WO2017026405A1 - Topical composition - Google Patents

Topical composition Download PDF

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Publication number
WO2017026405A1
WO2017026405A1 PCT/JP2016/073159 JP2016073159W WO2017026405A1 WO 2017026405 A1 WO2017026405 A1 WO 2017026405A1 JP 2016073159 W JP2016073159 W JP 2016073159W WO 2017026405 A1 WO2017026405 A1 WO 2017026405A1
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WO
WIPO (PCT)
Prior art keywords
composition
glucosamine
mass
polymer
external
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PCT/JP2016/073159
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French (fr)
Japanese (ja)
Inventor
佳子 藤原
謙 菅原
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大正製薬株式会社
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Priority to JP2017534417A priority Critical patent/JP6770693B2/en
Publication of WO2017026405A1 publication Critical patent/WO2017026405A1/en

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60—Sugars; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/70—Carbohydrates; Sugars; Derivatives thereof
    • A61K31/7008—Compounds having an amino group directly attached to a carbon atom of the saccharide radical, e.g. D-galactosamine, ranimustine
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • A61K47/38—Cellulose; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin

Definitions

  • the present invention relates to a composition for external use. More specifically, by blending a glucosamine-containing external composition with a carboxyvinyl polymer and a cellulosic polymer or a polyvinyl polymer, the usability (ease of taking out from the container) and the feeling of use (coating)
  • the present invention relates to a technique that improves ease of spreading and / or skin familiarity.
  • Glucosamine is a natural amino sugar in which a part of the hydroxyl group of glucose is substituted with an amino group, and exists as a structural unit in various complex carbohydrates in the living body.
  • Hyaluronic acid is known as a representative example of the above-mentioned glycoconjugate, and it is distributed in a large amount in connective tissue, skin tissue, cartilage, joint fluid, etc., and its high water retention maintains the function and form of cells and acts as a lubricant.
  • it plays an important role in terms of cell surface functions such as cell adhesion, proliferation, and differentiation.
  • Patent Document 1 proposes a cosmetic containing glucosamine.
  • glucosamine is known as a Maillard reaction because it is colored (brown) under the influence of heating and pH, and in this reaction, the coloring becomes remarkable in a basic pH range. Therefore, from the viewpoint of suppression of coloring by glucosamine, it is desirable that the glucosamine-containing composition such as a glucosamine combination preparation be prepared in the acidic region.
  • a carboxyvinyl polymer known as a gelling agent is widely used in order to impart hardness to an external preparation (external composition).
  • Carboxyvinyl polymer is an acrylic acid-based hydrophilic cross-linked polymer, thickens by adding a pH adjusting agent, and exhibits properties as a gelling agent.
  • glucosamine is added to the carboxyvinyl polymer, the preparation (composition) does not gel sufficiently and is in a watery and loose state when prepared in the acidic region in consideration of coloring by glucosamine.
  • the problem is that the preparation tends to sag from the mouth of the container, and similarly, when stored in a jar container, there is a problem that it is difficult to handle and inferior in usability. Further, when the pH is brought close to neutrality, while the viscosity of the preparation increases, there arises a problem that it is difficult to spread and conform to the skin.
  • the present invention has been made in view of the above-described problems of the prior art, and includes a glucosamine-containing external composition that has improved usability (ease of taking out from a container) and usability (ease of spreading and / or skin familiarity).
  • the purpose is to provide goods.
  • composition of an external composition containing glucosamine can be obtained by combining glucosamine, a carboxyvinyl polymer, and a cellulose-based polymer or a polyvinyl-based polymer. As a result, the present invention was completed.
  • the present invention is as follows.
  • a composition for external use comprising A) glucosamine, B) carboxyvinyl polymer, and C) cellulose-based polymer or polyvinyl-based polymer.
  • the C-based polymer is at least one selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylcellulose, and methylcellulose.
  • composition for external use according to (1) or (2) wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone and polyvinyl alcohol.
  • the present invention it is possible to improve the properties of an external composition containing glucosamine, and the external composition is excellent in usability (ease of taking out from a container) and feeling in use (ease of spreading and / or skin familiarity). Things can be provided.
  • A) Glucosamine used in the present invention includes a compound represented by the chemical formula C 6 H 13 NO 5 , its derivatives and salts thereof, and is obtained from a chitin decomposition product such as a synthetic product, a fermentation product, crab, and shrimp. Any of the resulting degradation products can be used, and is not particularly limited. One of these may be used alone or a mixture of two or more.
  • the derivatives include, for example, derivatives such as N-acetylglucosamine, and the salts include salts such as glucosamine hydrochloride and glucosamine nitrate.
  • A) glucosamine is preferably N-acetylglucosamine.
  • A) Content of glucosamine (content of a compound represented by the chemical formula C 6 H 13 NO 5 , a derivative thereof, or a salt thereof, or a total content thereof when they are a mixture) is not particularly limited However, it is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total amount of the composition for external use.
  • the B) carboxyvinyl polymer of the present invention is selected from the group consisting of homopolymers of vinyl monomers having a carboxy group such as acrylic acid and methacrylic acid, and copolymers of the vinyl monomer having the carboxy group and other vinyl monomers. Means at least one selected, preferably: —CH 2 —C (COOX) H— [X represents a hydrogen atom, an alkali metal or an ammonium group. ]
  • X in the structural unit is preferably a hydrogen atom.
  • the B) carboxyvinyl polymer includes, for example, a 0.5% aqueous solution (pH: 6.5 to 7.5) having a viscosity of 4000 to 10,000 mPa ⁇ s, 40000 to 60000 mPa ⁇ s, and the like.
  • a 0.5% aqueous solution pH: 6.5 to 7.5
  • the viscosity is preferably from 40,000 to 60,000 mPa ⁇ s.
  • the content of the carboxyvinyl polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.01 to 5% by mass, preferably 0.02 to 2% by mass.
  • A) is preferably 0.02 to 20 parts by mass, more preferably 0.04 to 5 parts by mass, and further preferably 0.04 to 1.5 parts by mass with respect to 1 part by mass of glucosamine. is there.
  • the content is less than the lower limit, excellent usability in the composition for external use, that is, the ease of taking out from the container tends not to be sufficiently exhibited.
  • the content exceeds the upper limit the composition for external use is excellent. There is a tendency that the feeling of use, i.e., ease of spreading and / or skin familiarity, is not fully exhibited.
  • composition for external use of the present invention contains C) a cellulose polymer or a polyvinyl polymer.
  • the cellulosic polymer includes cellulose and cellulose derivatives obtained by partially modifying cellulose, and one of these may be used alone or a mixture of two or more.
  • cellulose derivatives obtained by partially modifying cellulose, and one of these may be used alone or a mixture of two or more.
  • hydroxyalkyl cellulose such as hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose
  • Alkyl cellulose such as ethylcellulose and methylcellulose
  • the cellulose polymer is preferably hydroxypropylmethylcellulose, methylcellulose, or hydroxypropylcellulose.
  • Hydroxypropyl methylcellulose has different types such as 50%, 400, 1500, 4000, 10000, 15000, and 100000 mPa ⁇ s in the viscosity of 2% aqueous solution (20 ° C.).
  • the higher viscosity is the composition for external use. From the standpoint that better usability (ease of taking out from the container) tends to be exhibited in the product, the viscosity is preferably 10,000 mPa ⁇ s or more.
  • there are different types of methylcellulose such as 15%, 25, 100, 1500, and 4000 mPa ⁇ s, in a 2% aqueous solution (20 ° C.).
  • the higher the viscosity, the better the use in the composition for external use From the viewpoint of exhibiting the property (ease of taking out from the container), those of 1500 mPa ⁇ s or more are preferable. Furthermore, there are different types of hydroxypropyl cellulose, such as 6-10, 150-400, 1000-4000 mPa ⁇ s, in a 2% aqueous solution, but in the present invention, the higher the viscosity, the better the use in external compositions. From the viewpoint of exhibiting the property (ease of taking out from the container), the viscosity is preferably 150 mPa ⁇ s or more.
  • the content of the cellulosic polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.02 to 10% by mass, preferably 0.05, based on the total amount of the composition for external use. Is 3% by mass, more preferably 0.05-1% by mass, and still more preferably 0.06-0.5% by mass.
  • B) is preferably 0.1 to 5 parts by mass, more preferably 0.25 to 3 parts by mass, and further preferably 0.3 to 3 parts by mass with respect to 1 part by mass of the carboxyvinyl polymer. 2.5 parts by mass.
  • the content is less than the lower limit, sufficiently excellent usability (ease of taking out from the container) tends not to be exhibited in the composition for external use.
  • the content exceeds the upper limit the composition for external use is sufficient. There is a tendency that an excellent feeling of use (ease of spreading and / or skin familiarity) is not exhibited.
