WO2012132603A1 - External preparation for skin - Google Patents

External preparation for skin Download PDF

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Publication number
WO2012132603A1
WO2012132603A1 PCT/JP2012/053607 JP2012053607W WO2012132603A1 WO 2012132603 A1 WO2012132603 A1 WO 2012132603A1 JP 2012053607 W JP2012053607 W JP 2012053607W WO 2012132603 A1 WO2012132603 A1 WO 2012132603A1
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WO
WIPO (PCT)
Prior art keywords
skin
external preparation
zeolite
polypropylene glycol
silver ion
Prior art date
Application number
PCT/JP2012/053607
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French (fr)
Japanese (ja)
Inventor
洋明 小沢
佐代子 長谷川
吉田　晋
有喜子 蛭間
Original Assignee
株式会社資生堂
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Publication of WO2012132603A1 publication Critical patent/WO2012132603A1/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
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/26—Aluminium; Compounds 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
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0216—Solid or semisolid forms
    • A61K8/022—Powders; Compacted Powders
    • 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
    • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
    • A61K8/86—Polyethers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q15/00—Anti-perspirants or body deodorants
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations

Definitions

  • the present invention relates to an external preparation for skin. More specifically, the present invention relates to a skin external preparation containing a silver ion-carrying antibacterial zeolite powder, in which whitening derived from silver ion-carrying antibacterial zeolite powder is reduced or prevented.
  • Antibacterial zeolite powders are blended in skin preparations such as cosmetics and quasi-drugs as antiseptics and deodorants.
  • an antibacterial spray composition Patent Document 1
  • an anti-odor cosmetic Patent Document 2
  • Antibacterial zeolite carrying silver ions is often used as an antibacterial zeolite for the purpose of deodorization and deodorization (Patent Documents 4 and 5).
  • a skin external preparation containing silver ion-carrying antibacterial zeolite has a problem of whitening derived from silver ion-carrying antibacterial zeolite. That is, when a skin external preparation containing silver ion-carrying antibacterial zeolite is used, there is a problem of whitening that whiteness is conspicuous in the applied body part.
  • Patent Document 6 discloses a technique of blending a certain amount of ethanol and glycerin. However, the effect is not always sufficient, and there is a problem that odors and black spots occur at high temperatures.
  • Patent Document 7 discloses a cosmetic material in which the whiteness after use is not noticeable by blending a specific alkylene oxide derivative with an antiperspirant aerosol cosmetic material blended with an antibacterial zeolite carrying silver ions.
  • Patent Document 7 is only a technique specified for aerosol cosmetics. Further, in the case of liquid cosmetics, not aerosol cosmetics, when white ion-supporting antibacterial zeolite and a specific alkylene oxide derivative are combined, whitening cannot be prevented. Further, the antiperspirant aerosol cosmetic of Patent Document 7 has a problem of odor change.
  • the present inventors conducted extensive research to prevent whitening caused by silver ion-carrying antibacterial zeolite powder in a skin external preparation containing silver ion-carrying antibacterial zeolite powder.
  • a polypropylene glycol of 700 to 4000 a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol, a whitening after application is inconspicuous, and a skin external preparation capable of reducing or preventing whitening is obtained.
  • the present invention was completed.
  • An object of the present invention is to provide a skin external preparation that reduces or prevents whitening derived from silver ion-supported antibacterial zeolite powder in a skin external preparation formulated with silver ion-supported antibacterial zeolite powder.
  • the present invention relates to (A) a silver ion-carrying antibacterial zeolite and (B) a polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol.
  • the present invention provides an external preparation for skin characterized by containing any of them.
  • the derivative of (B) polypropylene glycol is any one of polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether having a number average molecular weight of 700 to 4000.
  • An external preparation for skin is provided.
  • the present invention provides the above-mentioned skin external preparation characterized by containing 30% by mass or more of ethanol with respect to the total amount of the external preparation for skin.
  • the present invention also provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a deodorizing cosmetic filled in a roll-on container.
  • the present invention provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a mist-like deodorant cosmetic filled in an aerosol or dispenser container.
  • the present invention provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a sheet-like deodorant cosmetic impregnated in a sheet.
  • the effect of the present invention is that whitening derived from silver ion-carrying antibacterial zeolite powder can be reduced or prevented in a skin external preparation containing silver ion-carrying antibacterial zeolite powder.
  • a zeolite powder holding antibacterial silver ions in the ion-exchangeable part of the zeolite is used. That is, it is a zeolite powder in which part or all of the ion-exchangeable ions of the zeolite are substituted with antibacterial silver ions.
  • Silver ion-carrying antibacterial zeolite can be easily produced from zeolite by a conventional method.
  • a zeolite carrying zinc ions and ammonium ions together with antibacterial silver ions is preferable.
  • a commercially available product (Ceramedic AJ10N: Sinane Zeomic Co., Ltd.) can be used in the present invention.
  • the average particle diameter of the silver ion-supporting antibacterial zeolite powder is preferably 10 ⁇ m or less. More preferably, it is 0.1 to 5 ⁇ m. Further, when the average particle diameter is within this range, the particle size distribution preferably having a particle diameter exceeding 1 ⁇ m is 20% or less.
  • the zeolite may be either natural zeolite or synthetic zeolite.
  • Zeolites is generally an aluminosilicate having a three-dimensional skeleton structure, the formula is displayed in XM 2 / n O ⁇ Al 2 O 3 ⁇ YSiO 2 ⁇ ZH 2 O.
  • M represents an ion-exchangeable ion, and is usually a monovalent or divalent metal ion.
  • n is the valence of the (metal) ion.
  • X and Y are the metal oxide and silica coefficient, respectively, and Z is the number of crystal water.
  • zeolites include, for example, A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcite, clinoptilolite, chabasite, erionite. Etc.
  • the ion exchange capacities of these zeolites are: A-type zeolite 7 meq / g, X-type zeolite 6.4 meq / g, Y-type zeolite 5 meq / g, T-type zeolite 3.4 meq / g, Sodalite 11.5 meq / G, mordenite 2.6 meq / g, analsim 5 meq / g, clinoptilolite 2.6 meq / g, chabasite 5 meq / g, erionite 3.8 meq / g. Both have sufficient capacity for ion exchange with antibacterial metal ions and ammonium ions.
  • ion-exchangeable ions in the zeolite examples include sodium ions, calcium ions, potassium ions, magnesium ions, and iron ions.
  • antibacterial metal ions that are substituted with these ions include, for example, silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, or thallium ions. Use what was done.
  • Antibacterial silver ions are preferably contained in the zeolite in an amount of 0.1 to 15% by mass from the viewpoint of antibacterial properties.
  • an antibacterial zeolite containing 0.1 to 15% by mass of silver ions and 0.1 to 8% by mass of zinc ions is preferable.
  • ammonium ions are preferably contained up to 20% by mass in the zeolite, but from the viewpoint of effectively preventing discoloration of the zeolite, 0.5 to 5% by mass in the zeolite is more preferable, and 0.5 to 2%. More preferred is mass%.
  • the mass% is a mass percentage in the zeolite on the basis of 110 ° C. drying.
  • the antibacterial zeolite is prepared as follows. That is, the zeolite is brought into contact with a mixed aqueous solution containing silver ions, zinc ions and the like prepared in advance, and the ions capable of ion exchange in the zeolite are replaced with the ions.
  • the contact can be carried out at 10 to 70 ° C., preferably 40 to 60 ° C. for 3 to 24 hours, preferably 10 to 24 hours by a batch method or a continuous method (for example, a column method).
  • the pH of the mixed aqueous solution is suitably adjusted to 3 to 10, preferably 5 to 7.
  • Each ion in the mixed aqueous solution is usually supplied as a salt.
  • silver ions are silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, and the like.
  • Zinc ions are zinc nitrate (II), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate and the like.
  • the content of antibacterial silver ions in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution.
  • concentration of each ion (salt) in the mixed aqueous solution By setting the silver ion concentration in the mixed aqueous solution to 0.002 M / l to 0.15 M / l, an antibacterial zeolite having a silver ion content of 0.1 to 5% can be appropriately obtained.
  • the antibacterial zeolite further contains zinc ions
  • the zinc ion concentration in the mixed aqueous solution is suitably 0.15 M / l to 1.2 M / l, so that the zinc ion content is suitably 0.1 to 8 M / l.
  • % Antibacterial zeolite can be obtained.
  • the antibacterial zeolite can be ion-exchanged by using an aqueous solution containing each ion alone and sequentially contacting each aqueous solution with the zeolite.
  • the concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.
  • the zeolite after ion exchange is thoroughly washed and dried. Drying is preferably performed at 105 to 115 ° C. or 70 to 90 ° C. under reduced pressure (1 to 30 Torr).
