JP2016098222A - External composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external composition comprising a high content of a carboxyvinyl polymer and/or an alkyl-modified carboxyvinyl polymer, which has good spreading and compatibility with the skin at the time of application, achieves coating feeling without a tight feeling after application and is excellent in moisture feeling.SOLUTION: There is provided an external composition which comprises (A) 0.2 wt.% or more of a carboxyvinyl polymer and/or an alkyl-modified carboxyvinyl polymer and (B) a hyaluronic acid oligosaccharide and/or a salt thereof.SELECTED DRAWING: None

Description

  The present invention relates to a composition for external use containing 0.2% by weight or more of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer. More specifically, the present invention contains 0.2% by weight or more of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer, and has good elongation and skin familiarity when applied. It is related with the composition for external use which is hard to remember and is excellent in a film feeling and a moisturizing feeling.

  Conventionally, it is known to contain a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer for the purpose of improving the coating feeling (application feeling) of the composition for external use. However, when a large amount of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer is blended, there is a problem that elongation and skin familiarity are inferior at the time of application, and after application, a feeling of tension appears and the moisturizing feeling is impaired.

  Conventionally, the formulation which improves the fault of such a carboxy vinyl polymer and / or an alkyl modified carboxy vinyl polymer is examined. For example, carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer, ethanol and / or isopropanol, water-insoluble powder as a composition that eliminates the stickiness that is observed after application of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer A hand sanitizer composition containing a specific amount of body and oil solid at room temperature is known (see Patent Document 1).

  However, the hand disinfectant composition disclosed in Patent Document 1 is not satisfactory in terms of skin familiarity and moisturizing feeling because the feeling of coating is suppressed at the same time as the feeling of tension. Further, the hand disinfectant composition disclosed in Patent Document 1 has a problem that its use is limited because it contains a large amount of ethanol and / or isopropanol.

  As described above, according to the conventional technology, in a composition for external use containing a high content of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer, the coating feeling (softness after application), elongation at the time of application, skin familiarity, and feeling of tension after application is not soft. The present condition is that the formulation which satisfies all of the film feeling of impression) and the moisturizing feeling has not been developed.

JP 2012-144481 A

  The object of the present invention is that the composition for external use containing a high content of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer has good elongation at the time of application and skin familiarity, and there is no feeling of tension after application. An object of the present invention is to provide an external composition that achieves a coating feeling and is excellent in a moisturizing feeling.

  As a result of intensive studies to solve the above-mentioned problems, the present inventor blends hyaluronic acid oligosaccharide and / or a salt thereof with 0.2% by weight or more of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer. This makes it possible to obtain a composition for external use that is excellent in elongation at the time of application and familiarity with the skin even after compounding a large amount of carboxyvinyl polymer, and that it is difficult to memorize after application, and that is excellent in film feeling and moisturizing feeling. I found.

  Furthermore, the present inventor blends hyaluronic acid and / or a salt thereof together with a carboxyvinyl polymer and / or an alkyl-modified carboxyvinyl polymer and a hyaluronic acid oligosaccharide and / or a salt thereof constituting the composition for external use. The solubility of acid and / or its salt in water is improved, so that it is possible to dissolve hyaluronic acid and / or its salt in water in a short time, elongation at the time of application, no feeling of tension after application, film It has been found that the feeling and the moisturizing feeling can be further improved.

The present invention has been completed by further studies based on these findings. That is, this invention provides the invention of the aspect hung up below.
Item 1. A composition for external use containing (A) carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer 0.2% by weight or more and (B) hyaluronic acid oligosaccharide and / or a salt thereof.
Item 2. The external composition according to Item 1, further comprising (C) glycerin and / or polyglycerin.
Item 3. Item 3. The composition for external use according to Item 2, wherein the content of (C) glycerol and / or polyglycerol is 3% by weight or more.
Item 4. Item 4. The external composition according to any one of Items 1 to 3, further comprising (D) hyaluronic acid and / or a salt thereof.
Item 5. Item 5. The external composition according to any one of Items 1 to 4, which is a cosmetic.

  According to the present invention, while containing a high content of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer, it is excellent in elongation at the time of application and skin familiarity, and after application, it is difficult to memorize a feeling of tension, It is possible to obtain a composition for external use having excellent coating feeling and moisturizing feeling. Therefore, according to the present invention, it is possible to provide an external composition having a good feeling of use.

  In addition, according to the present invention, the solubility of hyaluronic acid and / or its salt in water can be improved, so that an external composition containing a high content of hyaluronic acid and / or its salt is produced. Even in such a case, hyaluronic acid and / or a salt thereof can be dissolved in water in a short time, and the lead time can be shortened and the manufacturing cost can be reduced. Provision becomes possible.

