JP3566336B2 - pH-sensitive soluble microcapsules and cosmetics containing the same - Google Patents

Description

【００７８】
酵素が水系中では速やかに失活してしまうことは周知の事実であるが、以上の結果から、ｐＨ感受ＭＣ中に内包された各酵素は、緩衝液中で４０℃で保存しても失活は殆ど認められなかった。
【００７９】
試 験 例 ２
各ｐＨにおける放出量変化の測定（１）：
製造例１に従って製造したリパーゼ内包ｐＨ感受ＭＣについて、各ｐＨにおけるリパーゼの放出量の変化を調べた。 測定は、ｐＨ感受ＭＣを各ｐＨの緩衝液に分散して１０分経過後、濾過した濾液についてロウリー（Ｌｏｗｒｙ）法によりタンパク質を定量して行った。
【００８０】
この結果、ｐＨ感受ＭＣに内包されたリパーゼは、ｐＨ５．５で放出され始め、ｐＨ６．５ではすべてが放出された。
【００８１】
試 験 例 ３
各ｐＨにおける放出量変化の測定（２）：
製造例５に従って製造したＳＯＤ内包ｐＨ感受ＭＣについて、各ｐＨにおけるＳＯＤの放出量の変化を調べた。 測定は、試験例２と同様にしてロウリー（Ｌｏｗｒｙ）法によりタンパク質を定量して行った。
【００８２】
この結果、ＳＯＤはｐＨ６．０で放出され始め、ｐＨ５．５ではすべてが放出された。
【００８３】
試 験 例 ４
安 定 性 試 験 ：
製造例６および７において得られたビタミン類内包ｐＨ感受ＭＣの安定性を調べるため、４０℃に保持したｐＨ５．０のリン酸系緩衝液中における各ビタミン類の残存量を経時的に測定した。 また比較のため単品のビタミン類についても同様の測定を行った。 その結果を表２に示す。
【００８４】

【００８５】
アスコルビン酸類は、特に水系中で安定性を保証することは困難であることが知られている。 しかし、以上の結果から、ｐＨ感受ＭＣ中に内包されたアスコルビン酸類は、緩衝液中で４０℃で保存しても経時安定性の低下は全く認められないことが明かになった。
【００８６】
試 験 例 ５
各ｐＨにおける放出量変化の測定（３）：
製造例６に従って製造したリン酸Ｌ−アスコルビルマグネシウム内包ｐＨ感受ＭＣについて、各ｐＨにおけるリン酸Ｌ−アスコルビルマグネシウムの放出量の変化を調べた。 測定は、ｐＨ感受ＭＣを各ｐＨの緩衝液に分散して１０分経過後、濾過した濾液について吸光光度法によりリン酸Ｌ−アスコルビルマグネシウムを定量して行った。
【００８７】
この結果、ｐＨ感受ＭＣに内包されたリン酸Ｌ−アスコルビルマグネシウムは、ｐＨ５．５で放出され始め、ｐＨ６．５ではすべてが放出された。
【００８８】
試 験 例 ６
各ｐＨにおける放出量変化の測定（４）：
製造例１０に従って製造したアスコルビン酸内包ｐＨ感受ＭＣについて、各ｐＨにおけるアスコルビン酸の放出量の変化を調べた。 測定は、試験例５と同様にして吸光光度法によりアスコルビン酸を定量して行った。
【００８９】
この結果、アスコルビン酸はｐＨ６．０で放出され始め、ｐＨ５．５ではすべてが放出された。
【００９０】
実 施 例 １
Ｏ／Ｗ型乳液：
製造例１において得られたリパーゼ内包ｐＨ感受ＭＣを用い、下記の組成のＯ／Ｗ型乳液を調製した。 なお、乳液のｐＨは５．０であった。
【００９１】

【００９２】

【００９３】
（ 製 法 ）
Ａ． 成分（１１）に（６）〜（９）を加え、加熱混合し、７０℃に保つ（水相）。
Ｂ． 成分（１）〜（５）を加熱混合し、７０℃に保つ（油相）。
Ｃ． 上記Ｂを、先のＡに加えて混合し、均一に乳化した後、撹拌しながら冷却し、（１０）および（１２）を添加して均一に混合し乳液を得た。
【００９４】
得られた乳液中では、ｐＨ感受ＭＣは不溶であるが、皮膚に塗布すると皮膚のｐＨおよび皮膚上の水分の影響を受けて徐々にマイクロカプセルが溶解し、内包成分であるリパーゼが放出される。
【００９５】
実 施 例 ２
水乾両用ファンデーション：
製造例２において得られたリパーゼ内包ｐＨ感受ＭＣを用い、下記の組成のファンデーションを調製した。
【００９６】

【００９７】

【００９８】
（ 製 法 ）
成分（１）〜（８）を混合撹拌し、これに（９）〜（１４）の成分を加え均一に混合し、
粉砕処理した後に圧縮成型した。
【００９９】
本発明のパウダーファンデーション中では、ｐＨ感受ＭＣは不溶であるが、皮膚に塗布することで皮膚のｐＨおよび皮膚上の水分により徐々にマイクロカプセルが溶解し、内包成分であるリパーゼを放出する。
特に両用ファンデーションとして、スポンジに水を含ませて肌に塗布する使用法では、より好ましい効果が発揮される。
【０１００】
実 施 例 ３
二剤混合型化粧水：
製造例４において得られたＳＯＤ内包ｐＨ感受ＭＣを用い、下記の組成で二剤混合型化粧水を調製した。 なお、マイクロカプセルはパウダー部に配合し、ローション部のｐＨは６．５であった。
【０１０１】

【０１０２】

【０１０３】
（ 製 法 ）
パウダー部の組成（１）〜（４）を均一に撹拌し、混合することによりパウダーを 製造する。
また、ローション部の組成（１）〜（４）を均一に分散し、これを組成（５）〜（７）を 混合したものに添加しローションを製造する。
【０１０４】
本発明の二剤混合型化粧水は、使用時にパウダー１部をローション１０部に分散させ皮膚に適用するものであり、ローションを加えることでｐＨ感受ＭＣが溶解するため内包物であるＳＯＤを放出する。
【０１０５】
実 施 例 ４
クリーム状洗顔料：
製造例３において得られたプロテアーゼ内包ｐＨ感受ＭＣを用い、下記の組成でクリーム状洗顔料を調製した。 なお、クリーム状洗顔料のｐＨは５．５であった。
【０１０６】

【０１０７】
（ 製 法 ）
上記（１）〜（８）を加熱溶解し、混合した後、冷却し、脱泡して充填した。
【０１０８】
本発明のクリーム状洗顔料は、ｐＨが酸性側であるため、製品中ではプロテアーゼ内包ｐＨ感受ＭＣは実質上不溶であるが、洗浄時に手のひらにとり水分を含ませることで、また、皮膚上にのせることで、あるいは、すすぎを続けることで、ｐＨが中性になると内包成分であるプロテアーゼを放出する。
【０１０９】
実 施 例 ５
養 毛 料：
製造例１において得られたリパーゼ内包ｐＨ感受ＭＣを用い、下記の組成に基づき、養毛料を調製した。 なお、養毛料のｐＨは５．０である。
【０１１０】

