JP5162698B2 - Method for producing polyphenol composition - Google Patents

Description

  The present invention relates to a method for producing a polyphenol composition having excellent solubility in water.

Recently, various materials having physiological functions have been proposed, and many health foods containing these have been put on the market. Among them, polyphenols are known to have an antioxidant power and are expected to have effects such as anti-arteriosclerosis, anti-allergy and blood flow enhancement, and thus are recognized as important ingredients in health foods.
However, many polyphenols have poor water solubility, and it is difficult to use them for aqueous foods such as soft drinks.

  Therefore, a technique for solubilizing poorly water-soluble polyphenols in water has been studied. For example, a method in which hesperidin glycoside is added to citrus fruit juice and juice drink and then heated to dissolve the contained flavonoid compound (Patent Document 1). ); A method in which a poorly water-soluble flavonoid and β-cyclodextrin are heat-treated to include a poorly water-soluble flavonoid in β-cyclodextrin, and then α-glucosyl hesperidin is allowed to coexist (Patent Document 2); There has been proposed a method (Patent Document 3) in which a slightly soluble flavonoid and soybean saponin and / or malonyl isoflavone glycoside are coexisted and heat-treated to solubilize the flavonoid. In these methods, the heat treatment of the poorly water-soluble polyphenol is performed at around 70 ° C to 90 ° C.

JP 2000-236856 A JP 2008-271839 A International Publication No. 2005/003112 Pamphlet

Since hesperidin glycosides such as α-glucosyl hesperidin are complicated in production process and high in cost, it is economically undesirable to use this as a solubilizer. In addition, use of solubilizers such as malonyl isoflavone glycosides can increase the solubility of poorly water-soluble polyphenols, but the use of solubilizers is limited due to the unique grain odor derived from soybeans. The problem of being done is considered.
Therefore, the subject of this invention is providing the method of manufacturing the polyphenol composition excellent in the solubility to water using the cheap raw material with little influence on the flavor of a composition.

  The inventors of the present invention have made various studies on the solubilization techniques of poorly water-soluble polyphenols. By the heat treatment as described above, the dissolution concentration of the hardly water-soluble polyphenols is dramatically increased. In addition, the composition subjected to such a treatment suppresses the precipitation of the hardly water-soluble polyphenols even at room temperature. We found that sex is maintained. Furthermore, it discovered that the influence on the flavor of the composition by the methylated product of catechins, chlorogenic acids or poorly water-soluble polyphenols was small.

  That is, in the present invention, in the presence of an aqueous medium, one or more selected from (A) a poorly water-soluble polyphenol and (B) a catechin, a chlorogenic acid, and a methylated product of a poorly water-soluble polyphenol are 100 to 100. The manufacturing method of the polyphenol composition including the process heat-processed at 180 degreeC is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the polyphenol composition excellent in the solubility to water can be provided at low cost. The polyphenol composition of the present invention is useful for various foods and beverages and pharmaceuticals because it has little influence on the flavor of the solubilizer.

  In the method for producing a polyphenol composition of the present invention, in the presence of an aqueous medium, (A) one selected from (A) poorly water-soluble polyphenols and (B) catechins, chlorogenic acids and methylated products of poorly water-soluble polyphenols or The process of heat-processing 2 or more types at 100-180 degreeC is included. Hereinafter, “one kind or two or more kinds selected from methylated products of catechins, chlorogenic acids and poorly water-soluble polyphenols” is also simply referred to as component (B).

  In the present specification, “poorly water-soluble polyphenols” refers to those having a log P value of −1.0 to 4.0. The slightly water-soluble polyphenols preferably have a log P value of -0.5 to 3.5. The log P value is a value obtained by taking the common logarithm of the distribution coefficient between 1-octanol / water and is an index indicating the hydrophobicity of an organic compound. The larger the value, the higher the hydrophobicity. The log P value of polyphenols can be measured by a flask shaking method described in Japanese Industrial Standard Z7260-107. Details are described in the examples.

(A) As the poorly water-soluble polyphenols, phenolic substances in which one or more, and more than two, hydroxyl groups are bonded to the benzene ring can be preferably applied. For example, plant-derived flavonoids, tannins, phenolic acids and the like can be mentioned. Examples of the poorly water-soluble polyphenols that can be more preferably applied include flavonols, flavanones, flavones, isoflavones, and phenolcarboxylic acids.
Specifically, rutin, quercitrin, isoquercitrin, quercetin, myricitrin, daidzein, daidzin, glycitein, glycitin, genistein, genistin, myricetin, hesperidin, neohesperidin, hesperetin, naringin, curcumin, ringenin, prnin, astragaline, Kaempferol, Resveratrol, Apine, Apigenin, Delphinidin, Delphin, Nasnin, Peonidin, Peonin, Petunin, Peonidin, Malvidin, Malvin, Enine, Cyanidine, Leucocyanidin, Cyanine, Chrysanthemin, Kerocyanine, Ideine, Mecocyanine, Pelargonidin, Pelargonidin Caffeic acid, ferulic acid, p-coumaric acid and the like can be mentioned. Of these, rutin, quercetin, hesperidin, naringin, curcumin, resveratrol, caffeic acid, and ferulic acid are preferable. The poorly water-soluble polyphenols may be one kind or a mixture of two or more kinds.

