JP2003034612A - Composition for percutaneous absorption of carbon dioxide and use and usage thereof - Google Patents
Composition for percutaneous absorption of carbon dioxide and use and usage thereofInfo
- Publication number
- JP2003034612A JP2003034612A JP2001248842A JP2001248842A JP2003034612A JP 2003034612 A JP2003034612 A JP 2003034612A JP 2001248842 A JP2001248842 A JP 2001248842A JP 2001248842 A JP2001248842 A JP 2001248842A JP 2003034612 A JP2003034612 A JP 2003034612A
- Authority
- JP
- Japan
- Prior art keywords
- composition
- carbon dioxide
- carbonic acid
- water
- percutaneous absorption
- 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.)
- Granted
Links
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- Cosmetics (AREA)
Abstract
Description
【0001】[0001]
【発明が属する技術分野】本発明は溶解性炭酸ガスを高
濃度に含む水溶性組成物に関し、人体の皮膚と接触させ
て皮膚を通して炭酸ガスを有効に人体に吸収させ皮膚の
血行促進を図ることが可能な炭酸経皮吸収用組成物、そ
れを用いた化粧水、該組成物をシート状支持体に複合化
させた炭酸経皮吸収用シート状物、さらにこれらの使用
方法及び製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-soluble composition containing a high concentration of soluble carbon dioxide, and to contact the skin of the human body to effectively absorb the carbon dioxide into the human body to promote blood circulation in the skin. The present invention relates to a composition for percutaneous absorption of carbonic acid, a lotion containing the same, a sheet-like material for percutaneous absorption of carbonic acid in which the composition is combined with a sheet-like support, and a method of using and a method for producing the same.
【0002】[0002]
【従来の技術】炭酸ガスを含む水が人体の血行を促進す
ることは古くから良く知られており、特に全身の血行を
良くするために炭酸泉に入浴することが古くから行われ
ている。これは炭酸ガスの経皮からの侵入により毛細管
床の増加及び拡張が起こり皮膚の血行を促進するためと
考えられている。このような炭酸ガスの特徴を利用して
化粧水、養毛・育毛料やパック剤に用いることが提案さ
れている。特公平3−14284号公報には炭酸ガスを
所定量含むPHが5−6.5の化粧水が開示されてい
る。また、特開昭60−215606号公報や特開平1
1−228334号公報には炭酸ガスを含むパック剤や
粘度の高い化粧料が開示されている。2. Description of the Related Art It has long been known that water containing carbon dioxide promotes blood circulation in the human body, and in particular, bathing in a carbonated spring to improve blood circulation in the whole body has been performed for a long time. It is considered that this is because the percutaneous invasion of carbon dioxide causes an increase and expansion of the capillary bed to promote blood circulation in the skin. It has been proposed to use such characteristics of carbon dioxide gas as a lotion, a hair nourishing / hair-growth material, and a pack. Japanese Examined Patent Publication No. 3-14284 discloses a lotion containing PH of 5-6.5 containing a predetermined amount of carbon dioxide. Further, JP-A-60-215606 and JP-A-1
JP-A 1-228334 discloses a pack agent containing carbon dioxide gas and a cosmetic material having high viscosity.
【0003】[0003]
【発明が解決しようとする課題】炭酸ガスの血行促進効
果は化粧料やパック剤(本発明ではこれらを炭酸経皮吸
収用組成物と称す)に溶解している炭酸ガスの濃度が高
いほど大きい。一方、水に炭酸ガスのみを溶解させると
その水のアルカリ度によっても変化するが、図1の様に
PHが低下してくる。このようにPHが低下した水溶液
は皮膚に対する刺激性が強く化粧料として用いることが
困難であった。PHの低下はPH調整剤を添加してPH
を5以上にすることも可能であるが、化粧水などの敏感
な用途には添加剤が悪い効果をもたらすことも考えられ
る。本発明はPHが低くても皮膚に対する刺激性の少な
い安全な添加剤を見つけることを第1の課題とした。第
2の課題は炭酸ガスを高濃度に含有する水溶液は保存中
に容器を通して炭酸ガスが空気中に逃散したり、常圧で
の使用時に空気中に水溶液から炭酸ガスが直ちに逃散し
てしまう欠点があった。これらの欠点を解決することを
第2の課題とした。この第2の課題については従来技
術、例えば特開平11−228834号公報にも開示さ
れているがいまだ十分ではなかった。The blood circulation promoting effect of carbon dioxide is greater as the concentration of carbon dioxide dissolved in cosmetics and packs (these are referred to as carbonic acid percutaneous absorption compositions in the present invention) is higher. . On the other hand, when only carbon dioxide gas is dissolved in water, the pH decreases as shown in FIG. 1, though it changes depending on the alkalinity of the water. Such an aqueous solution having a lowered PH has a strong irritation to the skin and is difficult to use as a cosmetic. To decrease PH, add PH adjuster
It is possible to set the ratio to 5 or more, but it is also considered that the additive has a bad effect for sensitive applications such as lotion. The first object of the present invention is to find a safe additive that is less irritating to the skin even if the pH is low. The second problem is that an aqueous solution containing carbon dioxide at a high concentration may escape into the air through the container during storage, or the carbon dioxide may immediately escape from the aqueous solution into the air when used at normal pressure. was there. The second problem was to solve these drawbacks. The second problem is disclosed in the prior art, for example, Japanese Patent Laid-Open No. 11-228834, but it has not been sufficient yet.
【0004】[0004]
【課題を解決するための手段】本発明の第1は遊離炭酸
を300ppm以上含み、且つトレハロースを必須成分
として含む実質的に気泡状の炭酸ガスを含まない水溶液
からなることを特徴とする炭酸経皮吸収用組成物であ
る。また、この組成物を化粧水として用いる場合はその
PH(水素イオン濃度)が5.0未満であることが好ま
しい。本発明の第2は少なくとも水、水溶性高分子、遊
離炭酸からなる組成物であって、該組成物中の遊離炭酸
は濃度が300ppm以上であり、実質的に気泡状では
存在せずに溶解状態で存在してなる炭酸経皮吸収用組成
物において、前記組成物がゾルーゲル転移又はゲルーゾ
ル転移(以下相転移と略す)を示し、その転移温度が0
℃以上、45℃未満の範囲にあることを特徴とする炭酸
経皮吸収用組成物である。本発明の第3は少なくとも
水、水溶性高分子、遊離炭酸からなる組成物であって、
該組成物中の遊離炭酸は濃度が300ppm以上であ
り、実質的に気泡状では存在せずに溶解状態で存在して
なるゲル状の炭酸経皮吸収用組成物である。第2、第3
発明においてトレハロースを必須成分として含む炭酸経
皮吸収用組成物が好ましい。本発明の第4は上記の炭酸
経皮吸収用組成物がシート状支持体に含浸又は/及びコ
ーティングされてなる炭酸経皮吸収用シート状物であ
る。本発明の第5は炭酸経皮吸収用組成物の使用方法に
おいて、使用時に該組成物を相転移させることにより組
成物の粘度を変化させて使用することを特徴とする炭酸
経皮吸収用組成物の使用方法である。この使用方法にお
いて組成物の相転移を温度又は/及び添加剤で行うこと
が好ましい。本発明の第6は炭酸経皮吸収用組成物の製
造方法において、炭酸ガスを含まない組成物原料水溶液
を調整し、次いで前記原料水溶液に300ppm以上の
炭酸ガスを加圧溶解させて炭酸経皮吸収用組成物を調整
し、次いで前記組成物を密閉容器に充填することを特徴
とする炭酸経皮吸収用組成物の製造方法である。この製
造方法において精密ろ過器と膜式炭酸ガス溶解器が接続
された装置を用いて異物のろ過と炭酸ガスの溶解を連続
して行うことが好ましい。本発明の第7は熱ゲル化特性
を示す水溶性高分子を用いて炭酸経皮吸収用組成物を製
造する方法において、前記水溶性高分子をゲル化温度以
上で水又は水溶液に分散し、次いで前記分散液を冷却し
又は冷却しながら炭酸ガスを溶解させることを特徴とす
る炭酸経皮吸収用組成物の製造方法である。The first aspect of the present invention is characterized by comprising an aqueous solution containing 300 ppm or more of free carbonic acid and substantially free of carbon dioxide gas containing trehalose as an essential component. It is a composition for skin absorption. When this composition is used as a lotion, its PH (hydrogen ion concentration) is preferably less than 5.0. A second aspect of the present invention is a composition comprising at least water, a water-soluble polymer, and free carbonic acid, wherein the free carbonic acid has a concentration of 300 ppm or more and is dissolved without substantially existing in the form of bubbles. In the composition for percutaneous absorption of carbonic acid, which is present in a state, the composition exhibits a sol-gel transition or a gel-sol transition (hereinafter abbreviated as phase transition), and the transition temperature is 0.
It is a composition for percutaneous absorption of carbonic acid, which is in the range of not less than 0 ° C and less than 45 ° C. A third aspect of the present invention is a composition comprising at least water, a water-soluble polymer and free carbonic acid,
The free carbonic acid in the composition has a concentration of 300 ppm or more, and is a gel-like composition for percutaneous absorption of carbonic acid in the form of a solution which does not substantially exist in the form of bubbles. 2nd, 3rd
In the present invention, a composition for percutaneous absorption of carbonic acid containing trehalose as an essential component is preferable. A fourth aspect of the present invention is a carbonic acid percutaneous absorption sheet-shaped product obtained by impregnating and / or coating the above-mentioned carbonic acid percutaneous absorption composition on a sheet-shaped support. A fifth aspect of the present invention is a method for using a composition for percutaneous absorption of carbonic acid, which comprises changing the viscosity of the composition by phase transition of the composition at the time of use. How to use things. In this method of use, the phase transition of the composition is preferably carried out at temperature and / or additives. A sixth aspect of the present invention is a method for producing a composition for percutaneous absorption of carbonic acid, which comprises preparing an aqueous solution of a composition raw material containing no carbon dioxide gas, and then dissolving 300 ppm or more of carbon dioxide gas in the aqueous solution of the raw material under pressure to transdermally carbonate A method for producing a carbonic acid percutaneous absorption composition, which comprises preparing an absorption composition and then filling the composition into a closed container. In this manufacturing method, it is preferable to continuously filter the foreign matter and dissolve the carbon dioxide gas using an apparatus in which a microfilter and a membrane carbon dioxide gas dissolver are connected. A seventh aspect of the present invention is a method for producing a carbonic acid percutaneous absorption composition using a water-soluble polymer having a thermogelling property, wherein the water-soluble polymer is dispersed in water or an aqueous solution at a gelling temperature or higher, Then, a method for producing a composition for percutaneous absorption of carbonic acid, which comprises cooling the dispersion or dissolving carbon dioxide while cooling.
【0005】[0005]
【発明の実施の形態】炭酸ガス(CO2)は20℃、1
気圧で水に対して0.88(ml/ml水)の溶解度を
持つ(化学大事典)。水に溶解した炭酸ガスは水と反応
して炭酸(H2CO3 )、さらに水の水素イオン濃度
(PH)が6を越えて高くなると、炭酸が解離して炭酸
水素イオンや炭酸イオンとなる。本発明で言う遊離炭酸
とは炭酸ガスが水中に溶解して炭酸ガス及び炭酸の状態
で存在しているもので、水のアルカリ度によっても変化
するが、PHが6以下では大部分の炭酸ガスは遊離炭酸
として水中に存在する。血行促進効果は炭酸水素イオン
や炭酸イオンでは見られず、炭酸ガスの状態が必要であ
る。上述のごとく1気圧の炭酸ガスは水1gに約0.8
8ml溶解するが、この炭酸ガスを質量に換算すると約
0.0016gとなる。即ち、約1600ppm(質量
基準)である。本発明では炭酸経皮吸収用組成物に溶解
している遊離炭酸の質量をppmで表示するが、該組成
物は水が大部分であるため、近似的に該組成物を構成す
る水に溶解している遊離炭酸と考えて差し支えない。BEST MODE FOR CARRYING OUT THE INVENTION Carbon dioxide gas (CO2) is 20 ° C., 1
It has a solubility of 0.88 (ml / ml water) in water at atmospheric pressure (Chemical Encyclopedia). Carbon dioxide gas dissolved in water reacts with water to generate carbonic acid (H2CO3), and when the hydrogen ion concentration (PH) of water exceeds 6 and becomes high, the carbonic acid dissociates to hydrogen carbonate ions or carbonate ions. The free carbonic acid referred to in the present invention means that carbon dioxide gas is dissolved in water and exists in the state of carbon dioxide gas and carbon dioxide, and it changes depending on the alkalinity of water, but when PH is 6 or less, most of carbon dioxide gas is present. Exists in water as free carbonic acid. The blood circulation promoting effect is not seen with hydrogen carbonate ion or carbonate ion, and the state of carbon dioxide gas is necessary. As mentioned above, 1 atm of carbon dioxide is about 0.8 in 1 g of water.