【０１１１】
（ 製 法 ）
Ａ． 成分（３）、（４）を（１０）に混合溶解する。
Ｂ． 成分（１）、（２）、（５）〜（９）を混合溶解する。
Ｃ． 上記Ｂを先のＡに加えて混合撹拌し、ヘアリキッドタイプの養毛料を得た。
得られた養毛料中では、ｐＨ感受ＭＣは不溶であるが、頭皮のｐＨおよび頭皮上の水分の影響を受けて徐々にマイクロカプセルが溶解し、内包成分であるリパーゼが放出される。
【０１１２】
実 施 例 ６
二剤混合型化粧水：
製造例５において得られたＳＯＤ内包ｐＨ感受ＭＣを用い、下記の組成で二剤混合型化粧水を調製した。 なお、マイクロカプセルはパウダー部に配合し、ローション部のｐＨは５．０であった。
【０１１３】

【０１１４】

【０１１５】
（ 製 法 ）
パウダー部の組成（１）〜（４）を均一に撹拌し、混合することによりパウダーを 製造する。
また、ローション部の組成（１）〜（４）を均一に分散し、これを組成（５）〜（７）を 混合したものに添加しローションを製造する。
【０１１６】
本発明の二剤混合型化粧水は、使用時にパウダー１部をローション１０部で溶解させ皮膚に適用するものであり、ローションを加えることで全体のｐＨが酸性となり、ｐＨ感受ＭＣが溶解するため内包物であるＳＯＤを放出する。
【０１１７】
実 施 例 ７
Ｏ／Ｗ型乳液：
製造例６において得られたリン酸Ｌ−アスコルビルマグネシウム内包ｐＨ感受ＭＣを用い、下記の組成のＯ／Ｗ型乳液を調製した。 なお、乳液のｐＨは５．０であった。
【０１１８】

【０１１９】

【０１２０】
（ 製 法 ）
Ａ． 成分（１１）に（６）〜（９）を加え、加熱混合し、７０℃に保つ（水相）。
Ｂ． 成分（１）〜（５）を加熱混合し、７０℃に保つ（油相）。
Ｃ． 上記Ｂを、先のＡに加えて混合し、均一に乳化した後、撹拌しながら冷却し、（１０）および（１２）を添加して均一に混合し乳液を得た。
【０１２１】
得られた乳液中では、ｐＨ感受ＭＣは不溶であるが、皮膚に塗布すると皮膚のｐＨおよび皮膚上の水分の影響を受けて徐々にマイクロカプセルが溶解し、内包成分であるリン酸Ｌ−アスコルビルマグネシウムが放出される。
【０１２２】
実 施 例 ８
水乾両用ファンデーション：
製造例７において得られたアスコルビン酸内包ｐＨ感受ＭＣを用い、下記の組成のファンデーションを調製した。
【０１２３】

【０１２４】

【０１２５】
（ 製 法 ）
成分（１）〜（８）を混合撹拌し、これに（９）〜（１４）の成分を加え均一に混合し、粉砕処理した後に圧縮成型した。
【０１２６】
本発明のパウダーファンデーション中では、ｐＨ感受ＭＣは不溶であるが、皮膚に塗布することで皮膚のｐＨおよび皮膚上の水分により徐々にマイクロカプセルが溶解し、内包成分であるアスコルビン酸を放出する。
特に両用ファンデーションとして、スポンジに水を含ませて肌に塗布する使用法では、より好ましい効果が発揮される。
【０１２７】
実 施 例 ９
二剤混合型化粧水：
製造例９において得られたリン酸Ｌ−アスコルビルマグネシウム内包ｐＨ感受ＭＣを用い、下記の組成で二剤混合型化粧水を調製した。 なお、マイクロカプセルはパウダー部に配合し、ローション部のｐＨは６．５であった。
【０１２８】

【０１２９】

【０１３０】
（ 製 法 ）
パウダー部の組成（１）〜（４）を均一に撹拌し、混合することによりパウダーを 製造する。
また、ローション部の組成（１）〜（４）を均一に分散し、これを組成（５）〜（７）を 混合したものに添加しローションを製造する。
【０１３１】
本発明の二剤混合型化粧水は、使用時にパウダー１部をローション１０部に分散させ皮膚に適用するものであり、ローションを加えることでｐＨ感受ＭＣが溶解するため内包物であるリン酸Ｌ−アスコルビルマグネシウムを放出する。
【０１３２】
実 施 例 １０
クリーム状洗顔料：
製造例８において得られたＬ−アスコルビン酸硫酸エステル二ナトリウム内包ｐＨ感受ＭＣを用い、下記の組成でクリーム状洗顔料を調製した。 なお、クリーム状洗顔料のｐＨは５．５であった。
【０１３３】

【０１３４】
（ 製 法 ）
上記（１）〜（８）を加熱溶解し、混合した後、冷却し、脱泡して充填した。
【０１３５】
本発明のクリーム状洗顔料は、ｐＨが酸性側であるため、製品中ではＬ−アスコルビン酸硫酸エステル二ナトリウム内包ｐＨ感受ＭＣは実質上不溶であるが、洗浄時に手のひらにとり水分を含ませることで、また、皮膚上にのせることで、あるいは、すすぎを続けることで、ｐＨが中性になると内包成分であるＬ−アスコルビン酸硫酸エステル二ナトリウムを放出する。
【０１３６】
実 施 例 １１
養 毛 料：
製造例６において得られたリン酸Ｌ−アスコルビルマグネシウム内包ｐＨ感受ＭＣを用い、下記の組成に基づき、養毛料を調製した。 なお、養毛料のｐＨは５．０である。
【０１３７】

【０１３８】
（ 製 法 ）
Ａ． 成分（３）、（４）を（１０）に混合溶解する。
Ｂ． 成分（１）、（２）、（５）〜（９）を混合溶解する。
Ｃ． 上記Ｂを先のＡに加えて混合撹拌し、ヘアリキッドタイプの養毛料を得た。
得られた養毛料中では、ｐＨ感受ＭＣは不溶であるが、頭皮のｐＨおよび頭皮上の水分の影響を受けて徐々にマイクロカプセルが溶解し、内包成分であるリン酸Ｌ−アスコルビルマグネシウムが放出される。
【０１３９】
実 施 例 １２
二剤混合型化粧水：
製造例１０において得られたアスコルビン酸内包ｐＨ感受ＭＣを用い、下記の組成で二剤混合型化粧水を調製した。 なお、マイクロカプセルはパウダー部に配合し、ローション部のｐＨは５．０であった。
【０１４０】