  • the polyvinyl polymer means at least one selected from the group consisting of homopolymers and copolymers of vinyl monomers other than the vinyl monomer having a carboxy group, preferably the following formula: —CH 2 —C (R) H— [R is the following formula: -COOX [X represents a hydrogen atom, an alkali metal or an ammonium group. ] A monovalent group other than the group represented by ]
  • the vinyl polymer which consists of the structural unit shown by these, The type of these may be individual, or 2 or more types of mixtures may be sufficient. Examples of R include a hydroxyl group and a 5-membered lactam ring.
  • the polyvinyl polymer In the external composition of the present invention, all or part of R in the structural unit may be neutralized.
  • the polyvinyl polymer is not particularly limited, and examples thereof include polyvinyl pyrrolidone and polyvinyl alcohol.
  • Polyvinyl pyrrolidone has different types such as 5% aqueous solution (25 ° C.) having a viscosity of 3, 10, 150, 350 mPa ⁇ s.
  • the higher the viscosity the better the usability in the composition for external use. From the viewpoint of exhibiting (ease of taking out from the container), those of 150 mPa ⁇ s or more are preferable.
  • Polyvinyl alcohol includes different types such as a 4% aqueous solution (20 ° C.) having a viscosity of 20.0 to 24.5, 27.0 to 33.0, and 40.0 to 46.0 mPa ⁇ s.
  • the viscosity is preferably 40.0 to 46.0 mPa ⁇ s. .
  • the content of the polyvinyl polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.1 to 20% by mass, preferably 0.2%, based on the total amount of the composition for external use. ⁇ 10% by mass.
  • B is preferably 1 part by mass to 50 parts by mass, and more preferably 10 parts by mass to 25 parts by mass with respect to 1 part by mass of B) carboxyvinyl polymer.
  • the pH of the composition for external use in the present invention is 3.5 to 7, preferably 3.5 to 6.
  • compositions for external use of the present invention for example, a solution system, a solubilization system, an emulsification system, a powder dispersion system in the form of gel, cream, emulsion, serum, lotion, pump spray, aerosol, etc.
  • a solution system for example, a solubilization system, an emulsification system, a powder dispersion system in the form of gel, cream, emulsion, serum, lotion, pump spray, aerosol, etc.
  • gels and creams are preferable from the viewpoint that the effects of the present invention (excellent usability and usability) are more fully exhibited.
  • these external compositions can be used in a jar container or a tube-shaped container.
  • These forms can be prepared by conventional methods. For example, in the gel, first, A) glucosamine is dissolved and dispersed in water or a mixture of water and ethanol and / or polyhydric alcohol, and C) a cellulose polymer or polyvinyl polymer is added. Next, B) a carboxyvinyl polymer and other gelling agent as necessary are added, and further a pH adjuster is added as necessary, whereby a gel-like external composition can be obtained.
  • additives such as an antioxidant, a refreshing agent, and a fragrance can be appropriately blended as necessary within a range not impairing the effects of the present invention.
  • the pH adjuster is not particularly limited as long as it can adjust the pH.
  • basic substances inorganic bases such as sodium hydroxide and potassium hydroxide; organic amines such as triethanolamine and diisopropanolamine
  • Acidic substances organic acids such as citric acid, tartaric acid and lactic acid; inorganic acids such as phosphoric acid, sulfuric acid, nitric acid and hydrochloric acid
  • a basic compound and the organic acid or the inorganic acid can be used.
  • Acid addition salts can also be used.
  • the antioxidant may be edetic acid (EDTA), dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA) or the like.
  • compositions for external use of Examples 1 to 3 and Comparative Examples 1 to 4 were prepared so as to have the formulations (compositions) shown in Table 1, respectively.
  • N-acetylglucosamine was dissolved in purified water, and then hydroxypropylmethylcellulose, methylcellulose or hydroxypropylcellulose was added and dissolved according to the formulation.
  • hydroxypropylmethylcellulose a 2% hydroxypropylmethylcellulose aqueous solution prepared in advance (hydroxypropylmethylcellulose (viscosity of 2% aqueous solution at 20 ° C: 100000 mPa ⁇ s, the same shall apply) is dispersed while heating purified water at 70-80 ° C).
  • hydroxypropylmethylcellulose was added and dissolved so that the final concentration of hydroxypropylmethylcellulose was 0.4 parts by mass (0.4% by mass) in the composition for external use. Further, methylcellulose (2% aqueous solution viscosity at 20 ° C .: 4000 mPa ⁇ s) was added and dispersed, and then dissolved at 70 to 80 ° C. As for hydroxypropylcellulose, hydroxypropylcellulose (2% aqueous solution viscosity: 150 to 400 mPa ⁇ s) was added at room temperature to be dispersed and dissolved.
  • a 2% carboxyvinyl polymer aqueous solution (carboxyvinyl polymer: 0.5% aqueous solution viscosity at pH 6.5 to 7.5: 40000 to 60000 mPa ⁇ s, the same shall apply hereinafter) prepared in advance is added to these solutions.
  • a pH adjuster sodium hydroxide solution
  • the unit of numerical values (excluding pH) in Table 1 is “part by mass (more specifically,“ g / 100 g ”)”, and “total 100” of purified water is combined with other components. It shows that purified water is contained so that the total amount of the composition is 100 parts by mass (the same applies hereinafter).
  • Examples 4 to 5, Comparative Examples 5 to 7 The compositions for external use of Example 4, Example 5, and Comparative Examples 5 to 7 were prepared so as to have the formulations (compositions) shown in Table 2, respectively.
  • N-acetylglucosamine is dissolved in purified water, and then polyvinylpyrrolidone (5% aqueous solution viscosity at 25 ° C .: 150 mPa ⁇ s) or polyvinyl alcohol (4% aqueous solution viscosity at 20 ° C .: 40.0 ⁇ ) depending on the formulation. 46.0 mPa ⁇ s) was added and dissolved.
  • Polyvinylpyrrolidone was dispersed and dissolved at room temperature.
  • Polyvinyl alcohol was dispersed at room temperature and dissolved while heating at 70 to 80 ° C., and then this solution was returned to room temperature.
  • a 2% carboxyvinyl polymer aqueous solution prepared in advance is added to these solutions so that the final concentration of the carboxyvinyl polymer is 0.2 parts by mass (0.2% by mass) in the composition for external use.
  • a regulator sodium hydroxide solution
  • Example 6, Comparative Examples 8 to 9 The compositions for external use of Example 6, Comparative Example 8 and Comparative Example 9 were prepared so as to have the formulations (compositions) shown in Table 3, respectively.
  • glucosamine hydrochloride was dissolved in purified water, and then hydroxypropylmethylcellulose was dispersed while heating at 70 to 80 ° C. and dissolved while cooling with ice. After returning this solution to room temperature, a 2% carboxyvinyl polymer aqueous solution prepared in advance was added to the external composition where the final concentration of carboxyvinyl polymer was obtained to 0.5 parts by mass (0.5% by mass).
  • a pH adjuster sodium hydroxide solution
  • the total amount was made 100 parts by mass with purified water, and this was used as an external composition (gel agent).
  • Example 7, Comparative Examples 10 to 11 The compositions for external use of Example 7, Comparative Example 10 and Comparative Example 11 were prepared so as to have the formulations (compositions) shown in Table 4, respectively.
  • glucosamine sulfate was dissolved in purified water, and then hydroxypropylmethylcellulose was dispersed while heating at 70 to 80 ° C. and dissolved while cooling with ice. After returning this solution to room temperature, a 2% carboxyvinyl polymer aqueous solution prepared in advance was added to the external composition where the final concentration of carboxyvinyl polymer was obtained to 0.5 parts by mass (0.5% by mass).
  • a pH adjuster sodium hydroxide solution
  • the total amount was made 100 parts by mass with purified water, and this was used as an external composition (gel agent).
  • Test Example 1 Evaluation of ease of taking out from container Containers (aluminum tubes) were filled with the compositions for external use prepared in each Example and Comparative Example, and the ease of taking out from the container was evaluated from the viewpoint of usability.
  • the ease of taking out from the container evaluated in this test specifically means that the external composition is pushed out of the aluminum tube and taken up by the hand. (1: very difficult to take out, 2: hard to take out, 3: normal, 4: easy to put out, 5: very easy to put out).
  • the test was conducted by four evaluators, and the average score of the four people was used as the score.
  • Test Example 2 Evaluation of ease of spreading The ease of spreading when an appropriate amount of the composition for external use prepared in each Example and Comparative Example was applied to the skin was evaluated (1: very difficult to spread, 2: difficult to spread) 3: normal, 4: easy to spread, 5: very easy to spread) The test was conducted by four evaluators, and the average score of the four people was used as the score.
  • Test Example 3 Skin familiarity evaluation The skin familiarity when an appropriate amount of the composition for external use prepared in each Example and Comparative Example was applied to the skin was evaluated (1: unfamiliar, 2: somewhat unfamiliar, 3: normal, 4 : Familiarity 5: Familiarity) The test was conducted by four evaluators, and the average score of the four people was used as the score.