8 ml is dissolved, but when this carbon dioxide gas is converted into mass, it becomes about 0.0016 g. That is, it is about 1600 ppm (mass basis). In the present invention, the mass of free carbonic acid dissolved in the composition for percutaneous absorption of carbonic acid is expressed in ppm. However, since the composition is mostly water, it is approximately dissolved in water constituting the composition. You can think of it as free carbon dioxide.
【0006】本発明の遊離炭酸を所定量含む炭酸経皮吸
収用組成物の製造方法は後に詳述するが、炭酸ガスを直
接組成物を構成する水や組成物水溶液に加圧して溶解さ
せるものである。従って従来入浴剤として用いられてい
る炭酸塩と有機酸の反応で炭酸ガスを発生させ炭酸ガス
の気泡による刺激作用と一部水に溶解した炭酸ガスの血
行促進作用を狙う技術とは本質的に異なるものである。
このような化学反応によって炭酸ガスを水に溶解させる
ことが出来るが、反応生成物が水中に残存するため化粧
水のような肌に敏感な用途には好ましくないと考えられ
る。これらの技術と区別するために本組成物水溶液は実
質的に気泡状の炭酸ガスを含まないものである。「実質
的に」とは一旦水あるいは水溶液に溶解した遊離炭酸が
攪拌作用、気温、圧力変動等により炭酸ガスの溶解度が
変化して気泡として発生するものは本発明の範囲内に含
まれることを意味する。A method for producing a composition for percutaneous absorption of carbonic acid containing a predetermined amount of free carbonic acid of the present invention will be described later in detail. Carbon dioxide is directly pressurized and dissolved in water or an aqueous solution of the composition. Is. Therefore, the technology that aims at the stimulating action of carbon dioxide gas generated by the reaction of carbonate salt and organic acid, which is conventionally used as a bathing agent, and the blood circulation promoting action of carbon dioxide gas partially dissolved in water is essentially It is different.
Although carbon dioxide can be dissolved in water by such a chemical reaction, it is considered to be unsuitable for skin-sensitive applications such as lotion because the reaction product remains in water. In order to distinguish from these techniques, the aqueous solution of the composition is substantially free of bubbled carbon dioxide gas. The term “substantially” means that free carbonic acid once dissolved in water or an aqueous solution is included in the scope of the present invention as a bubble generated by changing the solubility of carbon dioxide gas due to stirring action, temperature change, pressure fluctuation and the like. means.
【0007】本発明の炭酸経皮吸収用組成物の血行促進
作用は以下のようにして調べることが出来る。肌の色が
白い部分、例えば腕の内側で日光が比較的にあたらない
部分や足の膝部分に、炭酸経皮吸収用組成物を十分しみ
込ませた脱脂綿やガーゼを5ないし10分間貼付してそ
の前後の皮膚の状態を観察する。比較として純水や水道
水をしみ込ませたものを同時に隣に貼付しておく。所定
時間経過後、貼付した脱脂綿等を剥がして皮膚の状態を
観察する。血行促進作用を示す炭酸経皮吸収用組成物は
貼付部分の皮膚が赤くなり、比較試料は添付前の状態と
変わらないので区別が容易につく。即ち、本発明で言う
血行促進作用とはこのようなテストで皮膚が赤化するこ
とを意味する。このようにして血行促進作用を調べる
と、組成物中の遊離炭酸濃度が300ppm以上、好ま
しくは500ppm以上で血行促進作用を示すことが明
らかとなった。また、遊離炭酸濃度の上限は、炭酸経皮
吸収用組成物の使用が大気圧下であることから、使用時
の温度にもよるが2000ppm近傍である。数気圧の
炭酸ガスを水溶液に圧入すると、ヘンリーの法則に従っ
て上記以上の炭酸ガスを水溶液に溶解させることが可能
であるが、使用時が常圧であるのでこのような水溶液は
空気に触れた段階で発泡して過飽和の炭酸ガスは直ちに
空気中に逃散してしまう。The blood circulation promoting action of the composition for percutaneous absorption of carbonic acid of the present invention can be examined as follows. Apply absorbent cotton or gauze thoroughly impregnated with the composition for percutaneous absorption of carbonic acid to the part with a white skin color, for example, the part of the inside of the arm where the sunlight is not relatively exposed or the knee part of the foot, for 5 to 10 minutes. Observe the condition of the skin before and after that. As a comparison, paste soaked pure water or tap water at the same time next to it. After a lapse of a predetermined time, remove the attached absorbent cotton etc. and observe the condition of the skin. The composition for percutaneous absorption of carbonic acid which has a blood circulation promoting effect makes the skin of the applied part red, and the comparative sample is the same as the state before the application, and therefore can be easily distinguished. That is, the blood circulation promoting action in the present invention means that the skin becomes red in such a test. When the blood circulation promoting action was examined in this manner, it was revealed that the composition exhibits a blood circulation promoting action when the free carbonic acid concentration in the composition is 300 ppm or more, preferably 500 ppm or more. The upper limit of the free carbonic acid concentration is around 2000 ppm, although it depends on the temperature at the time of use because the composition for transdermal absorption of carbonic acid is used under atmospheric pressure. It is possible to dissolve the above carbon dioxide gas in an aqueous solution according to Henry's law by injecting carbon dioxide gas of several atmospheres into the aqueous solution. However, since the atmospheric pressure is at the time of use, such an aqueous solution is not exposed to air. The carbon dioxide gas that is supersaturated by foaming due to the bubbles immediately escapes into the air.
【0008】図1は水道水に炭酸ガスを溶解して調整し
た炭酸水の炭酸ガス濃度とPHの関係である。炭酸ガス
の濃度は二酸化炭素電極を用いて測定した。このグラフ
から300ppmの炭酸ガスを含む炭酸水のPHは4.
95であった。従って本発明では血行促進効果を機能さ
せるためには上述の通り300ppm以上の遊離炭酸が
必要であり、そのためには炭酸水のPHを5以下、好ま
しくは4.9以下にする必要がある。一方、炭酸水は人
体の皮脂を溶解する作用があり、PHが5以下の炭酸水
を化粧水とした場合、皮脂が溶解して顔がヒリヒリする
ためそのままでの使用は困難であることが解った。この
欠点を無くすために本発明者らは化粧品に用いられてい
る添加剤を各種検討したが、その中でトレハロースが非
常に効果があることを見出した。炭酸水とトレハロース
の組み合わせがなぜ優れるのか原因は不明であるが、ト
レハロースが2分子の水を結晶水として保持しえるこ
と、吸湿特性が特異であることなどが関係していると今
のところ想定している。また、トレハロースは脂質の変
敗抑制作用があり加齢臭や体臭の防止効果も期待され、
化粧料に用いることはこの意味からも好ましい添加剤で
ある。炭酸経皮吸収用組成物に含有させるトレハロース
の量は0.1wt%以上、好ましくは0.5wt%以
上、さらに好ましくは1wt%以上である。上限はべた
つき等の使用感から10wt%以下、好ましくは7wt
%以下である。遊離炭酸を300ppm以上且つトレハ
ロースを含むPHが5未満の炭酸経皮吸収用組成物を化
粧水として用いると、弱酸性による皮膚の収斂作用と共
に血行が促進されトレハロースの特異な作用と相まっ
て、皮膚に対する刺激性が少なくしっとり感や美白など
多くの優れた効果を示す化粧水が得られることを発見し
た。FIG. 1 shows the relationship between the carbon dioxide concentration of carbonated water prepared by dissolving carbon dioxide in tap water and the pH. The concentration of carbon dioxide was measured using a carbon dioxide electrode. From this graph, the PH of carbonated water containing 300 ppm of carbon dioxide is 4.
It was 95. Therefore, in the present invention, 300 ppm or more of free carbonic acid is required as described above in order to function the blood circulation promoting effect, and for that purpose, the pH of carbonated water needs to be 5 or less, preferably 4.9 or less. On the other hand, carbonated water has a function of dissolving sebum of the human body, and when carbonated water having a PH of 5 or less is used as a lotion, it is difficult to use as it is because the sebum is dissolved and the face becomes tingling. It was In order to eliminate this drawback, the present inventors have studied various additives used in cosmetics, and found that trehalose is very effective. The reason why the combination of carbonated water and trehalose is superior is unknown, but it is assumed that trehalose can hold two molecules of water as crystal water and its unique hygroscopic property. is doing. In addition, trehalose has the effect of suppressing lipid spoilage, and is expected to have the effect of preventing age-related odors and body odors.
Use in cosmetics is also a preferable additive in this sense. The amount of trehalose contained in the composition for percutaneous absorption of carbonic acid is 0.1 wt% or more, preferably 0.5 wt% or more, more preferably 1 wt% or more. The upper limit is 10 wt% or less, preferably 7 wt, from the feeling of stickiness.
% Or less. When a carbonated percutaneous absorption composition containing free carbonic acid of 300 ppm or more and trehalose having a PH of less than 5 is used as a skin lotion, blood circulation is promoted together with the astringent action of the skin due to weak acidity, and this is combined with the unique action of trehalose, which has a negative effect on the skin. It has been discovered that a lotion having less irritation and a lot of excellent effects such as moisturizing feeling and whitening can be obtained.
【0009】本発明の化粧水にはトレハロース以外に公
知の保湿成分や角質軟化剤を併用することが出来る。保
湿成分としてはエチレングリコール、グリセリン、プロ
ピレングリコール、ジエチレングリコール、1,3−ブ
チレンジオール、1,2−ペンタンジオール、ポリエチ
レングリコール、ポリプロピレングリコール、ソルビト
ール等の多価アルコール類、これら多価アルコールの脂
肪酸エステル類、キシリトールなどの多糖類、アミノ酸
類、ヒアルロン酸、エラスチン、コラーゲン、キチン、
キトサン誘導体 等が例示される。この中でも使用経験
から、グリセリン、セリンやグルタミン酸ナトリウムの
ようなアミノ酸又はアミノ酸塩、ヒアルロン酸やその塩
が好ましい保湿成分である。また、これらの保湿成分は
単独あるいは2種類以上混合して使用してもよい。角質
軟化剤としてはアミノ酸、ピログルタミン酸、乳酸、尿
素、アルカリ金属などの天然保湿因子のほか、乳酸塩、
トリエタノールアミン、α−ヒドロキシ酸、等が例示さ
れる。In addition to trehalose, well-known moisturizing ingredients and keratin softening agents can be used in combination with the lotion of the present invention. Moisturizing ingredients include polyhydric alcohols such as ethylene glycol, glycerin, propylene glycol, diethylene glycol, 1,3-butylene diol, 1,2-pentanediol, polyethylene glycol, polypropylene glycol, sorbitol, and fatty acid esters of these polyhydric alcohols. , Polysaccharides such as xylitol, amino acids, hyaluronic acid, elastin, collagen, chitin,
Examples include chitosan derivatives. Among them, glycerin, amino acids or amino acid salts such as serine and sodium glutamate, hyaluronic acid and its salts are preferable moisturizing ingredients from the experience of use. These moisturizing ingredients may be used alone or in admixture of two or more. As keratin softeners, in addition to natural moisturizing factors such as amino acids, pyroglutamic acid, lactic acid, urea and alkali metals, lactate,
Examples are triethanolamine and α-hydroxy acid.
