JP2009040704A - Method for producing 3-deoxyanthocyanidin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing 3-deoxyanthocyanidin from a composition containing a gallate-type catechin, an addition composition for an acidic fermented tea containing 3-deoxyanthocyanidin, and a fermented tea drink incorporated with 3-deoxyanthocyanidin. <P>SOLUTION: 3-Deoxyanthocyanidin is produced by heating a composition containing a gallate-type catechin in powdery form. The production efficiency of 3-deoxyanthocyanidin can be improved by amorphosizing a solution containing a bivalent or trivalent metal ion and a gallate-type catechin and heat-treating the amorphous product. A composition containing 3-deoxyanthocyanidin and usable as an additive for an acidic fermented tea can be prepared by adjusting the composition ratio of tricetinidin to luteolinidin, and a fermented tea drink having improved color can be produced by adding 3-deoxyanthocyanidin to a fermented tea drink. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

The present invention relates to a method for producing 3-deoxyanthocyanidins obtained by using gallate catechin, which is a main polyphenol contained in tea ( Camellia sinensis ), as a main raw material, a composition for addition of acidic fermented tea containing tricetinidine and luteolinidine, and fermented tea Regarding beverages.

Anthocyanins are compounds characterized by having a flavilium cation in their molecular structure, and generally cause plant tissues such as flowers, fruits and leaves to be colored red, purple or blue. Conventionally, anthocyanins have been widely used for food coloring because of their vivid color tone.

Anthocyanins often exist as glycosides in plant tissues, but there are also cases where anthocyanidins, which are aglycones, are free. General anthocyanidins have a hydroxyl group at the 3-position, whereas 3-deoxyanthocyanidins are anthocyanidins that are unsubstituted at the 3-position and the stability of the compound compared to general anthocyanidins substituted at the 3-position with a hydroxyl group Is known to be high (Non-patent Document 1). As representative compounds of 3-deoxyanthocyanidins, 5,7,3′-trihydroxyflavylium salt (apigenidin, R ₁ and R _{2 in} formula (I) are hydrogen atoms), 5,7,3 ′, 4 '-Tetrahydroxyflavylium salt (luteolinidine, _one of R ₁ and R _{2 in} the general formula (I) is a hydrogen atom and the other is a hydroxyl group), 5,7,3', 4 ', 5'-pentahydroxy Flavilium salts (tricetinidine, R ₁ and R _{2 in} the general formula (I) are hydroxyl groups), and apigeninidine and luteolinidine contained in the cucurean seed of Gramineae are used as edible pigments as natural reddish brown pigments. In addition, it is also used for coloring the skin (Patent Document 1) and ink (Patent Document 2).

(I)
(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydroxyl group)

However, 3-deoxyanthocyanidins, which are mainly composed of pulyan-derived apigeninidine and luteolinidine, which are currently commercially available, have a brown color tone that is slightly reddish than caramel (Non-patent Document 2). For this reason, when trying to add the composition to an object having a clear red color, such as a fermented tea beverage, the original color tone of the object to be added is impaired, and further, the object to which the composition is added is heated. Since the color tone is markedly browned, the range of usable addition objects is limited.

Further, the conventional fermented tea beverage has a drawback that when it is an acidic beverage, the color tone turns brown or changes to a light color tone, and the neutral fermented tea beverage has a clearly different color tone. For this reason, an acid fermented tea beverage that has a bright red color close to that of a neutral fermented tea beverage is desired.

On the other hand, as a means for industrially obtaining conventional 3-deoxyanthocyanidins, there is a method of extracting the above-mentioned cuolian as a raw material. However, since 3-deoxyanthocyanidin derived from sorghum tends to be insolubilized at pH 6.0 or lower, it is not easy to solubilize in a wide range of aqueous objects (Non-patent Document 2). Furthermore, in the means for reacting gallate-type catechin with catechol oxidase (Non-patent Document 3) and the method for obtaining 3-deoxyanthocyanidin by hydrolyzing polymerized polyphenol (Patent Document 3), catechin is strongly oxidized and various kinds of catechins are oxidized. While a by-product is generated, it is difficult to say that it is a suitable method because the amount of 3-deoxyanthocyanidin produced is small. In addition, 3-deoxyanthocyanidins are also contained in the fermented tea leaves, but the amount thereof is extremely small (Non-patent Document 4), so it is not easy to extract and purify 3-deoxyanthocyanidins from fermented tea leaves. Absent.

Therefore, a means for obtaining a large amount of 3-deoxyanthocyanidins excellent in solubility by a simple technique has not been proposed so far.
JP 2005-232176 A JP 2004-346099 A JP 2001-279125 A Tetrahedron, 37, pp. 1481-1483 (1981) San-Ei Gen FFI Co., Ltd. homepage “Koryang dye” [online] “Search June 25, 2007” Internet [http://www.saneigenffi.co.jp/color/nkaolia.html] J. et al. Agr. Food Chem. , 21 (4), pp. 727-733 (1973) J. et al. Sci. Food Agric. , 9 (4), pp. 217-223 (1958)

Therefore, a first object of the present invention is to provide a method for easily and efficiently producing 3-deoxyanthocyanidins having a clear red color tone and excellent solubility. The second object of the present invention is to provide a composition for adding acidic fermented tea containing 3-deoxyanthocyanidin, and the third object of the present invention is an excellent fermentation having a clear red color tone. It is to provide tea drinks. Furthermore, when a fermented tea drink is a liquid form, it aims at provision of the fermented tea drink with little color tone change after heat processing.

Since the present inventors have a small amount of 3-deoxyanthocyanidin in fermented tea, but hardly exist in green tea, 3-deoxyanthocyanidin is secondarily generated during the production process of fermented tea. I thought it was. Therefore, as a result of intensive studies on the conditions that can produce 3-deoxyanthocyanidins using tea leaf ingredients as raw materials, a vivid red color tone is obtained by means of heating gallate catechins contained in tea leaves as a main raw material in a powder state. It came to find the manufacturing method of 3-deoxyanthocyanidin which can produce | generate 3-deoxyanthocyanidin which was excellent in the solubility with a simple method in large quantities.

In the conventional method for extracting cucumber as a raw material, only apigeninidine and luteolinidine out of 3-deoxyanthocyanidins were obtained, and tricetinidine could not be obtained. Further, the means for reacting gallate-type catechin with catechol oxidase and the means for hydrolyzing polymerized polyphenol have poor conversion efficiency to tricetinidine, and there has been no method for obtaining tricetinidine simply and efficiently. Therefore, the method for producing 3-deoxyanthocyanidins of the present invention has been found for the first time to obtain a large amount of tricetinidine by a simple technique.

In addition, the present inventors have found that the composition prepared by adjusting the tricetinidine content and the luteolinidine content within a certain range is easily dissolved in the acid fermented tea, and the acid fermented tea added with the composition is fermented tea. It was found that the color tone change after heat treatment was reduced. Since conventional 3-deoxyanthocyanidins have a tendency to be insolubilized in an acidic solution, it has been impossible to use as a composition for adding to acidic fermented tea. Therefore, the composition for adding acidic fermented tea of the present invention is the first example used for the purpose of adding 3-deoxyanthocyanidin to an acidic fermented tea beverage.

