JP3668161B2 - Method for producing carbonic acid transdermal composition - Google Patents
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Description
【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。
【0002】
【従来の技術】
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。
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11−228334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。
【0003】
【発明が解決しようとする課題】
しかしながら、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という欠点があった。こ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。
【0004】
【課題を解決するための手段】
前記課題は、水、熱ゲル化特性を示す水溶性高分子、及び、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遊離炭酸からなる炭酸経皮吸収用組成物の製造方法であって、熱ゲル化特性を示す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て分散液を得、次いでこの分散液をゲル化温度未満に冷却した後又は冷却しながら炭酸ガスを溶解させることによって解決することができる。
【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0.88ml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。
【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。
【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。
【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。
【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。
【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。
【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。
【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DSC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。
【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37℃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。
【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。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。
【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。
【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。
【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。
【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5mm以下が取り扱い性から好ましい。
【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。
【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。
【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。
【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。ゲル化温度未満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未満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。
【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。
【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。
【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。
【0026】
参考例2
イオン交換水(DI水)を用いて参考例1と同様して1000ppm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。
【0027】
比較例1
参考例2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。各化粧水について参考例2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。
【0028】
参考例3
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。
【0029】
参考例4
参考例2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。
【0030】
参考例5
参考例2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。
【0031】
参考例6
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%
エタノール 3wt%
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参考例3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。
【0032】
参考例7
下記の組成を有する炭酸経皮吸収用組成物を参考例6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、59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。
【0033】
実施例1
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1500mPa・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。
【0034】
実施例2
実施例1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18℃)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。
【0035】
実施例3
実施例1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1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1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、PH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、参考例3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。
【0036】
実施例4
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1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1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3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。
【0037】
参考例8
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参考例3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。
【0038】
参考例9
参考例8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。
【0039】
参考例10
参考例8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2mm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。
【0040】
【表1】
【表2】
【表3】
【表4】
【表5】
【表6】
【0041】
【発明の効果】
本発明の炭酸経皮吸収用組成物によれば、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。
【図面の簡単な説明】
【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。
【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。[0001]
[Technical field to which the invention belongs]
TECHNICAL FIELD The present invention relates to a water-soluble composition containing a high concentration of soluble carbon dioxide gas, and percutaneous carbon dioxide absorption that can contact the human skin and effectively absorb the carbon dioxide gas through the skin to promote blood circulation of the skin. The present invention relates to a composition for skin, a lotion using the same, a sheet for carbon percutaneous absorption in which the composition is combined with a sheet-like support, and a method for using and manufacturing the same.
[0002]
[Prior art]
The blood circulation promoting effect of carbon dioxide increases as the concentration of carbon dioxide dissolved in cosmetics and packs (in the present invention, these are called carbonic percutaneous absorption compositions) increases. On the other hand, when only carbon dioxide gas is dissolved in water, it varies depending on the alkalinity of the water, but the pH decreases as shown in FIG.
It has been well known for a long time that water containing carbon dioxide gas promotes blood circulation in the human body, and in particular, bathing in carbonated springs has been practiced for a long time in order to improve blood circulation throughout the body. This is thought to be due to the increase and expansion of the capillary bed due to the permeation of carbon dioxide through the skin, and to promote blood circulation in the skin. It has been proposed to use such characteristics of carbon dioxide as a lotion, hair nourishing and hair restorer, and pack agent.
Japanese Patent Publication No. 3-14284 discloses a lotion having a pH of 5-6.5 and containing a predetermined amount of carbon dioxide. JP-A-60-215606 and JP-A-11-228334 disclose pack agents containing carbon dioxide and cosmetics with high viscosity.
[0003]
[Problems to be solved by the invention]
However,An aqueous solution containing a high concentration of carbon dioxide gas escapes into the air through a container during storage, or carbon dioxide gas immediately escapes from the aqueous solution into the air when used at normal pressure.ThatThere were drawbacks.This taskIs disclosed in the prior art, for example, Japanese Patent Application Laid-Open No. 11-228834, but is still not sufficient.
[0004]
[Means for Solving the Problems]
The subject is a method for producing a composition for percutaneous absorption of carbon dioxide comprising water, a water-soluble polymer exhibiting thermal gelation properties, and free carbonic acid that is present in a dissolved state without being substantially in the form of bubbles. A water-soluble polymer exhibiting thermal gelation characteristics is dispersed in water or an aqueous solution at a temperature equal to or higher than the gelation temperature to obtain a dispersion, and then the dispersion is cooled to a temperature lower than the gelation temperature or carbonated while being cooled. It can be solved by dissolving the gas.
