JP5926944B2 - 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 are hardly water-soluble, and it is difficult to use them for food and drink.

  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.

  Further, a method for modifying a poorly water-soluble flavonoid that dries an alkaline solution or the like in which a poorly water-soluble flavonoid and quercetin-3-O-glycoside coexist (Patent Document 4). A method of improving the water solubility of hesperidin by dissolving in water and drying to an amorphous state has been proposed (Patent Document 5).

JP 2000-236856 A JP 2008-271839 A International Publication No. 2005/003112 JP 7-10898 A JP 2007-308414 A

As in Patent Documents 1 to 3, a conventionally known method for increasing the solubility of a poorly water-soluble polyphenol using a solubilizer such as a sugar adduct needs to use a large amount of the solubilizer. For this reason, only a composition having a low content of poorly water-soluble polyphenol has been obtained, which is not an economical method.
On the other hand, as in Patent Documents 4 and 5, the method of increasing the solubility as an amorphous state after dissolving the poorly water-soluble polyphenol and the solubilizing agent in the alkaline aqueous solution requires steps of alkali neutralization and desalting. There is concern about complications.

  Accordingly, an object of the present invention is to provide a method for efficiently producing a polyphenol composition having a high content of poorly water-soluble polyphenol and excellent solubility in water.

  The inventors of the present invention have made various studies on the solubilization technique of poorly water-soluble polyphenols, and after heat-treating the poorly water-soluble polyphenols in a specific temperature range in the presence of an aqueous medium, spray drying or freezing within a specific time. It has been found that when dried, the dissolution concentration of the poorly water-soluble polyphenol can be greatly increased and the polyphenol composition having excellent water solubility can be obtained in a high yield while maintaining the high concentration.

That is, the present invention includes the following steps (1) and (2):
(1) A step of heat-treating the hardly water-soluble polyphenol (A) at 100 to 180 ° C. in the presence of an aqueous medium
(2) A step of spray drying or freeze drying the treatment liquid within 600 minutes after the heat treatment,
Including
In the heat treatment, the mass ratio [(B) / ((A) + (B))] of the solubilizer (B) to the total of the poorly water-soluble polyphenol (A) and the solubilizer (B) is 0.1. The manufacturing method of the polyphenol composition performed on the conditions which are less than this is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the melt | dissolution density | concentration of the poorly water-soluble polyphenol with respect to water can be increased, and the polyphenol composition which is excellent in solubility with a high yield can be manufactured. In addition, it is possible to dissolve a poorly water-soluble polyphenol without using a solubilizer or even when the amount of solubilizer used is reduced, so that it is possible to obtain a composition having a high purity of the poorly water-soluble polyphenol. is there.

It is a figure which shows the result of the X-ray diffraction of the polyphenol composition I. It is a figure which shows the result of the X-ray diffraction of polyphenol composition II. It is a figure which shows the result of the X-ray diffraction of polyphenol composition III. It is a figure which shows the result of the X-ray diffraction of polyphenol composition IV. It is a figure which shows the result of the X-ray diffraction of the polyphenol composition V. It is a figure which shows the result of the X-ray diffraction of the polyphenol composition VI.

  As used herein, “poorly water-soluble polyphenol” refers to a polyphenol having a log P value of −1.0 to 4.0. The poorly water-soluble polyphenol preferably has 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 polyphenol can be measured by a flask shaking method described in Japanese Industrial Standard Z7260-107. Details are described in the examples.

The poorly water-soluble polyphenol (A) in the present specification refers to a phenolic substance in which one or more, preferably two or more hydroxyl groups are bonded to a benzene ring. For example, plant-derived flavonoids, tannins, phenolic acids and the like can be mentioned. Examples of poorly water-soluble polyphenols that can be more preferably applied include flavonols, flavanones, flavones, isoflavones, phenol carboxylic acids, and the like.
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, Idein, Mecocyanine, Pelargonidin Examples include ferulic acid, p-coumaric acid, and derivatives thereof. Examples of the derivatives include acetylated products, malonylated products, methylated products, and glycosides. Of these, flavonols and flavanones are preferable, and hesperidin, naringin and rutin are more preferable. The poorly water-soluble polyphenol may be one type or a mixture of two or more types.