Furthermore, the present inventors have a clear red color tone by adjusting the tricetinidine content and the luteolinidine content in the fermented tea beverage within a certain range, and when the fermented tea beverage is liquid, It has been found that the change in color tone after the heat treatment is reduced, and the present invention has been completed.

That is, the present invention according to claim 1 provides a method for producing 3-deoxyanthocyanidins characterized by heating a gallate-type catechin-containing composition in a powder state.

The “gallate-type catechin-containing composition” in the present invention may be anything as long as it contains an amorphous gallate-type catechin. For example, a composition composed only of an amorphous gallate-type catechin or an amorphous state A gallate-type catechin containing a mixture (for example, tea extract) and the like. Here, amorphous means all powders having no crystal structure. In the present invention, crystalline gallate catechins may be contained in the gallate catechin-containing composition, but 3-deoxy can be obtained from crystalline gallate catechins using the production method of the present invention. Since it is difficult to produce anthocyanidins, the content of the crystalline gallate catechins in the gallate catechin-containing composition in the present invention is preferably small.
The “gallate-type catechin” refers to a single compound of any one of amorphous epicatechin gallate, catechin gallate, epigallocatechin gallate, gallocatechin gallate, epiafzerekin gallate and afzelekin gallate Or the thing which mixed 2 or more types of single compounds is meant.

Similarly, “3-deoxyanthocyanidin” in the present invention includes at least one of tricetinidine, luteolinidine, and apigeninidine.

The present invention according to claim 2 provides the method for producing 3-deoxyanthocyanidins according to claim 1, wherein the gallate-type catechin-containing composition contains a metal salt.

The present invention described in claim 3 provides the method for producing 3-deoxyanthocyanidin according to claim 1 or 2, wherein the gallate catechin-containing composition is a tea extract.

In the present invention according to claim 4, the raw material gallate catechin-containing composition comprises the following components (X) and (Y):
(X) Galate type catechin 45% (w / w) or more (Y) Epigallocatechin gallate and / or gallocatechin gallate, and the content weight ratio of the components (Y) and (X) [(Y) / ( X)] is 0.67 or more,
The method for producing 3-deoxyanthocyanidins according to claims 1 to 3, wherein the produced 3-deoxyanthocyanidins contain 0.1% (w / w) or more of tricetinidine.

In the fifth aspect of the present invention, the raw material gallate catechin-containing composition comprises the following components (X), (Y) and (Z):
(X) Galate type catechin 45% (w / w) or more (Y) epigallocatechin gallate and / or gallocatechin gallate (Z) epicatechin gallate and / or catechin gallate, (Y) and (Z) The content weight ratio [(Y) / (Z)] is 0.3 to 80,
The 3-deoxyanthocyanidin-containing 3-deoxyanthocyanidin has a weight ratio [(A) / (B)] of (A) tricetinidine and (B) luteolinidine of 0.3 to 80. A manufacturing method is provided.

Invention of Claim 6 contains tricetinidine (A) and luteolinidine (B), The content weight ratio [(A) / (B)] is 0.3-80, The composition for acidic fermentation tea addition It provides things.

The present invention according to claim 7 includes the following components (A) and (B):
(A) Tricetinidine 0.05 mg / 100 mL or more (B) Luteolinidine, (A) Tricetinidine and (B) Luteolinidine content weight ratio [(A) / (B)] is 0.3-80 Beverages are provided.

The present invention according to claim 8 provides the fermented tea beverage according to claim 7, which has a pH of 4.5 or less.

The method for producing 3-deoxyanthocyanidins in the present invention does not require a special apparatus, and can be easily and efficiently produced using a general production facility. The 3-deoxyanthocyanidin obtained by the production method of the present invention has a clear red color tone and can be solubilized in various solutions having a pH of 6.0 or less, so that it can be easily solubilized in a wide range of objects. It is.
Moreover, since the composition for acidic fermented tea addition containing tricetinidine and luteolinidine of the present invention can be easily dissolved in acidic fermented tea, it is possible to provide an acidic fermented tea beverage exhibiting a red color tone similar to fermented tea. is there.

In addition, the fermented tea beverage containing a certain amount of tricetinidine and luteolinidine according to the present invention has a vivid red color tone inherent to fermented tea, and when it is a liquid fermented tea beverage, it has a clear color tone even after heat treatment. Therefore, it can be used without affecting the original properties of the fermented tea beverage.

Hereinafter, the present invention will be described in detail.
The method for producing 3-deoxyanthocyanidins in the present invention is to obtain 3-deoxyanthocyanidins by heating the gallate-type catechin-containing composition in a powder state. Specifically, 3-deoxyanthocyanidins represented by the general formula (I) are obtained by using the gallate catechin represented by the general formula (II) as a main raw material and heating it in a powder state.

Here, the “gallate-type catechin-containing composition” in the present invention may be anything as long as it contains amorphous gallate-type catechins, for example, those composed only of amorphous gallate-type catechins or amorphous The mixture (for example, tea extract) etc. which contain these gallate type catechins and are comprised from several components are included. The “gallate-type catechin” is an amorphous epicatechin gallate represented by the general formula (II), catechin gallate, epigallocatechin gallate, gallocatechin gallate, epiafuzerekin gallate and afzelekin gallate. It means any one single compound or a mixture of two or more single compounds.

The “3-deoxyanthocyanidin” in the present invention includes at least one of tricetinidine, luteolinidine and apigeninidine.

(II)
(In the formula, R ₃ and R ₄ each independently represent a hydrogen atom or a hydroxyl group, and the configuration at the 2-position and 3-position of the benzopyran ring may be either R configuration or S configuration)

(I)
(Wherein R ₁ and R ₂ each independently represent a hydrogen atom or a hydroxyl group)

At this time, if epigallocatechin gallate and / or gallocatechin gallate in which R ₃ and R _{4 in} formula (II) are hydroxyl groups are heated in a powder state, R ₁ and R _{2 in} formula (I) are hydroxyl groups. If tricatetinidine that is a compound is heated in the form of powder, epicatechin gallate and / or catechin gallate in which one of R ₃ and R _{4 in} general formula (II) is a hydrogen atom and the other is a hydroxyl group can be obtained. Rteolinidine in which _one of R ₁ and R ₂ in general formula (I) is a hydrogen atom and the other is a hydroxyl group can be obtained, and R ₃ and R _{4 in} general formula (II) are hydrogen atoms. If piafzerekin gallate and / or afzerekin gallate is heated in a powder state, apigeninidine in which R ₁ and R _{2 in} formula (I) are hydrogen atoms can be obtained. At this time, in addition to tricetinidine, trace amounts of luteolinidine and apigeninidine may be obtained from epigallocatechin gallate and / or gallocatechin gallate in which R ₃ and R ₄ in general formula (II) are hydroxyl groups, and general formula (II) From epicatechin gallate and / or catechin gallate in which either one of R ₃ and R ₄ is a hydrogen atom and the other is a hydroxyl group, a trace amount of apigenin may be obtained in addition to luteolinidine.