【0010】本発明の炭酸経皮吸収用組成物及び化粧水
は上述のごとく遊離炭酸及びトレハロースを必須成分と
するものであるが、上記保湿成分や角質軟化剤に加えて
使用目的に応じて公知の添加剤成分を加えても良い。こ
れらの添加剤としては、オリーブオイル、セチルアルコ
ール、ラノリン、ステアリルアルコールなどの柔軟化
剤、ミネラル、各種栄養剤、アロエや甘草など薬草等の
植物抽出成分、クロレラエキス、海藻抽出物、ローズマ
リーエキス、カモミラエキス、ラベンダーエキスなどの
ハーブ、各種香料、アルブチン、ビタミンC、コウジ酸
などの美白剤が挙げられる。また、皮膚のターンオーバ
ーを促進しシワの改善が期待されるレチン酸、レチノー
ル、γ―アミノ酪酸なども用途によって適宜添加するこ
ともできる。使用目的によってはグリチルリチン酸のよ
うな抗炎剤を添加して薬効を期待することも出来る。さ
らに使用時に清涼感を付与するためにエチルアルコール
なども少量添加することもできる。また、本発明の化粧
水は遊離炭酸を含むため防腐効果がそれ自身であるが、
高温での長期間保管などの過酷な使用条件が想定される
場合は、パラベンやクエン酸などの防腐剤や酸化防止剤
を添加することもできる。これらの添加剤の添加量は本
発明の目的である肌にやさしい化粧水、即ち添加物の少
ない化粧水を提供するために出来るだけ少なくすべきで
ある。The composition for percutaneous absorption of carbonic acid and lotion of the present invention contains free carbonic acid and trehalose as essential components as described above, but it is known depending on the purpose of use in addition to the above moisturizing component and keratin softener. You may add the additive component of. These additives include olive oil, cetyl alcohol, lanolin, softeners such as stearyl alcohol, minerals, various nutrients, plant extract components such as aloe and licorice herbs, chlorella extract, seaweed extract, rosemary extract. Herbs such as chamomile extract and lavender extract, various flavors, whitening agents such as arbutin, vitamin C and kojic acid. Further, retinoic acid, retinol, γ-aminobutyric acid, etc., which are expected to promote skin turnover and improve wrinkles, may be appropriately added depending on the application. Depending on the purpose of use, an anti-inflammatory agent such as glycyrrhizic acid may be added to expect a medicinal effect. Further, a small amount of ethyl alcohol or the like can be added to give a refreshing feeling when used. Further, the lotion of the present invention contains free carbonic acid and therefore has an antiseptic effect itself,
When harsh use conditions such as long-term storage at high temperature are expected, a preservative such as paraben or citric acid or an antioxidant can be added. The amount of these additives to be added should be as small as possible in order to provide a skin-friendly lotion, that is, a lotion with few additives, which is the object of the present invention.
【0011】次に第2発明、第3発明の炭酸経皮吸収用
組成物並びにその使用方法に関する第5発明について、
その好ましい実施形態も含めて説明する。上述の第1発
明と重複する構成要件の説明は省略する。この発明の遊
離炭酸を含む組成物は人体の局部に塗布ないしは貼って
使用するのがその主要な目的であるので、粘度はその使
用形態によって適宜選ぶことが好ましい。一方、炭酸ガ
スの拡散による空気中への逃散の速度は組成物の粘度に
反比例することを考えると粘度は高いほうが好ましい。
少なくとも室温で5dPa・s、好ましくは10dPa
・s以上であるものが好ましい。このような粘度の調整
は高分子の種類、重合度と水溶液への濃度を変える事に
よって行うことが出来る。場合によっては高分子水溶液
に無機や有機の低分子塩を添加することで粘度を変化さ
せることも可能である。本発明で言うゲルとは粘度が無
限大に大きい状態で流動性が無い状態を示し、組成物中
の水溶性高分子が分子間相互作用により3次元編目構造
を形成してゲル化する。ゲル状態では粘度が無限大に大
きいため組成物からの炭酸ガスの逃散は遅くなるため組
成物の保存には好適である。しかし使用時には流動性が
ないため塗布などが困難であるので、ゲルをゾル化して
用いることが好ましい。本発明ではゲルは上記説明の通
り流動性を示さない状態であり粘度が測定できないもの
で、一般に化粧品関係でジェルと称されているものとは
異なるものである。化粧品関係では粘度が高く指先で掬
い取ることが出来るような状態をジェルと称している
が、このジェルは粘度が測定できるもので、本発明では
流動性を示す状態をゾルと定義しているので、いわゆる
ジェルは本発明ではゾルの範疇に入るものである。Next, the fifth invention relating to the composition for percutaneous absorption of carbonic acid of the second invention and the third invention and the method of using the same,
The preferred embodiment will be described as well. The description of the constituent elements overlapping the first invention described above will be omitted. Since the main purpose of the composition containing free carbonic acid of the present invention is to apply it to or apply it to a local part of the human body, it is preferable to select the viscosity appropriately depending on the use form. On the other hand, considering that the rate of escape of carbon dioxide gas into the air due to diffusion is inversely proportional to the viscosity of the composition, the higher viscosity is preferable.
5 dPa · s at least at room temperature, preferably 10 dPa
-S or more is preferable. Such adjustment of the viscosity can be performed by changing the type of polymer, the degree of polymerization and the concentration in the aqueous solution. In some cases, it is possible to change the viscosity by adding an inorganic or organic low molecular salt to the aqueous polymer solution. The gel referred to in the present invention refers to a state in which the viscosity is infinitely large and there is no fluidity, and the water-soluble polymer in the composition forms a three-dimensional stitch structure by intermolecular interaction and gels. Since the viscosity in the gel state is infinitely large, the escape of carbon dioxide gas from the composition is delayed, which is suitable for storing the composition. However, it is preferable to use the gel in the form of a sol because it is difficult to apply it because it has no fluidity during use. In the present invention, the gel does not exhibit fluidity as described above and its viscosity cannot be measured, which is different from what is generally called a gel in cosmetics. In terms of cosmetics, a state in which the viscosity is high and can be scooped with a fingertip is called a gel, but this gel has a viscosity that can be measured. In the present invention, so-called gels fall under the category of sol.
【0012】本発明ではゾルからゲルへ転移する過程を
ゾルーゲル転移と呼び、その逆をゲルーゾル転移と呼
び、これらの転移を纏めて相転移と呼ぶ。本発明ではこ
の相転移は水溶性高分子の分子間相互作用の変化によっ
て起こるものであるが、分子間相互作用の変化は該水溶
液に物理的、化学的な作用を与えることによってもたら
される。物理的な作用としては温度変化を与えるのが好
ましい。温度によって転移を起す、即ち転移温度はDS
CやNMRなどの分析機器を用いれば正確に求めること
が出来るが本発明では簡便的に以下の方法で求めた。ゲ
ル化やゾル化の場合、系の全体の粘度が変化して流動性
を失ったり、流動性を回復したりするため転移が完了す
るまで時間を要するのが一般的である。本発明では組成
物を入れた試験管を恒温水槽で温度を変えながら流動性
即ち粘度変化が起こり始める温度を観察し、組成物の粘
度が温度変化以上に大きく変化し始める温度を転移温度
と定義した。化学的な作用としては水溶性高分子の溶解
性を変化させるような添加剤を加えることで行なうこと
ができる。本発明では添加剤として水溶液に良く溶ける
低分子塩を添加することが好ましい。この場合は水溶液
の温度を一定にして、所定量の添加剤を加えてしばらく
放置してゲル化するかゾル化するかを上記試験管法で確
認することが出来る。添加剤の量によって転移温度は異
なるので、所定量の添加剤を含む水溶液の転移温度は上
述のようにして求めることが出来る。In the present invention, the process of transition from sol to gel is called sol-gel transition, and the reverse is called gel-sol transition, and these transitions are collectively called phase transition. In the present invention, this phase transition is caused by a change in intermolecular interaction of the water-soluble polymer, and the change in intermolecular interaction is brought about by giving a physical or chemical action to the aqueous solution. It is preferable to give a temperature change as a physical action. A transition occurs depending on temperature, that is, the transition temperature is DS
It can be accurately determined by using an analytical instrument such as C or NMR, but in the present invention, it was simply determined by the following method. In the case of gelation or sol formation, it takes a long time to complete the transition because the viscosity of the entire system changes to lose fluidity or restore fluidity. In the present invention, the test tube containing the composition is observed in the constant temperature water bath while observing the temperature at which the fluidity, that is, the change in viscosity begins to occur, and the temperature at which the viscosity of the composition begins to change more than the temperature change is defined as the transition temperature. did. The chemical action can be performed by adding an additive that changes the solubility of the water-soluble polymer. In the present invention, it is preferable to add, as an additive, a low molecular weight salt that is well soluble in an aqueous solution. In this case, it is possible to confirm by the test tube method whether the temperature of the aqueous solution is constant, a predetermined amount of the additive is added, and the solution is left to stand for a while to gel or sol. Since the transition temperature differs depending on the amount of the additive, the transition temperature of the aqueous solution containing the predetermined amount of the additive can be obtained as described above.
【0013】本発明の炭酸経皮吸収用組成物の上記転移
温度は人体に使用する観点から0℃以上45℃未満、好
ましくは0−40℃を有するものである。この温度範囲
でゾルーゲル転移を示す組成物はいわゆる熱ゲル化特性
を示す組成物である。本発明の組成物は炭酸水に水溶性
高分子を溶解させるか、高分子水溶液に炭酸ガスを溶解
させて製造されるが、いずれにしても炭酸ガスの水への
溶解度は温度が低いほど大きいため低温で行う必要があ
る。また、水溶液の場合その粘度が低い方が炭酸ガスの
水溶液への拡散速度が速くなり好ましい。従って、低温
でゾル状態を示しさらに粘度が低い高分子水溶液は高濃
度の炭酸ガスを組成物に溶解させることが出来る。一
方、組成物を保存する場合は炭酸ガスの逃散の観点から
粘度が大きい状態、好ましくはゲル状態である。また、
使用時にはゾル状態で適切な粘度に調節できることが好
ましい。これらの相転移は簡便に出来ることが好まし
く、本発明では温度や低分子塩などの添加剤またはこれ
らの組み合わせで行なうことが好ましい。転移温度が高
いと使用に適した粘度にするために組成物を高温度にす
る必要があり、組成物からの炭酸ガスの逃散が起こりや
すく好ましくない。この観点からも転移温度は45℃未
満、好ましくは40℃以下である。最も好ましいのは3
7℃付近に転移温度を有する組成物であり、人体にゾル
状態で塗布した場合、体温でゲル化が進行し炭酸ガスの
空気中への逃散が起こりにくくなるので好ましい。下限
の温度は実用的な観点から冷蔵庫の温度で保存する場合
ゲル化やゾル化が容易に起こるものが好ましく0℃以上
である。ゲルーゾル転移を示す組成物についても事情は
同じであるが、組成物の調整段階、即ち水溶液に炭酸ガ
スを溶解させる時はゾル状態で行う必要があり、低温好
ましくは35℃以下に転移温度を示すものが好ましい。The above-mentioned transition temperature of the composition for percutaneous absorption of carbonic acid of the present invention is 0 ° C. or higher but lower than 45 ° C., preferably 0-40 ° C. from the viewpoint of use in the human body. A composition exhibiting a sol-gel transition in this temperature range is a composition exhibiting so-called thermal gelation characteristics. The composition of the present invention is produced by dissolving a water-soluble polymer in carbonated water or by dissolving carbon dioxide gas in an aqueous polymer solution. In any case, the solubility of carbon dioxide gas in water increases as the temperature decreases. Therefore, it needs to be performed at a low temperature. Further, in the case of an aqueous solution, it is preferable that the viscosity of the aqueous solution is lower because the diffusion rate of carbon dioxide gas into the aqueous solution becomes faster. Therefore, a polymer aqueous solution which exhibits a sol state at a low temperature and has a low viscosity can dissolve a high concentration of carbon dioxide gas in the composition. On the other hand, when the composition is stored, it has a high viscosity, preferably a gel state, from the viewpoint of escape of carbon dioxide gas. Also,
At the time of use, it is preferable that the sol state can be adjusted to an appropriate viscosity. It is preferable that these phase transitions can be easily carried out, and in the present invention, it is preferable to carry out by temperature, an additive such as a low molecular weight salt, or a combination thereof. If the transition temperature is high, it is necessary to raise the temperature of the composition in order to obtain a viscosity suitable for use, and carbon dioxide gas is likely to escape from the composition, which is not preferable. From this viewpoint as well, the transition temperature is lower than 45 ° C, preferably 40 ° C or lower. 3 is most preferable
It is a composition having a transition temperature near 7 ° C., and when applied in a sol state to a human body, gelation proceeds at body temperature and carbon dioxide gas is less likely to escape into the air, which is preferable. From a practical point of view, the lower limit temperature is preferably 0 ° C. or higher, which easily causes gelation or sol formation when stored at a refrigerator temperature. The situation is the same for a composition exhibiting a gel-sol transition, but it is necessary to carry out in a sol state at the preparation stage of the composition, that is, when carbon dioxide gas is dissolved in an aqueous solution, and the transition temperature is preferably low at 35 ° C. or lower. Those are preferable.
