JPWO2018128167A1 - Skin sheet - Google Patents
Skin sheet Download PDFInfo
- Publication number
- JPWO2018128167A1 JPWO2018128167A1 JP2018560397A JP2018560397A JPWO2018128167A1 JP WO2018128167 A1 JPWO2018128167 A1 JP WO2018128167A1 JP 2018560397 A JP2018560397 A JP 2018560397A JP 2018560397 A JP2018560397 A JP 2018560397A JP WO2018128167 A1 JPWO2018128167 A1 JP WO2018128167A1
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen gas
- skin sheet
- containing layer
- skin
- gum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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Classifications
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- A—HUMAN NECESSITIES
- A45—HAND OR TRAVELLING ARTICLES
- A45D—HAIRDRESSING OR SHAVING EQUIPMENT; EQUIPMENT FOR COSMETICS OR COSMETIC TREATMENTS, e.g. FOR MANICURING OR PEDICURING
- A45D44/00—Other cosmetic or toiletry articles, e.g. for hairdressers' rooms
- A45D44/22—Face shaping devices, e.g. chin straps; Wrinkle removers, e.g. stretching the skin
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- 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
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
- Epidemiology (AREA)
- Dermatology (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
従来の肌用シートに比べ肌に水素ガスを多く供給できる肌用シートを提供する。水素ガス含有層（１０）を有する肌用シート（１）であり；水素ガス含有層（１０）は、液状媒体を含む基材（１２）に溶存する水素ガスおよび基材（１２）内に包含された気泡状態の水素ガス（１４）を含み；水素ガス含有層（１０）中の気泡状態の水素ガス（１４）の含有率が、０．１〜７０体積％［ｖ／ｗ］である、肌用シート（１）。Provided is a skin sheet that can supply more hydrogen gas to the skin than a conventional skin sheet. A skin sheet (1) having a hydrogen gas-containing layer (10); the hydrogen gas-containing layer (10) is included in the hydrogen gas dissolved in the substrate (12) containing the liquid medium and the substrate (12). The hydrogen content (14) in the bubble state; the hydrogen gas content layer (10) in the hydrogen gas-containing layer (10) has a content of 0.1 to 70% by volume [v / w]. Sheet for skin (1).
Description
本発明は、肌用シートに関する。
本願は、２０１７年１月６日に、日本出願された特願２０１７−００１０００号に基づき優先権を主張し、その内容をここに援用する。The present invention relates to a skin sheet.
This application claims priority on January 6, 2017 based on Japanese Patent Application No. 2017-001000 for which it applied to Japan, and uses the content here.
近年、水素ガスについては、活性酸素を除去する機能、生物活性を高める機能等の様々な機能を有することが期待されている。そのため、水素ガスを含む化粧料、食品、飲料等が注目されている。 In recent years, hydrogen gas is expected to have various functions such as a function of removing active oxygen and a function of enhancing biological activity. Therefore, cosmetics, foods, beverages and the like containing hydrogen gas have attracted attention.
肌に水素ガスを効率よく供給するためのアイテムとしては、肌に水素ガスを供給する水素保持層と、水素保持層の肌と接しない側を覆う水素反射層とを有する肌用シートが提案されている（特許文献１）。 As an item for efficiently supplying hydrogen gas to the skin, a skin sheet having a hydrogen retaining layer that supplies hydrogen gas to the skin and a hydrogen reflective layer that covers the side of the hydrogen retaining layer that does not contact the skin has been proposed. (Patent Document 1).
特許文献１の肌用シートにおける水素保持層は、精製水に水素ガスを溶存させた水素水をベースとした肌用剤（化粧水、クリーム、ジェル、軟膏等）からなる（特許文献１の段落［００２２］）。そのため、水素保持層の水素ガス含有率は、最大でも２０℃の水に対する水素ガスの飽和溶解度の１．６ｐｐｍ（２体積％［ｖ／ｗ］）程度であり、わずかでしかない。
The hydrogen retention layer in the skin sheet of
肌に水素ガスを多く供給して、水素ガスが有する様々な機能を十分に発現させるためには、肌用シートに含まれる水素ガスの含有率をさらに増やすことが望まれる。 In order to supply a large amount of hydrogen gas to the skin and fully develop various functions of the hydrogen gas, it is desired to further increase the content of the hydrogen gas contained in the skin sheet.
本発明は、従来の肌用シートに比べ肌に水素ガスを多く供給できる肌用シートを提供する。 The present invention provides a skin sheet that can supply more hydrogen gas to the skin than a conventional skin sheet.
本発明は、下記の態様を有する。
＜１＞水素ガス含有層を有する肌用シートであり；前記水素ガス含有層は、液状媒体を含む基材に溶存する水素ガスおよび前記基材内に包含された気泡状態の水素ガスを含み；前記水素ガス含有層中の前記気泡状態の水素ガスの含有率が、０．１〜７０体積％［ｖ／ｗ］である、肌用シート。
＜２＞前記水素ガス含有層の前記基材が、ゲル化剤または増粘剤をさらに含む、前記＜１＞の肌用シート。
＜３＞前記ゲル化剤または増粘剤が、ゼラチン、寒天、カラギーナン、ペクチン、グアーガム、タマリンドガム、グルコマンナン、カロブビーンガム、キサンタンガム、プルラン、カルボキシメチルセルロース、アルギン酸、アルギン酸塩、アルギン酸誘導体、カルボキシビニルポリマー、カルボキシビニルポリマー誘導体、ポリビニルアルコール、ポリビニルアルコール誘導体、ポリビニルピロリドン、ポリビニルピロリドン誘導体、ポリアクリル酸からなる群から選ばれる少なくとも１種である、前記＜２＞の肌用シート。
＜４＞前記水素ガス含有層の全面を覆う水素ガスバリア層をさらに有する、前記＜１＞〜＜３＞のいずれかの肌用シート。
＜５＞前記水素ガスバリア層が、前記水素ガス含有層を収容し、かつ一部に開口が形成された包装部と、前記開口を塞ぐように前記開口のまわりの前記包装部に剥離可能に貼着された蓋体部とを有する、前記＜４＞の肌用シート。The present invention has the following aspects.
<1> a skin sheet having a hydrogen gas-containing layer; the hydrogen gas-containing layer includes hydrogen gas dissolved in a substrate containing a liquid medium and hydrogen gas in a bubble state contained in the substrate; The skin sheet | seat whose content rate of the said gaseous hydrogen gas in the said hydrogen gas content layer is 0.1-70 volume% [v / w].
<2> The skin sheet according to <1>, wherein the base material of the hydrogen gas-containing layer further includes a gelling agent or a thickener.
<3> The gelling agent or thickener is gelatin, agar, carrageenan, pectin, guar gum, tamarind gum, glucomannan, carob bean gum, xanthan gum, pullulan, carboxymethylcellulose, alginic acid, alginate, alginic acid derivative, carboxyvinyl polymer, The skin sheet according to <2>, which is at least one selected from the group consisting of a carboxyvinyl polymer derivative, polyvinyl alcohol, a polyvinyl alcohol derivative, polyvinyl pyrrolidone, a polyvinyl pyrrolidone derivative, and polyacrylic acid.
<4> The skin sheet according to any one of <1> to <3>, further including a hydrogen gas barrier layer covering the entire surface of the hydrogen gas-containing layer.
<5> The hydrogen gas barrier layer accommodates the hydrogen gas-containing layer and is detachably attached to the packaging part in which an opening is formed in part and the packaging part around the opening so as to close the opening. The skin sheet according to <4>, including a lid portion that is worn.
本発明の肌用シートは、従来の肌用シートに比べ肌に水素ガスを多く供給できる。 The skin sheet of the present invention can supply more hydrogen gas to the skin than the conventional skin sheet.
以下の用語の定義は、本明細書および請求の範囲にわたって適用される。
「ゲル化剤」とは、水素結合等による物理的凝集または共有結合等による架橋によって液状媒体を保持できる網目構造を形成し得る化合物をいう。
「増粘剤」とは、液状媒体に粘性を付与し得る化合物をいう。
「水素ガス含有層中の気泡状態の水素ガスの含有率（体積％［ｖ／ｗ］）」とは、水素ガス含有層の所定質量（１００ｇ）に気泡状態で含まれる水素ガスの体積（ｃｍ３）の割合をいう。
「液状組成物」とは、ゲル化剤または増粘剤と液状媒体とを含み、ゲル化または増粘化させる前の組成物をいう。
「ゲル状組成物」とは、ゲル化剤を含む液状組成物をゲル化させた組成物をいう。
「粘性組成物」とは、増粘剤を含む液状組成物を増粘化させた組成物をいう。
「液状媒体に対する水素ガスの飽和溶解度」とは、液状媒体（水等）に対する水素ガスの大気圧下での飽和溶解度をいう。なお、飽和溶解度を規定する「ガスの溶解」は、ヘンリーの法則が成立し、ガスが圧力に応じて分子状で溶解している状態である。The following term definitions apply throughout this specification and the claims.
The “gelling agent” refers to a compound capable of forming a network structure capable of holding a liquid medium by physical aggregation by hydrogen bonding or the like or crosslinking by covalent bonding or the like.
“Thickener” refers to a compound capable of imparting viscosity to a liquid medium.
“Hydrogen gas content in the hydrogen gas-containing layer (volume% [v / w])” is the volume of hydrogen gas contained in a predetermined mass (100 g) of the hydrogen gas-containing layer (cm 3 ) The ratio.