Moreover, if the mixture containing 2 or more types of gallate type catechin represented by general formula (II) is used as a raw material, the resulting 3-deoxyanthocyanidin is also a mixture containing at least 2 types of tricetinidine, luteolinidine, and apigeninidine. For example, epigallocatechin gallate and / or gallocatechin gallate in which R ₃ and R _{4 in} general formula (II) are hydroxyl groups, and either R ₃ or R _{4 in} general formula (II) If a mixture of epicatechin gallate and / or catechin gallate, one of which is a hydrogen atom and the other is a hydroxyl group, is used as a raw material, a mixture containing tricetinidine and luteolinidine can be obtained.

Further, in the present invention, it is preferable to use a tea extract (a powder obtained by drying a tea extract) as the gallate catechin-containing composition because 3-deoxyanthocyanidin can be easily prepared. Similarly, when a tea extract is used, the amount of 3-deoxyanthocyanidin produced can be increased as the gallate catechin content in the extract is increased. For this reason, it is desirable to use a green tea extract as a raw material among tea extracts. As the tea extract, tea leaves may be extracted with water or a solvent to prepare a tea extract, and then used as a dry powder, or a commercially available extract may be used. Commercially available tea extracts include Mitsui Norin Co., Ltd., trade name “Polyphenon”, ITO EN Co., Ltd., trade name “Theafranc”, Taiyo Kagaku Co., Ltd., trade name “Sunphenon”, and DSM Nutritional Products, Inc. The brand name “Teavigo” can be mentioned.

In the gallate catechin-containing composition of the present invention, the higher the gallate catechin content is, the higher the production amount of 3-deoxyanthocyanidins can be increased. Therefore, the content of gallate catechin is 45% (w / w) or more. Preferably, 55% (w / w) or more is more preferable, and 70% (w / w) or more is more preferable.

Furthermore, among 3-deoxyanthocyanidins, in order to increase the production efficiency of tricetinidine, the gallate catechin-containing composition used as a raw material contains epigallocatechin gallate and / or gallocatechin gallate 30% (w / w) or more. It is preferably 35% (w / w) or more, more preferably 45% (w / w) or more, and the ratio of epigallocatechin gallate and / or gallocatechin gallate to gallate catechin [ (Epigallocatechin gallate and / or gallocatechin gallate) / gallate catechin] is preferably 0.67 or more.

Moreover, the gallate catechin-containing composition in the present invention contains epicatechin gallate and / or catechin gallate in addition to the above-described conditions of epigallocatechin gallate and / or gallocatechin gallate content, and epigallocatechin gallate and The content weight ratio [(epigallocatechin gallate and / or gallocatechin gallate) / (epicatechin gallate and / or catechin gallate)] to / or gallocatechin gallate is 0.3 to 80, more preferably 0.5 to 50 More preferably, when it is prepared to be in the range of 1 to 10, the content weight ratio of tricetinidine and luteolinidine in the produced 3-deoxyanthocyanidin can be easily adjusted to 0.3 to 80, and as a result, a preferable color tone is obtained. Of 3-deoxyanthocyanidins Can for desirable.

Although it is possible to produce 3-deoxyanthocyanidins simply by heating a gallate-type catechin-containing composition in a powder state, the use of a powder containing gallate-type catechins and a metal salt enables generation efficiency of 3-deoxyanthocyanidins. Can be further increased. Although the method in particular of containing a metal salt is not restrict | limited, For example, after dissolving and mixing a metal salt and gallate type catechin, the method of pulverizing again is mentioned.

In addition, the amount of 3-deoxyanthocyanidin produced is greater when a powder containing a large amount of metal salt is prepared, but depending on the type of metal salt, a gallate type that is a raw material when an excessive amount of metal salt is contained In some cases, catechin is decomposed and 3-deoxyanthocyanidins cannot be produced. Therefore, for example, in metals such as aluminum, manganese and magnesium, it is preferable to contain 0.00000001 to 1 mol of metal with respect to 1 mol of gallate catechin.

In addition, when metals such as calcium and iron (III) are contained in an equimolar amount or more with respect to the gallate catechin, the amount of gallate catechin is 1 mol because the formation of 3-deoxyanthocyanidins cannot proceed well. The amount is preferably 0.00000001 to 0.8 mol, and more preferably 0.0000005 to 0.5 mol. The metal is preferably divalent or trivalent, and more preferably in the order of aluminum, magnesium, and manganese.

Therefore, for example, metals such as aluminum, manganese, and magnesium preferably contain a gallate catechin / metal chloride salt = 1 / 0.000000005 to 0.5 (w / w). In addition, in the case of a metal such as calcium or iron (III), if it is contained in an amount equivalent to the above metal amount relative to the amount of gallate catechin, it may become an excess amount, and the production of 3-deoxyanthocyanidins can be progressed well. Therefore, in calcium, gallate catechin / metal chloride salt = 1 / 0.000000003 to 0.3 (w / w), more preferably 1 / 0.000000016 to 0.16 (w / w), In iron (III), gallate catechin / metal chloride salt = 1 / 0.000000006 to 0.5 (w / w), more preferably 1 / 0.0000003 to 0.3 (w / w). It is good to contain.

When powdering a gallate-type catechin-containing composition that is a raw material, it is generally powdered by freeze drying, vacuum drying, spray drying, etc. It is not limited to this.
Here, amorphous means all powders having no crystal structure.

The method of heating the dry powder obtained by the above method in a powder state is not particularly limited, but it is desirable to spread the powder in an open heat-resistant container so as to increase the surface area in contact with air, preferably Heating should be performed in the temperature range of 80 to 150 ° C, more preferably 100 to 130 ° C, and most preferably 110 to 125 ° C. When heated below 80 ° C., the efficiency of obtaining 3-deoxyanthocyanidins is significantly reduced, and when heated at temperatures exceeding 150 ° C., the resulting powder has a low 3-deoxyanthocyanidin content, black color, and extremely low solubility. Therefore, the heating temperature for obtaining the desired 3-deoxyanthocyanidin is not preferable. In addition, when heating, you may stir or stand still as needed.

The heating time of the dry powder depends on the heating temperature. If heated for a long time, a large amount of 3-deoxyanthocyanidin can be obtained. However, if the heating is performed for a long time, not only the production efficiency is poor, but also the solubility of 3-deoxyanthocyanidin is lowered. For this reason, when heating at 120 ° C., the heating time is preferably 0.5 to 7 days. When the raw material is only gallate catechin, heating at 120 ° C. for 3 to 5 days is more preferable, and when the raw material is a mixture such as tea extract, heating at 120 ° C. for 0.5 to 2 days is further performed. preferable.

As described above, if 3-deoxyanthocyanidin obtained by heating a dry powder containing gallate-type catechin in the powder state is once dissolved and purified by a separation method using an adsorption resin, a brighter red color is obtained. A refined product of 3-deoxyanthocyanidin can be obtained.

As the adsorption resin, a synthetic adsorption resin having a high adsorption capability is suitable. Specifically, the dissolved 3-deoxyanthocyanidin is passed through a column packed with a synthetic adsorption resin, 3-deoxyanthocyanidin is adsorbed on the resin, and the target 3-deoxyanthocyanidin is obtained using an acidified organic solvent. Elute from the resin to obtain purified 3-deoxyanthocyanidins. This operation is usually performed using a column packed with a synthetic adsorption resin, but can also be performed in a batch manner without using a column.