[0005]
DETAILED DESCRIPTION OF THE INVENTION
Carbon dioxide (CO2) has a solubility of 0.88 (ml / ml water) in water at 20 ° C. and 1 atm (Encyclopedia of Chemistry). Carbon dioxide dissolved in water reacts with water to form carbonic acid (
The blood circulation promoting effect is not seen with bicarbonate ions or carbonate ions, and the state of carbon dioxide is required. As described above, about 0.88 ml of carbon dioxide gas at 1 atm is dissolved in 1 g of water, 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 the water constituting the composition. You can think of it as free carbonic acid.
[0006]
A method for producing a composition for percutaneous absorption of carbon dioxide containing a predetermined amount of free carbonic acid according to the present invention will be described in detail later. Carbon dioxide is directly pressurized and dissolved in water constituting the composition or an aqueous solution of the composition. Therefore, the technology that generates carbon dioxide by the reaction of carbonate and organic acid used as a bathing agent in the past to stimulate the action of carbon dioxide bubbles and the blood circulation promoting action of carbon dioxide partially dissolved in water is essential. Is different.
Carbon dioxide gas can be dissolved in water by such a chemical reaction. However, since the reaction product remains in water, it is considered not preferable for skin sensitive use such as skin lotion. In order to distinguish from these techniques, the aqueous solution of the present composition is substantially free of cellular carbon dioxide. “Substantially” means that free carbonic acid once dissolved in water or an aqueous solution is generated as bubbles by changing the solubility of carbon dioxide due to stirring action, temperature, pressure fluctuation, etc., is included in the scope of the present invention. means.
[0007]
The blood circulation promoting action of the composition for percutaneous carbon dioxide absorption of the present invention can be examined as follows. Apply absorbent cotton or gauze with a carbon dioxide percutaneous absorption composition soaked for 5 to 10 minutes on areas with white skin, for example, on the inner side of the arm where the sunlight is not relatively exposed or on the knees of the feet. Observe the skin condition before and after. For comparison, a water soaked with pure water or tap water is attached next to it at the same time. After a predetermined time has passed, the attached absorbent cotton or the like is peeled off and the skin condition is observed. The composition for percutaneous absorption of carbon dioxide that exhibits a blood circulation promoting action makes the skin of the applied part red, and the comparison sample is not different from the state before attachment, so that it can be easily distinguished.
That is, the blood circulation promoting action referred to in the present invention means that the skin turns red in such a test. When the blood circulation promoting action was examined in this manner, it was revealed that the blood circulation promoting action was exhibited when the free carbonic acid concentration in the composition was 300 ppm or more, preferably 500 ppm or more. The upper limit of the free carbonic acid concentration is around 2000 ppm depending on the temperature at the time of use since the use of the composition for percutaneous absorption of carbonic acid is under atmospheric pressure. When carbon dioxide at a pressure of several atmospheres is injected into the aqueous solution, the above carbon dioxide can be dissolved in the aqueous solution according to Henry's law. The supersaturated carbon dioxide gas immediately escapes into the air.
[0008]
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 gas was measured using a carbon dioxide electrode. From this graph, the pH of carbonated water containing 300 ppm of carbon dioxide was 4.95. Therefore, in the present invention, 300 ppm or more of free carbonic acid is necessary as described above in order to make the blood circulation promoting effect function, 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 an action of dissolving sebum of the human body. 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 dissolves and the face becomes irritated. It was.
In order to eliminate this defect, 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 excellent is unclear, but it is assumed that trehalose is able to retain two molecules of water as crystal water and that its hygroscopic properties are unique. doing. In addition, trehalose has a lipid degradation inhibiting action and is expected to have an effect of preventing aging odor and body odor, and it is a preferred additive from this point of view for use in cosmetics. The amount of trehalose contained in the carbonic acid transdermal absorption composition 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% or less, from the feeling of use such as stickiness. When a percutaneous absorption composition containing 300 ppm or more of free carbonic acid and trehalose and having a pH of less than 5 is used as a lotion, blood circulation is promoted together with the astringent action of the skin due to weak acidity, coupled with the specific action of trehalose, It was discovered that a lotion that is less irritating and has many excellent effects such as moist feeling and whitening can be obtained.
[0009]
In addition to trehalose, known moisturizing ingredients and keratin softeners can be used in combination with the lotion of the present invention. Examples of moisturizing components include ethylene glycol, glycerin, propylene glycol, diethylene glycol, 1,3-butylene diol, 1,2-pentanediol, polyethylene glycol, polypropylene glycol, sorbitol and other polyhydric alcohols, and fatty acid esters of these polyhydric alcohols. And polysaccharides such as xylitol, amino acids, hyaluronic acid, elastin, collagen, chitin, chitosan derivatives and the like.
Among these, from the experience of use, amino acids or amino acid salts such as glycerin, serine and sodium glutamate, hyaluronic acid and salts thereof are preferable moisturizing ingredients. These moisturizing components may be used alone or in combination of two or more. Examples of the keratin softener include natural moisturizing factors such as amino acids, pyroglutamic acid, lactic acid, urea, and alkali metals, as well as lactate, triethanolamine, α-hydroxy acid, and the like.
