed to stand at room temperature for 24 hours.

  For each of the obtained products (Experimental Examples 64 to 71), a gel was obtained by measuring the viscosity at a rotational speed of 6 rpm using a No. 4 rotor and a B-type viscometer (manufactured by Brookfeed, product name: VISCOMETER). The ability to form was evaluated. The gel forming ability is “good” when the viscosity is remarkably increased before and after standing for 24 hours and the viscosity is 10000 mPa · s or more, and the viscosity is increased to form a gel. However, the case where the viscosity was less than 10,000 mPa · s was evaluated as “good”, and the case where no gel was formed due to the increase in the viscosity was evaluated as “bad”. Table 20 shows the relationship between the difference in average molecular weight of N-myristoyl carboxymethyl chitosan and the gel-forming ability.

  As a result, as shown in Table 20, when the weight average molecular weight is 4,000 to 2,000,000, it is understood that a gel is formed.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the skin external preparation, cosmetics, etc. which can exhibit the outstanding usability, the outstanding stability, etc.

Claims (12)

General formula (1):

[Wherein, n represents an integer of 10 or more, R ¹ independently represents a hydrogen atom or an acyl group having 8 to 18 carbon atoms, and R ² each independently represents a carboxymethyl group or a hydrogen atom. Indicates
A zwitterionic compound having a weight average molecular weight of 4,000 to 2,000,000 as measured by gel permeation chromatography, wherein the acyl group content in the compound is 0.1 to 50.0% An aqueous gel comprising a complex of an amphiphilic polymer compound and an anionic polymer compound.   The aqueous gel according to claim 1, wherein the acyl group has 10 to 18 carbon atoms.   The complex comprises an amphoteric amphiphilic polymer compound and an anionic polymer compound in a weight ratio (amphoteric amphiphilic polymer compound / anionic polymer compound) of 1/10 to 100 /. The aqueous gel according to claim 1 or 2, wherein the aqueous gel is combined so as to be 1.   The aqueous gel according to any one of claims 1 to 3, wherein the acyl group content is 1.0 to 25.0%.   The aqueous gel according to any one of claims 1 to 4, wherein the acyl group content is 2.0 to 10.0%.   The aqueous gel according to any one of claims 1 to 5, wherein the pH value is 5.0 to 9.0.   The aqueous gel according to any one of claims 1 to 6, further comprising an electrolyte.   The aqueous gel according to any one of claims 1 to 7, wherein the electrolyte is ascorbic acid or a derivative thereof.   A skin external preparation comprising the aqueous gel according to any one of claims 1 to 8.   A cosmetic comprising the aqueous gel according to any one of claims 1 to 8.   The cosmetic according to claim 10, further comprising a liquid oil agent, which is an oil-in-water emulsion.   The cosmetic according to claim 10 or 11, further comprising a component having ultraviolet protective ability.