  In the present specification, the aqueous medium 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%.

  From the viewpoint of the stability of the poorly water-soluble polyphenol, the pH of the aqueous medium is preferably 3 or more and less than 9, more preferably 3.5 to 8.5, and still more preferably 4 to 8.

  Since the poorly water-soluble polyphenol (A) has low solubility in water, it is preferably dispersed in an aqueous medium and present in a slurry state. The content of the poorly water-soluble polyphenol (A) in the aqueous medium varies depending on the kind of the poorly water-soluble polyphenol, but is preferably 0.1 to 100 g / L, and preferably 0.5 to 50 g / L from the viewpoint of the fluidity of the slurry. L is more preferable, 0.7 to 20 g / L is more preferable, and 0.7 to 10 g / L is still more preferable.

Step (1) in the method of the present invention is a step of heat-treating the poorly water-soluble polyphenol (A) at 100 to 180 ° C. in the presence of an aqueous medium.
The method for heat-treating the poorly water-soluble polyphenol (A) in the presence of an aqueous medium is not particularly limited, and a known method can be applied.
Although the temperature of heat processing is 100-180 degreeC, 110-170 degreeC is more preferable, 120-160 degreeC is still more preferable, 120-150 degreeC is still more preferable. A significant improvement in solubility is achieved at 100 ° C. or higher, and the stability of the poorly water-soluble polyphenol is ensured at 180 ° C. or lower. 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. The gauge pressure is a pressure at atmospheric pressure of 0 MPa. Moreover, it is preferable to set it more than the saturated vapor pressure of water. Pressurization higher than the saturated vapor pressure may be adjusted by a back pressure valve, or gas may be used. As a gas used, for example, an inert gas is preferable, and nitrogen gas, helium gas, and the like are more preferable.

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

The time for the heat treatment is preferably 0.1 to 30 minutes after the aqueous medium reaches the set temperature, more preferably 0.2 to 15 minutes, and further 0 from the viewpoint of improving the solubility of the poorly water-soluble polyphenol and the thermal stability. .5-8 minutes is preferred.
In the case of using the flow treatment method, the heat treatment time is an average residence time calculated by dividing the volume of the high-temperature high-pressure part of the processor by the supply rate of the aqueous medium.

It is preferable from the viewpoint of preventing thermal degradation of the polyphenol that the treatment liquid is cooled to 90 ° C. or less, preferably 50 ° C. or less, more preferably 30 ° C. or less after the heat treatment and before spray drying or freeze drying. During cooling, the treatment liquid may be mixed and stirred.
The cooling rate of the treatment liquid calculated from the time required to decrease from the heat treatment temperature to 90 ° C is 0.1 ° C / s or more, further 0.2 ° C / s or more, further 0.5 ° C / s or more, It is preferably 1 ° C./s or more, more preferably 3 ° C./s or more, and further preferably 5 ° C./s or more. As the cooling rate increases, the solubility of the poorly soluble polyphenol can be improved. For this reason, although the upper limit of a cooling rate is not specifically defined, 100 degrees C / s or less, for example, 50 degrees C / s or less are preferable from viewpoints, such as restrictions of manufacturing equipment.

  Furthermore, it is preferable to perform the step of removing the solid part remaining without being dissolved from the treatment liquid from the viewpoint of increasing the solubility of the resulting polyphenol composition. The method for removing the solid part is not particularly limited, and can be performed, for example, by centrifugation, decantation, or filtration.

