JP5733669B2 - Hair dye - Google Patents
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- JP5733669B2 JP5733669B2 JP2012157582A JP2012157582A JP5733669B2 JP 5733669 B2 JP5733669 B2 JP 5733669B2 JP 2012157582 A JP2012157582 A JP 2012157582A JP 2012157582 A JP2012157582 A JP 2012157582A JP 5733669 B2 JP5733669 B2 JP 5733669B2
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- 239000000118 hair dye Substances 0.000 title claims description 43
- XVARCVCWNFACQC-RKQHYHRCSA-N indican Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1=CNC2=CC=CC=C12 XVARCVCWNFACQC-RKQHYHRCSA-N 0.000 claims description 97
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 60
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 55
- 229940097275 indigo Drugs 0.000 claims description 53
- BXFFHSIDQOFMLE-UHFFFAOYSA-N indoxyl sulfate Natural products C1=CC=C2C(OS(=O)(=O)O)=CNC2=C1 BXFFHSIDQOFMLE-UHFFFAOYSA-N 0.000 claims description 48
- XVARCVCWNFACQC-UHFFFAOYSA-N indoxyl-beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OC1=CNC2=CC=CC=C12 XVARCVCWNFACQC-UHFFFAOYSA-N 0.000 claims description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 102000004190 Enzymes Human genes 0.000 claims description 38
- 108090000790 Enzymes Proteins 0.000 claims description 38
- 239000000843 powder Substances 0.000 claims description 36
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- 241001062009 Indigofera Species 0.000 description 49
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- PCKPVGOLPKLUHR-UHFFFAOYSA-N indoxyl Chemical group C1=CC=C2C(O)=CNC2=C1 PCKPVGOLPKLUHR-UHFFFAOYSA-N 0.000 description 14
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- COHYTHOBJLSHDF-BUHFOSPRSA-N indigo dye Chemical compound N\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-BUHFOSPRSA-N 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
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- 244000283207 Indigofera tinctoria Species 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
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Description
本発明は植物色素を用いた染毛剤に係り、特に、沖縄県産の琉球藍やヘナを用い、頭皮や毛髪に優しく且つ染毛効果に優れ、使用性の高い染毛剤に関する。 The present invention relates to a hair dye using a plant pigment, and more particularly to a hair dye that uses Ryukyu indigo and henna produced in Okinawa Prefecture, is gentle on the scalp and hair, has an excellent hair dyeing effect, and is highly usable.
植物色素を用いた自然の染毛剤は、合成染料等に比べて染毛力や色の堅牢性が劣るものの、頭皮等への刺激が少なく安全性が高いことから見直され、近年の 安全・健康志向と相まって再び注目されている。
このような植物染料としては、例えば、明るい赤色系のヘナ染料や青系のインド藍、蓼藍、琉球藍等の藍染料がよく知られている。特に、ヘナや藍を併用すると、ヘナにより白髪を赤色系に染め上げ、これに藍の青系色が加わり、全体として日本人の髪の色調にあった黒色系の染毛ができることから、より染毛力の向上を目的に、その染毛方法・条件や配合比等の実用的検討が盛んに行われている。
Natural hair dyes using plant pigments have been reviewed because they have less hair dyeing and color fastness than synthetic dyes, but are less irritating to the scalp, etc. and are highly safe. Coupled with health consciousness, it is attracting attention again.
As such plant dyes, for example, bright red-based henna dyes and blue-based indigo dyes such as indigo indigo, blue indigo, and Ryukyu indigo are well known. In particular, when combined with henna or indigo, white hair is dyed red with henna, and the blue color of indigo is added to this, resulting in black dyeing that matches the color of Japanese hair as a whole. For the purpose of improving hair strength, practical studies such as the hair dyeing method, conditions, and blending ratio have been actively conducted.
藍染料の場合、生葉に含まれるインジカンが最終的にインジゴに変化して青色を発色する。すなわち、まず、インジカンが同様に生葉に含まれるインジカン分解酵素により加水分解して水溶性のインドキシルを生成する。これが毛髪に吸着・浸透し空気中の酸素により酸化されてインジゴを生成し青系色に染毛する。従って、インドキシルが髪に浸透する前にインジゴに変化してしまうともはや染毛効果は失われてしまうことから、インジカンをできるかぎり未反応のまま保存する必要がある。なお、インジカンの加水分解反応は、藍の種類によっても異なり、例えばインド藍は比較的遅く、琉球藍や蓼藍は速いと言われている。 In the case of indigo dye, the indican contained in the fresh leaves will eventually change to indigo to develop a blue color. That is, first, indican is similarly hydrolyzed by an indican-degrading enzyme contained in fresh leaves to produce water-soluble indoxyl. This adsorbs and permeates into the hair and is oxidized by oxygen in the air to produce indigo and dye the hair blue. Therefore, if indoxyl is converted to indigo before penetrating into the hair, the hair dyeing effect is no longer lost, so indican must be stored as unreacted as much as possible. The hydrolysis reaction of indican varies depending on the type of indigo. For example, Indian indigo is relatively slow, and it is said that Ryukyu indigo and catalyzed are fast.