  The catechins used in the present invention include non-epimeric catechins such as catechin, gallocatechin, catechin gallate and gallocatechin gallate and epicatechins such as epicatechin, epigallocatechin, epicatechin gallate and epigallocatechin gallate. It is a collective term. The content of catechins is defined based on the total amount of the above eight types.

As catechins, tea extracts may be used. As the tea extract, at least one selected from a tea extract, a concentrate thereof, and a purified product thereof can be used.
Here, the “tea extract” refers to an extract extracted from tea leaves using hot water or a water-soluble organic solvent, and has not been concentrated or purified. As the water-soluble organic solvent, for example, a lower alcohol such as ethanol can be used. As the extraction method, known methods such as kneader extraction, stirring extraction (batch extraction), countercurrent extraction (drip extraction), and column extraction can be employed.
The tea leaves used for extraction can be roughly classified into non-fermented tea, semi-fermented tea, and fermented tea depending on the processing method. Examples of non-fermented tea include green tea such as sencha, bancha, gyokuro, mochi tea, kettle tea, stem tea, stick tea, and bud tea. Examples of the semi-fermented tea include oolong tea such as iron kannon, color type, golden katsura, and martial arts tea. Furthermore, examples of fermented tea include black teas such as Darjeeling, Assam, Sri Lanka and the like. These can be used alone or in combination of two or more. Among these, green tea is preferable from the viewpoint of the content of catechins.

The “tea extract concentrate” refers to removing a part of the water content of a solution extracted from hot leaves or a water-soluble organic solvent from tea leaves selected from non-fermented tea, semi-fermented tea and fermented tea. The concentration of catechins is increased, for example, by the method described in JP-A-59-219384, JP-A-4-20589, JP-A-5-260907, JP-A-5-306279, etc. Can be prepared. Examples of the form include various forms such as a solid, an aqueous solution, and a slurry. Commercially available products may be used as the concentrate of the tea extract, for example, green tea extraction such as “Polyphenone” from Mitsui Norin Co., “Theafranc” from ITO EN, “Sunphenon” from Taiyo Kagaku Co., Ltd. There is a liquid concentrate.
Purification of the tea extract or the like can be performed by purification using a solvent or a column.

The chlorogenic acids used in the present invention include 3-caffeoylquinic acid, 4-caffeoylquinic acid and monocaffeoylquinic acid of 5-caffeoylquinic acid, 3-feruloylquinic acid, and 4-feruloylquinic acid. And 5-feruloylquinic acid monoferuloylquinic acid and 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid dicaffeoylquinic acid Is a collective term. The content of chlorogenic acids is defined based on the total amount of the above nine types.
Also, chlorogenic acids may be in the form of a salt, such as a salt with an alkali metal such as sodium or potassium, a salt with an alkaline earth metal such as magnesium or calcium, monoethanolamine, diethanolamine, triethanolamine, etc. And salts with organic amines, salts with basic amino acids such as arginine, lysine, histidine, ornithine, and the like.

As the chlorogenic acids, a plant extract containing the same, a concentrate thereof, a purified product thereof, or the like can be used. Such plant extracts include, for example, sunflower seeds, apple immature fruits, fresh coffee beans, Simon leaves, pine cones, pine plant seed shells, sugarcane southern leaves, burdock, eggplant skin, Examples include those extracted from ume fruit, dandelion, and vines. Among these, raw coffee bean extract is preferable from the viewpoint of chlorogenic acid content and the like. The type of coffee tree may be any of Arabica, Robusta, Revelica and Arabsta. In addition, the method and conditions for extraction, concentration and purification are not particularly limited, and known methods and conditions can be employed.
Commercially available chlorogenic acid-containing preparations may be used as chlorogenic acids, and examples include flavor holder RC (Hasegawa Fragrance Co., Ltd.).

  The methylated product of the poorly water-soluble polyphenols used in the present invention is a methylated product of the aforementioned poorly water-soluble polyphenols solubilized in water. The position and number of methylation are not particularly limited. Specific examples include methyl hesperidin, methyl quercetin, methyl resveratrol, methyl rutin and the like, and methyl hesperidin is preferred. Methyl hesperidin is known to mainly contain chalcone type compounds (1) and flavanone type compounds (2), and examples of the constituents include those having the structures shown below.

(In the formula, R represents a hydrogen atom or a methyl group.)

  Here, methyl hesperidin as a pharmaceutical additive and a food additive is mainly handled as a mixture of the compounds (3) and (4).

(In the formula, Gl represents a glucose residue, Rh represents a rhamnose residue, and Gl-2 represents the 2-position of the glucose residue (including 3-position in the case of (3-1)), Rh- 2 represents position 2 of the rhamnose residue.)

  Hesperidin methyl chalcone as a cosmetic raw material is handled as a compound represented by (5). In the case of a composition containing a large amount of chalcone type compound, it is also called hesperidin methyl chalcone.

(In the formula, R represents a hydrogen atom or a methyl group.)

The methyl hesperidin used in the present invention may contain both the chalcone type compound (1) and the flavanone type compound (2) shown above, or may contain only one of them.
In the present invention, more preferred methyl hesperidin includes a mixture of compound (3) and compound (4).