【0014】本発明の組成物の水溶性高分子は合成高分
子、天然高分子、天然高分子を原料として誘導される半
合成高分子のいずれでも良い。合成高分子としてはポリ
アクリルアミド、ポリ(メタ)アクリル酸並びにその
塩、ポリエチレンオキシド、ポリビニルアルコール、ポ
リビニルピロリドンなど、天然高分子としてはゼラチ
ン、加水分解コラーゲン、寒天、カラギーナン、グアー
ガム、ペクチン、デキストラン、ヒアルロン酸、でんぷ
んなど、半合成高分子としてはメチルセルロース、エチ
ルセルロース、カルボキシメチルセルロース、ヒドロキ
シエチルメチルセルロース、ヒドキシプロピルメチルセ
ルロース等のセルロース誘導体等を用いることが出来
る。しかしながら人体に触れることから天然高分子、半
合成高分子が好ましい。また、これらの水溶性高分子を
2種以上混合して使用してもよい。組成物中の水溶性高
分子の濃度は0.5−5wt%の範囲が好ましい。The water-soluble polymer of the composition of the present invention may be a synthetic polymer, a natural polymer, or a semi-synthetic polymer derived from a natural polymer as a raw material. Synthetic polymers include polyacrylamide, poly (meth) acrylic acid and its salts, polyethylene oxide, polyvinyl alcohol, polyvinylpyrrolidone, etc., and natural polymers include gelatin, hydrolyzed collagen, agar, carrageenan, guar gum, pectin, dextran, hyaluronic acid. As the semi-synthetic polymer such as acid or starch, cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethyl methyl cellulose, and hydroxypropyl methyl cellulose can be used. However, natural polymers and semi-synthetic polymers are preferable because they touch the human body. Further, two or more of these water-soluble polymers may be mixed and used. The concentration of the water-soluble polymer in the composition is preferably in the range of 0.5-5 wt%.
【0015】低温でゾル状態、高温でゲル化特性を示す
水溶性高分子としてはメチルセルロースがよく知られて
いる。また、合成高分子ではポリーN―イソプロピルア
クリルアミド、ポリーN―ビニルアセトアミド、ポリー
N―ビニルイソブチルアミド、N―ビニルイソブチルア
ミドとN―ビニルアセトアミドの共重合体などが知られ
ている。人体に用いる観点から半合成高分子であるメチ
ルセルロースが好ましい。メチルセルロースの場合、そ
の2wt%水溶液の転移温度は本発明の方法で測定する
と45℃であり、転移温度を45℃未満にするためには
低分子塩を添加するのが好ましい。このような塩として
は塩化ナトリウム、硫酸ナトリウム、炭酸ナトリウム、
炭酸水素ナトリウム、クエン酸ナトリウムなどのナトリ
ウム塩が例示される。本発明の好ましい実施形態はこの
ような熱ゲル化特性を示す水溶性高分子を用いて低温で
水溶液に炭酸ガスを十分溶解させて密閉容器に保存し、
必要ならば冷蔵庫に保管して、使用時に30−40℃の
雰囲気に密閉容器を放置することでゲル化に伴う増粘を
起こさしめ、塗布しやすい粘度に調節してから容器を開
封して人体の局部に塗布することである。ゲル化に伴う
増粘作用は使用時に上述の低分子塩を組成物に添加する
ことでも行なうことが出来る。この方法は炭酸経皮吸収
用組成物に塩を均一に溶解させるために攪拌を必要とす
るが、その時に組成物に溶解している炭酸ガスが逃散す
るので注意が必要である。溶解しやすい塩や攪拌を短時
間で且つ低温で行うことにより組成物の相転移による粘
度変化を炭酸ガスの逃散を最小限にして達成することが
出来る。Methyl cellulose is well known as a water-soluble polymer which exhibits a sol state at low temperature and a gelling property at high temperature. As synthetic polymers, poly-N-isopropylacrylamide, poly-N-vinylacetamide, poly-N-vinylisobutyramide, copolymers of N-vinylisobutyramide and N-vinylacetamide, etc. are known. From the viewpoint of use in the human body, methylcellulose, which is a semi-synthetic polymer, is preferable. In the case of methyl cellulose, the transition temperature of its 2 wt% aqueous solution is 45 ° C. when measured by the method of the present invention, and it is preferable to add a low molecular weight salt in order to keep the transition temperature below 45 ° C. Such salts include sodium chloride, sodium sulfate, sodium carbonate,
Examples of the sodium salt include sodium hydrogen carbonate and sodium citrate. A preferred embodiment of the present invention uses a water-soluble polymer having such thermal gelation property to sufficiently dissolve carbon dioxide in an aqueous solution at low temperature and store it in a closed container,
If necessary, store in a refrigerator and leave the closed container in an atmosphere of 30-40 ° C during use to increase the viscosity associated with gelation, adjust the viscosity to an easy-to-apply state, and then open the container to remove the human body. Is to be applied locally. The thickening effect associated with gelation can also be achieved by adding the above-mentioned low molecular weight salt to the composition at the time of use. This method requires stirring in order to uniformly dissolve the salt in the composition for percutaneous absorption of carbonic acid, but care must be taken because carbon dioxide gas dissolved in the composition at that time escapes. By performing a salt which is easily dissolved or stirring at a low temperature for a short time, the viscosity change due to the phase transition of the composition can be achieved while minimizing the escape of carbon dioxide gas.
【0016】一方、低温でゲル状態を取り、高温でゾル
状態を示す炭酸経皮吸収用組成物はゲル状態で保存が出
来るので組成物からの炭酸ガスの逃散を最小にすること
が出来るので好ましい。例えばゼラチンの水溶液からな
る炭酸経皮吸収用組成物はゼラチンの濃度によっても多
少変化するが2wt%水溶液では約25℃以下でゲル化
を起こす。従って、25−30℃の範囲のゾル状態で炭
酸ガスを溶解させて25℃以下、例えば冷蔵庫に保管し
ておけば炭酸ガスの逃散がほとんど起こらない炭酸経皮
吸収用組成物が得られる。使用時にこのゲルを30℃以
上に加熱することでゾル化して人体の局部等に塗布して
使用することが出来る。このように昇温と共にゲルーゾ
ル転移を示す水溶性高分子は多く知られている。高温溶
解性を示す水溶性高分子、でんぷん、寒天、アガロー
ス、グアーガム、ローカストビーンガム、キサンタンガ
ム、カラギーナン、ペクチン、マンナン、デキストラン
等の天然高分子、ヒドロキシプロピルメチルセルロー
ス、ヒドロキシエチルメチルセルロース、カルボキシメ
チルセルロース、などの半合成高分子、ポリビニルピロ
リドン、ポリ(メタ)アクリル酸やその塩、ポリアクリ
ルアミドやその部分加水分解物、ポリエチレンオキシド
などの合成高分子が例示されるが、転移温度は水溶液中
の高分子の重合度や濃度によって変化する。一般に重合
度が高く濃度が高いと相転移温度は高くなる。On the other hand, a composition for percutaneous absorption of carbonic acid which takes a gel state at a low temperature and shows a sol state at a high temperature can be stored in a gel state, so that the escape of carbon dioxide gas from the composition can be minimized, which is preferable. . For example, a composition for percutaneous absorption of carbonic acid comprising an aqueous solution of gelatin changes to some extent depending on the concentration of gelatin, but a 2 wt% aqueous solution causes gelation at about 25 ° C. or lower. Therefore, if carbon dioxide is dissolved in a sol state in the range of 25 to 30 ° C. and stored at 25 ° C. or lower, for example, in a refrigerator, a composition for percutaneous absorption of carbonic acid in which carbon dioxide hardly escapes can be obtained. At the time of use, the gel can be heated to 30 ° C. or higher to form a sol, which can be applied to a local area of the human body and used. Many water-soluble polymers that exhibit a gel-sol transition as the temperature rises are known. High-temperature soluble water-soluble polymers, starch, agar, agarose, guar gum, locust bean gum, xanthan gum, carrageenan, pectin, mannan, natural polymers such as dextran, hydroxypropylmethylcellulose, hydroxyethylmethylcellulose, carboxymethylcellulose, etc. Semi-synthetic polymers, polyvinylpyrrolidone, poly (meth) acrylic acid and its salts, polyacrylamide and its partial hydrolysates, synthetic polymers such as polyethylene oxide are exemplified, but the transition temperature is the polymerization of the polymer in an aqueous solution. It changes depending on the degree and concentration. Generally, the higher the degree of polymerization and the higher the concentration, the higher the phase transition temperature.
【0017】本第2、第3発明に関する組成物は炭酸ガ
スを300ppm以上含むものであるためPHが5以下
に低下する場合がある。その場合、水、遊離炭酸、水溶
性高分子以外に第1発明で説明したようにトレハロース
を加えることによりPHが低くても使用感に優れた炭酸
経皮吸収用組成物が得られるので好ましい。さらに必要
であれば第1発明で説明した保湿成分、角質軟化剤、薬
剤等使用目的に応じて各種の添加剤を加えて用いること
が出来る。本発明の炭酸経皮吸収用組成物は高濃度に炭
酸ガスを含み、且つ後の実施例で示すごとく人体の局部
に貼付した場合、30分後でも皮膚の赤化現象を示し血
行促進が認められるものであり、炭酸ガスの空気中の逃
散速度が遅く血行促進が必要な患部に貼付してその治癒
を図ることが出来る。Since the compositions according to the second and third aspects of the present invention contain carbon dioxide gas in an amount of 300 ppm or more, PH may drop to 5 or less. In that case, by adding trehalose as described in the first invention in addition to water, free carbonic acid and a water-soluble polymer, a composition for percutaneous absorption of carbonic acid having an excellent feeling of use can be obtained even if the pH is low, which is preferable. Further, if necessary, various additives such as the moisturizing component, the keratin softening agent, and the medicine described in the first invention can be added and used according to the purpose of use. The composition for percutaneous absorption of carbonic acid of the present invention contains carbon dioxide at a high concentration, and when applied to a local area of the human body as shown in the Examples below, reddening of the skin is observed even after 30 minutes and blood circulation is promoted. Since the rate of escape of carbon dioxide in the air is slow, it can be attached to an affected area where blood circulation is required to be healed.
【0018】次に本発明の第4について説明する。粘度
が低くて人体に塗布した場合流動して流れてしまうよう
な組成物や逆に室温でゲル化している組成物はそのまま
では人体の局部に塗布するのが困難である。このような
場合はシート状の支持体に組成物をゾル状態で含浸させ
たり、コーティングして組成物を担持したシート状物を
人体の局部に貼って使用することが出来る。支持体とし
ては繊維からなる柔軟性のある編地、織物、不織布、フ
ェルト状物、高分子からなるフイルム等を用いることが
出来る。また、人体の局部に貼った後に炭酸ガスの逃散
を防いだり、組成物が外部に漏れ出すのを防ぐために、
組成物の含浸層として機能する支持体と高分子フイルム
などガスバリヤー機能を有する支持体を複合した複合支
持体を用いることも出来る。シート状支持体の厚みは5
mm以下が取り扱い性から好ましい。Next, the fourth aspect of the present invention will be described. It is difficult to apply a composition which has a low viscosity and flows and flows when applied to a human body or a composition which is gelled at room temperature as it is to a human body as it is. In such a case, a sheet-shaped support may be impregnated with the composition in a sol state, or a sheet-shaped material carrying the composition by coating may be attached to a local part of the human body for use. As the support, a flexible knitted fabric made of fibers, a woven fabric, a non-woven fabric, a felt-like material, a film made of a polymer, or the like can be used. In addition, in order to prevent the escape of carbon dioxide gas after being applied to a local area of the human body, or to prevent the composition from leaking to the outside,
It is also possible to use a composite support in which a support functioning as an impregnated layer of the composition and a support having a gas barrier function such as a polymer film are combined. The thickness of the sheet-like support is 5
mm or less is preferable in terms of handleability.
