JP7615248B2 - Fragrance composition containing polygodial and isothiocyanates - Google Patents

Description

The present invention relates to a flavor composition for use in food and beverage compositions having the flavor of a cruciferous plant, which is characterized by containing polygodial and isothiocyanates, and optionally further containing spilanthol.
More specifically, the present invention relates to a flavor composition for enhancing the spiciness of a wasabi-flavored food or drink composition or a mustard-flavored food or drink composition, as well as a flavor composition for masking the deterioration odor of these food or drink compositions.

Isothiocyanates, such as allyl isothiocyanate, which are contained in cruciferous plants, such as wasabi, mustard, radish, and mustard greens, are known to have a unique spicy taste and play an important role in expressing the flavor of cruciferous plants.
However, isothiocyanates are highly volatile and gradually decrease in food, resulting in the issue of losing their characteristic flavor.
In addition, due to its chemical structure, it is susceptible to hydrolysis, which causes a problem of loss of flavor, particularly in aqueous foods and beverages.
When isothiocyanates are hydrolyzed, there is a problem that not only does the flavor deteriorate, but the flavor is also impaired by a deteriorated odor generated by the decomposition.
Therefore, various measures have been proposed to enhance or maintain the pungency.

As methods for enhancing or maintaining the pungency of cruciferous plants or allyl isothiocyanate, a method of stabilizing the pungency and flavor components contained in wasabi by adding vitamin E to wasabi (Patent Document 1) and a method of enhancing the pungency of wasabi-containing foods by adding an emulsified flavoring composition containing menthol (Patent Document 2) have been proposed.

Also proposed is a pungent preparation (Patent Document 3) that contains at least one aroma component selected from the group consisting of maltol, isomaltol, anisaldehyde, anethole, sotolon, ethyl maltol, maple syrup flavor, fenugreek oleoresin, lobegi oleoresin, licorice oleoresin, and glycyrrhizin, and isothiocyanates.

However, with the above-mentioned technology, after the food and beverage composition is produced, the flavor deteriorates due to a decrease in allyl isothiocyanate even during distribution and storage (during warehouse storage and in-store display), making it difficult to maintain the natural pungency and flavor for a long period of time.
It has been proposed to add a larger amount of allyl isothiocyanate in anticipation of the decrease during storage, but this method causes problems such as a poor balance of the initial flavor and a stronger deterioration odor caused by the decomposition of allyl isothiocyanate, which actually reduces the commercial value.
In this situation, there is a demand for further technological development in response to consumer trends toward gourmet food and the pursuit of higher quality and safer food and beverages.

Japanese Patent Application Publication No. 8-89208 JP 2011-19457 A Japanese Patent Application Publication No. 10-155451

The problem that the present invention aims to solve is to provide a flavoring composition that can be added to a food or beverage composition having the flavor of a cruciferous plant, such as a wasabi-flavored food or beverage composition or a mustard-flavored food or beverage composition, and that exhibits good pungency and a pungency-enhancing effect not only immediately after production but also after long-term storage.
Another object of the present invention is to provide a flavoring composition that has an excellent masking effect and can be added to a cruciferous plant-flavored food or beverage composition to give the food or beverage composition a flavor with a weak deterioration odor not only immediately after production but also after long-term storage.
Furthermore, the present invention provides a flavor composition for a cruciferous plant-flavored food or drink composition that naturally expresses pungency.

As a result of intensive research conducted by the present inventors to solve the above problems, they discovered that a flavoring composition having a cruciferous plant flavor, which is characterized by containing polygodial and isothiocyanates, and optionally further spilanthol, can maintain a good pungency in a cruciferous plant-flavored food or beverage composition for a long period of time, can effectively mask the deterioration odor of isothiocyanates, and can express a natural pungency in a cruciferous plant-flavored food or beverage composition, thereby completing the present invention.

That is, the present invention is as follows.
[1] A flavor composition having the flavor of a plant of the Brassicaceae family, characterized by containing polygodial and isothiocyanates.
[2] The fragrance composition as described above, wherein the isothiocyanates are one or more isothiocyanates selected from the group consisting of ω-alkenyl isothiocyanates represented by the following formula [1], ω-methylthioalkyl isothiocyanates represented by the following formula [2], and ω-alkyl isothiocyanates represented by the following formula [3]:

[3] The fragrance composition as described above, characterized in that the ratio of polygodial to 1,000 parts by mass of isothiocyanates is 0.0001 to 10.
[4] The fragrance composition as described above, characterized in that the concentration of the polygodial is 100 ppb to 1% and the concentration of the isothiocyanates is 100 ppm to 99%.
[5] The fragrance composition as described above, wherein the polygodial is contained in a plant extract or essential oil containing polygodial.
[6] The above flavor composition, wherein the Brassicaceae plant is wasabi or mustard.

[7] The above fragrance composition, characterized in that it is used in combination with spilanthol.
[8] The fragrance composition described above, characterized in that spilanthol is used in combination in a ratio of 0.01 to 100 parts by mass per part by mass of polygodial.
[9] The flavor composition as described above, characterized in that the flavor composition is a flavor composition for enhancing the pungency of a food or beverage composition having the flavor of a cruciferous plant.
[10] The above-mentioned flavor composition, characterized in that the flavor composition is a flavor composition for masking the deterioration odor of a food or beverage composition having the flavor of a cruciferous plant.

[11] A method for enhancing the pungency of a food or beverage composition having the flavor of a cruciferous plant, comprising adding polygodial to the food or beverage composition at a concentration of 0.5 ppb to 1000 ppb and isothiocyanates to the food or beverage composition at a concentration of 10 to 5000 ppm.
[12] The above-mentioned method for enhancing pungency, wherein the food or beverage composition having the flavor of a cruciferous plant is a wasabi-flavored food or beverage composition or a mustard-flavored food or beverage composition.
[13] A food or beverage composition having the flavor of a Brassicaceae plant, the pungency of which has been enhanced by the above method.