“Liquid composition” refers to a composition before gelation or thickening, which includes a gelling agent or thickener and a liquid medium.
The “gel composition” refers to a composition obtained by gelling a liquid composition containing a gelling agent.
“Viscous composition” refers to a composition obtained by thickening a liquid composition containing a thickener.
“Saturated solubility of hydrogen gas in a liquid medium” refers to the saturated solubility of hydrogen gas in a liquid medium (water or the like) under atmospheric pressure. The “dissolution of gas” that defines the saturation solubility is a state in which Henry's law is established and the gas is dissolved in a molecular form according to the pressure.
水素ガス含有層中の気泡状態の水素ガスの含有率は、次のように求める。大気圧、２５℃の条件下で水素ガス含有層の０．５〜１ｇをＧＣ分析で用いるヘッドスペースＧＣ分析用サンプル瓶（容量：２０ｍＬ）に精秤して入れ、水の１０ｍＬを加えて密閉する。サンプル瓶を手でよく振った後、超音波洗浄機で十分に混合する。サンプル瓶を７０℃に加熱し、水素ガス含有層から気泡が消えるまで７０℃で加熱を続ける。気泡が消えた後、サンプル瓶内の気相ガスを採取して、ガスクロマトグラフ（ＧＣ）分析（ＴＣＤ検出器）によって水素ガスを定量し、水素ガス含有層中の気泡状態の水素ガスの含有率（体積％［ｖ／ｗ％］）を算出する。水に対する水素ガスの飽和溶解度は、２０℃で１．６ｐｐｍ（２体積％［ｖ／ｗ］）、７０℃で１．５ｐｐｍ（１．８体積％［ｖ／ｗ］）であってほとんど変わらない、すなわち水素ガス含有層の基材（ほぼ水）中の溶存水素ガスの量は測定前後でほとんど変わらない為、前記方法によって求めた水素ガスの含有率は、基材内に包含された気泡状態の水素ガスの含有率と見なすことができる。
本明細書および請求の範囲において数値範囲を示す「〜」は、その前後に記載された数値を下限値および上限値として含むことを意味する。
図１〜図２における寸法比は、説明の便宜上、実際のものとは異なったものである。The content rate of hydrogen gas in a bubble state in the hydrogen gas-containing layer is obtained as follows. Under conditions of atmospheric pressure and 25 ° C., 0.5 to 1 g of the hydrogen gas containing layer is precisely weighed into a head space GC analysis sample bottle (capacity: 20 mL) used for GC analysis, and 10 mL of water is added and sealed. To do. After shaking the sample bottle well by hand, mix thoroughly with an ultrasonic cleaner. Heat the sample bottle to 70 ° C. and continue heating at 70 ° C. until bubbles disappear from the hydrogen gas containing layer. After the bubbles disappear, the gas phase gas in the sample bottle is collected, the hydrogen gas is quantified by gas chromatograph (GC) analysis (TCD detector), and the content of the hydrogen gas in the bubble state in the hydrogen gas containing layer (Volume% [v / w%]) is calculated. The saturation solubility of hydrogen gas in water is 1.6 ppm (2% by volume [v / w]) at 20 ° C. and 1.5 ppm (1.8% by volume [v / w]) at 70 ° C., which is almost unchanged. That is, since the amount of dissolved hydrogen gas in the base material (substantially water) of the hydrogen gas-containing layer is almost unchanged before and after the measurement, the hydrogen gas content determined by the above method is the state of bubbles contained in the base material. It can be regarded as the hydrogen gas content.
In the present specification and claims, “to” indicating a numerical range means that numerical values described before and after the numerical value are included as a lower limit value and an upper limit value.
The dimensional ratios in FIGS. 1 and 2 are different from actual ones for convenience of explanation.
＜肌用シート＞
本発明の肌用シートは、水素ガス含有層を有する。
本発明の肌用シートは、水素ガス含有層からの水素ガスの気相中への揮散を抑える点から、水素ガス含有層の全面を覆う水素ガスバリア層をさらに有することが好ましい。<Skin sheet>
The skin sheet of the present invention has a hydrogen gas-containing layer.
The skin sheet of the present invention preferably further has a hydrogen gas barrier layer covering the entire surface of the hydrogen gas-containing layer from the viewpoint of suppressing the volatilization of hydrogen gas from the hydrogen gas-containing layer into the gas phase.
＜水素ガス含有層＞
水素ガス含有層は、液状媒体を含む基材に溶存する水素ガスおよび基材内に包含された気泡状態の水素ガスを含む。
すなわち、水素ガス含有層は、液状媒体に対する水素ガスの飽和溶解度（液状媒体が水の場合は２０℃で１．６ｐｐｍ（２体積％［ｖ／ｗ］））に相当する溶存水素ガスと、基材の液状媒体に溶解しきれなかった余剰の水素ガスである気泡状態の水素ガスを含んでいる。<Hydrogen gas containing layer>
The hydrogen gas-containing layer includes hydrogen gas dissolved in the base material including the liquid medium and hydrogen gas in a bubble state contained in the base material.
That is, the hydrogen gas-containing layer includes dissolved hydrogen gas corresponding to the saturation solubility of hydrogen gas in the liquid medium (1.6 ppm (2% by volume [v / w]) at 20 ° C. when the liquid medium is water), It contains hydrogen gas in a bubble state that is excess hydrogen gas that could not be completely dissolved in the liquid medium of the material.
（気泡状態の水素ガス）
水素ガス含有層中の気泡状態の水素ガスの含有率は、０．１〜７０体積％［ｖ／ｗ］であり、２〜６０体積％［ｖ／ｗ］が好ましく、６〜５０体積％［ｖ／ｗ］がより好ましく、１０〜４５体積％［ｖ／ｗ］がさらに好ましい。水素ガス含有層中の気泡状態の水素ガスの含有率が前記範囲の下限値以上であれば、基材中の溶存水素ガスの量と合計した水素ガス含有層中の全水素ガスの含有率が、溶存水素ガスのみである従来の肌用シート（最大でも２０℃の水に対する水素ガスの飽和溶解度の１．６ｐｐｍ（２体積％［ｖ／ｗ］）程度）に比べ多くなり、肌に水素ガスを多く供給できる。水素ガス含有層中の気泡状態の水素ガスの含有率が前記範囲の上限値までは、基材内への水素ガスの気泡分散が可能である。(Bubble hydrogen gas)
The hydrogen gas content in the hydrogen gas-containing layer is 0.1 to 70% by volume [v / w], preferably 2 to 60% by volume [v / w], and 6 to 50% by volume [v / w]. v / w] is more preferable, and 10 to 45% by volume [v / w] is further preferable. If the hydrogen gas content in the hydrogen gas containing layer is equal to or higher than the lower limit of the above range, the total hydrogen gas content in the hydrogen gas containing layer combined with the amount of dissolved hydrogen gas in the substrate is Compared with the conventional skin sheet that contains only dissolved hydrogen gas (maximum of 1.6 ppm (2% by volume [v / w]) of the saturation solubility of hydrogen gas in water at 20 ° C.) Can supply more. As long as the hydrogen gas content in the hydrogen gas-containing layer is up to the upper limit of the above range, the hydrogen gas bubbles can be dispersed into the substrate.
水素ガス含有層中の気泡状態の水素ガスの含有率は、後述する製造方法において、ゲル化剤または増粘剤の量、液状組成物に気泡状態の水素ガスを包含させる際の水素ガスの供給量ならびに液状組成物の撹拌条件（回転数、時間等）等を調整することによって調製できる。 The hydrogen gas content in the hydrogen gas-containing layer is determined by the amount of the gelling agent or the thickener in the production method described later, and the supply of hydrogen gas when the liquid composition includes the hydrogen gas in the bubble state. It can be prepared by adjusting the amount and stirring conditions (rotation speed, time, etc.) of the liquid composition.
（基材）
基材は、水素ガス含有層において水素ガスを溶存するとともに気泡状態の水素ガスを包含するためのベースとなるものであり、液状媒体を必須成分として含む。
基材は、気泡状態の水素ガスを長時間包含でき、かつ水素ガス含有層からの水素ガスの放出速度を制御できる点から、ゲル化剤または増粘剤をさらに含むことが好ましい。
基材としては、気泡状態の水素ガスを長時間包含でき、かつ水素ガス含有層からの水素ガスの放出速度を制御できるとともに、水素ガス含有層の形状を保持できる点から、ゲル状組成物または粘性組成物からなるものが好ましい。(Base material)
The base material serves as a base for dissolving the hydrogen gas in the hydrogen gas-containing layer and containing the hydrogen gas in a bubble state, and includes a liquid medium as an essential component.
It is preferable that the base material further contains a gelling agent or a thickening agent from the viewpoint that hydrogen gas in a bubble state can be included for a long time and the release rate of the hydrogen gas from the hydrogen gas-containing layer can be controlled.
As the base material, it is possible to include hydrogen gas in a bubble state for a long time, control the release rate of hydrogen gas from the hydrogen gas-containing layer, and maintain the shape of the hydrogen gas-containing layer. What consists of a viscous composition is preferable.