1. External Composition The external composition of the present invention contains (A) carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer 0.2% by weight or more, and (B) hyaluronic acid oligosaccharide and / or a salt thereof. It is characterized by. Hereinafter, the external composition of the present invention will be described in detail.

(A) Carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer The composition for external use of the present invention comprises 0.2% by weight or more of carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer (hereinafter referred to as “component (A)”). In some cases). The carboxyvinyl polymer is a water-soluble vinyl polymer having a carboxyl group, and specifically, a polymer having a cross-linked structure with allyl sucrose or allyl ether of pentaerythritol with acrylic acid and / or methacrylic acid as the main chain. is there. The alkyl-modified carboxyvinyl polymer is a polymer in which at least a part of the carboxyl group of the carboxyvinyl polymer is esterified with an alkyl group. In the alkyl-modified carboxyvinyl polymer, the alkyl group bonded by an ester bond may be linear or branched. Moreover, although it does not restrict | limit especially about carbon number of the said alkyl group, For example, 8-35, Preferably 8-30 is mentioned. In the present invention, the carboxyvinyl polymer and / or the alkyl-modified carboxyvinyl polymer may be used alone or in combination.

  The carboxyvinyl polymer and / or the alkyl-modified carboxyvinyl polymer has a viscosity of 5000 mPa · s or more, preferably 5000 to 100,000 mPa · s in a 0.5 wt% aqueous solution (20 ° C.) adjusted to pH = 6.5. used. Here, for the viscosity, a B-type viscometer “TOKI SANGYO VISCOMETER TVB-10” (manufactured by Toki Sangyo Co., Ltd.) uses a rotor: M3 (rotation speed: 20 rpm, time: 1 min, unit: mPa · s). This is the value measured.

  Commercial products can be used for the carboxyvinyl polymer and the alkyl-modified carboxyvinyl polymer. Specific examples of commercially available carboxyvinyl polymers include “AQPEC HV-501E” and “AQUPEC HV-505E” manufactured by Sumitomo Seika Co., Ltd .; “Carbopol 940” and “Carbopol” manufactured by Lubrizol Advanced Materials. 941 ”,“ Carbopol 980 ”,“ Carbopol 981 ”;“ Hibiswaco 103 ”,“ Hibiswaco 104 ”,“ Hibiswaco 105 ”manufactured by Wako Pure Chemical Industries, Ltd .;“ Sintalen K ”manufactured by 3V Sigma , “Syntalen L” and the like. Moreover, as a commercial item of the alkyl-modified carboxyvinyl polymer, specifically, “AQUPEC HV-501ER” manufactured by Sumitomo Seika Co., Ltd .; “Carbopol ultraz20”, “Carbopol ultraz21” manufactured by Lubrizol Advanced Materials, “Carbopol 1342”, “Carbopol ETD2020”, “Pemlen TR-1”, “Pemlen TR-2” and the like.

  In the composition for external use of the present invention, the content of the component (A) is not particularly limited as long as it is 0.2% by weight or more. Specifically, the total amount of the component (A) is 0.2. The range is -3% by weight, preferably 0.2-2% by weight, more preferably 0.2-1.5% by weight. In combination with such a high content of component (A), hyaluronic acid oligosaccharide and / or a salt thereof, which will be described later, in the composition for external use, elongation at the time of application and skin familiarity, and a feeling of tension after application In addition, it is possible to improve the coating feeling and the moisturizing feeling.

(B) Hyaluronic acid oligosaccharide and / or salt thereof The composition for external use of the present invention may be referred to as hyaluronic acid oligosaccharide and / or salt thereof (hereinafter referred to as “component (B)”) together with the component (A). Contains). By using hyaluronic acid oligosaccharides and / or salts thereof, even when the component (A) is contained at a high content of 0.2% by weight or more, the elongation at the time of application and the skin fit, and the feeling of tension after application In other words, it is possible to improve the coating feeling and the moisturizing feeling. Further, according to the composition for external use of the present invention, even when hyaluronic acid and / or a salt thereof to be described later is blended, not only the hyaluronic acid and / or a salt thereof can be easily dissolved, but also the elongation at the time of application is increased. Further, it is possible to further improve the feeling of tightness after coating, the coating feeling and the moisturizing feeling.

  Hyaluronic acid oligosaccharides are oligosaccharides containing one or more repeating units with a disaccharide in which the first carbon atom of glucuronic acid and the third carbon atom of N-acetylglucosamine are bonded by a glycosidic bond. is there.