In the method of the present invention, the heat treatment is performed by mass ratio of the solubilizer (B) to the total of the poorly water-soluble polyphenol (A) and the solubilizer (B) [(B) / ((A) + (B)). ] Is less than 0.1. That is, the relationship between the poorly water-soluble polyphenol (A) and the solubilizer (B) is
0 ≦ (B) / ((A) + (B)) <0.1
It can be expressed as.
From the viewpoint of increasing the purity of the poorly water-soluble polyphenol in the composition, the mass ratio is preferably 0.09 or less, more preferably 0.07 or less, further preferably 0.05 or less, and further preferably 0.04 or less. 0 (conditions in which the solubilizer (B) is not present) is particularly preferred.

As the solubilizer (B), a sugar adduct of a poorly water-soluble polyphenol (A) is preferable, and a hesperidin sugar adduct is more preferably used. The sugar adduct of the poorly water-soluble polyphenol (A) is a compound in which 1 to 10 sugars are bonded to the poorly water-soluble polyphenol (A). Examples of the sugar include glucose, maltose, fructose, rhamnose, lactose and the like. In addition, the poorly water-soluble polyphenol includes glycosides in which sugar is bound to aglycone. For example, hesperidin is a compound in which rutinose (L-rhamnosyl- (α1 → 6) -D-glucose) is β-bonded to the 7-position hydroxyl group of hesperetin (5,7,3′-trihydroxy-4′-methoxyflavanone). It is a saccharide. In the present invention, for distinction from this, a product in which a saccharide is further bound to a poorly water-soluble polyphenol is referred to as a sparingly water-soluble polyphenol sugar adduct, and a product in which a sugar is further bound to hesperidin is referred to as a hesperidin sugar adduct.

Step (2) in the method of the present invention is a step of spray-drying or freeze-drying the treatment liquid within 600 minutes after the heat treatment.
In this specification, “within 600 minutes” after the heat treatment refers to the time from the time when the heat treatment is completed, that is, the time when the treatment liquid is lowered to less than 100 ° C. to the start of spray drying or freeze drying. The time from the heat treatment to the start of spray drying or freeze drying is preferably from 0.1 to 600 minutes, more preferably from 0.1 to 200 minutes, from the viewpoint of polyphenol yield.

The method of spray drying or freeze 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 polyphenol composition thus obtained is in an amorphous state and is extremely excellent in solubility in water. Here, the amorphous refers to a solid substance having no crystallinity. The amorphous state can be confirmed by the fact that no clear diffraction peak is detected when X-ray diffraction is performed.
For example, in the case of the hesperidin composition of the present invention, the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° in X-ray diffraction (diffraction angle (2θ ) Diffraction intensity at 15.5 ° / Diffraction angle (2θ) (Diffraction intensity at 14.5 °) is preferably 3.0 or less from the viewpoint of initial solubility in water and solubility, and further 2 0.0 or less is preferable.

  Moreover, the initial solubility (25 degreeC) of the poorly water-soluble polyphenol (A) with respect to the water in a polyphenol composition becomes like this. Preferably it is 1-1000 (g / L), More preferably, it is 10-1000 (g / L). “Initial” refers to a period of up to 30 minutes, preferably up to 5 minutes from the time of dissolution in water.

According to the production method of the present invention, the solubility of the poorly water-soluble polyphenol can be increased even if the amount of the solubilizer is decreased. That is, the purity of the poorly water-soluble polyphenol (A) of the polyphenol composition can be increased. The purity is preferably 95% or more, and more preferably 97% or more and substantially 100% from the viewpoint of suppressing the off-flavor of the solubilizer. In the present specification, the purity (mass%) of the poorly water-soluble polyphenol (A) refers to [slightly water-soluble polyphenol / (slightly water-soluble polyphenol + solubilizer) × 100].
For example, when a hesperidin sugar adduct is used as a solubilizer for hesperidin, the purity of hesperidin in the polyphenol composition can be preferably 95% or more, and more preferably 97% or more, substantially 100%. % Can be obtained more preferably. In the present specification, the purity (mass%) of hesperidin refers to [hesperidin / (hesperidin + hesperidin sugar adduct) × 100].