  Methyl hesperidin is a known method, for example, hesperidin is dissolved in an aqueous sodium hydroxide solution, a corresponding amount of dimethyl sulfate is allowed to act on the alkaline solution, the reaction solution is neutralized with sulfuric acid, and extracted with n-butyl alcohol. It can be produced by distilling off and then recrystallizing with isopropyl alcohol (Saki Bath, Nippon Kagaku Kagaku, 79, 733-6 (1958)), but the production method is not limited to this.

Commercially available methyl hesperidin-containing preparations may be used as methyl hesperidin, for example, “Methyl Hesperidin” (Tokyo Chemical Industry Co., Ltd.), “Hesperidin Methyl Chalcone” (Sigma), “Methyl Hesperidin” (Hamari Pharmaceutical Co., Ltd.) Co., Ltd.).
In the present invention, catechins, chlorogenic acids or methyl hesperidin can be used alone or in combination of two or more as component (B).

  The aqueous medium used in the present invention refers to water and an aqueous solution of an organic solvent. Examples of water include tap water, distilled water, ion exchange water, and purified water. The organic solvent is not particularly limited as long as it is uniformly mixed with water. As the organic solvent, alcohol having 4 or less carbon atoms is preferable, methanol and ethanol are more preferable, and ethanol is more preferable from the viewpoint of being applicable to foods. The concentration of the organic solvent in the aqueous solution is preferably 0.1 to 80% by mass (hereinafter simply referred to as “%”), more preferably 1 to 70%, and still more preferably 5 to 60%.

  (A) Since poorly water-soluble polyphenols have low solubility in water, it is preferable to disperse them in an aqueous medium and present them in a slurry state. The content of the (A) poorly water-soluble polyphenols in the aqueous medium varies depending on the kind of the poorly water-soluble polyphenols. 50 g / L is more preferable, 0.7 to 20 g / L is more preferable, and 0.72 to 10 g / L is still more preferable.

  On the other hand, the component (B) of the present invention is preferably used after being dissolved in an aqueous medium. The content of the component (B) in the aqueous medium is preferably 0.1 to 200 g / L, more preferably 0.5 to 100 g / L, still more preferably 1 to 50 g / L, from the viewpoint of fluidity. More preferably, it is 28 to 4.31 g / L.

  In the aqueous medium, the mass ratio ((A) / (B)) of the (A) poorly water-soluble polyphenols to the component (B) is from the viewpoint of the solubility of the polyphenol composition obtained after the heat treatment and cooling. 005 to 10 is preferable, 0.01 to 10 is more preferable, 0.02 to 3 is still more preferable, and 0.168 to 2.33 is still more preferable.

The method for heat-treating (A) the poorly water-soluble polyphenols and component (B) in the presence of an aqueous medium is not particularly limited, and known methods can be applied.
The temperature of the heat treatment is 100 to 180 ° C. from the viewpoint of improvement in solubility of the poorly water-soluble polyphenols and thermal stability, more preferably 110 to 170 ° C., further preferably 120 to 160 ° C., and 120 to 150. C is more preferred. Examples of the heating means include water vapor and electricity.

  The pressure during the heat treatment is preferably 0 to 10 MPa, more preferably 0.1 to 8 MPa, further preferably 0.1 to 6 MPa, further preferably 0.2 to 6 MPa, and further preferably 0.2 to 4 MPa in terms of gauge pressure. Preferably, 0.25 to 2 MPa is more preferable, 0.3 to 1.5 MPa is further preferable, and 0.3 to 0.6 MPa is further preferable. Moreover, it is preferable to set it more than the saturated vapor pressure of water. Gas may be used for pressurization, and examples of the gas used include inert gas, water vapor, nitrogen gas, helium gas, and the like. The pressurization may be adjusted by a back pressure valve without using gas.

  The heat treatment can be performed by any method such as a batch method, a semi-batch method, and a flow reaction method. Among these, the flow-type reaction method is preferable in that the reaction time can be easily controlled.

The heat treatment time is preferably from 0.1 to 30 minutes after the aqueous medium reaches the set temperature from the viewpoint of improving the solubility of the poorly water-soluble polyphenols and heat stability, and further 0.2 to 15 minutes, 0.5-8 minutes are preferred.
In the case of the flow reaction method, the heat treatment time is an average residence time calculated by dividing the volume of the high-temperature and high-pressure part of the reactor by the supply rate of the aqueous medium.

  The flow rate of the aqueous medium in the case of the flow reaction method varies depending on the volume of the reactor. For example, when the reactor volume is 100 mL, 3.3 to 200 mL / min is preferable, and further 6.7 to 150 mL / min. Is preferred.

  After the heat treatment, it is preferable to perform a step of cooling the reaction solution obtained by the heat treatment to 90 ° C. or lower, preferably 50 ° C. or lower, more preferably 30 ° C. or lower. When obtaining a liquid polyphenol composition, 0 degreeC or more is preferable and 10 degreeC or more is preferable. During cooling, the reaction solution may be mixed and stirred for 0.5 to 5 days, preferably 1 to 3 days. When obtaining a solid polyphenol composition, the reaction solution may be subjected to freeze-drying.