基材は、必要に応じて、化粧料に用いられる原料をさらに含んでいてもよい。化粧料に用いられる原料としては、化粧料のベースとなる他の成分（ただし、液状媒体、ゲル化剤および増粘剤を除く。）；化粧料に各種機能を付与する薬剤；視覚、嗅覚等に作用する満足感を付与する官能的特徴付与原料；化粧料の品質を保持する品質保持原料薬剤等が挙げられる。 The base material may further contain the raw material used for cosmetics as needed. As raw materials used in cosmetics, other ingredients that are the bases of cosmetics (excluding liquid media, gelling agents and thickeners); drugs that give various functions to cosmetics; vision, smell, etc. Examples include raw materials for imparting sensory characteristics that give satisfaction that acts on the skin; quality-maintaining raw materials that maintain the quality of cosmetics, and the like.
（液状媒体）
液状媒体は、ゲル化剤や増粘剤、および他の成分を溶解または分散させるための媒体となるものである。
液状媒体としては、ゲル化剤または増粘剤を溶解させる点から、ゲル化剤または増粘剤を溶解可能な水および炭素数が１〜５の低級アルコール、グリコールから選ばれる少なくとも１種の液状媒体が好ましい。水としては、精製水等が挙げられる。低級アルコールとしては、エチルアルコール、イソプロピルアルコール等が挙げられる。グリコールとしては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブタンジオール、１，４−ブタンジオール等が挙げられる。(Liquid medium)
The liquid medium serves as a medium for dissolving or dispersing the gelling agent, the thickening agent, and other components.
The liquid medium is at least one liquid selected from water capable of dissolving the gelling agent or thickener, lower alcohol having 1 to 5 carbon atoms, and glycol from the viewpoint of dissolving the gelling agent or thickener. A medium is preferred. Examples of water include purified water. Examples of the lower alcohol include ethyl alcohol and isopropyl alcohol. Examples of the glycol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, and the like.
液状媒体としては、水を含む水性媒体が好ましい。水性媒体は、低級アルコールをさらに含んでいてもよい。水性媒体中の水の割合は、水性媒体（１００質量％）のうち、５０質量％以上が好ましく、７０質量％以上がより好ましく、１００質量％が特に好ましい。
水性媒体中の水の割合が前記範囲の下限値以上であれば、ゲル化しやすく、基材中に気泡状態の水素ガスを多量に、かつ長時間にわたり保持しやすい。As the liquid medium, an aqueous medium containing water is preferable. The aqueous medium may further contain a lower alcohol. The proportion of water in the aqueous medium is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 100% by mass in the aqueous medium (100% by mass).
If the ratio of water in the aqueous medium is equal to or higher than the lower limit of the above range, gelation is likely, and a large amount of hydrogen gas in a bubble state is easily retained in the substrate for a long time.
（ゲル化剤、増粘剤）
ゲル化剤としては、例えば、天然物由来の蛋白類または多糖類、水素結合性基を有するポリマー、凝集性の疎水性基を有するポリマー、架橋性官能基を有するポリマー、多官能モノマー、単官能モノマー、シリコーン系ポリマー、カルボキシビニルポリマーまたはその誘導体等が挙げられる。
天然物由来の蛋白類または多糖類としては、例えば、ゼラチン、寒天、カラギーナン、ペクチン、グルコマンナン、プルラン、アルギン酸、アルギン酸ナトリウム、アルギン酸カリウム、アルギン酸カルシウム、アルギン酸アンモニウムなどのアルギン酸塩、アルギン酸プロピレングリコールエステルなどのアルギン酸誘導体、アウレオバシジウム培養液、スクシノグリカン、アマシードガム、アラビアガム、アラビノガラクタン、ウェランガム、カシアガム、ガティガム、カードラン、カラヤガム、カロブビーンガム、キサンタンガム、キトサン、グアーガム、グアーガム酵素分解物、酵母細胞壁、サイリウムシードガム、サバクヨモギシードガム、ジェランガム、タマリンドシードガム、タラガム、デキストラン、トラガントガム、トロロアオイ、微小繊維状セルロース、ファーセレラン、フクロノリ抽出物、マクロホモプシスガム、ラムザンガム、レバン、オクラ抽出物、海藻セルロース、褐藻抽出物、コンニャクイモ抽出物、サツマイモセルロース、ダイズ多糖類、ナタデココ、カルボキシメチルセルロース、アガロース等が挙げられる。
ゲル化剤は、１種を単独で用いてもよく、２種以上を併用してもよい。(Gelling agent, thickener)
Examples of the gelling agent include proteins or polysaccharides derived from natural products, polymers having a hydrogen bonding group, polymers having an aggregating hydrophobic group, polymers having a crosslinkable functional group, polyfunctional monomers, monofunctional Monomers, silicone-based polymers, carboxyvinyl polymers, derivatives thereof, and the like.
Examples of proteins or polysaccharides derived from natural products include gelatin, agar, carrageenan, pectin, glucomannan, pullulan, alginic acid, sodium alginate, potassium alginate, calcium alginate, alginate, propylene glycol alginate, etc. Alginate derivative, aureobasidium culture solution, succinoglycan, ama seed gum, gum arabic, arabinogalactan, welan gum, cassia gum, gati gum, curdlan, caraya gum, carob bean gum, xanthan gum, chitosan, guar gum, guar gum enzyme degradation product, yeast cell wall, Psyllium seed gum, mackerel mugwort seed gum, gellan gum, tamarind seed gum, tara gum, dextran, tragacanth gum, toro Aoi, Microfibrous cellulose, Far celerane, Fukuronori extract, Macrohomopsis gum, Ramzan gum, Levan, Okra extract, Seaweed cellulose, Brown algae extract, Konjac potato extract, Sweet potato cellulose, Soy polysaccharide, Nata de coco, Carboxymethyl cellulose, Agarose Etc.
A gelling agent may be used individually by 1 type, and may use 2 or more types together.
増粘剤としては、水溶性高分子等が挙げられる。水溶性高分子としては、有機系水溶性高分子、無機系水溶性高分子が挙げられる。
有機系水溶性高分子としては、天然高分子（キサンタンガム、マンナン、ペクチン等）、セルロース系半合成高分子（カルボキシメチルセルロース、カルボキシメチルセルロースナトリウム等）、合成高分子（カルボキシビニルポリマー、カルボキシビニルポリマー誘導体、ポリビニルアルコール、ポリビニルアルコール誘導体、ポリビニルピロリドンおよびポリビニルピロリドン誘導体、ポリヒドロキシエチルメタクリレート、ポリアクリル酸およびポリスチレンスルホン酸、シリコーン（ジメチコン、環状ジメチコン、メチルフェニルポリシロキサン、架橋型のジメチルポリシロキサン、メチルシロキサン網状重合体、ポリエーテル変性シリコーン、アクリル変性シリコーン、アメジコン等）等が挙げられる。
無機系水溶性高分子としては、粘土鉱物の一種であるべントナイト等が挙げられる。
増粘剤は、１種を単独で用いてもよく、２種以上を併用してもよい。Examples of the thickener include water-soluble polymers. Examples of the water-soluble polymer include organic water-soluble polymers and inorganic water-soluble polymers.
Organic water-soluble polymers include natural polymers (xanthan gum, mannan, pectin, etc.), cellulose semisynthetic polymers (carboxymethylcellulose, sodium carboxymethylcellulose, etc.), synthetic polymers (carboxyvinyl polymer, carboxyvinyl polymer derivatives, Polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl pyrrolidone and polyvinyl pyrrolidone derivatives, polyhydroxyethyl methacrylate, polyacrylic acid and polystyrene sulfonic acid, silicone (dimethicone, cyclic dimethicone, methylphenyl polysiloxane, cross-linked dimethylpolysiloxane, methylsiloxane network weight Coalesced, polyether-modified silicone, acrylic-modified silicone, amedicon, etc.).
Examples of the inorganic water-soluble polymer include bentonite, which is a kind of clay mineral.
A thickener may be used individually by 1 type and may use 2 or more types together.