【0019】最後に本発明の炭酸経皮吸収用組成物の製
造方法に関する第6、第7発明について説明する。従来
技術の製造法では耐圧容器内に化粧水やローションと言
った化粧料の原液を入れてその容器内を炭酸ガスで加圧
して炭酸ガスを含む化粧料を製造していた。この方法は
一見製造法としては簡便に思われるが、加圧注入する炭
酸ガスを容器内の水やアルコールに溶解させて所定量の
炭酸ガスを溶解した化粧料とするものであるから、高濃
度の炭酸ガスを溶解させるためには炭酸ガスの圧力を高
くする必要がある。そのため容器は十分な耐圧構造にす
る必要があった。また、炭酸ガスの溶解はガスと接触す
る液体の表面からしか起こらないため高濃度の炭酸ガス
を溶解させるには長時間が必要である。時間の問題は炭
酸ガスを加圧注入し密閉して放置すれば徐々に溶解が進
行するので、製品の保管中に行なうことが可能と思われ
るが、そのためには容器内に炭酸ガス気体の占める空間
を十分確保しておく必要がある。従って容器に占める化
粧料の量は必然的に少なくなってしまう。Finally, the sixth and seventh inventions concerning the method for producing the composition for percutaneous absorption of carbonic acid of the present invention will be explained. In the conventional manufacturing method, a cosmetic liquid such as lotion or lotion was put in a pressure resistant container, and the container was pressurized with carbon dioxide to manufacture a cosmetic containing carbon dioxide. This method seems to be simple as a manufacturing method at first glance, but it is a high-concentration product because the carbon dioxide gas to be injected under pressure is dissolved in water or alcohol in a container to dissolve a predetermined amount of carbon dioxide gas. In order to dissolve the carbon dioxide gas, it is necessary to increase the pressure of the carbon dioxide gas. Therefore, the container had to have a sufficient pressure resistant structure. Further, since the carbon dioxide gas is dissolved only from the surface of the liquid that comes into contact with the gas, it takes a long time to dissolve the high concentration carbon dioxide gas. The problem of time is that it is possible to carry out during the storage of the product because the dissolution gradually progresses if carbon dioxide gas is injected under pressure and left sealed and left to stand. It is necessary to secure enough space. Therefore, the amount of cosmetics occupied in the container is inevitably small.
【0020】本発明者らはこのような欠点を無くすため
に、組成物への炭酸ガスの溶解工程と得られた炭酸ガス
含有組成物の容器への充填を別工程とした炭酸経皮吸収
用組成物の製造方法を発明した。組成物への炭酸ガスの
溶解工程は炭酸ガスを含まない組成物原料水溶液を調整
してその水溶液を炭酸ガスと接触させることが一工程で
済むので好ましい。この場合、予め原料水溶液を脱気し
ておくことが好ましい。また、炭酸ガスの水等の液体へ
の溶解度は低温ほど大きいので30℃以下、好ましくは
25℃以下で溶解させるのが好ましい。さらに炭酸ガス
と原料水溶液の接触面積を大きくした装置を用いるのが
好ましい。原料水溶液の粘度が低い場合は膜式炭酸ガス
溶解器を用いて短時間で高濃度の炭酸ガスを溶解させる
ことが出来ることを見出した。このような膜式炭酸ガス
溶解器は例えば特許2810694号公報や特開平7−
779号公報に開示されている中空糸膜を用いたものが
気体と液体の接触面積が大きくて効率的で好ましい。膜
式炭酸ガス溶解器を用いた場合、その前段又は後段に精
密ろ過装置を連続して設けることにより、細菌や異物の
ろ過を行って無菌状態の炭酸経皮吸収用組成物が容易に
得られる。In order to eliminate such drawbacks, the present inventors have proposed a method for transdermal absorption of carbon dioxide in which a step of dissolving carbon dioxide gas in the composition and a step of filling the obtained composition containing carbon dioxide gas into a container are separate steps. The method of making the composition was invented. In the step of dissolving carbon dioxide gas in the composition, it is preferable to prepare a composition raw material aqueous solution containing no carbon dioxide gas and bring the aqueous solution into contact with carbon dioxide gas in one step. In this case, it is preferable to degas the raw material aqueous solution in advance. Further, since the solubility of carbon dioxide gas in a liquid such as water is higher at lower temperatures, it is preferable to dissolve it at 30 ° C. or lower, preferably 25 ° C. or lower. Furthermore, it is preferable to use an apparatus in which the contact area between the carbon dioxide gas and the raw material aqueous solution is increased. It has been found that when the viscosity of the raw material aqueous solution is low, high concentration carbon dioxide can be dissolved in a short time by using a membrane type carbon dioxide dissolver. Such a membrane type carbon dioxide gas dissolver is disclosed, for example, in Japanese Patent No. 2810694 or Japanese Patent Laid-Open No. 7-
The one using the hollow fiber membrane disclosed in Japanese Patent No. 779 is preferable since it has a large contact area between gas and liquid and is efficient. When a membrane-type carbon dioxide dissolver is used, a sterile carbonic acid percutaneous absorption composition can be easily obtained by continuously providing a microfiltration device in the preceding stage or the subsequent stage to filter bacteria and foreign substances. .
【0021】一方、水溶性高分子を含んだ比較的に粘度
の大きい原料組成物の場合は水溶液を攪拌装置の具備し
たオートクレーブ等の加圧容器にいれて攪拌しながら脱
気後、炭酸ガスを加圧して溶解させることが出来る。炭
酸ガスの供給は炭酸ガスボンベを用いるのが簡単で好ま
しいが、固体炭酸(ドライアイス)をオートクレーブに
水溶液と共に入れて密閉することも出来る。また、連続
して高粘度の水溶液に炭酸ガスを溶解させるための装置
としては、濡れ壁装置やスタティックミキサー内で炭酸
ガスを導入し水溶液と接触ないしは混合しながら溶解さ
せて取り出す方法なども好ましい方法である。炭酸ガス
の圧力は0.1−0.5MPaの範囲が好ましい。この
ようにして300ppm以上の炭酸ガスを溶解した組成
物は目的に応じて各種容器に密閉して収納して保管され
る。収納容器は容器の壁を通して炭酸ガスの逃散が起こ
りにくいものが好ましく、プラスチック製であればポリ
エチレンテレフタレート(PET)や塩化ビニリデン、
アクリルニトリル共重合体などのガス透過性の低い材料
が好ましい。またアルミ等の金属とのラミネート包装材
料や、粘度が低ければ金属製のスプレー容器も好ましい
容器である。On the other hand, in the case of a relatively viscous raw material composition containing a water-soluble polymer, the aqueous solution is placed in a pressure vessel such as an autoclave equipped with a stirrer and deaerated while stirring, and then carbon dioxide gas is removed. It can be pressed and dissolved. It is preferable to use a carbon dioxide gas cylinder for supplying carbon dioxide gas, but it is also possible to put solid carbon dioxide (dry ice) in an autoclave together with an aqueous solution and seal it. Further, as a device for continuously dissolving carbon dioxide in a high-viscosity aqueous solution, a method in which carbon dioxide is introduced in a wet wall device or a static mixer and dissolved and taken out while contacting or mixing with the aqueous solution is also a preferable method. Is. The pressure of carbon dioxide gas is preferably in the range of 0.1-0.5 MPa. The composition in which 300 ppm or more of carbon dioxide gas is dissolved is sealed and stored in various containers according to the purpose and stored. The storage container is preferably one in which carbon dioxide gas does not easily escape through the wall of the container. If it is made of plastic, polyethylene terephthalate (PET), vinylidene chloride,
Materials with low gas permeability, such as acrylonitrile copolymers, are preferred. A laminated packaging material with a metal such as aluminum or a spray container made of metal if the viscosity is low is also a preferable container.
【0022】熱ゲル化特性を示す水溶性高分子を組成物
に含む場合、そのゲル化温度以上で高分子を水もしくは
トレハロースや低分子塩を含む水溶液に分散させること
が好ましい。ゲル化温度以下では高分子の溶解速度が速
く水溶液の粘度が上昇し数%の濃度でも高分子を均一に
溶解させることが困難である。一方、ゲル化温度以上で
分散させた場合、高分子の溶解は起こらないため分散液
の粘度は低く均一な分散液を得ることが出来る。この分
散液をゲル化温度以下の温度に攪拌しながら冷却すると
均一な高分子水溶液を得ることが出来る。炭酸ガスの溶
解度は低温ほど大きいためこの均一溶液を冷却状態で炭
酸ガス溶解装置に充填して炭酸ガスを溶解することが出
来るが、好ましくは粘度の低い均一な分散液を冷却しな
がら炭酸ガスを溶解させることが好ましい。冷却温度は
30℃以下、好ましくは25℃以下、さらに好ましくは
20℃以下である。When the composition contains a water-soluble polymer exhibiting thermal gelation properties, it is preferable to disperse the polymer in water or an aqueous solution containing trehalose or a low-molecular salt at a temperature not lower than the gelation temperature. Below the gelation temperature, the dissolution rate of the polymer is high and the viscosity of the aqueous solution rises, making it difficult to uniformly dissolve the polymer even at a concentration of several percent. On the other hand, when the dispersion is carried out at the gelation temperature or higher, the polymer does not dissolve, so that the viscosity of the dispersion is low and a uniform dispersion can be obtained. A uniform aqueous polymer solution can be obtained by cooling the dispersion with stirring at a temperature below the gelation temperature. Since the solubility of carbon dioxide gas is higher at lower temperatures, this homogeneous solution can be charged into a carbon dioxide gas dissolving device in a cooled state to dissolve carbon dioxide gas, but it is preferable to cool carbon dioxide gas while cooling a uniform dispersion liquid having low viscosity. It is preferable to dissolve it. The cooling temperature is 30 ° C or lower, preferably 25 ° C or lower, more preferably 20 ° C or lower.
【0023】このようにして調整した組成物中の炭酸ガ
ス濃度は幾つかの方法で求めることが出来る。二酸化炭
素電極法や標準試薬による化学滴定法は水道水や粘度の
低い液体の場合に有効であるが、高粘度の組成物では用
いることは出来ない。水溶性高分子を含む高粘度の組成
物の場合、本発明では炭酸ガス溶解工程で組成物に吸収
された炭酸ガスの質量及び該組成物の血行促進作用から
その濃度を定性的に判断した。The carbon dioxide concentration in the composition thus prepared can be determined by several methods. The carbon dioxide electrode method and the chemical titration method using standard reagents are effective for tap water and liquids with low viscosity, but cannot be used for high-viscosity compositions. In the present invention, in the case of a highly viscous composition containing a water-soluble polymer, its concentration was qualitatively determined from the mass of carbon dioxide gas absorbed in the composition in the carbon dioxide dissolving step and the blood circulation promoting action of the composition.
【0024】本発明の炭酸経皮吸収用組成物は血行促進
作用による顔の肌の健康、美容のために用いられる基礎
化粧水として、具体的には肌に潤いをもたらす、しみや
そばかすの改善、にきびの改善、日焼けの改善、美白効
果、シワの改善などが挙げられる。また、炭酸ガスの血
行促進作用から頭皮に用いる事による育毛剤、体の踵や
肘等の角質層が発達しやすい部位に於ける角質柔軟剤と
しても用いることが出来る。更に、皮膚の乾燥が起因す
ると考えられるアトピー性皮膚炎に対しても治癒が期待
される。また、高粘度の炭酸経皮吸収用組成物はエステ
用品として上記作用効果を示すほか、血行不良に基づく
患部、例えば寝たきり患者の床ずれ患部等に塗布あるい
は貼付することにより、患部の血行が促進され治癒が期
待される。以下に実施例、参考例及び比較例で本発明を
さらに説明するが本発明の技術範囲はこれらの実施例に
限定されるものではない。The composition for percutaneous absorption of carbonic acid of the present invention is used as a basic lotion used for the health and beauty of facial skin due to its blood circulation promoting action, specifically, it brings moisturizing to the skin and improves stains and freckles. , Improvement of acne, improvement of sunburn, whitening effect, and improvement of wrinkles. Further, it can be used as a hair-growing agent for use on the scalp due to the blood circulation promoting action of carbon dioxide, and as a keratin softening agent on the part where the stratum corneum is likely to develop, such as the heel and elbow of the body. Furthermore, healing is expected for atopic dermatitis, which is thought to be caused by dry skin. In addition, the high-viscosity carbonic acid transdermal absorption composition exhibits the above-mentioned effects as an beauty treatment product, and is also applied to or adhered to an affected area due to poor blood circulation, such as bed sore affected area of a bedridden patient, thereby promoting blood circulation in the affected area. Healing is expected. The present invention will be further described below with reference to Examples, Reference Examples and Comparative Examples, but the technical scope of the present invention is not limited to these Examples.
【0025】参考例1
水道水を用いて中空糸膜式炭酸ガス溶解器で異なる濃度
の遊離炭酸を含む炭酸水を調整した。炭酸ガスの濃度は
水道水の流量と炭酸ガス溶解器に供給する炭酸ガスの流
量を変える事によって行った。炭酸水中の遊離炭酸の濃
度は二酸化炭素電極(ORION RESEARCH 社製)で測定し
た。この炭酸水の炭酸ガス濃度とPHの関係を図1に示
した。Reference Example 1 Using tap water, carbonated water containing different concentrations of free carbon dioxide was prepared in a hollow fiber membrane type carbon dioxide gas dissolver. The concentration of carbon dioxide was determined by changing the flow rate of tap water and the flow rate of carbon dioxide supplied to the carbon dioxide dissolver. The concentration of free carbonic acid in carbonated water was measured with a carbon dioxide electrode (manufactured by ORION RESEARCH). The relationship between the carbon dioxide concentration of this carbonated water and PH is shown in FIG.