Synthetic adsorption resins that can be used at this time include styrene divinylbenzene, methacrylic, styrene, modified styrene, acrylic, amide, dextran, cellulose, and polyvinyl resins that are commercially available. For example, styrene divinylbenzene-based Diaion HP-20, Diaion HP-21 (above, manufactured by Mitsubishi Chemical Corporation), Amberlite XAD-2, Amberlite XAD-4 (above, US Rohm and Manufactured by Haas Co., Ltd.), methacrylic diaion HP-2MG (manufactured by Mitsubishi Chemical Co., Ltd.), Amberlite XAD-16 (manufactured by Rohm and Haas, USA) as styrene, and Sepa beads sp207 (manufactured by Mitsubishi Chemical) as a modified styrene ), Acrylic Diaion WK-20 (manufactured by Mitsubishi Chemical Corporation), Mid-based XAD-11 (manufactured by Rohm and Haas, USA), dextran-based Sephadex LH-20 (manufactured by Pharmacia), cellulose-based INDION DS-3 (manufactured by Phoenix Chemicals), polyvinyl-based Toyopearl HW- 40 (manufactured by Tosoh Corporation).

As a solvent used for elution, an organic solvent arbitrarily mixed with water, such as ethanol, methanol, propanol, and acetone, can be used in addition to water. As the acid to be used, any acid that is generally used industrially, such as acetic acid, hydrochloric acid, nitric acid, sulfuric acid, trichloroacetic acid, and trifluoroacetic acid, can be used without any problem.

Particularly preferred examples include acetic acid or hydrochloric acid, and the resulting 3-deoxyanthocyanidins form salts with them. As a combination of the resin and the elution solvent, any of the above can be used in combination, but when used for beverages and the like, from the viewpoint of the food hygiene law, especially after adsorbing to the hydrophilic vinyl polymer resin It is preferable to elute with ethanol acidic with hydrochloric acid or acidic with acetic acid (which may contain water). This eluate can be dried to dryness by a usual method to obtain the desired 3-deoxyanthocyanidin.

As described above, the method for producing a 3-deoxyanthocyanidin-containing composition in the present invention needs to heat the gallate-type catechin-containing composition in a powder state. If an instant powdered tea is heated as it is, an instant powdered fermented tea having an appearance like a fermented tea with enhanced red color tone can be easily produced.

Here, instant powdered tea is dissolved in a liquid form in a powdered tea beverage that is dissolved in a liquid form using an aqueous medium such as water, hot water, milk, teas, fruit juice extract, and a water-soluble extract. It means the previous powder state. A general method for producing instant powdered tea includes extraction of raw tea leaves or pressing, concentration, drying and granulation.

At this time, the instant powdered tea used as a raw material may be any instant powdered tea containing gallate catechins such as black tea, oolong tea, green tea, and roasted tea. In addition, the instant powdered tea obtained by the present method is preferably instant powdered black tea and further instant powdered acidic black tea for the purpose of the present invention to enhance the red color tone that is typical of fermented tea.

Since tricetinidine is present in a very small amount in fermented tea extract or fermented tea extract (less than 0.01 mg / 100 mL), 3-deoxyanthocyanidin is extracted and purified from fermented tea extract or fermented tea extract as a starting material In such a case, the production efficiency is poor, and it is not easy to obtain a large amount of tricetinidine. On the other hand, when the method for producing 3-deoxyanthocyanidins in the present invention is used, a large amount of tricetinidine can be easily obtained as compared with the conventional method.

The 3-deoxyanthocyanidins in the present invention are preferably tricetinidine 0.1% (w / w) or more, more preferably 0.2% (w / w) or more, and further preferably 0.5% (w / w). As mentioned above, it contains most preferably 1% (w / w) or more. It is preferable to adjust the tricetinidine content within the above range since the color tone of the composition becomes red.

The 3-deoxyanthocyanidin obtained by the production method of the present invention preferably has a tricetinidine and luteolinidine content weight ratio [tricetinidine / luteolinidine] of 0.3 to 80, more preferably 0.5 to 50, still more preferably 1 to 1. It will be 10.

Furthermore, when 3-deoxyanthocyanidins obtained by the production method of the present invention are not purified at all after production, the total content of tricetinidine and luteolinidine is preferably 0.1 to 30% (w / w), more The content is preferably 0.2 to 20% (w / w), more preferably 0.5 to 15% (w / w), and most preferably 1 to 10% (w / w).

The 3-deoxyanthocyanidin-containing composition mainly composed of pulyan-derived apigeninidine and luteolinidine that are commercially available in the past has a reddish brown to brown color tone, and when a solution in which the composition is dissolved is heated. The color tone of the solution was browned and the color tone stability was not excellent. The 3-deoxyanthocyanidin obtained by the production method of the present invention exhibits a vivid red color by taking the content ratio of tricetinidine and luteolinidine and the total content of tricetinidine and luteolinidine in 3-deoxyanthocyanidin, and The light blue color of the solution in which 3-deoxyanthocyanidin is dissolved has a clear orange to red color that seems to be fermented tea, and the color tone can be maintained even when the solution is heated.

Further, when 3-deoxyanthocyanidins are not purified at all after production, catechins are 3% (w / w) or more, preferably 4% (w / w) or more, more preferably 5% (w / w). ) Or more, more preferably 6-deoxyanthocyanidins containing 6% (w / w) or more can be obtained. Thereby, the antioxidant effect | action by catechins works and the color tone stability of 3-deoxyanthocyanidin can be improved more. When the content of catechins in 3-deoxyanthocyanidins exceeds 90% (w / w), the original color of fermented tea is lost when added to acidic fermented tea beverages, and the bitter and astringent taste derived from catechins is strong. It is too unfavorable.

Since 3-deoxyanthocyanidin in the present invention has high stability, it can be used for various objects such as foods and drinks, cosmetics, quasi drugs, and pharmaceuticals. In addition, the 3-deoxyanthocyanidin of the present invention is not browned like the conventional 3-deoxyanthocyanidins even when the liquid in which the composition is dissolved is heated, and thus an object having a clear red color tone, particularly a fermented tea beverage, etc. It can be suitably used.

The fermented tea beverage in the present invention refers to an extract obtained by extracting fermented tea tea leaves with hot water, hot water, cold water, ethanol, hydrous ethanol, or the like, or a diluted solution thereof. In the present invention, in addition to such a liquid type, a powder type obtained by concentrating, drying and granulating the obtained extract can also be included in the fermented tea beverage. A powder type is preferred because stability during storage is increased.

As a general method for producing a fermented tea beverage, first, fermented tea tea leaves as raw materials are extracted with 20 to 50 times the weight of hot water or hot water. Here, the fermented tea tea leaves used in the present invention, the Chinese species is the evergreen of theales Theaceae Camellia is a "tea tree" Camellia sinensis (var. Sinensis) and Assam species (var. Assamica) or their hybrids All of the tea leaves obtained from the tea leaves through the fermentation process are included, and examples include black tea leaves called strong fermented tea or fermented tea, oolong tea leaves called semi-fermented tea, and the like.

