JP6527220B1 - Willow tree extract and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an industrially useful willow tree extract free from coloring and unique flavor, and a simple manufacturing method for obtaining the same. SOLUTION: A willow tree extract extract is a distillate obtained by distillation at a temperature of 150 ° C. or less of a willow tree extract solvent extraction solution. [Selected figure] None

Description

The present invention relates to a willow tree extract extract containing polygodial as an active ingredient, and a method for producing the same.
According to the present invention, by distilling a solvent extract of willow tree extract, it is possible to provide a willow tree extract extract having no color or unique flavor and improved in stability, and a method for producing the same.

  Yanagi-tade (Sakai-yanagi, scientific name: Persicaria hydropiper) is an annual herb of the family Acoideae, which is a plant that exhibits a characteristic hot taste that has also been derived from the "I like insects and worms". Although the level of recognition as an edible plant is not high, the history of its use for food is very old, and the description is already seen in the Enoki style (967), which summarizes the detailed rules of the mid-season events during the Heian period. It can be said that it is one of the spices. In modern times, it is mainly used such as adding a sashimi dish with a sprout (tsuma) and adding a color to the dish by making use of bright reddish purple.

  In recent years, insecticidal effects (non-patent document 1) and antibacterial actions (non-patent document 2) etc. have been clarified from a scientific point of view, for example, agricultural crop pests using polygodial, which is a characteristic component of willowfish, as an active ingredient Hygienic pests, haematophagous pests, clothing pests and shellfish pest repellants (Patent Document 1), antifungal compositions (Patent Document 2), methods for improving the flavor of mint flavors and mint flavor compositions (Patent 3), Methods for improving the aftertaste of sweeteners (Patent Document 4) and the like have been reported.

  However, the use of willow tree extract as it is gives the final product a grass-like flavor unique to willow tree extract and also contains anthocyanin pigment, which is another valuable component of willow tree, so even minor amounts of coloring There is a problem in that the color tone changes greatly depending on the pH and the color, and coloring occurs with time, etc., and there is a problem to be widely used in industry.

  In a method for producing miso excellent in maintainability (Patent Document 5), an ethanol extract of a mixture of willow tree leaves and twigs is dissolved in hexane, filtered, distilled off by hexane, and then separated and purified by silica gel chromatography. Therefore, purification of polygodial was carried out, and it was necessary to carry out a very complicated purification method in order to remove the unique flavor and coloring components of willow tree extract. Therefore, in order to widely use polygodial in industries such as food and drink and cosmetics, it contains polygodial which is industrially easy to use without coloring and unique flavors considering that the raw material price itself of willow is expensive. There is a demand for inexpensive and easy to obtain willow tree extract.

Japanese Patent Application Laid-Open No. 63-166814 Japanese Patent Application Laid-Open No. 7-135942 Japanese Patent Application Laid-Open No. 7-145398 U.S. Pat. No. 5,948,460 JP-A-3-259058

Isr. J. Chem. , 16, 28 (1977) J. Natural Products, 51, 22 (1988)

  The problem to be solved by the present invention is that there is no coloring or unique flavor, and for example, it is industrially useful extractable willow extract as pest repellent, preservative, flavor improver, antioxidant, whitening agent, anti-aging agent, etc. It is an object of the present invention to provide an article and a simple manufacturing method for obtaining the same.

As a result of intensive investigations to solve the above problems, the present inventor distills a solvent extract of willow treedee, so that the willow tree extract without coloration and unique flavor inexpensively and simply without going through complicated purification steps The present invention has been completed.
That is, the present invention is characterized by the following.

(1) A willow tree extract extract characterized by being a distillate obtained by distilling a willow tree extract solvent extract at a temperature of 150 ° C. or less.
(2) The willow tree extract according to the above (1), wherein the solvent is one or a mixture of water, acetone, ethanol and ethyl acetate.
(3) The willow tree extract according to (1) or (2) above, wherein the distillate is a short-step distillation fraction of 40 Pa or less and 140 ° C. or less.
(4) Any one of the above (1) to (3), wherein the distillate is a distillate of an extract containing an auxiliary solvent having a boiling point of 180 ° C. to 700 ° C. at atmospheric pressure. Willowfish extract described.
(5) The above-mentioned (4), wherein the co-solvent is one selected from the group consisting of propylene glycol, glycerin, medium-chain fatty acid ester, triacetin and triethyl citrate, or a mixture thereof. Willowfish extract.

