WO2010123008A1 - Method for evaluating skin barrier function recovery-accelerator using work function as indication - Google Patents

Method for evaluating skin barrier function recovery-accelerator using work function as indication Download PDF

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WO2010123008A1
WO2010123008A1 PCT/JP2010/057019 JP2010057019W WO2010123008A1 WO 2010123008 A1 WO2010123008 A1 WO 2010123008A1 JP 2010057019 W JP2010057019 W JP 2010057019W WO 2010123008 A1 WO2010123008 A1 WO 2010123008A1
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skin
skin barrier
barrier function
recovery
substance
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French (fr)
Japanese (ja)
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光洋 傳田
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株式会社資生堂
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/242—Gold; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/243—Platinum; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/244—Lanthanides; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K33/00—Medicinal preparations containing inorganic active ingredients
    • A61K33/24—Heavy metals; Compounds thereof
    • A61K33/38—Silver; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P43/00—Drugs for specific purposes, not provided for in groups A61P1/00-A61P41/00

Definitions

  • the present invention relates to a method for evaluating a skin barrier function recovery promoting substance using a work function as an index, and a preparation and a cosmetic method using the substance.
  • TEWL transdermal moisture transpiration
  • Cation gradients such as calcium and magnesium ions in the epidermis are known to be involved in maintaining the skin barrier homeostasis (Lee SH et al. J. Clin. Invest (1992) 89: 530-538). Further, the present inventor has previously found that improvement of the skin barrier function can be promoted by applying a negative potential to specific skin having a low skin barrier function (Japanese Patent Laid-Open No. 2002-291909). Thus, it has been found that charges and the like play a major role in maintaining and improving the function of the skin barrier.
  • the inventor examined the effect of various substances for promoting the recovery of the skin barrier function, and it was found that samarium and zirconium, which have a higher ionization tendency than gold, also promote the recovery of the skin barrier function. Since these metals are substances whose electrons are likely to be emitted from the surface, the present inventor, rather than the conventionally thought low ionization tendency, the ease of taking out electrons from the substance surface, that is, the work function is the skin function. It was concluded that it was important for the barrier function recovery promoting effect, and the present invention was completed.
  • this application includes the following inventions: [1] A method for evaluating a skin barrier function recovery promoting substance, wherein the work function (eV) of the substance is used as an index of the skin barrier function recovery promoting effect. [2] The evaluation method according to [1], wherein a substance having a work function in the range of 2.5 to 6.0 eV is evaluated as having a high effect of promoting the recovery of skin barrier function. [3] A skin barrier function recovery promoting preparation comprising one or more substances having a work function of 2.5 to 6.0 eV. [4] The skin barrier function recovery promoting preparation according to [3], wherein the substance is samarium, zirconium, indium, silver, gold, or platinum.
  • a cosmetic method for promoting the recovery of skin barrier function comprising applying on the skin one or more substances having a work function of 2.5-6.0 eV.
  • a low work function means that electrons on the surface of the material are easily emitted. While not intending to be bound by theory, when a substance with a low work function is applied to the skin, electrons emitted from the substance migrate to the skin surface, affecting the skin's homeostasis. It is thought that there is. This coincides with the result that the skin barrier function recovery effect by gold is completely inhibited when an earth or plastic film is interposed between gold and skin (Japanese Patent Laid-Open No. 2006-335733).
  • FIG. 1 is a graph showing the recovery rate (%) of skin barrier function by platinum, gold, silver, indium, zirconium, and samarium when compared with the untreated group.
  • FIG. 2 shows the correlation between the recovery rate of the skin barrier function by each metal and the work function (eV) of each metal.
  • a method for evaluating a skin barrier function recovery promoting substance characterized in that the work function (eV) of the substance is used as an index of the skin barrier function recovery promoting effect.
  • the term “work function” means the minimum amount of work (eV) required to remove an electron from a solid into a vacuum (Tokyo Chemical Doujin “Chemical Dictionary” 1st Edition).
  • eV work-like work
  • thermionic work function calculated from thermionic emission
  • photowork function calculated from the photoelectron emission.
  • the thermal work function can be measured by a thermal electron emission experiment, and the photo work function can be measured by a photoelectron emission experiment.
  • Herbert B. Michaelson "The work function of the elements and its periodicity”. J. Appl. Phys. 48, 4729 (1977), chemical handbooks, etc. Reference may be made to the values described in.
  • a substance having a lower work function when applied to the skin, the effect of promoting the recovery of the skin barrier function is exhibited.
  • a substance having a low work function for example, a substance having a work function in the range of 2.5 to 6.0 eV, preferably a substance having a work function in the range of 2.5 to 5.2 eV is recovered. Evaluate as a substance with high promotion effect.
  • the work function of a metal having free electrons is lower than that of nonionic organic compounds such as proteins and lipids.
  • its work function increases.
  • the desired effect can be exhibited by polishing the surface into a metal state.
  • metals having a low work function and applicable to the skin are, for example, platinum, gold, silver, indium, zirconium, and samarium.
  • the substance contained in the skin barrier function recovery promoting preparation of the present invention is not limited to these metals.
  • metal compounds having a low work function such as zinc oxide (ZnO) (4.68 eV), gallium phosphide (GaP) (2.95 eV), silicon carbide (SiC) (4.75 eV), zinc sulfide (ZnS) ( 5.40 eV) and gallium nitride (GaN) (1.0 eV) are also considered to have a high effect of restoring the skin barrier function.
  • ZnO zinc oxide
  • GaP gallium phosphide
  • SiC silicon carbide
  • ZnS zinc sulfide
  • GaN gallium nitride
  • skin barrier function means the retention of water in the body by the epidermis and the prevention of entry of viruses, bacteria, etc., among the skin.