インジカンを加水分解させずに保存する方法としては、生葉に含まれるインジカンとインジカン分解酵素(β−グルコシターゼ)を反応しない条件下で併存させて保存する方法(特許文献1)や、熱水や蒸気を用いた熱処理によりインジカン分解酵素を失活させインジカンだけを残し保存する方法が知られている(非特許文献1)。
前者の場合、インジカンの加水分解反応は水分の存在で進行することから、例えば、生葉を凍結乾燥など、できるかぎり湿気のこもらない雰囲気で乾燥し、保管する方法が用いられる。乾燥葉の粉末を水等で混練りしてペースト状とし、これを毛髪に塗布して染毛処理する(特許文献1)。
As a method for preserving indican without hydrolysis, a method for preserving indican contained in fresh leaves and indican degrading enzyme (β-glucosidase) by coexisting them (Patent Document 1), hot water or steam A method is known in which the indican degrading enzyme is inactivated by heat treatment using a soot, and only the indican is left and stored (Non-patent Document 1).
In the former case, since the hydrolysis reaction of indican proceeds in the presence of moisture, for example, a method is used in which fresh leaves are dried and stored in an atmosphere with as little moisture as possible, such as freeze-drying. The dried leaf powder is kneaded with water or the like to make a paste, and this is applied to the hair and dyed (Patent Document 1).
後者の場合、例えば、藍の生葉を80℃以上の熱水で短時間熱処理し、酵素を失活させた後、生煮えの葉を集めて布袋に入れ、液を搾り取る方法である。この液では酵素が失活しているので、インジカンの加水分解は起こらずインジカンを安定して保持することができる。染色の際には、例えば、生葉の破砕抽出液や塩揉み液等、酵素を含有する粗酵素液と混合して使用する(非特許文献1)。なお、この文献には、熱水の代わりに蒸気を用いて酵素を失活処理できる旨記載されている。
その他、藍の生葉やその絞り汁を加熱処理(温度60〜100℃、約3分〜60分)、蒸気処理、電子レンジ処理、天日乾燥処理等の酵素失活方法が記されている(特許文献2)。なお、具体的な失活方法として、非特許文献1と同様に、生葉を80〜90℃の熱湯に約10〜20分間漬けて酵素を失活させ、インジカンを抽出する方法が開示されている。
In the latter case, for example, indigo green leaves are heat-treated with hot water at 80 ° C. or higher for a short time to inactivate the enzyme, and then the raw boiled leaves are collected and placed in a cloth bag, and the liquid is squeezed out. Since the enzyme is inactivated in this solution, indican is not hydrolyzed and indican can be stably retained. At the time of dyeing, for example, the mixture is used by mixing with a crude enzyme solution containing an enzyme such as a crushed extract of fresh leaves or a salt mash (Non-Patent Document 1). This document states that the enzyme can be inactivated using steam instead of hot water.
In addition, enzyme inactivation methods such as heat treatment (temperature: 60 to 100 ° C., about 3 minutes to 60 minutes), steam treatment, microwave treatment, sun drying treatment, etc. are described for indigo green leaves and their juices ( Patent Document 2). As a specific deactivation method, as in Non-Patent Document 1, a method of extracting indican by immersing fresh leaves in hot water at 80 to 90 ° C. for about 10 to 20 minutes to deactivate the enzyme is disclosed. .
しかしながら、琉球藍の場合、上記従来の酵素失活方法では、酵素を失活させる前に多くのインジカンが加水分解反応してしまい、高濃度のインジカンを含む粉体を作製するのは実際上困難であることが分かった。すなわち、種々の乾燥・熱処理条件を検討してみたところ、ほとんどの場合、処理の過程で葉にインジゴの青色斑点の浮き上がりが見られ、また作製した琉球藍粉末の染毛力は弱く、多くのインジカンが失われていることが分かった。 However, in the case of Ryukyu Indigo, in the conventional enzyme deactivation method, many indicans are hydrolyzed before the enzyme is deactivated, and it is practically difficult to produce a powder containing a high concentration of indican. It turns out that. That is, when various drying and heat treatment conditions were examined, in most cases, indigo blue spots were lifted on the leaves during the treatment, and the hair dyeing power of the produced Ryukyu indigo powder was weak, I found that indican was lost.
そこで、酵素失活と加熱処理方法との関係を種々検討した結果、高濃度インジカンの実現には、生葉を単に酵素の失活温度以上に加熱するだけでは不十分で、できるかぎり急速に失活温度に上昇させることが重要であり、このための方法として水蒸気の凝縮潜熱を利用した加熱方法が極めて有効であることが分かった。その一方、この方法は処理時間が従来処理法のように長くなると染毛能力は逆に低下してしまうことも分かった。
本発明は、かかる知見を基にさらに検討を加えて完成したものである。
Therefore, as a result of various investigations on the relationship between enzyme deactivation and heat treatment methods, it was not sufficient to simply heat fresh leaves above the enzyme deactivation temperature to achieve high-concentration indican. It is important to raise the temperature, and it has been found that a heating method using latent heat of condensation of water vapor is very effective as a method for this purpose. On the other hand, it has also been found that the hair dyeing ability of this method decreases when the treatment time becomes longer as in the conventional treatment method.
The present invention has been completed by further studies based on such knowledge.
また、従来の藍を用いた染毛剤は粉体の形態で提供され、使用する直前に水で混練しペースト状にして用いるものであって、合成の染毛剤のようにプラスチックチューブからペーストを絞り出してすぐ塗布できるというものではなく、使い勝手が非常に悪いという問題があった。又、水の量や水質、混練りの程度により染毛結果が変わってしまうという問題があった。 In addition, the conventional hair dye using indigo is provided in the form of powder, and is kneaded with water and used as a paste just before use, and is pasted from a plastic tube like a synthetic hair dye. There is a problem that it is not easy to apply immediately after squeezing out, and is very inconvenient. In addition, there is a problem that the hair dyeing result varies depending on the amount of water, water quality, and degree of kneading.