【0026】実施例1
イオン交換水(DI水)を用いて参考例1と同様して1
000ppmの遊離炭酸を含む炭酸水を調整した。この
炭酸水にトレハロースを表1に示す量を溶解して化粧水
を作製した。この化粧水のPHは4.6であった。この
化粧水及び比較のためにトレハロースを含まない炭酸水
のみを用いて乾燥肌を訴える女子被験者20名(年齢:
23−53歳)に、化粧水を毎日朝と夜の2回顔に付与
させ20日間の試用テストを行った。評価項目として顔
がヒリヒリする等の「皮膚に対する刺激性」を訴えた人
数、「皮膚の潤い」、「美白」について使用前に比べて
改善効果を認めた人の人数を調べた。その結果を表1に
纏めた。この結果より本発明のトレハロースと炭酸ガス
を含む化粧水はPHが4.6と低いにも拘らず刺激性が
少なく、且つ皮膚の潤いや美白効果を示すことが解っ
た。Example 1 Ion-exchanged water (DI water) was used in the same manner as in Reference Example 1
Carbonated water containing 000 ppm of free carbonic acid was prepared. The amount of trehalose shown in Table 1 was dissolved in this carbonated water to prepare a lotion. The pH of this lotion was 4.6. 20 female subjects who complain of dry skin using only this lotion and carbonated water containing no trehalose for comparison (age:
23-53 years old), lotion was applied to the face twice daily in the morning and at night, and a trial test for 20 days was performed. As the evaluation items, the number of people who complained of "irritancy to the skin" such as tingling of the face and the number of people who recognized improvement effects of "skin moisturization" and "whitening" compared to before use were examined. The results are summarized in Table 1. From these results, it was found that the lotion containing trehalose and carbon dioxide of the present invention has a low PH of 4.6 and is less irritating, and exhibits moisturizing and whitening effects on the skin.
【0027】比較例1
実施例1と同様に1000ppmの遊離炭酸を含むDI
水に表2で示す保湿剤を2wt%添加した化粧水を作製
した。但し、ヒアルロン酸ナトリウム液は増粘効果が大
きいため添加量を1%水溶液で3wt%添加した。化粧
水のPHはいずれも4.6であった。各化粧水について
実施例1と同じ女性被験者20名に同様に顔に付与させ
て、1週間の試用テストを評価項目として「皮膚に対す
る刺激性」についてのみ行った。その結果を表2に纏め
て示した。Comparative Example 1 DI containing 1000 ppm of free carbonic acid as in Example 1
A lotion was prepared by adding 2 wt% of the moisturizer shown in Table 2 to water. However, since the sodium hyaluronate solution has a large thickening effect, 3 wt% of a 1% aqueous solution was added. The pH of the lotion was 4.6 in all cases. For each lotion, the same 20 female subjects as in Example 1 were applied to the face in the same manner, and a one-week trial test was performed as an evaluation item only for "skin irritation". The results are summarized in Table 2.
【0028】実施例2
参考例1と同様にしてDI水に濃度の異なる炭酸ガスを
溶解した炭酸水を調整した。夫々の炭酸水にトレハロー
スを2wt%になるように溶解して炭酸経皮吸収用組成
物を得た。この組成物を縦3cm、横1.5cm、厚み
3mmの脱脂綿シートに十分しみ込ませて腕の内側の白
い皮膚に5分間貼付して皮膚の状態を観察した。結果を
表3に纏めて示した。Example 2 Carbonated water prepared by dissolving carbon dioxide gas having different concentrations in DI water was prepared in the same manner as in Reference Example 1. Trehalose was dissolved in each carbonated water so as to be 2 wt% to obtain a composition for percutaneous absorption of carbonic acid. The composition was thoroughly soaked in a cotton wool sheet having a length of 3 cm, a width of 1.5 cm, and a thickness of 3 mm, and the sheet was applied to the white skin inside the arm for 5 minutes to observe the skin condition. The results are summarized in Table 3.
【0029】実施例3
実施例1と同様にして1000ppmの遊離炭酸を含む
炭酸水を調整し、これに下記化合物を添加して化粧水を
調整した。
グリセリン 2wt%
トレハロース 0.5wt%
ヒアルロン酸ナトリウム 0.03wt%
クエン酸 0.05wt%
本化粧水をオイリー性肌を有する女性被験者(年齢20
−35才)10名に毎日朝晩の2回顔に塗布させて肌の
改良状況を観察した。その結果、2週間後からにきび等
の吹き出物の改善を認めた被験者は8名存在した。Example 3 Carbonated water containing 1000 ppm of free carbonic acid was prepared in the same manner as in Example 1, and the following compounds were added to this to prepare a lotion. Glycerin 2wt% Trehalose 0.5wt% Sodium hyaluronate 0.03wt% Citric acid 0.05wt% This lotion was applied to female subjects with oily skin (age 20
10 people (-35 years old) were applied to the face twice daily in the morning and evening, and the condition of skin improvement was observed. As a result, there were 8 subjects who showed improvement of acne and other pimples after 2 weeks.
【0030】実施例4
実施例1と同様にして1000ppmの遊離炭酸を含む
炭酸水を調整し、これに下記化合物を添加して化粧水を
調整した。
グリセリン 5wt%
トレハロース 0.5wt%
ヒアルロン酸ナトリウム 0.03wt%
クエン酸 0.05wt%
コウジ酸 0.5wt%
本化粧品を顔にくすみを訴える女性被験者(年齢30−
50才)10名に毎日朝晩顔に塗布させてくすみの改善
効果を調べた。その結果、2週間後からくすみの改善を
認めた被験者は7名存在した。Example 4 Carbonated water containing 1000 ppm of free carbonic acid was prepared in the same manner as in Example 1, and the following compounds were added to this to prepare a lotion. Glycerin 5 wt% Trehalose 0.5 wt% Sodium hyaluronate 0.03 wt% Citric acid 0.05 wt% Kojic acid 0.5 wt% A female subject (age 30-
10 people (50 years old) were applied to the face every morning and evening to examine the effect of improving dullness. As a result, there were 7 subjects who showed improvement of dullness after 2 weeks.
【0031】実施例5
下記の組成物を含むDI水1Kgを調整して化粧水原水
とした。
トレハロース 1wt%
グリセリン 2.5wt%
L−セリン 1wt%
にがり液(30%溶液) 3wt%
この化粧水原水を精密ろ過器と参考例1の炭酸ガス溶解
器が接続された装置に通して異物のろ過と炭酸ガスの溶
解を同時に行った。得られた化粧水には1000ppm
の炭酸ガスが溶解しており(供給炭酸ガス量から計
算)、PHは4.8であった。この化粧水について実施
例2と同様にして皮膚の赤化テストを行ったところ皮膚
は赤化した。また、比較例1と同様にして女性被験者に
皮膚の刺激性をテストしたところ刺激感を訴えた女性は
20名中3名であった。Example 5 1 kg of DI water containing the following composition was prepared to prepare a lotion raw water. Trehalose 1 wt% Glycerin 2.5 wt% L-serine 1 wt% Bittern solution (30% solution) 3 wt% This lotion raw water is passed through an apparatus in which a microfilter and a carbon dioxide dissolver of Reference Example 1 are connected to filter foreign substances. And carbon dioxide were dissolved at the same time. 1000 ppm in the obtained lotion
Carbon dioxide gas was dissolved (calculated from the supplied carbon dioxide gas amount), and PH was 4.8. When this skin lotion was tested for skin redness in the same manner as in Example 2, the skin was reddened. Further, when a female subject was tested for skin irritation in the same manner as in Comparative Example 1, 3 out of 20 women complained of irritation.
【0032】実施例6
下記の組成を有する炭酸経皮吸収用組成物を実施例5と
同じ方法で調整した。
トレハロース 2wt%
グリセリン 2.5wt%
尿素 5wt%
遊離炭酸 1500ppm
PH 4.5
足の踵部が乾燥してひび割れの激しい被験者(男性、5
9歳)にこの組成物を毎朝右足踵部に塗布させ、夜の入
浴後に踵部のひび割れの改善状態を観察させた。約1週
間でひび割れの改善が観察された。Example 6 A carbonic acid transdermal absorption composition having the following composition was prepared in the same manner as in Example 5. Trehalose 2 wt% Glycerin 2.5 wt% Urea 5 wt% Free carbonic acid 1500 ppm PH 4.5 Subjects with severe cracks due to dry heels of feet (male, 5
This composition was applied to the right heel area every morning (9 years old), and the improvement of cracks on the heel area was observed after bathing at night. Improvement of cracking was observed in about 1 week.
【0033】実施例7
DI水1Kgに3wt%になるように硫酸ナトリウムを
溶解した。この水溶液を50−60℃に加熱してメチル
セルロース(2wt%水溶液の粘度のカタログ値は15
00mPa・s)を分散させた。分散溶液を30℃まで
冷却して(この状態ではポリマーの溶解は起こらず分散
状態である)内容積が1.5Lの攪拌機が装備したオー
トクレーブに充填して密閉した。この状態で攪拌しなが
ら30分間真空ポンプで脱気した後、オートクレーブを
15℃に冷却した。真空ラインを炭酸ガス供給ラインに
切り替えて炭酸ガスボンベより0.2MPaの炭酸ガス
をオートクレーブに供給した。時間の経過と共に炭酸ガ
スの溶解が起こりオートクレーブの圧力は低下するの
で、適宜炭酸ガスを供給して圧力を0.2MPaに戻し
た。図2はオートクレーブのガス空間容積と圧力変化か
ら求めた水溶液に吸収された炭酸ガス質量と時間の関係
である。30分間で4g以上の炭酸ガスが溶解した様子
がわかる。4時間炭酸ガスの溶解を行いオートクレーブ
を開封して水溶液をPETボトルに収納した。水溶液は
オートクレーブの開封と同時にかなり発泡し、ポリマー
の溶解はまだ完全ではなく半透明状態であった。PET
ボトルを1夜冷蔵庫に保管するとポリマーの溶解が進行
し透明な溶液となった。この溶液の一部を試験管に取り
恒温水槽中で昇温しながら増粘挙動を調べたところ30
℃近辺から急激な増粘を認めたのでゾル−ゲル転移温度
を30℃とした。Example 7 Sodium sulfate was dissolved in 1 kg of DI water to a concentration of 3 wt%. This aqueous solution was heated to 50-60 ° C. and methylcellulose (the catalog value of the viscosity of a 2 wt% aqueous solution was 15
00 mPa · s) was dispersed. The dispersion solution was cooled to 30 ° C. (in this state, the polymer was not dissolved and was in a dispersed state), and the autoclave equipped with a stirrer having an internal volume of 1.5 L was filled and sealed. After degassing with a vacuum pump for 30 minutes while stirring in this state, the autoclave was cooled to 15 ° C. The vacuum line was switched to the carbon dioxide gas supply line, and 0.2 MPa carbon dioxide gas was supplied to the autoclave from the carbon dioxide gas cylinder. Carbon dioxide was dissolved over time and the pressure in the autoclave dropped, so carbon dioxide was appropriately supplied to return the pressure to 0.2 MPa. FIG. 2 shows the relationship between the mass of carbon dioxide gas absorbed in the aqueous solution and the time, which was obtained from the change in the gas space volume of the autoclave and the pressure change. It can be seen that 4 g or more of carbon dioxide gas was dissolved in 30 minutes. Carbon dioxide was dissolved for 4 hours, the autoclave was opened, and the aqueous solution was stored in a PET bottle. The aqueous solution foamed considerably at the same time when the autoclave was opened, and the dissolution of the polymer was not completely completed but was in a semitransparent state. PET
When the bottle was stored in the refrigerator overnight, the dissolution of the polymer proceeded to give a transparent solution. A part of this solution was placed in a test tube and the thickening behavior was investigated while raising the temperature in a constant temperature water bath.
A sharp increase in viscosity was observed from around ℃, so the sol-gel transition temperature was set to 30 ℃.
【0034】実施例8
実施例7で調整した炭酸経皮吸収用組成物をシャーレ
(開放面積:56.7cm2)に40ml広げ室温(約1
8℃)で空気中に放置してPHの経持変化を追跡した。
比較のために同じ条件で炭酸水、ブランクテストとして
水道水についても行った。結果を表4に示した。本発明
の炭酸経皮吸収用組成物の方が炭酸水に比べてPHの変
化速度が小さく炭酸ガスの逃散速度が遅いことが解る。Example 8 40 ml of the composition for percutaneous absorption of carbonic acid prepared in Example 7 was spread on a petri dish (open area: 56.7 cm 2) at room temperature (about 1
It was left to stand in the air at 8 ° C.) and the change with time of PH was traced.