  The salt of the hyaluronic acid oligosaccharide used in the present invention is not particularly limited as long as it is pharmaceutically acceptable. For example, alkali metal salts such as sodium salt and potassium salt; calcium salt and magnesium salt Examples include alkaline earth metal salts; amine salts such as tri (n-butyl) amine salts, triethylamine salts, pyridine salts, amino acid salts, and the like. Among these hyaluronic acid oligosaccharide salts, an alkali metal salt is preferable, and a sodium salt is more preferable. These hyaluronic acid salts may be used alone or in combination of two or more.

  The number of constituent monosaccharides of the hyaluronic acid oligosaccharide and / or its salt is not particularly limited, and examples thereof include about 2 to 16 sugars. From the viewpoint of more effectively improving the elongation at the time of application and the familiarness of the skin and the feeling of tension after application, the film feeling and the moisturizing feeling, the number of constituent monosaccharides of hyaluronic acid oligosaccharide and / or its salt is as follows: Preferably 2-12 sugars, More preferably, 2-10 sugars, More preferably, 2-8 sugars are mentioned.

  As the hyaluronic acid oligosaccharide and / or salt thereof used in the present invention, either a saturated type or an unsaturated type may be used alone, or a saturated type and an unsaturated type may be used in combination. In the present invention, the saturated hyaluronic acid oligosaccharide and / or a salt thereof is a hyaluronic acid oligosaccharide and / or a salt thereof in which the pyranose skeleton of all constituent monosaccharides is formed by a single bond. The unsaturated hyaluronic acid oligosaccharide and / or salt thereof is hyaluronic acid oligosaccharide and / or salt thereof in which a double bond is contained in the pyranose skeleton of at least one constituent monosaccharide. As the unsaturated hyaluronic acid oligosaccharide and / or salt thereof, specifically, the hydroxyl group bonded to the 4-position carbon atom of glucuronic acid located at the non-reducing end is removed, and the 4-position carbon atom is removed. Examples include hyaluronic acid oligosaccharides in which the 5-position carbon atom is bonded by a double bond and / or a salt thereof.

  Hyaluronic acid oligosaccharides and / or salts thereof can be produced by hydrolyzing hyaluronic acid, and can also be produced by enzymatic reaction, chemical synthesis, microbial culture, and the like. Examples of the method for producing hyaluronic acid oligosaccharide and / or a salt thereof by hydrolyzing hyaluronic acid include known methods such as an enzymatic decomposition method, an alkali decomposition method, a heat treatment method, and an ultrasonic treatment method. Specifically, the enzymatic degradation method includes a method of degrading hyaluronic acid with a hyaluronic acid hydrolase such as hyaluronic acid degrading enzyme (hyaluronidase (derived from testicles), hyaluronidase (derived from Streptomyces), hyaluronidase SD, etc.). . Specific examples of the alkali decomposition method include a method of adding a base such as 1N sodium hydroxide to an aqueous solution containing hyaluronic acid and heating it for several hours to lower the molecular weight. Furthermore, as a method for producing by microbial culture, for example, in an aqueous solution of hyaluronic acid and / or a salt thereof, a microorganism having a resolution of hyaluronic acid and / or a salt thereof (for example, Streptomyces, Streptococcus, Peptococcus, Arthrobacter, Proteus, Flavobacterium, etc.) can be cultured.

  Hyaluronic acid oligosaccharides and / or salts thereof are commercially available. In the present invention, commercially available products may be used. As a commercial product of hyaluronic acid oligosaccharide and / or a salt thereof, specifically, as a saturated hyaluronic acid oligosaccharide and / or a salt thereof, the trade name “hyaluronic acid oligosaccharide hexasaccharide” (Carbohydrate Co., Ltd.) Scientific Research Laboratories), trade name "Hyaluronic Acid Oligosaccharide Octasaccharide" (Glucose Science Laboratories), trade name "Hyaluronic Acid Oligosaccharide 10 Sugar" (Glucose Science Laboratories), Oligosaccharide 12 sugars "(Carbohydrate Science Laboratories, Inc.), trade name" Hyaluronic Acid Oligosaccharide "(mixture of disaccharides and tetrasaccharides, manufactured by AdipoGen), trade name" Hyaluronic Acid Oligosaccharide "(mixture of 4-8 sugars) , Manufactured by AdipoGen), trade name “Hyaluronic Acid Oligosacchar” de (<1.5 kDa) ”(mixture of disaccharide and tetrasaccharide, manufactured by AdipoGen), trade name“ microhyaluronic acid FCH ”((mixture of 12-14 sugar, manufactured by Kikkoman Biochemifa)), and the like. Further, as the unsaturated hyaluronic acid oligosaccharide and / or a salt thereof, specifically, the trade name “Hyaluronic Acid Oligosaccharide, dp2” (manufactured by Iduron Ltd), the trade name “Hyaluronic Acid Oligosaccharide, dp4” (IduronLt) ), Trade name “Hyaluronic Acid Oligosaccharide, dp6” (manufactured by Iduron Ltd), trade name “Hyaluronic Acid Oligosaccharide, dp8” (Iduron) Ltd.), trade name “Hyaluronic Acid Oligosaccharide, dp10” (manufactured by Iduron Ltd), trade name “Hyaluronic Acid Oligosaccharide, dp12” (manufactured by Iduronic Ltd), trade name “Hylauronic Acid 14” Examples include the name “Hyaluronic Acid Oligosaccharide, dp18” (manufactured by Iduron Ltd) and the product name “Hyaluronic Acid Oligosaccharide, dp20” (manufactured by Iduron Ltd).