このような状況の中で、本発明はインジカンを高濃度に含有する琉球藍の染毛剤を提供することを目的とする。さらには、藍を用いた染毛剤でありながら、ペーストの状態で保存可能な、極めて使用性の高い染毛剤を提供することを目的とする。
さらに本発明は、沖縄県産のヘナと琉球藍とを用いて、染毛力及びトリートメントが高く安全な白髪染めを提供することを目的とする。
Under such circumstances, an object of the present invention is to provide a hair dye of Ryukyu indigo containing high concentration of indican. It is another object of the present invention to provide a hair dye with extremely high usability that can be stored in a paste state while being a hair dye using indigo.
A further object of the present invention is to provide safe hair dyeing with high hair dyeing power and treatment using henna and Ryukyu indigo from Okinawa.
本発明の染毛剤は、100℃以上の水蒸気の凝縮潜熱を利用し琉球藍の生葉を急速加熱処理して、インジカンの分解を抑えつつインジカン分解酵素を失活させた琉球藍の乾燥葉を含むことを特徴とする。さらに、前記急速加熱処理において、前記生葉の温度が80℃に達した後の水蒸気による加熱処理時間を10〜90秒とするのが好ましい。 The hair dye of the present invention uses the latent heat of condensation of water vapor of 100 ° C. or more to rapidly heat raw leaves of Ryukyu indigo, and to dry dried leaves of Ryukyu indigo, which inactivates indican degrading enzyme while suppressing decomposition of indican. It is characterized by including. Furthermore, in the rapid heat treatment, it is preferable that the heat treatment time with water vapor after the temperature of the fresh leaves reaches 80 ° C. is 10 to 90 seconds.
即ち、100℃以上の水蒸気の凝縮熱を利用することにより、短時間で生葉を酵素失活温度まで加熱することができ、従来法に比べてインジカンの分解を抑え高濃度インジカンを含む琉球藍の粉状体を安定して提供することが可能となる。さらに、熱処理時間を10〜90秒とすることにより、乾燥葉中のインジカン濃度をより一層高濃度とすることができる。 That is, by utilizing the heat of condensation of water vapor at 100 ° C. or higher, fresh leaves can be heated to the enzyme deactivation temperature in a short time, and the decomposition of indican is suppressed compared to the conventional method. It becomes possible to provide a powdery body stably. Furthermore, the indican concentration in the dried leaf can be further increased by setting the heat treatment time to 10 to 90 seconds.
本発明の他の染毛剤は、 藍の生葉中のインジカン分解酵素を失活させた第1の粉状体と、インジカン分解酵素を含む第2の粉状体を所定の割合で混合し、該混合粉状体を水で混練りしペースト状としたものを冷凍したことを特徴とする。ここで、第1の粉末には100℃以上の水蒸気で加熱処理した琉球藍の乾燥葉が好適に用いられる。なお、粉状体とは、粉体の他、葉を細かく刻んだものも含む意である。 Another hair dye of the present invention comprises mixing a first powdery body inactivated indican-degrading enzyme in indigo green leaves and a second powdery body containing indican-degrading enzyme at a predetermined ratio, The mixed powder is kneaded with water to obtain a paste, which is frozen. Here, dry leaves of Ryukyu indigo heat-treated with water vapor of 100 ° C. or higher are preferably used for the first powder. In addition, a powdery body means the thing which finely chopped the leaf other than powder.
ペースト中にはインジカンと酵素及び水が存在し、従来はすぐ反応しインジゴを生成してしまうため、従来はペーストとして保存し、販売することは不可能と考えられていたが、以上のように作製したペーストを例えばプラスチックフィルム容器に入れ、例えば−20℃で冷凍することにより、インジカンの加水分解反応又はインドキシルの酸化反応の一方若しくは両方が抑制されると考えられ、少なくとも3ヶ月放置しても、染毛能力はほとんど低下せず、製品として実用上問題ないことが確認された。このように藍を用いた染毛剤でペースト化したものは本発明により初めて開示されたものである。
また、染毛時には自然解凍又は湯や流水につけて解凍すればよく、解凍後容器からペーストを取り出しそのまま髪に塗布すればよい。このように、粉末状の染毛剤に比べて、極めて使い勝手が良く、使用性に優れたものである。また、予め適切条件でペースト化しているため、従来の混練り時のバラツキを防止し、安定した染毛を行うことができる。
Indican, enzyme, and water exist in the paste, and in the past, they reacted immediately to produce indigo, so it was traditionally considered impossible to store and sell as a paste. It is considered that one or both of the hydrolysis reaction of indican and the oxidation reaction of indoxyl is suppressed by placing the prepared paste in, for example, a plastic film container and freezing at −20 ° C., and left for at least 3 months. However, it was confirmed that the hair dyeing ability was hardly lowered and there was no practical problem as a product. Such a paste made with indigo hair dye was first disclosed by the present invention.
When hair is dyed, it may be thawed by natural thawing or hot water or running water, and after thawing, the paste is taken out from the container and applied to the hair as it is. Thus, it is extremely convenient and excellent in usability as compared with powdered hair dyes. Moreover, since it is paste-formed under appropriate conditions in advance, it is possible to prevent variation during conventional kneading and perform stable hair dyeing.