  • the silver ion-carrying antibacterial zeolite powder is preferably a hydrophobized powder that has been surface-treated with MQ resin by a conventional method.
  • the MQ resin used in the present invention is a partially crosslinked known organosilicone resin (trimethylsiloxysilicate) composed of SiO 2 units (Q units) and R 3 SiO 1/2 units (M units). It is. It has a structure represented by the average formula (1), and its M / Q molar ratio is 0.7 to 1.0.
  • MQ resin is conventionally used alone as a cosmetic raw material for foundations, eye creams, emulsions, creams, sunscreens and the like as a water repellent, and also as a surface treatment agent for cosmetic powders ( Patent No. 3378590).
  • the molecular weight of the MQ resin used in the present invention is not particularly limited, but is preferably between 500 and 10,000. This is because when the molecular weight is less than 500, the treated powder tends to aggregate, and when it exceeds 10,000, the solubility of the MQ resin in an organic solvent is lowered and the powder surface cannot be uniformly coated. It is.
  • the method for coating the MQ resin on the silver ion-carrying antibacterial zeolite powder is not particularly limited. For example, it is obtained by adding and mixing MQ resin dissolved in a solvent while stirring antibacterial zeolite with a Henschel mixer or the like, and then removing the solvent and drying.
  • the solvent used is a volatile organic solvent in which MQ resin is dissolved, and examples thereof include decamethylcyclopentasiloxane, 2-propanol, n-hexane, and cyclohexane.
  • the coating amount of the MQ resin on the silver ion-carrying antibacterial zeolite is 0.5% by mass or more with respect to the silver ion-carrying antibacterial zeolite, and preferably 0.5 to 10% by mass from the viewpoint of usability. It is. More preferably, it is 1 to 3% by mass.
  • the compounding amount of the silver ion-carrying antibacterial zeolite is 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 3 to 7% by mass with respect to the total amount of the external preparation for skin. It is determined appropriately according to the product form, and an appropriate amount is blended.
  • (B) Polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol”
  • the component (B) blended to reduce or prevent whitening is as follows. One or more of the following (1) to (3) components (B) are blended.
  • Polypropylene glycol having a number average molecular weight of 700 to 4000 (2) Copolymer of polypropylene glycol and polybutylene glycol having a number average molecular weight of 700 to 4000 (3) Derivative of polypropylene glycol having a number average molecular weight of 700 to 4000 (Specific examples include polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether having a number average molecular weight of 700 to 4000)
  • the number average molecular weight can be determined by the method described on page 942 of Cosmetic Raw Material Standard, Second Edition Comment I (1984, Yakuji Nippo).
  • Polypropylene glycol having a number average molecular weight of 700 to 4000 is Newpol PP-1000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1000, and Newpol PP-2000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 2000. Co., Ltd.) and Newpol PP-4000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 4000 can be preferably used.
  • a copolymer of polypropylene glycol and polybutylene glycol having a number average molecular weight of 700 to 4000 a PBG / PPG-9 / 1 copolymer having a number average molecular weight of 700 (9: 1 of polybutylene glycol and polypropylene glycol).
  • a copolymer of Uniol PB-700 (Nippon Yushi Co., Ltd.) can be preferably used.
  • Polypropylene glycol derivatives having a number average molecular weight of 700 to 4000 are preferably polyoxypropylene glyceryl ether, polyoxypropylene sorbite, and polyoxypropylene butyl ether.
  • Newpol GP-1000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1000
  • Newpol GP-4000 Synanyo Chemical Industries Co., Ltd.
  • polyoxypropylene sorbit Newpol SP-750 (Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 700 can be preferably used.
  • Newpol LB-285 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1200 and Newpol LB-625 (Sanyo Chemical Industries Co., Ltd.) having an average molecular weight of 1870 can be preferably used.
  • the components (1) to (3) are components that are usually blended as a moisturizing agent in a skin external preparation.
  • the whitening caused by silver ion-carrying antibacterial zeolite powder can be reduced. It is an essential component that exhibits a preventive effect and is blended as an anti-whitening agent.
  • the blending amount of the component (B) is 0.1 to 20% by mass, preferably 1 to 20% by mass, more preferably 5 to 20% by mass, based on the total amount of the external preparation for skin.
  • the compounding quantity of a component is suitably determined according to a product form, and a suitable quantity is mix
  • the external preparation for skin of the present invention is not limited to the effects of the present invention, and other components that are usually blended in external preparations for skin such as cosmetics and quasi drugs, such as powder Ingredient, liquid fat, solid fat, wax, hydrocarbon oil, higher fatty acid, higher alcohol, ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, Film agent, UV absorber, sequestering agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, fragrance Water or the like can be appropriately blended as necessary, and can be produced by a conventional method according to the intended dosage form.
  • cosmetics and quasi drugs such as powder Ingredient, liquid fat, solid fat, wax, hydrocarbon oil, higher fatty acid, higher alcohol, ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer
  • a liquid skin external preparation in which silver ion-carrying antibacterial zeolite powder is dispersed is preferable.
  • ethanol is at least 30% by mass, preferably 30% by mass to 95% by mass with respect to the total amount of the external preparation for skin, from the viewpoint of increasing the solubility of the component B and imparting a refreshing feeling and quick drying.
  • a liquid skin external preparation blended by mass% is preferred.
  • the product form of the external preparation for skin of the present invention is not particularly limited.
  • a liquid cosmetic in which silver ion-carrying antibacterial zeolite powder is dispersed is (1) a deodorant cosmetic filled in a roll-on container, (2) a mist deodorant cosmetic filled in an aerosol or dispenser container, (3) A product form such as a sheet-like deodorant cosmetic impregnated in a sheet such as a non-woven fabric is preferred, and these products are produced by a conventional method.
  • deodorant cosmetics such as powder type, pressed powder type, and stick type are produced by a conventional method as the external preparation for skin of the present invention.
  • a compounding quantity is the mass% with respect to the whole quantity unless there is particular notice.
  • a liquid cosmetic in which silver ion-carrying antibacterial zeolite was dispersed according to the formulation shown in “Table 1” was produced by a conventional method, and whitening after coating, which is an effect of the present invention, was confirmed by the following evaluation method. Further, the occurrence of black color was also confirmed by the following evaluation method.
  • “Table 2” to “Table 5” describe only the B component (Example) blended in the liquid cosmetic composition of “Table 1” or various moisturizers (comparative examples) other than the B component. The evaluation when these are blended is shown.
  • MQ resin treatment of silver ion-carrying antibacterial zeolite is performed by putting 50 g of antibacterial zeolite powder (silver ion, zinc ion, ammonium ion-carrying zeolite (Celamedic AJ10N: Sinanen Zeomic Co., Ltd.) into a small grinder.
  • the MQ resin treating agent dissolved in the solvent was added with stirring, followed by stirring for about 3 minutes, and the resulting powder was dried in a dryer for 24 hours at 120 ° C.
  • the MQ resin used was in M units. : Trimethylsiloxysilicic acid composed of (CH 3 ) 3 SiO 1/2 and Q unit: SiO 2 .
  • the examples of the present invention are excellent in the effect of preventing whitening, and at the same time, excellent in the generation of black spots.
  • the comparative example in which a moisturizing agent such as polypropylene glycol 200, polypropylene glycol 400, or POE / POP dimethyl ether is blended in place of the component (B) of the present invention has no whitening prevention effect, and black May occur.
  • the following is a formulation example of the external preparation for skin of the present invention. Both of these cosmetics are excellent in the effect of reducing and preventing whitening and are free from black spots.
  • Prescription Example 1 Cosmetics suitable for roll-on containers (liquid cosmetics)” Compounding ingredients Mass% Ethanol Residual water 5 Silver ion supported antibacterial zeolite 1 Hydroxypropyl cellulose 0.2 Glutathione 0.5 Paraphenolsulfonic acid zinc salt 0.5 Polypropylene glycol (number average molecular weight 4000) 10
  • “Formulation Example 2 Cosmetics suitable for roll-on containers (liquid cosmetics)” Compounding ingredients Mass% Ethanol Residual water 5 Silver ion supported antibacterial zeolite 10 Hydroxypropyl cellulose 0.2 Glutathione 0.5 Paraphenolsulfonic acid zinc salt 0.5 Polypropylene glycol (number average molecular weight 2000) 10
  • “Formulation Example 4 Sheet-like deodorant cosmetic impregnated in sheet” Compounding ingredients Mass% Ethanol Residual water 40 Silver ion supported antibacterial zeolite 1 Talc 3 Glutathione 0.5 Paraphenolsulfonic acid zinc salt 0.5 Polyoxypropylene butyl ether (number average molecular weight 1870) 5
  • support antibacterial zeolite powder can be provided. Furthermore, since the external preparation for skin of the present invention is free from the problem of black spots, it can provide a new and useful external preparation for skin with no problems as a product.