  Furthermore, it is preferable to perform the process of removing a solid part from a reaction liquid from the point which improves the solubility of the polyphenol composition obtained. The method for removing the solid part is not particularly limited, and can be performed, for example, by centrifugation, decantation, or filtration.

Although the polyphenol composition thus obtained has a high content of poorly water-soluble polyphenols, precipitation of the hardly water-soluble polyphenols is suppressed even at room temperature, and the solubility in water is excellent. Moreover, the influence of the catechins, chlorogenic acids, or methylated products of poorly water-soluble polyphenols on the flavor of the composition is small. Therefore, the polyphenol composition of the present invention can be used for various foods and beverages, pharmaceuticals and the like. For example, as food and drink, confectionery such as beverages, breads, noodles, cookies, snacks, jelly, dairy products, frozen foods, instant foods such as powdered coffee, starch processed products, processed meat products, and other processed foods , Liquid, solid or semi-solid foods and beverages such as seasonings and dietary supplements. Examples of pharmaceuticals include dosage forms such as tablets (such as chewable tablets), capsules, and powders. In particular, it is useful to be used for a packaged beverage. Examples of the packaged beverage include tea-based beverages such as green tea, and non-tea beverages such as sports beverages, isotonic beverages, and near water.
The reason why the solubility of the poorly water-soluble polyphenols can be improved by heat-treating the (A) poorly water-soluble polyphenols and the component (B) at 100 ° C. or higher is not clear, So guessed. Methylated products of poorly water-soluble polyphenols, catechins, chlorogenic acids, and poorly water-soluble polyphenols have different solubility, but each molecule self-associates, and the hydrophobic part is laminated to the hydrophilic part. It is thought that it is dissolved in water due to its structure. Here, when both components coexist in an aqueous medium and heat of 100 ° C. or higher is applied, the laminated structure is broken and broken, and there is an interaction between the poorly water-soluble polyphenols and the component (B). And a new layered structure in which the poorly water-soluble polyphenols and the component (B) are mixed is created, and the solubility of the poorly water-soluble polyphenols is greatly improved by maintaining this layered structure even after cooling. It is done.

  The content of the (A) poorly water-soluble polyphenols in the polyphenol composition varies depending on the kind of the poorly water-soluble polyphenols, but is preferably 0.1 to 70%, more preferably 0.2 to 50%.

The form of the polyphenol composition of the present invention may be in the form of an aqueous solution, or may be a paste obtained by adjusting the amount of water. In addition, it is possible to remove the water to form a solid state such as a powder, granule, or solid. Examples of means for adjusting and removing moisture include freeze drying, evaporation to dryness, and spray drying.
In particular, the reaction solution obtained by the heat treatment is subjected to freeze drying or spray drying so that the polyphenol composition is in a solid state having no crystallinity. This is further preferred because (A) the initial solubility of the poorly water-soluble polyphenols is improved. The reaction solution obtained by the heat treatment is subjected to a process of cooling the reaction solution to 90 ° C. or less, preferably 50 ° C. or less, more preferably 30 ° C. or less before freeze-drying or spray drying. It is preferable from the point of prevention.

The method of freeze drying or spray drying is not particularly limited, and a known method can be applied.
For example, in the case of spray drying, the treatment liquid can be sprayed from a nozzle and dried by dropping in hot air at 100 to 220 ° C., preferably 130 to 190 ° C.
In the case of lyophilization, the treatment liquid can be frozen in liquid nitrogen, a cool bath, a freezer, etc., crushed, sieved, and then dried by sublimating moisture in a vacuum. The freezing temperature of the treatment liquid is preferably -70 to 0 ° C. The absolute pressure during drying is preferably 0.1 to 1000 Pa, more preferably 0.5 to 100 Pa, and still more preferably 1 to 10 Pa.
After spray drying or freeze drying, classification, granulation, pulverization, and the like may be performed as necessary.
The time from the heat treatment to the start of freeze-drying or spray-drying, that is, the time from when the reaction solution obtained by heat-treatment falls below 100 ° C. to the start of freeze-drying or spray-drying is the polyphenol yield. From this point, 0.1 to 600 minutes is preferable, and 0.1 to 200 minutes is more preferable.

[Measurement of poorly water-soluble polyphenols and methyl hesperidin]
For the measurement of poorly water-soluble polyphenols and methyl hesperidin, a high-performance liquid chromatograph manufactured by Hitachi, Ltd., equipped with a column Cadenza CD-C18 (4.6 mmφ × 150 mm, 3 μm) manufactured by Intact Inc., and a gradient method at a column temperature of 40 ° C. It went by. The mobile phase A solution was 0.05 mol / L acetic acid aqueous solution, the B solution was acetonitrile, and the solution was fed at 1.0 mL / min. The gradient conditions are as follows.
Time (min) A liquid (%) B liquid (%)
0 85 15
20 80 20
35 10 90
50 10 90
40.1 85 15
60 85 15
The sample injection amount was 10 μL, the detection was determined by absorbance at a wavelength of 360 nm for rutin and methyl hesperidin, the wavelength at 320 nm for ferulic acid and caffeic acid, the wavelength at 425 nm for curcumin, and the other water-soluble polyphenols at a wavelength of 283 nm.

