JP3527614B2 - Production method of chlorophyll solution - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a bear chlorophyll liquor having a nutritional tonic effect and a natural healing power activating effect containing weakly alkaline chlorophyllin and various amino acids, etc., efficiently and without degrading the chlorophyll component in bear bamboo. , And a method for collecting it as a paste-like acidic bear bamboo chlorophyll which is its precursor.

[0002]

BACKGROUND ART As a method for collecting chlorophyll liquor from Kuma bamboo, it has long been known that Kuma bamboo is dried to remove water and then extracted with an organic solvent, and oil-soluble chlorophyll is permeated without destroying cell membranes. There is a method in which it is dissolved in a solvent together with a resin, an oil component and the like and then evaporated, and the residue is dissolved in an alkaline solution of methyl alcohol and simultaneously saponified to collect it as a water-soluble chlorophyllin alkali salt. After that, as a method developed, first, raw bear bamboo grass was heated and stirred in a copper sulfate solution, and then heat treated in an aqueous solution of acidic sodium sulfite to remove lignin, and then the treated bear bamboo grass was diluted with dilute caustic soda. Immerse in the solution, filter the solution after treatment into solid and solution, slightly acidify the obtained solution with hydrochloric acid to form a precipitate, and neutralize it with alkali to obtain a green solution There is a method to obtain
No. 82).

[0003]

Among these conventional techniques, in the former method, the extraction of the chlorophyll component is carried out by an organic solvent, so it is necessary to pay sufficient attention to the handling of the organic solvent and at the same time, the cost is low. There is a problem that it takes. On the other hand, in the latter method, the extraction is performed with water,
As a result, the problems of the former method are avoided.
However, no consideration is given to the continuous production of a large amount of chlorophyll liquor in a stable manner. Since Kuma bamboo collects wild plants, the collection depends on the weather and natural environment.

That is, in many areas where bear bamboo grasses are clustered, it is required to strictly protect the natural environment such as in national parks. It is becoming more difficult due to the increase. In addition, its native area is north of the Chubu region, in the central region it is near the middle of the high mountains, and in the Tohoku region it is a mountainous region although its altitude is low, and as a result, it is a mountainous area due to the influence of snow in winter and before and after that. It is impossible to collect, and the collection period is naturally limited.

Under the above-mentioned restrictions, we will automate the production equipment as much as possible and operate irrespective of the season throughout the year to produce a large amount of chlorophyll liquor efficiently and stably. I considered to do. For that we
First of all, I thought about stable acquisition of the raw material, Kuma-sasa, from many areas, and at the same time, the installation of storage equipment for it. Especially when it comes to a storage facility for winter production, which would be impossible to obtain, a considerably large facility would be required.

[0006] However, Kuma bamboo leaves discolored when it is stored as it is for about 3 days, and its quality is changed. Therefore, long-term storage is an inappropriate production method from the viewpoint of stable production of good quality products. I understood it. At that time, even if the storage temperature was lowered, the period until discoloration was extended to some extent, which was not a fundamental solution. Also, in order to efficiently store a large amount of bear bamboo, it is necessary to compress it to reduce the capacity, but this makes discoloration even faster, and since the temperature is high from summer to early autumn, discoloration It has also been found that the progress of the is fast and it is impossible to store it for a long time.

Further, when we were also studying the chlorophyll content in bear bamboo, the content varied depending on the time of collection, and the results shown in Table 1 were obtained. From these results, the content of chlorophyll in Kuma bamboo is 1 from August.
It is gradually increasing toward the end of October. It can also be understood that Kuma-sasa grows relatively in cold regions, so that the emergence of buds is delayed, and the content of chlorophyll increases from the yellowish young shoots to the deep green color. . Furthermore, in November, the temperature drops, and as a result, it begins to turn brown, disappears from green, and withers around the leaves (rim), making it unsuitable for harvesting. From the above, the optimum sampling time is from August to October.

[0008]

[Table 1]

The content was measured by the following method. That is, Kuma bamboo was first cut with a cutting machine for about 1 minute, and after cutting, sieved with a 12-mesh sieve to collect 0.4 g of a passing portion. 20 ml of ethanol on this
After adding, shaker (25 ° C, 6 hours, 120 times / mi
n) and then filtered, and the filtrate is quantified to 100 ml with ethanol using a volumetric flask. Then, the transmittance at specific wavelengths of 665 nm and 649 nm is measured with a spectrophotometer to determine the chlorophyll content in the bear bamboo grass.