なお、上記のインジカン分解酵素含有粉状体(第2の粉状体)は、琉球藍の生葉を60〜70℃で温風加熱して粉砕したもの、又は前記生葉を凍結乾燥し粉砕したものが好ましい。温風加熱したものは、インジカンのほとんどはインジゴに変化しているが酵素は高濃度に存在し、さらに凍結乾燥したものはインジカンも残留しているため、より濃い効果的な染毛が可能となる。 The indican-degrading enzyme-containing powder (second powder) is obtained by pulverizing fresh leaves of Ryukyu incense with heating with hot air at 60 to 70 ° C., or freeze-dried and pulverized of the fresh leaves. Is preferred. When heated with warm air, most of the indican is converted to indigo, but the enzyme is present at a high concentration, and the lyophilized product also contains indican, which enables more effective and effective hair dyeing. Become.
さらに本発明の染毛剤は、琉球藍の混合粉状体に、琉球ヘナの生葉を乾燥し粉砕して得られたヘナの粉状体を所定の割合で加えたことを特徴とする。
このようにして、ヘナによる赤色系の染色と、琉球藍による青色系の染色とが重なり合って、全体として黒色系の白髪染めが可能となる。しかも、ペースト状の白髪染めであり、藍染料を用いたものとしては画期的な白髪染めである。
Further, the hair dye of the present invention is characterized in that a powdered henna powder obtained by drying and crushing fresh leaves of Ryukyu henna is added to a mixed powder of Ryukyu indigo in a predetermined ratio.
In this manner, the red dyeing with henna and the blue dyeing with Ryukyu indigo overlap, making it possible to dye black as a whole. Moreover, it is a paste-like white hair dye, and is an epoch-making white hair dye using an indigo dye.
本発明は、上述したように、インジカン分解酵素の失活に100℃以上の水蒸気の凝縮潜熱を利用していることから生葉の急速加熱が可能となり、酵素によるインジカン分解反応が進む前に酵素を不活性化することができ、大部分のインジカンを未反応の状態で残留させることができる。その結果、染毛剤中のインジカン濃度はより一層高くなり、より染毛力の高い染毛剤を実現することができる。 As described above, the present invention utilizes the latent heat of condensation of water vapor of 100 ° C. or more for inactivation of indican degrading enzyme, so that quick heating of fresh leaves is possible, and the enzyme is inactivated before the indican decomposing reaction proceeds. It can be inactivated and most of the indican can remain unreacted. As a result, the indican concentration in the hair dye is further increased, and a hair dye having a higher hair dyeing power can be realized.
また、本発明の染毛剤はペースト状としたものであり、酵素を含んでいることからインジカンの加水分解反応が進み、染毛成分としては加水分解生成物のインドキシル(及び未反応のインジカン)を含む染毛剤である。このようにして、藍を原材料とする染毛剤では、本発明が初めてペースト状の剤型を実現したものである。その結果、粉末の染毛剤のように使用時に水で混練する煩わしさや、また、水質や水との混合比のバラツキによる染毛効果の変動という問題も解決でき、極めて使用性・染毛安定性に優れた染毛剤を実現することができる。 In addition, the hair dye of the present invention is in the form of a paste, and since it contains an enzyme, the hydrolysis reaction of indican progresses, and as the hair dye component, the hydrolysis product indoxyl (and unreacted indican) ). Thus, in the hair dye made from indigo, the present invention realizes a paste-like dosage form for the first time. As a result, it is possible to solve the problems of the trouble of kneading with water at the time of use like a powder hair dye and the fluctuation of the hair dyeing effect due to variations in the water quality and the mixing ratio with water. A hair dye excellent in properties can be realized.
また、ペースト状とする際に、沖縄県産ヘナ(琉球ヘナ)の粉状体を併せて加えることにより、日本人の髪の色調にあった黒色系の白髪染めが可能となる。しかも、琉球ヘナを用いることにより、インド産のヘナに比べて、より高いトリートメント効果及び高い染色堅牢性が得られる。 In addition, by adding a powder of Okinawa Prefecture henna (Ryukyu henna) when making it into a paste, it is possible to dye black hair that matches the color of Japanese hair. Moreover, by using Ryukyu henna, a higher treatment effect and higher dyeing fastness can be obtained as compared with Indian henna.
以下に、実施例を挙げて本発明をより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
インジカン分解酵素を失活させた琉球藍の第1の粉状体の試料(粉末試料1)を次の手順で作製した。琉球藍は、沖縄本島北部で栽培したもので葉の部分を用いた。
スチームコンベクションオーブン(株式会社エフ・エム・アイ製ウノックスXV−5050)のステンレス製トレイに琉球藍の生葉300gを盛り上げ、100℃の水蒸気を導入して生葉の熱処理を行った。
水蒸気を導入後、生葉の温度が80℃になった時点、それから10秒、20秒、40秒、90秒、及び120秒後に水蒸気の導入を停止し、生葉をオーブンから取り出した。なお、生葉の温度が80℃に達するのは、水蒸気導入後20秒程度であった。また、蒸気処理した葉の表面は、もえぎ色であり、従来法のように葉の青変は観られなかった。なお、生葉の温度は盛り上げた葉の中芯部に熱電対を挿入して測定した。
その後、72℃(2時間)で送風乾燥し、得られた乾燥葉を遠心粉砕機(MRK-Retch社製ZM100)で粉砕して、インジカンを高濃度に含有する粉末が生葉の約10%得られた。
A sample (powder sample 1) of the first powder of Ryukyu indigo inactivated indican degrading enzyme was prepared by the following procedure. Ryukyu indigo was cultivated in the northern part of the main island of Okinawa and used the leaves.