[Measurement of log P value of poorly water-soluble polyphenols]
It was measured according to the flask shaking method described in Japanese Industrial Standard Z7260-107. First, 1-octanol and distilled water were equilibrated by shaking at 25 ° C. for 24 hours. Next, 10 mg of polyphenol was weighed into a glass bottle with a lid, 4 mL each of 1-octanol and distilled water that had been equilibrated were added, and the mixture was shaken at 25 ° C. for 4 days. The 1-octanol phase and the aqueous phase were separated by centrifugation, and the concentration of polyphenols in each phase was measured by HPLC in the same manner as in the above [Measurement of poorly water-soluble polyphenol]. The value obtained by taking the common logarithm of the distribution coefficient between the two phases was defined as the logP value.

[Measurement of catechins]
A sample is appropriately diluted with distilled water, and a high-performance liquid chromatograph (model) manufactured by Shimadzu Corporation, equipped with a packed column for liquid chromatography L-column TM ODS (4.6 mmφ × 250 mm: manufactured by Chemical Substance Evaluation Research Organization) SCL-10AVP) and a gradient method at a column temperature of 35 ° C. The mobile phase A solution was a distilled aqueous solution containing 0.1 mol / L of acetic acid, the B solution was an acetonitrile solution containing 0.1 mol / L of acetic acid, the sample injection amount was 20 μL, and the UV detector wavelength was 280 nm. .

(Concentration gradient condition)
Time (min) A liquid (% (v / v)) B liquid (% (v / v))
0 97 3
5 97 3
37 80 20
43 80 20
43.5 0 100
48.5 0 100
49 97 3
62 97 3

[Measurement of chlorogenic acids]
(Analytical equipment)
HPLC (manufactured by Hitachi, Ltd.) was used. The model numbers of the unit units are as follows.
Liquid feeding unit (built-in degasser): L-2130,
Autosampler (with cooler): L-2200,
Column oven: L-2300
Separation column: Cadenza CD-C18, Size: 4.6 mm i. d. × 150 mm, 3 μm (Intact Corporation)
Detector (ultraviolet visible absorption photometer): L-2420:

(Analysis conditions)
Sample injection volume: 10 μL,
Flow rate: 1.0 mL / min,
UV absorption photometer detection wavelength: 325 nm (chlorogenic acids),
Eluent A: 5% acetonitrile containing 0.05 mol / L acetic acid, 0.01 mol / L sodium acetate, and 0.1 mmol / L HEDPO,
Eluent B: Acetonitrile

(Concentration gradient condition)
Time (min) A liquid (% (v / v)) B liquid (% (v / v))
0 100 0
10 100 0
15 95 5
20 95 5
22 92 8
50 92 8
52 10 90
60 10 90
60.1 100 0
70 100 0

Example 1
Hesperidin preparation (Hesperidin “Hamari” (trade name), manufactured by Hamari Pharmaceutical Co., Ltd., hesperidin content 90%, the same applies hereinafter) and epigallocatechin gallate (EGCG) preparation (TEAVIGO, EGCG content manufactured by DMS Nutritional Products) 100%, the same applies hereinafter) was dispersed in distilled water at 10 g / L, dissolved at 4.29 g / L, and uniformly stirred in the slurry supply tank. The liquid in the slurry supply tank was supplied at 100 mL / min to a stainless-steel flow reactor (made by Nitto Koatsu Co., Ltd.) having an internal volume of 100 mL, and the reaction was carried out at 120 ° C. (average residence time 1 minute). The pressure was adjusted to 0.3 MPa (gauge pressure) with an outlet valve. The reaction liquid was extracted from the reactor outlet, cooled to room temperature (25 ° C.) and recovered. The collected liquid was stirred and shaken at room temperature for 3 days, and then the solid part was filtered off to obtain a hesperidin composition as a hesperidin-containing aqueous solution. Table 1 shows the reaction conditions and the results of measuring the concentrations of hesperidin and EGCG in the composition.

Example 2
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 1 except that the reaction temperature was 110 ° C. Table 1 shows the reaction conditions and the results of measuring the concentrations of hesperidin and EGCG in the composition.

Comparative Examples 1 and 2
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 1 except that the reaction temperature was 90 ° C. or 70 ° C. and the gauge pressure was 0 MPa. Table 1 shows the reaction conditions and the results of measuring the concentrations of hesperidin and EGCG in the composition.

Example 3
Hesperidin was used as a hesperidin-containing aqueous solution in the same manner as in Example 1 except that a purified coffee bean extract (chlorogenic acid content 40%, the same applies hereinafter) was used at 10.7 g / L instead of the EGCG preparation. A composition was obtained. Table 1 shows the reaction conditions and the results of measuring the concentrations of hesperidin and chlorogenic acids in the composition.

Comparative Example 3
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 3 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 1 shows the reaction conditions and the results of measuring the concentrations of hesperidin and chlorogenic acids in the composition.