In the present invention, these tea leaves may be used individually or mixed, but it is preferable to use tea leaves containing black tea leaves. The extraction time and the extraction temperature are appropriately adjusted depending on the production area and purpose of the fermented tea used, but usually, extraction is performed at 75 ° C. or more and 95 ° C. or less for 3 to 30 minutes, and stirring is performed as necessary. Next, a tea extract is obtained by solid-liquid separation of solid components such as tea husks by methods such as filtration and centrifugation. Water is added to this and diluted to a concentration suitable for tea beverages to obtain a blended solution.

In the tea preparation liquid, as necessary, antioxidants such as ascorbic acid and sodium ascorbate, flavoring agents, pH adjusters such as sodium bicarbonate, emulsifiers, preservatives, sweeteners, coloring agents, thickening stabilizers, Additives such as seasonings and reinforcing agents can be blended alone or in combination. In addition, the pH of the preparation liquid is preferably 2.0 to 7.0 in terms of 25 ° C., and preferably 2.5 to 6.0 from the viewpoint of improving the solubility of 3-deoxyanthocyanidin and the color tone after the addition. Is more preferable, and 2.5 to 4.5 is more preferable. At this time, you may use citric acid or its salt, citrus fruit juices, such as lemon, etc. as a pH adjuster. The fermented tea beverage thus prepared contains a very small amount (less than 0.01 mg / 100 mL) of 3-deoxyanthocyanidins.

When the tricetinidine of the present invention is contained in the fermented tea beverage, it may be contained as a powder, but the final concentration of tricetinidine contained in the fermented tea beverage is 0% as an aqueous solution, an alcohol aqueous solution or an alcohol solution of several percent. 0.05 mg / 100 mL or more, preferably 0.1 to 5 mg / 100 mL, more preferably 0.2 to 3 mg / 100 mL, and still more preferably 0.5 to 2 mg / 100 mL. When adjusted to this range, a fermented tea beverage exhibiting a preferable red color is obtained.

The fermented tea beverage in the present invention further contains luteolinidine in addition to the above-mentioned conditions for tricetinidine content, and the weight ratio of tricetinidine and luteolinidine [tricetinidine / luteolinidine] is 0.3 to 80, preferably 0.5 to 50. More preferably, it is 1-10. When the weight ratio of tricetinidine and luteolinidine contained in the fermented tea beverage [tricetinidine / luteolinidine] is less than 0.3, the color of the fermented tea beverage is yellowish, and the red color of fermented tea that is the object of the present invention Since it does not exhibit a color tone, it is not preferable, and when [Tricetinidine / Luteolinidine] exceeds 80, not only red is too strong, but also the color tone becomes brown when the beverage is heated, which is not preferable.

Further, the total content of tricetinidine and luteolinidine contained in the fermented tea beverage is preferably 0.05 mg / 100 mL or more, more preferably 0.1 to 6 mg / 100 mL, and further preferably 0.2 to 4 mg / 100 mL. Most preferably, it is prepared to be 0.5 to 3 mg / 100 mL. If the total content of tricetinidine and luteolinidine in the solution exceeds the upper limit, it will be difficult to dissolve uniformly, precipitates and floats will be generated in the solution, and a clear solution cannot be obtained. It is not preferable because it exhibits an unsuitable color tone. Moreover, when the total content of tricetinidine and luteolinidine in the solution is less than the lower limit, it does not have the clear red color tone inherent to fermented tea, which is inappropriate.

Measurement of tricetinidine and luteolinidine can be performed using high performance liquid chromatography (hereinafter, HPLC) under the following conditions.

(Measurement conditions for tricetinidine)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical), mobile phase: (A) ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) ultrapure water / phosphoric acid / acetonitrile / methanol = 100 /0.05/2.5/50, (A) 100% hold for 0-3 min, 3-25 min for (B) 0% → 100% linear gradient elution, 25-26 min ( A) Return to 100%, equilibrate at 26% for (A) 100%, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 500 nm, injection volume: 10 μL.

(Measurement conditions for luteolinidine)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical), mobile phase: (A) ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) ultrapure water / phosphoric acid / acetonitrile / methanol = 100 /0.05/2.5/50, (A) 100% hold for 0-3 min, 3-25 min for (B) 0% → 100% linear gradient elution, 25-26 min ( A) Return to 100%, equilibrate at 26% for (A) 100%, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 500 nm, injection volume: 10 μL.

In addition, when 3-deoxyanthocyanidins with a high degree of purification are used, the effect of improving the color tone of a fermented tea beverage or the like is greatly recognized even when a small amount is added. Also, if 3-deoxyanthocyanidins containing a large amount of catechins are added to fermented tea beverages, the antioxidant stability of catechins increases the color stability of 3-deoxyanthocyanidins and provides high-quality fermented tea beverages can do. Furthermore, when 3-deoxyanthocyanidins in which raw materials such as gallate catechin are mixed are used, an added value that the amount of catechins that are polyphenols can be increased can be provided.

Here, the catechins are epicatechin, catechin, epigallocatechin, gallocatechin, epicatechin gallate, catechin gallate, epigallocatechin gallate, gallocatechin gallate, epiafzerekin, afzerekin, epiafzerekin gallate and afzelekin It is a generic name for gallate.

Among the catechins, eight components of epicatechin, catechin, epigallocatechin, gallocatechin, epicatechin gallate, catechin gallate, epigallocatechin gallate and gallocatechin gallate can generally be quantitatively analyzed by HPLC under the following conditions. .

(Measurement conditions for catechins)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical), mobile phase: (A) ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) ultrapure water / phosphoric acid / acetonitrile / methanol = 100 /0.05/2.5/50, (A) 100% hold for 0-3 min, 3-25 min for (B) 0% → 100% linear gradient elution, 25-26 min ( A) Return to 100%, equilibrate at 26% for (A) 100%, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 230 nm, injection volume: 10 μL.

When the fermented tea beverage in the present invention is an acidic fermented tea beverage, the light blue color is orange to red-orange. In this case, orange to red-orange means that in the Munsell color system of Japanese Industrial Standard JIS Z 8721, the hue is in the range of 7.5R to 2.5Y, the lightness is 4 to 9, and the saturation is It is preferable that it is the orange-red orange color shown in the range of 6-12.

The following examples further illustrate the present invention. However, the present invention is not limited to these. The tannin concentration is measured by the Japan Food Analysis Center, “Explanation of the 5th edition Japanese Food Standards Component Analysis Manual”, Central Law, July 2001, p. 252 according to the official method (iron tartrate reagent method) described in 252.

Aluminum chloride, magnesium, manganese, calcium, and iron (III) metal chlorides were added to 0.001 micromole per 2 milligrams of EGCg (about 0.92 g), dissolved in water, and then adjusted to 100 mL. I was satisfied. The solution was dried with a freeze dryer to obtain each metal-added EGCg. 10 mg of these metal-added EGCg and untreated crystalline EGCg as a control were weighed and placed in a glass vial to spread the powder flat. The vials were then placed in a dry heat drier previously at 120 ° C. and heated for 1.5 hours, 3.0 hours, 6.0 hours, 8.0 hours, and 24.0 hours. . The tricetinidine content of the unheated powder and the heated powder was measured under the following conditions using HPLC. An isolated tricetinidine standard was used for quantification. The results are shown in Table 1 and FIG.

