JP2008182924A - Alcoholic beverage of clitoria ternatea - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To industrially advantageously obtain Clitoria ternatea coloring matter which does not cause a precipitate when added to an alcoholic beverage, has excellent brightness, chroma and resistance in high concentration safely without denaturation in an existing component by efficiently preparing Clitoria ternatea coloring matter as an extracted material. <P>SOLUTION: The alcoholic beverage uses coloring matter extracted from Clitoria ternatea flower. The Clitoria ternatea coloring matter is obtained by a process for naturally drying Clitoria ternatea flower for ≥3-6 hours in shade, a process for drying the Clitoria ternatea flower by an oven at 50°C to 100°C until the weight of the Clitoria flower reaches 1/11-1/8 weight in picking, a process for mixing the dried flower with water or an aqueous solution having dissolved 0.5-2 wt.% of an organic acid to elute the coloring matter, a process for adsorbing the eluted solution of the coloring matter on an ion exchange resin and a process for eluting and purifying the adsorbed coloring matter with water or an organic solvent so as to extract the coloring matter. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a blue alcoholic beverage using a butterfly flower pigment.

  Butterfly (Clitoria ternatea L.) is a plant belonging to the Leguminosae family and produces beautiful blue flowers. This plant is widely cultivated in tropical regions, and its plant body is used for green manure, pasture, cover crops, and the like. Butterfly beans have a bright blue color and are generally cultivated for ornamental purposes. Butterflies are also used to dye rice blue in Indonesia. The blue pigment extracted from this flower has long been used for coloring mats and rice cakes in Malaysia, or for confectionery coloring in Thailand.

  In the coloring of foods, the proportion of synthetic colorants, mainly tar-based products that are inexpensive, stable, and excellent in coloration, is high, but recently there has been some doubt about their safety. The use began to be greatly restricted. Along with that, natural coloring, traditionally used and considered safe, is being reviewed again. As plant pigments exhibiting red to blue, pigments of vegetables such as purple corn and red cabbage, and fruits such as grapes and berries have been put into practical use and used despite the low stability to light. By the way, despite the large number of flower pigments, only the hibiscus anthocyanins are currently used. However, its stability is very bad.

As for extraction from butterfly beans, Norihiko Terahara et al. Have reported the extraction of delphinidin 3,3,5-triglucoside compound (blue pigment) from petals of butterfly (Criteria ternatea) (Patent Document 1 and Non-Patent Document 1). reference).
In this document, a dried product of a petal of butterfly is used, but there is no description about a drying method, and no mention is made of a method for efficiently obtaining an industrially good pigment.
The butterfly is a plant suitable for cultivation in a relatively warm area, and in order to extract the pigment from this flower efficiently, it is necessary to treat so that the flower that has been picked can be extracted efficiently. In addition, the extraction workplace may be a remote location generally suitable for cultivation of butter beans, and good treatment as an extraction raw material will maintain the pigment in the flower and play a major role in the extraction process . A processing method from this point of view has not yet been studied.
In addition, Terahara et al. Report that acetic acid (formic acid) -methanol solvent is used when purifying the extract of the pea petals.

  In this method, even if acetic acid or formic acid must be finally removed, it is considered that a part of the dye structure reacts during the heat concentration, and as a result, the original natural dye structure May not be obtained. There are other acid removal methods, but the process requires enormous effort and puts it into practical use. Furthermore, the presence of acid increases the adsorptive power to the adsorbent, requiring a large amount of solvent and time for the release treatment from the adsorbent, and at the same time, the color value of the resulting release liquid is too low, so a long concentration time Is required, and as a result, the decomposition of the butterfly pigment component may be promoted.

  In this way, it is seen that the application is not practical.

  In addition, it is obvious that if the crude extract from the butterfly petal is used as it is, a large amount of contaminants such as sugars and proteins are mixed, which adversely affects the concentration and powdering process. In addition, when added to foods, precipitates are generated over time, and there is a concern that it may adversely affect lightness, saturation and tolerance.