(6) A method for producing willow tree extract, which comprises the following steps:
(A) a step of extracting the willow tree extract with a solvent selected from water, an organic solvent, or a mixture thereof to obtain an extract, and (b) distilling the extract obtained in step (a) at a temperature of 150 ° C. or less Distillation step to obtain a polygodial-containing fraction,
Said manufacturing method characterized by containing.
(7) The solvent described in the step (a) is one or more selected from water, alcohols having 1 to 3 carbon atoms, acetone, or ethyl acetate, described in the above (6) Of the willow tree extract extract.
(8) The process for producing the willow tree extract extract according to (6) or (7) above, wherein the distillation step described in the step (b) is short-step distillation at 40 Pa or less and 140 ° C. or less.
(9) Any of the above-mentioned (6) to (8) characterized by adding an auxiliary solvent having a boiling point of 180 ° C. to 700 ° C. at atmospheric pressure before distillation of the step (a) or the step (b). The manufacturing method of the willow treedew extract described in a crab.
(10) The above-mentioned (9), wherein the co-solvent is one selected from the group consisting of propylene glycol, glycerin, medium-chain fatty acid ester, triacetin and triethyl citrate, or a mixture thereof. Method of producing willow tree extract.

  According to the present invention, since it is possible to obtain an industrially usable willow extract without coloration or unique flavor, it can be used, for example, as a pest repellent, preservative, flavor improver, antioxidant for various food and drink products and cosmetics. It can be used widely as an agent, a whitening agent, an anti-aging agent, etc.

The invention is described in detail below.
[A] Raw materials The willow tree (Persicaria hydropiper) used in the present invention can be used without particular limitation as long as it is a site containing polygodial such as sprouts, seeds, leaves of grown bodies, etc. . Sprouts with food experience are preferred given their availability and use in food.

[B] Extraction step The extraction solvent used for the extraction of willow tree water is water, alcohols (for example, lower alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol, isopropanol etc.), acetone, ethyl acetate etc. Alternatively, it can be used as a mixture of two or more kinds. Among extraction solvents, it is preferable to use water, ethanol, acetone or ethyl acetate alone or as a mixture of two or more, from the viewpoint of extraction rate, price, safety of operation, etc. Ethyl acetate and ethanol are particularly preferable. preferable.
The amount of the extraction solvent is not particularly limited and can be appropriately adjusted according to the purpose, but 300 to 3000 parts by mass, more preferably 500 to 2000 parts by mass is used with respect to 100 parts by mass of willowfish.
The extraction temperature is usually 0 to 100 ° C, preferably 20 to 50 ° C, more preferably 30 to 40 ° C.
The extraction time depends on the temperature to be extracted, but is usually 30 minutes to 5 hours, preferably 1 to 2 hours.
The obtained extract is subjected to solid-liquid separation using a filter paper or the like to obtain a crude extract containing polygodial. The crude extract can be subjected to a distillation step as it is, but it is preferable to distill off the extraction solvent to obtain a concentrate.

  In addition, the crude extract solution extracts the active ingredient, polygodial, into a solvent of low polarity side by liquid-liquid distribution extraction before distilling off the extraction solvent, or makes a highly polar contaminating component into a solvent of high polarity side. Extraction can also remove highly polar contaminants. When liquid-liquid distribution extraction is performed, 50 to 200 parts by mass of a solvent immiscible with the crude extract is added to 100 parts by mass of the crude extract. For example, when the extraction solvent is ethyl acetate, water, or a mixture of water and alcohol can be used, and when the extraction solvent is water, or a mixture of water and alcohol, acetic acid Ethyl, hexane, heptane or the like can be used.

[C] Distillation step A distillate containing polygodial is obtained by distilling a willow seed concentrate.
A well-known distillation installation can be used for a distillation process. Specifically, simple distillation, rectification, flash distillation, short-step distillation and the like can be mentioned.
If the evaporation temperature exceeds 150 ° C., polygodial is decomposed to cause a significant decrease in yield, so distillation at 150 ° C. or less is necessary, preferably 140 ° C. or less, more preferably 130 ° C. It is desirable that the distillation be carried out at 120 ° C. or less. Therefore, it is necessary to carry out under reduced pressure using a known vacuum pump such as an oil rotary pump, a mechanical booster pump, and a diffusion pump. When the size of the apparatus increases, the amount of heat required for distillation increases, and there are problems such as decomposition of the active ingredient and deterioration of energy efficiency, so short-step distillation is most preferable, and centrifugal thin film type or falling film type apparatus should be used. it can.
The degree of reduced pressure at the time of distillation is not limited as long as it is a pressure at which polygodial is distilled at 150 ° C. or less, but distillation at a lower pressure is desirable, 40 Pa or less is preferable, 30 Pa or less is more preferable, and further preferably 20 Pa or less is there.