Example 4
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 1 except that a methyl hesperidin preparation (manufactured by Hamari Pharmaceutical Co., Ltd., methyl hesperidin content 100%, the same applies hereinafter) was used instead of the EGCG preparation. It was. Table 1 shows the reaction conditions and the results of measuring the concentration of hesperidin and methyl hesperidin in the composition.

Example 5
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 4 except that the reaction temperature was 150 ° C. and the gauge pressure was 0.6 MPa. Table 1 shows the reaction conditions and the results of measuring the concentration of hesperidin and methyl hesperidin in the composition.

Comparative Examples 4 and 5
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 4 except that the reaction temperature was 90 ° C. or 25 ° C. and the gauge pressure was 0 MPa. Table 1 shows the reaction conditions and the results of measuring the concentration of hesperidin and methyl hesperidin in the composition.

Comparative Example 6
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 1 except that the EGCG preparation was not added, the reaction temperature was 25 ° C., and the gauge pressure was 0 MPa. The reaction conditions and the results of measuring the hesperidin concentration in the composition are shown in Table 1.

Example 6
A quercetin composition as a quercetin-containing aqueous solution in the same manner as in Example 1 except that a quercetin preparation (manufactured by ACROS ORGANICS, quercetin content 95%) was used as the poorly water-soluble polyphenol, and the reaction temperature was 150 ° C. and the gauge pressure was 0.6 MPa. I got a thing. Table 2 shows the reaction conditions and the results of measuring the concentrations of quercetin and EGCG in the composition.

Comparative Example 7
A quercetin composition was obtained as a quercetin-containing aqueous solution in the same manner as in Example 6 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 2 shows the reaction conditions and the results of measuring the concentrations of quercetin and EGCG in the composition.

Comparative Example 8
A quercetin composition was obtained as a quercetin-containing aqueous solution in the same manner as in Example 6 except that the EGCG preparation was not added, the reaction temperature was 25 ° C., and the gauge pressure was 0 MPa. Table 2 shows the reaction conditions and the results of measuring the quercetin concentration in the composition.

Example 7
Resveratrol as a resveratrol-containing aqueous solution in the same manner as in Example 1 except that 0.72 g / L of resveratrol preparation (manufactured by Wako Pure Chemical Industries, Ltd., for biochemistry) was used as a poorly water-soluble polyphenol. A composition was obtained. Table 3 shows the reaction conditions and the results of measuring the resveratrol and EGCG concentrations in the composition.

Comparative Example 9
A resveratrol composition was obtained as a resveratrol-containing aqueous solution in the same manner as in Example 7 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 3 shows the reaction conditions and the results of measuring the resveratrol and EGCG concentrations in the composition.

Comparative Example 10
A resveratrol composition was obtained as a resveratrol-containing aqueous solution in the same manner as in Example 7 except that the EGCG preparation was not added, the reaction temperature was 25 ° C., and the gauge pressure was 0 MPa. Table 3 shows the reaction conditions and the results of measuring the resveratrol concentration in the composition.

Example 8
A naringin-containing aqueous solution in the same manner as in Example 1 except that a naringin preparation (manufactured by ACROS ORGANICS, naringin content 97%, the same applies hereinafter) was used as the hardly water-soluble polyphenol, and the reaction temperature was 150 ° C. and the gauge pressure was 0.6 MPa. As obtained Naringin composition. Table 4 shows the reaction conditions and the results of measuring the concentrations of naringin and EGCG in the composition.

Example 9
A naringin composition was obtained as a naringin-containing aqueous solution in the same manner as in Example 8, except that the reaction temperature was 110 ° C. and the gauge pressure was 0.3 MPa. Table 4 shows the reaction conditions and the results of measuring the concentrations of naringin and EGCG in the composition.

Comparative Examples 11 and 12
A naringin composition was obtained as a naringin-containing aqueous solution in the same manner as in Example 8 except that the reaction temperature was 90 ° C or 70 ° C and the gauge pressure was 0 MPa. Table 4 shows the reaction conditions and the results of measuring the concentrations of naringin and EGCG in the composition.

Example 10
A naringin composition was obtained as a naringin-containing aqueous solution in the same manner as in Example 1 except that the naringin preparation and the methyl hesperidin preparation were each dispersed in distilled water at 5 g / L and dissolved at 4.29 g / L. Table 4 shows the reaction conditions and the results of measuring the concentrations of naringin and methyl hesperidin in the composition.

Comparative Example 13
A naringin composition was obtained as a naringin-containing aqueous solution in the same manner as in Example 10 except that the reaction temperature was 25 ° C. and the gauge pressure was 0 MPa. Table 4 shows the reaction conditions and the results of measuring the concentrations of naringin and methyl hesperidin in the composition.

Comparative Example 14
A naringin composition was obtained as a naringin-containing aqueous solution in the same manner as in Example 8, except that the EGCG preparation was not added, the reaction temperature was 25 ° C., and the gauge pressure was 0 MPa. Table 4 shows the reaction conditions and the results of measuring the naringin concentration in the composition.

Example 11
Contains curcumin in the same manner as in Example 1, except that 10 g / L of curcumin preparation (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) is used as the poorly water-soluble polyphenol, the reaction temperature is 150 ° C., and the gauge pressure is 0.6 MPa. A curcumin composition was obtained as an aqueous solution. Table 5 shows the reaction conditions and the results of measurement of curcumin and EGCG concentrations in the composition.