Patent Document 2 describes a blue pigment composition using a blue pigment extract from dried pea petals. Although there are descriptions about foods, cosmetics and pharmaceutical-related products, no specific application is shown. (2003-292810)
Patent Document 3 describes a method for producing a butterfly flower extract by contacting with a macroporous aromatic adsorbent. (2004-187524)
However, none of them deal with butterfly flowers prepared in large quantities as industrial materials, and the cause of yield reduction due to leakage, decomposition, etc. of pigments is not taken into account for handling in large quantities. There is no description about the process before extraction of a butterfly petal. Therefore, a method for extracting a good pigment has not been sufficiently studied.
JP-A-3-223298 Report of Faculty of Horticulture, Minamikyushu University-No. 23-Reprint (Received July 30, 1992 "Structural Determination and Stability of Acylated Anthocyanin Dyes") JP 2003-292810 A JP 2004-187524 A

  The present invention adjusts the butterfly flower pigment efficiently as an extraction material without leaking the pigment of a good hue when it is flowered, and as a natural food pigment, without denaturation of the endogenous components, at a high concentration, The purpose of this invention is to obtain industrially advantageous butterfly flower pigments that are safe and do not generate precipitates over time when added to alcoholic beverages, and have good lightness, saturation and tolerance. As a result of intensive studies, it has been found that by sufficiently treating the flowers that have been picked up the butter beans, it is possible to eliminate the deterioration of the pigment content and to ensure the pigment content efficiently, leading to good coloring in alcoholic beverages and completing the present invention. .

  The present invention relates to an alcoholic beverage characterized by using 0.01 to 10% by weight of a pigment extracted from a butterfly flower.

  In addition, the present invention is a process in which a pigment extracted from a butterfly flower is picked up in an oven at 50 ° C. to 100 ° C. The step of drying until the weight becomes 1/11 to 1/8 of the time, the dried flower is mixed with water or an aqueous solution in which 0.5 to 2% by weight of organic acid is dissolved to elute the dye It is related with the said alcoholic beverage extracted by the process to make it adsorb | suck, the process to adsorb | suck the eluate of a pigment | dye with an ion exchange resin, and the process to elute the adsorbed pigment | dye from an ion exchange resin with water or an organic solvent.

  Furthermore, this invention relates to the said alcoholic beverage using the porous resin in which the particle size of an ion exchange resin is contained in the range of 300-1180micro or more 96% or more.

  Furthermore, the present invention relates to the above-mentioned colored preparation for a blue alcoholic beverage, which is further concentrated under reduced pressure after the step of elution purification from an ion exchange resin.

  According to the present invention, a blue pigment contained in a butterfly petal can be separated and obtained with a high yield. And the alcoholic beverage which used the swallow flower pigment | dye does not generate | occur | produce a precipitate with time, and is an alcoholic beverage with good brightness, chroma, and tolerance, and can obtain this industrially advantageously.

  In the present invention, an extract from a butterfly flower is extracted with a solvent such as water or alcohol from petals. This extraction causes the outflow of the pigment component from the mixture of the petal of the butterfly and water or alcohol, and is appropriately obtained by a method of concentrating this liquid. However, a good extract into an alcoholic beverage can be obtained by the following operation. That is, butterfly petals are flowered from about 1.5 m to 2 m adult trees, but have excessive moisture when picked. This picked petal is collected and used for processing as appropriate, but in the subsequent drying process and later extraction process, it is necessary to lay down after appropriate picking and leave it naturally in a well-ventilated environment. The disappearance of the pigment in the artificial drying process is reduced. For this reason, the flower petals are arranged in a layered form with a thickness of 0.5 to 5 cm in a net-like shelf having an opening of 1 to 2 cm, and in a state of taking sufficient air permeability for 3 to 6 hours. Hold above.

  This state induces effective changes in the extraction of pigments in the plant, and can prevent processing incompatibility (stickiness, burn-in, discoloration, fading) in the artificial drying process. Moreover, the efficient extraction of the pigment | dye in the post-drying process is exhibited.

  Note that the mesh opening is a mesh opening where the butterfly flower does not fall, and forms a shelf with a maximum air permeability.

  Moreover, when a butterfly flower is arranged in a layer with a thickness of 0.5 to 5 cm, it is possible to prevent the dye solution from leaking out due to the pressure due to the dead weight of the butterfly.

  Moreover, the drying process after such natural leaving shall be set to 1/11 to 1/8 of the weight at the time of flowering at 60-100 degreeC. This step is also a condition that does not impair the decomposition or alteration of the pigment.

  In addition, such a drying process has an effect of stabilizing the preservative petal preservability for a long period of time, and the flower cultivation place and the pigment extraction place are good even in an area separated by a distance. Made it possible to fulfill.