[14] A method for masking the deterioration odor of a food or beverage composition having the flavor of a cruciferous plant, comprising adding polygodial to the food or beverage composition at a concentration of 0.5 ppb to 1000 ppb and isothiocyanates to the food or beverage composition at a concentration of 10 to 5000 ppm.
[15] The method for masking a deterioration odor, wherein the food or beverage composition having the flavor of a cruciferous plant is a wasabi-flavored food or beverage composition or a mustard-flavored food or beverage composition.
[16] A food or beverage composition having the flavor of a Brassicaceae plant masked by the above method.

[17] A food or beverage composition having the flavor of a Brassicaceae plant, characterized by containing polygodial and isothiocyanates.
[18] The food or beverage composition having the flavor of a cruciferous plant, characterized in that the ratio of polygodial to 1,000 parts by mass of isothiocyanates is 0.0001 to 10.
[19] The food or drink composition having the flavor of a cruciferous plant, characterized in that the concentration of polygodial in the food or drink is 0.5 ppb to 1000 ppb and the concentration of isothiocyanates in the food or drink is 10 to 5000 ppm.
[20] The food or drink composition having the flavor of a cruciferous plant, wherein the food or drink composition is a food or drink composition having a wasabi flavor or a food or drink composition having a mustard flavor. [21] The food or drink composition as described above, which is used in combination with spilanthol.
[22] The food and beverage composition as described above, characterized in that spilanthol is used in combination in a ratio of 0.01 to 100 parts by mass per part by mass of polygodial.
[23] A food or beverage composition for enhancing spiciness having the flavor of a cruciferous plant, comprising the flavor composition for enhancing spiciness described above added thereto.

[24] A food or beverage composition for masking deterioration odors having the flavor of a cruciferous plant, comprising the above-described masking fragrance composition added thereto.
[25] A method for producing a cruciferous plant-flavored food or beverage composition, comprising adding polygodial to a food or beverage composition having a cruciferous plant flavor so that the concentration of polygodial is 0.5 ppb to 1000 ppb and the concentration of isothiocyanates is 10 to 5000 ppm.
[26] A method for producing a cruciferous plant-flavored food or beverage composition, comprising adding the above-mentioned flavor composition for enhancing spiciness in order to enhance the spiciness.

[27] A method for producing a cruciferous plant-flavored food or beverage composition, comprising adding the above-mentioned fragrance composition for masking deterioration odors in order to mask deterioration odors.
[28] A method for producing the above-mentioned Brassicaceae plant-flavored food and beverage composition, characterized in that the polygodial is contained in a distillate obtained by distilling an organic solvent extract of Polygonum officinalis at a temperature of 150°C or lower.
[29] A method for producing a cruciferous plant-flavored food or beverage composition, wherein the food or beverage composition having the flavor of a cruciferous plant is a wasabi-flavored food or beverage composition or a mustard-flavored food or beverage composition.

The flavor composition of the present invention uses isothiocyanates and polygodial in combination, and can provide a cruciferous plant (e.g., wasabi, mustard, etc.)-flavored food and drink composition that has a pungent taste and a good flavor even when the amount of isothiocyanates has decreased over time. It is particularly suitable for aqueous wasabi-flavored food and drink, in which the pungent taste is significantly reduced.

(Spicy taste enhancing effect)
The combined use of isothiocyanates and polygodial provides a pungent taste enhancement effect. This enhancement effect is exerted even at low concentrations where pungent taste is not felt when isothiocyanates alone are used. The quality of the pungent taste generated by the enhancement is suitable for a Brassicaceae-flavored food and drink composition and does not give an unpleasant feeling. Therefore, it is possible to obtain a flavor with a natural pungent taste even when the amount of isothiocyanates is reduced due to changes over time.

(Effect on odor of deterioration)
Isothiocyanates produce a deterioration odor upon decomposition. The deterioration odor produced by decomposition differs depending on the compound; for example, allyl isothiocyanate produces a garlic odor, while 3-butenyl isothiocyanate produces a solvent odor. By using polygodial in combination, the deterioration odor of isothiocyanates, such as garlic odor and solvent odor, is masked, so that a good flavor can be maintained even after storage. The deterioration odor that is particularly problematic in terms of causing an unpleasant flavor is the garlic odor produced by the decomposition of allyl isothiocyanate.

(Effect of combined use with Spilanthol)
By using the three ingredients, isothiocyanates, polygodial and spilanthol, in combination, the spiciness is expressed more naturally.
One characteristic of the spiciness of the Brassicaceae plant-flavored food and drink composition is that it is felt strongly from the initial to mid-point. When isothiocyanates and polygodial are used in combination, the mid-point spiciness is felt strongly, but the initial spiciness is somewhat lacking.
Therefore, by using spilanthol in combination, the initial spiciness is felt more strongly, making the onset of the spiciness feel more natural.
In addition, by using spilanthol in combination, it is possible to mask the deterioration odor of isothiocyanates more effectively than when polygodial is added alone.

The present invention will be described in detail below with reference to the embodiments.
<A> Fragrance Composition The fragrance composition of the present invention is composed of the following components.

[1] Isothiocyanates The isothiocyanates used in the present invention are one or more isothiocyanates selected from the group consisting of ω-alkenyl isothiocyanates, ω-methylthioalkyl isothiocyanates, and ω-alkyl isothiocyanates.

ω-Alkenyl isothiocyanates are represented by the following formula [1]:
Formula [1]: CH ₂ =CH-(CH ₂ ) _m -NSC
In the above formula, m represents an integer of 1 to 10, with 1 to 8 being preferred, and 1 to 5 being particularly preferred.