(Method of measuring tricetinidine)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical Co., Inc.), mobile phase: (A) Ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) Ultrapure water / phosphoric acid / acetonitrile / methanol = 100 / 0.05 / 2.5 / 50, (A) 100% hold for 0-3 minutes, 3-25 minutes for (B) 0% → 100% linear gradient elution, 25-26 minutes (A) to 100%, equilibrated at (A) 100% for 26-30 minutes, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 500 nm, injection volume: 10 μL.

Tricetinidine content

As shown in Table 1 and FIG. 1, almost no tricetinidine was detected even when the crystalline EGCg was heated. On the other hand, EGCg heated by adding a metal detected not only the metal species but also tricetinidine.

Aluminum, magnesium, manganese, calcium, and iron (III) metal chlorides were added to give an equivalent (2 mmol) to 2 mmol of EGCg (about 0.92 g), dissolved in water, and then adjusted to 100 mL. I was satisfied. As a control, no metal was added, and after dissolving with water, a volume of 100 mL was prepared. These solutions were dried by a freeze dryer to obtain EGCg to which each metal was added and EGCg without addition. 10 mg of EGCg to which each metal was added and EGCg to which no metal was added were weighed and placed in a glass vial to spread the powder flatly. The vials were placed in a dry heat drier previously set at 120 ° C. and heated for 7 days. The tricetinidine content of the unheated powder and the heated powder was measured by HPLC in the same manner as in Example 1. An isolated tricetinidine standard was used for quantification. The results of quantifying the amount of tricetinidine in each heated EGCg with and without added metal are shown in Table 2 and FIG.

Tricetinidine content

Tricetinidine was not detected from each unheated EGCg.
As shown in Table 2 and FIG. 2, 0.29% (w / w) of tricetinidine was detected from EGCg heated to powder by freeze-drying without adding a metal salt. From Example 1, since tricetinidine was not produced even when crystalline EGCg was heated (Table 1 or FIG. 1), it was found that tricetinidine was produced from EGCg by heat treatment by making it amorphous.

In EGCg heated by adding EGCg equivalent of each metal, tricetinidine was detected from EGCg added with magnesium, aluminum, calcium and manganese, and about 5-6% (w / w) of tricetinidine was contained from EGCg added with magnesium, aluminum and manganese. 3-deoxyanthocyanidins were obtained. On the other hand, tricetinidine was not detected from iron (III) -added EGCg. Moreover, the amount of tricetinidine produced | generated from calcium addition EGCg is about 1.39% (w / w), compared with 2.34% (w / w) (Table 1) of the 24-hour heating goods in Example 1. The amount of iron (III) and calcium was considered to be excessive in terms of equivalent amount.

From the results of Example 1 and Example 2, it was found that tricetinidine was produced by heating EGCg in an amorphous state, and that the production efficiency was improved by adding metal ions during pulverization. .

Manganese chloride salt was added so as to be equivalent (2 mmol) to 2 mmol (about 0.88 g) of ECg, dissolved in water, and adjusted to 100 mL. The solution was dried with a freeze dryer to obtain manganese-added ECg. It was weighed 10 mg and placed in a glass vial to spread the powder flat. The vials were placed in a dry heat dryer pre-heated at 120 ° C. and heated for 1, 2, 3, 4, 7, and 14 days. The luteolinidine content of the unheated powder and the heated powder was measured under the following conditions using HPLC. An isolated luteolinidine standard was used for quantification. The results are shown in Table 3 and FIG.

(Measurement method of luteolinidine)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical), mobile phase: (A) ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) ultrapure water / phosphoric acid / acetonitrile / methanol = 100 /0.05/2.5/50, (A) 100% hold for 0-3 min, 3-25 min for (B) 0% → 100% linear gradient elution, 25-26 min ( A) Return to 100%, equilibrate at 26% for (A) 100%, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 500 nm, injection volume: 10 μL.

Luteolinidine content

As shown in Table 3 or FIG. 3, luteolinidine was detected from ECg heated with manganese added. When heated for 7 days, 3-deoxyanthocyanidin containing 7.17% (w / w) luteolinidine was obtained.

Commercial green tea extract (trade name: Polyphenon 70A, manufactured by Mitsui Norin Co., Ltd., EGCg + GCg = 61% (w / w), ECg + Cg = 16% (w / w), gallate catechin = 77% / (w), ( 500 mg of EGCg + GCg) / gallate catechin = 0.8, (EGCg + GCg) / (ECg + Cg) = 3.9, metal ion = 250 ppm or more) was weighed, and placed in a glass vial to spread the powder flatly. The vials were placed in a dry heat drier previously at 120 ° C. and heated for 4 hours, 8 hours, 12 hours, 24 hours, 48 hours (2 days), and 72 hours (3 days). The tricetinidine and luteolinidine contents and catechin content of the unheated powder and the heated powder were measured using HPLC. The tricetinidine and luteolinidine contents were measured by HPLC according to the measurement method described in Example 1 and Example 3, and the catechins content was measured by HPLC under the following analytical conditions. For the quantification, isolated tricetinidine and luteolinidine standards and catechin standards manufactured by Mitsui Norin Co., Ltd. were used. The results are shown in Table 4 and FIG.

(Measurement method of catechins)
Column: Mightysil RP-18GP 4.6 mmI. D. × 150 mm (particle diameter 5 μm, Kanto Chemical), mobile phase: (A) ultrapure water / phosphoric acid / acetonitrile = 100 / 0.05 / 2.5 (B) ultrapure water / phosphoric acid / acetonitrile / methanol = 100 /0.05/2.5/50, (A) 100% hold for 0-3 min, 3-25 min for (B) 0% → 100% linear gradient elution, 25-26 min ( A) Return to 100%, equilibrate at 26% for (A) 100%, flow rate: 1 mL / min, column temperature: 40 ° C., detection wavelength: 230 nm, injection volume: 10 μL.

As shown in Table 4 or FIG. 4, tricetinidine and luteolinidine were detected from the heated green tea extract. When heated for 72 hours, tricetinidine and luteolinidine were combined and contained 4.32% (w / w), and 3-deoxyanthocyanidin having a tricetinidine and luteolinidine content weight ratio [tricetinidine / luteolinidine] of 3.32. The green tea extract heated for 24 hours contained 73.9% (w / w) of catechins in total. The obtained 3-deoxyanthocyanidin had a clear red color tone and was stored for 12 months, but the color tone and flavor did not change and was excellent in long-term stability.
Tricetinidine and luteolinidine were not produced from the unheated green tea extract.

30 g of tea leaves (Darjeelin) was added to about 900 g of water heated to 75 ° C., extracted for 5 minutes with stirring, and tea leaves were separated with a 100 mesh stainless steel filter. After cooling to 20 ° C., the mixture was filtered using filter paper (No. 26, manufactured by Advantech Co., Ltd.) to obtain 771.0 g of black tea extract (tannin concentration: 344.8 mg / 100 mL by the iron tartrate reagent method). Using this black tea extract, an acidic black tea beverage and a neutral black tea beverage were prepared by the following method.