[0010]
The carbonic percutaneous absorption composition and lotion of the present invention contain free carbonic acid and trehalose as essential components as described above, but in addition to the moisturizing component and keratin softener, known additives depending on the intended use Ingredients may be added. These additives include olive oil, cetyl alcohol, lanolin, stearyl alcohol and other softening agents, minerals, various nutrients, plant extract ingredients such as aloe and licorice, chlorella extract, seaweed extract, rosemary extract Whitening agents such as herbs such as chamomile extract and lavender extract, various fragrances, arbutin, vitamin C, and kojic acid.
In addition, retinoic acid, retinol, γ-aminobutyric acid, etc., which promote skin turnover and are expected to improve wrinkles, can be appropriately added depending on the application. Depending on the purpose of use, an anti-inflammatory agent such as glycyrrhizic acid can 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 during use. In addition, the skin lotion of the present invention contains free carbonic acid and thus has an antiseptic effect itself. However, when severe use conditions such as long-term storage at high temperatures are assumed, a preservative such as paraben or citric acid may be used. Antioxidants can also be added.
The addition amount of these additives should be as small as possible in order to provide a skin-friendly lotion that is the object of the present invention, that is, a lotion with few additives.
[0011]
Next, the carbon dioxide percutaneous absorption composition of the second invention and the third invention and the fifth invention relating to the method of using the same will be described including preferred embodiments thereof. A description of the same constituent elements as those in the first invention is omitted. Since the main purpose of the composition containing free carbonic acid according to the present invention is to be applied or pasted to a local part of the human body, the viscosity is preferably selected as appropriate depending on the form of use. On the other hand, considering that the rate of escape into the air due to the diffusion of carbon dioxide is inversely proportional to the viscosity of the composition, a higher viscosity is preferred. It is preferably at least 5 dPa · s at room temperature, preferably 10 dPa · s or more.
Such viscosity adjustment can be performed by changing the type of polymer, the degree of polymerization, and the concentration in an aqueous solution. In some cases, the viscosity can be changed by adding an inorganic or organic low-molecular salt to the aqueous polymer solution. The gel referred to in the present invention indicates a state where the viscosity is infinitely large and there is no fluidity, and the water-soluble polymer in the composition gels by forming a three-dimensional stitch structure by intermolecular interaction. Since the viscosity is infinitely large in the gel state, the escape of carbon dioxide from the composition is slow, which is suitable for storing the composition. However, since there is no fluidity at the time of use, coating and the like are difficult. Therefore, it is preferable to use the gel in a sol form.
In the present invention, the gel does not exhibit fluidity as described above, and the viscosity cannot be measured, which is different from what is generally referred to as a gel for cosmetics. In cosmetics, the state where the viscosity is high and can be scooped with a fingertip is called a gel, but this gel can measure the viscosity, and in the present invention, the state showing fluidity is defined as sol. So-called gels fall within the sol category in the present invention.
[0012]
In the present invention, the process of transition from sol to gel is called sol-gel transition, the opposite 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 the intermolecular interaction of the water-soluble polymer. The change in the intermolecular interaction is brought about by giving a physical and chemical action to the aqueous solution. As a physical action, it is preferable to change the temperature. The transition occurs depending on the temperature, that is, the transition temperature can be accurately determined by using an analytical instrument such as DSC or NMR, but in the present invention, it is simply determined by the following method. In the case of gelation or solification, it generally takes time to complete the transition because the entire viscosity of the system changes to lose fluidity or restore fluidity.
In the present invention, the temperature of the test tube containing the composition is changed in a constant temperature bath while observing the fluidity, that is, the temperature at which the viscosity change starts to occur, and the temperature at which the viscosity of the composition starts 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 a low molecular salt that dissolves well in an aqueous solution as an additive. In this case, the temperature of the aqueous solution is kept constant, a predetermined amount of an additive is added, and it is allowed to stand for a while, so that it can be confirmed by the above-mentioned test tube method whether to gel or sol. Since the transition temperature varies depending on the amount of the additive, the transition temperature of the aqueous solution containing a predetermined amount of the additive can be determined as described above.
[0013]
The transition temperature of the composition for percutaneous absorption of carbon dioxide of the present invention is 0 ° C. or higher and lower than 45 ° C., preferably 0-40 ° C., from the viewpoint of use in the human body. Compositions exhibiting a sol-gel transition in this temperature range exhibit so-called thermal gelation propertiesIt is a composition.