  In the composition for external use of the present invention, as the component (B), either hyaluronic acid oligosaccharide or a salt thereof may be used alone, or a combination thereof may be used.

  In the composition for external use of the present invention, the content of the component (B) is not particularly limited, and examples thereof include 0.0001 to 1.5% by weight. From the viewpoint of more effectively improving the elongation at the time of application, the familiarness to the skin and the feeling of tension after application, the film feeling and the moisturizing feeling, the content of the component (B) is preferably 0.0001 to 1 weight. %, More preferably 0.00025 to 1% by weight, more preferably 0.001 to 1% by weight, particularly preferably 0.1 to 1% by weight.

  Further, in the composition for external use of the present invention, the ratio of the component (A) and the component (B) is not particularly limited, but the elongation at the time of application and the familiarity with the skin and the feeling of tension after the application, the film feeling and the moisturizing feeling From the standpoint of improving the amount more effectively, the component (B) is preferably 0.1 parts by weight or more, more preferably 0.1 to 600 parts by weight per 100 parts by weight of the component (A).

(C) Glycerin and / or polyglycerin The composition for external use of the present invention may further contain glycerin and / or polyglycerin (hereinafter sometimes referred to as “component (C)”).

  The composition for external use of the present invention contains glycerin and / or polyglycerin together with the component (A) and the component (B), thereby containing the component (A) at a high content of 0.2% by weight or more. Even in this case, it is possible to further improve the elongation at the time of application and the feeling of tension after application and the moisturizing feeling.

  Although it does not restrict | limit especially about the polymerization degree of polyglycerol, For example, 2-16, Preferably it is 2-10, More preferably, it is 2-6, Especially preferably, 2 (namely, diglycerol) is mentioned.

  As the component (C), one kind of glycerin and polyglycerin may be used alone, or two or more kinds may be used in appropriate combination. From the viewpoint of more effectively imparting a moisturizing feeling excellent in elongation and sustainability during application, glycerin and diglycerin are preferable, and glycerin is more preferable.

  In the composition for external use of the present invention, the content of the component (C) is not particularly limited, and examples thereof include 0.5% by weight or more. From the viewpoint of further improving the elongation at the time of application and the feeling of tension after application and the moisturizing feeling, the content of the component (C) is preferably 1% by weight or more, more preferably 3% by weight or more, and still more preferably. 5 to 25% by weight.

(D) Hyaluronic acid and / or salt thereof The composition for external use of the present invention may further contain hyaluronic acid and / or a salt thereof (also referred to as component (D)).

  Hyaluronic acid is a polysaccharide containing as a repeating unit a disaccharide in which the carbon atom at position 1 of glucuronic acid and the carbon atom at position 3 of N-acetylglucosamine are linked by a glycosidic bond.

  The hyaluronic acid salt used in the present invention is not particularly limited as long as it is pharmaceutically acceptable. For example, alkali metal salts such as sodium salts and potassium salts; alkaline earth salts such as calcium salts and magnesium salts; Metal salts; amine salts such as tri (n-butyl) amine salts, triethylamine salts, pyridine salts, amino acid salts, and the like. Among these hyaluronic acid salts, an alkali metal salt is preferable, and a sodium salt is more preferable. These hyaluronic acid salts may be used alone or in combination of two or more.

  The average molecular weight of hyaluronic acid and / or a salt thereof used in the present invention is not particularly limited, but is, for example, 88,000 or more, preferably 50,000 or more, more preferably 100,000 or more, and further preferably 500,000 or more. Particularly preferred is 500,000 to 3,000,000. In particular, the average molecular weight of hyaluronic acid is preferably 500,000 to 2,500,000, more preferably, from the viewpoint of more effectively improving the elongation at the time of coating and the feeling of tension after coating, the film feeling and the moisturizing feeling. 800,000 to 2.5 million may be mentioned. In the present invention, the average molecular weight of hyaluronic acid and / or a salt thereof is a weight average molecular weight determined using pullulan as a standard substance by gel filtration chromatography (GPC).