  • Test Examples 1 to 3 were carried out for the compositions for external use obtained in Examples 1 to 7 and Comparative Examples 1 to 11, and the obtained results are shown in Tables 5 to 8.
  • the composition for external use can be easily taken out from the container, spread easily, and / or Or it turned out that skin familiarity is excellent. Moreover, as shown in Table 7 and Table 8, the same result was obtained when glucosamine hydrochloride or glucosamine sulfate was added as glucosamine. Further, the compositions for external use (Examples 1 to 7) were less likely to sag when picked up and had good usability.
  • compositions for external use of Examples 8 to 12 and Comparative Example 12 were prepared so as to have the formulations (compositions) shown in Table 9, respectively.
  • N-acetylglucosamine was dissolved in purified water, and then hydroxypropylmethylcellulose was added and dissolved according to the formulation.
  • hydroxypropylmethylcellulose was added and dissolved according to the formulation.
  • the solution in which N-acetylglucosamine was dissolved was heated and heated at 70 to 80 ° C. to add and disperse hydroxypropylmethylcellulose, and dissolved while cooling with ice.
  • Test Examples 1 to 3 were carried out on the compositions for external use obtained in Examples 8 to 12 and Comparative Example 12, and the obtained results are shown in Table 10.
  • composition for external use was prepared according to the formulation described in Table 11.
  • oil components stearyl alcohol, octyldodecyl myristate, hard fat, polyoxyl 40 stearate, dimethylpolysiloxane
  • a 2% carboxyvinyl polymer solution prepared in advance was weighed in an external composition that gives a final concentration of carboxyvinyl polymer to be 0.5 parts by mass (0.5% by mass). Warmed at 0 ° C.
  • the dissolved oil component was added to a warmed 2% carboxyvinyl polymer solution and stirred. This was cooled to room temperature and designated as Liquid A.
  • purified water was weighed in another beaker to dissolve N-acetylglucosamine. Hydroxypropylmethylcellulose was added and dispersed while heating this solution at 70 to 80 ° C., and the solution dissolved while cooling was designated as solution B. Liquid B was added to liquid A and stirred uniformly, then the pH was adjusted with a sodium hydroxide solution, and the total amount was 100 parts by mass with purified water to obtain an external composition (cream).
  • glucosamine-containing external composition having excellent usability and usability. Therefore, development to cosmetics, quasi-drugs, pharmaceutical industry, etc. is expected through the commercialization of glucosamine-containing external composition with high commercial value.

Abstract

Glucosamine has the property of being discolored by the effects of heating and pH; glucosamine-containing compositions are preferably prepared in the acidic range from the viewpoint of suppressing discoloration. There were problems, however, with the ease of removal from the container and the feel on use when a carboxy vinyl polymer alone or cellulose-based polymer alone was blended in the acidic region in consideration of discoloration by glucosamine. The present invention provides a topical composition having improved usability (ease of removal from the container) and feel on use (spreadability and/or skin penetration) by containing glucosamine, carboxy vinyl polymer, and cellulose-based polymer or polyvinyl-based polymer.

Description

外用組成物Composition for external use
　本発明は外用組成物に関する。さらに詳しくは、グルコサミン含有外用組成物にカルボキシビニルポリマーとセルロース系高分子又はポリビニル系高分子とを配合することにより、前記外用組成物の使用性（容器からの出しやすさ）及び使用感（塗り広げやすさ及び／又は肌なじみ）を向上させた技術に関する。 The present invention relates to a composition for external use. More specifically, by blending a glucosamine-containing external composition with a carboxyvinyl polymer and a cellulosic polymer or a polyvinyl polymer, the usability (ease of taking out from the container) and the feeling of use (coating) The present invention relates to a technique that improves ease of spreading and / or skin familiarity.
　グルコサミンは、グルコースの一部の水酸基がアミノ基に置換された天然アミノ糖であり、生体中の様々な複合糖質中に構成単位として存在している。前記複合糖質の代表例としてはヒアルロン酸が知られており、結合組織や皮膚組織、軟骨、関節液などに多く分布し、その高い保水性によって細胞の機能や形態を維持したり滑剤として働いたりする他、細胞接着、増殖、分化など細胞表面における機能に関して重要な働きを担っている。また、ヒアルロン酸やグルコサミンから生成されるコンドロイチンの減少は、肌の老化にも関与すると考えられている。 Glucosamine is a natural amino sugar in which a part of the hydroxyl group of glucose is substituted with an amino group, and exists as a structural unit in various complex carbohydrates in the living body. Hyaluronic acid is known as a representative example of the above-mentioned glycoconjugate, and it is distributed in a large amount in connective tissue, skin tissue, cartilage, joint fluid, etc., and its high water retention maintains the function and form of cells and acts as a lubricant. In addition, it plays an important role in terms of cell surface functions such as cell adhesion, proliferation, and differentiation. Moreover, it is thought that the reduction | decrease of the chondroitin produced | generated from a hyaluronic acid or glucosamine is concerned also in skin aging.
　この様なグルコサミンの生体内機能を反映するものとして、変形性関節炎等の鎮痛作用及び症状の改善効果、美肌効果、血流改善効果等が奏されることが報告されており、内服では食品やサプリメント、外用では化粧水やゲル剤、クリーム剤等のグルコサミン含有製品が市販されている。例えば、特開２０１２－０４１３０２号公報（特許文献１）には、グルコサミンを含有した化粧料が提案されている。 As a reflection of such in vivo functions of glucosamine, it has been reported that analgesic effects such as osteoarthritis, symptom improving effects, skin beautifying effects, blood flow improving effects, etc. are achieved. For supplements and external use, glucosamine-containing products such as lotions, gels, and creams are commercially available. For example, Japanese Unexamined Patent Publication No. 2012-041302 (Patent Document 1) proposes a cosmetic containing glucosamine.
　また、グルコサミンは加熱やｐＨの影響により着色（褐変）する性質がメイラード反応として知られており、この反応ではｐＨが塩基性領域で着色が顕著になる。したがって、グルコサミンによる着色抑制の観点から、グルコサミン配合製剤等のグルコサミン含有組成物は酸性領域で調製されることが望ましい。 In addition, glucosamine is known as a Maillard reaction because it is colored (brown) under the influence of heating and pH, and in this reaction, the coloring becomes remarkable in a basic pH range. Therefore, from the viewpoint of suppression of coloring by glucosamine, it is desirable that the glucosamine-containing composition such as a glucosamine combination preparation be prepared in the acidic region.
　他方、一般に、外用製剤（外用組成物）に硬さを付与するために、ゲル化剤として知られるカルボキシビニルポリマーが汎用される。カルボキシビニルポリマーはアクリル酸系の親水性架橋ポリマーであり、ｐＨ調節剤を添加することにより増粘し、ゲル化剤としての性状を示す。しかしながら、カルボキシビニルポリマーにグルコサミンを配合する場合、グルコサミンによる着色を考慮して酸性領域で調製すると、製剤（組成物）が十分にゲル化せず、水っぽくゆるい状態であるため、チューブ状の容器に収納した場合には製剤が容器の口元から垂れやすいという課題が生じ、ジャー容器に収納した場合にも同様に、手に取りづらく使用性に劣るという課題が生じる。また、ｐＨを中性に近づけていくと、製剤は粘度が増す一方で、塗り広げにくく肌になじみ難くなるという課題が生じる。 On the other hand, generally, a carboxyvinyl polymer known as a gelling agent is widely used in order to impart hardness to an external preparation (external composition). Carboxyvinyl polymer is an acrylic acid-based hydrophilic cross-linked polymer, thickens by adding a pH adjusting agent, and exhibits properties as a gelling agent. However, when glucosamine is added to the carboxyvinyl polymer, the preparation (composition) does not gel sufficiently and is in a watery and loose state when prepared in the acidic region in consideration of coloring by glucosamine. When stored, the problem is that the preparation tends to sag from the mouth of the container, and similarly, when stored in a jar container, there is a problem that it is difficult to handle and inferior in usability. Further, when the pH is brought close to neutrality, while the viscosity of the preparation increases, there arises a problem that it is difficult to spread and conform to the skin.
　また、製剤に粘度を付与するために、ヒドロキシプロピルメチルセルロース等のセルロース系高分子を単独で添加した場合には、配合量が少量の場合、製剤がゆるい状態であるため、チューブ状の容器に収納した場合には容器の口元から垂れやすいという課題が、ジャー容器に収納した場合には手に取りづらく使用性に劣るという課題が、それぞれ生じる。また、ある程度の粘度を付与するために配合量を増やすと、べたついたり肌になじみ難くなって使用感に劣るという課題が生じる。 In addition, when a cellulosic polymer such as hydroxypropylmethylcellulose is added alone to give viscosity to the preparation, it is stored in a tube-shaped container because the preparation is loose when the amount is small. In such a case, the problem that the container tends to sag from the mouth of the container arises, and the problem that it is difficult to handle and inferior in usability occurs when stored in the jar container. Further, when the blending amount is increased in order to impart a certain degree of viscosity, there arises a problem that the feeling of use is inferior due to stickiness or difficulty in conforming to the skin.