Composition of the present inventionIs produced by dissolving a water-soluble polymer in carbonated water or by dissolving carbon dioxide in a polymer aqueous solution, but in any case, the solubility of carbon dioxide in water is higher as the temperature is lower. There is. In the case of an aqueous solution, a lower viscosity is preferable because the diffusion rate of carbon dioxide into the aqueous solution is increased. Therefore, a polymer aqueous solution that shows a sol state at a low temperature and has a low viscosity can dissolve a high concentration of carbon dioxide in the composition. On the other hand, when the composition is stored, it is in a state of high viscosity, preferably a gel state, from the viewpoint of escape of carbon dioxide. Moreover, it is preferable that it can be adjusted to an appropriate viscosity in a sol state at the time of use.
It is preferable that these phase transitions can be easily performed, and in the present invention, it is preferable to carry out with an additive such as temperature and low molecular salt or a combination thereof. If the transition temperature is high, the composition needs to be at a high temperature in order to obtain a viscosity suitable for use, and carbon dioxide escapes from the composition, which is not preferable. Also from this viewpoint, the transition temperature is less than 45 ° C., preferably 40 ° C. or less. Most preferred is a composition having a transition temperature in the vicinity of 37 ° C., and when applied to the human body in a sol state, gelation proceeds at the body temperature and the escape of carbon dioxide into the air hardly occurs. From the practical viewpoint, the lower limit temperature is preferably 0 ° C. or higher when gelation or solification easily occurs when stored at the refrigerator temperature.
The situation is the same for a composition exhibiting a gel-sol transition, but it is necessary to carry out the preparation stage of the composition, that is, when dissolving carbon dioxide in an aqueous solution, in a sol state, and exhibit a transition temperature at a low temperature, preferably 35 ° C. or lower. Those are preferred.
[0014]
The water-soluble polymer of the composition of the present invention is a synthetic polymer, a natural polymer, a semi-synthetic polymer derived from a natural polymer as a raw material.Either is fine. HoweverNatural polymers and semi-synthetic polymers are preferred because they touch the human body. 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]
Methylcellulose is well known as a water-soluble polymer exhibiting a sol state at low temperatures and gelling properties at high temperatures. As synthetic polymers, poly-N-isopropylacrylamide, poly-N-vinylacetamide, poly-N-vinylisobutyramide, a copolymer of N-vinylisobutyramide and N-vinylacetamide, and the like are known. Methyl cellulose which is a semi-synthetic polymer is preferable from the viewpoint of use in the human body. In the case of methylcellulose, the transition temperature of the 2 wt% aqueous solution is 45 ° C. as measured by the method of the present invention, and it is preferable to add a low molecular salt to make the transition temperature less than 45 ° C. Examples of such salts include sodium salts such as sodium chloride, sodium sulfate, sodium carbonate, sodium bicarbonate, sodium citrate and the like.
A preferred embodiment of the present invention uses a water-soluble polymer exhibiting such a thermal gelation property, sufficiently dissolves carbon dioxide gas in an aqueous solution at low temperature and stores it in a sealed container, and if necessary, stores it in a refrigerator for use. In some cases, the closed container is left in an atmosphere of 30 to 40 ° C. to cause thickening due to gelation, and after adjusting the viscosity to be easy to apply, the container is opened and applied to a local part of the human body.
The thickening action accompanying gelation can also be performed by adding the above-mentioned low molecular salt to the composition at the time of use. This method requires stirring in order to dissolve the salt uniformly in the composition for percutaneous absorption of carbonic acid, but care must be taken because the carbon dioxide dissolved in the composition at that time escapes. By performing a salt that is easily dissolved and stirring at a low temperature in a short time, the viscosity change due to the phase transition of the composition can be achieved with minimum escape of carbon dioxide gas.
[0016]
On the other hand, a composition for percutaneous absorption of carbon dioxide that takes a gel state at a low temperature and shows a sol state at a high temperature is preferable because it can be stored in a gel state, so that escape of carbon dioxide from the composition can be minimized. For example, a composition for percutaneous absorption of carbonic acid comprising an aqueous solution of gelatin slightly changes depending on the gelatin concentration, but gelation occurs at about 25 ° C. or less in a 2 wt% aqueous solution. Therefore, if the carbon dioxide gas is dissolved in a sol state in the range of 25-30 ° C. and stored in a refrigerator at 25 ° C. or lower, for example, in a refrigerator, a carbon dioxide percutaneous absorption composition can be obtained in which almost no carbon dioxide escapes. At the time of use, this gel is heated to 30 ° C or higher to be sol and applied to the human body.Can be used.
[0017]
Since the compositions relating to the second and third inventions contain 300 ppm or more of carbon dioxide, PH may be lowered to 5 or less. In that case, it is preferable to add trehalose as described in the first invention in addition to water, free carbonic acid, and water-soluble polymer, since a composition for percutaneous absorption of carbon dioxide having excellent usability can be obtained even if PH is low. Furthermore, if necessary, various additives such as a moisturizing component, a keratin softening agent, and a drug described in the first invention can be added and used. The composition for percutaneous absorption of carbonic acid according to the present invention contains carbon dioxide at a high concentration, and when applied to a local part of the human body as shown in the following examples, it shows reddening of the skin even after 30 minutes and promotes blood circulation. It can be cured by applying it to an affected area where the escape rate of carbon dioxide in the air is slow and blood circulation needs to be promoted.