  The polyphenol composition obtained by the production method of the present invention can be used for various foods and beverages, pharmaceuticals and the like. For example, foods and beverages include confectionery such as breads, noodles, cookies, snacks, jelly, dairy products, frozen foods, instant foods such as powdered coffee, processed starch products, processed meat products, other processed foods, seasonings Solid or semi-solid foods and beverages such as food and nutritional supplements.

[Measurement of poorly water-soluble polyphenols]
The measurement of poorly water-soluble polyphenols was performed by a gradient method using a high-performance liquid chromatograph manufactured by Hitachi, equipped with an intact column Cadenza CD-C18 (4.6 mmφ × 150 mm, 3 μm) and a column temperature of 40 ° C. 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
50.1 85 15
60 85 15
The sample injection amount was 10 μL, the detection was quantified by absorbance at a wavelength of 360 nm for rutin, and the other water-insoluble polyphenols at a wavelength of 283 nm.

[Measurement of log P value of poorly water-soluble polyphenol]
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 polyphenol concentration 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.

[Evaluation of solubility]
Polyphenol compositions I to IX are dispersed in distilled water so that 0.1 g of sample is 10 g / L, and polyphenol compositions X to XI are dispersed in distilled water so that 0.1 g of sample is 1 g / L. Each was put in a 20 mL glass sample bottle, and the state after shaking at 25 ° C. for 3 hours with a rotary shaker (manufactured by ASONE, 50 rpm) was visually confirmed. The solubility was evaluated according to the following evaluation criteria.
3: Complete dissolution and no precipitation 2: Turbidity due to insoluble solids but no sediment 1: Precipitation deposited in layers at the bottom of the sample bottle

[X-ray diffraction analysis]
X-ray diffraction intensity is “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation.
Was measured under the following conditions.
X-ray source: Cu / Kα-radiation, tube voltage: 40 kv, tube current: 120 mA, measurement range: 2θ = 5-45 °. The measurement sample was prepared by compressing a pellet having an area of 320 mm ² × thickness of 1 mm. X-ray scanning speed is 10 ° / min.

[Measurement of pH]
The pH was measured with a pH meter (F-22) manufactured by Horiba, Ltd. at 20 ° C. in the aqueous medium.

Example 1
Hesperidin preparation (Hesperidin “Hamari” (trade name), Hamari Pharmaceutical Co., Ltd., Hesperidin (HES) content 90%) is dispersed in distilled water (pH 7) at 10 g / L and uniformly stirred in a slurry supply tank. did. The liquid in the slurry supply tank was supplied at a rate of 100 mL / min to a stainless steel flow-type processing device (manufactured by Nitto Koatsu Co., Ltd.) with an internal volume of 100 mL, and heat treatment was performed at 120 ° C. (average residence time 1 minute). The gauge pressure in the processor was adjusted to 0.3 MPa by an outlet valve. The processing solution was extracted from the processing unit outlet, cooled to 25 ° C. with a heat exchanger, passed through a sintered metal filter having a pore diameter of 7 μm, and then recovered by returning the pressure of the solution to atmospheric pressure with an outlet valve. The solution is supplied to a spray dryer (manufactured by Niro, mobile minor mic, inlet air temperature 160 ° C., outlet air temperature 72 ° C.) 5 minutes after the end of the heat treatment, and in the form of powder, polyphenol composition I Got. Table 1 shows the results of HES concentration, HES purity, yield, and solubility evaluation of polyphenol composition I in the solution. The X-ray diffraction result of the polyphenol composition I is shown in FIG. 1, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

  Furthermore, in order to check the solubility of the polyphenol composition, 0.3 g of distilled water (25 ° C.) was added to 0.25 g of polyphenol composition I and shaken, and after 5 minutes, filtered through a 0.2 μm membrane filter to measure the concentration of hesperidin. As a result, it was 530 g / L, which was significantly higher than the solubility (0.02 g / L) of the commercially available hesperidin preparation.