The flowers that weighed 1/11 to 1/8 from the dry picking are then immersed in water or an aqueous solution in which 0.5 to 2% by weight of organic acid is dissolved to elute the pigment into the solution. .
The mixing ratio of the dried flower and water at this time is 1 to 100 parts by weight of water with respect to 1 part by weight of the dried flower. This is preferably 5 to 30 parts by weight.

  The mixing immersion time is 1 to 24 hours. Preferably it is performed in 5 to 20 hours. The solution in which the dye solution is dissolved by immersion is removed by removing impurities by filtration.

  This filtrate is then poured into a column of ion exchange resin to adsorb the dye component. The dye adsorbed on the ion exchange resin by this column is further purified by elution from the ion exchange resin with non-acidic water or an organic solvent to obtain a beautiful blue dye solution of butterfly flower dye. If necessary, the pigment can also be powdered by concentration, further spray drying, freeze drying, or the like.

  In addition, when an acidic substance is used in an adsorption | suction process, it has the effect | action which raises the adsorption power to the ion exchange resin (adsorbent) in the next process. The acidic substance used here can be easily removed by washing with water in the next adsorption step.

In the present invention, since heat treatment is not necessary, there is no fear of decomposing the dye component and other coexisting components if the concentration is adjusted. The acidic substance used here may be a mineral acid such as hydrochloric acid, sulfuric acid or phosphoric acid, an organic acid such as acetic acid, citric acid, malic acid, tartaric acid or lactic acid, or a buffer solution, and the concentration may be 0.001-1. Any molar concentration may be used.
Examples of the buffer include phosphate buffer, citrate buffer, acetate buffer, Tris-HCl buffer, ammonium acetate buffer, sodium pyrophosphate buffer, glycine-sodium buffer, and Good buffer. The pH is preferably 2-7.

  In the present invention, the ion exchange resin is a resin having a network structure obtained by blending a vinyl monomer such as macroporous styrene or vinyl pyrrolidone with a crosslinkable monomer such as divinylbenzene. Product names include Duolite S-30, ES-33, S-37, S-862, S-861, S-587, S-761 from Diamond Shamrock Chemical, and Amberlite XAD from Rohm and Haas. -2, XAD-4, XAD-7, XAD-8, XAD-16, XAD-1180, XAD-2000, XAD-2010, etc., Diaion HP-10, HP-20, HP- 21, HP-40, Sepabead SP-850, etc., Dowex XUS-40323, X of Dow Chemical S-40285, etc., KS, HS, AF, L-1, etc. of Hokuetsu Carbon Industry Co., Ltd., Polyclar SB-100, Polyclar Super R, Polyclar 10 etc., Toyo Soda Industry Co., Ltd., Toyopearl HW-40, etc. However, it is not limited to these. Moreover, it is preferable that the particle size of these ion exchange resins is 96% or more in the range of 200 to 1180 μm.

 In addition, an ion exchange resin having a cross-linked structure obtained from styrene and divinylbenzene can also be used, and is formed into particles containing electron-withdrawing groups such as chlorine atoms and bromine atoms. Sepa beads SP-207 manufactured by Mitsubishi Chemical Industries Ltd. Furthermore, these may be used not only alone but in a plurality of combinations.

As the organic solvent used for eluting the dye adsorbed on the ion exchange resin in the present invention, a solvent that has been approved for the production of food additives is used. Ethanol, methanol, acetone, nitrous oxide, ethyl methyl ketone, glycerin, ethyl acetate, methyl acetate, diethyl ether, cyclohexane, dichloromethane, edible oils and fats, 1,1,1,2-tetrafluoroethane, 1,1,2- Examples include trichloroethene, carbon dioxide, 1-butanol, 2-butanol, butane, 1-propanol, 2-propanol, propane, propylene glycol, and hexane. (According to the manufacturing standards of the Food Additives Standard) However, methanol and 2-propanol are 50 μg / g, acetone is 30 μg / g, dichloromethane and 1,1,2-trichloroethene are 30 μg / g, and hexane is 25 μg. / G is not preferred because it must be used so that it does not remain above each.
It is most preferable to use a solvent common to the above-mentioned solvent and this rule. For example, ethanol, glycerin, edible fats and oils, propylene glycol and the like can be mentioned.

 A mixed solvent of these solvents and water can also be used. If the mixing ratio is 1 to 99:99 to 1 in volume ratio, it can be freely selected according to the adjustment value of the product color value.