Since the content of polygodial in the willow tree extract is very low, it may adhere to the cooling unit for condensing the fraction and the recovery rate may decrease, and if necessary, the fraction adhered to the cooling unit using a solvent Can also be recovered. There is no restriction | limiting in the solvent which can be used, It can select suitably from a price, the ease of handling, the use, etc. For example, water, ethanol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, 1,2-pentanediol, 1,3-propanediol, medium-chain fatty acid ester, triacetin, triethyl citrate and the like Is preferred, and if the extract of willow tree extract is to be obtained as a water-soluble preparation, ethanol or a hydrate thereof, if it is obtained as a fat-soluble preparation, a medium-chain fatty acid ester (a medium-chain fatty acid having 5 to 12 carbon atoms of the constituent fatty acids Triglycerides etc. are particularly preferred.

[D] Auxiliary solvent Depending on the distillation apparatus used, the fraction attached to the cooling section can not be recovered by the solvent, or complicated operations may be necessary, and recovery may be difficult. It is preferable to add an auxiliary solvent to the solution in advance. By distilling the willow tree extract extract containing the auxiliary solvent, the amount of fractions increases, and it is possible to efficiently recover the polysaccharide-containing fractions without performing the recovery operation using the solvent. The type and amount of auxiliary solvent to be used can be appropriately selected according to the purpose in view of price, safety, ease of handling, application and the like, but the boiling point is preferably equivalent to that of polygodial, preferably under atmospheric pressure ( A solvent having a boiling point of 180 ° C. or more, more preferably 200 ° C. or more, and 700 ° C. or less is preferable, and 600 ° C. or less is more preferable. If the boiling point of the auxiliary solvent used is 180 ° C. or lower, the auxiliary solvent recovery efficiency in the cooling pipe is poor, and if it is 700 ° C. or higher, the auxiliary solvent is hardly distilled, which is unsuitable. Examples of the co-solvents include glycerin (boiling point at atmospheric pressure (1 atm), etc. thereafter: 290 ° C.), propylene glycol (188 ° C.), dipropylene glycol (232 ° C.), medium-chain fatty acid ester (constituting fatty acid Medium-chain fatty acid triglyceride having 5 to 12 carbon atoms (370 to 670 ° C), triacetin (260 ° C), triethyl citrate (294 ° C) and the like are preferable. Glycerin, propylene glycol, or a mixture thereof is particularly preferred when the willow extract is obtained as a water-soluble preparation, and when it is obtained as a fat-soluble preparation, a medium-chain fatty acid ester (a medium-chain fatty acid having 5 to 10 carbon atoms having 5 to 10 carbon atoms) Triglycerides are particularly preferred. The auxiliary solvent may be added at any step before distillation, but it is preferable to add it before extraction or before distilling off the extraction solvent from the crude extract. The amount of the auxiliary solvent is not particularly limited and can be appropriately adjusted according to the purpose, but 10 to 500 parts by mass, more preferably 50 to 200 parts by mass is used with respect to 100 parts by mass of willowade used as an extraction raw material.

  When the auxiliary solvent is added before extraction or before distilling off the extraction solvent from the crude extract, the extraction solvent is distilled off under the condition that the auxiliary solvent is not distilled off.

[E] Willow Tree Extract Extract The willow tree extract extract of the present invention obtained by the above-mentioned method is a plant-like flavor derived from willow tree extract or an anthocyanin which affects coloration has been removed or reduced.
Here, the willow tree extract obtained by the above-described method contains, as with the extracts of other plants, a great many components other than the active ingredients. That is, various components such as fat, vitamins, and aroma components are contained in a complicated state or blending ratio.
Therefore, in order to directly identify the willow tree extract according to the present invention by structure or specification, identification and quantification of components are essential, but identifying and quantifying all the components is at the bottom of technical common sense. Impossible or not nearly practical.
Therefore, the willow tree extract according to the present invention is an invention that can not be specified by the production method.