On the premise of the above, an attempt was made to develop a more optimal production method, and as a result, the present invention was developed. In other words, we will develop a technology to automate the production equipment as much as possible without storing the raw material bamboo grass for a long period of time and operate it throughout the year regardless of the season to produce a large amount of chlorophyll liquid efficiently and stably. Therefore, the latter method of the above-mentioned conventional technique was variously examined in the case where the intermediate product in each step of the production process was stored for a long period of time. As a result, surprisingly, by stabilizing the raw bamboo grass with a heated dilute copper sulfate solution and then freezing the treated bear bamboo, the bear bamboo can be stably stored for a long time without discoloration or deterioration. It was found that a certain quality can be produced by continuing the subsequent steps after storage.

We tried to store it at other than this step, but could not find an appropriate means. For example, we also examined long-term storage of paste-like acidic bear bamboo chlorophyll,
When this was frozen and stored for a long period of time, solid-liquid separation occurred, and even if an attempt was made to dissolve the separated solid in water to produce a chlorophyll liquid, this was not dissolved in water and it was impossible to produce the target product. . In addition, miscellaneous bacteria were generated in low-temperature storage, and it was not possible to store it properly. We also considered storing the final product for a long time, but this method requires strict control because the product is stored after sterilization, and at the same time, deterioration of quality is not acceptable, so it is extremely difficult. Moreover, the adoption of this method is not suitable because it is not suitable for the purpose of operating the production line throughout the year to produce the chlorophyll liquor in large quantities, efficiently and stably.

[0012]

In the present invention, the production equipment is automated as much as possible without long-term storage of the raw bamboo grass, and it is operated throughout the year regardless of the season, in a large amount and efficiently. It is intended to provide a technique for stably producing chlorophyll liquid and paste-like chlorophyll which is a precursor thereof. Further, the present invention provides a technique for producing a chlorophyll liquor that enables the production facility to be operated throughout the year without long-term storage of the bear bamboo which has a high chlorophyll content rate from August to October.

That is, according to the present invention, raw bear bamboo grass is subjected to a stabilizing treatment with a heated diluted copper sulfate solution, a step of refrigerating the treated bear bamboo grass, and a treatment of the preserved bear bamboo grass with a heated dilute acidic sodium sulfite solution. To remove lignin,
The step of cutting the bear bamboo grass after lignin removal, the step of treating the cut bear bamboo grass with a heated dilute caustic soda solution, the step of solid-liquid separation of the treated bear bamboo grass-containing liquid, and the obtained alkaline bear bamboo leaf chlorophyll solution is neutralized It consists of the steps of producing acidic bear bamboo leaf chlorophyll precipitate, dehydration of the obtained precipitate to recover paste acidic bear bamboo leaf chlorophyll, and preparation of bear bamboo leaf chlorophyll liquid by adding sodium hydrogencarbonate to this paste acidic bear bamboo leaf chlorophyll The method is a method for producing Kuma bamboo leaf chlorophyll liquid, and the method for producing a precursor is up to the step of collecting paste-like acidic bear bamboo leaf chlorophyll. In the present invention, by freezing and storing the bear bamboo after the stabilization treatment of the raw bear bamboo with the heated dilute copper sulfate solution, the bear bamboo can be stably stored for a long period of time without being discolored or deteriorated, and then stored. By continuing the process, a good constant quality chlorophyll liquid can be produced, and the existence of this process is a feature of the present invention. The whole process of this invention is illustrated in FIG.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The type of bear bamboo grass used in the present invention is not particularly limited, and various kinds such as, for example, kumizasa, chimakizasa and chishimazasa (scientific name) can be used. From the viewpoint of the above, Chishimasa is more preferable. The collection time is not limited, but August to October is preferable because of high content of active ingredients such as chlorophyll and amino acids.