  The type of butterfly petal used in the present invention is not limited to any kind or variety of butterfly such as Japanese, Thai, Chinese, Malaysian, Myanmar, or Vietnamese, but the pigment yield is good. In order to achieve this, it is preferable to use double-flowered seeds.

  In the present invention, alcoholic beverages include various types such as cocktails, shochu, beer, sparkling wine, wine, vodka, gin, and sake. In many cases, these are usually colorless and transparent, but in the present invention, a blue color can be obtained with a transparency that cannot be formed by conventional natural pigments.

In addition, the alcoholic beverage of the present invention provides a beverage that is stable over time without a precipitate or the like, although it is a beverage having a high alcohol component.

  In addition, butterfly extract pigment has an antioxidant property as an anthocyanin type, and is expected to have an effect on eyestrain. Therefore, it becomes an alcoholic beverage which expects a fresh color and an intake effect.

The process of the present invention will be described in further detail.
(Drying treatment of butterfly 1)
After weighing 500 kg of the pickled butterfly petals from the octopus species, they were arranged on a wire mesh shelf with an opening of 1.5 cm so as to have a thickness of about 2 cm. This shelf was made into a multistage shelf with space above and below, and was left in the shade for about 5 hours to promote appropriate water evaporation and pigment fixation in the plant. Thereafter, drying was performed in an oven at 60 ° C. for about 3 to 4 hours to obtain a weight (49.5 kg) of about 1/10 of the above measured value.
(Dried processing of butter beans 2)
After weighing 500 kg of the pickled butterfly petals from the octopus species, they were arranged on a wire mesh shelf with an opening of 1.5 cm so as to have a thickness of about 2 cm. This shelf was made into a multistage shelf with space above and below, and left in the shade for about 4 hours to promote appropriate water evaporation and pigment fixation in the plant. Thereafter, drying was performed in an oven at 65 ° C. for about 4 hours to obtain a weight (48.5 kg) of about 1/10 of the above measured value. This dried product was used as a raw material flower for extraction.
(Drying of butterfly 3)
The pickled butterfly petals were dried under hot weather. In this drying step, sufficient drying could not be performed and the state was uneven. The generation of some mold was also confirmed, and it was judged that it could not be used for pigment extraction.
(Drying of butterfly 4)
Forced drying was performed using multi-stage shelves, with the pickled butterfly petals in stainless steel bats. The petals are likely to be deteriorated on the contact surface between the petals and the stainless steel surface, and there are many fading parts of the pigment.
(Drying treatment of butter beans 5)
The pickled butterfly petals were drawn on a 1.5-mesh wire mesh, and forced drying was performed suddenly.
(Dried processing of butterfly 6)
Forced drying was performed using multi-stage shelves, with the pickled butterfly petals in stainless steel bats. Although the drying was good by raising the temperature, the petals that faded at the contact portion with the stainless steel surface increased. Table 1 shows a comparison of dried petals subjected to the drying treatments 1 to 6 described above. It can be seen that the methods of the drying treatment 1 and the drying treatment 2 have fewer defective dry flowers than the methods of the drying treatments 3 to 6.

[Example 1]
The raw material flowers subjected to the drying treatment 2 and the drying treatment 6 were transported to a remote area equipped with industrial facilities from the cultivation land and the drying treatment land, and the following extraction process was performed as an extraction raw material.

After 5 kg of the dried flowers 2 and 6 kg of dried petals were soaked in 500 liters of 1% acetic acid water for 15 hours, filtration was performed to obtain 450 liters of a rough extract of the peanut petals. It was. This filtrate was applied to a column packed with Diaion HP-20 (average particle size 500 μm (90% or more is 250 μm or more)) and 15 liter capacity to adsorb the butterfly pigment component. The resin adsorbed with the dye was washed with 20 liters of water, and then the dye component was separated and extracted with 50% ethanol to obtain a dark blue extract having a capacity of 10 liters. As a result of measuring the color value E10% using a pH 6 buffer solution, a butterfly flower extract having E10% = 175 was obtained. This butterfly flower extract was concentrated and powdered at 60 ° C. and then dissolved in 10 liters of ion-exchanged water to completely redissolve. When the color value was measured at pH 6, a value of E10% = 172 was obtained. It was found that the pigment residual ratio in the concentration treatment was 98%, and no pigment decomposition occurred.