【０１４１】

【０１４２】
（ 製 法 ）
パウダー部の組成（１）〜（４）を均一に撹拌し、混合することによりパウダーを 製造する。
また、ローション部の組成（１）〜（４）を均一に分散し、これを組成（５）〜（７）を 混合したものに添加しローションを製造する。
【０１４３】
本発明の二剤混合型化粧水は、使用時にパウダー１部をローション１０部で溶解させ皮膚に適用するものであり、ローションを加えることで全体のｐＨが酸性となり、ｐＨ感受ＭＣが溶解するため内包物であるアスコルビン酸を放出する。
【０１４４】
【発明の効果】
本発明のｐＨ感受ＭＣは、凝集や粒径のバラツキがなく、均一な粒径のマイクロカプセルとして得ることができ、内包量のコントロールが容易であるので、マイクロカプセルの品質を一定に保つことができ、従来のｐＨ感受ＭＣ以上に化粧料への添加が容易なものである。 同時に、粒径のばらつきのないマイクロカプセルを配合した本発明化粧料は、優れた使用感を有するものであり、利用度が高いものである。
【０１４５】
また、酵素やビタミン類等製品中で不安定であり、従来化粧料への配合が困難であった成分についても、多孔性粉体の細孔に取り込まれ、保持されるため、極めて安定した状態で配合することが可能であり、しかも得られた化粧料は長期間の保存においても分離や変性などの心配が少ないものである。
【０１４６】
更に、ｐＨ感受ＭＣの素材を種々選択することで、幅広い形態の化粧料への適用が可能となり、従来の化粧料に比べ配合成分の選択の自由度を広げることを可能とするものである。
また更に、皮膚に直接塗布する態様で使用する化粧料の場合、製品の安定化だけでなく、内包成分の徐放化により、長時間にわたり持続的効果をも期待できる。
以 上[0001]
[Industrial applications]
TECHNICAL FIELD The present invention relates to a pH-sensitive soluble microcapsule and a cosmetic containing the same, and more particularly, various active ingredients of cosmetics can be blended, and the encapsulated active ingredient is released by a change in pH. The present invention relates to a pH-sensitive dissolvable microcapsule which can be used and a cosmetic composition containing the microcapsule which has an excellent feeling in use.
[0002]
[Prior art and its problems]
Some of the active ingredients to be incorporated into cosmetics are unstable when added to products as they are, or adversely affect the physical properties of the products. This has been a bottleneck in incorporating into cosmetics.
[0003]
For example, enzymes and vitamins incorporated in cosmetics are very unstable in the formulation, and even a small amount of moisture often causes inactivation and decomposition, resulting in quality deterioration. In many cases, compounding was difficult. In addition, crude drug components containing tannins, flavonoids, and the like sometimes affect the physical properties of the preparation when blended in products such as cosmetics.
[0004]
Conventionally, various measures such as immobilization, modification, and addition of polyhydric alcohols have been proposed in order to improve the stability when such an active ingredient is incorporated into cosmetics. It was not always satisfactory.
[0005]
On the other hand, it has been reported that a compression-disintegrating microcapsule is blended in a cosmetic for the purpose of stably maintaining the quality of the active ingredient blended in the cosmetic and the overall quality of the cosmetic (JP-A-60-224609). And JP-A-4-1118).
The compressible disintegrable microcapsules are intended to stably hold the active ingredient in the microcapsules in the formulation and to stabilize the microcapsules during use, thereby disintegrating the microcapsules by compression with a finger or the like to release the encapsulated active ingredients. .
[0006]
However, in cosmetics containing compressible disintegrable microcapsules, it is difficult to control the strength of the microcapsules, and if the strength of the capsules is too weak, the microcapsules may break down in the product or the active ingredient may leak. Conversely, if the strength of the microcapsules is too high, there is a problem that the disintegration due to compression during use is not sufficient, and the contained active ingredient does not act sufficiently. In particular, when the stability of the microcapsules in the product over time is poor, the stability of the product system is eventually impaired, and there is a disadvantage that aggregation, separation, caking and the like occur.
[0007]
The present inventors have long studied to obtain cosmetics that stably maintain various active ingredients of cosmetics including enzymes and vitamins until use, and that fully exert their effects at the time of use. Although it was repeated, it is possible to achieve the object by previously encapsulating the component in a pH-sensitive soluble microcapsule prepared with a resin that can be disintegrated by a change in pH and blending this in a cosmetic. A headline was filed and a patent application was filed (Japanese Patent Application No. 4-35795).
[0008]
[Means for Solving the Problems]
Although almost satisfactory cosmetics can be obtained by the above invention, the present inventors have conducted research to obtain cosmetics having an even better feeling of use. The use of a porous powder as a core material eliminates the aggregation and particle size variation of the microcapsules, and furthermore, the active ingredient is captured and retained in the pores of the porous powder, thereby further improving the stability. The present inventors have found that the cosmetics containing the microcapsules thus obtained have a very good feeling in use, and completed the present invention.
[0009]
That is, the present invention provides a pH-sensitive soluble microcapsule in which an active ingredient and a porous powder are encapsulated in a resin that can be disintegrated by a change in pH, and a cosmetic containing the microcapsule.
[0010]
The pH-sensitive microcapsules of the present invention (hereinafter abbreviated as “pH-sensitive MC”) are resins capable of disintegrating the active ingredient and the porous powder by a change in pH (hereinafter, referred to as “pH-sensitive resin”). It should be included in.
[0011]
The method for producing this pH-sensitive MC is not particularly limited except that a porous powder is used as a core substance, and conventionally used in-liquid drying methods, phase separation methods, spray drying granulation methods, fluidized bed methods, Any method such as an interfacial polymerization method may be used.
Taking the submerged drying method as an example, the method for producing the pH-sensitive MC will be specifically described as follows.
[0012]
First, 0.5% to 50% by weight of a pH-sensitive resin is added to a solvent and dissolved therein. Then, a porous powder as an active ingredient and a core substance to be included in the solution is added and dispersed. Make a suspension.
[0013]
Next, the obtained suspension is poured into a large amount of a dispersion medium while stirring, and after dispersing the dispersion medium, it is heated under normal pressure or reduced pressure to form microcapsules.
[0014]
Further, the microcapsules obtained from the dispersion medium are recovered by means of filtration, sedimentation, centrifugation, etc., washed with an organic solvent such as hexane which does not dissolve the capsule membrane, and dried to obtain powdery pH-sensitive MC. it can.
[0015]
On the other hand, when the pH-sensitive MC is manufactured by the phase separation method, first, as in the case of the submerged drying method, the active ingredient to be included in the solution of the pH-sensitive resin and the porous powder which is the core substance are added and dispersed. A suspension is prepared, and then a phase-separation attractant is added thereto to precipitate a pH-sensitive resin to form microcapsules. Finally, this is recovered and dried to obtain a powdery pH-sensitive MC. Just get it.
[0016]
Examples of the solvent used to dissolve the pH-sensitive resin include organic solvents such as methanol, ethanol, acetone, methylene chloride, chloroform, ethyl acetate, propanol, toluene, benzene, carbon tetrachloride, and ether, and water. They can be used alone or in combination of two or more.
[0017]
Examples of the dispersion medium include liquid paraffin, oil agents such as silicone oil, polyhydric alcohols such as glycerin, 1,3-butylene glycol, and propylene glycol, water, and organic solvents. These may be used alone or in combination of two or more. Can be used in combination. If necessary, a surfactant may be added to the dispersion medium in an amount of 0.5 to 10% by weight (hereinafter simply referred to as “%”).
[0018]
The active ingredient included in the pH-sensitive MC is not particularly limited, and various active ingredients can be used. For example, (1) enzymes such as enzymes and vitamins are unstable in the preparation, (2) a component that has a problem with the stability over time, (2) a component that affects the physical properties of the preparation, such as a crude drug component containing salts, tannin, etc., which causes separation, aggregation, thickening, etc. ▼ Particularly excellent effects can be obtained when an aqueous component such as a moisturizing component or a crude drug extract, which cannot be incorporated into cosmetics such as a powder or an oil gel as it is, is used as the encapsulated active ingredient.
[0019]
Among the above, examples of the active ingredient (1) include enzymes such as lipase, protease, superoxide dismutase (SOD), lysozyme, alkaline phosphatase, amylase, pancreatin, glutathione peroxidase, catalase, and vitamin A; Vitamin B, Vitamin C, Vitamin D ₂ , Vitamin D ₃ , Vitamins such as vitamin E and their derivatives, cysteine and its derivatives, guaiazulene and its derivatives, and glutathione and its derivatives.
[0020]
Examples of the active ingredient (2) include herbal ingredients and various salts containing tannins, flavonoids, and the like, such as green tea, sophora, and yellow bean.
Further, examples of the active ingredient of (3) include whitening agents such as placenta extract and soybean extract, photosensitizers, fungicides such as salicylic acid, hinokitiol, and sulfur, ultraviolet absorbers such as γ-oryzanol, and mucopoly. Humectants such as sugars, proteins, urea and the like can be mentioned.
[0021]
Each of the above components may be contained in an animal or plant-derived component, and the enzymes may be immobilized or modified.
[0022]
Examples of the vitamins to which the method of the present invention can be suitably applied include vitamin C (ascorbic acid) and vitamin C derivatives such as magnesium L-ascorbyl phosphate and disodium L-ascorbic acid sulfate. . That is, ascorbic acid has a disadvantage that it is decomposed and colored by a trace amount of moisture and light, and this disadvantage is particularly remarkable on the alkali side, and it has been difficult to incorporate it into cosmetics and the like. Further, L-ascorbyl magnesium phosphate, a derivative, is a compound having poor stability on the acidic side and causing coloration, and may cause problems when blended in cosmetics.
[0023]
On the other hand, the porous powder used as the core material in the present invention is a porous fine spherical or granular material, and may be inorganic or organic.
[0024]
Among the porous powders, examples of inorganic porous powders include, for example, silicic anhydride, alumina, magnesium oxide, zinc oxide, cadmium oxide, titanium oxide, iron oxide, nickel oxide, cobalt oxide, chromium oxide, Oxides such as manganese oxide, lead oxide, copper oxide, zirconium oxide, antimony oxide; magnesium hydroxide, calcium hydroxide, aluminum hydroxide, zinc hydroxide, cadmium hydroxide, iron hydroxide, nickel hydroxide, cobalt hydroxide Hydroxides such as aluminum, chromium hydroxide, lead hydroxide, and copper hydroxide; aluminum carbonate, magnesium carbonate, zinc carbonate, calcium carbonate, barium carbonate, cadmium carbonate, cobalt carbonate, nickel carbonate, chromium carbonate, lead carbonate, and copper carbonate Etc .; magnesium silicate, calcium silicate, barium silicate, zinc silicate, silicic acid Silicates such as dodium, aluminum silicate, lead silicate, cobalt silicate, nickel silicate, copper silicate; sulfates such as magnesium sulfate, calcium sulfate, barium sulfate, zinc sulfate, cadmium sulfate, lead sulfate; sulfurous acid Sulfites such as magnesium, calcium sulfite, barium sulfite, zinc sulfite, cadmium sulfite, lead sulfite; sulfides such as magnesium sulfide, calcium sulfide, barium sulfide, zinc sulfide, cadmium sulfide, lead sulfide; magnesium phosphate, calcium phosphate, phosphorus Phosphates such as barium phosphate, zinc phosphate, aluminum phosphate, cadmium phosphate, lead phosphate, and copper phosphate; phosphorous acids such as magnesium phosphite, calcium phosphite, barium phosphite, and lead phosphite Salts: magnesium borate, calcium borate, barium borate, borate Borates such as zinc, cadmium borate, aluminum borate, lead borate, copper borate, iron borate, cobalt borate, nickel borate; magnesium chlorate, calcium chlorate, zinc chlorate, aluminum chlorate , Magnesium bromate, calcium bromate, barium bromate, zinc bromate; halogen oxyacid salts; magnesium perchlorate, calcium perchlorate, barium perchlorate, zinc perchlorate, magnesium perbromate, perbromine Perhalogen oxyacid salts such as calcium acid, barium perbromate and zinc perbromate; hydrotalcite compounds and zeolite compounds.
[0025]
Examples of the organic porous powder include a porous powder composed of a polyacrylic acid-based resin, a polyamide-based resin, a polyolefin-based resin, and a porous potato starch.
[0026]
The porosity of these porous powders may be at least 0.01 ml / g in pore volume, preferably about 0.1 to 3.0 ml / g. Further, the pore diameter may be 20 Å or more, and preferably about 20 to 2,000 Å. Further, the size of the porous powder is 1 mm or less, preferably about 0.1 μm to 1 mm as a long diameter.
[0027]
As these porous powders, commercially available products can be suitably used.In addition, these powders are used to prevent agglomeration of generated particles and to improve the affinity between a pH-sensitive resin and a core material. A hydrophobic treatment may be performed.
[0028]
Chemicals used for the hydrophobizing treatment include thermosetting silicone oils such as dimethylpolysiloxane and methylhydrogenpolysiloxane, silicone resins such as silicone emulsions and silicone resins, methyltrimethoxysilane, hexamethyldisilane, and trimethylchlorosilane. Silane coupling agents such as dihydrogenhexamethylcyclotetrasiloxane and trihydrogenpentamethylcyclotetrasiloxane; and titanate couplings such as isopropyltristearyl titanate and isopropyl-tri-N-aminoethyltitanate. Agents, aluminum-based coupling agents such as acetoalkoxyl aluminum diisopropylate, and fluorine-based coating agents.
[0029]
The material of the porous powder to be used may be appropriately selected according to the kind of the active ingredient to be included in the pH-sensitive MC.
[0030]
The pH at which the pH-sensitive MC of the present invention dissolves (hereinafter referred to as “dissolution pH”) is determined by the material of the pH-sensitive resin used for the microcapsules.
[0031]
In the present invention, it is desirable that the dissolution pH is not strongly alkaline or strongly acidic from the viewpoint of cosmetics, and usually, a pH-sensitive resin having a dissolution pH in the range of pH 4 to 9 can be suitably used. However, it is not necessarily limited only to this range, and it is also possible to use a resin having a lower dissolution pH or a resin having a higher dissolution pH depending on the mode of the product used.
[0032]
The pH-sensitive resin used in the present invention does not dissolve in the acidic region but dissolves in the neutral / alkaline region due to its dissolution pH (hereinafter referred to as “medium / alkaline dissolvable resin”) and the neutral / alkaline region In this case, the resin is not dissolved, but is dissolved in an acidic region (hereinafter, referred to as “acid-soluble resin”).
[0033]
Preferred examples of the medium-alkaline dissolvable resin include resins that are stable on the acidic side and start dissolving at pH 4 or higher, and examples of acidic dissolvable resins are stable on the alkaline side and start dissolution at pH 9 or lower. Resin.
The following resins can be exemplified as the medium / alkaline soluble resin and the acidic soluble resin that can be suitably used in the present invention.
[0034]