特開２０１２－０４１３０２号公報JP 2012-041302 A
　本発明は上記従来技術の有する課題に鑑みてなされたものであり、使用性（容器からの出しやすさ）及び使用感（塗り広げやすさ及び／又は肌なじみ）を向上させたグルコサミン含有外用組成物を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and includes a glucosamine-containing external composition that has improved usability (ease of taking out from a container) and usability (ease of spreading and / or skin familiarity). The purpose is to provide goods.
　本発明者らは、上記課題を解決するため種々検討した結果、グルコサミンと、カルボキシビニルポリマーと、セルロース系高分子又はポリビニル系高分子とを組み合わせることにより、グルコサミンを含有する外用組成物の性状が向上し、容器から出しやすく、かつ、塗り広げやすく肌なじみがよくなることを見出し、本発明を完成した。 As a result of various studies to solve the above problems, the present inventors have found that the composition of an external composition containing glucosamine can be obtained by combining glucosamine, a carboxyvinyl polymer, and a cellulose-based polymer or a polyvinyl-based polymer. As a result, the present invention was completed.
　すなわち本発明は、以下のとおりである。
（１）Ａ）グルコサミン、Ｂ）カルボキシビニルポリマー、及び、Ｃ）セルロース系高分子又はポリビニル系高分子を含有することを特徴とする外用組成物。
（２）Ａ）グルコサミンが、Ｎ－アセチルグルコサミン、グルコサミン塩酸塩及びグルコサミン硫酸塩からなる群から選ばれる少なくとも１種である（１）に記載の外用組成物。
（３）Ｃ）セルロース系高分子が、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルセルロース及びメチルセルロースからなる群から選ばれる少なくとも１種である（１）又は（２）に記載の外用組成物。
（４）Ｃ）ポリビニル系高分子が、ポリビニルピロリドン及びポリビニルアルコールからなる群から選ばれる少なくとも１種である（１）又は（２）に記載の外用組成物。
（５）ｐＨが、３．５～７である（１）～（４）のいずれかに記載の外用組成物。 That is, the present invention is as follows.
(1) A composition for external use comprising A) glucosamine, B) carboxyvinyl polymer, and C) cellulose-based polymer or polyvinyl-based polymer.
(2) A) The composition for external use according to (1), wherein the glucosamine is at least one selected from the group consisting of N-acetylglucosamine, glucosamine hydrochloride and glucosamine sulfate.
(3) The composition for external use according to (1) or (2), wherein the C-based polymer is at least one selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylcellulose, and methylcellulose.
(4) The composition for external use according to (1) or (2), wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinyl pyrrolidone and polyvinyl alcohol.
(5) The composition for external use according to any one of (1) to (4), wherein the pH is 3.5 to 7.
　本発明により、グルコサミンを含有する外用組成物の性状を向上させることが可能となり、使用性（容器からの出しやすさ）及び使用感（塗り広げやすさ及び／又は肌なじみ）に優れた外用組成物の提供が可能となる。 According to the present invention, it is possible to improve the properties of an external composition containing glucosamine, and the external composition is excellent in usability (ease of taking out from a container) and feeling in use (ease of spreading and / or skin familiarity). Things can be provided.
　本発明に使用するＡ）グルコサミンは、化学式Ｃ６Ｈ１３ＮＯ５で示される化合物の他、その誘導体及びそれらの塩を包含し、合成物や発酵産物、カニ、えび等のキチン分解物から得られる分解産物等いずれも使用可能であり、特に限定されず、これらのうちの一種を単独であっても二種以上の混合物であってもよい。また、前記誘導体とは、例えば、Ｎ－アセチルグルコサミンなどの誘導体を包含し、前記塩とは、グルコサミン塩酸塩、グルコサミン硝酸塩などの塩類を包含する。これらの中でも、Ａ）グルコサミンとしては、好ましくはＮ－アセチルグルコサミンである。 A) Glucosamine used in the present invention includes a compound represented by the chemical formula C 6 H 13 NO 5 , its derivatives and salts thereof, and is obtained from a chitin decomposition product such as a synthetic product, a fermentation product, crab, and shrimp. Any of the resulting degradation products can be used, and is not particularly limited. One of these may be used alone or a mixture of two or more. The derivatives include, for example, derivatives such as N-acetylglucosamine, and the salts include salts such as glucosamine hydrochloride and glucosamine nitrate. Among these, A) glucosamine is preferably N-acetylglucosamine.
　Ａ）グルコサミンの含有量（化学式Ｃ６Ｈ１３ＮＯ５で示される化合物、その誘導体、若しくはそれらの塩の含有量、又は、これらが混合物である場合にはそれらの合計含有量）は特に限定されないが、外用組成物全量に対して、通常０．０１～２０質量％、好ましくは０．１～１０質量％である。 A) Content of glucosamine (content of a compound represented by the chemical formula C 6 H 13 NO 5 , a derivative thereof, or a salt thereof, or a total content thereof when they are a mixture) is not particularly limited However, it is usually 0.01 to 20% by mass, preferably 0.1 to 10% by mass, based on the total amount of the composition for external use.
　本発明のＢ）カルボキシビニルポリマーは、アクリル酸及びメタクリル酸等のカルボキシ基を有するビニルモノマーの単独重合体、及び前記カルボキシ基を有するビニルモノマーと他のビニルモノマーとの共重合体からなる群から選ばれる少なくとも１種を意味し、好ましくは、次式：
　　－ＣＨ２－Ｃ（ＣＯＯＸ）Ｈ－
［Ｘは水素原子、アルカリ金属又はアンモニウム基を示す。］
で示される構成単位からなるビニルポリマーであり、これらのうちの一種を単独であっても二種以上の混合物であってもよい。Ｂ）カルボキシビニルポリマーとしては、前記構成単位中のＸが水素原子であることが好ましいが、本発明の外用組成物中においては、カルボキシ基が中和されてかかる水素原子の全て又は一部がアルカリ金属又はアンモニウム基に置換されていてもよい。また、かかるＢ）カルボキシビニルポリマーには、例えば、０．５％水溶液（ｐＨ：６．５～７．５）の粘度が４０００～１００００ｍＰａ・ｓ、４００００～６００００ｍＰａ・ｓなど粘度の異なるいくつかのタイプがあり、本発明では特に限定されず、外用組成物としたときの態様に応じて適宜に使い分けることができるが、外用組成物の容器からの出しやすさがさらに向上し、より使用性に優れる傾向にある観点から、好ましくは前記粘度が４００００～６００００ｍＰａ・ｓのものである。 The B) carboxyvinyl polymer of the present invention is selected from the group consisting of homopolymers of vinyl monomers having a carboxy group such as acrylic acid and methacrylic acid, and copolymers of the vinyl monomer having the carboxy group and other vinyl monomers. Means at least one selected, preferably:
—CH 2 —C (COOX) H—
[X represents a hydrogen atom, an alkali metal or an ammonium group. ]
The vinyl polymer which consists of the structural unit shown by these, The type of these may be individual, or 2 or more types of mixtures may be sufficient. B) As the carboxyvinyl polymer, X in the structural unit is preferably a hydrogen atom. However, in the composition for external use of the present invention, all or part of the hydrogen atom is neutralized by neutralizing the carboxy group. It may be substituted with an alkali metal or ammonium group. In addition, the B) carboxyvinyl polymer includes, for example, a 0.5% aqueous solution (pH: 6.5 to 7.5) having a viscosity of 4000 to 10,000 mPa · s, 40000 to 60000 mPa · s, and the like. There are types, and it is not particularly limited in the present invention, and can be properly used depending on the mode when it is used as an external composition, but the ease of taking out the external composition from the container is further improved, and it is more usable. From the viewpoint of superiority, the viscosity is preferably from 40,000 to 60,000 mPa · s.
　Ｂ）カルボキシビニルポリマーの含有量（混合物である場合にはそれらの合計含有量）は特に限定されないが、外用組成物全量に対して、通常０．０１～５質量％、好ましくは０．０２～２質量％である。また、Ａ）グルコサミン１質量部に対して、好ましくは０．０２～２０質量部であり、より好ましくは０．０４～５質量部であり、さらに好ましくは０．０４～１．５質量部である。前記含有量が前記下限未満であると、外用組成物において優れた使用性、すなわち、容器からの出しやすさが十分に発揮されない傾向にあり、他方、前記上限を超えると、外用組成物において優れた使用感、すなわち、塗り広げやすさ及び／又は肌なじみが十分に発揮されない傾向にある。 B) The content of the carboxyvinyl polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.01 to 5% by mass, preferably 0.02 to 2% by mass. In addition, A) is preferably 0.02 to 20 parts by mass, more preferably 0.04 to 5 parts by mass, and further preferably 0.04 to 1.5 parts by mass with respect to 1 part by mass of glucosamine. is there. When the content is less than the lower limit, excellent usability in the composition for external use, that is, the ease of taking out from the container tends not to be sufficiently exhibited. On the other hand, when the content exceeds the upper limit, the composition for external use is excellent. There is a tendency that the feeling of use, i.e., ease of spreading and / or skin familiarity, is not fully exhibited.