For comparison, carbonated water was also used under the same conditions, and tap water was used as a blank test. The results are shown in Table 4. It can be seen that the composition for percutaneous absorption of carbonic acid of the present invention has a smaller change rate of PH and a lower escape rate of carbon dioxide than carbonated water.
【0035】実施例9
実施例7と同様にして炭酸経皮吸収用組成物を調整し
た。但し、本実験では硫酸ナトリウムに加えて2wt%
のトレハロースを添加した水溶液に実施例7と同様にし
てメチルセルロースを分散して炭酸ガスを溶解させた。
炭酸ガスの溶解曲線は実施例7とほぼ同様であった。ま
た、この溶液のゾルーゲル転移温度は30℃であり、P
Hは4.5であった。冷蔵庫に保管したこの炭酸経皮吸
収用組成物を30℃の雰囲気に半日放置することで増粘
させて、実施例2と同様にして皮膚の赤化テストを行っ
た。比較のために炭酸水についても行った。この実験で
は皮膚への貼付時間を5、10,20,30分と変えて
時間経過を観察した。結果を表5に示した。この結果よ
り、炭酸水の場合時間が経過すると炭酸ガスの逃散によ
り赤化が消滅するが、本発明の炭酸経皮吸収用組成物の
場合30分経過しても赤化現象が見られることが解っ
た。Example 9 A composition for transdermal absorption of carbonic acid was prepared in the same manner as in Example 7. However, in this experiment, in addition to sodium sulfate, 2 wt%
In the same manner as in Example 7, methyl cellulose was dispersed in the aqueous solution containing trehalose of Example 1 to dissolve carbon dioxide gas.
The dissolution curve of carbon dioxide was almost the same as in Example 7. The sol-gel transition temperature of this solution is 30 ° C, and P
H was 4.5. The composition for percutaneous absorption of carbonic acid stored in a refrigerator was left in an atmosphere of 30 ° C. for half a day to increase the viscosity, and a skin reddening test was conducted in the same manner as in Example 2. Carbonated water was also used for comparison. In this experiment, the time of application was changed to 5, 10, 20, 30 minutes and the time course was observed. The results are shown in Table 5. From these results, it was found that in the case of carbonated water, the reddening disappears due to the escape of carbon dioxide over time, but in the case of the composition for transdermal absorption of carbonate of the present invention, the reddening phenomenon is observed even after 30 minutes. .
【0036】実施例10
硫酸ナトリウムの代わりに炭酸水素ナトリウムの5wt
%水溶液を調整して、実施例7と同様にしてメチルセル
ロースの分散液を調整し、同じく炭酸ガスを溶解させ
た。炭酸ガスの溶解曲線を図2に示した。図2からこの
水溶液には炭酸ガスは30分間で5g以上の溶解を示し
た。4時間の溶解後、溶液は半透明状態でオートクレー
ブの開放に伴ってかなりの発泡が見られた。実施例7と
同様にPETボトルに水溶液を入れて冷蔵庫に1夜保管
すると透明な溶液が得られた。この溶液のPHは7.3
であり、ゾル−ゲル転移温度は32℃であった。冷蔵庫
に保管していた溶液を35℃の雰囲気に半日放置して増
粘させた後、赤化テストを実施例9と同様に行なったと
ころ5−30分の貼付時間で皮膚の赤化が認められた。Example 10 5 wt% of sodium hydrogen carbonate instead of sodium sulfate
% Aqueous solution, a methylcellulose dispersion was prepared in the same manner as in Example 7, and carbon dioxide gas was also dissolved. The dissolution curve of carbon dioxide is shown in FIG. From FIG. 2, 5 g or more of carbon dioxide was dissolved in this aqueous solution in 30 minutes. After dissolution for 4 hours, the solution was translucent and considerable foaming was observed with the opening of the autoclave. A transparent solution was obtained by putting the aqueous solution in a PET bottle and storing it in the refrigerator overnight as in Example 7. The pH of this solution is 7.3.
And the sol-gel transition temperature was 32 ° C. The solution stored in the refrigerator was left to stand in an atmosphere of 35 ° C. for half a day to be thickened, and then a reddish test was conducted in the same manner as in Example 9. When the patching time was 5 to 30 minutes, reddening of the skin was observed. .
【0037】実施例11
料理用市販ゼラチンを用いて2wt%の水溶液1Kgを
調整した。この水溶液をオートクレーブにいれて30℃
で攪拌しながら30分減圧状態に真空ポンプで保った。
次いで0.2MPaの炭酸ガスをボンベから導入して1
時間加圧した。その間、炭酸ガスがゼラチン溶液に吸収
されるためオートクレーブの圧力が低下するたびに圧力
を0.2MPaに戻した。オートクレーブの空間と炭酸
ガスの減圧度から計算したゼラチン水溶液に吸収された
炭酸ガスの量は全部で800ppmであった。また、こ
のゼラチン水溶液のPHは5.5であった。このゼラチ
ン水溶液は室温(約20℃)で放置するとゲル化を起こ
した。このゼラチン水溶液を30℃の温水に浸漬してゾ
ル状態とし実施例2と同様にして皮膚の赤化テストを行
った結果、皮膚に貼付した時間を5分、10分、20分
と変化させたが、いずれの時間も赤化が認められた。Example 11 1 kg of a 2 wt% aqueous solution was prepared using commercially available gelatin for cooking. Put this aqueous solution in an autoclave at 30 ℃
The mixture was kept under reduced pressure for 30 minutes with a vacuum pump while being stirred.
Then, introduce carbon dioxide gas of 0.2 MPa from the cylinder to obtain 1
Pressurized for hours. During that time, carbon dioxide was absorbed by the gelatin solution, so that the pressure was returned to 0.2 MPa each time the pressure in the autoclave decreased. The total amount of carbon dioxide gas absorbed in the aqueous gelatin solution calculated from the space of the autoclave and the degree of decompression of carbon dioxide gas was 800 ppm in total. The pH of this gelatin aqueous solution was 5.5. This gelatin aqueous solution caused gelation when left at room temperature (about 20 ° C.). This gelatin aqueous solution was dipped in warm water at 30 ° C. to be in a sol state, and the skin redness test was conducted in the same manner as in Example 2. As a result, the time of application to the skin was changed to 5 minutes, 10 minutes and 20 minutes. , Redness was observed at all times.
【0038】実施例12
実施例11で調整した炭酸ガスを溶解したゼラチン水溶
液を室温(約20℃)でゲル化させそのゲルをシュパチ
ュラで掬い取りシャーレ上に広げて空気中に放置して炭
酸ガスの逃散速度をPH変化で調べた。比較のために炭
酸水についても同じ条件でPHの変化を調べた。結果を
表6に示したがゲルの場合、炭酸水に比べてPHの変化
が小さく炭酸ガスの逃散速度が小さいことが解った。Example 12 The aqueous gelatin solution prepared by dissolving carbon dioxide prepared in Example 11 was gelled at room temperature (about 20 ° C.), the gel was scooped with a spatula, spread on a petri dish, and allowed to stand in the air for carbon dioxide. The escape rate was examined by the change in pH. For comparison, the changes in PH were also examined for carbonated water under the same conditions. The results are shown in Table 6, and it was found that in the case of gel, the change in PH was small and the escape rate of carbon dioxide was small as compared with carbonated water.
【0039】実施例13
実施例11と同様にしてゼラチン水溶液に炭酸ガスを吸
収させた。但し、この実験では0.2MPaの炭酸ガス
を2時間加圧供給し、1500ppmの炭酸ガスを吸収
させたがその時のPHは4.8であった。この炭酸ガス
を溶解したゼラチン水溶液をゾル状態で100mm角、
厚み3mmのフェルト状シートの上にコーティングし
た。ゾル溶液はフェルトの内部に浸透したが表面には2
mm程度の溶液が残る状態にして直ちに2℃に保たれた
冷蔵庫の中でゲル化させた。ゲル化後のシート状物は取
り扱いが容易で鋏で任意の大きさに切断できるものであ
った。鋏みで幅15mm、長さ30mmに切断し腕の内
側の皮膚に貼付して皮膚の赤化度合いを観察した。貼付
時間を5、10、20分と変更したが5分では赤化は見
られず、10分後から観察された。Example 13 Carbon dioxide gas was absorbed in an aqueous gelatin solution in the same manner as in Example 11. However, in this experiment, 0.2 MPa carbon dioxide gas was supplied under pressure for 2 hours to absorb 1500 ppm carbon dioxide gas, but the PH at that time was 4.8. The gelatin aqueous solution in which this carbon dioxide gas is dissolved is 100 mm square in a sol state,
It was coated on a felt-like sheet having a thickness of 3 mm. The sol solution penetrated inside the felt, but 2 on the surface.
The solution of about mm was left and immediately gelled in a refrigerator kept at 2 ° C. The sheet-like material after gelation was easy to handle and could be cut into arbitrary sizes with scissors. The scissors were cut into a piece having a width of 15 mm and a length of 30 mm and attached to the skin inside the arm to observe the degree of reddening of the skin. The application time was changed to 5, 10 and 20 minutes, but no reddishness was observed at 5 minutes and it was observed after 10 minutes.
【0040】[0040]
【表1】 [Table 1]
【表2】 [Table 2]
【表3】 [Table 3]
【表4】 [Table 4]
【表5】 [Table 5]
【表6】 [Table 6]
【0041】[0041]
【発明の効果】本発明の炭酸経皮吸収用組成物からなる
化粧水は高濃度の炭酸ガスを含むためPHが低下するが
トレハロースの作用で刺激性が緩和され、炭酸ガスの血
行促進作用に基づいて顔の皮膚の健康促進、美容(潤い
のある肌、美白、にきび等吹き出物の解消等)、ひび割
れの改善などを達成することが出来た。また、水溶性高
分子の相転移現象を利用することにより高濃度の炭酸ガ
スを含み且つ使用時に空気中への炭酸ガスの逃散の少な
い炭酸経皮吸収用組成物が得られるため人体の患部に塗
布ないしは貼付して血行促進による治癒が期待される。The lotion containing the composition for percutaneous absorption of carbonic acid of the present invention contains a high concentration of carbon dioxide gas, so that the pH is lowered, but the stimulant effect is mitigated by the action of trehalose, and the blood circulation promoting action of carbon dioxide gas is enhanced. Based on this, we were able to achieve health promotion of facial skin, beauty (moisturized skin, whitening, elimination of acne such as acne), and improvement of cracks. Further, by utilizing the phase transition phenomenon of the water-soluble polymer, it is possible to obtain a composition for transdermal absorption of carbon dioxide which contains a high concentration of carbon dioxide and has little escape of carbon dioxide into the air at the time of use. It is expected to cure by promoting blood circulation by applying or attaching.
【図1】第1図は参考例として示す炭酸水の炭酸ガス濃
度とPHの関係を示す図である。FIG. 1 is a diagram showing the relationship between the carbon dioxide concentration of carbonated water and PH shown as a reference example.