  • the function can be evaluated by measuring the transdermal moisture transpiration (TEWL) (unit: g / m 2 ⁇ h) under the condition of not sweating.
  • TEWL transdermal moisture transpiration
  • “promoting the recovery of skin barrier function” means that the TEWL value immediately after tape stripping of the skin is 0%, the value before tape stripping is 100%, and the TEWL value at each measurement time is 4% dodecyl according to the method of Andrew et al. (J Invest Dermatol, 86; 598, 1986), which means that there is a clear significant difference when compared to the control, and that it has the effect of promoting the recovery rate of TEWL. This is different from the so-called rough skin improvement preventing effect in which the skin is treated with a cotton ball soaked with an aqueous solution of sodium sulfate (SDS) and judged.
  • SDS sodium sulfate
  • the skin that needs to be restored to the skin barrier function includes skin diseases, various stresses, skin having a reduced skin barrier function due to rough skin, skin having a low skin barrier function because the skin barrier layer is not sufficiently formed in the transplanted skin, Or the skin etc. whose skin barrier function fell by transplant are mentioned. Therefore, the evaluation method of the present invention intends not only to recover a reduced skin barrier function but also to evaluate a substance that improves the function of skin having a low skin barrier function.
  • mammals are considered as subjects to which a substance evaluated to have an effect of promoting the recovery of skin barrier function according to the present invention, and is particularly applied to human skin.
  • the skin barrier function recovery promoting substance may be applied to the skin of elderly people.
  • the substance can also be applied to artificial skin. This is because artificial skin obtained by culturing skin cells or the like isolated from a living body may have an incomplete formation of a skin barrier layer, and its skin barrier function is generally low.
  • the present invention provides a skin barrier function recovery promoting preparation comprising one or more substances having a work function of 2.5 to 6.0 eV.
  • the form of the preparation of the present invention includes beauty instruments, for example, roller-type massage devices such as beauty rollers, patches, such as sheets and packs.
  • all parts (for example, roller parts) applied on the skin are made of a substance having a low work function, or only the surface thereof is covered with the substance.
  • the substance is a metal
  • it can be placed at a predetermined site of the preparation as a metal foil after rolling.
  • the coating thickness is not limited. However, even if it is a very thin film
  • the part that comes into contact with the skin may be coated with the substance.
  • the material can be impregnated into a sheet or pack.
  • the preparations of the present invention include foundations, lotions, creams, emulsions, lotions, packs, bath preparations, ointments, hair lotions, hair licks, hair liquids, shampoos, rinses, hair nourishing / hair growth agents and the like. is there.
  • the substance is included in the preparation at 0.1 to 10%, preferably 5%. These substances may be incorporated into the preparation in the form of a salt.
  • the present invention is a cosmetic method for promoting the recovery of skin barrier function, wherein one or more substances having a work function of 2.5 to 6.0 eV are applied onto the skin.
  • a method comprising the steps of:
  • the cosmetic method of the present invention is to apply a substance having a low work function to the skin that needs to recover the skin barrier function.
  • the application method is not particularly limited.
  • a beauty tool whose surface is made of the above-described substance may be applied to the subject's skin with a scissors or rolled on the skin. Or it is covered with the said substance, or the pack or sheet containing the said substance is applied to skin by mounting or sticking on skin.
  • it may be applied to the skin as a cosmetic containing the substance as an active ingredient.
  • the number and time of applying the substance to the skin varies depending on the condition of the skin, but in the case of skin broken by stripping with cello tape (registered trademark), recovery of the skin barrier function should be achieved in 1 hour. Can do.
  • Skin barrier function recovery promoting effect test Skin barrier function recovery promoting effect was evaluated for samarium, zirconium, indium, silver, gold, and platinum having a low work function. Metals other than gold and platinum were used after being made into a metallic state by polishing the surface with sandpaper.
  • the skin barrier function recovery promoting effect is that the process of recovering the skin barrier function destroyed by applying tape stripping to the skin of hairless mice (Type HR-1, HOSHINO, Japan) returns to the original state.
  • TEWL amount of transpiration
  • the transcutaneous moisture transpiration (TEWL) near the back of the hairless mouse is measured by a moisture transpiration measuring device MEECO (Meeco, Warrington, PA, USA). The value at this time is assumed to be a TEWL recovery rate of 100%.
  • MEECO moisture transpiration measuring device
  • the skin barrier is broken by peeling off the epidermal stratum of hairless mice using cellophane tape. At this time, this operation is repeated until the value of TEWL becomes about 800 to 900.
  • the value obtained by subtracting the measured value before peeling the stratum corneum from the measured value after peeling the stratum corneum is the deepest damage state, that is, the recovery rate is 0%.
  • each metal (area 2 ⁇ 2 cm 2 , thickness 0.5 mm) is stuck on the stratum corneum.
  • the control is skin with nothing applied.
  • 4.1 After elapse of 1 hour, the pure gold plate is peeled off, and TEWL is measured by MEECO. As in the case of removing the stratum corneum, the TEWL value before removing the stratum corneum is subtracted from the measured value at each time to obtain the recovery rate. That is, the recovery rate is calculated according to the following formula.
  • the recovery rate (%) of the skin barrier function measured by the test is shown in FIG.
  • the barrier function was remarkably recovered in 1 hour after application of the skin after barrier destruction, regardless of which of the metals used was applied.
  • the one with the metal having a low work function stuck showed a significant improvement in the barrier function recovery rate compared to the control.
  • the samarium with the lowest work function had the highest recovery effect.
  • FIG. 2 a significant correlation is recognized between the work function and the skin barrier function recovery effect.
  • the work function of a substance can be a good indicator for promoting the recovery of skin barrier function. According to the present invention, by using the work function of a substance as an evaluation index of a skin barrier function recovery promoting effect, it is possible to determine the presence or absence of the effect before applying to the skin of an animal or the like in advance.