Examples of the medium / alkaline dissolvable resin include hydroxypropylmethylcellulose acetate succinate (hereinafter, referred to as “HPMCAS”), cellulose acetate phthalate (hereinafter, referred to as “CAP”), hydroxypropylmethylcellulose phthalate (hereinafter, referred to as “HPMCP”), Hydroxypropyl methylcellulose (hereinafter, referred to as “HPMC”), carboxymethylethylcellulose (hereinafter, referred to as “CMEC”), acrylic acid / acrylate copolymer, methacrylic acid / methyl methacrylate copolymer, methacrylic acid / ethyl acrylate copolymer And the like.
[0035]
Examples of the acidic dissolvable resin include methyl methacrylate / butyl methacrylate / dimethylaminoethyl methacrylate copolymer, polyvinyl acetal diethylaminoacetate, aminoalkyl methacrylate copolymer, and hydroxypropyl cellulose.
[0036]
Among these, HPMCAS and CAP are preferable for the medium- and alkaline-soluble resins, and methyl methacrylate / butyl methacrylate / dimethyl methacrylate for the acidic-soluble resins. An aminoethyl copolymer and polyvinyl acetal diethylaminoacetate can be mentioned.
[0037]
In the present invention, commercially available products can be suitably used as the above-mentioned pH-sensitive resin. For example, as HPMCAS, AQOAT LG, AQOATMG, AQOAT LF, AQOAT MF, AQOAT HF, AQOAT HG (all manufactured by Shin-Etsu Chemical Co., Ltd.) and the like, and as HPMCP, for example, HP-55, HP-55S, HP-50 ( As mentioned above, as methacrylic acid / methyl methacrylate copolymer, Eudragit L-100 and Eudragit S-100 (above, manufactured by Rohm Pharma) and the like are exemplified by methacrylic acid / acrylic acid. Examples of the ethyl acid copolymer include Eudragit L-30 and Eudragit D-55 (both manufactured by Rohm Pharma Co.) as commercial products.
[0038]
As CMEC, CMEC OS, CMEC AQ (above, manufactured by Freund Corporation) and the like, as CAP, cellulose acetate phthalate (manufactured by Wako Pure Chemical Industries, Ltd.) and the like, and as polyvinyl acetal diethylaminoacetate, AEA (Sankyo) And Eudragit E-100 (manufactured by Rohm Pharma) as aminoalkyl methacrylate copolymers.
[0039]
Further, as HPMC, TC-5E, TC-5MW, TC-5R (RW), TC-55 (all manufactured by Shin-Etsu Chemical Co., Ltd.), E-5, E-15 (all manufactured by Dow Corning) and the like. Examples of HPC include HPC-SL, HPC-L (all manufactured by Nippon Soda Co., Ltd.), HPC-LEP, and HPC-LEG (all manufactured by Hercules), and the like.
[0040]
The above-mentioned medium- and alkaline-soluble resins are widely used as enteric coatings in the field of pharmaceutical preparations, and acid-soluble resins are widely used as gastric coatings, and are easily available. Its use in the cosmetics field is not known.
[0041]
In addition, the material of the capsule membrane used for the conventional compressible disintegrating microcapsules was basically selected from water-insoluble resins for the purpose of forming capsules. And a resin whose dissolution can be controlled by changing the pH.
[0042]
The amount and ratio of the active ingredient and the porous powder contained in the pH-sensitive MC vary depending on the intended use, the aspect of the cosmetic described below, the dosage form, the use, and the like. It is sufficient that about 1 to 70% of the whole and about 20 to 90% of the porous powder, and preferably about 10 to 35% and about 40 to 80%, respectively.
[0043]
If the encapsulation amount of both components is less than the above range, the effect of the present invention may not be sufficiently exhibited, and conversely, if the amount is too large, the strength of the microcapsules decreases and causes the outflow of inclusions. For example, there may be a problem in stability with time.
[0044]
Further, the pH-sensitive MC used in the present invention is generally spherical, and its particle diameter is obtained as being in the range of about 1 to 1000 μm. Therefore, the particle diameter depends on the kind of the encapsulated active ingredient and the kind of the intended cosmetic. It is also possible to select.
The adjustment of the particle diameter can be made by variously selecting the size of the porous powder to be used.
[0045]
The pH-sensitive MC of the present invention obtained as described above is blended in a known cosmetic base to prepare a cosmetic.
The amount of the pH-sensitive MC varies depending on the intended form, dosage form, application, etc. of the cosmetic, but is generally in the range of 0.001 to 90% with respect to the product. The base also varies depending on the intended form, dosage form, application, and the like of the cosmetic.
[0046]
That is, the cosmetic of the present invention is (a) a type of cosmetic which is used by being applied or dropped on the skin, in which the pH-sensitive MC is dissolved by the water on the skin surface and the pH of the skin to release the contained components. (B) The two agents are mixed and used at the time of use, and the pH-sensitive MC dissolves due to a change in pH due to the mixing, and the cosmetic releases the contained components. Cosmetics that dissolve the pH-sensitive MC by the change in pH and release the encapsulated components can be mentioned, and a cosmetic base can be selected according to this.
[0047]
Among the above three embodiments, examples of the cosmetic of the embodiment (a) include, for example, emulsions, creams, lotions, essences, packs, powders, foundations, lipsticks, hair tonics, and hair styling materials.
[0048]
The pH-sensitive MC to be incorporated in the cosmetic of the present embodiment needs to be soluble in the pH of the skin (the pH of the skin is usually 4.5 to 6.5). In addition, in the cosmetic of this embodiment, the dissolution of the pH-sensitive MC occurs gradually, so that the release of the encapsulated component is performed for a long time, and the sustained action and effect of the active ingredient can be expected.
[0049]
Examples of the cosmetic of the embodiment (b) include, for example, milky lotions, lotions, essences, foundations, hair tonics, hair stylings, and the like.
[0050]
In the cosmetic of this embodiment, the pH-sensitive MC is blended and stored in a cosmetic having a pH at which it does not dissolve or a cosmetic containing no water, and is mixed with a cosmetic having a different pH when used. The microcapsules are disintegrated due to the change, and the encapsulated components are released and used, or these cosmetics are sequentially applied to release the encapsulated components.
[0051]
In this cosmetic, any dissolvable resin can be suitably used, and a resin having a wide range of dissolution pH can be selected.
[0052]
Furthermore, examples of the cosmetic of the embodiment (c) include face wash, shampoo, and rinsing. Examples of the face wash include a powder type, an acidic cream type, and an alkaline cream type. Any of these can be used.
[0053]
Since these cosmetics are applied to the skin and hair and then rinsed with water, they do not dissolve at the pH of the cosmetic itself, but are washed with water, and dissolve as the pH approaches neutrality. It is necessary to use a pH-sensitive MC prepared using a sensitive resin.
[0054]
In addition, it goes without saying that the cosmetics of the present invention can be blended with the active ingredient conventionally used in the field of cosmetics in addition to the pH-sensitive MC.
[0055]
【Example】
Next, the present invention will be described in more detail with reference to Production Examples, Examples and Test Examples, but the present invention is not limited thereto.
[0056]
Manufacturing example 1
Production of lipase-encapsulated pH-sensitive MC (1):
To 5 parts of lipase, 100 parts of a methylene chloride solution of 5% HPMCAS (AQOAT HG; manufactured by Shin-Etsu Chemical) and 20 parts of silicon-treated silicic anhydride (average particle size: 3.5 μm; manufactured by Suzuki Yushi Kogyo Co., Ltd.) were added. Stir well.
To this mixture, 100 parts of toluene was added as a phase separation inducer, and HPMCAS was precipitated by a phase separation method. Then, this was filtered by suction and dried at room temperature to obtain pH-sensitive MC.
[0057]
The obtained lipase-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but in an aqueous solution having a pH of 5.5 or more or on the skin (the pH of the skin is usually pH 4.5 to 6.5). It dissolves and releases lipase.
[0058]
Manufacturing example 2
Production of lipase-encapsulated pH-sensitive MC (2):
To 5 parts of lipase, 100 parts of an acetone solution of 5% methacrylic acid copolymer (Eudragit S-100; manufactured by Rohm Pharma) and 20 parts of hydroxyapatite (average particle size: 10 μm; manufactured by Sekisui Chemical Co., Ltd.) were added. Stir.
To this mixture, 200 parts of hexane was added as a phase separation attractant, and a methacrylic acid copolymer was precipitated by a phase separation method. Then, this was filtered by suction and dried at room temperature to obtain a pH-sensitive MC.
[0059]
The obtained lipase-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but dissolves in an aqueous solution having a pH of 5.5 or more and on the skin to release lipase.
[0060]
Manufacturing example 3
Production of protease-enclosed pH-sensitive MC:
To 5 parts of the protease, 100 parts of a 18% methylene chloride solution of HPMCAS (AQOAT HG; manufactured by Shin-Etsu Chemical Co., Ltd.) was added and stirred to obtain a dispersion. While gently stirring 25 parts of cellulose (average particle size: 500 μm; manufactured by Rengo Co., Ltd.), the above dispersion was gradually added to form microcapsules. The microcapsules were collected by filtration and dried with warm air at 40 ° C. to obtain pH-sensitive MC.
[0061]
The obtained protease-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but dissolves in an aqueous solution having a pH of 5.5 or more and on the skin to release the protease.
[0062]
Manufacturing example 4
Production of SOD-encapsulated pH-sensitive MC (1):
To 1 part of SOD, 10 parts of an acetone solution of 10% CAP (manufactured by Wako Pure Chemical Industries) is added and stirred. To this solution, 10 parts of silicon-treated titanium oxide (average particle size: 0.2 μm; manufactured by Ishihara Sangyo Co., Ltd.) was added and dispersed.
[0063]
This dispersion is gradually added to 100 parts of liquid paraffin containing 1% of sorbitan trioleate while stirring, and the temperature is gradually increased while continuing stirring, to 50 to 60 ° C. Next, the formed microcapsules are collected by filtration, washed with hexane and dried.
The obtained SOD-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but dissolves in an aqueous solution having a pH of 5.5 or more and on the skin to release SOD.
[0064]
Manufacturing example 5
Production of SOD-encapsulated pH-sensitive MC (2):
Production Example 1 except that 5 parts of SOD were used instead of 5 parts of lipase and 5% of methacrylic acid / butyl methacrylate / dimethylaminoethyl methacrylate copolymer (Eudragit E-100; manufactured by Rohm-Pharma) was used instead of 5% of HPMCAS. In the same manner as in the above, a pH-sensitive MC containing SOD was obtained.
[0065]
The obtained SOD-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the alkaline side, but dissolves in an aqueous solution having a pH of 6.0 or less or on the skin to release SOD.
[0066]
Manufacturing example 6
Production of pH-sensitive MC containing L-ascorbyl magnesium phosphate (1): 100 parts of a 5% HPMCAS (AQOATHG; manufactured by Shin-Etsu Chemical Co., Ltd.) methylene chloride solution in 5 parts of magnesium L-ascorbyl phosphate and silicon-treated silicic anhydride (Average particle size: 3.5 μm; manufactured by Suzuki Yushi Kogyo Co., Ltd.) is added and stirred well.
To this mixture, 100 parts of toluene was added as a phase separation inducer, and HPMCAS was precipitated by a phase separation method. Then, this was filtered by suction and dried at room temperature to obtain pH-sensitive MC.
[0067]
The obtained L-ascorbyl magnesium phosphate-encapsulated pH-sensitive MC is insoluble in an acidic aqueous solution, but in an aqueous solution having a pH of 5.5 or more or on the skin (the pH of the skin is usually pH 4.5 to 4.5). 6.5) and release L-ascorbyl magnesium phosphate.
[0068]
Manufacturing example 7
Production of pH-sensitive MC containing ascorbic acid (1):
To 5 parts of ascorbic acid, 100 parts of an acetone solution of 5% methacrylic acid copolymer (Eudragit S-100; manufactured by Rohm Pharma) and 20 parts of hydroxyapatite (average particle size: 10 μm; manufactured by Sekisui Plastics Co., Ltd.) were added. Stir well.
To this mixture, 200 parts of hexane was added as a phase separation attractant, and a methacrylic acid copolymer was precipitated by a phase separation method. Then, this was filtered by suction and dried at room temperature to obtain a pH-sensitive MC.
[0069]
The resulting ascorbic acid-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but dissolves in an aqueous solution having a pH of 5.5 or more and on the skin to release ascorbic acid.
[0070]
Manufacturing example 8
Preparation of pH-sensitive MC containing L-ascorbic acid sulfate disodium ester
To 5 parts of disodium L-ascorbic acid sulfate, 100 parts of a 18% HPMCAS (AQOAT HG; manufactured by Shin-Etsu Chemical Co., Ltd.) methylene chloride solution was added and stirred to obtain a dispersion. While gently stirring 25 parts of cellulose (average particle size: 500 μm; manufactured by Rengo Co., Ltd.), the above dispersion was gradually added to form microcapsules. The microcapsules were collected by filtration and dried with warm air at 40 ° C. to obtain pH-sensitive MC.
[0071]
The obtained L-ascorbic acid sulfate disodium-encapsulated pH-sensitive MC is insoluble in an acidic aqueous solution, but dissolves in an aqueous solution having a pH of 5.5 or more and on the skin to give L-ascorbic acid sulfate. It releases disodium ester.
[0072]
Manufacturing example 9
Production of pH-sensitive MC containing L-ascorbyl magnesium phosphate (2):
To 1 part of magnesium L-ascorbyl phosphate, 10 parts of an acetone solution of 10% CAP (manufactured by Wako Pure Chemical Industries, Ltd.) is added and stirred. To this solution, 10 parts of silicon-treated titanium oxide (average particle size: 0.2 μm; manufactured by Ishihara Sangyo Co., Ltd.) was added and dispersed.
[0073]
This dispersion is gradually added to 100 parts of liquid paraffin containing 1% of sorbitan trioleate while stirring, and the temperature is gradually increased while continuing stirring to reach 50 to 60 ° C. Next, the formed microcapsules are collected by filtration, washed with hexane and dried.
The resulting L-ascorbyl magnesium phosphate-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the acidic side, but dissolves in an aqueous solution having a pH of 5.5 or more or on the skin to form L-ascorbyl magnesium phosphate. Release.
[0074]
Manufacturing example 10
Production of pH-sensitive MC containing ascorbic acid (2):
Replacement of 5 parts of ascorbic acid with 5 parts of L-ascorbyl magnesium phosphate and 5% of HPMCAS with 5% of methacrylic acid / butyl methacrylate / dimethylaminoethyl methacrylate copolymer (Eudragit E-100; manufactured by Rohm-Pharma) Ascorbic acid-encapsulated pH-sensitive MC was obtained in the same manner as in Production Example 6 except that
[0075]
The obtained ascorbic acid-encapsulated pH-sensitive MC is insoluble in an aqueous solution on the alkaline side, but dissolves in an aqueous solution having a pH of 6.0 or less or on the skin to release ascorbic acid.
[0076]
Test example 1
Stability test:
In order to examine the stability of the enzyme-encapsulated pH-sensitive MCs obtained in Production Examples 1, 3 and 4, the residual activity ratio of each enzyme in a pH 5.0 phosphate buffer maintained at 40 ° C. was measured over time. did. For comparison, the same measurement was performed for a single enzyme. In addition, comparative products of lipase and protease were measured at room temperature. Table 1 shows the results.
[0077]