Specific examples of the compound having the structure of formula [1] include allyl isothiocyanate, 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, 5-hexenyl isothiocyanate, 6-heptenyl isothiocyanate, etc. Among these, allyl isothiocyanate, 3-butenyl isothiocyanate, 4-pentenyl isothiocyanate, and 5-hexenyl isothiocyanate are preferred.

The ω-alkenyl isothiocyanates used in the present invention can be either those contained in natural raw materials such as wasabi, or those obtained synthetically.
The synthesis method of this compound is disclosed in, for example, JP-A-2-221255. The outline of the synthesis method is as follows:
CH ₂ =CH-(CH ₂ ) _m -X
(wherein m has the same meaning as above, and X represents a halogen atom such as bromine, chlorine, or iodine.)
This compound can be obtained by reacting an ω-alkenyl halide having the following structure with a thiocyanate, and isomerizing the resulting ω-alkenyl thiocyanate in a polar aprotic solvent.

ω-Methylthioalkyl isothiocyanates are represented by the following formula [2]:
Formula [2]: CH ₃ -S-(CH ₂ ) _n -NCS
In the above formula, n represents an integer of 1 to 10, preferably 2 to 8, and particularly preferably 3 to 7.

Specific examples of compounds having the structure of formula [2] include 3-(methylthio)propyl isothiocyanate, 6-methylthiohexyl isothiocyanate, 5-methylthiopentyl isothiocyanate, and 7-methylthioheptyl isothiocyanate. Among these, 3-(methylthio)propyl isothiocyanate and 6-methylthiohexyl isothiocyanate are preferred.

The ω-methylthioalkyl isothiocyanates used in the present invention can be either those contained in natural raw materials such as wasabi, or those obtained synthetically.
The synthesis method of this compound is disclosed in, for example, JP-A-7-215931. The outline of the synthesis method is as follows:
CH ₂ =CH-(CH ₂ ) _n -2-NCS
(wherein n represents an integer of 3 to 10).
This can be obtained by reacting an ω-alkenyl isothiocyanate having the following structure with methyl mercaptan.

The ω-alkyl isothiocyanates are represented by the following formula [3].
Formula [3]: R-(CH ₂ ) _p -NCS
In the above formula, p represents an integer of 0 to 10, preferably 0 to 8, and particularly preferably 0 to 5. Furthermore, R represents a phenyl group or a linear or branched alkyl group having 1 to 4 carbon atoms.
Preferred examples of the straight-chain or branched alkyl group having 1 to 4 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and sec-butyl, with methyl, isopropyl, and sec-butyl being preferred.

Examples of the compound having the structure of formula [3] include sec-butyl isothiocyanate, isobutyl isothiocyanate, n-butyl isothiocyanate, hexyl isothiocyanate, 2-phenylethyl isothiocyanate, isopropyl isothiocyanate, amyl isothiocyanate, 3-methylbutyl isothiocyanate, benzyl isothiocyanate, etc. Among these, sec-butyl isothiocyanate, isobutyl isothiocyanate, butyl isothiocyanate, hexyl isothiocyanate, and 2-phenylethyl isothiocyanate are preferred.

The ω-alkyl isothiocyanates used in the present invention can be either those contained in natural raw materials such as wasabi, or those obtained synthetically.
Synthetic products may be commercially available and may be used, for example, from Sigma-Aldrich, Tokyo Chemical Industry Co., Ltd., Wako Pure Chemical Industries, Ltd., etc.

When the flavor composition of the present invention, which is characterized by containing polygodial and isothiocyanates, and optionally further spilanthol, and has the flavor of a cruciferous plant, is used to enhance the pungency of a food or beverage composition, it is added so that the concentration of isothiocyanates in the food or beverage composition is 10 to 5,000 ppm, preferably 100 to 2,500 ppm.

On the other hand, when used for the purpose of masking the deterioration odor of a food or drink composition, the isothiocyanates are added so that the concentration of the isothiocyanates in the food or drink composition becomes 10 to 5000 ppm, preferably 100 to 2500 ppm.
In this case, the concentration of isothiocyanates is the total amount of isothiocyanates contained in the flavor composition and the amount of isothiocyanates contained in the cruciferous plant-flavored food or beverage composition.
Furthermore, isothiocyanates can be added as appropriate during the processing of foods and beverages, and they do not necessarily have to be added at the same time as polygodial.

[2] Polygodial Polygodial (IUPAC name: (1R,4aS,8aS)-5,5,8a-Trimethyl-1,4,4a,6,7,8-hexahydronaphthalene-1,2-dicarboxaldehyde) used in the present invention is a diterpene aldehyde having the molecular formula _C15H22O2 , molecular weight 234.33, melting point 57 _° C _and the following structure.

Polygodial is known as a stimulant component of the plants Polygonum polyglutum and Mountain pepper.
The polygodial used in the present invention may be a synthetic product synthesized by chemical method, or may be extracted from animals or plants.The polygodial obtained by any method can be used in the present invention, and it does not need to be of high purity as long as it can obtain the effect of the present invention.
As long as the taste and smell of other ingredients do not affect the flavor of the cruciferous plant-flavored food or drink, plant extracts and essential oils containing polygodial may be used without purification.

Plants known to contain polygodial include Persicaria hydropiper (also known as water pepper), mountain pepper (Polygonum punctatum var. punctatum), the ferns Blechnum fluviatile and Thelypteris hispidula, and the moss Porella vernicosa.