ゲル化剤または増粘剤としては、ゼラチン、寒天、カラギーナン、ペクチン、グルコマンナン、プルラン、アルギン酸、アルギン酸塩、アルギン酸誘導体、アウレオバシジウム培養液、スクシノグリカン、アマシードガム、アラビアガム、アラビノガラクタン、ウェランガム、カシアガム、ガティガム、カードラン、カラヤガム、カロブビーンガム、キサンタンガム、キトサン、グアーガム、グアーガム酵素分解物、酵母細胞壁、サイリウムシードガム、サバクヨモギシードガム、ジェランガム、タマリンドシードガム、タラガム、デキストラン、トラガントガム、トロロアオイ、微小繊維状セルロース、ファーセレラン、フクロノリ抽出物、マクロホモプシスガム、ラムザンガム、レバン、オクラ抽出物、海藻セルロース、褐藻抽出物、コンニャクイモ抽出物、サツマイモセルロース、ダイズ多糖類、ナタデココ、カルボキシメチルセルロース、アガロース、カルボキシビニルポリマー、カルボキシビニルポリマー誘導体、ポリビニルアルコール、ポリビニルアルコール誘導体、ポリビニルピロリドン、ポリビニルピロリドン誘導体、ポリヒドロキシエチルメタクリレート、ポリアクリル酸、ポリスチレンスルホン酸、シリコーンからなる群から選ばれる１種または２種以上であることが好ましく、ゼラチン、寒天、カラギーナン、ペクチン、グアーガム、タマリンドガム、グルコマンナン、カロブビーンガム、キサンタンガム、プルラン、カルボキシメチルセルロース、アルギン酸、アルギン酸塩、アルギン酸誘導体、カルボキシビニルポリマー、カルボキシビニルポリマー誘導体、ポリビニルアルコール、ポリビニルアルコール誘導体、ポリビニルピロリドン、ポリビニルピロリドン誘導体、ポリアクリル酸からなる群から選ばれる１種または２種以上であることがより好ましく、ゼラチンがさらに好ましい。 Gelling agents or thickeners include gelatin, agar, carrageenan, pectin, glucomannan, pullulan, alginic acid, alginates, alginic acid derivatives, aureobasidium broth, succinoglycan, ama seed gum, gum arabic, arabinogalactan, Welan gum, cassia gum, gati gum, curdlan, karaya gum, carob bean gum, xanthan gum, chitosan, guar gum, guar gum enzyme degradation product, yeast cell wall, psyllium seed gum, mackerel mugwort seed gum, gellan gum, tamarind seed gum, tara gum, dextran, tragacanth gum, troro aoi, Microfibrous cellulose, Farcerellan, Fukuronori extract, Macrohomopsis gum, Ramzan gum, Levan, Okra extract, Seaweed cellulose, Brown algae extract, Co Naku potato extract, sweet potato cellulose, soybean polysaccharide, nata de coco, carboxymethyl cellulose, agarose, carboxyvinyl polymer, carboxyvinyl polymer derivative, polyvinyl alcohol, polyvinyl alcohol derivative, polyvinyl pyrrolidone, polyvinyl pyrrolidone derivative, polyhydroxyethyl methacrylate, polyacrylic acid, It is preferably one or more selected from the group consisting of polystyrene sulfonic acid and silicone, gelatin, agar, carrageenan, pectin, guar gum, tamarind gum, glucomannan, carob bean gum, xanthan gum, pullulan, carboxymethyl cellulose, alginic acid, Alginates, alginic acid derivatives, carboxyvinyl polymers, carboxyvinyl polymer derivatives Body, polyvinyl alcohol, polyvinyl alcohol derivatives, polyvinyl pyrrolidone, polyvinyl pyrrolidone derivatives, more preferably one or more selected from the group consisting of polyacrylic acid, more preferably gelatin.
（他の成分）
他の成分（ただし、液状媒体、ゲル化剤および増粘剤を除く。）としては、界面活性剤、油性成分、粉末成分等が挙げられる。(Other ingredients)
Examples of other components (excluding the liquid medium, the gelling agent, and the thickening agent) include surfactants, oily components, and powder components.
界面活性剤としては、非イオン性界面活性剤、陰イオン性界面活性剤、陽イオン性界面活性剤、両性界面活性剤等が挙げられる。
非イオン性界面活性剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシアルキレン誘導体、反応性界面活性剤、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビトール脂肪酸エステル、グリセリン脂肪酸エステル、グリセリン脂肪酸エステル、ポリオキシエチレン脂肪酸エステル、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルアミン、アルキルアルカノールアミド等が挙げられる。
陰イオン性界面活性剤としては、アルキル硫酸エステル塩、ポリオキシエチレンアルキルエーテル硫酸エステル塩、アルキルベンゼンスルフォン酸塩、その他のスルフォン酸塩、反応性界面活性剤、脂肪酸塩、ナフタレンスルフォン酸ホルマリン縮合物等が挙げられる。
陽イオン性界面活性剤としては、アルキルアミン塩、第四級アンモニウム塩等が挙げられる。
両性界面活性剤としては、アルキルベタイン、アルキルアミンオキサイド等が挙げられる。Examples of the surfactant include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants.
Nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyalkylene derivatives, reactive surfactants, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, glycerin fatty acids. Examples include esters, polyoxyethylene fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, and alkylalkanolamides.
Examples of anionic surfactants include alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkylbenzene sulfonates, other sulfonates, reactive surfactants, fatty acid salts, naphthalene sulfonate formalin condensates, etc. Is mentioned.
Examples of the cationic surfactant include alkylamine salts and quaternary ammonium salts.
Examples of amphoteric surfactants include alkylbetaines and alkylamine oxides.
油性成分としては、油脂類（ヒマシ油、ツバキ油、オリーブ油、アプリコット油等）、高級脂肪酸類（ステアリン酸等）、ロウ類（ミツロウ、ホホバ油等）、炭化水素類（ワセリン、流動パラフィン、スクワラン等）、高級アルコール（セタノール、イソステアリルアルコール等）、エステル類（モノグリセリド、ジグリセリド、トリグリセリド等の脂肪酸エステル）等が挙げられる。
粉末成分としては、有色顔料（アルミナ等）、白色顔料（酸化チタン、酸化亜鉛等）、パール剤（酸化鉄、雲母系合成パール等）、体質顔料（タルク、カオリン、マイカ等）等が挙げられる。Examples of oil components include fats and oils (castor oil, camellia oil, olive oil, apricot oil, etc.), higher fatty acids (eg stearic acid), waxes (eg beeswax, jojoba oil etc.), hydrocarbons (eg petroleum jelly, liquid paraffin, squalane). Etc.), higher alcohols (cetanol, isostearyl alcohol, etc.), esters (fatty acid esters such as monoglycerides, diglycerides, triglycerides) and the like.
Examples of powder components include colored pigments (such as alumina), white pigments (such as titanium oxide and zinc oxide), pearl agents (such as iron oxide and mica-based synthetic pearls), extender pigments (such as talc, kaolin, and mica). .
（薬剤）
薬剤としては、保湿成分（柔軟剤、エモリエント剤）、収斂剤（制汗剤）、清涼剤、紫外線防止剤、他の薬剤等が挙げられる。
保湿成分としては、加水分解コラーゲン、グリセリン、塩化ステアリルトリメチルアンモニウム、プロピレングリコール、１，３−ブチレングリコール、ベタイン、ヒアルロン酸、ラベンダー油等が挙げられる。
収斂剤としては、クエン酸、乳酸、硫酸アルミニウム、レモン水、ハマメリス等が挙げられる。
清涼剤としては、メントール、エチルアルコール、カンフル、ユーカリ油等が挙げられる。
紫外線防止剤としては、酸化チタン、酸化亜鉛、オクチルトリアゾン等が挙げられる。
他の薬剤としては、美白剤（ビタミンＣまたはその誘導体）、育毛剤、にきび用剤、ふけ・かゆみ用剤、腋臭防止剤、抗炎症剤（グリチルリチン酸ジカリウム等）、殺菌剤、栄養剤、賦活剤、生体生理機能向上剤等が挙げられる。(Drug)
Examples of the drug include moisturizing ingredients (softeners, emollients), astringents (antiperspirants), refreshing agents, ultraviolet inhibitors, and other drugs.
Examples of the moisturizing component include hydrolyzed collagen, glycerin, stearyltrimethylammonium chloride, propylene glycol, 1,3-butylene glycol, betaine, hyaluronic acid, lavender oil, and the like.
Examples of the astringent include citric acid, lactic acid, aluminum sulfate, lemon water, and hamamelis.
Examples of the refreshing agent include menthol, ethyl alcohol, camphor, and eucalyptus oil.
Examples of UV inhibitors include titanium oxide, zinc oxide, octyl triazone, and the like.
Other agents include whitening agents (vitamin C or derivatives thereof), hair restorers, acne agents, dandruff and itching agents, anti-odor agents, anti-inflammatory agents (such as dipotassium glycyrrhizinate), fungicides, nutrients, and activation Agents, biophysiological function improvers and the like.
（官能的特徴付与原料）
官能的特徴付与原料としては、香料、色素等が挙げられる。
香料としては、植物または動物由来の天然香料、有機合成された合成香料等が挙げられる。
色素としては、厚生労働省が定める化粧料に使用できるタール色素（有機合成色素等）、動植物または微生物から抽出された天然色素、無機顔料等が挙げられる。(Raw material with sensory characteristics)
Examples of the raw material for imparting sensory characteristics include fragrances and pigments.
Examples of the fragrances include natural fragrances derived from plants or animals, synthetic fragrances synthesized organically, and the like.
Examples of the pigment include tar pigments (such as organic synthetic pigments) that can be used in cosmetics specified by the Ministry of Health, Labor and Welfare, natural pigments extracted from animals, plants, and microorganisms, and inorganic pigments.
（品質保持原料）
品質保持原料としては、防腐剤、酸化防止剤、金属封鎖剤（金属イオン元素封止剤）、褪色防止剤、緩衝剤等が挙げられる。
防腐剤としては、パラオキシ安息香酸エステル（パラベン）、ソルビン酸、デヒドロ酢酸ナトリウム、第四級アンモニウム塩（塩化ベンザルコニウム、塩化ベンゼトニウム等）、クロロキシジン、ペンチレングリコール、フェノキシエタノール等が挙げられる。
酸化防止剤としては、トコフェロール（ビタミンＥ）、アスコルビン酸、ジブチルヒドロキシトルエン（ＢＨＴ）、ブチルヒドロキシアニソール（ＢＨＡ）等が挙げられる。
金属封鎖剤としては、キレート剤（エデト酸ナトリウム、エチレンジアミン四酢酸塩（ＥＤＴＡ）、クエン酸等）等が挙げられる。(Quality preservation raw material)
Examples of the quality-maintaining raw material include antiseptics, antioxidants, metal sequestering agents (metal ion element sealing agents), anti-fading agents, and buffering agents.