[0018]
Next, the fourth aspect of the present invention will be described. A composition that has a low viscosity and flows when it is applied to the human body, or a composition that gels at room temperature, is difficult to apply to a local part of the human body as it is. In such a case, the sheet-like support can be impregnated with the composition in a sol state, or a sheet-like article carrying the composition by coating can be applied to a local part of the human body. As the support, a flexible knitted fabric made of fibers, a woven fabric, a nonwoven 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 part of the human body or to prevent the composition from leaking to the outside, the support functioning as an impregnation layer of the composition and a support having a gas barrier function such as a polymer film. A composite support in which the bodies are combined can also be used. The thickness of the sheet-like support is preferably 5 mm or less from the viewpoint of handleability.
[0019]
Finally, the sixth and seventh inventions relating to the method for producing the carbonic percutaneous absorption composition of the present invention will be described. In the conventional manufacturing method, a cosmetic stock solution such as lotion or lotion is put in a pressure-resistant container, and the container is pressurized with carbon dioxide to produce a cosmetic containing carbon dioxide. Although this method seems simple as a manufacturing method at first glance, it is a cosmetic that dissolves a predetermined amount of carbon dioxide gas by dissolving the carbon dioxide gas injected under pressure in water or alcohol in the container. In order to dissolve the carbon dioxide gas, it is necessary to increase the pressure of the carbon dioxide gas. Therefore, the container has to have a sufficient pressure resistant structure. Further, since the dissolution of carbon dioxide gas occurs only from the surface of the liquid in contact with the gas, it takes a long time to dissolve the high concentration carbon dioxide gas.
The problem of time is that if carbon dioxide is injected under pressure and sealed, it will gradually dissolve, so it can be done while the product is being stored, but for that purpose the carbon dioxide gas occupies the container. It is necessary to secure enough space. Therefore, the amount of cosmetics in the container is inevitably reduced.
[0020]
In order to eliminate such drawbacks, the present inventors have proposed a carbon dioxide percutaneous absorption composition comprising a step of dissolving carbon dioxide in the composition and a filling of the obtained carbon dioxide-containing composition into a container as separate steps. A manufacturing method was invented. The step of dissolving carbon dioxide gas in the composition is preferable because it is only one step to prepare a composition raw material aqueous solution not containing carbon dioxide gas and bringing the aqueous solution into contact with carbon dioxide gas. 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 increases as the temperature decreases, it is preferably dissolved 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, a high-concentration carbon dioxide gas can be dissolved in a short time using a membrane carbon dioxide dissolver. As such a membrane type carbon dioxide gas dissolver, for example, one using a hollow fiber membrane disclosed in Japanese Patent No. 2810694 and Japanese Patent Laid-Open No. 7-779 is preferable because it has a large gas and liquid contact area. When a membrane-type carbon dioxide dissolver is used, a sterile filter for percutaneous absorption of carbon dioxide can be easily obtained by filtering bacteria and foreign substances by continuously providing a microfiltration device upstream or downstream thereof. .
[0021]
On the other hand, in the case of a relatively high viscosity 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 being stirred, and then the carbon dioxide gas is pressurized. Can be dissolved. Carbon dioxide gas can be supplied simply and preferably using a carbon dioxide gas cylinder, but solid carbon dioxide (dry ice) can be sealed together with an aqueous solution in an autoclave. Further, as a device for continuously dissolving carbon dioxide gas in an aqueous solution having a high viscosity, a method in which carbon dioxide gas 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. It is. The pressure of carbon dioxide gas is preferably in the range of 0.1-0.5 MPa.
Thus, the composition which melt | dissolved the carbon dioxide of 300 ppm or more is sealed and stored in various containers according to the objective, and is stored. The container is preferably one in which carbon dioxide gas hardly escapes through the wall of the container, and if it is made of plastic, a material having low gas permeability such as polyethylene terephthalate (PET), vinylidene chloride, and acrylonitrile copolymer is preferable. A laminate packaging material with a metal such as aluminum or a metal spray container if the viscosity is low is also a preferable container.
[0022]
When the composition contains a water-soluble polymer exhibiting thermal gelation characteristics, the polymer is preferably dispersed in water or an aqueous solution containing trehalose or a low molecular salt at a temperature equal to or higher than the gelation temperature. Gelation temperatureLess thanIn this case, the dissolution rate of the polymer is fast, the viscosity of the aqueous solution increases, and it is difficult to uniformly dissolve the polymer even at a concentration of several percent. On the other hand, when the dispersion is performed at a temperature equal to or higher than the gelation temperature, the polymer does not dissolve, so that the dispersion has a low viscosity and a uniform dispersion can be obtained. Gelation temperature of this dispersionLess thanA homogeneous polymer aqueous solution can be obtained by cooling with stirring at a temperature of 5 ° C.