[F] Additional component The above-mentioned willow tree extract extract can be used sufficiently as produced, but various modifications such as adding an additional component or combining it with other active ingredients are variously modified. Can be implemented.
For example, it is exemplified to combine Yanagidade extract with various known natural perfumes and synthetic perfumes to make perfume compositions.
In addition, it can be used as a preparation for cosmetics and quasi-drugs in combination with bases and additives usually used in cosmetics etc., as well as antioxidants (vitamin C, vitamin E, etc.), saccharides, It can be used as a composition for food and drink, health food, food additive, medicine, in combination with a sweetener, a thickening stabilizer, a pH adjuster and the like.
Furthermore, the willow tree extract is provided in any form other than liquid, for example, in the form of emulsion, paste, gel, powder (powder), granule, pellet, stick, solid, etc. May be

EXAMPLES The present invention will next be described in more detail by way of examples, which should not be construed as limiting the invention.
Production Example 1
1000 g of ethyl acetate was added to 100 g of willow tree sprout (Fukuoka Horticulture Co., Ltd.) and extracted at 40 ° C. for 1 hour, followed by solid-liquid separation with filter paper to obtain 900 g of a crude extract. Ethyl acetate was removed under reduced pressure (100 mmHg, 40 ° C.) of the obtained crude extract to obtain 50 g of a concentrated solution of willow tree crude extract.

Example 1
50 g of the concentrate obtained in Production Example 1 is distilled at 120 ° C. and 120 ° C. using a falling film short-step distillation apparatus, and the fraction obtained on the condensation surface is recovered with ethanol, and 100 g of the recovered solution obtained And Example 1.

Example 2
100 g of glycerin was added to 900 g of the crude extract obtained by the method described in Production Example 1, and concentrated under reduced pressure to obtain 120 g of a concentrated solution. The concentrate was distilled at 20 Pa and 120 ° C. using a falling film short-step distillation apparatus, and 90 g of the obtained fraction was used as Example 2.

[Example 3]
100 g of propylene glycol (PG) was added to 900 g of the crude extract obtained by the method described in Production Example 1 and concentrated under reduced pressure to obtain 120 g of a concentrate. The concentrate was distilled at 20 Pa and 120 ° C. using a falling film short-step distillation apparatus, and 90 g of the obtained fraction was used as Example 3.

Example 4
100 g of medium-chain fatty acid triglyceride (MCT, trade name: MASESTER-E7000 (manufactured by Chuo Kasei Co., Ltd.)) was added to 900 g of the crude extract obtained by the method described in Production Example 1, concentrated under reduced pressure, and 120 g of the concentrate Obtained. This concentrate was distilled at 10 Pa and 120 ° C. using a falling film short-step distillation apparatus, and 80 g of the obtained fraction was used as Example 4.

Comparative Example 1
After adding 1000 g of 95% ethanol to 100 g of willow tree extract (Fukuoka Horticulture Co., Ltd.) and extracting at 40 ° C. for 1 hour, solid-liquid separation with filter paper and concentrating 950 g of the obtained filtrate under reduced pressure, 90 g of the obtained concentrated solution This is Comparative Example 1.

Comparative Example 2
1000 g of ethyl acetate is added to 100 g of willow tree extract (Fukuoka Horticulture Co., Ltd.) and extracted at 40 ° C. for 1 hour, followed by solid-liquid separation with filter paper, and 900 g of the obtained filtrate is concentrated to dryness under reduced pressure (100 mmHg, 40 ° C.) After the addition, 95% ethanol was added to make 90 g, and this was taken as Comparative Example 2.

Comparative Example 3
100 g of medium-chain fatty acid triglyceride (MCT, trade name: MASESTER-E7000 (manufactured by Chuo Kasei Co., Ltd.)) was added to 900 g of the crude extract obtained by the method described in Production Example 1, concentrated under reduced pressure, and 120 g of the concentrate Obtained. This concentrate was distilled at 20 Pa and 160 ° C. using a falling film short-step distillation apparatus, and 60 g of the obtained fraction was regarded as Comparative Example 3.

[Test Example 1]
With respect to the willow tree extract obtained in Examples 1 to 4 and Comparative Examples 1 to 3, the content and recovery of polygodial were measured as follows. The results are shown in Table 1.
[HPLC measurement conditions]
Stationary phase: Capcell Pak C18, 4.6 mm i. d. x 250 mm
Mobile phase: acetonitrile 10% → 100%, pH 2.5 (25 min)
Detection wavelength: 235 nm
[Polygodial recovery amount]
A calibration curve is prepared by HPLC using a polygodial preparation (Wako Pure Chemical Industries, Ltd. 164-26231), and from the peak area of polygodial in the willow extract of Examples 1 to 4 and Comparative Examples 1 to 3 in willow extract The polygodial content of was calculated.