　本発明の外用組成物は、Ｃ）セルロース系高分子又はポリビニル系高分子を含有する。 The composition for external use of the present invention contains C) a cellulose polymer or a polyvinyl polymer.
　前記セルロース系高分子は、セルロースの他、セルロースを部分的に変性したセルロース誘導体を包含し、これらのうちの一種を単独であっても二種以上の混合物であってもよい。前記セルロース誘導体としては、特に限定されないが、例えば、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシエチルセルロース、ヒドロキシエチルメチルセルロース等のヒドロキシアルキルセルロース；エチルセルロース、メチルセルロース等のアルキルセルロースが挙げられる。これらの中でも、前記セルロース系高分子としては、好ましくはヒドロキシプロピルメチルセルロース、メチルセルロース、ヒドロキシプロピルセルロースである。また、ヒドロキシプロピルメチルセルロースには２％水溶液（２０℃）の粘度が５０、４００、１５００、４０００、１００００、１５０００、１０００００ｍＰａ・ｓなど異なるタイプがあるが、本発明では、より粘度が高いほうが外用組成物においてより優れた使用性（容器からの出しやすさ）が発揮される傾向にある観点から、前記粘度が１００００ｍＰａ・ｓ以上のものが好ましい。また、メチルセルロースには２％水溶液（２０℃）の粘度が１５、２５、１００、１５００、４０００ｍＰａ・ｓなど異なるタイプがあるが、本発明では、より粘度が高いほうが外用組成物においてより優れた使用性（容器からの出しやすさ）が発揮される傾向にある観点から、１５００ｍＰａ・ｓ以上のものが好ましい。さらに、ヒドロキシプロピルセルロースには２％水溶液の粘度が６～１０、１５０～４００、１０００～４０００ｍＰａ・ｓなど異なるタイプがあるが、本発明では、より粘度が高いほうが外用組成物においてより優れた使用性（容器からの出しやすさ）が発揮される傾向にある観点から、前記粘度が１５０ｍＰａ・ｓ以上のものが好ましい。 The cellulosic polymer includes cellulose and cellulose derivatives obtained by partially modifying cellulose, and one of these may be used alone or a mixture of two or more. Although it does not specifically limit as said cellulose derivative, For example, hydroxyalkyl cellulose, such as hydroxypropyl methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, hydroxyethyl methylcellulose; Alkyl cellulose, such as ethylcellulose and methylcellulose, is mentioned. Among these, the cellulose polymer is preferably hydroxypropylmethylcellulose, methylcellulose, or hydroxypropylcellulose. Hydroxypropyl methylcellulose has different types such as 50%, 400, 1500, 4000, 10000, 15000, and 100000 mPa · s in the viscosity of 2% aqueous solution (20 ° C.). In the present invention, the higher viscosity is the composition for external use. From the standpoint that better usability (ease of taking out from the container) tends to be exhibited in the product, the viscosity is preferably 10,000 mPa · s or more. In addition, there are different types of methylcellulose, such as 15%, 25, 100, 1500, and 4000 mPa · s, in a 2% aqueous solution (20 ° C.). In the present invention, the higher the viscosity, the better the use in the composition for external use. From the viewpoint of exhibiting the property (ease of taking out from the container), those of 1500 mPa · s or more are preferable. Furthermore, there are different types of hydroxypropyl cellulose, such as 6-10, 150-400, 1000-4000 mPa · s, in a 2% aqueous solution, but in the present invention, the higher the viscosity, the better the use in external compositions. From the viewpoint of exhibiting the property (ease of taking out from the container), the viscosity is preferably 150 mPa · s or more.
　前記セルロース系高分子の含有量（混合物である場合にはそれらの合計含有量）は、特に限定されないが、外用組成物全量に対して、通常０．０２～１０質量％、好ましくは０．０５～３質量％であり、より好ましくは０．０５～１質量％であり、さらに好ましくは０．０６～０．５質量％である。また、Ｂ）カルボキシビニルポリマー１質量部に対して、好ましくは０．１質量部～５質量部であり、より好ましくは０．２５質量部～３質量部であり、さらに好ましくは０．３～２．５質量部である。前記含有量が前記下限未満であると、外用組成物において十分に優れた使用性（容器からの出しやすさ）が発揮されない傾向にあり、他方、前記上限を超えると、外用組成物において十分に優れた使用感（塗り広げやすさ及び／又は肌なじみ）が発揮されない傾向にある。 The content of the cellulosic polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.02 to 10% by mass, preferably 0.05, based on the total amount of the composition for external use. Is 3% by mass, more preferably 0.05-1% by mass, and still more preferably 0.06-0.5% by mass. Further, B) is preferably 0.1 to 5 parts by mass, more preferably 0.25 to 3 parts by mass, and further preferably 0.3 to 3 parts by mass with respect to 1 part by mass of the carboxyvinyl polymer. 2.5 parts by mass. When the content is less than the lower limit, sufficiently excellent usability (ease of taking out from the container) tends not to be exhibited in the composition for external use. On the other hand, when the content exceeds the upper limit, the composition for external use is sufficient. There is a tendency that an excellent feeling of use (ease of spreading and / or skin familiarity) is not exhibited.
　前記ポリビニル系高分子は、前記カルボキシ基を有するビニルモノマー以外のビニルモノマーの単独重合体及び共重合体からなる群から選ばれる少なくとも１種を意味し、好ましくは、次式：
　　－ＣＨ２－Ｃ（Ｒ）Ｈ－
［Ｒは次式：
　　　－ＣＯＯＸ
　［Ｘは水素原子、アルカリ金属又はアンモニウム基を示す。］
で示される基以外の一価の基を示す。］
で示される構成単位からなるビニルポリマーであり、これらのうちの一種を単独であっても二種以上の混合物であってもよい。前記Ｒとしては、水酸基及び５員ラクタム環等が挙げられる。また、本発明の外用組成物中において、前記ポリビニル系高分子としては、前記構成単位中のＲの全て又は一部が中和されていてもよい。前記ポリビニル系高分子としては、特に限定されないが、例えば、ポリビニルピロリドン、ポリビニルアルコールである。また、ポリビニルピロリドンには５％水溶液（２５℃）の粘度が３、１０、１５０、３５０ｍＰａ・ｓなど異なるタイプがあるが、本発明では、より粘度が高いほうが外用組成物においてより優れた使用性（容器からの出しやすさ）が発揮される傾向にある観点から、１５０ｍＰａ・ｓ以上のものが好ましい。また、ポリビニルアルコールには４％水溶液（２０℃）の粘度が２０．０～２４．５、２７．０～３３．０、４０．０～４６．０ｍＰａ・ｓなど異なるタイプがあるが、本発明では、より粘度が高いほうが外用組成物においてより優れた使用性（容器からの出しやすさ）が発揮される傾向にある観点から、前記粘度が４０．０～４６．０ｍＰａ・ｓのものが好ましい。 The polyvinyl polymer means at least one selected from the group consisting of homopolymers and copolymers of vinyl monomers other than the vinyl monomer having a carboxy group, preferably the following formula:
—CH 2 —C (R) H—
[R is the following formula:
-COOX
[X represents a hydrogen atom, an alkali metal or an ammonium group. ]
A monovalent group other than the group represented by ]
The vinyl polymer which consists of the structural unit shown by these, The type of these may be individual, or 2 or more types of mixtures may be sufficient. Examples of R include a hydroxyl group and a 5-membered lactam ring. In the external composition of the present invention, as the polyvinyl polymer, all or part of R in the structural unit may be neutralized. The polyvinyl polymer is not particularly limited, and examples thereof include polyvinyl pyrrolidone and polyvinyl alcohol. Polyvinyl pyrrolidone has different types such as 5% aqueous solution (25 ° C.) having a viscosity of 3, 10, 150, 350 mPa · s. In the present invention, the higher the viscosity, the better the usability in the composition for external use. From the viewpoint of exhibiting (ease of taking out from the container), those of 150 mPa · s or more are preferable. Polyvinyl alcohol includes different types such as a 4% aqueous solution (20 ° C.) having a viscosity of 20.0 to 24.5, 27.0 to 33.0, and 40.0 to 46.0 mPa · s. In view of the fact that higher viscosity tends to exhibit better usability (ease of taking out from the container) in the external composition, the viscosity is preferably 40.0 to 46.0 mPa · s. .