Since the solubility of carbon dioxide gas increases as the temperature decreases, this homogeneous solution can be charged in a carbon dioxide dissolution apparatus in a cooled state to dissolve the carbon dioxide gas. Preferably, the carbon dioxide gas is added while cooling the uniform dispersion having a low viscosity. It is preferable to dissolve. The cooling temperature is 30 ° C. or lower, preferably 25 ° C. or lower, more preferably 20 ° C. or lower.
[0023]
The carbon dioxide concentration in the composition thus adjusted can be determined by several methods. The carbon dioxide electrode method and the chemical titration method using a standard reagent are effective for tap water or a liquid having a low viscosity, but cannot be used for a composition having a high viscosity. In the case of a high-viscosity composition containing a water-soluble polymer, in the present invention, the concentration was qualitatively determined from the mass of carbon dioxide absorbed in the composition in the carbon dioxide dissolution step and the blood circulation promoting action of the composition.
[0024]
The composition for transdermal absorption of carbonic acid of the present invention is a basic skin lotion used for facial skin health and beauty by promoting blood circulation, specifically moisturizing the skin, improving spots and freckles, acne Improvement, sunburn improvement, whitening effect, wrinkle improvement and the like. It can also be used as a hair-restoring agent by using it on the scalp due to the blood circulation promoting action of carbon dioxide, and as a keratin softening agent at sites where the stratum corneum such as the heel and elbow of the body is likely to develop. Furthermore, healing is expected for atopic dermatitis that is considered to be caused by dryness of the skin. In addition to having the above-mentioned effects as an esthetic product, a high-viscosity carbonic acid transdermal absorption composition promotes blood circulation in affected areas by applying or sticking to affected areas due to poor blood circulation, such as bed slippage affected areas of bedridden patients. 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]
Reference example 1
Carbonated water containing different concentrations of free carbonic acid was prepared with a hollow fiber membrane type carbon dioxide dissolver using tap water. 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 (ORION RESEARCH). The relationship between the carbon dioxide concentration of this carbonated water and the pH is shown in FIG.
[0026]
Reference example 2
Carbonated water containing 1000 ppm of free carbonic acid was prepared in the same manner as in Reference Example 1 using ion-exchanged water (DI water). A lotion was prepared by dissolving trehalose in this carbonated water in the amount shown in Table 1. The lotion had a pH of 4.6. 20 female subjects (age: 23-53 years old) who complain of dry skin using only this skin lotion and carbonated water without trehalose for comparison were given skin lotion twice daily in the morning and at night. A 20-day trial test was conducted. The number of people who complained of “irritation to the skin” such as tingling of the face as evaluation items, and the number of people who recognized the improvement effect of “moisturizing skin” 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 gas of the present invention is less irritating and has a skin moisturizing and whitening effect despite its low pH of 4.6.
[0027]
Comparative Example 1
Reference example 2Similarly, a lotion was prepared by adding 2 wt% of the moisturizer shown in Table 2 to DI water containing 1000 ppm of free carbonic acid. However, since the sodium hyaluronate solution has a large thickening effect, the addition amount was 3 wt% as a 1% aqueous solution. The pH of the lotion was 4.6. About each lotionReference example 2The same female 20 subjects were given to the face in the same manner, and a one-week trial test was conducted only for “stimulation to the skin” as an evaluation item. The results are summarized in Table 2.
[0028]
Reference example 3
In the same manner as in Reference Example 1, carbonated water in which carbon dioxide gas having different concentrations was dissolved in DI water was prepared. Trehalose was dissolved in each carbonated water so as to be 2 wt% to obtain a composition for percutaneous carbonate absorption. This composition was sufficiently impregnated into an absorbent cotton sheet having a length of 3 cm, a width of 1.5 cm, and a thickness of 3 mm, and applied to the white skin inside the arm for 5 minutes to observe the state of the skin. The results are summarized in Table 3.
[0029]
Reference example 4
Reference example 2In the same manner as above, carbonated water containing 1000 ppm of free carbonic acid was prepared, and the following compounds were added thereto to prepare lotion.
Glycerin 2wt%
Trehalose 0.5wt%
Sodium hyaluronate 0.03wt%
Citric acid 0.05wt%
This skin lotion was applied to the face of a female subject (aged 20-35 years old) having oily skin on the face twice daily in the morning and evening to observe the improvement of the skin. As a result, there were 8 subjects who showed improvement in pimples such as acne after 2 weeks.