[Example 2]
10 kg of dried butterfly petals similar to those in Example 1 were immersed in 500 liters of 1% acetic acid for 15 hours, followed by filtration to obtain 450 liters of crude extract of butterfly petals. This filtrate was applied to a column packed with Diaion HP-20, 15 liter capacity to adsorb the butterfly pigment component. The resin adsorbed with the dye was washed with 20 liters of 1% water, and then the dye component was separated and extracted with 1% acetic acid-70% methanol to obtain a 21 liter-volume dark red-purple extract. When the pH was adjusted to 6 using sodium hydroxide and the color value was measured, the result was E10% = 79. This indicates that E10% = 166 in terms of 1 liter. The recovered dye amount showed almost the same value, but the amount of the extracted extract was 2.2 times. It was clearly judged that the withdrawal efficiency was poor. The reddish purple extract was concentrated and powdered at 130 ° C., and then dissolved in 10 liters of ion-exchanged water. As a result, a precipitate was obtained without complete dissolution. When the color value was measured at pH 6 after filtering the precipitate, a value of E10% = 20 was obtained. The pigment remaining rate in the concentration treatment was 12%. As methanol was first removed and the acetic acid concentration was increased, a clear decrease in the amount of pigment was observed at 130 ° C., and a precipitate was also confirmed. Furthermore, acetic acid could not be removed even when powdered at 130 ° C., and the odor of acetic acid caused disgust.

  When the dye component is adsorbed on the column and then the dye is separated from the column and extracted, if a solvent containing acidic organic matter is used as the elution solution, the acidic organic matter is not removed in the subsequent formulation process, and the final product It was found that there was an adverse effect.

[Examples 3 to 8]
The following extraction steps were carried out using the dry raw material flowers subjected to the above-described dry treatments 1 to 6 (in the case of dry treatment 3 being used after removing mold-generating petals) as extraction raw materials.

  After 10 kg of dried petals were immersed in 500 liters of ion-exchanged water for 20 hours, filtration treatment was performed to obtain about 430 liters of rough extract of peanut petals. This was adjusted to 450 liters each. This filtrate was applied to a column packed with Sepa beads SP-207 (average particle size 500 μm (90% or more is 250 μm or more)) and 15 liters in volume, and the butterfly pigment component was adsorbed. The resin adsorbed with the dye was washed with 20 liters of water, and then the dye component was extracted with 70% ethanol to obtain an 8.5 liter volume dark blue extract. The color value E10% value was measured using a pH 6 buffer. Each of the blue extracts was concentrated at 60 ° C. and once concentrated to a volume of 0.5 L. Thereafter, the concentrated and thickened extract was dissolved again in ion-exchanged water to 8.5 liter capacity. The color value was measured at pH 6, and the pigment was remeasured in the concentration step.

  Separately, concentration was continued and the extract was once solidified, and then dissolved again to 8.5 liters. The dissolved state was compared. The results are shown in Table 2.

 Although the yield of the color value recovered by the drying method of the pea petals is affected, the same pigment preparation was obtained. Incidentally, the superiority of the amount of recovered pigment was confirmed in the dried petals of the drying treatment 1 and drying treatment 2 methods.

[Examples 9 to 12 and Comparative Examples 1 and 2]
According to the examples and comparative examples described in Table 3 below, alcoholic beverages were made as prototypes and evaluations about the alcoholic beverages were shown. The antioxidant activity was confirmed by a change in absorbance at 515 to 520 nm with an ethanol solution of DPPH (diphenylpicrylhydrazine).
It was found that alcoholic beverages containing pea coloring matter have high stability in properties such as light resistance, precipitation with time, and heat resistance, and also have antioxidant activity.

Claims (4)

An alcoholic drink characterized by using 0.01 to 10% by weight of a pigment extracted from a butterfly flower. The pigment extracted from the butterfly flower is a natural drying process in the shade for 3 to 6 hours or more on a net-like shelf. A step of drying until the weight becomes 1/8, a step of eluting the pigment by mixing the dried flower and an aqueous solution in which water or an organic acid of 0.5 to 2% by weight is dissolved, elution of the pigment An alcoholic beverage extracted in a step of adsorbing a liquid with an ion exchange resin and a step of eluting and purifying the adsorbed dye from the ion exchange resin with water or an organic solvent. The alcoholic beverage according to claim 1 or 2, wherein the ion-exchange resin has a porous resin having a particle diameter of 96% or more in a range of 200 to 1180 µm. The colored preparation for a blue alcoholic beverage according to any one of claims 1 to 3, which is further concentrated under reduced pressure after the step of elution and purification from an ion exchange resin.