Comparative Example 15
A curcumin composition was obtained as a curcumin-containing aqueous solution in the same manner as in Example 11 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 5 shows the reaction conditions and the results of measurement of curcumin and EGCG concentrations in the composition.

Comparative Example 16
A curcumin composition was obtained as a curcumin-containing aqueous solution in the same manner as in Example 11 except that the EGCG preparation was not added, the reaction temperature was 25 ° C., and the gauge pressure was 0 MPa. Table 5 shows the reaction conditions and the measurement results of the curcumin concentration in the composition.

Example 12
2 g / L of a rutin preparation (produced by Tokiwa Phytochemical Laboratories Co., Ltd., rutin content: 100%, hereinafter the same) as a poorly water-soluble polyphenol, and a purified green tea extract (catechin content 15) as catechins A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 1 except that 28.6 g / L of an aqueous solution containing 25% gallate body was used at 28.6 g / L. The reaction conditions and the results of measuring the concentrations of rutin and catechins in the composition are shown in Table 6.

Comparative Example 17
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 12 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. The reaction conditions and the results of measuring the concentrations of rutin and catechins in the composition are shown in Table 6.

Example 13
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 12 except that a purified coffee bean extract (chlorogenic acid content 40%) was used at 10.7 / L as chlorogenic acids. Table 6 shows the reaction conditions and the results of measuring the concentrations of rutin and chlorogenic acids in the composition.

Comparative Example 18
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 13 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 6 shows the reaction conditions and the results of measuring the concentrations of rutin and chlorogenic acids in the composition.

Example 14
Purified product of green tea extract as catechins (aqueous solution containing catechin content 15%, gallate body rate 30%) 14.3 g / L, and purified product of coffee bean extract as chlorogenic acids (chlorogenic acids content 40% ) A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 12 except that 5.4 g / L was used. Table 6 shows the reaction conditions and the results of measuring the concentrations of rutin, catechins and chlorogenic acids in the composition.

Comparative Example 19
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 14 except that the reaction temperature was 70 ° C. and the gauge pressure was 0 MPa. Table 6 shows the reaction conditions and the results of measuring the concentrations of rutin, catechins and chlorogenic acids in the composition.

Example 15
A hesperidin composition was obtained as a hesperidin-containing aqueous solution in the same manner as in Example 12 except that the methyl hesperidin preparation was used at 4.29 g / L instead of the purified green tea extract. Table 6 shows the reaction conditions and the results of measuring the concentration of hesperidin and methyl hesperidin in the composition.

Comparative Example 20
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 15 except that the reaction temperature was 25 ° C. and the gauge pressure was 0 MPa. Table 6 shows the reaction conditions and the results of measuring the concentrations of rutin, catechins and methyl hesperidin in the composition.

Comparative Example 21
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 12 except that catechins were not added. The results of measuring the reaction conditions and the rutin concentration in the composition are shown in Table 6.

Comparative Example 22
A rutin composition was obtained as a rutin-containing aqueous solution in the same manner as in Example 12 except that the catechins were not added and the reaction temperature was 25 ° C. and the gauge pressure was 0 MPa. The results of measuring the reaction conditions and the rutin concentration in the composition are shown in Table 6.

Example 16
Purification of coffee bean extract as chlorogenic acids instead of EGCG preparation using ferulic acid preparation (manufactured by Tokyo Chemical Industry Co., Ltd., ferulic acid content 100%, the same applies hereinafter) at 6 g / L as poorly water-soluble polyphenols A ferulic acid composition was obtained as a ferulic acid-containing aqueous solution in the same manner as in Example 1 except that the product was used at 10.7 g / L. Table 7 shows the reaction conditions and the measurement results of ferulic acid and chlorogenic acid concentrations in the composition.

Comparative Examples 23 and 24
A ferulic acid composition was obtained as a ferulic acid-containing aqueous solution in the same manner as in Example 16 except that the reaction temperature was 70 ° C or 25 ° C and the gauge pressure was 0 MPa. Table 7 shows the reaction conditions and the measurement results of ferulic acid and chlorogenic acid concentrations in the composition.

Example 17
10 g / L of a caffeic acid preparation (manufactured by Tokyo Chemical Industry Co., Ltd., 100% caffeic acid content) is used as a poorly water-soluble polyphenol, and instead of the EGCG preparation, a purified product of coffee bean extract is used as a chlorogenic acid. A caffeic acid composition was obtained as a caffeic acid-containing aqueous solution in the same manner as in Example 1 except that it was used at 7 g / L. Table 8 shows the reaction conditions and the results of measurement of caffeic acid and chlorogenic acid concentrations in the composition.

Comparative Examples 25 and 26
A caffeic acid composition was obtained as a caffeic acid-containing aqueous solution in the same manner as in Example 17 except that the reaction temperature was 80 ° C. or 25 ° C. and the gauge pressure was 0 MPa. Table 8 shows the reaction conditions and the results of measurement of caffeic acid and chlorogenic acid concentrations in the composition.