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Abstract

The present invention is an external preparation for the skin, which is characterized by containing (A) a silver ion-supporting antibacterial zeolite and (B) one of a polypropylene glycol having a number-average molecular weight of 700-4,000, a copolymer of a polypropylene glycol and a polybutylene glycol, and a derivative of a polypropylene glycol. The purpose of the present invention is to provide an external preparation for the skin, in which a silver ion-supporting antibacterial zeolite powder is blended and which is prevented from providing powdery look due to the silver ion-supporting antibacterial zeolite powder.

Description

皮膚外用剤Skin preparation
　本発明は皮膚外用剤に関する。さらに詳しくは、銀イオン担持抗菌性ゼオライト粉末を配合した皮膚外用剤において、銀イオン担持抗菌性ゼオライト粉末に由来する白浮きを低減乃至防止した皮膚外用剤に関する。 The present invention relates to an external preparation for skin. More specifically, the present invention relates to a skin external preparation containing a silver ion-carrying antibacterial zeolite powder, in which whitening derived from silver ion-carrying antibacterial zeolite powder is reduced or prevented.
　抗菌性ゼオライトの粉末は、防腐剤や消臭剤として化粧料や医薬部外品等の皮膚外用剤に配合されている。
　例えば、抗菌性ゼオライトを配合した抗菌性スプレー用組成物（特許文献１）や防臭化粧料（特許文献２）が開発されている。また、耐変色性を改良した防臭化粧料として、抗菌性ゼオライトにシリコーンを配合した技術が開示されている（特許文献３）。
　防臭や消臭を目的とした抗菌性ゼオライトには、銀イオンを担持した抗菌性ゼオライトを使用することが多い（特許文献４、特許文献５）。 Antibacterial zeolite powders are blended in skin preparations such as cosmetics and quasi-drugs as antiseptics and deodorants.
For example, an antibacterial spray composition (Patent Document 1) and an anti-odor cosmetic (Patent Document 2) containing antibacterial zeolite have been developed. Moreover, the technique which mix | blended silicone with the antibacterial zeolite is disclosed as the deodorizing cosmetics which improved discoloration resistance (patent document 3).
Antibacterial zeolite carrying silver ions is often used as an antibacterial zeolite for the purpose of deodorization and deodorization (Patent Documents 4 and 5).
　一方、銀イオン担持抗菌性ゼオライトを配合した皮膚外用剤は、銀イオン担持抗菌性ゼオライトに由来する白浮きという問題が生じる。すなわち、銀イオン担持抗菌性ゼオライトを配合した皮膚外用剤を使用すると、塗布した身体部位に白さが目立つという白浮きの問題である。
　銀イオン担持抗菌性ゼオライトに由来する白浮きを防止するために、特許文献６には、一定量のエタノールとグリセリンを配合する技術が開示されている。しかしながら、その効果は必ずしも十分ではなく、また、高温では、変臭や黒色のブツが発生するという問題点がある。
　また、特許文献７には、銀イオン担持抗菌性ゼオライトを配合した制汗エアゾール化粧料に特定のアルキレンオキシド誘導体を配合することによって、使用後の白さが目立ち難い化粧料が開示されている。しかしながら、特許文献７はエアゾール化粧料に特定された技術に過ぎない。また、エアゾール化粧料ではなく、液状化粧料において、銀イオン担持抗菌性ゼオライトと特定のアルキレンオキシド誘導体とを組み合わせた場合は白浮きを防止することが出来ない。さらに特許文献７の制汗エアゾール化粧料には変臭という問題も生じる。 On the other hand, a skin external preparation containing silver ion-carrying antibacterial zeolite has a problem of whitening derived from silver ion-carrying antibacterial zeolite. That is, when a skin external preparation containing silver ion-carrying antibacterial zeolite is used, there is a problem of whitening that whiteness is conspicuous in the applied body part.
In order to prevent white float derived from silver ion-carrying antibacterial zeolite, Patent Document 6 discloses a technique of blending a certain amount of ethanol and glycerin. However, the effect is not always sufficient, and there is a problem that odors and black spots occur at high temperatures.
Patent Document 7 discloses a cosmetic material in which the whiteness after use is not noticeable by blending a specific alkylene oxide derivative with an antiperspirant aerosol cosmetic material blended with an antibacterial zeolite carrying silver ions. However, Patent Document 7 is only a technique specified for aerosol cosmetics. Further, in the case of liquid cosmetics, not aerosol cosmetics, when white ion-supporting antibacterial zeolite and a specific alkylene oxide derivative are combined, whitening cannot be prevented. Further, the antiperspirant aerosol cosmetic of Patent Document 7 has a problem of odor change.
特開昭６３－２５０３２５号公報JP-A-63-250325 特開平８－２６９５６号公報JP-A-8-26956 特開平８－９２０５１号公報JP-A-8-92051 特開２００４－３０７３７５号公報JP 2004-307375 A 特開２０１０－１５９２１４号公報JP 2010-159214 A 特開２００９－２３４９９５号公報JP 2009-234995 A 特開２００４－１４９４３４号公報JP 2004-149434 A
　本発明者等は、上述した観点に鑑み、銀イオン担持抗菌性ゼオライト粉末を配合した皮膚外用剤において、銀イオン担持抗菌性ゼオライト粉末による白浮きを防止するため鋭意研究した結果、数平均分子量が７００～４０００であるポリプロピレングリコール、ポリプロピレングリコールとポリブチレングリコールとの共重合体、又は、ポリプロピレングリコールの誘導体を配合すると、塗布後の白さが目立たず、白浮きを低減乃至防止できる皮膚外用剤が得られることを見出し、本発明を完成するに至った。 In view of the above-mentioned viewpoints, the present inventors conducted extensive research to prevent whitening caused by silver ion-carrying antibacterial zeolite powder in a skin external preparation containing silver ion-carrying antibacterial zeolite powder. When blended with a polypropylene glycol of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol, a whitening after application is inconspicuous, and a skin external preparation capable of reducing or preventing whitening is obtained. As a result, the present invention was completed.
　本発明の目的は、銀イオン担持抗菌性ゼオライト粉末を配合した皮膚外用剤において、銀イオン担持抗菌性ゼオライト粉末に由来する白浮きを低減乃至防止した皮膚外用剤を提供することである。 An object of the present invention is to provide a skin external preparation that reduces or prevents whitening derived from silver ion-supported antibacterial zeolite powder in a skin external preparation formulated with silver ion-supported antibacterial zeolite powder.
　すなわち、本発明は、（Ａ）銀イオン担持抗菌性ゼオライトと、（Ｂ）数平均分子量が７００～４０００のポリプロピレングリコール、ポリプロピレングリコールとポリブチレングリコールとの共重合体、又は、ポリプロピレングリコールの誘導体の何れかを含有することを特徴とする皮膚外用剤を提供するものである。 That is, the present invention relates to (A) a silver ion-carrying antibacterial zeolite and (B) a polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol. The present invention provides an external preparation for skin characterized by containing any of them.
　また、本発明は、前記（Ｂ）ポリプロピレングリコールの誘導体が、数平均分子量が７００～４０００のポリオキシプロピレングリセリルエーテル、ポリオキシプロピレンソルビット、ポリオキシプロピレンブチルエーテルの何れかであることを特徴とする上記の皮膚外用剤を提供するものである。 In the present invention, the derivative of (B) polypropylene glycol is any one of polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether having a number average molecular weight of 700 to 4000. An external preparation for skin is provided.
　さらに、本発明は、皮膚外用剤全量に対して、エタノールが３０質量％以上含有されることを特徴とする上記の皮膚外用剤を提供するものである。 Furthermore, the present invention provides the above-mentioned skin external preparation characterized by containing 30% by mass or more of ethanol with respect to the total amount of the external preparation for skin.
　また、本発明は、前記皮膚外用剤が液状化粧料であって、ロールオン容器に充填された防臭化粧料であることを特徴とする上記の皮膚外用剤を提供するものである。 The present invention also provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a deodorizing cosmetic filled in a roll-on container.
　さらに、本発明は、前記皮膚外用剤が液状化粧料であって、エアゾール又はディスペンサー容器に充填されたミスト状防臭化粧料であることを特徴とする上記の皮膚外用剤を提供するものである。 Furthermore, the present invention provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a mist-like deodorant cosmetic filled in an aerosol or dispenser container.
　また、本発明は、前記皮膚外用剤が液状化粧料であって、シートに含浸されたシート状防臭化粧料であることを特徴とする上記の皮膚外用剤を提供するものである。 Also, the present invention provides the above-mentioned external preparation for skin, wherein the external preparation for skin is a liquid cosmetic and is a sheet-like deodorant cosmetic impregnated in a sheet.
　本発明の効果は、銀イオン担持抗菌性ゼオライト粉末を配合した皮膚外用剤において、銀イオン担持抗菌性ゼオライト粉末に由来する白浮きを低減乃至防止できることである。 The effect of the present invention is that whitening derived from silver ion-carrying antibacterial zeolite powder can be reduced or prevented in a skin external preparation containing silver ion-carrying antibacterial zeolite powder.