Examples of the preservative include p-hydroxybenzoate (paraben), sorbic acid, sodium dehydroacetate, quaternary ammonium salts (eg benzalkonium chloride, benzethonium chloride), chloroxidine, pentylene glycol, phenoxyethanol and the like.
Examples of the antioxidant include tocopherol (vitamin E), ascorbic acid, dibutylhydroxytoluene (BHT), butylhydroxyanisole (BHA) and the like.
Examples of the metal sequestering agent include chelating agents (sodium edetate, ethylenediaminetetraacetate (EDTA), citric acid, etc.) and the like.
（基材における各成分の割合）
基材における液状媒体の割合は、基材（１００質量％）のうち、５０〜９９質量％が好ましく、５５〜９７質量％がより好ましく、６５〜９５質量％がよりさらに好ましい。液状媒体の割合が前記範囲の上限値以下であれば、液状組成物が十分にゲル化され、基材中に気泡状態の水素ガスを多量に、かつ長時間にわたり保持しやすい。液状媒体の割合が前記範囲の下限値以上であれば、液状組成物の流動性が保たれるために、液状組成物に気泡状態の水素ガスを多量に、かつ長時間封じ込めることができる。(Ratio of each component in the substrate)
The proportion of the liquid medium in the substrate is preferably 50 to 99% by mass, more preferably 55 to 97% by mass, and even more preferably 65 to 95% by mass in the substrate (100% by mass). If the ratio of the liquid medium is equal to or less than the upper limit of the above range, the liquid composition is sufficiently gelled, and it is easy to hold a large amount of hydrogen gas in a bubble state in the substrate for a long time. If the ratio of the liquid medium is equal to or higher than the lower limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.
基材がゲル化剤を含む場合、ゲル化剤の割合は、基材（１００質量％）のうち、１〜５０質量％が好ましく、３〜４５質量％がより好ましく、５〜３５質量％がさらに好ましい。ゲル化剤の割合が前記範囲の下限値以上であれば、液状組成物が十分にゲル化され、基材中に気泡状態の水素ガスを多量に、かつ長時間にわたり保持しやすい。ゲル化剤の割合が前記範囲の上限値以下であれば、液状組成物の流動性が保たれるために、液状組成物に気泡状態の水素ガスを多量に、かつ長時間封じ込めることができる。 When a base material contains a gelatinizer, 1-50 mass% is preferable among a base material (100 mass%), 3-45 mass% is more preferable, 5-35 mass% is the ratio of a gelling agent. Further preferred. When the ratio of the gelling agent is at least the lower limit of the above range, the liquid composition is sufficiently gelled, and it is easy to hold a large amount of hydrogen gas in a bubble state in the substrate for a long time. If the ratio of the gelling agent is not more than the upper limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.
基材が増粘剤を含む場合、増粘剤の割合は、粘性組成物からなる基材（１００質量％）のうち、０．０１〜１０質量％が好ましく、０．０２〜５質量％がより好ましい。増粘剤の割合が前記範囲の下限値以上であれば、増粘効果が十分に発揮され、基材中に気泡状態の水素ガスを多量に、かつ長時間にわたり保持しやすい。増粘剤の割合が前記範囲の上限値以下であれば、液状組成物の流動性が保たれるために、液状組成物に気泡状態の水素ガスを多量に、かつ長時間封じ込めることができる。 When a base material contains a thickener, 0.01-10 mass% is preferable among the base materials (100 mass%) consisting of a viscous composition, and 0.02-5 mass% is the ratio of a thickener. More preferred. If the ratio of the thickener is equal to or more than the lower limit of the above range, the thickening effect is sufficiently exhibited, and it is easy to hold a large amount of hydrogen gas in the base material for a long time. If the ratio of the thickener is less than or equal to the upper limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.
液状媒体の割合は、組成物（１００質量％）のうち、９０〜９９．９９質量％が好ましく、９５〜９９．９８質量％がより好ましい。液状媒体の割合が前記範囲の上限値以下であれば、増粘効果が十分に発揮され、基材中に気泡状態の水素ガスを多量に、かつ長時間にわたり保持しやすい。液状媒体の割合が前記範囲の下限値以上であれば、液状組成物の流動性が保たれるために、液状組成物に気泡状態の水素ガスを多量に、かつ長時間封じ込めることができる。 The ratio of the liquid medium is preferably 90 to 99.99% by mass and more preferably 95 to 99.98% by mass in the composition (100% by mass). If the ratio of the liquid medium is equal to or less than the upper limit of the above range, the thickening effect is sufficiently exhibited, and it is easy to hold a large amount of hydrogen gas in the base material for a long time. If the ratio of the liquid medium is equal to or higher than the lower limit of the above range, the fluidity of the liquid composition is maintained, so that hydrogen gas in a bubble state can be contained in the liquid composition in a large amount for a long time.
基材が他の成分を含む場合、他の成分、薬剤、官能的特徴付与原料、および品質保持原料の割合は、肌用シートに要求される特性、機能等に応じて公知の配合割合の範囲内で適宜選択すればよい。 When the base material contains other components, the proportions of the other components, chemicals, sensory characteristic imparting raw materials, and quality-maintaining raw materials are within the range of known blending proportions depending on the properties, functions, etc. required for the skin sheet. May be selected as appropriate.
＜水素ガスバリア層＞
水素ガスバリア層としては、水素ガスの透過ロスを抑制するために、水素ガスを透過しにくい材料からなるものが好ましい。水素ガスバリア層の材料としては、例えば、アルミニウム箔からなる層を有するパウチ（アルミパウチ）、水素ガス透過性の低いフィルム、金属箔（アルミニウム箔等）、これらを組み合わせた複合材料等が挙げられる。<Hydrogen gas barrier layer>
The hydrogen gas barrier layer is preferably made of a material that hardly permeates hydrogen gas in order to suppress hydrogen gas permeation loss. Examples of the material for the hydrogen gas barrier layer include a pouch having an aluminum foil layer (aluminum pouch), a film having low hydrogen gas permeability, a metal foil (such as an aluminum foil), and a composite material combining these.
水素ガスバリア層としては、肌用シートの保管中においては、水素ガス含有層からの水素ガスの気相中への揮散を抑え、肌用シートを肌に貼付する際には、水素ガス含有層を容易に露出できる点から、水素ガス含有層を収容し、かつ一部に開口が形成された包装部と、開口を塞ぐように開口のまわりの包装部に剥離可能に貼着された蓋体部とを有するものが好ましい。 As the hydrogen gas barrier layer, during the storage of the skin sheet, the hydrogen gas containing layer suppresses the volatilization of the hydrogen gas into the gas phase, and when the skin sheet is applied to the skin, A packaging part that contains a hydrogen gas-containing layer and has an opening formed in part, and a lid part that is detachably attached to the packaging part around the opening so as to close the opening because it can be easily exposed Are preferred.
＜肌用シートの製造方法＞
本発明の肌用シートは、例えば、下記の工程（Ｉ）〜工程（ＩＶ）を順次有する方法で製造できる。
工程（Ｉ）：ゲル化剤または増粘剤と液状媒体とを含む液状組成物の調製。
工程（ＩＩ）：液状組成物への気泡状態の水素ガスの包含。
工程（ＩＩＩ）：気泡状態の水素ガスを包含する液状組成物を金型に入れ、ゲル化または増粘化させてシート状の水素ガス含有層を得る。
工程（ＩＶ）：必要に応じて、水素ガス含有層の全面を水素ガスバリア層で覆う。<Method for producing sheet for skin>
The skin sheet of this invention can be manufactured by the method of having the following process (I)-process (IV) sequentially, for example.
Step (I): Preparation of a liquid composition containing a gelling agent or thickener and a liquid medium.
Step (II): Inclusion of hydrogen gas in a bubble state in the liquid composition.
Step (III): A liquid composition containing hydrogen gas in a bubble state is placed in a mold and gelled or thickened to obtain a sheet-like hydrogen gas-containing layer.
Step (IV): If necessary, the entire surface of the hydrogen gas-containing layer is covered with a hydrogen gas barrier layer.
（工程（Ｉ））
工程（Ｉ）は、ゲル化剤または増粘剤と液状媒体とを含む液状組成物を調製する工程である。
液状組成物は、例えば、溶解槽にゲル化剤または増粘剤と液状媒体とを仕込み、撹拌によってゲル化剤または増粘剤を液状媒体に溶解させることによって調製できる。液状組成物には、ゲル化剤または増粘剤および液状媒体以外の他の成分をさらに添加してもよい。(Process (I))
Step (I) is a step of preparing a liquid composition containing a gelling agent or thickener and a liquid medium.
The liquid composition can be prepared, for example, by charging a gelling agent or thickener and a liquid medium in a dissolution tank and dissolving the gelling agent or thickener in the liquid medium by stirring. Other components other than the gelling agent or thickener and the liquid medium may be further added to the liquid composition.
液状組成物の調製に用いられる装置としては、撹拌機付きの槽または釜が挙げられる。装置の材料は、本発明の効果を損なわない範囲内で、ゲル化剤、増粘剤、液状媒体、水素ガス等に対する耐食性；使用温度における耐熱性；液状組成物への溶出等を考慮して選択できる。装置の材料としては、ステンレス鋼材、ガラスライニング、フッ素樹脂ライニング、プラスチック等が挙げられる。また、引火性の水素ガスを使用するため、引火または爆発を防止できる安全対策を講じた装置対応も考慮する必要がある。 Examples of the apparatus used for preparing the liquid composition include a tank or a kettle equipped with a stirrer. The material of the apparatus is within the range that does not impair the effects of the present invention, taking into consideration the corrosion resistance to gelling agent, thickener, liquid medium, hydrogen gas, etc .; heat resistance at operating temperature; elution into liquid composition, etc. You can choose. Examples of the material for the apparatus include stainless steel, glass lining, fluororesin lining, and plastic. In addition, since flammable hydrogen gas is used, it is also necessary to consider handling equipment with safety measures that can prevent ignition or explosion.