[0078]
It is a well-known fact that enzymes are quickly deactivated in an aqueous system, but from the above results, each enzyme encapsulated in pH-sensitive MC is lost even when stored at 40 ° C in a buffer solution. Activity was hardly recognized.
[0079]
Test example 2
Measurement of change in release amount at each pH (1):
For the lipase-encapsulated pH-sensitive MC produced according to Production Example 1, the change in the amount of lipase release at each pH was examined. The measurement was performed by dispersing the pH-sensitive MC in the buffer solution of each pH and elapse of 10 minutes, and then quantifying the protein in the filtered filtrate by the Lowry method.
[0080]
As a result, the lipase encapsulated in the pH-sensitive MC began to be released at pH 5.5, and all was released at pH 6.5.
[0081]
Test example 3
Measurement of change in release amount at each pH (2):
For the SOD-encapsulated pH-sensitive MC produced according to Production Example 5, the change in the amount of released SOD at each pH was examined. The measurement was performed by quantifying the protein by the Lowry method in the same manner as in Test Example 2.
[0082]
As a result, SOD began to be released at pH 6.0, and all was released at pH 5.5.
[0083]
Test example 4
Stability test:
In order to examine the stability of the vitamin-encapsulated pH-sensitive MC obtained in Production Examples 6 and 7, the remaining amount of each vitamin in a phosphate buffer at pH 5.0 maintained at 40 ° C. was measured over time. . For comparison, the same measurement was performed for single vitamins. Table 2 shows the results.
[0084]