【図2】第2図はオートクレーブを用いての炭酸ガスの
水溶液への溶解曲線である。FIG. 2 is a dissolution curve of carbon dioxide gas in an aqueous solution using an autoclave.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成14年8月8日(2002.8.8)[Submission date] August 8, 2002 (2002.8.8)
【手続補正1】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】特許請求の範囲[Name of item to be amended] Claims
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【特許請求の範囲】[Claims]
【手続補正2】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】0004[Correction target item name] 0004
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【0004】[0004]
【課題を解決するための手段】本発明の第1は遊離炭酸
を300ppm以上2000ppm以下含み、且つトレ
ハロースを必須成分として含む実質的に気泡状の炭酸ガ
スを含まない水溶液からなることを特徴とする炭酸経皮
吸収用組成物である。また、この組成物を化粧水として
用いる場合はそのPH(水素イオン濃度)が4.5以上
5.0未満であることが好ましい。本発明の第2は少な
くとも水、水溶性高分子、遊離炭酸からなる組成物であ
って、該組成物中の遊離炭酸は濃度が300ppm以上
2000ppm以下であり、実質的に気泡状では存在せ
ずに溶解状態で存在してなる炭酸経皮吸収用組成物にお
いて、前記組成物がゾルーゲル転移又はゲルーゾル転移
(以下相転移と略す)を示し、その転移温度が0℃以
上、45℃未満の範囲にあることを特徴とする炭酸経皮
吸収用組成物である。本発明の第3は少なくとも水、水
溶性高分子、遊離炭酸からなる組成物であって、該組成
物中の遊離炭酸は濃度が300ppm以上2000pp
m以下であり、実質的に気泡状では存在せずに溶解状態
で存在してなるゲル状の炭酸経皮吸収用組成物である。
第2、第3発明においてトレハロースを必須成分として
含む炭酸経皮吸収用組成物が好ましい。本発明の第4は
上記の炭酸経皮吸収用組成物がシート状支持体に含浸又
は/及びコーティングされてなる炭酸経皮吸収用シート
状物である。本発明の第5は炭酸経皮吸収用組成物の使
用方法において、使用時に該組成物を相転移させること
により組成物の粘度を変化させて使用することを特徴と
する炭酸経皮吸収用組成物の使用方法である。この使用
方法において組成物の相転移を温度又は/及び添加剤で
行うことが好ましい。本発明の第6は炭酸経皮吸収用組
成物の製造方法において、炭酸ガスを含まない組成物原
料水溶液を調整し、次いで前記原料水溶液に300pp
m以上の炭酸ガスを加圧溶解させて炭酸経皮吸収用組成
物を調整し、次いで前記組成物を密閉容器に充填するこ
とを特徴とする炭酸経皮吸収用組成物の製造方法であ
る。この製造方法において精密ろ過器と膜式炭酸ガス溶
解器が接続された装置を用いて異物のろ過と炭酸ガスの
溶解を連続して行うことが好ましい。また、炭酸ガスを
溶解させる装置としてスタティックミキサーを用いて原
料水溶液に炭酸ガスを溶解させる方法も好ましい。本発
明の第7は熱ゲル化特性を示す水溶性高分子を用いて炭
酸経皮吸収用組成物を製造する方法において、前記水溶
性高分子をゲル化温度以上で水又は水溶液に分散し、次
いで前記分散液を冷却し又は冷却しながら炭酸ガスを溶
解させることを特徴とする炭酸経皮吸収用組成物の製造
方法である。The first aspect of the present invention is characterized by comprising an aqueous solution containing free carbonic acid in an amount of 300 ppm or more and 2000 ppm or less and containing trehalose as an essential component and substantially free of carbon dioxide gas. A composition for transdermal absorption of carbonic acid. When this composition is used as a lotion, its PH (hydrogen ion concentration) is preferably 4.5 or more and less than 5.0. A second aspect of the present invention is a composition comprising at least water, a water-soluble polymer and free carbonic acid, wherein the free carbonic acid has a concentration of 300 ppm or more.
In the composition for percutaneous absorption of carbonic acid, which is 2000 ppm or less and is present in a dissolved state without being substantially in the form of bubbles, the composition exhibits a sol-gel transition or a gel-sol transition (hereinafter abbreviated as phase transition), The composition for transdermal absorption of carbonic acid is characterized in that its transition temperature is in the range of 0 ° C or higher and lower than 45 ° C. A third aspect of the present invention is a composition comprising at least water, a water-soluble polymer, and free carbonic acid, wherein the free carbonic acid in the composition has a concentration of 300 ppm or more and 2000 pp.
It is a gel-like composition for percutaneous absorption of carbonic acid in the form of gel, which is m or less , and is present in a dissolved state without being substantially present in the form of bubbles.
In the second and third inventions, a composition for percutaneous absorption of carbonic acid containing trehalose as an essential component is preferable. A fourth aspect of the present invention is a carbonic acid percutaneous absorption sheet-shaped product obtained by impregnating and / or coating the above-mentioned carbonic acid percutaneous absorption composition on a sheet-shaped support. A fifth aspect of the present invention is a method for using a composition for percutaneous absorption of carbonic acid, which comprises changing the viscosity of the composition by phase transition of the composition at the time of use. How to use things. In this method of use, the phase transition of the composition is preferably carried out at temperature and / or additives. A sixth aspect of the present invention is a method for producing a composition for percutaneous absorption of carbonic acid, which comprises preparing a carbon dioxide-free composition raw material aqueous solution and then adding 300 pp to the raw material aqueous solution.
A method for producing a composition for percutaneous absorption of carbonic acid, which comprises dissolving carbonic acid gas of m or more under pressure to prepare a composition for percutaneous absorption of carbonic acid, and then filling the composition into a closed container. In this manufacturing method, it is preferable to continuously filter the foreign matter and dissolve the carbon dioxide gas using an apparatus in which a microfilter and a membrane carbon dioxide gas dissolver are connected. In addition, carbon dioxide
Using a static mixer as a device for melting,
A method of dissolving carbon dioxide gas in the aqueous solution is also preferable. A seventh aspect of the present invention is a method for producing a carbonic acid percutaneous absorption composition using a water-soluble polymer having a thermogelling property, wherein the water-soluble polymer is dispersed in water or an aqueous solution at a gelling temperature or higher, Then, a method for producing a composition for percutaneous absorption of carbonic acid, which comprises cooling the dispersion or dissolving carbon dioxide while cooling.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 鎌田 健資 広島市東区曙2丁目8番3 (72)発明者 中濱 哲郎 広島市東区曙2丁目8番3 Fターム(参考) 4C083 AB051 AB052 AB131 AB132 AB272 AB352 AC122 AC302 AC582 AC682 AC842 AD211 AD212 AD332 AD412 BB36 CC04 DD12 DD23 DD41 DD42 EE06 EE10 EE12 EE14 EE16 FF01 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kensuke Kamata 2-8-3 Akebono, Higashi-ku, Hiroshima-shi (72) Inventor Tetsuro Nakahama 2-8-3 Akebono, Higashi-ku, Hiroshima-shi F-term (reference) 4C083 AB051 AB052 AB131 AB132 AB272 AB352 AC122 AC302 AC582 AC682 AC842 AD211 AD212 AD332 AD412 BB36 CC04 DD12 DD23 DD41 DD42 EE06 EE10 EE12 EE14 EE16 FF01
Claims (11)
レハロースを必須成分として含む実質的に気泡状の炭酸
ガスを含まない水溶液からなることを特徴とする炭酸経
皮吸収用組成物。1. A composition for percutaneous absorption of carbonic acid, which comprises an aqueous solution containing 300 ppm or more of free carbonic acid and containing trehalose as an essential component and substantially free of carbon dioxide gas in the form of bubbles.
る請求項1の炭酸経皮吸収用組成物からなる化粧水。2. A lotion comprising the composition for percutaneous absorption of carbonic acid according to claim 1, which has a PH (hydrogen ion concentration) of less than 5.0.
らなる組成物であって、該組成物中の遊離炭酸は濃度が
300ppm以上であり、実質的に気泡状では存在せず
に溶解状態で存在してなる炭酸経皮吸収用組成物におい
て、前記組成物がゾルーゲル転移又はゲルーゾル転移
(以下相転移と略す)を示し、その転移温度が0℃以
上、45℃未満の範囲にあることを特徴とする炭酸経皮
吸収用組成物。3. A composition comprising at least water, a water-soluble polymer, and free carbonic acid, wherein the free carbonic acid has a concentration of 300 ppm or more, and does not substantially exist in the form of bubbles and is in a dissolved state. In the composition for transdermal absorption of carbonic acid, the composition exhibits a sol-gel transition or a gel-sol transition (hereinafter abbreviated as phase transition), and the transition temperature is in the range of 0 ° C or higher and lower than 45 ° C. A characteristic composition for transdermal absorption of carbonic acid.
らなる組成物であって、該組成物中の遊離炭酸は濃度が
300ppm以上であり、実質的に気泡状では存在せず
に溶解状態で存在してなるゲル状の炭酸経皮吸収用組成
物。4. A composition comprising at least water, a water-soluble polymer and free carbonic acid, wherein the free carbonic acid has a concentration of 300 ppm or more, and does not substantially exist in the form of bubbles and is in a dissolved state. 1. A gel-like composition for percutaneous absorption of carbonic acid, which is present in 1.
特徴とする請求項3.又は4.の炭酸経皮吸収用組成
物。5. A trehalose is contained as an essential component. Or 4. A composition for transdermal absorption of carbonic acid.
物がシート状支持体に含浸又は/及びコーティングされ
てなる炭酸経皮吸収用シート状物。6. The method according to claim 1. To 5. A sheet-like material for percutaneous absorption of carbonic acid, which is obtained by impregnating and / or coating a sheet-like support with the composition for percutaneous absorption of carbonic acid.
て、使用時に該組成物を相転移させることにより組成物
の粘度を変化させて使用することを特徴とする炭酸経皮
吸収用組成物の使用方法。7. A method for using a composition for percutaneous absorption of carbonic acid, wherein the composition is used by changing the viscosity of the composition by phase transition during use. How to use.
行うことを特徴とする請求項7.の使用方法。8. The composition according to claim 7, wherein the phase transition of the composition is carried out at a temperature and / or an additive. How to use.
て、炭酸ガスを含まない組成物原料水溶液を調整し、次
いで前記原料水溶液に300ppm以上の炭酸ガスを加
圧溶解させて炭酸経皮吸収用組成物を調整し、次いで前
記組成物を密閉容器に充填することを特徴とする炭酸経
皮吸収用組成物の製造方法。9. A method for producing a composition for percutaneous absorption of carbonic acid, which comprises preparing an aqueous solution of a raw material for a composition which does not contain carbon dioxide, and then dissolving 300 ppm or more of carbon dioxide in the aqueous solution of the raw material under pressure to transdermally absorb carbonic acid. A method for producing a composition for percutaneous absorption of carbonic acid, which comprises preparing a composition for oral use, and then filling the composition in a closed container.
された装置を用いて異物のろ過と炭酸ガスの溶解を連続
して行うことを特徴とする請求項9.の製造方法。10. The filtration of foreign substances and the dissolution of carbon dioxide are continuously carried out by using a device in which a microfilter and a membrane carbon dioxide dissolver are connected. Manufacturing method.
て炭酸経皮吸収用組成物を製造する方法において、前記
水溶性高分子をゲル化温度以上で水又は水溶液に分散
し、次いで前記分散液を冷却し又は冷却しながら炭酸ガ
スを溶解させることを特徴とする炭酸経皮吸収用組成物
の製造方法。11. A method for producing a composition for percutaneous absorption of carbonic acid using a water-soluble polymer having a heat gelling property, wherein the water-soluble polymer is dispersed in water or an aqueous solution at a gelation temperature or higher, and then A method for producing a composition for percutaneous absorption of carbonic acid, which comprises cooling the dispersion or dissolving carbon dioxide while cooling.
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JP2005314379A (en) * | 2004-03-30 | 2005-11-10 | Hiromaito Co Ltd | Pack agent for cosmetic use and method for using the same |
JP2006068082A (en) * | 2004-08-31 | 2006-03-16 | Kao Corp | Sheet medication to be pasted to body |
JP2006089459A (en) * | 2004-08-24 | 2006-04-06 | Kao Corp | Sheet-like composition |
JP2007077035A (en) * | 2005-09-12 | 2007-03-29 | Hiromaito Co Ltd | Reducing aqueous composition |
JP2007269692A (en) * | 2006-03-31 | 2007-10-18 | Pola Chem Ind Inc | Cosmetic material for softening skin |
CN102462630A (en) * | 2010-11-01 | 2012-05-23 | 上海家化联合股份有限公司 | Aerosol composition for improving blood circulation |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005314379A (en) * | 2004-03-30 | 2005-11-10 | Hiromaito Co Ltd | Pack agent for cosmetic use and method for using the same |
JP2006089459A (en) * | 2004-08-24 | 2006-04-06 | Kao Corp | Sheet-like composition |
JP2006068082A (en) * | 2004-08-31 | 2006-03-16 | Kao Corp | Sheet medication to be pasted to body |
JP2007077035A (en) * | 2005-09-12 | 2007-03-29 | Hiromaito Co Ltd | Reducing aqueous composition |
JP2007269692A (en) * | 2006-03-31 | 2007-10-18 | Pola Chem Ind Inc | Cosmetic material for softening skin |
CN102462630A (en) * | 2010-11-01 | 2012-05-23 | 上海家化联合股份有限公司 | Aerosol composition for improving blood circulation |
JP2013018719A (en) * | 2011-07-08 | 2013-01-31 | Kao Corp | Cosmetic for promoting skin blood circulation |
JP2016049976A (en) * | 2014-08-28 | 2016-04-11 | 一夫 松村 | Electromagnetic wave radiation container and generation method of cleaning fluid using the same |
JP2019011262A (en) * | 2017-06-29 | 2019-01-24 | 日油株式会社 | Skin Cosmetic |
CN115335026A (en) * | 2020-04-07 | 2022-11-11 | 花王株式会社 | Method for producing water-containing gel article containing carbonic acid gas |
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