(Preparation of acidic tea beverage)
The black tea extract obtained above was diluted with ion-exchanged water so as to have a tannin concentration of 50 mg / 100 mL, and 200 mg of citric acid was added to 500 mL of this solution to obtain an acidic black tea beverage having a pH of 3.4. To this solution, the 3-deoxyanthocyanidin prepared in Example 4 heated for 24 hours (tricetinidine (A) = 1.64% (w / w), luteolinidine (B) = 0.52% (w / w), (A) + (B) = 2.17% (w / w), (A) / (B) = 3.14, catechins = 73.9% (w / w)) Each was added to 9 stages (Examples 1 to 8 and Comparative product 2).
Further, a product without addition of 3-deoxyanthocyanidin was designated as comparative product 1.

(Preparation of neutral tea beverage)
The black tea extract obtained above is diluted with ion-exchanged water so that the tannin concentration is 50 mg / 100 mL and the total amount is 500 mL, and sodium bicarbonate is added to this to adjust to pH 6.0. Obtained (Control 1).

And all the obtained tea drinks were 13 mmI. D. The solution was placed in a × 40 mm vial, and the color tone of the solution was defined from the Munsell color chart. Based on the following criteria, it was evaluated whether it had the original red color tone of fermented tea.
Furthermore, all the obtained black tea beverages were heated at 121 ° C. for 10 minutes using a heat block, the color tone changes before and after heating were compared, and the evaluation was performed based on the following criteria.
Moreover, visual evaluation was performed based on the following reference | standard about the solubility of 3-deoxyanthocyanidin.

(Evaluation criteria for color tone)
A: Close to the color tone of the control 1 and exhibiting a preferable red color O: A color tone close to the color tone of the control 1 Δ: Yellowish compared to the color tone of the control 1 ×: Compared to the color tone of the control 1 Yellow is too strong

(Evaluation of color stability after heating)
○: No change in color tone compared to before heating Δ: Vivid color tone decreased compared to before heating ×: Browned compared to before heating

(Evaluation criteria for solubility)
○: Completely dissolved △: Not dissolved completely, causing precipitation

Moreover, the tricetinidine content, the luteolinidine content, and catechin content in each black tea beverage were measured using HPLC. The contents of tricetinidine and luteolinidine were measured by the measuring method described in Example 1 and Example 3, and the catechin content was measured by the measuring method described in Example 4. For the quantification, isolated tricetinidine and luteolinidine standards and catechin standards manufactured by Mitsui Norin Co., Ltd. were used. The results are shown in Table 5.

From Table 5, the additive-free acidic black tea beverage (Comparative Product 1) exhibited a light yellow and orange intermediate color, whereas the acidic black tea beverages (practical products 1-8) added with 3-deoxyanthocyanidins were neutral. A near-orange to red-orange color similar to that of the black tea beverage (Control 1) was exhibited. In particular, the color tone of the products 2 to 8, particularly the products 3 to 6, was close to that of the control 1, and had a red color tone that seemed to be fermented tea. On the other hand, Comparative Product 1 to which the product of the present invention was not added and Comparative Product 2 in which the amount of the product of the present invention was a trace amount were yellowish compared to the color tone of Control 1.

In addition, in the product 8, 3-deoxyanthocyanidin was not completely dissolved, and precipitation occurred. Furthermore, the control 1 and the comparative product 1 to which the product of the present invention was not added turned brown after heating, but the comparative product 2 and the products 1 to 8 to which the product of the present invention was added were almost the same as before heating. There was no color change.
Although not shown in the table, all beverages had the original flavor of fermented tea, but the product 8 had a strong bitter taste due to the excessive amount of catechins contained in the tea beverage. It was.

24-hour heated product of 3-deoxyanthocyanidin prepared in Example 4 (tricetinidine (A) = 1.64% (w / w), luteolinidine (B) = 0.52%) (W / w), (A) + (B) = 2.17% (w / w), (A) / (B) = 3.14, catechins = 73.9% (w / w)) Purified tricetinidine and luteolinidine were added to prepare beverages having different weight ratios of tricetinidine and luteolinidine. The total content of tricetinidine and luteolinidine in the beverage was fixed at 1.3 mg / 100 mL, and adjusted to different ratios by changing the component amount of each composition (Examples 9 to 19 and Comparative products 3 to 4).

Further, as a control, an additive-free neutral black tea beverage was prepared in the same manner as in Example 5 (Control 2). And the color tone of these solutions, the color tone stability after heat processing, and the solubility were evaluated. In addition, the evaluation regarding the color tone of the solution was performed based on the following criteria, and the evaluation criteria described in Example 5 were used for the evaluation of the color tone stability and solubility after the heat treatment. The results are shown in Table 6.

(Evaluation criteria for color tone)
A: Close to the color tone of the control 1 and exhibiting a preferable red color O: A color tone close to the color tone of the control 1 Δ: Yellowish compared to the color tone of the control 1 ×: Compared to the color tone of the control 1 Yellow or red is too strong

From Table 6, the comparative product 3 in which the content ratio of tricetinidine and luteolinidine [tricetinidine / luteolinidine] was 0.25 exhibited a strong yellow color, whereas Examples 9 to 19 exhibited a preferable color tone of orange. The execution products 11-18 had a red color tone like tea. Further, Comparative Product 4 having [Tricetinidine / Luteolinidine] exceeding 80 was not preferable because the red color tone was too strong and the color tone was browned when heated.

3-Deoxyanthocyanidin prepared in Example 4 heated for 24 hours (Tricetinidine (A) = 1.64% (w / w), Luteolinidine (B) = 0.52% (w / w), (A) + (B) = 2.17% (w / w), (A) / (B) = 3.14, catechins = 73.9% (w / w)) and a commercially available anthocyanin-containing composition from purple potato “Powder Sun Red YM” (manufactured by San-Ei Gen FFI Co., Ltd., hereinafter referred to as “Composition A”) and a commercially available 3-deoxyanthocyanidin-containing composition “Powder Sun Brown K” (San-Ei Gen) FFI Co., Ltd. (hereinafter referred to as “Composition B”) was used to compare the solubility of the composition in black tea beverages, the color tone of the solution, and the color tone stability after heating.

First, to the acidic tea beverage prepared in Example 5, the above-mentioned three kinds of compositions were added so that the content of 3-deoxyanthocyanidin or anthocyanin in the solution was 1.3 mg / 100 mL (Example Product 20, Comparison) Products 6 and 9), and a black tea solution in which only the composition A was added 5 times and 10 times as described above (Comparative products 7 and 8). And the solubility of each composition with respect to these black tea beverages was evaluated visually by the same standard as Example 5. In addition, Example 20 and Comparative Products 6 to 9 to which the composition was added and Comparative Product 5 to which no composition was added were heated at 121 ° C. for 10 minutes using a heat block, and the color tone stability after the heat treatment was measured as an example. Evaluation was carried out according to the same criteria as 5. The results are shown in Table 7.

From Table 7, the comparative products 6 to 9 to which the compositions A and B were added were browned in the color of the beverage before heating by the heat treatment, whereas the embodiment product 20 to which the composition of the present invention was added was before and after the heat treatment. The color change was not seen.
The embodiment product 20 to which the composition of the present invention was added was a clear solution in which the composition was completely dissolved, but the comparative product 9 to which the composition B containing 3-deoxyanthocyanidin was added was allowed to stand for a while after mixing. When it was left, a precipitate was formed.