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Abstract

Disclosed is a method for evaluating a skin barrier function recovery-accelerator characterized by using the work function (eV) of the substance as an indication of the skin barrier function recovery-accelerating effect.

Description

仕事関数を指標とする皮膚バリアー機能回復促進物質の評価方法Evaluation method of skin barrier function recovery promoting substance using work function as an index
　本発明は、仕事関数を指標とする皮膚バリアー機能回復促進物質の評価方法、並びに当該物質を用いた製剤及び美容方法に関する。 The present invention relates to a method for evaluating a skin barrier function recovery promoting substance using a work function as an index, and a preparation and a cosmetic method using the substance.
　種々の皮膚疾患、例えば、アトピー性皮膚炎、乾癬、接触性皮膚炎等に見られる肌荒れ症状においては、皮膚からの水分の消失が、健常な皮膚に比べて盛んであることが知られている。このいわゆる経皮水分蒸散量（ＴＥＷＬ）の増加には、皮膚内において水分の保持やバリアーとしての機能を担っていると考えられる成分の減少が関与しているものと考えられてきた。 It is known that the loss of moisture from the skin is more prominent than that of healthy skin in various skin diseases such as atopic dermatitis, psoriasis, and contact dermatitis. . It has been considered that the increase in the so-called transdermal moisture transpiration (TEWL) is associated with a decrease in components that are thought to be responsible for moisture retention and as a barrier in the skin.
　これまでに、皮膚バリアー機能の低下に伴い皮膚の皮膚機能が低下し、その結果皮膚増殖性異常等が起こることが報告されている。特に高齢者の場合、低下した皮膚バリアー機能の回復には長い時間がかかるため、加齢に伴う皮膚の皮膚機能の低下による皮膚増殖性異常等を防止するのに有効な、新たな皮膚バリアー機能回復剤が要望されている。 So far, it has been reported that the skin function of the skin is reduced as the skin barrier function is lowered, and as a result, skin proliferative abnormality and the like occur. Especially for elderly people, it takes a long time to recover the reduced skin barrier function, so a new skin barrier function that is effective in preventing skin proliferative abnormalities due to a decrease in skin function due to aging. A recovery agent is desired.
　皮膚バリアー機能回復促進製剤等の化粧料に含めることが検討される物質は、動物実験においてその効果が確認される必要がある。しかしながら、近年化粧品開発の現場においては、倫理上の観点から動物実験が制限される傾向にあり、動物に適用することなく候補物質の有効性を評価する方法についての要求も高まっている。 物質 Substances that are considered to be included in cosmetics such as skin barrier function recovery promoting preparations need to be confirmed in animal experiments. However, in recent years, in the field of cosmetic development, animal experiments tend to be restricted from an ethical point of view, and there is an increasing demand for methods for evaluating the effectiveness of candidate substances without applying them to animals.
　表皮におけるカルシウムやマグネシウムイオン等の陽イオン勾配は皮膚バリアーの恒常性維持に関与することで知られる（Ｌｅｅ Ｓ．Ｈ． ｅｔ ａｌ． Ｊ． Ｃｌｉｎ． Ｉｎｖｅｓｔ （１９９２） ８９：５３０－５３８）。また、本発明者は以前、皮膚バリアー機能が低い特異的皮膚に負電位を負荷することでその皮膚バリアー機能の向上を促進できることを見出した（特開２００２－２９１９０９）。このように、皮膚バリアーの機能維持、向上等において、電荷等が大きな役割を果たしていることがわかっている。 Cation gradients such as calcium and magnesium ions in the epidermis are known to be involved in maintaining the skin barrier homeostasis (Lee SH et al. J. Clin. Invest (1992) 89: 530-538). Further, the present inventor has previously found that improvement of the skin barrier function can be promoted by applying a negative potential to specific skin having a low skin barrier function (Japanese Patent Laid-Open No. 2002-291909). Thus, it has been found that charges and the like play a major role in maintaining and improving the function of the skin barrier.
　このような知見に基づき、本発明者等は、硫酸バリウム、アニオン性高分子塩、イオン交換樹脂等の皮膚への適用が皮膚バリアー機能の回復を促進させることを見出している（特開２００２－２６５２１８号公報、特開２００３－２８６１５０号公報、特開２００４－２３１５７８号公報）。 Based on such knowledge, the present inventors have found that application of barium sulfate, anionic polymer salt, ion exchange resin, etc. to the skin promotes recovery of the skin barrier function (Japanese Patent Application Laid-Open No. 2002-2002). 265218, JP-A 2003-286150, JP-A 2004-231578).
特開２００２－２９１９０９号公報JP 2002-291909 A 特開２００２－２６５２１８号公報JP 2002-265218 A 特開２００３－２８６１５０号公報JP 2003-286150 A 特開２００４－２３１５７８号公報JP 2004-231578 A 特開２００６－３３５７３３号公報JP 2006-335733 A
　本発明者の研究により、金が皮膚バリアー機能の回復促進効果を有することが明らかとなっている（特開２００６－３３５７３３号公報）。同公報においては、金による皮膚バリアー機能の回復促進効果は金のイオン化傾向の低さに起因するとの仮説が立てられている。これは、金のイオン化傾向が低く、皮膚と接触した場合にその接触界面において電気二重層が形成され、表皮中の脂質を含む粒子の細胞外への放出が促進されると考えられたためである。しかしながら、金のどのような特性が実際にかかる効果に寄与しているのかは不明であった。 The inventors' research has revealed that gold has an effect of promoting the recovery of the skin barrier function (Japanese Patent Laid-Open No. 2006-335733). In this publication, it is hypothesized that the effect of promoting the recovery of the skin barrier function by gold is due to the low ionization tendency of gold. This is because the gold ionization tendency is low, and when it comes into contact with the skin, an electric double layer is formed at the contact interface, and it is thought that release of lipid-containing particles in the epidermis is promoted to the outside of the cell. . However, it was unclear what characteristics of gold actually contributed to this effect.