  The origin of the hyaluronic acid and / or salt thereof used in the present invention is not particularly limited, and may be naturally derived from a biological tissue such as chicken crown, umbilical cord, skin, joint fluid, or enzyme. It may be produced by reaction, chemical synthesis, microbial culture or the like.

  Hyaluronic acid and / or a salt thereof are commercially available, and in the present invention, commercially available products may be used. As a commercial product of hyaluronic acid and / or a salt thereof, specifically, the trade name “Hyaluronic Sun HA-LQH” (average molecular weight 1.2 to 220,000, QP Corporation), the commercial name “Hyaluronic Sun HA-LQ” (average molecular weight) 85 to 1.6 million; QP Corporation), trade name “hyaluronic acid FCH-200” (average molecular weight 1.8 to 2.2 million; Kikkoman Biochemifa Corporation), trade name “hyaluronic acid FCH-150” (average molecular weight 1.4 to 1.8 million) Kikkoman Biochemifa Co., Ltd.), trade name “hyaluronic acid FCH-120” (average molecular weight 1 to 1.4 million; Kikkoman Biochemifa Co., Ltd.), trade name “sodium biohyaluronate HA9” (average molecular weight 80 to 1.2 million; stock) Company Shiseido), trade name “Nato Biohyaluronate” “Lium HA12” (average molecular weight 110 to 1.6 million; Shiseido Co., Ltd.), trade name “Sodium Biohyaluronate HA20” (average molecular weight 190 to 2700,000; Shiseido Co., Ltd.), trade name “Hiro-oligo” (average molecular weight 10,000 or less, Kewpie Co., Ltd.), trade name “hyaluronic acid FCH-SU” (average molecular weight 5-110,000, Kikkoman Biochemifa Co., Ltd.), trade name “hyaluronic acid (L)” (average molecular weight 50,000 or less, FAP Japan Co., Ltd.) And trade name “hyaluronic acid (SL)” (average molecular weight of 10,000 or less, FAP Japan Co., Ltd.).

  In the composition for external use of the present invention, as component (D), either hyaluronic acid or a salt thereof may be used alone, or a combination thereof may be used.

In the composition for external use of the present invention, when the component (D) is blended, the content is not particularly limited, but is preferably set to 0.01% by weight or more. When blended with 0.01% by weight or more of the component (D), when combined with the component (A) and the component (B), there is no stretch at the time of coating, no feeling of tension after coating, a film feeling and a moisturizing feeling. It becomes possible to improve more effectively.
In addition, in the prior art, when the component (D) is contained at a high content, it tends to be difficult to stretch at the time of application or the skin familiarity tends to decrease, but in the external composition of the present invention, the component (A) And by containing (B) component, the improvement at the time of application | coating and the skin familiarity are aimed at. Moreover, it can be set as the composition for external use which was excellent also in the point of the absence of a feeling of tension after application | coating, a film feeling, and a moisturizing feeling. The content of component (D) is preferably 0 from the viewpoint of improving the balance at the time of application and familiarity with the skin, the feeling of tension after application, the balance between the film feeling and the moisturizing feeling, and further improving the feeling of use. 0.01 to 2% by weight, more preferably 0.01 to 1% by weight.

Composition for external use of the water present invention, water used as a base is prepared in the desired dosage form. In the external composition of the present invention, the water content may be appropriately set according to the dosage form of the external composition, for example, 20 to 99% by weight, preferably 30 to 99% by weight, more preferably 35-99 weight%, More preferably, 35-94.65 weight% is mentioned.

Other Components The composition for external use of the present invention may contain a functional component exhibiting physiologically useful functionality, if necessary, in addition to the components described above. Such a functional ingredient is not particularly limited as long as it can be incorporated into cosmetics, external medicines, etc., for example, water-soluble vitamins, oil-soluble vitamins, enzymes, peptides, amino acids , Hormones, various cytokines, various animal and plant extracts, steroids, moisturizers, whitening agents, crude drugs, antihistamines, astringents, cell activators, keratin softeners, local anesthetics, anti-inflammatory agents, antioxidants, antibacterial agents, Examples include antipruritic agents, skin protectants, blood circulation promoters, and sterols.

  Moreover, in order to prepare the external composition of this invention in a desired dosage form other than the component mentioned above, the other base and additive may be contained. Such bases and additives are not particularly limited as long as they can be blended in cosmetics, external medicines, etc., but for example, oily components, lower alcohols, surfactants, preservatives, thickeners , Fragrances, pigments, buffers, pH adjusters and the like.