As is clear from Table 1-8, a polyphenol composition having a high content of poorly water-soluble polyphenols could be obtained, and the solubility of the poorly water-soluble polyphenols could be remarkably increased.
In addition, none of the compositions has an off-flavor such as grain odor, and those using catechins and chlorogenic acids have moderate bitterness due to them, and have a flavor suitable for various foods and beverages and pharmaceuticals, especially functional beverages. there were.

Example 18
The ferulic acid preparation and the EGCG preparation were each dispersed in distilled water at 6 g / L, dissolved at 4 g / L, and uniformly stirred in the slurry supply tank. The liquid in the slurry supply tank was supplied at 100 mL / min to a stainless-steel flow reactor (made by Nitto Koatsu Co., Ltd.) having an internal volume of 100 mL, and the reaction was carried out at 120 ° C. (average residence time 1 minute). The pressure was adjusted to 0.3 MPa (gauge pressure) with an outlet valve. The reaction liquid was extracted from the reactor outlet, cooled to room temperature (25 ° C.) and recovered. The ferulic acid and EGCG in the reaction solution recovered at this time were all in a dissolved state.
The recovered reaction solution was pre-frozen in a −50 ° C. cool bath, and then dried under reduced pressure by a freeze dryer (ALPHA1-4LSC manufactured by CHRIST) 5 minutes after the end of the heat treatment. The absolute pressure at this time was 1 Pa. After 72 hours, a powdered ferulic acid composition was obtained. Reaction conditions and drying conditions are shown in Table 9.

Comparative Example 27
The ferulic acid formulation 6 g / L used in Example 18 and the EGCG formulation 4 g / L were physically mixed at room temperature (25 ° C.) for 2 minutes using a cartridge to obtain a ferulic acid composition.

Example 19
The reaction solution was recovered in the same manner as in Example 18 except that the ferulic acid preparation was used in place of 4.29 g / L and the EGCG preparation was used and a purified coffee bean extract was used at 10.7 g / L as chlorogenic acids. The ferulic acid and chlorogenic acid in the recovered reaction solution were all dissolved.
Subsequently, freeze-drying was performed in the same manner as in Example 18 to obtain a powdered ferulic acid composition. Reaction conditions and drying conditions are shown in Table 9.

Comparative Example 28
Ferulic acid composition obtained by physically mixing 4.29 g / L of ferulic acid preparation used in Example 18 and 10.7 g / L of a purified coffee bean extract at room temperature (25 ° C.) for 2 minutes using a shell. It was a thing.

The solubility and flavor of the ferulic acid compositions obtained in Examples 18 and 19 and Comparative Examples 27 and 28 were evaluated. The results are shown in Table 9.
[Evaluation of solubility]
Add 0.5 mL of distilled water (25 ° C.) to 0.525 g of the ferulic acid composition, put it in a 20 mL glass sample bottle, shake for 5 minutes at 25 ° C. on a rotary shaker (manufactured by ASONE, 150 r / min), and have a pore size of 0.2 μm The membrane was filtered through a membrane filter and the ferulic acid concentration was measured.
[Evaluation of flavor]
A panel of 3 persons put 0.1 g of the ferulic acid composition on the tongue, then swallowed it with 20 mL of distilled water, evaluated the flavor according to the criteria shown below, and scored the average value.
3: There is no roughness in the oral cavity and bitterness does not remain later 2: There is no roughness in the oral cavity, but bitterness remains strongly 1: There is roughness in the oral cavity, and bitterness remains strong

  As is apparent from Table 9, according to the method of the present invention, a ferulic acid composition having extremely excellent solubility in water could be obtained. Moreover, the ferulic acid composition obtained was excellent in flavor and easy to ingest.

Claims (8)

In the presence of an aqueous medium, one or two or more selected from (A) a poorly water-soluble polyphenol and (B) a methylated product of catechins, chlorogenic acids and poorly water-soluble polyphenols are heat-treated at 110 to 180 ° C. The manufacturing method of the polyphenol composition including a process.  (A) The manufacturing method of the polyphenol composition of Claim 1 whose logP value of slightly water-soluble polyphenols is -1.0-4.0.  (A) The polyphenol composition according to claim 1 or 2, wherein the poorly water-soluble polyphenol is one or more selected from hesperidin, quercetin, resveratrol, naringin, curcumin, rutin, caffeic acid and ferulic acid. Manufacturing method.   In the heat treatment step, (B) mass ratio of (A) poorly water-soluble polyphenols to one or more selected from (B) methylated products of catechins, chlorogenic acids and poorly water-soluble polyphenols (A) / (B ) Is 0.005-10, The manufacturing method of the polyphenol composition of any one of Claims 1-3.   The method for producing a polyphenol composition according to any one of claims 1 to 4, wherein the methylated product of poorly water-soluble polyphenols is methyl hesperidin.   Furthermore, the manufacturing method of the polyphenol composition of any one of Claims 1-5 including the process of cooling the reaction liquid obtained by heat-processing, and the process of removing a solid part from the cooled reaction liquid. .   Furthermore, the manufacturing method of the polyphenol composition of any one of Claims 1-6 including the process of freeze-drying or spray-drying the reaction liquid obtained by heat-processing.   The polyphenol composition obtained by the manufacturing method of any one of Claims 1-7.