[0030]
Reference Example 5
Reference example 2In the same manner as above, carbonated water containing 1000 ppm of free carbonic acid was prepared, and the following compounds were added thereto to prepare lotion.
Glycerin 5wt%
Trehalose 0.5wt%
Sodium hyaluronate 0.03wt%
Citric acid 0.05wt%
Kojic acid 0.5wt%
Ten female subjects (aged 30-50) who complain of dullness on their face were applied to the face every morning and evening to examine the effect of dullness improvement. As a result, there were 7 subjects who showed improvement in dullness after 2 weeks.
[0031]
Reference Example 6
1 kg of DI water containing the following composition was prepared to obtain raw lotion water.
Trehalose 1wt%
Glycerin 2.5wt%
L-serine 1wt%
Ethanol 3wt%
Bittern liquid (30% solution) 3wt%
This lotion raw water was passed through a device to which the microfilter and the carbon dioxide gas dissolver of Reference Example 1 were connected, and foreign matter filtration and carbon dioxide gas dissolution were simultaneously performed. 1000 ppm of carbon dioxide gas was dissolved in the obtained lotion (calculated from the amount of supplied carbon dioxide), and the pH was 4.8. About this lotionReference example 3When the skin redness test was performed in the same manner as described above, the skin turned red. Moreover, when skin irritation was tested on female subjects in the same manner as in Comparative Example 1, 3 out of 20 women complained of irritation.
[0032]
Reference Example 7
Carbon dioxide transdermal absorption composition having the following compositionReference Example 6Adjusted in the same way.
Trehalose 2wt%
Glycerin 2.5wt%
Urea 5wt%
Free carbonic acid 1500ppm
PH 4.5
This composition was applied to the right footpad every morning to a subject (male, 59 years old) who had dry and severe cracks in the footpad, and observed an improved state of cracking in the buttocks after bathing at night. Improvement of cracks was observed in about one week.
[0033]
Example 1
Sodium sulfate was dissolved in 1 kg of DI water to 3 wt%. This aqueous solution was heated to 50-60 ° C. to disperse methyl cellulose (catalog value of viscosity of 2 wt% aqueous solution is 1500 mPa · s). The dispersion solution was cooled to 30 ° C. (in this state, the polymer did not dissolve and was in a dispersed state), and filled in an autoclave equipped with a stirrer having an internal volume of 1.5 L and sealed. After deaeration 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 a carbon dioxide supply line, and carbon dioxide of 0.2 MPa was supplied to the autoclave from the carbon dioxide cylinder. Since the dissolution of carbon dioxide gas occurred with the passage of time and the pressure of the autoclave was lowered, carbon dioxide gas was appropriately supplied to return the pressure to 0.2 MPa.
FIG. 2 shows the relationship between the amount of carbon dioxide absorbed in the aqueous solution and the time determined from 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 as the autoclave was opened, and the dissolution of the polymer was not yet complete and was translucent. When the PET bottle was stored in the refrigerator overnight, dissolution of the polymer proceeded to give a transparent solution. A portion 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. As a result, a sudden thickening was observed from around 30 ° C, so the sol-gel transition temperature was 30 ° C.
[0034]
Example 2
Example 1The composition for percutaneous absorption of carbonic acid prepared in (1) was spread in a petri dish (open area: 56.7 cm 2) by 40 ml and allowed to stand in the air at room temperature (about 18 ° C.) to track changes in PH. For comparison, carbonated water was 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 according to the present invention has a lower change rate of PH and a slower escape rate of carbon dioxide than carbonated water.
[0035]
Example 3
Example 1The composition for percutaneous carbon dioxide absorption was prepared in the same manner as above. However, in this experiment, an aqueous solution containing 2 wt% trehalose in addition to sodium sulfate was added.Example 1In the same manner, methylcellulose was dispersed to dissolve carbon dioxide. The carbon dioxide dissolution curve isExample 1It was almost the same. Moreover, the sol-gel transition temperature of this solution was 30 degreeC, and PH was 4.5. The composition for percutaneous absorption of carbonic acid stored in the refrigerator is allowed to thicken by leaving it in an atmosphere of 30 ° C. for half a day,Reference example 3The skin redness test was conducted in the same manner as described above. For comparison, carbonated water was also used. In this experiment, the time elapsed was observed while changing the application time to the skin to 5, 10, 20, and 30 minutes. The results are shown in Table 5. From this result, it was found that redness disappears due to the escape of carbon dioxide gas in the case of carbonated water. .