300 g of fresh leaves of Ryukyu indigo were raised on a stainless steel tray of a steam convection oven (F.M.I. Unox XV-5050), and steam of 100 ° C. was introduced to heat the fresh leaves.
After the introduction of water vapor, when the temperature of the fresh leaves reached 80 ° C., and after 10 seconds, 20 seconds, 40 seconds, 90 seconds, and 120 seconds, the introduction of water vapor was stopped and the fresh leaves were taken out of the oven. In addition, it was about 20 seconds after water vapor | steam introduction | transduction that the temperature of a fresh leaf reached 80 degreeC. Further, the surface of the steam-treated leaves was mochi-colored, and no blue discoloration of the leaves was observed as in the conventional method. The temperature of fresh leaves was measured by inserting a thermocouple into the center of the raised leaves.
After that, it was blown and dried at 72 ° C. (2 hours), and the obtained dried leaves were pulverized with a centrifugal pulverizer (ZM100 manufactured by MRK-Retch) to obtain about 10% of the raw leaves with a powder containing indican at a high concentration. It was.
一方、インジカン分解酵素を含む第2の粉状体の試料は、熱風循環式乾燥機(アルプ株式会社製GT−150)を用いて、琉球藍の生葉を60〜70℃で8時間乾燥し、その後遠心粉砕器で粉砕して作製した(粉末試料2)。なお、乾燥処理後の葉は全体に常盤色となり、処理前の葉と比べかなり暗青色となった。
これは、処理中にインジカンが酵素により分解され、さらに酸化されてインジゴに変化したものと思われる。
On the other hand, a sample of the second powdery substance containing indican degrading enzyme was dried for 8 hours at 60 to 70 ° C. using fresh air circulation dryer (Alp Co., Ltd. GT-150). Thereafter, it was pulverized with a centrifugal pulverizer (powder sample 2). In addition, the leaves after the drying treatment became a whole board color, and became considerably dark blue compared with the leaves before the treatment.
This is probably because indican was decomposed by the enzyme during the treatment and further oxidized to indigo.
(染毛試験)
作製した粉末試料を用いて染毛試験を行い、各試料の染毛能力を評価した。
粉末試料1の各々2gと粉末試料2を1gとを混合し、25℃の精製水10gを添加しペースト状に混練りした。各々のペーストを毛束10g(ビューラックス社製人毛白髪)に塗布し、塩化ビニールフィルムで包み込み、常温で1時間放置した。その後、ペーストを水道水で洗い流し、自然乾燥して染毛評価を行った。
(Hair dye test)
A hair dyeing test was performed using the prepared powder samples, and the hair dyeing ability of each sample was evaluated.
2 g of each powder sample 1 and 1 g of
(染毛評価)
染色の評価には色彩色差計(オリンパス社製CR−300)を用いた。白色校正後、毛束の中央付近を5点測定し、その平均値を測定値とした。なお、表色系は、JIS Z8729 に従いL*a*b*表色系を採用した。L*a*b*表色系では、明度をL*で表現し、L*が大きくなるほど色が明るく、小さくなるほど暗くなることを示す。また、各色によって異なる色相をa*、b*の値で示し、a*は赤(+)から緑(−)方向、そしてb*は黄(+)から青(−)方向を示す。a*、b*が共にプラスの場合は、概ね赤系から黄系になる。逆に、a*、b*が共にマイナスの場合には青系になる。 さらに、彩度Cはa*とb*の2乗値の和の平方根で定義され、Cの値が大きいほど色鮮やかになり、0に近づくに従ってくすんだ色になる。
なお、色の表現については、日本色研事業株式会社の標準色カード230と比較して表現した。
(Hair dye evaluation)
A color difference meter (Olympus CR-300) was used for dyeing evaluation. After white calibration, five points near the center of the hair bundle were measured, and the average value was taken as the measured value. The L * a * b * color system was adopted as the color system according to JIS Z8729. In the L * a * b * color system, the lightness is expressed by L *, and indicates that the color becomes brighter as L * increases and becomes darker as it decreases. Also, hues that differ depending on each color are indicated by a * and b * values, where a * indicates a red (+) to green (−) direction, and b * indicates a yellow (+) to blue (−) direction. When both a * and b * are positive, the color changes from red to yellow. Conversely, if both a * and b * are negative, the color is blue. Further, the saturation C is defined by the square root of the sum of the square values of a * and b *. The larger the value of C, the brighter the color becomes, and the closer to 0, the darker the color.
The color expression was expressed in comparison with the standard color card 230 of Nippon Color Research Co., Ltd.
各々のペースト試料について、色彩測定の結果を、図1(a)〜(d)に示す。図1において、(a)は明度L*、(b)及び(c)はそれぞれ色相a*及びb*、(d)は彩度Cを表し、横軸の処理時間は、粉末試料1を作製する際のインジカン失活処理において、水蒸気を導入し生葉の温度が80℃になってから水蒸気を遮断するまでの時間を表している。また、参考のため白髪(毛束)及び成人の黒髪についての色彩測定結果を図2に示した。 About each paste sample, the result of a color measurement is shown to Fig.1 (a)-(d). In FIG. 1, (a) represents lightness L *, (b) and (c) represent hues a * and b *, and (d) represents saturation C, respectively. In the indican deactivation treatment, the time from the introduction of water vapor until the temperature of the fresh leaves reaches 80 ° C. until the water vapor is blocked is shown. For reference, the color measurement results for white hair (hair bundle) and adult black hair are shown in FIG.