　本発明者が種々の物質の皮膚バリアー機能回復促進効果について検討したところ、イオン化傾向が金よりも高いサマリウムやジルコニウムも、皮膚バリアー機能の回復を促進させることが明らかになった。これらの金属はその表面から電子が放出されやすい物質であるため、本発明者は、従来考えられていたイオン化傾向の低さよりも寧ろ、物質表面からの電子の取り出し易さ、すなわち仕事関数が皮膚バリアー機能回復促進効果にとって重要であると結論付け、本発明を完成させるに至った。 The inventor examined the effect of various substances for promoting the recovery of the skin barrier function, and it was found that samarium and zirconium, which have a higher ionization tendency than gold, also promote the recovery of the skin barrier function. Since these metals are substances whose electrons are likely to be emitted from the surface, the present inventor, rather than the conventionally thought low ionization tendency, the ease of taking out electrons from the substance surface, that is, the work function is the skin function. It was concluded that it was important for the barrier function recovery promoting effect, and the present invention was completed.
　即ち、本願は下記の発明を包含する：
[１]物質の仕事関数(eV)を皮膚バリアー機能回復促進効果の指標とすることを特徴とする、皮膚バリアー機能回復促進物質の評価方法。
[２]前記仕事関数が２．５～６．０eVの範囲にある物質を皮膚バリアー機能回復促進効果が高いと評価することを特徴とする、[１]に記載の評価方法。
[３]仕事関数が２．５～６．０eVである１又は複数の物質を含む、皮膚バリアー機能回復促進製剤。
[４]前記物質がサマリウム、ジルコニウム、インジウム、銀、金又は白金である、[３]に記載の皮膚バリアー機能回復促進製剤。
[５]皮膚バリアー機能の回復を促進させるための美容方法であって、仕事関数が２．５～６．０eVである１又は複数の物質を皮膚上に適用することを含んで成る方法。
[６]前記物質がサマリウム、ジルコニウム、インジウム、銀、金又は白金である、[４]に記載の美容方法。 That is, this application includes the following inventions:
[1] A method for evaluating a skin barrier function recovery promoting substance, wherein the work function (eV) of the substance is used as an index of the skin barrier function recovery promoting effect.
[2] The evaluation method according to [1], wherein a substance having a work function in the range of 2.5 to 6.0 eV is evaluated as having a high effect of promoting the recovery of skin barrier function.
[3] A skin barrier function recovery promoting preparation comprising one or more substances having a work function of 2.5 to 6.0 eV.
[4] The skin barrier function recovery promoting preparation according to [3], wherein the substance is samarium, zirconium, indium, silver, gold, or platinum.
[5] A cosmetic method for promoting the recovery of skin barrier function, comprising applying on the skin one or more substances having a work function of 2.5-6.0 eV.
[6] The cosmetic method according to [4], wherein the substance is samarium, zirconium, indium, silver, gold, or platinum.
　仕事関数の低いサマリウム、ジルコニウム、イリジウム等を皮膚に適用した場合、皮膚バリアー機能の回復を促進させることができる。仕事関数が低いということは、その物質表面の電子が放出され易いということである。理論に拘束されることを意図するものではないが、仕事関数の低い物質が皮膚に適用された場合、当該物質から放出された電子が皮膚表面に移動し、皮膚の恒常性に影響を及ぼしていると考えられる。これは、金と皮膚との間にアースやプラスチック膜を介在させた場合、金による皮膚バリアー機能回復効果が完全に阻害された結果とも一致する（特開２００６－３３５７３３号公報）。 When samarium, zirconium, iridium or the like having a low work function is applied to the skin, recovery of the skin barrier function can be promoted. A low work function means that electrons on the surface of the material are easily emitted. While not intending to be bound by theory, when a substance with a low work function is applied to the skin, electrons emitted from the substance migrate to the skin surface, affecting the skin's homeostasis. It is thought that there is. This coincides with the result that the skin barrier function recovery effect by gold is completely inhibited when an earth or plastic film is interposed between gold and skin (Japanese Patent Laid-Open No. 2006-335733).
　サマリウム等の金属は金よりもイオン化傾向が高く、これまで皮膚バリアー機能回復促進効果が検討されていなかった。本発明によれば、化粧品に従来使用されていなかった物質であっても、仕事関数をかかる効果の指標とすることで動物実験を経ずに予め皮膚バリアー機能回復効果を評価することが可能となる。 金属 Metals such as samarium have a higher ionization tendency than gold, and the effect of promoting skin barrier function recovery has not been studied so far. According to the present invention, it is possible to evaluate the skin barrier function recovery effect in advance without animal experiments by using the work function as an index of the effect even for substances that have not been used in cosmetics conventionally. Become.
図１は、無処置群と比較した場合の白金、金、銀、インジウム、ジルコニウム、サマリウムによる皮膚バリアー機能の回復率（％）を示すグラフである。FIG. 1 is a graph showing the recovery rate (%) of skin barrier function by platinum, gold, silver, indium, zirconium, and samarium when compared with the untreated group. 図２は、各金属による皮膚バリアー機能の回復率と各金属の仕事関数（eV）との相関関係を示す。FIG. 2 shows the correlation between the recovery rate of the skin barrier function by each metal and the work function (eV) of each metal.
　本発明の第一の観点において、物質の仕事関数(eV)を皮膚バリアー機能回復促進効果の指標とすることを特徴とする、皮膚バリアー機能回復促進物質の評価方法を提供する。 In a first aspect of the present invention, there is provided a method for evaluating a skin barrier function recovery promoting substance, characterized in that the work function (eV) of the substance is used as an index of the skin barrier function recovery promoting effect.