In addition, the animals include Dendrodoris limbata and Doriopsilla pharpa, which belong to the sea slug family.
It has also been reported to contain polygodial.
When used in food and beverage compositions, from the standpoint of safety it is preferable to use extracts or essential oils obtained from plants that are commonly eaten, and it is particularly preferable to use extracts or essential oils from willow knotweed and mountain pepper.

An example of a method for extracting polygodial from Polygonum officinalis is a method in which a liquid extracted from the leaves (including cotyledons), stems, and seeds of Polygonum officinalis using an extraction solvent is distilled to obtain a fraction containing polygodial.
The extraction solvent used in the extraction process of Polygonum salicina can be water, alcohols (e.g., lower alcohols having 1 to 3 carbon atoms such as methanol, ethanol, propanol, isopropanol, etc.), acetone, ethyl acetate, etc., which can be used alone or as a mixture of any two or more of them.
Among the extraction solvents, in view of extraction rate, cost, operational safety, etc., it is preferable to use water, ethanol, acetone, or ethyl acetate alone or in the form of a mixture of any two or more of them, with ethyl acetate and ethanol being particularly preferable.

The amount of the extraction solvent is not particularly limited and can be adjusted appropriately depending on the purpose, but 300 to 3,000 parts by mass, more preferably 500 to 2,000 parts by mass, is used per 100 parts by mass of Polygonum salicina.
The extraction temperature is usually 0 to 100°C, preferably 20 to 50°C, and more preferably 30 to 40°C.
The extraction time depends on the extraction temperature, but is usually from 30 minutes to 5 hours, preferably from 1 to 2 hours.
The obtained extract is subjected to solid-liquid separation using filter paper or the like to obtain a crude extract containing polygodial.

The crude extract can be directly subjected to the distillation process, but it is preferable to distill off the extraction solvent to obtain a concentrated liquid. In addition, the crude extract can be subjected to liquid-liquid partition extraction before distilling off the extraction solvent to extract the active ingredient polygodial into a solvent with low polarity, or to extract highly polar impurity components into a solvent with high polarity, thereby removing highly polar impurity components.

When performing liquid-liquid partition extraction, 50 to 200 parts by mass of a solvent that is immiscible with the crude extract is added per 100 parts by mass of the crude extract. For example, if the extraction solvent is ethyl acetate, water or a mixture of water and alcohols can be used, and if the extraction solvent is water or a mixture of water and alcohols, ethyl acetate, hexane, heptane, etc. can be used.

The willow polygonum concentrate is distilled to obtain a fraction containing polygodial.
The distillation step can be carried out using a known distillation apparatus, specifically, simple distillation, rectification, flash distillation, short-path distillation, etc.
If the evaporation temperature exceeds 150° C., the polygodial will decompose, resulting in a significant drop in yield, and therefore it is necessary to carry out the distillation at a temperature of 150° C. or less, preferably 140° C. or less, more preferably 130° C. or less, and further preferably 120° C. or less. For this reason, it is necessary to carry out the distillation under reduced pressure using a known vacuum pump such as an oil rotary pump, a mechanical booster pump, or a diffusion pump.

As the size of the apparatus increases, the amount of heat required for distillation increases, leading to problems such as decomposition of the active ingredient and deterioration of energy efficiency. Therefore, short-step distillation is most preferable, and a centrifugal thin-film or falling thin-film type apparatus can be used.
The degree of reduced pressure during distillation is not limited as long as the polygodial is distilled at 150°C or less, but it is desirable to distill at a lower pressure, which is generally 300 Pa or less, preferably 200 Pa or less, more preferably 100 Pa or less, and particularly preferably 50 Pa or less.

Because the content of polygodial in the willow knotweed extract is very low, it may adhere to the cooling section where the fraction is condensed, reducing the recovery rate; if necessary, the fraction adhering to the cooling section can be recovered using a solvent.
There is no limitation on the solvent that can be used, and it can be appropriately selected based on price, safety, ease of handling, application, and the like.

For example, water, ethanol, 1,3-butylene glycol, propylene glycol, dipropylene glycol, glycerin, diglycerin, 1,2-pentanediol, 1,3-propanediol, medium-chain fatty acid esters, triacetin, triethyl citrate, etc. are suitable, and when the willow knotweed extract is obtained as a water-soluble preparation, ethanol or its hydrate is particularly suitable, and when it is obtained as a fat-soluble preparation, medium-chain fatty acid esters (medium-chain fatty acid triglycerides with constituent fatty acids having 5 to 12 carbon atoms) are particularly suitable.

Depending on the distillation apparatus used, it may not be possible to recover the fraction adhering to the cooling section with a solvent, or complicated operations may be required to make recovery difficult. Therefore, in the distillation process, it is preferable to add an auxiliary solvent to the Polygonum salicina extract before distillation.
By distilling the willow knotweed extract containing the auxiliary solvent, the amount of the fraction is increased, and the fraction containing polygodial can be efficiently recovered without performing a recovery operation using a solvent.

The type and amount of the auxiliary solvent to be used can be appropriately selected depending on the purpose taking into account factors such as price, safety, ease of handling, and application, but it is preferable that the auxiliary solvent has a boiling point equivalent to that of the polygodial, and has a boiling point at atmospheric pressure (1 atm) of 180°C or higher, more preferably 200°C or higher, and is preferably a solvent having a boiling point of 700°C or lower, more preferably 600°C or lower.
If the boiling point of the auxiliary solvent used is below 180° C., the efficiency of recovery of the auxiliary solvent in the cooling tube is poor, whereas if it is above 700° C., the auxiliary solvent is hardly distilled, which is unsuitable.