Moreover, the comparative product 6 to which the composition A was added at the same concentration as the composition of the present invention had a light tone mixed with a light pink color, and had a color tone different from the original color tone of fermented tea. Similarly, the comparative product 9 in which the composition B was added at the same concentration as the composition of the present invention had a brown color like caramel, and the original color tone of the fermented tea was lost.
The product 1 of Table 5 (3-deoxyanthocyanidin content = 0.11 mg / 100 mL) and the unheated comparative product 9 of Table 7 (3-deoxyanthocyanidin content = 1.3 mg / 100 mL) have the same color tone. Therefore, it can be said that the effect of improving the color tone of the product was recognized about 12 times that of the commercial product.

Green tea extracts with different EGCg and ECg content weight ratios were prepared and heated at 120 ° C. to obtain 3-deoxyanthocyanidins having different tricetinidine and luteolinidine content weight ratios (Comparative products 10, 11 and Examples 22 to 22). 27).

Further, tricetinidine purified product was added to the obtained 3-deoxyanthocyanidin (Comparative product 10) to prepare 3-deoxyanthocyanidin having a tricetinidine and luteolinidine-containing weight ratio [tricetinidine / luteolinidine] of 0.41 ( Implementation product 21).
The color tone of the powder of the obtained 3-deoxyanthocyanidins (Examples 21 to 27 and Comparative products 10 and 11) and the color tone of the beverage after adding the composition to the acidic black tea beverage at equal weight (5 mg / 10 mL) were visually observed. It was evaluated by.

(Evaluation regarding color of powder)
◎: Clear red ○: Red

(Evaluation regarding the color tone of beverages after addition of acidic black tea beverages)
○: Preferred color tone of orange to red Δ: Yellow or red is strong ×: Yellow or red is too strong

From Table 8, all the compositions exhibited red to clear red. Moreover, while the tea beverages to which the implementation products 21 to 27 were added had a preferable orange to red color tone, the color tone of the tea beverage to which the comparison product 10 was added was not preferable because the yellow color was too strong, and the comparison product 11 was added. The color tone of the tea beverage was not preferable because the red color was too strong.

10 mg of EGCg added with aluminum prepared in Example 2 was weighed and placed in a glass vial to spread the powder flat. The vials were heated in a dry heat dryer at 60 ° C. and 80 ° C. for 24 hours, 100 ° C. for 1, 2, 3 weeks, 120 ° C. for 70 and 110 hours, 150 ° C. for 8, 24, 36 hours. The color tone of the obtained composition was visually evaluated according to the following criteria, and the tricetinidine and luteolinidine contents in the obtained composition were measured using HPLC by the method described in Example 1 and Example 3. Isolated tricetinidine and luteolinidine standards were used for quantification.

In addition, the composition obtained here and 3-deoxyanthocyanidin obtained by heating the green tea extract in Example 4 for 24 hours, 48 hours, and 72 hours as a 3-deoxyanthocyanidin content in black tea beverages Was dissolved in the acidic tea beverage prepared in Example 5 so as to contain 0.08 mg / 100 mL, and the solubility was evaluated according to the same criteria as in Example 5. The results of aluminum-added EGCg with different heating times are shown in Table 9 and FIG. 5, and the results of evaluating the solubility of the composition obtained in Example 4 are shown in Table 10.

(Evaluation regarding color of powder)
◎: Clear red ○: Red △: Black red ×: Black mixed with red

As shown in Table 9, tricetinidine was not detected from the powder obtained by heating the aluminum-added EGCg at 60 ° C. and 80 ° C. for 24 hours. Moreover, although the discoloration could not be confirmed visually by the powder heated at 60 ° C., the powder heated at 80 ° C. was slightly pinkish. Therefore, it is considered that tricetinidine can be detected by heating at 80 ° C. for a long time. The color tone of the powder heated at 100 ° C. and 120 ° C. was red and preferable, but the powder heated at 150 ° C. for 24 hours or more had a reddish color tone, and the powder heated for 36 hours was less soluble and heated. Time was considered undesirable.

Moreover, as shown in FIG. 5, decomposition | disassembly of the tricetinidine produced | generated when it heated at 150 degreeC for 24 hours or more was seen. Although not shown in the table, when the heating temperature exceeded 150 ° C., decomposition of tricetinidine proceeded and the color tone of the powder was blackened.

According to Table 10, beverages dissolved with 3-deoxyanthocyanidins obtained by heating green tea extract for 24 hours and 48 hours were clear, whereas 3-deoxyanthocyanidins obtained by heating for 72 hours were dissolved. Turbidity was observed in the beverage, and precipitation occurred when allowed to stand.

As described above, according to the present invention, 3-deoxyanthocyanidins can be efficiently produced from gallate-type catechins simply and using general equipment without requiring a special apparatus. Further, by adding 3-deoxyanthocyanidin according to the present invention to a fermented tea beverage, a fermented tea beverage having an improved color tone can be provided.

Amount of tricetinidine produced with heating time Amount of tricetinidine produced by EGCg with and without added metal heated for 7 days Luteolinidine production with heating time Amount of tricetinidine and luteolinidine produced with heating time Heating temperature and tricetinidine production

Claims (8)

A method for producing 3-deoxyanthocyanidins, comprising heating a gallate catechin-containing composition in a powder state. The method for producing 3-deoxyanthocyanidin according to claim 1, wherein the gallate-type catechin-containing composition contains a metal salt. The method for producing 3-deoxyanthocyanidins according to claim 1 or 2, wherein the gallate catechin-containing composition is a tea extract. The raw material gallate-type catechin-containing composition has the following components (X) and (Y):
(X) Galate type catechin 45% (w / w) or more (Y) Epigallocatechin gallate and / or gallocatechin gallate, and the content weight ratio of the components (Y) and (X) [(Y) / ( X)] is 0.67 or more,
The method for producing 3-deoxyanthocyanidins according to claims 1 to 3, wherein the produced 3-deoxyanthocyanidins contain 0.1% (w / w) or more of tricetinidine. The raw material gallate catechin-containing composition has the following components (X), (Y) and (Z):
(X) Galate type catechin 45% (w / w) or more (Y) epigallocatechin gallate and / or gallocatechin gallate (Z) epicatechin gallate and / or catechin gallate, (Y) and (Z) The content weight ratio [(Y) / (Z)] is 0.3 to 80,
The 3-deoxyanthocyanidin-containing 3-deoxyanthocyanidin has a weight ratio [(A) / (B)] of (A) tricetinidine and (B) luteolinidine of 0.3 to 80. Production method. The composition for acidic fermented tea addition containing tricetinidine (A) and luteolinidine (B), and the content weight ratio [(A) / (B)] is 0.3 to 80. The following components (A) and (B):
(A) Tricetinidine 0.05 mg / 100 mL or more,
A fermented tea beverage containing (B) luteolinidine and having a content weight ratio [(A) / (B)] of (A) tricetinidine and (B) luteolinidine of 0.3 to 80. The fermented tea beverage according to claim 7, which has a pH of 4.5 or less.