　本明細書で使用する場合、用語「仕事関数」とは、固体から真空中に電子を取出すのに要する最小限の仕事の大きさ（eV）を意味する（東京化学同人「化学辞典」第一版）。異なる仕事関数を有する２つの材料が存在している場合、仕事関数が低い物質の自由電子は、仕事関数が高い物質の表面に移動する。ここで、仕事関数には、熱電子放出から算出される熱電子仕事関数と、光電子放出から算出される光仕事関数の二種類がある。熱仕事関数は熱電子放出実験、光仕事関数は光電子放出実験により測定することができる。あるいは、物質によっては、Herbert B. Michaelson, "The work function of the elements and its periodicity". J. Appl. Phys. 48, 4729 (1977)、化学便覧等にその仕事関数が記載されており、これらに記載されている値を参照してもよい。 As used herein, the term “work function” means the minimum amount of work (eV) required to remove an electron from a solid into a vacuum (Tokyo Chemical Doujin “Chemical Dictionary” 1st Edition). When two materials having different work functions exist, free electrons of a substance having a low work function move to the surface of the substance having a high work function. Here, there are two types of work functions: a thermionic work function calculated from thermionic emission and a photowork function calculated from the photoelectron emission. The thermal work function can be measured by a thermal electron emission experiment, and the photo work function can be measured by a photoelectron emission experiment. Alternatively, depending on the substance, Herbert B. Michaelson, "The work function of the elements and its periodicity". J. Appl. Phys. 48, 4729 (1977), chemical handbooks, etc. Reference may be made to the values described in.
　実施例に記載のとおり、仕事関数が低い物質ほど皮膚に適用された場合、皮膚バリアー機能回復促進効果を発揮する。本発明の評価方法においては、仕事関数が低い物質、例えば仕事関数が２．５～６．０eVの範囲にある物質、好ましくは２．５～５．２eVの範囲にある物質を皮膚バリアー機能回復促進効果が高い物質と評価する。 As described in the Examples, when a substance having a lower work function is applied to the skin, the effect of promoting the recovery of the skin barrier function is exhibited. In the evaluation method of the present invention, a substance having a low work function, for example, a substance having a work function in the range of 2.5 to 6.0 eV, preferably a substance having a work function in the range of 2.5 to 5.2 eV is recovered. Evaluate as a substance with high promotion effect.
　Herbert B. Michaelson, 1977（前掲）には、様々な金属の仕事関数が記載されている。中でも、仕事関数が低い金属として、白金（5.65 eV）、金（5.10 eV）、銀（4.26 eV）、インジウム（4.05 eV）、ジルコニウム（4.05 eV）、サマリウム（2.70 eV）、バリウム（2.70 eV）、カリウム（2.30 eV）、ルビジウム（2.16 eV）、セシウム（2.14 eV）等が列挙されている。 Herbert B. son Michaelson, 1977 (above) describes work functions of various metals. Among them, platinum (5.65 eV), gold (5.10 eV), silver (4.26 eV), indium (4.05 eV), zirconium (4.05 eV), samarium (2.70 eV), barium (2.70 、 eV) , Potassium (2.30 eV), rubidium (2.16 eV), cesium (2.14 eV) and the like are listed.
　自由電子を有する金属の仕事関数は、タンパク質、脂質等の非イオン性有機化合物と比較して低い。しかし、金属の表面が酸化状態にある場合、その仕事関数は増大する。使用する金属の表面が酸化状態にある場合、その表面を研磨して金属状態にすることで所期の効果を発揮させることができる。また、仕事関数が低い金属であっても、ナトリウムやマグネシウムのように反応性の高い物質は安全性の観点から使用が制限される。従って、仕事関数が低く且つ皮膚に適用可能な金属は、例えば、白金、金、銀、インジウム、ジルコニウム、サマリウムである。しかしながら、本発明の皮膚バリアー機能回復促進製剤に含まれる物質は、これらの金属に限定されない。 The work function of a metal having free electrons is lower than that of nonionic organic compounds such as proteins and lipids. However, when the metal surface is in an oxidized state, its work function increases. When the surface of the metal to be used is in an oxidized state, the desired effect can be exhibited by polishing the surface into a metal state. Moreover, even if it is a metal with a low work function, use of a highly reactive substance like sodium and magnesium is restrict | limited from a viewpoint of safety | security. Accordingly, metals having a low work function and applicable to the skin are, for example, platinum, gold, silver, indium, zirconium, and samarium. However, the substance contained in the skin barrier function recovery promoting preparation of the present invention is not limited to these metals.
　上記金属の他、仕事関数が低い金属化合物、例えば酸化亜鉛（ＺｎＯ）（4.68 eV）、リン化ガリウム（ＧａＰ）（2.95 eV）、炭化ケイ素（ＳｉＣ）（4.75 eV）、硫化亜鉛（ＺｎＳ）（5.40 eV）、窒化ガリウム（ＧａＮ）(1.0 eV)も皮膚バリアー機能回復効果が高いと考えられる。 In addition to the above metals, metal compounds having a low work function such as zinc oxide (ZnO) (4.68 eV), gallium phosphide (GaP) (2.95 eV), silicon carbide (SiC) (4.75 eV), zinc sulfide (ZnS) ( 5.40 eV) and gallium nitride (GaN) (1.0 eV) are also considered to have a high effect of restoring the skin barrier function.
　本明細書で使用する用語「皮膚バリアー機能」とは、皮膚のなかでも表皮による体内の水分保持及びウイルス、細菌等の進入阻止、などを意味する。ここで、当該機能は、発汗しない条件下で経皮水分蒸散量（ＴＥＷＬ）（単位：ｇ／ｍ2・ｈ）を測定することにより評価することができる。 As used herein, the term “skin barrier function” means the retention of water in the body by the epidermis and the prevention of entry of viruses, bacteria, etc., among the skin. Here, the function can be evaluated by measuring the transdermal moisture transpiration (TEWL) (unit: g / m 2 · h) under the condition of not sweating.