（工程（ＩＩ））
工程（ＩＩ）は、工程（Ｉ）の後、液状組成物に気泡状態の水素ガスを包含させる工程である。
液状組成物に水素ガスを供給することによって、気泡状態の水素ガスを包含した液状組成物を得る。気泡状態の水素ガスを包含した液状組成物にはゲル化剤または増粘剤および液状媒体以外の他の成分をさらに添加してもよい。(Process (II))
Step (II) is a step in which hydrogen gas in a bubble state is included in the liquid composition after step (I).
By supplying hydrogen gas to the liquid composition, a liquid composition containing hydrogen gas in a bubble state is obtained. Other components other than the gelling agent or thickener and the liquid medium may be further added to the liquid composition containing the hydrogen gas in the bubble state.
水素ガス供給時の液状組成物の粘度は、１〜３０，０００ｍＰａ・ｓが好ましく、１０〜２０，０００ｍＰａ・ｓがより好ましく、１００〜１０，０００ｍＰａ・ｓがさらに好ましい。液状組成物の粘度が前記範囲の下限値未満では、液状組成物中に水素ガスを気泡として分散しやすいが、水素ガスが浮上しやすく液状組成物中に留まりにくい。液状組成物の粘度が前記範囲の上限値を超えると、液状組成物中に水素ガスを気泡として分散しにくく、水素ガスの均一分散が困難となる。
すなわち、液状組成物の粘度が前記下限値以上であれば、液状組成物中に水素ガスの気泡としての分散に当って、水素ガスの浮上を制御しやすく、水素ガスを液体組成物中に留めやすい。また、液状組成物の粘度が前記上限値以下であれば、液状組成物中に水素ガスを気泡として均一に分散しやすい。
水素ガス供給時の液状組成物の温度については、前記した液状組成物の粘度範囲が達成できる温度であればよく、適宜設定すればよい。The viscosity of the liquid composition at the time of supplying hydrogen gas is preferably 1 to 30,000 mPa · s, more preferably 10 to 20,000 mPa · s, and further preferably 100 to 10,000 mPa · s. When the viscosity of the liquid composition is less than the lower limit of the above range, hydrogen gas is likely to be dispersed as bubbles in the liquid composition, but hydrogen gas is likely to float and hardly stay in the liquid composition. When the viscosity of the liquid composition exceeds the upper limit of the above range, it is difficult to disperse hydrogen gas as bubbles in the liquid composition, and it is difficult to uniformly disperse hydrogen gas.
That is, if the viscosity of the liquid composition is equal to or higher than the lower limit, it is easy to control the rising of the hydrogen gas in dispersing the hydrogen gas as bubbles in the liquid composition, and the hydrogen gas is retained in the liquid composition. Cheap. Moreover, if the viscosity of a liquid composition is below the said upper limit, it will be easy to disperse | distribute hydrogen gas uniformly as a bubble in a liquid composition.
About the temperature of the liquid composition at the time of hydrogen gas supply, what is necessary is just the temperature which can achieve the viscosity range of an above described liquid composition, and should just set it suitably.
水素ガスの供給量は、液状組成物中に溶解した水素ガスと気泡状態の水素ガスとの合計量が、液状媒体（水等）に対する水素ガスの飽和溶解度を超える量となる量であり、最終的に得られる水素ガス含有層中の気泡状態の水素ガスの含有率が、０．１〜７０体積％［ｖ／ｗ］となる量である。 The supply amount of the hydrogen gas is an amount such that the total amount of the hydrogen gas dissolved in the liquid composition and the hydrogen gas in the bubble state exceeds the saturation solubility of the hydrogen gas in the liquid medium (water, etc.) The hydrogen gas content in the hydrogen gas-containing layer obtained in this way is an amount such that the hydrogen gas content in the bubble state is 0.1 to 70% by volume [v / w].
ゲル化剤または増粘剤および液状媒体の仕込量、水素ガスの供給量は、所望する水素ガス含有層中の気泡状態の水素ガスの含有率に応じて適宜設定すればよい。また、液状組成物の温度および粘度についても、ゲル化剤または増粘剤および液状媒体の種類、所望する水素ガス含有層中の気泡状態の水素ガスの含有率に応じて適宜設定すればよい。 What is necessary is just to set suitably the preparation amount of a gelatinizer or a thickener and a liquid medium, and the supply amount of hydrogen gas according to the content rate of the hydrogen gas of the bubble state in the desired hydrogen gas content layer. Further, the temperature and viscosity of the liquid composition may be appropriately set according to the kind of the gelling agent or thickener and the liquid medium, and the desired content of hydrogen gas in the bubble state in the hydrogen gas-containing layer.
工程（ＩＩ）に用いられる装置としては、液状組成物に水素ガスを所望する気泡として均一に分散できる装置であれば、公知の気液分散操作に用いられる装置、設備を用いることができる。装置の材料は、本発明の効果を損なわない範囲内で、ゲル化剤、増粘剤、液状媒体、水素ガス等に対する耐食性；使用温度における耐熱性；液状組成物への溶出等を考慮して選択できる。 As an apparatus used in the step (II), any apparatus and equipment used for a known gas-liquid dispersion operation can be used as long as the apparatus can uniformly disperse hydrogen gas as desired bubbles in the liquid composition. The material of the apparatus is within the range that does not impair the effects of the present invention, taking into consideration the corrosion resistance to gelling agent, thickener, liquid medium, hydrogen gas, etc .; heat resistance at operating temperature; elution into liquid composition, etc. You can choose.
工程（ＩＩ）においては、液状組成物を撹拌した状態で、液状組成物に水素ガスを供給する；または、液状組成物を撹拌せずに、液状組成物に水素ガスを供給した後、振とうすることが好ましい。
撹拌方法としては、撹拌機を用いる方法、ホモミキサーを用いる方法、ラインミキサーを用いる方法等が挙げられる。
振とう方法としては、振とう機を用いる方法等が挙げられる。In step (II), hydrogen gas is supplied to the liquid composition while the liquid composition is stirred; or, after the hydrogen gas is supplied to the liquid composition without stirring the liquid composition, the liquid composition is shaken. It is preferable to do.
Examples of the stirring method include a method using a stirrer, a method using a homomixer, a method using a line mixer, and the like.
Examples of the shaking method include a method using a shaker.
（工程（ＩＩＩ））
工程（ＩＩＩ）は、工程（ＩＩ）の後、気泡状態の水素ガスを包含する液状組成物をゲル化または増粘化させて水素ガス含有マテリアルを得る工程である。
気泡状態の水素ガスを包含する液状組成物を金型に入れ、ゲル化または増粘化させてシート状の水素ガス含有層を得る。
液状組成物に包含された気泡状態の水素ガスの揮散ロスを極力低減するために、液状組成物のゲル化または増粘化はできる限り速やかに行うことが好ましい。(Step (III))
Step (III) is a step of obtaining a hydrogen gas-containing material by gelling or thickening a liquid composition containing hydrogen gas in a bubble state after step (II).
A liquid composition containing hydrogen gas in a bubble state is placed in a mold and gelled or thickened to obtain a sheet-like hydrogen gas-containing layer.
In order to reduce the volatilization loss of the gaseous hydrogen contained in the liquid composition as much as possible, the liquid composition is preferably gelled or thickened as quickly as possible.
液状組成物がゲル化剤を含む場合は、液状組成物をゲル化することによってゲル状組成物からなる基材が形成される。
ゲル化方法は、ゲル化剤の種類に応じた方法を適宜選択すればよい。
ゲル化方法としては、ゲル化剤が天然物由来の蛋白類または多糖類のようにゲル化温度を有する場合は、ゲル化剤のゲル化温度以下に液状組成物を冷却することによって液状組成物をゲル化する方法が挙げられる。
ゲル化方法としては、ゲル化剤が架橋性官能基を有するポリマーのように架橋性基を有する場合は、ゲル化剤の架橋反応によって液状組成物をゲル化する方法が挙げられる。When the liquid composition contains a gelling agent, the substrate made of the gel composition is formed by gelling the liquid composition.
As the gelling method, a method corresponding to the type of the gelling agent may be appropriately selected.
As a gelling method, when the gelling agent has a gelling temperature like proteins or polysaccharides derived from natural products, the liquid composition is cooled by cooling the liquid composition below the gelling temperature of the gelling agent. The method of gelling is mentioned.
As a gelling method, when the gelling agent has a crosslinkable group like a polymer having a crosslinkable functional group, a method of gelling the liquid composition by a crosslinking reaction of the gelling agent can be mentioned.