  Examples of the oil component include animal oils, vegetable oils, synthetic oils and the like, and solid oils, semi-solid oils, liquid oils, volatile oils and the like, for example, hydrocarbons, fats and oils, higher alcohols, waxes, etc. , Hardened oils, ester oils, fatty acids, fluorine-based oils, lanolin derivatives, oil-based gelling agents, oil-soluble UV absorbers, and the like. Specific examples of oil components include hydrocarbons such as liquid paraffin, squalane, petrolatum, polyisobutylene, polybutene, paraffin wax, ceresin wax, microcrystalline wax, and fisher trops wax; olive oil, castor oil, jojoba oil, mink Oils and fats such as macadamian nut oil; waxes such as beeswax, carnauba wax, candelilla wax, gay wax, moclaw and montan wax; cetyl 2-ethylhexanoate, isotridecyl isostearate, isopropyl myristate, isopropyl palmitate Octyldodecyl myristate, cetyl trioctanoate, glyceryl tri-2-ethylhexanoate, polyglyceryl diisostearate, diglyceryl triisostearate, glyceride tribehenate , Rosin acid pentaerythritol ester, neopentyl glycol dioctanoate, diisostearyl malate, cholesterol fatty acid ester, N-lauroyl-L-glutamate di (cholesteryl, behenyl, octyldodecyl), esters of macadamian nut fatty acid phytosteryl, etc. Fatty acids such as stearic acid, lauric acid, myristic acid, behenic acid, isostearic acid, oleic acid; higher alcohols such as cetyl alcohol, stearyl alcohol, cetostearyl alcohol, behenyl alcohol; perfluoropolyether, perfluorodecane, Fluorine oils such as perfluorooctane; Lanolin derivatives such as lanolin, lanolin acetate, lanolin fatty acid isopropyl, lanolin alcohol; dextrin fatty acid ester Oil, gelling agents such as sucrose fatty acid ester, starch fatty acid ester, 12-hydroxystearic acid, aluminum stearate, calcium stearate; ethyl paraaminobenzoate, 2-ethylhexyl paramethoxycinnamate, 4-tert-butyl -4'-methoxydibenzoylmethane, octyltriazone, bisethylhexyloxyphenol methoxyphenyltriazine, hexyl diethylaminohydroxybenzoyl benzoate, methylenebisbenzotriazolyltetramethylbutylphenol, oxybenzone, etc. It is done. These oil components may be used alone or in combination of two or more.

  Examples of the lower alcohol include lower monohydric alcohols such as ethanol and isopropanol; polyhydric alcohols such as propylene glycol, 1,3-butylene glycol, dipropylene glycol and polyethylene glycol, and 1,2-pentanediol. These lower alcohols may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.

  Specific examples of the nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate). Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexylate); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, mono Glyceryl stearate, α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (eg, Propylene glycol nostearate); hardened castor oil derivative; glycerin alkyl ether, POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraole) POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE-glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate, POE-monooleate, etc.); POE-fatty acid ester (For example, POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE- 2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (for example, Pluronic etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyl tetradecyl) Ethers, POE / POP-monobutyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); tetra-POE / tetra-POP-ethylenediamine condensates (for example, Tetronic POE-castor oil hardened castor oil derivatives (for example, POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil) Monopyroglutamic acid monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.); alkanolamide (for example, coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.); sucrose fatty acid ester; alkylethoxydimethylamine Oxide; trioleyl phosphate and the like.

  Specific examples of the anionic surfactant include fatty acid soap (for example, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (for example, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfates Salts (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acids (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, N-myristoyl-N-methyl) Sodium taurine, coconut oil fatty acid methyl taurine sodium, lauryl methyl taurine sodium, etc.); sulfosuccinate (eg, di-2-ethylhexyl sodium sulfosuccinate, monolauroyl monoethanolamide polyoxy) Sodium ethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkylbenzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, triethanol amine linear dodecyl benzene sulfonate, linear dodecyl benzene sulfonic acid, etc.); higher fatty acid ester sulfate Salt (for example, hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.); N-acyl glutamate (for example, N-lauroyl glutamate monosodium, N-stearoyl glutamate disodium, N-myristoyl-L-glutamate monosodium, etc.); POE- Alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; lauroyl monoethanolamine Sodium dosuccinate; N-palmitoyl aspartate ditriethanolamine and the like.

  Specific examples of the cationic surfactant include alkyltrimethylammonium salts (for example, stearyltrimethylammonium chloride and lauryltrimethylammonium chloride); alkylpyridinium salts (for example, cetylpyridinium chloride); distearyldimethylammonium dialkyl chloride. Dimethylammonium salt; poly (N, N′-dimethyl-3,5-methylenepiperidinium); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; Benzalkonium; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactant (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, amidoamine type amphoteric surfactant, lauryldimethylaminoacetic acid) Betaine, alkyl betaine, amide betaine, sulfobetaine and the like).