Suitable examples of the auxiliary solvent include glycerin (boiling point at atmospheric pressure (1 atm): 290° C.), propylene glycol (188° C.), dipropylene glycol (232° C.), medium-chain fatty acid esters (medium-chain fatty acid triglycerides having constituent fatty acids with 5 to 12 carbon atoms) (370 to 670° C.), triacetin (260° C.), and triethyl citrate (294° C.).
When the extract of Polygonum salicina is obtained as a water-soluble preparation, glycerin, propylene glycol, triethyl citrate, or a mixture thereof is particularly preferred, and when the extract is obtained as a fat-soluble preparation, medium-chain fatty acid esters (medium-chain fatty acid triglycerides having constituent fatty acids with 5 to 10 carbon atoms) are particularly preferred.

The co-solvent may be added at any stage before distillation, but is preferably added before extraction or before the extraction solvent is distilled off from the crude extract.
There is no particular limit to the amount of auxiliary solvent, which can be appropriately adjusted depending on the purpose, but 10 to 500 parts by mass, more preferably 50 to 200 parts by mass, is used per 100 parts by mass of Polygonum salicina used as the extraction raw material.
When the auxiliary solvent is added before the extraction or before the extraction solvent is distilled off from the crude extract, the extraction solvent is distilled off under conditions that do not distill off the auxiliary solvent.

[3] Spilanthol By using spilanthol in addition to polygodial, it is possible to provide a flavor composition for enhancing spiciness, a method for enhancing spiciness, and a food and beverage composition that can express a more natural spiciness. In addition, by using spilanthol in combination, it is possible to provide a flavor composition for masking, a masking method, and a food and beverage composition that can mask the deterioration odor of isothiocyanates more effectively than when polygodial is added alone.

Spilanthol (IUPAC name: (2E,6Z,8E)-N- _Isobutyl -2,6,8-decatrienamide) used in the present invention has a molecular formula of _C14H23NO , a molecular weight of 221.34, and a melting point of 23°C.
It is a fatty acid amide having the following structure:

The spilanthol used in the present invention may be a synthetic product synthesized by a chemical method, or may be one extracted from animals or plants.
In the present invention, spilanthol obtained by any method can be used, and it is not necessary for the purity to be high so long as the effects of the present invention can be obtained.
As long as the taste and smell of other ingredients do not affect the flavor of the cruciferous plant-flavored food or drink, plant extracts and essential oils containing spilanthol may be used without purification.

When used in food and beverage compositions, it is preferable from the viewpoint of safety to use extracts or essential oils obtained from plants that have been eaten in the past, and from the viewpoint of practicality such as supply and price, it is particularly preferable to use extracts or essential oils from Spilanthes acmella or Spilanthes acmella var. oleracea, which have a high spilanthol content.

An example of a method for extracting spilanthol is a method in which the flower heads of Amaranthella or Amaranthella sulcata are dried and crushed, and then extracted with an organic solvent to obtain an extract containing spilanthol.
The organic solvent used for extraction is not particularly limited, and alcohols such as methanol, ethanol, propanol, and propylene glycol, ketones such as acetone, esters such as ethyl acetate, ethers such as diethyl ether, and hydrocarbons such as hexane and heptane can be used alone or in combination as appropriate.
Among them, polar organic solvents such as alcohols are preferred, and ethanol is particularly preferred from the viewpoint of safety. The solvent is distilled off from the obtained extract to obtain a spilanthol-containing extract.

[4] Ratio of Each Constituent Component The ratio of polygodial in the fragrance composition is generally 0.0001 to 10, preferably 0.0005 to 5, more preferably 0.001 to 2, even more preferably 0.001 to 1, and particularly preferably 0.005 to 0.5, based on 1,000 parts by mass of isothiocyanates.

In the fragrance composition, the concentration of polygodial is preferably 100 ppb to 1%, particularly preferably 1 to 1500 ppm, and the concentration of isothiocyanates is preferably 100 ppm to 99 ppm.
%, preferably 1000 ppm to 75%, and particularly preferably 1 to 50%.
When spilanthol is used in combination, spilanthol is generally used in a ratio of 0.01 to 100 parts by mass, preferably 0.02 to 50 parts by mass, and particularly preferably 0.1 to 10 parts by mass, per part by mass of Polygodial.

When used as a flavor composition for enhancing the pungency of a food or beverage composition having the flavor of a cruciferous plant, the blending ratio of polygodial per 1,000 parts by mass of isothiocyanates is generally 0.0001 to 10, preferably 0.0005 to 5, more preferably 0.001 to 2, even more preferably 0.001 to 1, and particularly preferably 0.005 to 0.5.
In this case, the concentration of polygodial in the flavor composition for enhancing pungency is preferably 100 ppb to 1%, particularly preferably 1 to 1500 ppm, and the concentration of isothiocyanates is 100 ppm to 99%, preferably 1000 ppm to 75%, particularly preferably 1 to 50%.

When used as a fragrance composition for masking a food or beverage composition having the flavor of a cruciferous plant, the blending ratio of polygodial is generally 0.0001 to 10, preferably 0.0005 to 5, more preferably 0.001 to 2, even more preferably 0.001 to 1, and particularly preferably 0.005 to 0.5, per 1,000 parts by mass of isothiocyanates.
In this case, the concentration of the polygodial in the masking fragrance composition is preferably 100 ppb to 1%, particularly preferably 1 to 1500 ppm, and the concentration of the isothiocyanates is 100 ppm to 99%, preferably 1000 ppm to 75%, particularly preferably 1 to 50%.

[5] Additional Components The flavor composition of the present invention may further contain flavor components, colorants, antioxidants, preservatives, and the like that are generally used in food and beverage compositions.
As the flavor component, various natural flavors and synthetic flavors described in the Japan Patent Office's "Collection of Well-Known and Commonly Used Technologies (Flavors) Part II Food Flavors" (published on January 14, 2000) and the like can be used without any particular restrictions, so long as they do not impair the effects of the present invention.