　以下、本発明を詳述する。 Hereinafter, the present invention will be described in detail.
＜（Ａ）銀イオン担持抗菌性ゼオライト＞
　本発明に（Ａ）成分として用いる銀イオン担持抗菌性ゼオライトは、ゼオライトのイオン交換可能な部分に抗菌性銀イオンを保持しているゼオライトの粉末が使用される。すなわち、ゼオライトのイオン交換可能なイオンの一部又は全部が抗菌性の銀イオンで置換されたゼオライトの粉末である。銀イオン担持抗菌性ゼオライトは常法によりゼオライトから容易に製造できる。
　本発明においては、抗菌性銀イオンと共に、亜鉛イオンとアンモニウムイオンを担持したゼオライトが好ましい。本発明には市販品（セラメディックＡＪ１０Ｎ：株式会社シナネンゼオミック）を使用できる。 <(A) Silver ion-carrying antibacterial zeolite>
As the silver ion-supporting antibacterial zeolite used as the component (A) in the present invention, a zeolite powder holding antibacterial silver ions in the ion-exchangeable part of the zeolite is used. That is, it is a zeolite powder in which part or all of the ion-exchangeable ions of the zeolite are substituted with antibacterial silver ions. Silver ion-carrying antibacterial zeolite can be easily produced from zeolite by a conventional method.
In the present invention, a zeolite carrying zinc ions and ammonium ions together with antibacterial silver ions is preferable. A commercially available product (Ceramedic AJ10N: Sinane Zeomic Co., Ltd.) can be used in the present invention.
　銀イオン担持抗菌性ゼオライトの粉末の平均粒径は１０μｍ以下であることが好ましい。さらに好ましくは０．１～５μｍである。また、平均粒径がこの範囲である場合に、その粒度分布において粒径が１μｍを超えるものが２０％以下であることが好ましい。 The average particle diameter of the silver ion-supporting antibacterial zeolite powder is preferably 10 μm or less. More preferably, it is 0.1 to 5 μm. Further, when the average particle diameter is within this range, the particle size distribution preferably having a particle diameter exceeding 1 μm is 20% or less.
　ゼオライトは天然ゼオライト及び合成ゼオライトのいずれでもよい。ゼオライトは、一般に三次元骨格構造を有するアルミノシリケートであり、一般式としては、ＸＭ2/nＯ・Ａｌ2Ｏ3・ＹＳｉＯ2・ＺＨ2Ｏで表示される。この一般式において、Ｍはイオン交換可能なイオンを表し、通常は１または２価の金属イオンである。ｎは（金属）イオンの原子価である。Ｘ及びＹはそれぞれ金属酸化物、シリカ係数、Ｚは結晶水の数を表示している。 The zeolite may be either natural zeolite or synthetic zeolite. Zeolites is generally an aluminosilicate having a three-dimensional skeleton structure, the formula is displayed in XM 2 / n O · Al 2 O 3 · YSiO 2 · ZH 2 O. In this general formula, M represents an ion-exchangeable ion, and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y are the metal oxide and silica coefficient, respectively, and Z is the number of crystal water.
　ゼオライトの具体例としては、例えば、Ａ－型ゼオライト、Ｘ－型ゼオライト、Ｙ－型ゼオライト、Ｔ－型ゼオライト、高シリカゼオライト、ソーダライト、モルデナイト、アナルサイム、クリノプチロライト、チャバサイト、エリオナイト等を挙げることができる。これらのゼオライトのイオン交換容量は、Ａ－型ゼオライト７ｍｅｑ／ｇ、Ｘ－型ゼオライト６．４ｍｅｑ／ｇ、Ｙ－型ゼオライト５ｍｅｑ／ｇ、Ｔ－型ゼオライト３．４ｍｅｑ／ｇ、ソーダライト１１．５ｍｅｑ／ｇ、モルデナイト２．６ｍｅｑ／ｇ、アナルサイム５ｍｅｑ／ｇ、クリノプチロライト２．６ｍｅｑ／ｇ、チャバサイト５ｍｅｑ／ｇ、エリオナイト３．８ｍｅｑ／ｇである。いずれも抗菌性金属イオンやアンモニウムイオンでイオン交換するに十分の容量を有している。 Specific examples of zeolites include, for example, A-type zeolite, X-type zeolite, Y-type zeolite, T-type zeolite, high silica zeolite, sodalite, mordenite, analcite, clinoptilolite, chabasite, erionite. Etc. The ion exchange capacities of these zeolites are: A-type zeolite 7 meq / g, X-type zeolite 6.4 meq / g, Y-type zeolite 5 meq / g, T-type zeolite 3.4 meq / g, Sodalite 11.5 meq / G, mordenite 2.6 meq / g, analsim 5 meq / g, clinoptilolite 2.6 meq / g, chabasite 5 meq / g, erionite 3.8 meq / g. Both have sufficient capacity for ion exchange with antibacterial metal ions and ammonium ions.
　ゼオライト中のイオン交換可能なイオンは、例えば、ナトリウムイオン、カルシウムイオン、カリウムイオン、マグネシウムイオン、鉄イオン等である。また、これらのイオンに置換される抗菌性金属イオンは、例えば、銀、銅、亜鉛、水銀、錫、鉛、ビスマス、カドミウム、クロム、又はタリウムのイオンがあるが、本発明は銀イオンで交換されたものを使用する。 Examples of ion-exchangeable ions in the zeolite include sodium ions, calcium ions, potassium ions, magnesium ions, and iron ions. In addition, antibacterial metal ions that are substituted with these ions include, for example, silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium, or thallium ions. Use what was done.
　抗菌性銀イオンは、抗菌性の観点からは、ゼオライト中に０．１～１５質量％含有されていることが好ましい。
　例えば、銀イオン０．１～１５質量％と亜鉛イオンを０．１～８質量％含有する抗菌性ゼオライトが好ましい。一方、アンモニウムイオンは、ゼオライト中に２０質量％まで含有させることが好ましいが、ゼオライトの変色を有効に防止するという観点から、ゼオライト中０．５～５質量％がより好ましく、０．５～２質量％がさらに好ましい。なお、質量％とは１１０℃乾燥基準のゼオライト中の質量百分率である。 Antibacterial silver ions are preferably contained in the zeolite in an amount of 0.1 to 15% by mass from the viewpoint of antibacterial properties.
For example, an antibacterial zeolite containing 0.1 to 15% by mass of silver ions and 0.1 to 8% by mass of zinc ions is preferable. On the other hand, ammonium ions are preferably contained up to 20% by mass in the zeolite, but from the viewpoint of effectively preventing discoloration of the zeolite, 0.5 to 5% by mass in the zeolite is more preferable, and 0.5 to 2%. More preferred is mass%. In addition, the mass% is a mass percentage in the zeolite on the basis of 110 ° C. drying.
　本発明において、銀イオン担持抗菌性ゼオライトは市販品を使用できる。抗菌性ゼオライトの製造方法としては、例えば、下記の如く調製される。すなわち、予め調製した銀イオン、亜鉛イオン等を含有する混合水溶液にゼオライトを接触させて、ゼオライト中のイオン交換可能なイオンと上記イオンとを置換させる。接触は、１０～７０℃、好ましくは４０～６０℃で３～２４時間、好ましくは１０～２４時間バッチ式又は連続式（例えば、カラム法）によって行うことができる。なお、上記混合水溶液のｐＨは３～１０、好ましくは５～７に調整することが適当である。該調整により、銀の酸化物等のゼオライト表面又は細孔内への析出を防止できるので好ましい。また、混合水溶液中の各イオンは、通常いずれも塩として供給される。例えば、銀イオンは、硝酸銀、硫酸銀、過塩素酸銀、酢酸銀、ジアンミン銀硝酸塩、ジアンミン銀硫酸塩等である。亜鉛イオンは硝酸亜鉛（ＩＩ）、硫酸亜鉛、過塩素酸亜鉛、チオシアン酸亜鉛、酢酸亜鉛等である。 In the present invention, commercially available silver ion-supporting antibacterial zeolite can be used. For example, the antibacterial zeolite is prepared as follows. That is, the zeolite is brought into contact with a mixed aqueous solution containing silver ions, zinc ions and the like prepared in advance, and the ions capable of ion exchange in the zeolite are replaced with the ions. The contact can be carried out at 10 to 70 ° C., preferably 40 to 60 ° C. for 3 to 24 hours, preferably 10 to 24 hours by a batch method or a continuous method (for example, a column method). The pH of the mixed aqueous solution is suitably adjusted to 3 to 10, preferably 5 to 7. This adjustment is preferable because precipitation of silver oxide or the like on the zeolite surface or pores can be prevented. Each ion in the mixed aqueous solution is usually supplied as a salt. For example, silver ions are silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, and the like. Zinc ions are zinc nitrate (II), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate and the like.
　ゼオライト中の抗菌性銀イオンの含有量は、前記混合水溶液中の各イオン（塩）濃度を調整することによって、適宜制御することができる。前記混合水溶液中の銀イオン濃度を０．００２Ｍ／ｌ～０．１５Ｍ／ｌとすることによって、適宜、銀イオン含有量０．１～５％の抗菌性ゼオライトを得ることができる。また、抗菌性ゼオライトがさらに亜鉛イオンを含有する場合、前記混合水溶液中の亜鉛イオン濃度は０．１５Ｍ／ｌ～１．２Ｍ／ｌとすることによって、適宜、亜鉛イオン含有量０．１～８％の抗菌性ゼオライトを得ることができる。抗菌性ゼオライトは、上記の混合水溶液以外に、各イオンを単独で含有する水溶液を用い、各水溶液とゼオライトとを逐次接触させることによって、イオン交換することもできる。各水溶液中の各イオンの濃度は、前記混合水溶液中の各イオン濃度に準じて定めることができる。 The content of antibacterial silver ions in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed aqueous solution. By setting the silver ion concentration in the mixed aqueous solution to 0.002 M / l to 0.15 M / l, an antibacterial zeolite having a silver ion content of 0.1 to 5% can be appropriately obtained. When the antibacterial zeolite further contains zinc ions, the zinc ion concentration in the mixed aqueous solution is suitably 0.15 M / l to 1.2 M / l, so that the zinc ion content is suitably 0.1 to 8 M / l. % Antibacterial zeolite can be obtained. In addition to the above mixed aqueous solution, the antibacterial zeolite can be ion-exchanged by using an aqueous solution containing each ion alone and sequentially contacting each aqueous solution with the zeolite. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.