  These surfactants may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the preservative include paraoxybenzoic acid ester, phenoxyethanol, benzoic acid, sodium benzoate, dehydroacetic acid, sodium dehydroacetate, benzyl alcohol, chlorobutanol, sorbic acid and salts thereof, and chlorhexidine gluconate. These preservatives may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of the thickener include, for example, methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxymethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, guar gum, locust bean gum, carrageenan, xanthan gum, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, bentonite, Examples include alginic acid, macrogol, sodium chondroitin sulfate, and carboxyethyl cellulose. These thickeners can be used as long as the effect of the component (A) is not inhibited, and may be used singly or in combination of two or more.

Production method The composition for external use of the present invention is added as necessary together with the components (A) and (B) (C), (D), other functional components, bases, additives, etc. Can be obtained by mixing and preparing the desired dosage form.

  When the component (D) is blended with the components (A) and (B), the solubility in water is improved. Therefore, in the production of the external composition of the present invention, the component (D) is dissolved in water. When used, it is preferable to coexist with the component (A) and the component (B). As a method of coexisting the component (A) and the component (B) when dissolving the component (D) in water, for example, a method of simultaneously adding the component (A), the component (B) and the component (D) to water. A method of adding the component (D) to water and adding the component (A) and the component (B) until the component (D) is dissolved; after adding the component (A) and the component (B) to water, (D) The method of adding a component is mentioned.

Dosage Form and Formulation Form The composition for external use of the present invention may be in any form such as liquid, solid, cream, or gel. Among these dosage forms, the liquid external composition is easy to realize the effects such as elongation at the time of application and skin familiarity, as well as a feeling of tension after application, a film feeling and a moisturizing feeling. It is suitable as a product form.

  The composition for external use of the present invention is used in the form of a preparation for external preparations for skin such as cosmetics and external medicines. The formulation form of the composition for external use of the present invention is not particularly limited. For example, cosmetics such as creams, lotions, cosmetic liquids, emulsions, gels, lipsticks and foundations; liquids (lotions, sprays, aerosols, And topical medicines such as foams, ointments, creams, gels, patches and the like. Among these preparation forms, from the viewpoint of making it possible to easily realize effects such as a heavy coating feeling, moisturizing feeling, easiness of stretching, and stickiness suppression, preferably cosmetics, more preferably lotion, cosmetic liquid and emulsion. Can be mentioned.

  EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited to these examples.

Production Example: Method for Producing “Unsaturated Hyaluronic Acid Oligosaccharide” (Unsaturated Hyaluronic Acid Disaccharide ) In the following Examples and Comparative Examples, “Unsaturated Hyaluronic Acid Oligosaccharide” is disclosed in Japanese Patent Application Laid-Open No. 2008-35858. What was manufactured according to the method described in gazette No. was used. Specifically, in a 1% by weight aqueous solution of sodium hyaluronate, Arthrobacter atrocyaneus JU-01 (Arthrobacter atrocyaneus JU-01) strain (National Institute of Technology and Evaluation, Patent Microorganism Depositary Center, Accession Number: NITE) P-245) was statically cultured at 25 ° C. for 120 hours. Thereafter, the strain was removed with a 0.22 μm membrane filter and lyophilized to obtain an unsaturated hyaluronic acid oligosaccharide. The resulting hyaluronic acid oligosaccharide is a disaccharide (the number of monosaccharides is 2), the hydroxyl group bonded to the 4-position carbon atom of glucuronic acid located at the non-reducing end is removed, and the 4-position carbon is removed. It had a structure in which the atom and the carbon atom at the 5-position were bonded by a double bond.

Test Example 1: Evaluation of composition for external use An external composition having the composition shown in Table 1 was prepared. Specifically, a predetermined amount of carboxyvinyl polymer, unsaturated hyaluronic acid disaccharide and glycerin was added to water at room temperature, and the mixture was stirred and dissolved at room temperature with a propeller stirrer at a speed of 500 rpm. Next, an aqueous solution of sodium hydroxide (pH 6.5) was prepared by adding an aqueous sodium hydroxide solution while stirring. About the obtained external composition, the usability | use_condition was evaluated with the following method.