図1から、毛束の明度L*は処理時間とともに減少し(即ち、濃く染まり)、40〜90秒の間で最小となった後、増加することが分かる。即ち、ペーストの染毛能力は40〜90秒で最大となり、その後減少する。この変化の理由は現在のところ明らかではないが、酵素の失活とインジカン自体の熱による分解・変質等が関係しているのではないかと推測している。 From FIG. 1, it can be seen that the lightness L * of the hair bundle decreases with the treatment time (i.e., darkly dyes), increases after reaching a minimum between 40 and 90 seconds. That is, the hair dyeing ability of the paste becomes maximum in 40 to 90 seconds and then decreases. The reason for this change is not clear at present, but it is presumed that the inactivation of the enzyme is related to the thermal decomposition / degeneration of indican itself.
また、スチームコンベクションオーブンを用い温度80℃の低温水蒸気で40秒、失活処理した場合、処理後の葉は青みがかり、また、トレイにも藍の葉から浸出した青い色が移っていた。この試料を用いたペーストにはほとんど染毛能力は観られなかった。
なお、粉末試料1又は2だけを用いて作製したペーストには、染毛能力がないことも確認した。
In addition, when the steam convection oven was used to inactivate with low-temperature steam at a temperature of 80 ° C. for 40 seconds, the leaves after the treatment were bluish, and the blue color leached from the indigo leaves was also transferred to the tray. Almost no hair dyeing ability was observed in the paste using this sample.
It was also confirmed that the paste produced using
以上の述べたように、本実施例のように、100℃以上の水蒸気の大きな凝縮潜熱を利用することにより、生葉中の酵素の失活温度まで瞬時に加熱することができ、大部分のインジカンを未反応の状態で残留保持させることができる。
また、本実施例では、第1の粉状体と第2の粉状体との混合比を2:1としたが、本発明はこれに限るものではない。通常4:1〜1:4が用いられ、混合比により染毛の明度及び色相を変化させることができる。
なお、第1の粉状体と第2の粉状体は通常別々に保存されるが、予め所望の割合に混合した混合粉状体として保存してもよい。但し、この場合は、水分や酸素が存在すると、加水分解やインジゴ生成反応が起こるため、水分等を遮断した密閉した状態で保存する必要がある。
As described above, by using the large latent heat of condensation of water vapor of 100 ° C. or higher as in the present embodiment, it can be instantaneously heated to the inactivation temperature of the enzyme in fresh leaves, and most indican Can be retained in an unreacted state.
Moreover, in the present Example, although the mixing ratio of the 1st powdery body and the 2nd powdery body was 2: 1, this invention is not limited to this. Usually, 4: 1 to 1: 4 is used, and the lightness and hue of the hair can be changed by the mixing ratio.
In addition, although a 1st powdery body and a 2nd powdery body are normally preserve | saved separately, you may preserve | save as a mixed powdery body previously mixed by the desired ratio. However, in this case, if moisture or oxygen is present, hydrolysis or indigo production reaction occurs, and therefore, it is necessary to store in a sealed state in which moisture and the like are blocked.
本実施例では、粉末の状態で保存する染毛剤でなく、予め粉末を水で混練りしペーストとして保存する染毛剤で、琉球藍と琉球ヘナからなる黒色系の白髪染めを作製した。
琉球藍の第1の粉状体には、実施例1の水蒸気熱処理時間を40秒とした粉末試料1を用い、第2の粉状体には、実施例1と同様の粉末試料2を用いた。
一方、ヘナ粉状体として、沖縄本島南部で栽培したヘナの葉の部分だけを用い、循環式箱型乾燥機(大紀産業株式会社TB−60)を用いて40〜45℃で熱風乾燥し、遠心粉砕器で粉砕したものを用いた。
In this example, not a hair dye stored in the form of a powder but a hair dye previously kneaded with water and stored as a paste, a black gray hair dye made of Ryukyu indigo and Ryukyu henna was prepared.
For the first powder of Ryukyu indigo, the powder sample 1 having a steam heat treatment time of 40 seconds in Example 1 was used, and for the second powder, the
On the other hand, as a henna powder, using only a portion of the henna leaf cultivated in the southern part of Okinawa main island, hot air drying at 40 to 45 ° C. using a circulation type box dryer (Taki Sangyo Co., Ltd. TB-60), What was grind | pulverized with the centrifugal grinder was used.
2gの粉末試料1、1gの粉末試料2、及び2gのヘナ粉末を、N2ガス雰囲気で混合し、脱気した精製水を12g加えて混練りしてペースト状とした。このペーストをガスバリア性の高いプラスチック製袋(明和産商株式会社製、HRS−14225)に封入した。これを常温保存及び−20℃で冷凍保存し、染毛能力の経時変化を調べた。ここで、ペーストの冷凍及び保管には、急速冷凍庫(三洋電機株式会社製MDF−U460BR)を用いた。
染毛試験は、上述したように、ペーストを人毛白髪に塗布し、常温で1時間放置後、洗い流して色彩測定を行った。冷凍保存した試料は、流水で解凍して用いた。
2 g of powder sample 1, 1 g of
In the hair dyeing test, as described above, the paste was applied to human white hair, allowed to stand at room temperature for 1 hour, washed off, and color measurement was performed. The frozen sample was used after thawing with running water.