　イオン交換が終了したゼオライトは、十分に洗浄した後乾燥する。乾燥は１０５℃～１１５℃又は減圧（１～３０Ｔｏｒｒ）下において７０～９０℃で行うことが好ましい。 The zeolite after ion exchange is thoroughly washed and dried. Drying is preferably performed at 105 to 115 ° C. or 70 to 90 ° C. under reduced pressure (1 to 30 Torr).
＜ＭＱレジンにて表面処理を行った銀イオン担持抗菌性ゼオライト＞
　本発明においては、銀イオン担持抗菌性ゼオライト粉末は、ＭＱレジンにて常法により表面処理を行った疎水化処理粉末であることが好ましい。本発明において使用するＭＱレジンとは、ＳｉＯ2単位（Ｑ単位）と、Ｒ3ＳｉＯ1/2単位（Ｍ単位）とからなる、部分的に架橋した公知の有機シリコーン樹脂（トリメチルシロキケイ酸）である。平均式（１）に示される構造を有し、そのＭ／Ｑモル比は０．７～１．０のものである。 <Silver ion-carrying antibacterial zeolite surface-treated with MQ resin>
In the present invention, the silver ion-carrying antibacterial zeolite powder is preferably a hydrophobized powder that has been surface-treated with MQ resin by a conventional method. The MQ resin used in the present invention is a partially crosslinked known organosilicone resin (trimethylsiloxysilicate) composed of SiO 2 units (Q units) and R 3 SiO 1/2 units (M units). It is. It has a structure represented by the average formula (1), and its M / Q molar ratio is 0.7 to 1.0.
［化１］
　（R3SiO1/2）2・ｎSiO2　　　（１）
（式中、Ｒは一価炭化水素基であり、ｎは１～５の数である。） [Chemical 1]
(R 3 SiO 1/2 ) 2・ nSiO 2 (1)
(In the formula, R is a monovalent hydrocarbon group, and n is a number from 1 to 5.)
　ＭＱレジンは、従来、撥水剤等としてファンデーション、アイクリーム、乳液、クリーム、サンスクリーン等の化粧品原料として単独で使用される他、化粧料用粉体の表面処理剤としても使用されている（特許第３３７８５９０号等）。 MQ resin is conventionally used alone as a cosmetic raw material for foundations, eye creams, emulsions, creams, sunscreens and the like as a water repellent, and also as a surface treatment agent for cosmetic powders ( Patent No. 3378590).
　また、本発明に用いるＭＱレジンの分子量は特に限定されないが、５００～１００００の間にあることが好ましい。これは、分子量が５００未満であると処理した粉末が凝集しやすいという欠点があり、１００００を超えるとＭＱレジンの有機溶媒に対する溶解性が低下し粉体表面に均一に被覆できないという欠点があるためである。 The molecular weight of the MQ resin used in the present invention is not particularly limited, but is preferably between 500 and 10,000. This is because when the molecular weight is less than 500, the treated powder tends to aggregate, and when it exceeds 10,000, the solubility of the MQ resin in an organic solvent is lowered and the powder surface cannot be uniformly coated. It is.
　銀イオン担持抗菌性ゼオライト粉末に対するＭＱレジンの被覆方法は特に限定されない。例えば、抗菌性ゼオライトをヘンシェルミキサー等で攪拌しながら溶媒に溶解したＭＱレジンを添加混合後、溶媒を除去、乾燥することによって得られる。使用する溶媒は、ＭＱレジンが溶解する揮発性有機溶媒であり、例えば、デカメチルシクロペンタシロキサン、２－プロパノール、ｎ－ヘキサン、シクロヘキサン等が例示される。 The method for coating the MQ resin on the silver ion-carrying antibacterial zeolite powder is not particularly limited. For example, it is obtained by adding and mixing MQ resin dissolved in a solvent while stirring antibacterial zeolite with a Henschel mixer or the like, and then removing the solvent and drying. The solvent used is a volatile organic solvent in which MQ resin is dissolved, and examples thereof include decamethylcyclopentasiloxane, 2-propanol, n-hexane, and cyclohexane.
　ＭＱレジンの銀イオン担抗菌性ゼオライトに対する被覆量は、銀イオン担持抗菌性ゼオライトに対して、質量比で０．５質量％以上であり、使用性の観点から好ましくは０．５～１０質量％である。さらに好ましくは、１～３質量％である。 The coating amount of the MQ resin on the silver ion-carrying antibacterial zeolite is 0.5% by mass or more with respect to the silver ion-carrying antibacterial zeolite, and preferably 0.5 to 10% by mass from the viewpoint of usability. It is. More preferably, it is 1 to 3% by mass.
＜（Ａ）銀イオン担持抗菌性ゼオライトの配合量＞
　銀イオン担持抗菌性ゼオライトの配合量は、皮膚外用剤全量に対して０．１～２０質量％、好ましくは１～１０質量％、さらに好ましくは３～７質量％である。製品形態に応じて適宜決定され、適する量が配合される。 <Amount of (A) silver ion-carrying antibacterial zeolite>
The compounding amount of the silver ion-carrying antibacterial zeolite is 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 3 to 7% by mass with respect to the total amount of the external preparation for skin. It is determined appropriately according to the product form, and an appropriate amount is blended.
「（Ｂ）数平均分子量が７００～４０００のポリプロピレングリコール、ポリプロピレングリコールとポリブチレングリコールとの共重合体、又は、ポリプロピレングリコールの誘導体」
　本発明において、白浮きを低減乃至防止するために配合される（Ｂ）成分は下記の通りである。下記（１）～（３）の一種または二種以上の（Ｂ）成分が配合される。
（１）数平均分子量が７００～４０００のポリプロピレングリコール
（２）数平均分子量が７００～４０００のポリプロピレングリコールとポリブチレングリコールとの共重合体
（３）数平均分子量が７００～４０００のポリプロピレングリコールの誘導体（具体的には、数平均分子量が７００～４０００のポリオキシプロピレングリセリルエーテル、ポリオキシプロピレンソルビット、ポリオキシプロピレンブチルエーテル等） “(B) Polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol”
In the present invention, the component (B) blended to reduce or prevent whitening is as follows. One or more of the following (1) to (3) components (B) are blended.
(1) Polypropylene glycol having a number average molecular weight of 700 to 4000 (2) Copolymer of polypropylene glycol and polybutylene glycol having a number average molecular weight of 700 to 4000 (3) Derivative of polypropylene glycol having a number average molecular weight of 700 to 4000 (Specific examples include polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether having a number average molecular weight of 700 to 4000)
　本発明において、数平均分子量は化粧品原料基準　第二版注解Ｉ（１９８４年　薬事日報社）の９４２頁に記載された方法で求めることが出来る。 In the present invention, the number average molecular weight can be determined by the method described on page 942 of Cosmetic Raw Material Standard, Second Edition Comment I (1984, Yakuji Nippo).
　上記（１）～（３）の成分はいずれも市販品を使用することが出来る。
　（１）数平均分子量が７００～４０００のポリプロピレングリコールとしては、数平均分子量が１０００のニューポールPP-1000(三洋化成工業株式会社)、数平均分子量が２０００のニューポールPP-2000(三洋化成工業株式会社)、数平均分子量が４０００のニューポールPP-4000(三洋化成工業株式会社)などを好ましく使用できる。
　（２）数平均分子量が７００～４０００のポリプロピレングリコールとポリブチレングリコールとの共重合体としては、数平均分子量が７００のＰＢＧ／ＰＰＧ－９／１コポリマー（ポリブチレングリコールとポリプロピレングリコールが９：１の共重合体。ユニオールPB-700　日本油脂株式会社）を好ましく使用できる。
　（３）数平均分子量が７００～４０００のポリプロピレングリコールの誘導体としては、ポリオキシプロピレングリセリルエーテル、ポリオキシプロピレンソルビット、ポリオキシプロピレンブチルエーテルが好ましく使用される。
　ポリオキシプロピレングリセリルエーテルとしては、数平均分子量が１０００のニューポールGP-1000(三洋化成工業株式会社)、数平均分子量が４０００のニューポールGP-4000（三洋化成工業株式会社）が好ましく使用できる。
　また、ポリオキシプロピレンソルビットとしては、数平均分子量が７００のニューポールSP-750(三洋化成工業株式会社)が好ましく使用できる。
　さらに、ポリオキシプロピレンブチルエーテルとしては、数平均分子量が１２００のニューポールLB-285（三洋化成工業株式会社）、平均分子量が１８７０のニューポールLB-625（三洋化成工業株式会社）が好ましく使用できる。 Commercially available products can be used for the components (1) to (3).
(1) Polypropylene glycol having a number average molecular weight of 700 to 4000 is Newpol PP-1000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1000, and Newpol PP-2000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 2000. Co., Ltd.) and Newpol PP-4000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 4000 can be preferably used.
(2) As a copolymer of polypropylene glycol and polybutylene glycol having a number average molecular weight of 700 to 4000, a PBG / PPG-9 / 1 copolymer having a number average molecular weight of 700 (9: 1 of polybutylene glycol and polypropylene glycol). A copolymer of Uniol PB-700 (Nippon Yushi Co., Ltd.) can be preferably used.
(3) Polypropylene glycol derivatives having a number average molecular weight of 700 to 4000 are preferably polyoxypropylene glyceryl ether, polyoxypropylene sorbite, and polyoxypropylene butyl ether.
As polyoxypropylene glyceryl ether, Newpol GP-1000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1000 and Newpol GP-4000 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 4000 can be preferably used.
As the polyoxypropylene sorbit, Newpol SP-750 (Sanyo Chemical Industries, Ltd.) having a number average molecular weight of 700 can be preferably used.
Further, as polyoxypropylene butyl ether, Newpol LB-285 (Sanyo Chemical Industries Co., Ltd.) having a number average molecular weight of 1200 and Newpol LB-625 (Sanyo Chemical Industries Co., Ltd.) having an average molecular weight of 1870 can be preferably used.