　前記ポリビニル系高分子の含有量（混合物である場合にはそれらの合計含有量）は、特に限定されないが、外用組成物全量に対して、通常０．１～２０質量％、好ましくは０．２～１０質量％である。また、Ｂ）カルボキシビニルポリマー１質量部に対して、好ましくは１質量部～５０質量部であり、より好ましくは１０質量部～２５質量部である。前記含有量が前記下限未満であると、外用組成物において十分に優れた使用性（容器からの出しやすさ）が発揮されない傾向にあり、他方、前記上限を超えると、外用組成物において十分に優れた使用感（塗り広げやすさ及び／又は肌なじみ）が発揮されない傾向にある。 The content of the polyvinyl polymer (the total content in the case of a mixture) is not particularly limited, but is usually 0.1 to 20% by mass, preferably 0.2%, based on the total amount of the composition for external use. ~ 10% by mass. In addition, B is preferably 1 part by mass to 50 parts by mass, and more preferably 10 parts by mass to 25 parts by mass with respect to 1 part by mass of B) carboxyvinyl polymer. When the content is less than the lower limit, sufficiently excellent usability (ease of taking out from the container) tends not to be exhibited in the composition for external use. On the other hand, when the content exceeds the upper limit, the composition for external use is sufficient. There is a tendency that an excellent feeling of use (ease of spreading and / or skin familiarity) is not exhibited.
　グルコサミンは、通常、塩基性では着色するため、本発明における外用組成物のｐＨは３．５～７、好ましくは３．５～６である。 Since glucosamine is usually colored when basic, the pH of the composition for external use in the present invention is 3.5 to 7, preferably 3.5 to 6.
　本発明の外用組成物の形態としては、例えば、溶液系、可溶化系、乳化系、粉末分散系として、ゲル、クリーム、乳液、美容液、ローション、ポンプスプレー、エアゾールなどの形態にしたものが挙げられる。特に、本発明の効果（優れた使用性及び使用感）がより十分に奏される観点からはゲルやクリームが好ましい。また、これらの外用組成物は、ジャー容器やチューブ状の容器に入れて用いることができる。 As the form of the composition for external use of the present invention, for example, a solution system, a solubilization system, an emulsification system, a powder dispersion system in the form of gel, cream, emulsion, serum, lotion, pump spray, aerosol, etc. Can be mentioned. In particular, gels and creams are preferable from the viewpoint that the effects of the present invention (excellent usability and usability) are more fully exhibited. Moreover, these external compositions can be used in a jar container or a tube-shaped container.
　これらの形態は、常法により調製可能である。例えば、ゲルは、先ず、Ａ）グルコサミンを、水、又は水とエタノール及び／又は多価アルコールとの混液に溶解・分散させ、Ｃ）セルロース系高分子又はポリビニル系高分子を添加する。次いで、Ｂ）カルボキシビニルポリマー及び必要に応じて他のゲル化剤を添加し、さらに必要に応じてｐＨ調節剤を加えることにより、ゲル状の外用組成物を得ることができる。このように調製した外用組成物（製剤）には、必要に応じて、酸化防止剤、清涼化剤、香料などの添加物を本発明の効果を損なわない範囲で適宜に配合することができる。 These forms can be prepared by conventional methods. For example, in the gel, first, A) glucosamine is dissolved and dispersed in water or a mixture of water and ethanol and / or polyhydric alcohol, and C) a cellulose polymer or polyvinyl polymer is added. Next, B) a carboxyvinyl polymer and other gelling agent as necessary are added, and further a pH adjuster is added as necessary, whereby a gel-like external composition can be obtained. In the externally prepared composition (formulation) thus prepared, additives such as an antioxidant, a refreshing agent, and a fragrance can be appropriately blended as necessary within a range not impairing the effects of the present invention.
　前記ｐＨ調節剤は、ｐＨを調製し得るものであれば特に限定されず、例えば、塩基性物質（水酸化ナトリウム、水酸化カリウムなどの無機塩基；トリエタノールアミン、ジイソプロパノールアミンなどの有機アミン等）、酸性物質（クエン酸、酒石酸、乳酸等の有機酸；リン酸、硫酸、硝酸、塩酸等の無機酸）を用いることができ、また、塩基性化合物と前記有機酸又は前記無機酸との酸付加塩を用いることもできる。また、前記酸化防止剤はエデト酸（ＥＤＴＡ）、ジブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）等を用いることができる。 The pH adjuster is not particularly limited as long as it can adjust the pH. For example, basic substances (inorganic bases such as sodium hydroxide and potassium hydroxide; organic amines such as triethanolamine and diisopropanolamine) ), Acidic substances (organic acids such as citric acid, tartaric acid and lactic acid; inorganic acids such as phosphoric acid, sulfuric acid, nitric acid and hydrochloric acid) can be used, and a basic compound and the organic acid or the inorganic acid can be used. Acid addition salts can also be used. The antioxidant may be edetic acid (EDTA), dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA) or the like.
　以下に、実施例、比較例を示し、本発明を詳細に説明するが、本発明は以下に限定されるものではない。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following.
　（実施例１～３、比較例１～４）
　実施例１～３、比較例１～４の外用組成物を、それぞれ、表１に示す処方（組成）となるように調製した。先ず、精製水にＮ－アセチルグルコサミンを溶解させた後、処方に応じてヒドロキシプロピルメチルセルロース、メチルセルロース又はヒドロキシプロピルセルロースを添加し、溶解させた。ヒドロキシプロピルメチルセルロースについては、予め調製した２％ヒドロキシプロピルメチルセルロース水溶液（精製水を７０～８０℃で加温しながらヒドロキシプロピルメチルセルロース（２０℃における２％水溶液粘度：１０００００ｍＰａ・ｓ、以下同じ）を分散させ、氷冷しながら溶解させた）をヒドロキシプロピルメチルセルロースの最終濃度が得られる外用組成物中の０．４質量部（０．４質量％）となるよう添加し、溶解させた。また、メチルセルロースについてはメチルセルロース（２０℃における２％水溶液粘度：４０００ｍＰａ・ｓ）を添加し分散させた後、７０～８０℃で溶解させた。ヒドロキシプロピルセルロースについては、ヒドロキシプロピルセルロース（２％水溶液粘度：１５０～４００ｍＰａ・ｓ）を常温で添加し分散・溶解させた。次いで、これらの溶液に、予め調製した２％カルボキシビニルポリマー水溶液（カルボキシビニルポリマー：ｐＨ６．５～７．５における０．５％水溶液粘度：４００００～６００００ｍＰａ・ｓ、以下同じ）をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．２質量部（０．２質量％）になるよう添加し、ｐＨ調節剤（水酸化ナトリウム溶液）を加え、精製水で全量を１００質量部としてこれを外用組成物（ゲル剤）とした。なお、表１中の数値（ｐＨを除く）の単位は「質量部（より具体的には「ｇ／１００ｇ」）」であり、精製水の「全１００」とは、他の成分と合わせた組成物の全量が１００質量部となるように精製水が含有されていることを示す（以下同じ）。 (Examples 1 to 3, Comparative Examples 1 to 4)
The compositions for external use of Examples 1 to 3 and Comparative Examples 1 to 4 were prepared so as to have the formulations (compositions) shown in Table 1, respectively. First, N-acetylglucosamine was dissolved in purified water, and then hydroxypropylmethylcellulose, methylcellulose or hydroxypropylcellulose was added and dissolved according to the formulation. For hydroxypropylmethylcellulose, a 2% hydroxypropylmethylcellulose aqueous solution prepared in advance (hydroxypropylmethylcellulose (viscosity of 2% aqueous solution at 20 ° C: 100000 mPa · s, the same shall apply) is dispersed while heating purified water at 70-80 ° C). And dissolved in an ice bath) was added and dissolved so that the final concentration of hydroxypropylmethylcellulose was 0.4 parts by mass (0.4% by mass) in the composition for external use. Further, methylcellulose (2% aqueous solution viscosity at 20 ° C .: 4000 mPa · s) was added and dispersed, and then dissolved at 70 to 80 ° C. As for hydroxypropylcellulose, hydroxypropylcellulose (2% aqueous solution viscosity: 150 to 400 mPa · s) was added at room temperature to be dispersed and dissolved. Next, a 2% carboxyvinyl polymer aqueous solution (carboxyvinyl polymer: 0.5% aqueous solution viscosity at pH 6.5 to 7.5: 40000 to 60000 mPa · s, the same shall apply hereinafter) prepared in advance is added to these solutions. Add 0.2 parts by mass (0.2% by mass) to the composition for external use to obtain the final concentration, add a pH adjuster (sodium hydroxide solution), and add 100 parts by mass with purified water. Was used as a composition for external use (gel agent). The unit of numerical values (excluding pH) in Table 1 is “part by mass (more specifically,“ g / 100 g ”)”, and “total 100” of purified water is combined with other components. It shows that purified water is contained so that the total amount of the composition is 100 parts by mass (the same applies hereinafter).