色彩測定の結果を図3に示す。図において、「対照」は、ペースト化した直後の染毛試験結果である。図から明らかなように、ペーストは、大気中で作製後1日経過すると染毛力は大きく低下してしまい(非密封1日後)、大部分のインジカン及びインドキシルはインジゴに変化しているものと思われる。
また、プラスチックス製袋中に密封し保存したペースト(常温14日後)は、「対照」試料と比べて低下しているものの、「非密封1日後」に比べ大きく改善され、インドキシル及び/又はインジカンの反応を抑制されていることが分かる。数日程度であれば、十分実用に耐えるものと思われる。
The results of color measurement are shown in FIG. In the figure, “control” is the result of the hair dyeing test immediately after making the paste. As can be seen from the figure, the hair dyeing power is greatly reduced after 1 day in the atmosphere (1 day after non-sealing), and most of the indican and indoxyl are changed to indigo. I think that the.
In addition, the paste (14 days after normal temperature) sealed and stored in a plastic bag is significantly lower than the “control” sample, but greatly improved compared to “after 1 day”, and indoxyl and / or It can be seen that the reaction of indican is suppressed. If it is only a few days, it seems that it will be sufficiently practical.
一方、冷凍保存したペーストについては、染毛能力の経時変化はほとんど観られず、3ヶ月後も初期と変わらない能力が維持されていることが分かる。藍を用いた染毛剤のペーストの染毛能力がかかる長期にわたって安定して維持されるという事実は、本発明者により初めて発見され、実現されたものであって、藍をペーストとして保存することなど当業者はあえて試みようとはしなかったことである。 On the other hand, with regard to the paste that was stored frozen, it was found that the hair dyeing ability was hardly changed over time, and the ability unchanged from the initial stage was maintained even after 3 months. The fact that the hair dyeing ability of a hair dye paste using indigo is stably maintained over a long period of time was first discovered and realized by the present inventors, and the indigo is stored as a paste. Those skilled in the art did not dare to try.
また、本実施例のペーストは必要に応じて殺菌することが出来る。例えば、第1の粉状体と第2の粉状体を2:1の割合で混合し、1/10Mクエン酸・1/5Mリン酸水素ナトリウム緩衝液(pH3.9)10mLを加えて混練して作成したペーストをプラスチックフィルムに封入し室温で6時間放置した後75℃で10分間加熱殺菌した。加熱殺菌により一般生菌数は300以下となり、大腸菌群も陰性となった。殺菌後も染色性は良好であった。
なお、混練後6時間程度経過してから加熱処理するのが好ましく、これにより染色性の低下を防ぐことができる。混練してから6時間放置するのは、インジカンからインドキシルへの反応を促すためであり、この工程を省くと酸性条件下での加熱のため75℃でもインジカン分解酵素が失活してしまうためと考えられる。また、このペーストも冷凍保存することにより3ヶ月は染色性を良好に保てた。
Moreover, the paste of a present Example can be sterilized as needed. For example, the first powder and the second powder are mixed at a ratio of 2: 1, and 10 mL of 1/10 M citric acid / 1/5 M sodium hydrogen phosphate buffer (pH 3.9) is added and kneaded. The paste thus prepared was sealed in a plastic film, allowed to stand at room temperature for 6 hours, and then sterilized by heating at 75 ° C. for 10 minutes. By heat sterilization, the number of general viable bacteria became 300 or less, and the coliform group also became negative. The dyeability was good even after sterilization.
In addition, it is preferable to heat-process after about 6 hours after kneading | mixing, and this can prevent a dyeability fall. The kneading is allowed to stand for 6 hours in order to promote the reaction from indican to indoxyl. If this step is omitted, the indican-degrading enzyme is inactivated even at 75 ° C. due to heating under acidic conditions. it is conceivable that. Moreover, this paste was also kept frozen for 3 months to maintain good dyeability.
なお、本実施例では、脱気した精製水を用いN2ガス雰囲気中で混練りしてペーストを作製し、容器へ封入する構成としたが、未脱気の精製水を用い大気中で混練り、容器封入したペースト試料であっても、冷凍保存さえすれば染毛力は若干低下はするものの、1ヶ月経過した時点で本実施例のペースト試料に近い染毛力を示すことが確認されている。 In this example, the paste was prepared by kneading in degassed purified water in an N 2 gas atmosphere and sealed in a container. However, the degassed purified water was mixed in the atmosphere. Even if the paste sample is kneaded and enclosed in a container, the hair dyeing power slightly decreases as long as it is stored frozen, but it is confirmed that it shows a hair dyeing power close to that of the paste sample of this example after one month. ing.
本実施例では、インジカン分解酵素の失活方法として、100℃以上の水蒸気加熱を採用したが、本発明のペースト状の染毛剤においてはこれに限らず、従来法(熱水処理等)を用いることもできるし、特別な装置が必要となるものの好適な結果(高濃度インジカン)が得られる、以下の電磁波乾燥法、ドラム乾燥法、焙煎乾燥法、流動層乾燥法を用いることもできる。 In this example, steam heating at 100 ° C. or higher was adopted as a method for deactivating indican degrading enzyme. However, the pasty hair dye of the present invention is not limited to this, and conventional methods (hot water treatment, etc.) are used. The following electromagnetic wave drying method, drum drying method, roasting drying method, and fluidized bed drying method can be used, which can provide suitable results (high-concentration indican), although a special apparatus is required. .