Stabilization with copper sulfate is a natural chlorophyll in bear bamboo that is photolyzed by chlorophyllase, which is a chlorophyll-degrading enzyme present in leaves, resulting in unstable M in chlorophyll.
The purpose is to prevent the g nucleus from becoming detached easily,
By this treatment, copper in the copper sulfate solution is replaced with Mg to avoid enzyme destruction. The concentration of the dilute copper sulfate solution used in this case may be 0.05 to 3.0% by weight, preferably 0.1 to 0.5% by weight.
If the concentration exceeds 0.5%, it is uneconomical because of excess.
When it is less than 0.1%, the substitution is insufficient due to the low concentration, which is inappropriate. The temperature of the solution may be 80 to 100 ° C, preferably 90 to 100 ° C. If the temperature exceeds 100 ° C, the active ingredient may decompose, which is inappropriate. If the temperature is lower than 80 ° C, the green color becomes brown and the stability is insufficient. Further processing time is 30
It is about 80 minutes, preferably about 60 minutes.

After the stabilization treatment, a step of refrigerating and storing the bamboo grass is provided, and the existence of this step is a feature of the present invention. The freezing temperature in this step can be 0 to -30 ° C, preferably -3 to -15 ° C, more preferably -5 to 5 ° C.
-10 ° C is good. Although a temperature of -30 ° C or lower is possible, it is not economical because refrigeration energy cost is involved. The storage period requires at least half a month, and it is preferable to store for at least 3 months. There is no particular upper limit to the storage period, and storage does not affect quality even if stored for 24 months or more, but it is not practical to store for 24 months or more in view of energy costs and the like. In addition, the volume of Kuma bamboo after the stabilization treatment is reduced to 1/3 of that of raw Kuma bamboo, which is a raw material, and this point also has an advantage over the case of storing raw Kuma bamboo.

Although it is possible to subject the frozen bamboo shoots to the lignin removal treatment in the next step as they are, it is preferable to carry out the lignin removal step after thawing. The thawing is preferably performed in a clean room that maintains a temperature of about 10 to 35 ° C. Air should be forcedly circulated in the clean room to efficiently perform thawing. When the outside air is in the above temperature range, it is not necessary to activate the heating device for maintaining the room temperature.

In the lignin removal step after frozen storage, lignin is removed by stirring in a heated acidic sodium sulfite solution to eliminate the blackish leachate. The concentration of the acidic sodium sulfite solution used at that time is
It can be in the range of 0.3 to 3.0% by weight, but preferably 0.5 to 2.5% by weight. The temperature is 80-1
Although it is possible to use 00 ° C, 90 to 100 ° C is preferable.
The processing time is about 1 hour. Note that this step may be a single piece of equipment, but may also be the equipment of the step of stabilizing treatment. That is, when only Kuma bamboo grass with a high chlorophyll content is used as a raw material, the operation period of the stabilization process is several months from 8 to 10 months, and the rest is stopped thereafter. Since both processes are processes in which Kuma bamboo is treated with a high temperature dilute solution, the same equipment can be used by simply replacing the treatment solution. In the case of dual use, the operating rate will be significantly improved compared to the case where a single facility is installed in each process.

The process of cutting bear bamboo after removing lignin is
In the process of cutting it into fine pieces by cutting bear bamboo grass, and consequently in the process of dilute caustic soda following this process,
This is to improve the efficiency when extracting active ingredients such as chlorophyll in Kuma bamboo grass with caustic soda. The cutting machine to be used can be a commercially available one as long as it has a function of cutting bear bamboo into a square or a rectangle with one side of several centimeters, but preferably it has a blade on a rotating shaft and It is preferable that the inner wall of the housing that surrounds the housing is also provided with a blade, and a part of the housing is provided with a screen so that a product having a predetermined size can be sieved and separated.

The step of treating the cut bamboo grass with a heated dilute caustic soda solution is for extracting active ingredients such as chlorophyll in the bear bamboo as described above. Saponification of chlorophyll to sodium copper chlorophyllin with caustic soda is carried out. , Which enhances the solubility of chlorophyll components in an aqueous solution. The concentration of caustic soda is 0.3 to 5.0% by weight, preferably 0.6 to 3.0% by weight. The processing temperature is 70 ~
It is possible at 100 ° C, but it is in a boiling state 10
Around 0 ° C is preferable. The treatment time varies depending on the treatment temperature, but it takes several hours.