液状組成物が増粘剤を含む場合は、液状組成物を増粘化することによって増粘組成物組成物からなる基材が形成される。
増粘方法は、増粘剤の種類に応じた方法を適宜選択すればよい。
増粘方法としては、増粘剤が天然高分子のようにゲル化温度を有する場合は、増粘剤のゲル化温度以下に液状組成物を冷却することによって液状組成物を増粘する方法が挙げられる。
増粘方法としては、増粘剤がカルボキシビニルポリマーおよびその誘導体、ポリビニルアルコール、ポリビニルピロリドンおよびこれらの誘導体からなる群から選ばれる１種以上である場合は、増粘剤を中和剤によって中和することによって液状組成物を増粘する方法が挙げられる。
中和剤としては、水酸化ナトリウム、水酸化カリウム、アンモニア、アミン類（トリエタノールアミン、トリエチルアミン、ジイソプロパノールアミン、ジ（２−エチルヘキシル）アミン等）等が挙げられる。中和剤としては、水酸化ナトリウムまたは水酸化カリウムが好ましい。When a liquid composition contains a thickener, the base material which consists of a thickening composition composition is formed by thickening a liquid composition.
What is necessary is just to select the method according to the kind of thickener suitably as a thickening method.
As a thickening method, when the thickener has a gelation temperature like a natural polymer, there is a method of thickening the liquid composition by cooling the liquid composition below the gelation temperature of the thickener. Can be mentioned.
As a thickening method, when the thickener is at least one selected from the group consisting of carboxyvinyl polymer and derivatives thereof, polyvinyl alcohol, polyvinylpyrrolidone and derivatives thereof, the thickener is neutralized with a neutralizing agent. The method of thickening a liquid composition by doing is mentioned.
Examples of the neutralizing agent include sodium hydroxide, potassium hydroxide, ammonia, amines (such as triethanolamine, triethylamine, diisopropanolamine, and di (2-ethylhexyl) amine). As the neutralizing agent, sodium hydroxide or potassium hydroxide is preferable.
（工程（ＩＶ））
工程（ＩＶ）は、工程（ＩＩＩ）の後、必要に応じて、水素ガス含有層の全面を水素ガスバリア層で覆う工程である。
シート状の水素ガス含有層をそのまま肌用シートとして用いてもよく、必要に応じて、水素ガス含有層の全面を水素ガスバリア層で覆ったものを肌用シートとして提供してもよい。
気泡状態の水素ガスの気相中への揮散ロスを抑制するために、水素ガス含有層の全面を水素ガスバリア層で覆う作業はできる限り速やかに行うことが好ましい。(Process (IV))
Step (IV) is a step of covering the entire surface of the hydrogen gas-containing layer with a hydrogen gas barrier layer as necessary after step (III).
The sheet-like hydrogen gas-containing layer may be used as it is as a skin sheet, and if necessary, the surface of the hydrogen gas-containing layer covered with a hydrogen gas barrier layer may be provided as a skin sheet.
In order to suppress the loss of volatilization of the hydrogen gas in the bubble state into the gas phase, it is preferable to perform the operation of covering the entire surface of the hydrogen gas-containing layer with the hydrogen gas barrier layer as quickly as possible.
＜肌用シートの具体例＞
図１は、本発明の肌用シートの一例を示す断面図である。
肌用シート１は、液状媒体を含む基材１２に溶存する水素ガスおよび基材１２内に包含された気泡状態の水素ガス１４を含む水素ガス含有層１０と；水素ガス含有層１０の全面を覆う水素ガスバリア層２０と；肌用シート１を肌に貼付し、固定するための両面テープ４０とを有する。<Specific examples of skin sheets>
FIG. 1 is a cross-sectional view showing an example of the skin sheet of the present invention.
The
水素ガスバリア層２０は、水素ガス含有層１０を収容し、かつ一部に開口２２ａが形成されたアルミパウチからなる包装部２２と；開口２２ａを塞ぐように開口２２ａのまわりの包装部２２に剥離可能に貼着された蓋体部２４とを有する。
蓋体部２４は、アルミニウム箔２６と粘着剤層２８とを有するアルミテープ３０と；粘着剤層２８が開口２２ａにおいて外部に露出した水素ガスバリア層２０に接触しないように、開口２２ａに対応する粘着剤層２８の表面に設けられた保護フィルム３２とを有する。The hydrogen
The
両面テープ４０は、開口２２ａを塞ぐ蓋体部２４の周囲を囲むように、包装部２２の周縁部の表面に設けられる。
両面テープ４０は、包装部２２の表面に接する粘着剤層４２と、粘着剤層４２の表面を保護する離型フィルム４４とを有する。The double-
The double-
肌用シート１は、図２に示すように、蓋体部２４および離型フィルム４４を肌用シート１から剥離した状態とした後、開口２２ａ側が肌に接するように肌に押し付けられ、粘着剤層４２の粘着力にて肌に貼付される。
As shown in FIG. 2, the
なお、本発明の肌用シートは、液状媒体を含む基材に溶存する水素ガスおよび基材内に包含された気泡状態の水素ガスを含み、かつ気泡状態の水素ガスの含有率が０．１〜７０体積％［ｖ／ｗ］である水素ガス含有層を有するものであればよく、図示例のものに限定はされない。 The skin sheet of the present invention contains hydrogen gas dissolved in a base material containing a liquid medium and hydrogen gas in a bubble state contained in the base material, and the content of the hydrogen gas in the bubble state is 0.1. What is necessary is just to have a hydrogen gas content layer which is -70 volume% [v / w], and it is not limited to the thing of the example of illustration.
＜作用機序＞
以上説明した本発明の肌用シートにあっては、液状媒体を含む基材に溶存する水素ガスおよび基材内に包含された気泡状態の水素ガスを含み、かつ気泡状態の水素ガスの含有率が０．１〜７０体積％［ｖ／ｗ］である水素ガス含有層を有するため、基材中には、液状媒体（水等）に対する水素ガスの飽和溶解度と等しい量の水素ガスが溶解していることになる。すなわち、基材中に溶解した水素ガスと気泡状態の水素ガスとの合計量は、液状媒体に対する水素ガスの飽和溶解度（従来の肌用シートに含まれる水素ガスの量）を超える量となる。このように水素ガスを多く含む肌用シートは、従来の肌用シートに比べ肌に水素ガスを多く供給でき、水素ガスが有する様々な機能（活性酸素を除去する機能、生物活性を高める機能等）を十分に発現できる。<Action mechanism>
In the skin sheet of the present invention described above, the hydrogen gas dissolved in the base material containing the liquid medium and the hydrogen gas in the bubble state contained in the base material, and the content rate of the hydrogen gas in the bubble state Has a hydrogen gas-containing layer of 0.1 to 70% by volume [v / w], so that an amount of hydrogen gas equal to the saturation solubility of hydrogen gas in a liquid medium (water, etc.) is dissolved in the substrate. Will be. That is, the total amount of the hydrogen gas dissolved in the base material and the hydrogen gas in the bubble state exceeds the saturation solubility of hydrogen gas in the liquid medium (the amount of hydrogen gas contained in the conventional skin sheet). Thus, the skin sheet containing a lot of hydrogen gas can supply more hydrogen gas to the skin than the conventional skin sheet, and various functions of the hydrogen gas (function to remove active oxygen, function to increase biological activity, etc.) ) Can be fully expressed.
以下、本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
＜測定＞
実施例における物性の測定方法、肌用シートの評価方法を以下に示す。<Measurement>
The measuring method of the physical property in an Example and the evaluation method of the sheet | seat for skin are shown below.
（水素ガス含有層中の気泡状態の水素ガスの含有率）
大気圧、２５℃の条件下で水素ガス含有層の０．５〜１ｇをＧＣ分析で用いるヘッドスペースＧＣ分析用サンプル瓶（容量：２０ｍＬ）に精秤して入れ、水を１０ｍＬ加えて密閉した。サンプル瓶を手でよく振った後、超音波洗浄機で十分に混合した。サンプル瓶を７０℃に加熱し、水素ガス含有層から気泡が消えるまで７０℃で加熱を続けた。気泡が消えた後、サンプル瓶内の気相ガスを採取して、ＧＣ分析（ＴＣＤ検出器）によって水素ガスを定量し、水素ガス含有層中の気泡状態の水素ガスの含有率（体積％［ｖ／ｗ％］）を算出した。(Content of hydrogen gas in the bubble state in the hydrogen gas containing layer)
Under conditions of atmospheric pressure and 25 ° C., 0.5 to 1 g of the hydrogen gas-containing layer was precisely weighed into a head space GC analysis sample bottle (capacity: 20 mL) used for GC analysis, and 10 mL of water was added and sealed. . The sample bottle was shaken well by hand and then thoroughly mixed with an ultrasonic cleaner. The sample bottle was heated to 70 ° C., and heating was continued at 70 ° C. until bubbles disappeared from the hydrogen gas-containing layer. After the bubbles disappear, the gas phase gas in the sample bottle is collected, the hydrogen gas is quantified by GC analysis (TCD detector), and the hydrogen gas content rate (volume% [volume% [ v / w%]).