Subsequently, the amount of polygodial recovered from willow was calculated according to the following equation from the following equation.
Recovery amount of polygodial from willow tree (mg / g) = A x B / C
Here, A to C are as follows.
A: Polygodial content of willow tree extract (mg / g)
B: Mass of willow tree extract (g)
C: willow mass used for extraction (g)

[Test Example 2]
About the willow treede extract obtained in Examples 1-4 and Comparative Examples 1-3, coloring was confirmed as follows with five trained sensory evaluation panels. The results are shown in Table 1.
[Evaluation method]
3: colorless and transparent 2: slightly colored 1: heavily colored

[Test Example 3]
With respect to the willow tree extract obtained in Examples 1 to 4 and Comparative Examples 1 to 3, 0.1% is added to water, and five trained sensory evaluation panels are as follows for the pungent taste and herbaceous odor: The presence or absence of flavor was confirmed. The results are shown in Table 1.
[Evaluation method]
[Pot], [Scent (grass-like)]
5: very strong 4: strong 3: weak 2: very weak 1: not feeling

[Test Example 4]
The willow tree extract extract obtained in Examples 1 to 4 and Comparative Examples 1 to 3 is stored at 5 ° C. for 3 months, and the content of polygodial which is an active ingredient is measured by HPLC according to Test Example 1 to prepare The residual rate to the content immediately after was determined. The results are shown in Table 1.

  From the results in Table 1, the willow tree extract extract of Example 1 to Example 3 distilled at 20 Pa and 120 ° C. using ethyl acetate as the extraction solvent has no auxiliary solvent, glycerin, propylene glycol as medium, and medium-chain fatty acid triglyceride. Even if any of the above was used, it was clear and colorless, had good flavor (very strong pungency, very weak grassy flavor), and did not decrease in polygodial over time. On the other hand, the willow tree extract extract of Comparative Example 1 which is not subjected to distillation after extraction with ethanol has a deep color, is weak in pungency, and significantly reduces polygodial over time. Moreover, in the willow tree extract extract of Comparative Example 2 which is extracted with ethyl acetate and is not subjected to a distillation process, although there is no decrease in polygodial over time, it has a deep red color and feels a strong pungency, The flavor of was strongly felt. The willow tree extract extract of Comparative Example 3 distilled at 20 Pa and 160 ° C. using ethyl acetate as an extraction solvent was colorless and transparent, but the recovery rate was poor and the pungency was weak because polygodial was decomposed.

The willow tree extract according to the present invention is free from grassy off-flavors, offensive odors, is colorless and transparent, and is excellent in stability over time, so various food products and cosmetic products such as pest repellents, preservatives and flavors are improved. It is expected to be used as an agent, an antioxidant, a whitening agent, an anti-aging agent, etc.

Claims (10)

A polygodial-containing willow extract extract characterized in that it is a distillate obtained by distilling a willow extract solvent extract at a temperature of 150 ° C. or less.   The willow tree extract extract according to claim 1, wherein the solvent is one or a mixture of water, acetone, ethanol and ethyl acetate.   The willow tree extract according to claim 1 or 2, wherein the distillate is a short-step distillation fraction of 40 Pa or less and 140 ° C. or less.   The willow tree extract according to claim 3, wherein the distillate is a distillate of an extract containing a cosolvent having a boiling point of 180 ° C to 700 ° C at atmospheric pressure. Characterized in that said cosolvent is propylene glycol, glycerol, medium-chain fatty acid Toriguriserai de carbon number 5-12 carbon atoms configurations fatty acids, triacetin, one or a mixture thereof selected from the group consisting of triethyl citrate The willow tree extract extract according to claim 4. A method for producing willow tree extract, which comprises the following steps:
(A) a step of extracting the willow tree extract with a solvent selected from water, an organic solvent, or a mixture thereof to obtain an extract, and (b) distilling the extract obtained in step (a) at a temperature of 150 ° C. or less Distillation step to obtain a polygodial-containing fraction,
Said manufacturing method characterized by containing.   The willow tree extract according to claim 6, wherein the solvent described in step (a) is at least one selected from water, alcohols having 1 to 3 carbon atoms, acetone, or ethyl acetate. Manufacturing method. The method for producing willow tree extract according to claim 6 or 7, wherein the distillation step described in the step (b) is short-step distillation at 40 Pa or less and 140 ° C. or less.   9. The process according to claim 8, wherein the auxiliary solvent having a boiling point of 180 ° C. to 700 ° C. under atmospheric pressure is added before the distillation of step (a) or step (b). Characterized in that said cosolvent is propylene glycol, glycerol, medium-chain fatty acid Toriguriserai de carbon number 5-12 carbon atoms configurations fatty acids, triacetin, one or a mixture thereof selected from the group consisting of triethyl citrate The manufacturing method of the willow tree extract extract according to claim 9.