The step of solid-liquid separating the liquid containing Kuma bamboo after the treatment is for separating the liquid containing a soluble active ingredient such as chlorophyll extracted with caustic soda and the residual Kuma bamboo after extraction, Various solid-liquid separators can be used,
A belt press can be preferably used. The residue may be re-extracted by adding warm water to it. Cool the extract to near room temperature.

The step of neutralizing the obtained alkaline bear bamboo leaf chlorophyll liquid to form an acidic bear bamboo leaf chlorophyll precipitate is carried out with dilute hydrochloric acid in a neutralization water washing tank. The hydrochloric acid used is about 1.0 to 10% by weight. Preferably 3.0-5.0
It is preferable that the content is about% by weight. As the neutralization proceeds, a chlorophyll precipitate is formed, and an acidic chlorophyll precipitate is obtained. The obtained acidic chlorophyll precipitate is washed with clean water (that is, water suitable for drinks) until the washing solution becomes acidic. PH wash
It is preferable to carry out until about 3.

Various solid-liquid separators can be used in the step of dehydrating the obtained precipitate and recovering the paste-like acidic bear bamboo chlorophyll, but a filter press is preferable.

The step of preparing the bear chlorophyll chlorophyll liquid is carried out by adding sodium hydrogencarbonate to neutralize, and the final product, the bear chlorophyll chlorophyll liquid, is obtained. In this process, P
Neutralization is performed until H becomes 7.0 to 8.0, and the paste is liquefied. It is preferable to neutralize until the pH becomes 7.1 to 7.6. The sodium hydrogen carbonate used for neutralization is preferably used as it is as a solid crystal powder, but it may be used as an aqueous solution.

The obtained chlorophyll liquor contains various amino acids, inorganic components such as iron and magnesium, vitamins and the like in addition to sodium copper chlorophyllin, and has a nutritional tonic effect and a natural healing power activating effect. , Is effective when mixed with carrot extract, red pine needle extract, etc. Amino acids contained therein include lysine, histidine, arginine, aspartic acid, threonine, serine, glutamic acid, proline, glycine, alanine, valine, methionine, isoleucine, leucine, phenylalanine and GABA. In addition, the acidic paste bear chlorophyll chlorophyll, which is a precursor, does not undergo solid-liquid separation when frozen and stored for about 10 days, and is useful when used as an additive for foods, cosmetics and the like.

[0026]

[Examples] 50 kg of raw striped bamboo shoots, which is the raw material of Kuma bamboo grass, on the third day after collection was immersed in a copper sulfate treatment liquid tank containing a 0.2 wt% copper sulfate aqueous solution at a temperature of 98 ° C for 1 hour. And stabilize the chlorophyll. As a result, Mg in the chlorophyll is replaced by Cu and the chlorophyll is stabilized. This treatment reduces the capacity of Kuma bamboo to about 1/3. The treated bear bamboo was stored in a freezer at a temperature of -5 ° C for 3 months. After the natural bear thaws after storage are thawed, they are immersed in a 1.4% acidic sodium sulfite solution at 98 ° C. for 1 hour to remove the blackish immersion liquid, thereby removing lignin. After removing the lignin, the bear bamboo grass is cut with a cutting machine having a blade on the rotating shaft, a blade on the inner wall of the housing surrounding it, and a screen on a part of the housing. Then, it is treated with a dissolution pot containing a caustic soda solution at a concentration of 1.5% by weight at 100 ° C. to form a liquid containing a chlorophyll component,
Then, this is separated from the residue by a belt press separator to obtain a chlorophyll liquid.

After the separation, the chlorophyll solution was cooled to 20 ° C. and neutralized by putting it in a neutralizing water washing tank containing 3.6% by weight hydrochloric acid to form an acidic bear bamboo precipitate, which was subjected to PH with ordinary water. Is 2.
Wash with water until it reaches 5. The precipitate (water content 99%) is dehydrated by a filter press to obtain paste-like acidic bear chlorophyll chlorophyll. Add sodium bicarbonate to this chlorophyll and add about PH
A 7.3 Kuma bamboo leaf chlorophyll solution was produced. In the produced Kuma bamboo leaf chlorophyll liquid, in addition to sodium copper chlorophyllin, various amino acids, inorganic components such as iron and magnesium,
Contains vitamins, etc. The various amino acids contained are
Lysine, histidine, arginine, aspartic acid, threonine, serine, glutamic acid, proline, glycine, alanine, valine, methionine, isoleucine, leucine, phenylalanine, GABA.