　また、本発明において、「皮膚バリアー機能の回復を促進する」とは、皮膚のテープストリッピング直後のＴＥＷＬの値を０％、テープストリッピング前の値を１００％として、各測定時間におけるＴＥＷＬの値が、コントロールと比較した場合に明らかに有意差が認められ、ＴＥＷＬ回復率を促進させる効果を有することを意味し、Ａｎｄｒｅｗらの方法（Ｊ Ｉｎｖｅｓｔ Ｄｅｒｍａｔｏｌ，８６；５９８，１９８６）に従って、４％のドデシル硫酸ナトリウム（ＳＤＳ）水溶液をしみ込ませたＣｏｔｔｏｎ ｂａｌｌにより皮膚を処理して判定を行ういわゆる肌荒れ改善防止効果とは異なる。 In the present invention, “promoting the recovery of skin barrier function” means that the TEWL value immediately after tape stripping of the skin is 0%, the value before tape stripping is 100%, and the TEWL value at each measurement time is 4% dodecyl according to the method of Andrew et al. (J Invest Dermatol, 86; 598, 1986), which means that there is a clear significant difference when compared to the control, and that it has the effect of promoting the recovery rate of TEWL. This is different from the so-called rough skin improvement preventing effect in which the skin is treated with a cotton ball soaked with an aqueous solution of sodium sulfate (SDS) and judged.
　皮膚バリアー機能の回復が必要な皮膚としては、皮膚疾患、種々のストレス、そして肌荒れ等により皮膚バリアー機能が低下した肌、移植皮膚で皮膚バリアー層の形成が充分でないため皮膚バリアー機能が低い肌、あるいは移植によって皮膚バリアー機能が低下した肌等が挙げられる。従って、本発明の評価方法は、低下した皮膚バリアー機能の回復だけでなく、皮膚バリアー機能が低い肌に対してその機能を向上させる物質の評価も意図する。このように、本発明により皮膚バリアー機能回復促進効果があると評価された物質を適用する対象者としては、哺乳類が考えられ、特にヒトの皮膚に対して適用される。 The skin that needs to be restored to the skin barrier function includes skin diseases, various stresses, skin having a reduced skin barrier function due to rough skin, skin having a low skin barrier function because the skin barrier layer is not sufficiently formed in the transplanted skin, Or the skin etc. whose skin barrier function fell by transplant are mentioned. Therefore, the evaluation method of the present invention intends not only to recover a reduced skin barrier function but also to evaluate a substance that improves the function of skin having a low skin barrier function. As described above, mammals are considered as subjects to which a substance evaluated to have an effect of promoting the recovery of skin barrier function according to the present invention, and is particularly applied to human skin.
　更に、上述の加齢に伴う皮膚機能の低下による皮膚増殖性異常等を防止する観点から、皮膚バリアー機能回復促進物質は、高齢者の皮膚に適用されることが考えられる。当該物質はまた、人工皮膚にも適用することができる。これは、生体より単離された皮膚細胞等を培養することによって得られる人工皮膚は、皮膚バリアー層の形成が不完全なことがあり、その皮膚バリアー機能は概して低いためである。 Furthermore, from the viewpoint of preventing the above-mentioned abnormal skin growth due to a decrease in skin function accompanying aging, the skin barrier function recovery promoting substance may be applied to the skin of elderly people. The substance can also be applied to artificial skin. This is because artificial skin obtained by culturing skin cells or the like isolated from a living body may have an incomplete formation of a skin barrier layer, and its skin barrier function is generally low.
　第二の観点において、本発明は、仕事関数が２．５～６．０eVである１又は複数の物質を含む、皮膚バリアー機能回復促進製剤を提供する。 In a second aspect, the present invention provides a skin barrier function recovery promoting preparation comprising one or more substances having a work function of 2.5 to 6.0 eV.
　本発明の製剤の形態には、美容器具、例えば、美容ローラーのようなローラー式のマッサージ具、貼付剤、例えばシート、パック等がある。マッサージ具の態様においては、皮膚上に適用される部分（例えばローラー部）全てが仕事関数の低い物質で構成されるか、あるいはその表面のみが前記物質で被覆される。前記物質が金属である場合、圧延した後、金属箔として製剤の所定の部位に配置され得る。尚、被覆厚は限定されない。しかし、極めて薄い膜であっても皮膚バリアー機能回復促進効果が得られる。貼付剤の場合、皮膚と接触される部分を前記物質で被覆してもよい。あるいは、シート又はパックの中に前記物質を含浸させることもできる。 The form of the preparation of the present invention includes beauty instruments, for example, roller-type massage devices such as beauty rollers, patches, such as sheets and packs. In the embodiment of the massage device, all parts (for example, roller parts) applied on the skin are made of a substance having a low work function, or only the surface thereof is covered with the substance. When the substance is a metal, it can be placed at a predetermined site of the preparation as a metal foil after rolling. The coating thickness is not limited. However, even if it is a very thin film | membrane, the skin barrier function recovery promotion effect is acquired. In the case of a patch, the part that comes into contact with the skin may be coated with the substance. Alternatively, the material can be impregnated into a sheet or pack.
　その他、本発明の製剤は、ファンデーション、化粧水、クリーム、乳液、ローション、パック、浴用剤、軟膏、ヘアーローション、ヘアートニック、ヘアーリキッド、シャンプー、リンス、養毛・育毛剤等を包含するものである。 In addition, the preparations of the present invention include foundations, lotions, creams, emulsions, lotions, packs, bath preparations, ointments, hair lotions, hair licks, hair liquids, shampoos, rinses, hair nourishing / hair growth agents and the like. is there.