<B> Brassicaceae Plants In the present invention, the Brassicaceae plants refer to plants classified in the Brassicaceae family (scientific name: Brassicaceae) and containing allyl isothiocyanates or glycosides thereof (glucosinolates or mustard oil glycosides).
Specifically, these include wasabi (Eutrema japonicum (Miq.) Koidz.), mustard (white mustard (Sinapis alba), black mustard (Brassica nigra)), horseradish (Armoracia rusticana), daikon radish, turnip, cabbage, and mustard greens.

<C> Cruciferous plant-flavored food and beverage composition>
The Brassicaceae plant-flavored food and beverage composition to which the flavoring composition of the present invention is blended or added refers to a food and beverage composition or processed food or beverage that is seasoned to resemble a Brassicaceae plant by containing the flavor components of the Brassicaceae plant described above, or by using synthetic flavorings or the like even if it does not actually contain wasabi components.

In other words, the food and drink compositions in which the flavoring composition of the present invention is used are not particularly limited as long as they are edible and flavored with a Brassicaceae plant, and examples thereof include beverages such as soup, confectioneries such as snack foods, tablet-shaped confectioneries, chewing gum, dairy and oil and fat products such as cheese, seasonings such as miso, soy sauce, vinegar, Worcestershire sauce, tomato ketchup, barbecue sauce, dressings, and spices, processed meat products, processed seafood products, cooked foods, frozen foods, oral products, and pharmaceuticals.
In particular, it is suitable for aqueous foods and beverages in which the reduction in pungency is remarkable. Aqueous foods and beverages are liquid foods whose main component is water, and examples thereof include tsuyu, sauce, dressing, stock, soup, Worcestershire sauce, pickling liquid, pickle liquid, ponzu sauce, consommé, soft drinks, and the like.

<D> Application of Flavoring Composition to Food and Beverage Compositions [1] Dosage Form For details of the above-mentioned food and beverage compositions and the manner of using the flavoring composition in said food and beverage compositions, the method described in “Japan Patent Office Gazette ‘Collection of Well-Known and Commonly Used Techniques (Flavors) Part II Food Flavors’, published on January 14, 2000, pp. 897-901, is usually adopted.
That is, the prepared flavor composition may be used in any form selected according to the purpose of use, such as directly, in the form of a solution optionally dissolved in alcohols such as ethanol, animal and vegetable oils, polyhydric alcohols such as propylene glycol and glycerin, in the form of a powder coated with known natural gums such as gum arabic and gum tragacanth, known natural gums such as glycerin fatty acid esters, sucrose fatty acid esters, known excipients such as gelatin and dextrin, or in a microcapsule obtained by a known encapsulation process. Furthermore, a method of encapsulating the composition with a known encapsulating agent such as cyclodextrin to stabilize and sustain the effect may be used. In addition, the composition may be in the form of a paste or granules.

The flavor composition of the present invention can also be used as an emulsion preparation or an emulsion powder preparation.
In this case, examples of emulsifiers that can be used in the present invention include soybean saponin, barley husk extract, gum arabic, starch sodium octenylsuccinate, polysorbates, Quillaja extract, glycerin fatty acid esters, enzyme-treated soybean saponin, enzyme-treated lecithin, enzymatically decomposed lecithin, plant sterols, plant lecithin, sphingolipids, sucrose fatty acid esters, calcium stearoyl lactylate, sorbitan fatty acid esters, soybean saponin, bile powder, tea seed saponin, and animal sterols. Examples of the lecithin include gum arabic, starch sodium octenylsuccinate, polysorbates, Quillaja quilla extract, glycerin fatty acid esters, enzyme-treated lecithin, vegetable lecithin, sphingolipids, sucrose fatty acid esters, calcium stearoyl lactylate, sorbitan fatty acid esters, propylene glycol fatty acid esters, egg yolk lecithin, etc., and preferable examples of the lecithin include gum arabic, starch sodium octenylsuccinate, polysorbates, Quillaja quilla extract, glycerin fatty acid esters, enzyme-treated lecithin, vegetable lecithin, sphingolipids, sucrose fatty acid esters, calcium stearoyl lactylate, sorbitan fatty acid esters, propylene glycol fatty acid esters, egg yolk lecithin, etc.

[2] Amount of Blend The flavor composition of the present invention is preferably blended into a food or beverage composition so that the concentration of polygodial in the food or beverage composition is 0.5 ppb to 1000 ppb, preferably 1 to 500 ppb, and the concentration of isothiocyanates in the food or beverage composition is 10 to 5000 ppm, preferably 100 to 2500 ppm.

When the flavor composition is used as a spiciness enhancer for a food or beverage composition having the flavor of a cruciferous plant, the flavor composition for enhancing spiciness is added so that the concentration of polygodial in the food or beverage composition is 0.5 ppb to 1000 ppb, preferably 1 to 500 ppb, and the concentration of isothiocyanates is 10 to 5000 ppm, preferably 100 to 2500 ppm.

When the flavor composition is used as a masking agent for the deterioration odor of a food or beverage composition having the flavor of a cruciferous plant, the masking flavor composition is added so that the concentration of polygodial in the food or beverage composition is 0.5 ppb to 1000 ppb, preferably 1 to 500 ppb, and the concentration of isothiocyanates is 10 to 5000 ppm, preferably 100 to 2500 ppm.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
Preparation Example 1
A marinade base with a pH of 4.5 was prepared by adding and dissolving 5 g of salt, 3.5 g of brewed vinegar (acidity 4.2%), and 0.5 g of sodium glutamate in 92 g of water.

Preparation Example 2
To the marinade base of Preparation Example 1, 0.075% by mass of wasabi flavoring (containing 33.3% allyl isothiocyanate, manufactured by Ogawa Fragrance Co., Ltd.) was added to prepare a wasabi-flavored marinade base containing 250 ppm allyl isothiocyanate.