電磁波乾燥法は、琉球藍の葉を電磁波殺菌装置(株式会社クメタ製作所製MSB−104)を用い、例えば電磁波発信量1.5kW/発信器、照射時間150秒で乾燥させる方法である。ドラム乾燥法は、ダブルドラムドライヤ(ジョンソンボイラ社製JMT)を用い、例えば、ドラム温度128℃、回転数2rpmの条件で琉球藍の葉を乾燥させる方法である。焙煎乾燥法は、焙煎機(静岡機械製作所製RD−3000)を用い、琉球藍の生葉を例えば投入温度190℃、回転数60rpmの条件で乾燥する方法である。流動層乾燥法は、流動層乾燥機(株式会社テンセイジャパン社製TS300G型)を用い、例えば200から500℃の熱風を吹き込んで、5秒程度で乾燥させる方法である。 The electromagnetic wave drying method is a method of drying Ryukyu indigo leaves using an electromagnetic wave sterilizer (MSB-104 manufactured by Kumeta Co., Ltd.), for example, an electromagnetic wave transmission amount of 1.5 kW / transmitter and an irradiation time of 150 seconds. The drum drying method is a method of drying Ryukyu indigo leaves under the conditions of a drum temperature of 128 ° C. and a rotation speed of 2 rpm, for example, using a double drum dryer (JMT manufactured by Johnson Boiler). The roasting and drying method is a method of drying raw leaves of Ryukyu indigo using a roasting machine (RD-3000 manufactured by Shizuoka Machinery Co., Ltd.) under conditions of, for example, an input temperature of 190 ° C. and a rotational speed of 60 rpm. The fluidized bed drying method is a method in which, for example, hot air of 200 to 500 ° C. is blown and dried in about 5 seconds using a fluidized bed dryer (TS300G type manufactured by Tensei Japan Co., Ltd.).
インジカン分解酵素を失活させるものではないが、インジカンと酵素とを未反応の状態で保存可能な粉体の作製方法として、凍結乾燥法がある。粉体は湿気ののない状態で保存する必要があるが、インジカンと酵素の両者を含有しているため、本発明では第1の粉状体としても第2の粉状体としても用いることができる。凍結乾燥法は、例えば、凍結乾燥機(株式会社宝製作所製TF10−50)を用い、琉球藍の生葉を−50℃で凍結後、手棚温度25℃で凍結乾燥させる方法である。
従って、本発明のペースト状の染毛剤としては、凍結乾燥法で作製した粉状体を精製水で混練りしペーストとしたものを冷凍保存したものであってもよい。
There is a freeze-drying method as a method for producing a powder that does not inactivate the indican degrading enzyme but can store the indican and the enzyme in an unreacted state. Although it is necessary to store the powder in a moisture-free state, since the powder contains both indican and an enzyme, it is used as the first powder or the second powder in the present invention. it can. The freeze-drying method is a method of freeze-drying fresh leaves of Ryukyu indigo at −50 ° C. and then freeze-drying at a hand shelf temperature of 25 ° C. using a freeze dryer (TF10-50, manufactured by Takara Seisakusho Co., Ltd.).
Therefore, the paste-like hair dye of the present invention may be a paste prepared by kneading a powdered material produced by a freeze-drying method with purified water to obtain a paste.
なお、ヘナの粉状体と琉球藍の粉状体の混合比を変えると、染毛後の色相が大きく変化するため、広範囲なカラーバリエーションの染毛剤を提供することができる。
また、ヘナと琉球藍のペーストを別々に調合し、別々に保存しておくことも可能である。この場合は、所望の染毛色に応じて両者の混合比を決めることができるという利点がある。また、ヘナペーストで処理した後、藍ペーストで処理するなど、種々の染毛方法を選択することができ、これによってもより広範囲はカラーバリエーションが可能となる。
本発明のペースト状染毛剤は、反応しやすい琉球藍に好適に適用されるが、藍として、例えばインド藍等を用いてもよいことは言うまでもない。
If the mixing ratio of the henna powder and the Ryukyu indigo powder is changed, the hue after dyeing changes greatly, so that a hair dye having a wide range of color variations can be provided.
It is also possible to prepare henna and Ryukyu indigo paste separately and store them separately. In this case, there is an advantage that the mixing ratio of both can be determined according to the desired hair color. In addition, various hair dyeing methods such as treatment with henna paste and treatment with indigo paste can be selected, which also enables a wide range of color variations.
The paste-like hair dye of the present invention is suitably applied to Ryukyu indigo which is easy to react, but it goes without saying that Indian indigo, for example, may be used as indigo.
Claims (7)
前記第1の粉状体は、100℃以上の水蒸気の凝縮潜熱を利用し藍の生葉を加熱処理した後、乾燥し粉砕したことを特徴とする染毛剤。 A first powdery body inactivated indican-degrading enzyme in indigo green leaves and a second powdery body containing indican-degrading enzyme are mixed at a predetermined ratio, and the mixed powdery body is mixed with water. A hair dye that is kneaded into a paste ,
A hair dye characterized in that the first powdery body is a heat treatment of indigo green leaves utilizing the condensation latent heat of water vapor at 100 ° C. or higher, and then dried and pulverized .
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