　上記（１）～（３）の成分は、皮膚外用剤において、通常、保湿剤として配合される成分であるが、本発明においては、銀イオン担持抗菌性ゼオライト粉末に由来する白浮きの低減乃至防止効果を発揮し、白浮き低減防止剤として配合される必須成分である。 The components (1) to (3) are components that are usually blended as a moisturizing agent in a skin external preparation. In the present invention, the whitening caused by silver ion-carrying antibacterial zeolite powder can be reduced. It is an essential component that exhibits a preventive effect and is blended as an anti-whitening agent.
＜「（Ｂ）数平均分子量が７００～４０００のポリプロピレングリコール、ポリプロピレングリコールとポリブチレングリコールとの共重合体、又は、ポリプロピレングリコールの誘導体の配合量＞
　上記（Ｂ）成分の配合量は、皮膚外用剤全量に対して０．１～２０質量％、好ましくは１～２０質量％、さらに好ましくは５～２０質量％である。（Ｂ）成分の配合量は製品形態に応じて適宜決定され、適する量が配合される。 <"(B) Blending amount of polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol>
The blending amount of the component (B) is 0.1 to 20% by mass, preferably 1 to 20% by mass, more preferably 5 to 20% by mass, based on the total amount of the external preparation for skin. (B) The compounding quantity of a component is suitably determined according to a product form, and a suitable quantity is mix | blended.
　本発明の皮膚外用剤には、上記した必須成分の他に、本発明の効果を損なわない範囲で、通常化粧品や医薬部外品等の皮膚外用剤に配合される他の成分、例えば、粉末成分、液体油脂、固体油脂、ロウ、炭化水素油、高級脂肪酸、高級アルコール、エステル油、シリコーン油、アニオン界面活性剤、カチオン界面活性剤、両性界面活性剤、非イオン界面活性剤、保湿剤、皮膜剤、紫外線吸収剤、金属イオン封鎖剤、低級アルコール、多価アルコール、糖、アミノ酸、有機アミン、高分子エマルジョン、ｐＨ調整剤、皮膚栄養剤、ビタミン、酸化防止剤、酸化防止助剤、香料、水等を必要に応じて適宜配合し、目的とする剤型に応じて常法により製造することが出来る。
　なお、本発明の剤型は限定されないが、銀イオン担持抗菌性ゼオライト粉末が分散した液状の皮膚外用剤が好ましい。
　特に、Ｂ成分の溶解性を上げたり、清涼感や乾きの早さを付与したりするという観点から、エタノールが、皮膚外用剤全量に対して少なくとも３０質量％以上、好ましくは３０質量％～９５質量％配合された液状の皮膚外用剤が好ましい。 In addition to the above-mentioned essential components, the external preparation for skin of the present invention is not limited to the effects of the present invention, and other components that are usually blended in external preparations for skin such as cosmetics and quasi drugs, such as powder Ingredient, liquid fat, solid fat, wax, hydrocarbon oil, higher fatty acid, higher alcohol, ester oil, silicone oil, anionic surfactant, cationic surfactant, amphoteric surfactant, nonionic surfactant, moisturizer, Film agent, UV absorber, sequestering agent, lower alcohol, polyhydric alcohol, sugar, amino acid, organic amine, polymer emulsion, pH adjuster, skin nutrient, vitamin, antioxidant, antioxidant aid, fragrance Water or the like can be appropriately blended as necessary, and can be produced by a conventional method according to the intended dosage form.
Although the dosage form of the present invention is not limited, a liquid skin external preparation in which silver ion-carrying antibacterial zeolite powder is dispersed is preferable.
In particular, ethanol is at least 30% by mass, preferably 30% by mass to 95% by mass with respect to the total amount of the external preparation for skin, from the viewpoint of increasing the solubility of the component B and imparting a refreshing feeling and quick drying. A liquid skin external preparation blended by mass% is preferred.
　本発明の皮膚外用剤の製品形態は特に限定されない。例えば、銀イオン担持抗菌性ゼオライト粉末が分散した液状化粧料を、（１）ロールオン容器に充填された防臭化粧料、（２）エアゾール又はディスペンサー容器に充填されたミスト状防臭化粧料、（３）不織布等のシートに含浸されたシート状防臭化粧料などの製品形態が好ましく、これらの製品は常法により製造される。
　上記の製品形態以外にも、パウダータイプ、プレストパウダータイプ、スチックタイプなどの防臭化粧料が、本発明の皮膚外用剤として常法により製造される。 The product form of the external preparation for skin of the present invention is not particularly limited. For example, a liquid cosmetic in which silver ion-carrying antibacterial zeolite powder is dispersed is (1) a deodorant cosmetic filled in a roll-on container, (2) a mist deodorant cosmetic filled in an aerosol or dispenser container, (3) A product form such as a sheet-like deodorant cosmetic impregnated in a sheet such as a non-woven fabric is preferred, and these products are produced by a conventional method.
In addition to the above product forms, deodorant cosmetics such as powder type, pressed powder type, and stick type are produced by a conventional method as the external preparation for skin of the present invention.
　次に実施例を挙げて本発明をさらに具体的に説明する。本発明はこれによって限定されるものではない。配合量は特に断りのない限り全量に対する質量％である。 Next, the present invention will be described more specifically with reference to examples. The present invention is not limited thereby. A compounding quantity is the mass% with respect to the whole quantity unless there is particular notice.
　「表１」に示す処方にて、銀イオン担持抗菌性ゼオライトが分散した液状化粧料を常法により製造し、本発明の効果である塗布後の白浮きを下記の評価方法により確認した。
　また、黒色の発生についても、下記の評価方法により確認した。
　なお、「表２」～「表５」は、「表１」の液状化粧料に配合されるＢ成分（実施例）、又は、Ｂ成分以外の各種保湿剤（比較例）のみを記載して、これらを配合した場合の評価を示している。 A liquid cosmetic in which silver ion-carrying antibacterial zeolite was dispersed according to the formulation shown in “Table 1” was produced by a conventional method, and whitening after coating, which is an effect of the present invention, was confirmed by the following evaluation method.
Further, the occurrence of black color was also confirmed by the following evaluation method.
“Table 2” to “Table 5” describe only the B component (Example) blended in the liquid cosmetic composition of “Table 1” or various moisturizers (comparative examples) other than the B component. The evaluation when these are blended is shown.
「白浮き防止の評価」
　「表１」～「表５」の皮膚外用剤を、黒色の人工皮膚上の１．５ｃｍ×１．５ｃｍの範囲に、マイクロピペットで１０μＬを塗布した。２時間後の白浮きを目視にて確認し、以下の基準で評価した。
＜評価基準＞
◎：白浮きが全く認められない。
○：若干の白浮きが認められるが、比較例１よりも白浮きが大幅に低減しており、許容範囲である。
×：白浮きが明確に認められる。 "Evaluation of whitening prevention"
10 μL of the external preparation for skin shown in “Table 1” to “Table 5” was applied to a range of 1.5 cm × 1.5 cm on the black artificial skin using a micropipette. The white float after 2 hours was visually confirmed and evaluated according to the following criteria.
<Evaluation criteria>
A: No whitening is observed.
○: Slight whitening is observed, but whitening is significantly reduced as compared with Comparative Example 1, which is an allowable range.
X: White floating is clearly recognized.
「黒色のブツの評価」
　「表１」～「表５」の皮膚外用剤を６０℃の恒温槽に１週間保存した。６０℃の恒温槽に１週間保存後の皮膚外用剤に、黒色のブツが存在するかについて目視にて観察し、以下の基準で評価した。
＜評価基準＞
○：黒色のブツが認められない。
×：黒色のブツが認められる。 "Evaluation of black shoes"
The skin external preparations of “Table 1” to “Table 5” were stored in a constant temperature bath at 60 ° C. for 1 week. The skin external preparation after storage for 1 week in a constant temperature bath at 60 ° C. was visually observed for the presence of black spots and evaluated according to the following criteria.
<Evaluation criteria>
○: Black spots are not recognized.
X: Black spots are recognized.
Figure JPOXMLDOC01-appb-T000001
 ＊１：銀イオン担持抗菌性ゼオライトのＭＱレジン処理は、抗菌性ゼオライトの粉末(銀イオン・亜鉛イオン・アンモニウムイオン担持ゼオライト（セラメディックＡＪ１０Ｎ：株式会社シナネンゼオミック)５０ｇを、小型粉砕機に入れ、攪拌しながら溶媒に溶解したＭＱレジン処理剤を添加した。添加後、約３分攪拌し、得られた粉末を乾燥機中１２０℃、２４時間乾燥した。なお、用いたＭＱレジンは、Ｍ単位：(CH3）3SiO1/2と、Ｑ単位：SiO2とからなるトリメチルシロキシケイ酸である。
Figure JPOXMLDOC01-appb-T000001
 * 1: MQ resin treatment of silver ion-carrying antibacterial zeolite is performed by putting 50 g of antibacterial zeolite powder (silver ion, zinc ion, ammonium ion-carrying zeolite (Celamedic AJ10N: Sinanen Zeomic Co., Ltd.) into a small grinder. The MQ resin treating agent dissolved in the solvent was added with stirring, followed by stirring for about 3 minutes, and the resulting powder was dried in a dryer for 24 hours at 120 ° C. The MQ resin used was in M units. : Trimethylsiloxysilicic acid composed of (CH 3 ) 3 SiO 1/2 and Q unit: SiO 2 .
「白浮きの低減・防止効果」
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
 "Reduction / prevention of whitening"
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
「黒色のブツの発生（６０℃　１Ｗ）」