Example 2
The solution was recovered in the same manner as in Example 1 except that the temperature of the heat treatment was 150 ° C. and the pressure was 0.6 MPa. The 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, polyphenol composition II was obtained. Table 1 shows the results of the HES concentration, HES purity, yield, and solubility evaluation of the polyphenol composition II in the solution. The X-ray diffraction result of the polyphenol composition II is shown in FIG. 2, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

Comparative Example 1
The hesperidin preparation used in Example 1 was used as polyphenol composition III as it was. The results of the solubility evaluation of the polyphenol composition III are shown in Table 1. The X-ray diffraction result of the polyphenol composition III is shown in FIG. 3, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

Comparative Example 2
After the heat treatment, polyphenol composition IV was obtained in the same manner as in Example 1 except that the time until the start of drying was 10 minutes, and drying was performed in a vacuum electric dryer set at 70 ° C. instead of the spray dryer. Table 1 shows the results of the HES concentration, HES purity, yield, and solubility evaluation of the polyphenol composition IV in the solution. The X-ray diffraction result of the polyphenol composition IV is shown in FIG. 4, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

Comparative Example 3
After the heat treatment, a polyphenol composition V was obtained in the same manner as in Example 1 except that the time until the start of drying was 1440 minutes. Table 1 shows the results of HES concentration, HES purity, yield, and solubility evaluation of the polyphenol composition V in the solution. The X-ray diffraction result of the polyphenol composition V is shown in FIG. 5, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

Comparative Example 4
A polyphenol composition VI was obtained in the same manner as in Example 2 except that the temperature of the heat treatment was 80 ° C. and the pressure was 0.3 MPa. Table 1 shows the results of HES concentration, HES purity, yield, and solubility evaluation of the polyphenol composition VI in the solution. The X-ray diffraction result of the polyphenol composition VI is shown in FIG. 6, and the ratio of the diffraction intensity at the diffraction angle (2θ) of 15.5 ° and the diffraction intensity at the diffraction angle (2θ) of 14.5 ° is shown in Table 1. Show.

As is apparent from Table 1, according to the method of the present invention, the concentration of hesperidin can be remarkably increased, and a hesperidin composition having excellent water solubility can be obtained with high yield. In particular, from Examples 1 and 2, a composition having a hesperidin purity of 100% and containing no solubilizer could be obtained. 1 and 2 and Table 1, it was confirmed that the hesperidin composition of the present invention was in an amorphous state.
On the other hand, Comparative Example 1 which is a commercially available hesperidin preparation and Comparative Example 2 which was dried with a 70 ° C. drier had low solubility in water. These were highly crystalline as shown in FIGS.
Moreover, the yield of hesperidin was bad in the comparative example 3 which started spray-drying 1440 minutes after completion | finish of heat processing, and the comparative example 4 which performed heat processing at a low temperature of 80 degreeC.

Example 3
The solution was recovered in the same manner as in Example 1 except that a naringin formulation (manufactured by ACROS ORGANICS, content of naringin 97%, the same applies hereinafter) was used instead of the hesperidin formulation. The cooling rate obtained from the cooling time from 120 ° C. to 90 ° C. was 7.58 ° C./s. 10 minutes after the end of the heat treatment, the solution was supplied to a spray dryer (manufactured by Yamato Kagaku, ADL311S-A, inlet air temperature 150 ° C., outlet air temperature 60 ° C.), and the polyphenol composition VII was in the form of powder. Obtained. Table 2 shows the results of the evaluation of naringin concentration, naringin purity, yield, and solubility of polyphenol composition VII in the solution.
Furthermore, in order to investigate the solubility of the polyphenol composition, 0.3 g of distilled water (25 ° C.) was added to 0.25 g of the polyphenol composition VII and shaken, and after 5 minutes, it was filtered through a 0.2 μm membrane filter to measure the naringin concentration. As a result, it was 584 g / L, which was significantly higher than the solubility (0.44 g / L) of the commercially available naringin preparation.