[0085]
Ascorbic acids are known to be difficult to guarantee stability, especially in aqueous systems. However, the above results revealed that ascorbic acids encapsulated in the pH-sensitive MC did not show any decrease in stability over time even when stored at 40 ° C. in a buffer solution.
[0086]
Test example 5
Measurement of change in release amount at each pH (3):
For the pH-sensitive MC containing L-ascorbyl magnesium phosphate produced according to Production Example 6, the change in the release amount of magnesium L-ascorbyl phosphate at each pH was examined. The measurement was performed by dispersing the pH-sensitive MC in the buffer solution of each pH, and after elapse of 10 minutes, quantifying L-ascorbyl magnesium phosphate in the filtered filtrate by an absorption spectrophotometry.
[0087]
As a result, L-ascorbyl magnesium phosphate contained in the pH-sensitive MC began to be released at pH 5.5, and all were released at pH 6.5.
[0088]
Test example 6
Measurement of change in release amount at each pH (4):
For ascorbic acid-encapsulated pH-sensitive MC produced according to Production Example 10, changes in the amount of ascorbic acid released at each pH were examined. The measurement was performed by quantifying ascorbic acid by an absorption spectrophotometric method in the same manner as in Test Example 5.
[0089]
As a result, ascorbic acid started to be released at pH 6.0, and all was released at pH 5.5.
[0090]
Example 1
O / W emulsion:
Using the lipase-encapsulated pH-sensitive MC obtained in Production Example 1, an O / W emulsion having the following composition was prepared. The pH of the emulsion was 5.0.
[0091]