[Production Example 1]
1000 g of ethyl acetate was added to 100 g of willow knotweed (JA Chikuzen Asakura, product name "Shikibeni") and extracted at 40°C for 1 hour, after which solid-liquid separation was performed to obtain 900 g of crude extract.
100 g of triethyl citrate was added to the obtained crude extract, and the ethyl acetate was removed under reduced pressure (100 mmHg, 40°C). The mixture was then distilled at 20 Pa and 120°C using a falling film short-stage distillation apparatus to obtain 90 g of Polygonum officinalis extract containing 500 ppm of polygodial.

Comparative Example 1
The wasabi-flavored marinade base of Preparation Example 2 was used as Comparative Example 1.
Comparative Example 2
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the marinade base of Preparation Example 1 to the concentration shown in Table 1 below, to prepare Comparative Example 2.
[Comparative Example 3, Examples 1 to 4]
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the wasabi-flavored marinade base of Comparative Example 1 to the concentrations shown in Table 1 below, and these were used as Comparative Example 3 and Examples 1 to 4.

Example 5
Example 5 was prepared by adding the Polygonum officinalis extract of Production Example 1 to the wasabi-flavored marinade base of Comparative Example 1 so that the polygodial content was 120 ppb.
Example 6
Example 6 was prepared by adding mountain pepper oil (manufactured by ESSENTIAL OILS OF TASMANIA PTY LTD., polygodial content 20%) to the wasabi-flavored marinade base of Comparative Example 1 so that the polygodial content became 120 ppb.

[Test Example 1]
A panel of 10 trained members performed a sensory evaluation using Comparative Example 1 immediately after preparation as a control, according to the following evaluation criteria.
The evaluation immediately after preparation was given a rating of 1, and the evaluation after storing in a refrigerator for two weeks was given a rating of 2. The scores were recorded, and the average of the scores from the 10 people was calculated for each sample to give the evaluation result. The results are shown in Table 1.

Evaluation criteria (strength of hotness)
0: No spiciness felt at all compared to the control
1: Slightly more spicy than the control
2: Less spicy than the control
3: Slightly less spicy than the control
4: Slightly less spicy than the control
5: Compared to the control, the spiciness is felt to the same degree.
6: Slightly more spicy than the control
7: Slightly more spicy than the control
8: Stronger spiciness than the control
9: Compared to the control, the spiciness is quite strong.
10: Very spicy compared to the control

As shown in Table 1, it was found that the spiciness was enhanced by adding 2 to 120 ppb of polygodial (0.008 to 0.48 parts by mass of polygodial per 1,000 parts by mass of allyl isothiocyanate) to a wasabi-flavored marinade base containing allyl isothiocyanate, and further, that the spiciness could be maintained even after storage in a refrigerator for two weeks.
In addition, when an extract of Polygonum officinalis and an extract of Mountain Pepper were used, the same effect of retaining the pungency as pure Polygodial was observed.
The addition of 200 ppb of polygodial did not affect the flavor.

[Test Example 2]
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) and spilanthol (manufactured by Ogawa Fragrance Co., Ltd.) were added to commercially available tubed paste wasabi (containing approximately 1,200 ppm of isothiocyanates; see Table 2 for the content of each isothiocyanate) to the concentrations shown in Table 3 below, producing Comparative Example 4 and Examples 7 to 24. A product without added polygodial or spilanthol was used as a control, and evaluation was performed by a panel of 10 trained members according to the following evaluation criteria.
The "top" spiciness described in the evaluation items refers to the spiciness felt the moment you put it in your mouth, while the "middle to last" spiciness refers to the spiciness felt after that. Additionally, the "wasabi-like flavor" refers to a flavor with a strong green feel and a spiciness similar to that of river wasabi.

Evaluation criteria : +++: Very effective (8 or more people recognized the effect compared to the control)
+ +: Effective (5 or more people recognized the effect compared to the control)
+: Somewhat effective (3 or more people recognized the effect compared to the control)
・ : No effect/change (less than 3 people recognized the effect compared to the control)

As is clear from Table 3, even when spilanthol was added up to 120 ppb to tube-packed wasabi paste, it was itself non-irritating and did not increase the spiciness of the wasabi, whereas the combined use of 2-400 ppb of polygodial (0.002-0.33 polygodial per 1000 parts by mass of isothiocyanates) or 0.03-25 parts by mass of spilanthol per 1 part by mass of polygodial could impart an overall spiciness from the top to the end.

[Test Example 3]
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) and spilanthol (manufactured by Ogawa Fragrance Co., Ltd.) were added to the wasabi-flavored marinade base of Preparation Example 2 to the concentrations shown in Table 4 below, and these were used as Comparative Example 5 and Examples 25 to 28.
The evaluation immediately after preparation was given an "Evaluation 1," and the evaluation after storing in a refrigerator for two weeks was given an "Evaluation 2." Comparative Example 1 was used as a control, and the evaluation was carried out by a panel of 10 skilled members according to the evaluation criteria described in Test Example 2.

As shown in Table 4, it was found that polygodial not only imparts a spiciness to the wasabi-flavored marinade base immediately after preparation, but also maintains the flavor after storage. In addition, polygodial alone imparts a spiciness in the middle to end, but by combining 0.5 to 25 parts by mass of spilanthol with 1 part by mass of polygodial, an overall spiciness is imparted, resulting in a stronger wasabi-like flavor.