（肌の老化抑制）
肌の老化の指標として、肌の角層におけるカルボニル化タンパクレベルについて下記のように評価した。
肌用シートを３０分間肌に貼付した。肌用シートを貼付した肌の部分をテープによってストリッピングして、角層を剥離した。テープの粘着剤側の表面に塩化ビニル樹脂系接着剤を薄く延ばし、接着剤によってテープをスライドガラスに貼着し、接着剤を十分に乾燥させた。テープ付きスライドガラスをエタノールに１０分間浸漬させ、角層の脱水を行った。テープ付きスライドガラスを乾燥させた後、キシレンに一晩浸漬させた。スライドガラスからテープを剥離させ、テープを乾燥させた。テープを２−（Ｎ−モルホリノ）エタンスルホン酸ナトリウム塩（ＭＥＳ−Ｎａ）バッファーに３分間浸漬させた。テープを５０μＭのフルオレセイン−５−チオセミカルバジド（ＦＴＳＣ）を含むＭＥＳ−Ｎａバッファーに浸漬させた。テープをリン酸緩衝生理食塩水（Ｃａ、Ｍｇ不含）（ＰＢＳ（−））にて洗浄した。テープをグリセリンにて封入した後、蛍光顕微鏡にて蛍光検出（蛍光：５３２ｎｍ、励起：４８２ｎｍ）および画像取り込みを行い、画像部分における角層部分の平均輝度をＰｈｏｔｏｓｈｏｐ（Ａｄｏｂｅ社製）を用いて算出し、得られた輝度値をカルボニル化タンパクレベルとした。数値が低いほど活性酸素除去機能が高い。(Skin aging control)
As an index of skin aging, the carbonylated protein level in the skin stratum corneum was evaluated as follows.
A skin sheet was applied to the skin for 30 minutes. The part of the skin on which the skin sheet was affixed was stripped with a tape to peel off the stratum corneum. A vinyl chloride resin adhesive was spread thinly on the adhesive side surface of the tape, and the tape was adhered to the slide glass with the adhesive, and the adhesive was sufficiently dried. The slide glass with tape was immersed in ethanol for 10 minutes to dehydrate the stratum corneum. The slide glass with tape was dried and immersed in xylene overnight. The tape was peeled from the slide glass, and the tape was dried. The tape was immersed in 2- (N-morpholino) ethanesulfonic acid sodium salt (MES-Na) buffer for 3 minutes. The tape was immersed in MES-Na buffer containing 50 μM fluorescein-5-thiosemicarbazide (FTSC). The tape was washed with phosphate buffered saline (Ca and Mg free) (PBS (−)). After sealing the tape with glycerin, fluorescence detection (fluorescence: 532 nm, excitation: 482 nm) and image capture are performed with a fluorescence microscope, and the average luminance of the stratum corneum in the image portion is calculated using Photoshop (manufactured by Adobe). The obtained luminance value was defined as the carbonylated protein level. The lower the value, the higher the active oxygen removal function.
＜実施例１＞
容器にゼラチンの７ｋｇおよび水の１３ｋｇを入れ、４０℃に加温してゼラチン水溶液を調製した。ゼラチン水溶液を撹拌しながら、ゼラチン水溶液に水素ガスを通気し、気泡状態の水素ガスを包含する高粘度のゼラチン水溶液を得た。ゼラチン水溶液をシート成形用の金型に入れ、徐々に冷却し、水素ガス含有層を形成した。水素ガス含有層をそのまま肌用シートとして用いた。肌用シート（水素ガス含有層）は、基材中に溶解した水素ガスおよび気泡状態の水素ガスを含んでいた。水素ガス含有層中の気泡状態の水素ガスの含有率は、３０体積％［ｖ／ｗ］であった。肌用シートを貼付した後の肌の角層におけるカルボニル化タンパクレベルを表１に示す。<Example 1>
7 kg of gelatin and 13 kg of water were placed in a container and heated to 40 ° C. to prepare an aqueous gelatin solution. While stirring the gelatin aqueous solution, hydrogen gas was passed through the gelatin aqueous solution to obtain a highly viscous gelatin aqueous solution containing hydrogen gas in a bubble state. The aqueous gelatin solution was placed in a mold for sheet forming and gradually cooled to form a hydrogen gas-containing layer. The hydrogen gas-containing layer was used as it was as a skin sheet. The skin sheet (hydrogen gas-containing layer) contained hydrogen gas dissolved in the substrate and hydrogen gas in a bubble state. The content rate of the gaseous hydrogen gas in the hydrogen gas-containing layer was 30% by volume [v / w]. Table 1 shows the carbonylated protein level in the stratum corneum of the skin after the skin sheet is applied.
＜比較例１＞
水素ガスを通気しないこと以外は実施例１と同様にして肌用シートを得た。肌用シートは、基材中に溶解した水素ガスおよび気泡状態の水素ガスを含んでいない。肌用シートを貼付した後の肌の角層におけるカルボニル化タンパクレベルを表１に示す。<Comparative Example 1>
A skin sheet was obtained in the same manner as in Example 1 except that hydrogen gas was not passed. The skin sheet does not contain hydrogen gas dissolved in the substrate and hydrogen gas in a bubble state. Table 1 shows the carbonylated protein level in the stratum corneum of the skin after the skin sheet is applied.
表１に示すように、気泡状態の水素ガスを含む実施例１の肌用シートを貼付した方が、角層のカルボニル化が抑制され、肌の老化が抑制されていることがわかる。 As shown in Table 1, it can be understood that carbonylation of the stratum corneum is suppressed and skin aging is suppressed when the skin sheet of Example 1 containing hydrogen gas in a bubble state is applied.
本発明の肌用シートは、肌に水素ガスを多く供給して、水素ガスが有する様々な機能を十分に発現できる肌用シートとして有用である。 The skin sheet of the present invention is useful as a skin sheet that can supply a large amount of hydrogen gas to the skin and sufficiently develop various functions of hydrogen gas.
１ 肌用シート、
１０ 水素ガス含有層、
１２ 基材、
１４ 気泡状態の水素ガス、
２０ 水素ガスバリア層、
２２ 包装部、
２２ａ 開口、
２４ 蓋体部、
２６ アルミニウム箔、
２８ 粘着剤層、
３０ アルミテープ、
３２ 保護フィルム、
４０ 両面テープ、
４２ 粘着剤層、
４４ 離型フィルム。1 skin sheet,
10 Hydrogen gas containing layer,
12 substrate,
14 Hydrogen gas in a bubble state,
20 Hydrogen gas barrier layer,
22 Packaging Department,
22a opening,
24 lid,
26 aluminum foil,
28 adhesive layer,
30 Aluminum tape,
32 protective film,
40 Double-sided tape,
42 adhesive layer,
44 Release film.
Claims (5)
前記水素ガス含有層は、液状媒体を含む基材に溶存する水素ガスおよび前記基材内に包含された気泡状態の水素ガスを含み、
前記水素ガス含有層中の前記気泡状態の水素ガスの含有率が、０．１〜７０体積％［ｖ／ｗ］である、肌用シート。It is a skin sheet having a hydrogen gas-containing layer,
The hydrogen gas-containing layer contains hydrogen gas dissolved in a base material containing a liquid medium and hydrogen gas in a bubble state contained in the base material,
The skin sheet | seat whose content rate of the said gaseous hydrogen gas in the said hydrogen gas content layer is 0.1-70 volume% [v / w].
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| JP2017001000 | 2017-01-06 | ||
| JP2017001000 | 2017-01-06 | ||
| PCT/JP2017/047291 WO2018128167A1 (en) | 2017-01-06 | 2017-12-28 | Sheet for skin |
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| JPWO2018128167A1 true JPWO2018128167A1 (en) | 2019-11-07 |
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|---|---|---|---|---|
| JP2002369835A (en) * | 2001-04-13 | 2002-12-24 | Kokuriyuudou:Kk | Warmth retaining material for sticking to skin |
| JP2007077035A (en) * | 2005-09-12 | 2007-03-29 | Hiromaito Co Ltd | Reducing aqueous composition |
| JP2007238535A (en) * | 2006-03-10 | 2007-09-20 | Hiroshima Kasei Ltd | Milky lotion and method for producing milky lotion |
| KR20130055738A (en) * | 2011-11-21 | 2013-05-29 | 문세라 | Product method of disposable beauty treatment mask cool pack |
| JP2014234374A (en) * | 2013-06-04 | 2014-12-15 | クラシエホームプロダクツ株式会社 | Packing method and cosmetic sheet |
| JP2015203024A (en) * | 2014-04-15 | 2015-11-16 | クラシエホームプロダクツ株式会社 | Hydrogen-containing composition, hydrogen-containing sheet, and production method thereof |
| JP2015218124A (en) * | 2014-05-15 | 2015-12-07 | 株式会社エムジェイ | Cosmetic |
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| WO2017179621A1 (en) * | 2016-04-14 | 2017-10-19 | 株式会社新菱 | Gas-containing base material and manufacturing method therefor |
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002369835A (en) * | 2001-04-13 | 2002-12-24 | Kokuriyuudou:Kk | Warmth retaining material for sticking to skin |
| JP2007077035A (en) * | 2005-09-12 | 2007-03-29 | Hiromaito Co Ltd | Reducing aqueous composition |
| JP2007238535A (en) * | 2006-03-10 | 2007-09-20 | Hiroshima Kasei Ltd | Milky lotion and method for producing milky lotion |
| KR20130055738A (en) * | 2011-11-21 | 2013-05-29 | 문세라 | Product method of disposable beauty treatment mask cool pack |
| JP2014234374A (en) * | 2013-06-04 | 2014-12-15 | クラシエホームプロダクツ株式会社 | Packing method and cosmetic sheet |
| JP2015203024A (en) * | 2014-04-15 | 2015-11-16 | クラシエホームプロダクツ株式会社 | Hydrogen-containing composition, hydrogen-containing sheet, and production method thereof |
| JP2015218124A (en) * | 2014-05-15 | 2015-12-07 | 株式会社エムジェイ | Cosmetic |
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