[0092]

[0093]
(Production method)
A. (6) to (9) are added to the component (11), mixed by heating, and maintained at 70 ° C. (aqueous phase).
B. The components (1) to (5) are mixed by heating and kept at 70 ° C. (oil phase).
C. The above B was added to the above A, mixed and uniformly emulsified, then cooled while stirring, and (10) and (12) were added and uniformly mixed to obtain an emulsion.
[0094]
In the obtained emulsion, the pH-sensitive MC is insoluble, but when applied to the skin, the microcapsules are gradually dissolved under the influence of the pH of the skin and the moisture on the skin, and the lipase, which is an encapsulated component, is released. .
[0095]
Example 2
Water-drying foundation:
Using the lipase-encapsulated pH-sensitive MC obtained in Production Example 2, a foundation having the following composition was prepared.
[0096]

[0097]

[0098]
(Production method)
The components (1) to (8) are mixed and stirred, and the components (9) to (14) are added thereto and mixed uniformly.
After the pulverization, compression molding was performed.
[0099]
In the powder foundation of the present invention, the pH-sensitive MC is insoluble, but when applied to the skin, the microcapsules gradually dissolve due to the pH of the skin and the water on the skin, releasing lipase as an internal component.
In particular, a more preferable effect is exhibited in a usage method in which water is contained in a sponge and applied to the skin as a dual-use foundation.
[0100]
Example 3
Two-part mixed lotion:
Using the SOD-containing pH-sensitive MC obtained in Production Example 4, a two-part mixture type lotion was prepared with the following composition. The microcapsules were blended in the powder part, and the pH of the lotion part was 6.5.
[0101]

[0102]

[0103]
(Production method)
A powder is manufactured by uniformly stirring and mixing the compositions (1) to (4) of the powder portion.
Further, the compositions (1) to (4) of the lotion portion are uniformly dispersed and added to a mixture of the compositions (5) to (7) to produce a lotion.
[0104]
The two-part mixture type lotion of the present invention disperses 1 part of powder in 10 parts of lotion at the time of use and applies it to the skin. When the lotion is added, the pH-sensitive MC dissolves, and the SOD, which is an inclusion, is released. I do.
[0105]
Example 4
Creamy facial cleanser:
Using the protease-containing pH-sensitive MC obtained in Production Example 3, a creamy face wash was prepared with the following composition. The pH of the creamy facial cleanser was 5.5.
[0106]

[0107]
(Production method)
The above (1) to (8) were dissolved by heating, mixed, cooled, defoamed and filled.
[0108]
Since the creamy facial cleanser of the present invention has a pH on the acidic side, protease-encapsulated pH-sensitive MC is substantially insoluble in the product, but is absorbed in the palm of the hand at the time of washing to contain moisture, and also, When the pH is neutralized by releasing or by continuing the rinsing, the protease, which is an encapsulated component, is released.
[0109]
Example 5
Hair restorer:
Using the lipase-encapsulated pH-sensitive MC obtained in Production Example 1, a hair restorer was prepared based on the following composition. In addition, the pH of the hair tonic is 5.0.
[0110]

[0111]
(Production method)
A. Components (3) and (4) are mixed and dissolved in (10).
B. Components (1), (2) and (5) to (9) are mixed and dissolved.
C. The above B was added to the above A and mixed and stirred to obtain a hair liquid type hair restorer.
In the obtained hair restoration, the pH-sensitive MC is insoluble, but the microcapsules are gradually dissolved under the influence of the pH of the scalp and the moisture on the scalp, and the lipase, which is an encapsulated component, is released.
[0112]
Example 6
Two-part mixed lotion:
Using the SOD-encapsulated pH-sensitive MC obtained in Production Example 5, a two-part mixture type lotion was prepared with the following composition. The microcapsules were blended in the powder part, and the pH of the lotion part was 5.0.
[0113]

[0114]

[0115]
(Production method)
A powder is manufactured by uniformly stirring and mixing the compositions (1) to (4) of the powder portion.
Further, the compositions (1) to (4) of the lotion portion are uniformly dispersed and added to a mixture of the compositions (5) to (7) to produce a lotion.
[0116]
The two-part mixture type lotion of the present invention dissolves 1 part of powder with 10 parts of lotion at the time of use, and applies it to the skin. By adding the lotion, the entire pH becomes acidic and the pH-sensitive MC dissolves. Releases SOD as inclusions.
[0117]
Example 7
O / W emulsion:
Using the L-ascorbyl magnesium phosphate-containing pH-sensitive MC obtained in Production Example 6, an O / W emulsion having the following composition was prepared. The pH of the emulsion was 5.0.
[0118]