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
 "Generation of black spots (60 ° C, 1W)"

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
　上記で使用したＢ成分、Ｂ成分以外の各種保湿剤として使用した市販品は以下の通りである。
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
 Commercial products used as various humectants other than the B component and B component used above are as follows.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000007
　上記「表２」～「表５」の結果から、本発明の実施例は、白浮きの防止効果に優れていると同時に、黒色のブツの発生についても優れた効果を有している。
　これに対して、本発明の（Ｂ）成分の代わりに、ポリプロピレングリコール２００、ポリプロピレングリコール４００、ＰＯＥ・ＰＯＰジメチルエーテル等の保湿剤を配合した比較例は、白浮きの防止効果がなく、また、黒色のブツが発生する場合がある。 From the results of the above “Table 2” to “Table 5”, the examples of the present invention are excellent in the effect of preventing whitening, and at the same time, excellent in the generation of black spots.
On the other hand, the comparative example in which a moisturizing agent such as polypropylene glycol 200, polypropylene glycol 400, or POE / POP dimethyl ether is blended in place of the component (B) of the present invention has no whitening prevention effect, and black May occur.
　以下に、本発明の皮膚外用剤の処方例を挙げる。いずれも、白浮きの低減・防止効果に優れていると同時に、黒色のブツの発生がない化粧料である。 The following is a formulation example of the external preparation for skin of the present invention. Both of these cosmetics are excellent in the effect of reducing and preventing whitening and are free from black spots.
「処方例１：ロールオン容器に適する化粧料（液状化粧料）」
配合成分　　　　　　　　　　　　　　　　　　　　　　　質量％
エタノール　　　　　　　　　　　　　　　　　　　　　　残余
水　　　　　　　　　　　　　　　　　　　　　　　　　　　5
銀イオン担持抗菌性ゼオライト　　　　　　　　　　　　　　1
ヒドロキシプロピルセルロース　　　　　　　　　　　　　　0.2
グルタチオン　　　　　　　　　　　　　　　　　　　　　　0.5
パラフェノールスルホン酸亜鉛塩　　　　　　　　　　　　　0.5
ポリプロピレングリコール（数平均分子量４０００）　　　 10 “Prescription Example 1: Cosmetics suitable for roll-on containers (liquid cosmetics)”
Compounding ingredients Mass%
Ethanol Residual water 5
Silver ion supported antibacterial zeolite 1
Hydroxypropyl cellulose 0.2
Glutathione 0.5
Paraphenolsulfonic acid zinc salt 0.5
Polypropylene glycol (number average molecular weight 4000) 10
「処方例２：ロールオン容器に適する化粧料（液状化粧料）」
配合成分　　　　　　　　　　　　　　　　　　　　　　　質量％
エタノール　　　　　　　　　　　　　　　　　　　　　　残余
水　　　　　　　　　　　　　　　　　　　　　　　　　　　5
銀イオン担持抗菌性ゼオライト　　　　　　　　　　　　　 10
ヒドロキシプロピルセルロース　　　　　　　　　　　　　　0.2
グルタチオン　　　　　　　　　　　　　　　　　　　　　　0.5
パラフェノールスルホン酸亜鉛塩　　　　　　　　　　　　　0.5
ポリプロピレングリコール（数平均分子量２０００）　　　 10 “Formulation Example 2: Cosmetics suitable for roll-on containers (liquid cosmetics)”
Compounding ingredients Mass%
Ethanol Residual water 5
Silver ion supported antibacterial zeolite 10
Hydroxypropyl cellulose 0.2
Glutathione 0.5
Paraphenolsulfonic acid zinc salt 0.5
Polypropylene glycol (number average molecular weight 2000) 10
「処方例３：エアゾール又はディスペンサー容器に充填されたミスト状防臭化粧料」
配合成分　　　　　　　　　　　　　　　　　　　　　　　質量％
エタノール　　　　　　　　　　　　　　　　　　　　　　残余
水　　　　　　　　　　　　　　　　　　　　　　　　　　 45
銀イオン担持抗菌性ゼオライト　　　　　　　　　　　　　　5
シリカ　　　　　　　　　　　　　　　　　　　　　　　　　1
グルタチオン　　　　　　　　　　　　　　　　　　　　　　0.5
パラフェノールスルホン酸亜鉛塩　　　　　　　　　　　　　0.5
ポリオキシプロピレングリセリルエーテル
（数平均分子量１０００）　　　　　　　　　　　　　　　 10 “Prescription Example 3: Mist-like deodorant cosmetic filled in aerosol or dispenser container”
Compounding ingredients Mass%
Ethanol Residual water 45
Silver ion supported antibacterial zeolite 5
Silica 1
Glutathione 0.5
Paraphenolsulfonic acid zinc salt 0.5
Polyoxypropylene glyceryl ether (number average molecular weight 1000) 10
「処方例４：シートに含浸されたシート状防臭化粧料」
配合成分　　　　　　　　　　　　　　　　　　　　　　　質量％
エタノール　　　　　　　　　　　　　　　　　　　　　　残余
水　　　　　　　　　　　　　　　　　　　　　　　　　　 40
銀イオン担持抗菌性ゼオライト　　　　　　　　　　　　　　1
タルク　　　　　　　　　　　　　　　　　　　　　　　　　3
グルタチオン　　　　　　　　　　　　　　　　　　　　　　0.5
パラフェノールスルホン酸亜鉛塩　　　　　　　　　　　　　0.5
ポリオキシプロピレンブチルエーテル
（数平均分子量１８７０）　　　　　　　　　　　　　　　　5 “Formulation Example 4: Sheet-like deodorant cosmetic impregnated in sheet”
Compounding ingredients Mass%
Ethanol Residual water 40
Silver ion supported antibacterial zeolite 1
Talc 3
Glutathione 0.5
Paraphenolsulfonic acid zinc salt 0.5
Polyoxypropylene butyl ether (number average molecular weight 1870) 5
　本発明によれば、銀イオン担持抗菌性ゼオライト粉末を配合した皮膚外用剤において、銀イオン担持抗菌性ゼオライト粉末に由来する白浮きを低減乃至防止した皮膚外用剤を提供できる。
　さらに本発明の皮膚外用剤は、黒色のブツの発生の問題もないので、製品として問題がない新規有用な皮膚外用剤を提供できる。 ADVANTAGE OF THE INVENTION According to this invention, in the skin external preparation which mix | blended silver ion carrying | support antibacterial zeolite powder, the skin external preparation which reduced or prevented the whitening derived from silver ion carrying | support antibacterial zeolite powder can be provided.
Furthermore, since the external preparation for skin of the present invention is free from the problem of black spots, it can provide a new and useful external preparation for skin with no problems as a product.