[0036]
Example 4
Prepare a 5 wt% aqueous solution of sodium bicarbonate instead of sodium sulfate,Example 1In the same manner, a dispersion of methylcellulose was prepared, and carbon dioxide gas was similarly dissolved. The dissolution curve of carbon dioxide gas is shown in FIG. From FIG. 2, carbon dioxide gas dissolved in this aqueous solution at 5 g or more in 30 minutes. After 4 hours of dissolution, the solution was translucent and significant foaming was observed as the autoclave was opened.Example 1Similarly, a transparent solution was obtained when an aqueous solution was put in a PET bottle and stored in a refrigerator overnight. The pH of this solution was 7.3, and the sol-gel transition temperature was 32 ° C. The solution stored in the refrigerator is left to stand in an atmosphere of 35 ° C for half a day to increase the viscosity.Example 3When performed in the same manner, reddening of the skin was observed after 5-30 minutes.
[0037]
Reference Example 8
1 kg of a 2 wt% aqueous solution was prepared using a commercially available gelatin for cooking. This aqueous solution was placed in an autoclave and kept under reduced pressure for 30 minutes with a vacuum pump while stirring at 30 ° C. Next, 0.2 MPa of carbon dioxide gas was introduced from the cylinder and pressurized for 1 hour. Meanwhile, since the carbon dioxide gas was absorbed into the gelatin solution, the pressure was returned to 0.2 MPa each time the autoclave pressure decreased. The total amount of carbon dioxide absorbed in the gelatin aqueous solution calculated from the space of the autoclave and the degree of decompression of carbon dioxide was 800 ppm. The pH of this aqueous gelatin solution was 5.5. The gelatin aqueous solution gelled when left at room temperature (about 20 ° C.). This gelatin aqueous solution is immersed in warm water at 30 ° C. to form a sol state.Reference example 3As a result of performing a skin redness test in the same manner as described above, the time applied to the skin was changed to 5 minutes, 10 minutes, and 20 minutes, and redness was observed at any time.
[0038]
Reference Example 9
Reference Example 8The gelatin aqueous solution in which the carbon dioxide gas prepared in
[0039]
Reference Example 10
Reference Example 8In the same manner, carbon dioxide gas was absorbed in the gelatin aqueous solution. However, in this experiment, 0.2 MPa of carbon dioxide gas was supplied under pressure for 2 hours to absorb 1500 ppm of carbon dioxide gas, and the pH at that time was 4.8. This gelatin aqueous solution in which carbon dioxide gas was dissolved was coated on a felt sheet having a 100 mm square and a thickness of 3 mm in a sol state. The sol solution penetrated into the felt, but was gelled in a refrigerator kept at 2 ° C. with a solution of about 2 mm remaining on the surface. The sheet-like material after gelation was easy to handle and could be cut into any size with a scissors. The skin was cut to a width of 15 mm and a length of 30 mm and affixed to the skin inside the arm to observe the degree of redness of the skin. The affixing time was changed to 5, 10, and 20 minutes, but no redness was observed at 5 minutes and was observed after 10 minutes.
[0040]
[Table 1]
[Table 2]
[Table 3]
[Table 4]
[Table 5]
[Table 6]
[0041]
【The invention's effect】
According to the carbonate transdermal absorption composition of the present invention, the water-soluble polymerBy using the phase transition phenomenon, a carbon dioxide percutaneous absorption composition containing a high concentration of carbon dioxide gas and with little carbon dioxide escape to the air during use can be obtained. Expected to be cured by
[Brief description of the drawings]
FIG. 1 is a graph showing the relationship between the carbon dioxide concentration of carbonated water and PH shown as a reference example.
FIG. 2 is a dissolution curve of carbon dioxide gas in an aqueous solution using an autoclave.
Claims (2)
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JP2006089459A (en) * | 2004-08-24 | 2006-04-06 | Kao Corp | Sheet-like composition |
JP4719441B2 (en) * | 2004-08-31 | 2011-07-06 | 花王株式会社 | Sheet preparation for body patch |
JP5060032B2 (en) * | 2005-09-12 | 2012-10-31 | 株式会社ヒロマイト | Reducing aqueous composition |
JP4871624B2 (en) * | 2006-03-31 | 2012-02-08 | ポーラ化成工業株式会社 | Cosmetics for softening the skin |
JP2012097013A (en) * | 2010-11-01 | 2012-05-24 | Nisshin Kagaku Kk | Blood circulation promoting aerosol composition |
JP6006478B2 (en) * | 2011-07-08 | 2016-10-12 | 花王株式会社 | Skin circulation promoting cosmetics |
JP6410348B2 (en) * | 2014-08-28 | 2018-10-24 | 一夫 松村 | Method for generating cleaning liquid using electromagnetic irradiation container |
JP6844451B2 (en) * | 2017-06-29 | 2021-03-17 | 日油株式会社 | Skin cosmetics |
EP4134065A4 (en) * | 2020-04-07 | 2024-04-10 | Kao Corporation | Method for producing carbon dioxide-containing hydrogel article |
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CN103698500B (en) * | 2013-12-20 | 2016-01-27 | 上海执诚生物科技有限公司 | A kind of method strengthening stability of carbon dioxide detection reagent |
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