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　（実施例４～５、比較例５～７）
　実施例４及び実施例５、比較例５～７の外用組成物を、それぞれ、表２に示す処方（組成）となるように調製した。先ず、精製水にＮ－アセチルグルコサミンを溶解させた後、処方に応じてポリビニルピロリドン（２５℃における５％水溶液粘度：１５０ｍＰａ・ｓ）又はポリビニルアルコール（２０℃における４％水溶液粘度：４０．０～４６．０ｍＰａ・ｓ）を添加し、溶解させた。ポリビニルピロリドンについては、常温にて分散、溶解させた。ポリビニルアルコールについては、常温にて分散し、７０～８０℃で加温しながら溶解させた後にこの溶液を常温に戻した。次いで、これらの溶液に、予め調製した２％カルボキシビニルポリマー水溶液をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．２質量部（０．２質量％）になるよう添加し、ｐＨ調節剤（水酸化ナトリウム溶液）を加え、精製水で全量を１００質量部としてこれを外用組成物（ゲル剤）とした。 (Examples 4 to 5, Comparative Examples 5 to 7)
The compositions for external use of Example 4, Example 5, and Comparative Examples 5 to 7 were prepared so as to have the formulations (compositions) shown in Table 2, respectively. First, N-acetylglucosamine is dissolved in purified water, and then polyvinylpyrrolidone (5% aqueous solution viscosity at 25 ° C .: 150 mPa · s) or polyvinyl alcohol (4% aqueous solution viscosity at 20 ° C .: 40.0˜) depending on the formulation. 46.0 mPa · s) was added and dissolved. Polyvinylpyrrolidone was dispersed and dissolved at room temperature. Polyvinyl alcohol was dispersed at room temperature and dissolved while heating at 70 to 80 ° C., and then this solution was returned to room temperature. Next, a 2% carboxyvinyl polymer aqueous solution prepared in advance is added to these solutions so that the final concentration of the carboxyvinyl polymer is 0.2 parts by mass (0.2% by mass) in the composition for external use. A regulator (sodium hydroxide solution) was added, and the total amount was 100 parts by mass with purified water to obtain an external composition (gel agent).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　（実施例６、比較例８～９）
　実施例６、比較例８及び比較例９の外用組成物を、それぞれ、表３に示す処方（組成）となるように調製した。先ず、精製水にグルコサミン塩酸塩を溶解させた後、７０～８０℃で加温しながらヒドロキシプロピルメチルセルロースを分散させ、氷冷しながら溶解させた。この溶液を室温に戻した後、予め調製した２％カルボキシビニルポリマー水溶液をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．５質量部（０．５質量％）になるよう添加し、ｐＨ調節剤（水酸化ナトリウム溶液）を加え、精製水で全量を１００質量部としてこれを外用組成物（ゲル剤）とした。 (Example 6, Comparative Examples 8 to 9)
The compositions for external use of Example 6, Comparative Example 8 and Comparative Example 9 were prepared so as to have the formulations (compositions) shown in Table 3, respectively. First, glucosamine hydrochloride was dissolved in purified water, and then hydroxypropylmethylcellulose was dispersed while heating at 70 to 80 ° C. and dissolved while cooling with ice. After returning this solution to room temperature, a 2% carboxyvinyl polymer aqueous solution prepared in advance was added to the external composition where the final concentration of carboxyvinyl polymer was obtained to 0.5 parts by mass (0.5% by mass). Then, a pH adjuster (sodium hydroxide solution) was added, and the total amount was made 100 parts by mass with purified water, and this was used as an external composition (gel agent).
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　（実施例７、比較例１０～１１）
　実施例７、比較例１０及び比較例１１の外用組成物を、それぞれ、表４に示す処方（組成）となるように調製した。先ず、精製水にグルコサミン硫酸塩を溶解させた後、７０～８０℃で加温しながらヒドロキシプロピルメチルセルロースを分散させ、氷冷しながら溶解させた。この溶液を室温に戻した後、予め調製した２％カルボキシビニルポリマー水溶液をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．５質量部（０．５質量％）になるよう添加し、ｐＨ調節剤（水酸化ナトリウム溶液）を加え、精製水で全量を１００質量部としてこれを外用組成物（ゲル剤）とした。 (Example 7, Comparative Examples 10 to 11)
The compositions for external use of Example 7, Comparative Example 10 and Comparative Example 11 were prepared so as to have the formulations (compositions) shown in Table 4, respectively. First, glucosamine sulfate was dissolved in purified water, and then hydroxypropylmethylcellulose was dispersed while heating at 70 to 80 ° C. and dissolved while cooling with ice. After returning this solution to room temperature, a 2% carboxyvinyl polymer aqueous solution prepared in advance was added to the external composition where the final concentration of carboxyvinyl polymer was obtained to 0.5 parts by mass (0.5% by mass). Then, a pH adjuster (sodium hydroxide solution) was added, and the total amount was made 100 parts by mass with purified water, and this was used as an external composition (gel agent).
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　（試験例１）容器からの出しやすさ評価
　各実施例及び比較例で調製した外用組成物を容器（アルミチューブ）に充填し、使用性の観点から、容器からの出しやすさを評価した。本試験で評価した容器からの出しやすさとは、具体的に、前記外用組成物をアルミチューブから押し出し、手に取った時の外用組成物の垂れにくさ、指への取りやすさを意味する（１：とても出しにくい、２：出しにくい、３：普通、４：出しやすい、５：とても出しやすい）。試験は評価者４人で実施し、４人の平均点を評点とした。 (Test Example 1) Evaluation of ease of taking out from container Containers (aluminum tubes) were filled with the compositions for external use prepared in each Example and Comparative Example, and the ease of taking out from the container was evaluated from the viewpoint of usability. The ease of taking out from the container evaluated in this test specifically means that the external composition is pushed out of the aluminum tube and taken up by the hand. (1: very difficult to take out, 2: hard to take out, 3: normal, 4: easy to put out, 5: very easy to put out). The test was conducted by four evaluators, and the average score of the four people was used as the score.
　（試験例２）塗り広げやすさ評価
　各実施例及び比較例で調製した外用組成物を肌に適量塗布した際の塗り広げやすさを評価した（１：とても塗り広げにくい、２：塗り広げにくい、３：普通、４：塗り広げやすい、５：とても塗り広げやすい）。試験は評価者４人で実施し、４人の平均点を評点とした。 (Test Example 2) Evaluation of ease of spreading The ease of spreading when an appropriate amount of the composition for external use prepared in each Example and Comparative Example was applied to the skin was evaluated (1: very difficult to spread, 2: difficult to spread) 3: normal, 4: easy to spread, 5: very easy to spread) The test was conducted by four evaluators, and the average score of the four people was used as the score.
　（試験例３）肌なじみ評価
　各実施例及び比較例で調製した外用組成物を肌に適量塗布した際の肌なじみを評価した（１：なじまない、２：ややなじみにくい、３：普通、４：ややなじむ、５：なじむ）。試験は評価者４人で実施し、４人の平均点を評点とした。 (Test Example 3) Skin familiarity evaluation The skin familiarity when an appropriate amount of the composition for external use prepared in each Example and Comparative Example was applied to the skin was evaluated (1: unfamiliar, 2: somewhat unfamiliar, 3: normal, 4 : Familiarity 5: Familiarity) The test was conducted by four evaluators, and the average score of the four people was used as the score.
　実施例１～７及び比較例１～１１で得られた外用組成物について、試験例１～３をそれぞれ実施し、得られた各結果を表５～８に示す。 Test Examples 1 to 3 were carried out for the compositions for external use obtained in Examples 1 to 7 and Comparative Examples 1 to 11, and the obtained results are shown in Tables 5 to 8.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表５及び表６に示すように、Ｎ－アセチルグルコサミンにカルボキシビニルポリマー、及びセルロース系高分子又はポリビニル系高分子を組み合わせると、外用組成物の容器からの出しやすさ、塗り広げやすさ及び／又は肌なじみが優れていることが分かった。また、表７及び表８に示すように、グルコサミンとしてグルコサミン塩酸塩、又はグルコサミン硫酸塩を配合した場合も同様な結果だった。さらに、本外用組成物（実施例１～７）は、手に取った時に垂れにくく、良好な使用性を有していた。 As shown in Tables 5 and 6, when N-acetylglucosamine is combined with a carboxyvinyl polymer and a cellulose-based polymer or a polyvinyl-based polymer, the composition for external use can be easily taken out from the container, spread easily, and / or Or it turned out that skin familiarity is excellent. Moreover, as shown in Table 7 and Table 8, the same result was obtained when glucosamine hydrochloride or glucosamine sulfate was added as glucosamine. Further, the compositions for external use (Examples 1 to 7) were less likely to sag when picked up and had good usability.