[0028]

EFFECTS OF THE INVENTION In the present invention, while the production of Kuma bamboo, which is a raw material, is limited seasonally and regionally, the production equipment is automated as much as possible and operated throughout the year regardless of the season. It is possible to produce chlorophyll liquor in a large amount, efficiently and stably. That is, there is no need for a large storage for storing raw bear bamboo, and there is no discoloration or deterioration of bear bamboo that accompanies storage. Furthermore, it has the merit that it is possible to intensively use bear bamboo grass, which has a high chlorophyll content and was collected in August to October, as a raw material. In addition, since the equipment is not seasonally operated and can be operated for almost one year throughout the entire process, there is also an advantage that smaller equipment is required compared to seasonal operation.

[Brief description of drawings]

FIG. 1 shows all the steps of the present invention from bear bamboo shoot collection to bear bamboo leaf chlorophyll liquid preparation.

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Claims (8)

(57) [Claims] 1. A step of stabilizing treatment of raw bear bamboo with a heated dilute copper sulfate solution, a step of refrigerating the treated bear bamboo at -3 to -15 ° C., and a heating of the bear bamboo after preservation. To remove lignin by treating with diluted acidic sodium sulfite solution, to cut bear bamboo after removing lignin, to process the treated bear bamboo with heated dilute caustic soda solution, solid-liquid Kuma bamboo-containing liquid after treatment Paste-like acidic bear bamboo leaf chlorophyll, which comprises a step of separating, a step of neutralizing the obtained alkaline bear bamboo leaf chlorophyll liquid to form an acidic bear bamboo leaf chlorophyll precipitate, and a step of dehydrating the obtained precipitate to recover paste acidic bear bamboo leaf chlorophyll Manufacturing method. 2. A step of stabilizing treatment of raw bear bamboo grass with a heated dilute copper sulfate solution, a step of storing the treated bear bamboo grass frozen and stored at -3 to -15 ° C., and heating the bear bamboo grass after storage. To remove lignin by treating with diluted acidic sodium sulfite solution, to cut bear bamboo after removing lignin, to process the treated bear bamboo with heated dilute caustic soda solution, solid-liquid Kuma bamboo-containing liquid after treatment A step of separating, a step of neutralizing the obtained alkaline bear bamboo leaf chlorophyll liquid to produce an acidic bear bamboo leaf chlorophyll precipitate, a step of dehydrating the obtained precipitate and collecting the paste acidic bear bamboo leaf chlorophyll, and this paste acidic bear bamboo leaf chlorophyll A method for producing Kuma bamboo leaf chlorophyll liquid, which comprises the steps of adding sodium hydrogen carbonate to and preparing a Kuma bamboo leaf chlorophyll liquid. 3. The method according to claim 1, wherein the concentration of the diluted copper sulfate solution is 0.1 to 0.5% by weight in the step of stabilizing the raw bear bamboo grass with the heated diluted copper sulfate solution. Production method. 4. A process of cryopreservation, either one of claims 1 to 3, at least 3 months of storage period 1
The manufacturing method according to item . 5. A process for removing lignin process according to any one of claims 1 to 4 allowed to 0.5 to 2.5 wt% concentration of the dilute acidic sodium sulfite solution. 6. A process for treating a dilute sodium hydroxide solution, the production method according to any one of claims 1 to 5 allowed to a concentration of sodium hydroxide solution and 0.6 to 3.0 wt%. 7. A process allowed to generate by neutralizing the alkaline striped bamboo chlorophyll liquid acidic striped bamboo chlorophyll precipitate claims 1 allowed to the hydrochloric acid concentration and 3.0 to 5.0 wt% 6
The process according to any one of. 8. The method according to claim 2, wherein sodium hydrogencarbonate is added to the paste-like acidic bear bamboo chlorophyll to prepare a bear bamboo leaf chlorophyll solution to obtain a bear bamboo leaf chlorophyll solution having a pH of 7.1 to 7.6. 7. The manufacturing method according to any one of 7.