[Test Example 4]
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) and spilanthol (manufactured by Ogawa Fragrance Co., Ltd.) were added to the wasabi-flavored marinade base of Preparation Example 2 to the concentrations shown in Table 5 below, and these were used as Comparative Example 6 and Examples 29 and 30.
The evaluation immediately after preparation was given a rating of 1, and the evaluation after storage at room temperature for one week was given a rating of 2. A panel of six trained people performed a sensory evaluation of the intensity of spiciness and the deterioration odor caused by storage at room temperature according to the following evaluation criteria, using Comparative Example 1 as a control. The scores were recorded, and the average of the scores of the six people was calculated for each sample to obtain the evaluation result.

Evaluation criteria : 1: Very weak 2: Quite weak 3: Weak 4: Same as control 5: Strong 6: Quite strong 7: Very strong

As shown in Table 5, it was found that polygodial suppresses the deterioration odor generated in the wasabi-flavored food and beverage composition. It was found that the combined use of polygodial and spilanthol suppresses the deterioration odor more than polygodial alone.

[Test Example 5]
Polygodial (manufactured by Wako Pure Chemical Industries, Ltd.) and spilanthol (manufactured by Ogawa Fragrance Co., Ltd.) were added to commercially available tubed mustard paste (containing 1000 ppm allyl isothiocyanate) to the concentrations shown in Table 6 below to produce Examples 31 and 32. A product without added polygodial or spilanthol was used as a control, and the intensity of the pungency was evaluated by a panel of six trained members in accordance with the evaluation criteria described in Test Example 4.

As shown in Table 6 above, it was found that the use of polygodial or a combination of polygodial and spilanthol in tubed mustard paste enhanced the pungency of the mustard without any unpleasant taste or odor.

[Test Example 6]
According to the composition in Table 7 below, isothiocyanates were weighed out and dissolved in medium-chain fatty acid glycerin ester (Kao Corporation, product name: Coconard) to prepare compositions having the flavor of cruciferous plants containing polygodial and isothiocyanates, which were designated as Products 1 to 17 of the present invention.

[Production Example 2]
400g of liquid sugar (Bx.75°) with Kirayanin (Maruzen Pharmaceuticals' Kirayanin C-100)
An aqueous phase was prepared by mixing and dissolving 50 g of Quillaja japonica extract (containing 20% Quillaja japonica extract), 66 g of water, and 34 g of 95% ethanol.
This was mixed with 420 g of wasabi oil (containing 95% isothiocyanates, manufactured by Ogawa Fragrance Co., Ltd.) and 30 g of the Polygonum officinalis extract of Production Example 1, and stirred at 10,000 rpm for 20 minutes using a TK-Homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) to obtain 1,000 g of wasabi-flavored emulsified flavoring, designated as Invention Product 18.
The content ratio of each isothiocyanate in wasabi oil is shown in Table 8.

[Application to food and beverages]
(1) Dressings Samples of dressings were obtained by adding the present invention products 1 to 18, allyl isothiocyanate, and wasabi oil (containing 95% isothiocyanates, manufactured by Ogawa Fragrance Co., Ltd.) shown in "Table 8" at the addition ratios shown in "Table 9" to a commercially available Japanese-style dressing (containing no isothiocyanates) and mixing well.
(2) Mayonnaise To commercially available mayonnaise (containing no isothiocyanates), the present invention products 1 to 18, allyl isothiocyanate, and wasabi oil (containing 95% isothiocyanates, manufactured by Ogawa Fragrance Co., Ltd.) shown in "Table 8" were added in the addition ratios shown in "Table 9", and mixed well to obtain mayonnaise samples.
(3) Tsukudani Samples of nori tsukudani were obtained by adding the present invention products 1 to 18, allyl isothiocyanate, and wasabi oil (containing 95% isothiocyanates, manufactured by Ogawa Fragrance Co., Ltd.) shown in Table 8 at the addition ratios shown in Table 9 to commercially available nori tsukudani (containing no isothiocyanates) and mixing well.

The samples prepared in (1) to (3) were evaluated by a panel of six trained members immediately after production and after two weeks of refrigerated storage. As a result, all six members commented that the samples had a good spiciness as wasabi both immediately after production and after two weeks of refrigerated storage.

Claims (8)

A food or beverage composition having the flavor of a cruciferous plant, characterized by containing polygodial and isothiocyanates such that the ratio of polygodial to 1,000 parts by mass of isothiocyanates is 0.005 to 10 parts by mass. The food or drink composition having the flavor of a cruciferous plant according to claim 1, characterized in that the concentration of polygodial in the food or drink is 0.5 ppb to 1000 ppb and the concentration of isothiocyanates is 10 to 5000 ppm. The food and drink composition having the flavor of a cruciferous plant according to claim 1 or 2, wherein the food and drink composition having the flavor of a cruciferous plant is a wasabi-flavored food and drink composition or a mustard-flavored food and drink composition. A food or drink composition having the flavor of a cruciferous plant according to any one of claims 1 to 3, characterized in that it is used in combination with spilanthol. The food and drink composition having the flavor of a cruciferous plant according to claim 4, characterized in that spilanthol is used in combination in a ratio of 0.01 to 100 parts by mass per part by mass of polygodial. A method for producing a cruciferous plant-flavored food or drink composition, comprising adding polygodial and isothiocyanates to a cruciferous plant-flavored food or drink composition such that the ratio of polygodial to 1,000 parts by mass of isothiocyanates is 0.005 to 10 parts by mass . The method for producing a cruciferous plant-flavored food or beverage composition according to claim 6, characterized in that the polygodial is contained in a distillate obtained by distilling an organic solvent extract of Polygonum salicina at a temperature of 150°C or less. The method for producing a cruciferous plant-flavored food or beverage composition according to claim 6 or 7, wherein the food or beverage composition having the flavor of a cruciferous plant is a wasabi-flavored food or beverage composition or a mustard-flavored food or beverage composition.