　皮膚バリアー機能回復促進効果の観点からは、サマリウム、ジルコニウム、インジウム、銀の金属が前記物質として好ましい。製剤がファンデーションの場合、当該物質は０．１～１０％、好ましくは５％に製剤中に含められる。これらの物質は塩の形態で当該製剤中に配合されることもある。 From the viewpoint of the skin barrier function recovery promoting effect, samarium, zirconium, indium and silver metals are preferable as the substance. When the preparation is a foundation, the substance is included in the preparation at 0.1 to 10%, preferably 5%. These substances may be incorporated into the preparation in the form of a salt.
　第三の観点において、本発明は、皮膚バリアー機能の回復を促進させるための美容方法であって、仕事関数が２．５～６．０eVである１又は複数の物質を皮膚上に適用することを含んで成る方法を提供する。 In a third aspect, the present invention is a cosmetic method for promoting the recovery of skin barrier function, wherein one or more substances having a work function of 2.5 to 6.0 eV are applied onto the skin. A method comprising the steps of:
　本発明の美容方法は、皮膚バリアー機能回復が必要とされる皮膚に仕事関数の低い物質を適用するものである。適用方法は特に限定されず、例えば、前記物質で表面が構成されている美容器具を対象の皮膚に撫で付けたり、その皮膚上で転がしてもよい。あるいは、前記物質で覆われているか、又は前記物質を含有するパック又はシートを皮膚上に載せ、あるいは貼り付けることで皮膚に適用される。その他、前記物質を有効成分として含む化粧料として皮膚に塗布されることもある。前記物質を皮膚に適用する回数、時間は、その皮膚の状態によって変化するが、セロテープ（登録商標）によるストリッピングで破壊された皮膚の場合、１時間あれば皮膚バリアー機能の回復を達成することができる。 The cosmetic method of the present invention is to apply a substance having a low work function to the skin that needs to recover the skin barrier function. The application method is not particularly limited. For example, a beauty tool whose surface is made of the above-described substance may be applied to the subject's skin with a scissors or rolled on the skin. Or it is covered with the said substance, or the pack or sheet containing the said substance is applied to skin by mounting or sticking on skin. In addition, it may be applied to the skin as a cosmetic containing the substance as an active ingredient. The number and time of applying the substance to the skin varies depending on the condition of the skin, but in the case of skin broken by stripping with cello tape (registered trademark), recovery of the skin barrier function should be achieved in 1 hour. Can do.
　次に、本願発明を以下の実施例により更に具体的に説明する。 Next, the present invention will be described more specifically with reference to the following examples.
皮膚バリアー機能回復促進効果試験
　以下の実験において、仕事関数が低いサマリウム、ジルコニウム、インジウム、銀、金、白金についての皮膚バリアー機能回復促進効果を評価した。金、白金以外の金属は、サンドペーパーで表面を研磨することにより金属状態にした後使用した。皮膚バリアー機能回復促進効果は、ヘアレスマウス（Ｔｙｐｅ ＨＲ－１， ＨＯＳＨＩＮＯ， Ｊａｐａｎ）の皮膚にテープストリッピングを施すことによって破壊された皮膚バリアー機能がもとの状態へ回復していく過程を経皮水分蒸散量（ＴＥＷＬ）を指標とし、以下の通り評価した。 Skin barrier function recovery promoting effect test In the following experiment, skin barrier function recovery promoting effect was evaluated for samarium, zirconium, indium, silver, gold, and platinum having a low work function. Metals other than gold and platinum were used after being made into a metallic state by polishing the surface with sandpaper. The skin barrier function recovery promoting effect is that the process of recovering the skin barrier function destroyed by applying tape stripping to the skin of hairless mice (Type HR-1, HOSHINO, Japan) returns to the original state. Using the amount of transpiration (TEWL) as an index, the evaluation was as follows.
１．水分蒸散量測定装置ＭＥＥＣＯ（Ｍｅｅｃｏ社製， Ｗａｒｒｉｎｇｔｏｎ， ＰＡ， ＵＳＡ）によりヘアレスマウス背部付近の経皮水分蒸散量（ＴＥＷＬ）を測定する。この際の値をＴＥＷＬの回復率１００％とする。
２．皮膚のバリアーを、セロファンテープを使用し、ヘアレスマウスの表皮角層を剥がすことにより破壊する。このときＴＥＷＬの値が約８００～９００となるまでこの作業を繰り返す。角層を剥がした後の測定値から角層を剥がす前の測定値を差し引いた値を、最もダメージの深い状態、即ち回復率０％とする。
３．角層を剥がしてから所定の時間（１，３，６又は２４時間）経過後、各金属（面積２ｘ２ｃｍ2、厚さ０．５ｍｍ）を上記角層の上に貼り付ける。何も貼り付けていない皮膚をコントロールとする。
４．１時間経過後、純金板を剥がし、ＭＥＥＣＯによりＴＥＷＬを測定する。角層除去時と同様、各時間の測定値から角層除去前のＴＥＷＬ値を差し引き、回復率をもとめる。
即ち、回復率は以下の式に従い算出する。
Figure JPOXMLDOC01-appb-M000001
 1. The transcutaneous moisture transpiration (TEWL) near the back of the hairless mouse is measured by a moisture transpiration measuring device MEECO (Meeco, Warrington, PA, USA). The value at this time is assumed to be a TEWL recovery rate of 100%.
2. The skin barrier is broken by peeling off the epidermal stratum of hairless mice using cellophane tape. At this time, this operation is repeated until the value of TEWL becomes about 800 to 900. The value obtained by subtracting the measured value before peeling the stratum corneum from the measured value after peeling the stratum corneum is the deepest damage state, that is, the recovery rate is 0%.
3. After elapse of a predetermined time (1, 3, 6 or 24 hours) after peeling off the stratum corneum, each metal (area 2 × 2 cm 2 , thickness 0.5 mm) is stuck on the stratum corneum. The control is skin with nothing applied.