Claims (6)

  1. 　（Ａ）銀イオン担持抗菌性ゼオライトと、（Ｂ）数平均分子量が７００～４０００のポリプロピレングリコール、ポリプロピレングリコールとポリブチレングリコールとの共重合体、又は、ポリプロピレングリコールの誘導体の何れかを含有することを特徴とする皮膚外用剤。 (A) containing silver ion-supporting antibacterial zeolite, and (B) polypropylene glycol having a number average molecular weight of 700 to 4000, a copolymer of polypropylene glycol and polybutylene glycol, or a derivative of polypropylene glycol. An external preparation for skin.
  2. 　前記（Ｂ）ポリプロピレングリコールの誘導体が、数平均分子量が７００～４０００のポリオキシプロピレングリセリルエーテル、ポリオキシプロピレンソルビット、ポリオキシプロピレンブチルエーテルの何れかであることを特徴とする請求項１記載の皮膚外用剤。 2. The skin external application according to claim 1, wherein the derivative of (B) polypropylene glycol is any one of polyoxypropylene glyceryl ether, polyoxypropylene sorbitol, polyoxypropylene butyl ether having a number average molecular weight of 700 to 4000. Agent.
  3. 　皮膚外用剤全量に対して、エタノールが３０質量％以上含有されることを特徴とする請求項１又は２記載の皮膚外用剤。 3. The skin external preparation according to claim 1 or 2, wherein ethanol is contained in an amount of 30% by mass or more based on the total amount of the external preparation for skin.
  4. 　前記皮膚外用剤が液状化粧料であって、ロールオン容器に充填された防臭化粧料であることを特徴とする請求項１～３の何れか１項記載の皮膚外用剤。 The skin external preparation according to any one of claims 1 to 3, wherein the skin external preparation is a liquid cosmetic and is a deodorant cosmetic filled in a roll-on container.
  5. 　前記皮膚外用剤が液状化粧料であって、エアゾール又はディスペンサー容器に充填されたミスト状防臭化粧料であることを特徴とする請求項１～３の何れか１項記載の皮膚外用剤。 The skin external preparation according to any one of claims 1 to 3, wherein the external preparation for skin is a liquid cosmetic and is a mist-like deodorant cosmetic filled in an aerosol or dispenser container.
  6. 　前記皮膚外用剤が液状化粧料であって、シートに含浸されたシート状防臭化粧料であることを特徴とする請求項１～３の何れか１項記載の皮膚外用剤。 The skin external preparation according to any one of claims 1 to 3, wherein the external preparation for skin is a liquid cosmetic and is a sheet-like deodorant cosmetic impregnated in a sheet.
PCT/JP2012/053607 2011-03-30 2012-02-16 External preparation for skin WO2012132603A1 (en)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
JP2016084317A (en) * 2014-10-28 2016-05-19 花王株式会社 Sheet-type cosmetic
US20170143613A1 (en) * 2014-06-23 2017-05-25 Rohm And Haas Company Oil-free emollients in personal care compositions

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6983664B2 (en) * 2016-01-29 2021-12-17 株式会社カネカ Peptide-containing compositions and peptide stabilizers, stabilization and storage methods
JP7174594B2 (en) * 2018-10-31 2022-11-17 株式会社マンダム sheet cosmetics

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Publication number Priority date Publication date Assignee Title
JP2004149434A (en) * 2002-10-29 2004-05-27 Shiseido Co Ltd Antiperspirant aerosol cosmetic
JP2009235016A (en) * 2008-03-28 2009-10-15 Shiseido Co Ltd Agent for improving skin circulation and agent for increasing skin temperature

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004149434A (en) * 2002-10-29 2004-05-27 Shiseido Co Ltd Antiperspirant aerosol cosmetic
JP2009235016A (en) * 2008-03-28 2009-10-15 Shiseido Co Ltd Agent for improving skin circulation and agent for increasing skin temperature

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170143613A1 (en) * 2014-06-23 2017-05-25 Rohm And Haas Company Oil-free emollients in personal care compositions
JP2016084317A (en) * 2014-10-28 2016-05-19 花王株式会社 Sheet-type cosmetic

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