About 10 g of each of the evaluation monitors applied about 0.5 g of each external composition to the arm, and the feeling during use (ease of stretching, familiarity with the skin) and the feeling after application (no stickiness, film feeling, moisturizing feeling) ) Was evaluated. The evaluation was performed by conducting a questionnaire using Visual Analogue Scale (hereinafter referred to as VAS), which was scored between 1 and 10 points according to the criteria shown below. The questionnaire results were averaged, and the obtained results were rounded off to the second decimal place. For the evaluation points of each Example and Comparative Example, a value with the evaluation point of Comparative Example 1 as a reference (100) is calculated, that is, the evaluation point of each Example and Comparative Example is the evaluation point of Comparative Example 1 ( Divided by the standard) to give 100 percent (rounded to the first decimal place).
<Ease of extension>
1 point: Difficult to extend at the time of application 10 points: Easy to extend at the time of application <Skin familiarity>
1 point: There is no feeling that adjusts to the skin at the time of application 10 points: There is a feeling that adjusts to the skin at the time of application
1 point: Tensile feeling 20 seconds after application 10 points: No tension feeling 20 seconds after application <Film feeling>
1 point: There is no feeling covered with a film 20 seconds after application 10 points: There is a feeling covered with a film 20 seconds after application <Moisturizing feeling>
1 point: No moist feeling 30 seconds after application 10 points: Moist feeling 30 seconds after application

  The results are shown in Table 1. When 0.2% by weight of carboxyvinyl polymer is contained alone, it is inferior in easiness of stretching at the time of application and familiarity with the skin, and after application, a sufficient film feeling is recognized, but at the same time, a very strong feeling of tension occurs. The result was inferior in terms of moisturizing feeling. In addition, when containing 0.1% by weight of unsaturated hyaluronic acid disaccharide alone, it is excellent in terms of easiness of stretching at the time of application, familiarity with the skin, and lack of a feeling of tension after application. In addition, since a moisturizing feeling was not felt, sufficient usability was not obtained. Even when 0.05% by weight of carboxyvinyl polymer and 0.1% by weight of unsaturated hyaluronic acid disaccharide were included, as in Comparative Example 4, the film feeling and moisturizing feeling after application were not recognized, and the feeling of use was inferior. It was.

  On the other hand, when 0.2% by weight or more of carboxyvinyl polymer and unsaturated hyaluronic acid disaccharide are included, the amount of carboxyvinyl polymer compared to Comparative Example 1 is twice or more, At the time of application, it was excellent in stretchability and familiarity with the skin, and even after application, the film feeling and moisturizing feeling were good while suppressing the tension feeling (Examples 1 to 6). Furthermore, by including glycerin, it was possible to obtain an external composition excellent in all aspects of ease of stretching and skin familiarity at the time of application, as well as lack of a feeling of tension after application, film feeling and moisturizing feeling (implementation). Examples 7-8).

  Further, the same as in Examples 1 to 3 except that the carboxyvinyl polymer was changed to “Carbopol 940”, “Carbopol 941”, “Carbopol 981”, and “Pemlen TR-1” manufactured by Lubrizol Advanced Materials. The composition for external use was prepared under the conditions described above. These external compositions were also evaluated by the same method as described above, and they were excellent in both ease of stretching during application and skin familiarity, lack of feeling of tension after application, film feeling and moisturizing feeling. Admitted.

Test Example 2: Evaluation of hyaluronic acid solubility in water Purified water at room temperature was placed in a 200 mL container to which a predetermined amount of carboxyvinyl polymer, unsaturated hyaluronic acid disaccharide and hyaluronic acid shown in Table 2 were added. A fixed amount (100 g of the total contents in the container) was added, and stirring was started at room temperature with a propeller stirrer at a speed of 500 rpm. The time (dissolution time) from the start of stirring until hyaluronic acid was completely removed and hyaluronic acid was completely dissolved was measured. Finally, an aqueous sodium hydroxide solution was added to prepare an external composition (pH 6.5).

  The obtained results are shown in Table 2. It was confirmed that by dissolving hyaluronic acid in water in the presence of carboxyvinyl polymer and unsaturated hyaluronic acid disaccharide, the time required for the dissolution of hyaluronic acid can be greatly shortened.

  Moreover, as a result of evaluating the obtained external composition in the same manner as in Test Example 1, compared with Comparative Example 1, the ease of stretching and skin familiarity at the time of application, and the lack of a feeling of tension after application, the film feeling and the moisture retention It was excellent in both feelings (Example 11).

Claims (5)

  A composition for external use containing (A) carboxyvinyl polymer and / or alkyl-modified carboxyvinyl polymer 0.2% by weight or more and (B) hyaluronic acid oligosaccharide and / or a salt thereof.   The external composition according to claim 1, further comprising (C) glycerin and / or polyglycerin.   The composition for external use according to claim 2, wherein the content of (C) glycerol and / or polyglycerol is 3% by weight or more.   Furthermore, the external composition in any one of Claims 1-3 containing (D) hyaluronic acid and / or its salt.   The composition for external use in any one of Claims 1-4 which is cosmetics.