[0119]

[0120]
(Production method)
A. (6) to (9) are added to the component (11), mixed by heating, and maintained at 70 ° C. (aqueous phase).
B. The components (1) to (5) are mixed by heating and kept at 70 ° C. (oil phase).
C. The above B was added to the above A, mixed and uniformly emulsified, then cooled while stirring, and (10) and (12) were added and uniformly mixed to obtain an emulsion.
[0121]
In the obtained emulsion, the pH-sensitive MC is insoluble, but when applied to the skin, the microcapsules are gradually dissolved under the influence of the pH of the skin and the moisture on the skin, and the L-ascorbyl phosphate, an encapsulated component, is dissolved. Magnesium is released.
[0122]
Example 8
Water-drying foundation:
Using the ascorbic acid-containing pH-sensitive MC obtained in Production Example 7, a foundation having the following composition was prepared.
[0123]

[0124]

[0125]
(Production method)
The components (1) to (8) were mixed and stirred, and the components (9) to (14) were added thereto, mixed uniformly, pulverized, and then compression-molded.
[0126]
In the powder foundation of the present invention, the pH-sensitive MC is insoluble, but when applied to the skin, the microcapsules are gradually dissolved by the pH of the skin and the water on the skin to release ascorbic acid, which is a component contained therein.
In particular, a more preferable effect is exhibited in a usage method in which water is contained in a sponge and applied to the skin as a dual-use foundation.
[0127]
Example 9
Two-part mixed lotion:
Using the L-ascorbyl magnesium phosphate-containing pH-sensitive MC obtained in Production Example 9, a two-part mixture type lotion was prepared with the following composition. The microcapsules were blended in the powder part, and the pH of the lotion part was 6.5.
[0128]

[0129]

[0130]
(Production method)
A powder is manufactured by uniformly stirring and mixing the compositions (1) to (4) of the powder portion.
Further, the compositions (1) to (4) of the lotion portion are uniformly dispersed and added to a mixture of the compositions (5) to (7) to produce a lotion.
[0131]
The two-part mixture type lotion of the present invention disperses 1 part of powder in 10 parts of lotion at the time of use and applies it to the skin. -Releases ascorbyl magnesium.
[0132]
Example 10
Creamy facial cleanser:
Using the pH-sensitive MC containing disodium L-ascorbic acid sulfate obtained in Production Example 8, a cream-like face wash was prepared with the following composition. The pH of the creamy facial cleanser was 5.5.
[0133]

[0134]
(Production method)
The above (1) to (8) were dissolved by heating, mixed, cooled, defoamed and filled.
[0135]
Since the creamy facial cleanser of the present invention has an acidic pH, the pH-sensitive MC containing L-ascorbic acid sulfate disodium in the product is practically insoluble in the product. In addition, by disposing it on the skin or continuing rinsing, when the pH becomes neutral, L-ascorbic acid sulfate disodium, which is an encapsulated component, is released.
[0136]
Example 11
Hair restorer:
Using L-ascorbyl magnesium phosphate-containing pH-sensitive MC obtained in Production Example 6, a hair restorer was prepared based on the following composition. In addition, the pH of the hair tonic is 5.0.
[0137]

[0138]
(Production method)
A. Components (3) and (4) are mixed and dissolved in (10).
B. Components (1), (2) and (5) to (9) are mixed and dissolved.
C. The above B was added to the above A and mixed and stirred to obtain a hair liquid type hair restorer.
In the obtained hair restorer, the pH-sensitive MC is insoluble, but the microcapsules are gradually dissolved under the influence of the pH of the scalp and the water on the scalp, and the L-ascorbyl magnesium phosphate, which is an encapsulated component, is released. Is done.
[0139]
Example 12
Two-part mixed lotion:
Using the ascorbic acid-containing pH-sensitive MC obtained in Production Example 10, a two-component mixed type lotion was prepared with the following composition. The microcapsules were blended in the powder part, and the pH of the lotion part was 5.0.
[0140]

[0141]

[0142]
(Production method)
A powder is manufactured by uniformly stirring and mixing the compositions (1) to (4) of the powder portion.
Further, the compositions (1) to (4) of the lotion portion are uniformly dispersed and added to a mixture of the compositions (5) to (7) to produce a lotion.
[0143]
The two-part mixture type lotion of the present invention dissolves 1 part of powder with 10 parts of lotion at the time of use, and applies it to the skin. The addition of the lotion makes the whole pH acidic and dissolves the pH-sensitive MC. Releases ascorbic acid, an inclusion.
[0144]
【The invention's effect】
The pH-sensitive MC of the present invention can be obtained as microcapsules having a uniform particle size without aggregation or particle size variation, and the encapsulation amount can be easily controlled, so that the quality of the microcapsules can be kept constant. It can be added to cosmetics more easily than conventional pH-sensitive MC. At the same time, the cosmetic of the present invention containing microcapsules having no variation in particle size has an excellent feeling in use and is highly used.
[0145]
In addition, components that were unstable in products such as enzymes and vitamins, and were difficult to mix into cosmetics in the past, were taken up and retained in the pores of the porous powder, resulting in an extremely stable state. And the obtained cosmetic is less likely to be separated or denatured even during long-term storage.
[0146]
Further, by selecting various materials for the pH-sensitive MC, it is possible to apply the composition to a wide variety of cosmetics, and it is possible to increase the degree of freedom in selecting the components as compared with conventional cosmetics.
Furthermore, in the case of a cosmetic used in a form of being directly applied to the skin, not only stabilization of the product but also sustained effect over a long period of time can be expected due to sustained release of the encapsulated components.
that's all

Claims (10)

pH sensitive microcapsules for skin cosmetics comprising an active ingredient and a porous powder contained in a resin that can be disintegrated at pH 4.5 to 6.5. The pH-sensitive microcapsules for skin cosmetics according to claim 1, wherein the pH-sensitive microcapsules are formed of a resin that is stable at a pH higher than pH9. The pH-sensitive soluble microcapsule for skin cosmetics according to claim 1, wherein the pH-sensitive soluble microcapsule is formed of a resin stable at a pH of less than 4. Porous powder average particle diameter claim skin cosmetic pH sensitive solubility Microcapsules according to claims 1 to 3 which is 0.001~1000μm of. Claim skin cosmetic pH sensitive solubility Microcapsules according to claims 1 to 4 the porous powder is a porous anhydrous silicic acid. The active ingredient is an enzyme such or vitamins claim 1 or claim skin cosmetic pH sensitive solubility Microcapsules according to claim 5. A skin cosmetic containing the pH-sensitive soluble microcapsules for skin cosmetic according to any one of claims 1 to 6. The skin cosmetic according to claim 7, which is used by being applied or dropped on the skin. The skin cosmetic according to claim 7 or 8, wherein the cosmetic is a two-component cosmetic used at the time of use, wherein the pH-sensitive microcapsules disintegrate due to a change in pH due to the mixing and release the contained components. Fees. The cosmetic according to any one of claims 7 to 9, wherein the cosmetic is used together with water, wherein the pH-sensitive microcapsules disintegrate due to a change in pH due to dilution of the water, and the encapsulated components are released. Skin cosmetics.