JP2014019656A - Hair dyeing agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hair dyeing agent which comprises a powdery body of Ryukyu indigo (Assam indigo) containing indican at high concentration, and to provide an extremely highly usable hair dyeing agent which is preservable in a pasty state while using indigo.SOLUTION: The hair dyeing agent contains dried leaves of Ryukyu indigo (Assam indigo) which is produced by rapidly heating raw leaves of the indigo using latent heat of condensation of steam at 100°C or higher. It is preferable to set heating time after the temperature of raw leaves reached 80°C to 10 to 90 seconds. Further, a first powdery body produced by performing heat treatment to the raw leaves of the indigo to deactivate indican-degrading enzyme and a second powdery body containing indican-degrading enzyme are mixed at a predetermined ratio, and the mixed powdery body is mixed and kneaded with water into a pasty state, and then frozen. Furthermore, black color-based hair dye can be realized by adding powdery body of Ryukyu henna.

Description

  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.

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.

  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 into indigo before penetrating into the hair, the hair dyeing effect is lost, so it is necessary to store indican 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.

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).

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. .

JP2003-300845 JP 2001-64134 A

Yutaka Takagi “Introduction to Basic Knowledge of Indigo Dye” Dyed α, No. 182, p18-23 (1996).

  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.

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.

  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.

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.

  The hair dye of the present invention uses the latent heat of condensation of water vapor at 100 ° C. or higher 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.

  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.

  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.

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.

  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.

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.

  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.

  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.

  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.

It is a graph which shows the relationship between the heat processing time by water vapor | steam, and hair dyeing ability. It is a graph which shows the result of a color measurement of black hair and white hair. It is a graph which shows the time-dependent change of the hair dyeing power of the paste-like hair dye which consists of Ryukyu indigo and Ryukyu henna.

  Hereinafter, the present invention will be described in more detail with reference to examples.

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.

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.

(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 powder sample 2 were mixed, and 10 g of purified water at 25 ° C. was added and kneaded into a paste. Each paste was applied to 10 g of a hair bundle (human white hair manufactured by Beaulux), wrapped in a vinyl chloride film, and allowed to stand at room temperature for 1 hour. Thereafter, the paste was washed away with tap water, dried naturally and evaluated for hair dyeing.

(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.

  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.

  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.

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 only powder sample 1 or 2 has no hair dyeing ability.

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.

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 same powder sample 2 as in Example 1 was used. It was.
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.

2 g of powder sample 1, 1 g of powder sample 2, and 2 g of henna powder were mixed in an N ₂ gas atmosphere, and 12 g of degassed purified water was added and kneaded to obtain a paste. This paste was enclosed in a plastic bag having a high gas barrier property (HRS-14225, manufactured by Meiwa Sansho Co., Ltd.). This was stored at room temperature and frozen at −20 ° C., and the change over time in the hair dyeing ability was examined. Here, a quick freezer (MDF-U460BR manufactured by Sanyo Electric Co., Ltd.) was used for freezing and storing the paste.
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.

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.

  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.

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.

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.

  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. .

  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.).

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.

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 (8)

  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 characterized by being frozen in a kneaded paste.  2. The hair dye according to claim 1, wherein the first powdery body is obtained by subjecting fresh leaves of Ryukyu indigo to rapid heating using the condensation latent heat of water vapor at 100 ° C. or higher, and then drying and pulverizing.   The hair dye according to claim 2, wherein in the heat treatment, the heat treatment time with water vapor after the temperature of the fresh leaves reaches 80 ° C is 10 to 90 seconds.   The second powdery body is obtained by drying fresh leaves of Ryukyu indigo by heating with hot air at 60 to 70 ° C, or freeze-drying and pulverizing the fresh leaves. The hair dye according to item 1.   The powdered body of henna obtained by drying and crushing fresh leaves of Ryukyu henna is added to the mixed powder at a predetermined ratio. Hair dye.   A hair dye comprising a frozen paste prepared by kneading a powdered body obtained by freeze-drying and pulverizing fresh leaves of Ryukyu indigo with water.   It comprises dry dried leaves of Ryukyu indigo, in which the raw leaves of Ryukyu indigo are rapidly heated using the latent heat of condensation of water vapor of 100 ° C. or higher to suppress hydrolysis of indican and inactivate the indican degrading enzyme. Hair dye.   In the said heat processing, the heat processing time by water vapor | steam after the temperature of the said raw leaf reached 80 degreeC was 10 to 90 second, The hair dye of Claim 7 characterized by the above-mentioned.

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