Example 4
150 mL of dispersed water obtained by dispersing a naringin preparation in distilled water (pH 7) at 10 g / L was placed in a batch hydrothermal apparatus (Start 200 New Quick, volume 180 mL) manufactured by Nitto Koatsu, and the upper space was purged with nitrogen and heated. The temperature elevation rate was 3.4 ° C./min. After reaching 120 ° C., the device was immersed in a water bath after 1 minute and cooled to 25 ° C. The cooling rate obtained from the cooling time from 120 ° C. to 90 ° C. was 0.38 ° C./s. The solution was recovered through a membrane filter having a pore size of 3 μm. The solution was spray dried as in Example 3 to obtain a polyphenol composition VIII in the form of a powder. Table 2 shows the results of the evaluation of naringin concentration, naringin purity, yield, and solubility of polyphenol composition VIII in the solution.

Comparative Example 5
The naringin formulation used in Example 3 was used as polyphenol composition IX as it was. The results of the solubility evaluation of the polyphenol composition IX are shown in Table 2.

Example 5
Instead of the hesperidin preparation, a rutin preparation (manufactured by Tokiwa Plant Chemical Research Co., Ltd., rutin content 100%, hereinafter the same) was dissolved in distilled water at 5 g / L in the same manner as in Example 1. Was recovered. The solution was freeze-dried 10 minutes after the end of the heat treatment in the same manner as in Example 2 to obtain a polyphenol composition X in the form of a powder. Table 2 shows the results of the rutin concentration, rutin purity, yield, and solubility evaluation of the polyphenol composition X in the solution.
Furthermore, in order to investigate the solubility of the polyphenol composition, 0.3 g of distilled water (25 ° C.) was added to 0.25 g of the polyphenol composition X, and the mixture was shaken, and after 5 minutes, it was filtered through a 0.2 μm membrane filter to measure the rutin concentration. As a result, it was 14 g / L, which was significantly higher than the solubility (0.03 g / L) of the commercially available rutin preparation.

Comparative Example 6
The rutin preparation used in Example 5 was used as polyphenol composition XI as it was. The results of solubility evaluation of the polyphenol composition XI are shown in Table 2.

As is apparent from Table 2, according to the method of the present invention, the dissolution concentration of naringin and rutin can be remarkably increased, the solubility in water is extremely excellent, and the purity is 100% with no solubilizer. The composition could be obtained with good yield.
On the other hand, Comparative Examples 5 and 6 which are commercially available naringin preparations and rutin preparations had low solubility in water.

Claims (6)

Next steps (1) and (2):
(1) A step of heat-treating the poorly water-soluble polyphenol (A) at 100 to 180 ° C. in the presence of an aqueous medium , and further cooling the treatment liquid obtained by the heat treatment ,
(2) A step of spray drying or freeze drying the treatment liquid within 10 minutes after the heat treatment,
Including
The poorly water-soluble polyphenol (A) is one or more selected from flavanones and flavonols, and the following solubilizer (B) is a sugar adduct of the poorly water-soluble polyphenol (A),
In the heat treatment, the mass ratio [(B) / ((A) + (B))] of the solubilizer (B) to the total of the poorly water-soluble polyphenol (A) and the solubilizer (B) is 0.1. The manufacturing method of the polyphenol composition performed on the conditions which are less than. PH of the aqueous medium is less than 3 to 9, a manufacturing method of claim 1 polyphenol composition. Further comprising the step of removing the solid portion from the cooling has been treated liquid The process according to claim 1 or 2 polyphenol composition. The manufacturing method of the polyphenol composition of any one of Claims 1-3 whose cooling rate from heat processing temperature to 90 degreeC is 0.5 degrees C / s or more in the process of cooling a process liquid. The method for producing a polyphenol composition according to any one of claims 1 to 4 , wherein the slightly water-soluble polyphenol (A) has a log P value of -1.0 to 4.0. The method for producing a polyphenol composition according to any one of claims 1 to 5 , wherein the poorly water-soluble polyphenol (A) is one or more selected from hesperidin, naringin and rutin.

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