　（実施例８～１２、比較例１２）
　実施例８～１２及び比較例１２の外用組成物を、それぞれ、表９に示す処方（組成）となるように調製した。先ず、精製水にＮ－アセチルグルコサミンを溶解させた後、処方に応じてヒドロキシプロピルメチルセルロースを添加し、溶解させた。ヒドロキシプロピルメチルセルロースを溶解する際は、Ｎ－アセチルグルコサミンを溶解した溶液を７０～８０℃で加温しながらヒドロキシプロピルメチルセルロースを添加し分散させ、氷冷しながら溶解させた。次いで、この溶液に、予め調製した２％カルボキシビニルポリマー水溶液をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．２質量部（０．２質量％）になるよう添加し、ｐＨ調節剤（水酸化ナトリウム溶液）を加え、精製水で全量を１００質量部としてこれを外用組成物（ゲル剤）とした。 (Examples 8 to 12, Comparative Example 12)
The compositions for external use of Examples 8 to 12 and Comparative Example 12 were prepared so as to have the formulations (compositions) shown in Table 9, respectively. First, N-acetylglucosamine was dissolved in purified water, and then hydroxypropylmethylcellulose was added and dissolved according to the formulation. When dissolving hydroxypropylmethylcellulose, the solution in which N-acetylglucosamine was dissolved was heated and heated at 70 to 80 ° C. to add and disperse hydroxypropylmethylcellulose, and dissolved while cooling with ice. Next, a 2% carboxyvinyl polymer aqueous solution prepared in advance was added to this solution so that the final concentration of the carboxyvinyl polymer was 0.2 parts by mass (0.2% by mass) to adjust the pH. An agent (sodium hydroxide solution) was added, and the total amount was 100 parts by mass with purified water to obtain an external composition (gel agent).
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
　実施例８～１２及び比較例１２で得られた外用組成物について、試験例１～３をそれぞれ実施し、得られた各結果を表１０に示す。 Test Examples 1 to 3 were carried out on the compositions for external use obtained in Examples 8 to 12 and Comparative Example 12, and the obtained results are shown in Table 10.
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
　表１０に示すように、実施例８～１２で得られた外用組成物ではいずれも容器からの出しやすさ、塗り広げやすさ及び／又は肌なじみが優れていることが分かった。 As shown in Table 10, it was found that any of the compositions for external use obtained in Examples 8 to 12 was excellent in ease of taking out from the container, ease of spreading and / or skin familiarity.
　（クリーム剤）
　表１１に記載の処方に従い外用組成物（クリーム剤）を調製した。先ず、油成分（ステアリルアルコール、ミリスチン酸オクチルドデシル、ハードファット、ステアリン酸ポリオキシル４０、ジメチルポリシロキサン）を７０～８０℃で加温しながら溶解させた。次いで、予め調製しておいた２％カルボキシビニルポリマー溶液をカルボキシビニルポリマーの最終濃度が得られる外用組成物中に０．５質量部（０．５質量％）となるよう秤量し、７０～８０℃で加温した。加温した２％カルボキシビニルポリマー溶液に、上記の溶解させた油成分を添加し、攪拌した。これを室温まで冷却したものをＡ液とした。また、別のビーカーに精製水を秤量し、Ｎ－アセチルグルコサミンを溶解させた。この溶液を７０～８０℃で加温しながらヒドロキシプロピルメチルセルロースを添加して分散させた後、冷却しながら溶解させたものをＢ液とした。Ａ液にＢ液を添加し、均一に攪拌した後、水酸化ナトリウム溶液でｐＨ調整し、精製水で全量を１００質量部としたものを外用組成物（クリーム剤）とした。 (Cream)
A composition for external use (cream) was prepared according to the formulation described in Table 11. First, oil components (stearyl alcohol, octyldodecyl myristate, hard fat, polyoxyl 40 stearate, dimethylpolysiloxane) were dissolved while heating at 70 to 80 ° C. Next, a 2% carboxyvinyl polymer solution prepared in advance was weighed in an external composition that gives a final concentration of carboxyvinyl polymer to be 0.5 parts by mass (0.5% by mass). Warmed at 0 ° C. The dissolved oil component was added to a warmed 2% carboxyvinyl polymer solution and stirred. This was cooled to room temperature and designated as Liquid A. Further, purified water was weighed in another beaker to dissolve N-acetylglucosamine. Hydroxypropylmethylcellulose was added and dispersed while heating this solution at 70 to 80 ° C., and the solution dissolved while cooling was designated as solution B. Liquid B was added to liquid A and stirred uniformly, then the pH was adjusted with a sodium hydroxide solution, and the total amount was 100 parts by mass with purified water to obtain an external composition (cream).
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
　本発明により、使用性及び使用感の優れたグルコサミン含有外用組成物を提供することが可能となった。よって、商品価値の高いグルコサミン配合外用組成物の市販を通じて化粧品・医薬部外品・医薬品産業等への発展が期待される。 According to the present invention, it has become possible to provide a glucosamine-containing external composition having excellent usability and usability. Therefore, development to cosmetics, quasi-drugs, pharmaceutical industry, etc. is expected through the commercialization of glucosamine-containing external composition with high commercial value.

Claims (5)

  1. 　Ａ）グルコサミン、Ｂ）カルボキシビニルポリマー、及び、Ｃ）セルロース系高分子又はポリビニル系高分子を含有することを特徴とする外用組成物。 A composition for external use comprising A) glucosamine, B) carboxyvinyl polymer, and C) cellulose polymer or polyvinyl polymer.
  2. 　Ａ）グルコサミンが、Ｎ－アセチルグルコサミン、グルコサミン塩酸塩及びグルコサミン硫酸塩からなる群から選ばれる少なくとも１種である請求項１に記載の外用組成物。 A) The composition for external use according to claim 1, wherein the glucosamine is at least one selected from the group consisting of N-acetylglucosamine, glucosamine hydrochloride and glucosamine sulfate.
  3. 　Ｃ）セルロース系高分子が、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルセルロース及びメチルセルロースからなる群から選ばれる少なくとも１種である請求項１又は２に記載の外用組成物。 C) The composition for external use according to claim 1 or 2, wherein the cellulosic polymer is at least one selected from the group consisting of hydroxypropylmethylcellulose, hydroxypropylcellulose and methylcellulose.
  4. 　Ｃ）ポリビニル系高分子が、ポリビニルピロリドン及びポリビニルアルコールからなる群から選ばれる少なくとも１種である請求項１又は２に記載の外用組成物。 C) The external composition according to claim 1 or 2, wherein the polyvinyl polymer is at least one selected from the group consisting of polyvinylpyrrolidone and polyvinyl alcohol.
  5. 　ｐＨが、３．５～７である請求項１～４のいずれかに記載の外用組成物。 The external composition according to any one of claims 1 to 4, wherein the pH is 3.5 to 7.
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JP2019011299A (en) * 2017-06-30 2019-01-24 小林製薬株式会社 Oral composition with carbohydrate material coated with non-amino acid material
JP2021102655A (en) * 2017-06-23 2021-07-15 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ Composition and method for improving appearance of skin
US11583488B2 (en) 2020-06-01 2023-02-21 The Procter & Gamble Company Method of improving penetration of a vitamin B3 compound into skin
US11911498B2 (en) 2020-06-01 2024-02-27 The Procter & Gamble Company Low pH skin care composition and methods of using the same

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JP2004002329A (en) * 2002-03-22 2004-01-08 Lion Corp Skin-activating composition for external use
JP2012176903A (en) * 2011-02-25 2012-09-13 Kracie Home Products Ltd Composition of skin care preparation for external use
WO2016080495A1 (en) * 2014-11-20 2016-05-26 大正製薬株式会社 Composition for external use

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JP2003128557A (en) * 2001-10-16 2003-05-08 Teikoku Seiyaku Co Ltd Glucosamine-containing cataplasm
JP2004002329A (en) * 2002-03-22 2004-01-08 Lion Corp Skin-activating composition for external use
JP2012176903A (en) * 2011-02-25 2012-09-13 Kracie Home Products Ltd Composition of skin care preparation for external use
WO2016080495A1 (en) * 2014-11-20 2016-05-26 大正製薬株式会社 Composition for external use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021102655A (en) * 2017-06-23 2021-07-15 ザ プロクター アンド ギャンブル カンパニーＴｈｅ Ｐｒｏｃｔｅｒ ＆ Ｇａｍｂｌｅ Ｃｏｍｐａｎｙ Composition and method for improving appearance of skin
JP2019011299A (en) * 2017-06-30 2019-01-24 小林製薬株式会社 Oral composition with carbohydrate material coated with non-amino acid material
JP7274813B2 (en) 2017-06-30 2023-05-17 小林製薬株式会社 Oral composition in which carbohydrate material is coated with non-amino acid material
US11583488B2 (en) 2020-06-01 2023-02-21 The Procter & Gamble Company Method of improving penetration of a vitamin B3 compound into skin
US11911498B2 (en) 2020-06-01 2024-02-27 The Procter & Gamble Company Low pH skin care composition and methods of using the same

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