4.1 After elapse of 1 hour, the pure gold plate is peeled off, and TEWL is measured by MEECO. As in the case of removing the stratum corneum, the TEWL value before removing the stratum corneum is subtracted from the measured value at each time to obtain the recovery rate.
That is, the recovery rate is calculated according to the following formula.
Figure JPOXMLDOC01-appb-M000001
　当該試験によって測定された皮膚バリアー機能の回復率（％）を図１に示す。図１から明らかなように、バリアー破壊後の皮膚は、使用した金属のいずれを貼り付けた場合であっても、貼り付け後１時間でバリアー機能が顕著に回復した。貼り付け後のいずれの時間においても、仕事関数の低い金属を貼り付けたものはコントロールと比較して有意なバリアー機能回復率の向上を示した。中でも、仕事関数が最も低いサマリウムは回復効果が最も高かった。図２に示すとおり、仕事関数と皮膚バリアー機能回復効果の間には有意な相関関係が認められる。 The recovery rate (%) of the skin barrier function measured by the test is shown in FIG. As is apparent from FIG. 1, the barrier function was remarkably recovered in 1 hour after application of the skin after barrier destruction, regardless of which of the metals used was applied. At any time after pasting, the one with the metal having a low work function stuck showed a significant improvement in the barrier function recovery rate compared to the control. Among them, the samarium with the lowest work function had the highest recovery effect. As shown in FIG. 2, a significant correlation is recognized between the work function and the skin barrier function recovery effect.
　以上の結果から、物質の仕事関数は皮膚バリアー機能の回復を促進させる良好な指標となり得ると結論付けられる。本発明によれば、物質の仕事関数を皮膚バリアー機能回復促進効果の評価指標とすることで、動物等の皮膚に予め適用する前にその効果の有無を決定することができる。 From the above results, it can be concluded that the work function of a substance can be a good indicator for promoting the recovery of skin barrier function. According to the present invention, by using the work function of a substance as an evaluation index of a skin barrier function recovery promoting effect, it is possible to determine the presence or absence of the effect before applying to the skin of an animal or the like in advance.

Claims (6)

  1. 　物質の仕事関数(eV)を皮膚バリアー機能回復促進効果の指標とすることを特徴とする、皮膚バリアー機能回復促進物質の評価方法。 A method for evaluating a skin barrier function recovery promoting substance, wherein the work function (eV) of the substance is used as an index of the effect of promoting the skin barrier function recovery.
  2. 　前記仕事関数が２．５～６．０eVの範囲にある物質を皮膚バリアー機能回復促進効果が高いと評価することを特徴とする、請求項１に記載の評価方法。 2. The evaluation method according to claim 1, wherein a substance having a work function in the range of 2.5 to 6.0 eV is evaluated as having a high effect of promoting skin barrier function recovery.
  3. 　仕事関数が２．５～６．０eVである１又は複数の物質を含む、皮膚バリアー機能回復促進製剤。 A skin barrier function recovery promoting preparation containing one or more substances having a work function of 2.5 to 6.0 eV.
  4. 　前記物質がサマリウム、ジルコニウム、インジウム、銀、金又は白金である、請求項３に記載の皮膚バリアー機能回復促進製剤。 The skin barrier function recovery promoting preparation according to claim 3, wherein the substance is samarium, zirconium, indium, silver, gold or platinum.
  5. 　皮膚バリアー機能の回復を促進させるための美容方法であって、仕事関数が２．５～６．０eVである１又は複数の物質を皮膚上に適用することを含んで成る方法。 A cosmetic method for promoting the recovery of the skin barrier function, comprising applying one or more substances having a work function of 2.5 to 6.0 eV on the skin.
  6. 　前記物質がサマリウム、ジルコニウム、インジウム、銀、金又は白金である、請求項５に記載の美容方法。 The cosmetic method according to claim 5, wherein the substance is samarium, zirconium, indium, silver, gold or platinum.
PCT/JP2010/057019 2009-04-20 2010-04-20 Method for evaluating skin barrier function recovery-accelerator using work function as indication WO2010123008A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012191968A (en) * 2011-03-14 2012-10-11 Shiseido Co Ltd Skin barrier function recovery promoting device

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JP2002265218A (en) * 2001-03-08 2002-09-18 Shiseido Co Ltd Barium sulfate powder and makeup material containing the same
JP2002291909A (en) * 2001-03-30 2002-10-08 Shiseido Co Ltd Method for promoting improvement of skin barrier function
JP2003286150A (en) * 2002-03-28 2003-10-07 Shiseido Co Ltd Skin care preparation
JP2004231578A (en) * 2003-01-30 2004-08-19 Shiseido Co Ltd Preparation for external use for promoting restoration of skin barrier function containing anionic polymer salt
JP2006335733A (en) * 2005-06-03 2006-12-14 Shiseido Co Ltd Skin barrier function recovery-accelerating agent

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002265218A (en) * 2001-03-08 2002-09-18 Shiseido Co Ltd Barium sulfate powder and makeup material containing the same
JP2002291909A (en) * 2001-03-30 2002-10-08 Shiseido Co Ltd Method for promoting improvement of skin barrier function
JP2003286150A (en) * 2002-03-28 2003-10-07 Shiseido Co Ltd Skin care preparation
JP2004231578A (en) * 2003-01-30 2004-08-19 Shiseido Co Ltd Preparation for external use for promoting restoration of skin barrier function containing anionic polymer salt
JP2006335733A (en) * 2005-06-03 2006-12-14 Shiseido Co Ltd Skin barrier function recovery-accelerating agent

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012191968A (en) * 2011-03-14 2012-10-11 Shiseido Co Ltd Skin barrier function recovery promoting device

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