WO2008072360A1

WO2008072360A1 - Catechin composition and method for producing the same

Info

Publication number: WO2008072360A1
Application number: PCT/JP2006/325454
Authority: WO
Inventors: Eisei Nishitani; Yuji Kubota; Takanobu Takihara
Original assignee: Ito En, Ltd.
Priority date: 2006-12-14
Filing date: 2006-12-14
Publication date: 2008-06-19

Abstract

It is intended to provide a catechin composition with less unpleasant bitterness although containing unpolymerized catechins at a high concentration. When the weight ratio of the content of (A) gallate type catechins to the content of (B) unpolymerized catechins [(A)/(B)] is in the range of from 0.50 to 0.75, the weight ratio of the content of (B) the unpolymerized catechins to the content of (C) total polyphenols [(B)/(C)] is in the range of from 0.80 to 0.97, the weight ratio of the content of (D) a flavonol aglycone to the content of (B) the unpolymerized catechins [(D)/(C)] is less than 0.002, the weight ratio of the content of (E) caffeine to the content of (B) the unpolymerized catechins [(E)/(C)] is less than 0.1 and the CPA value of an aqueous solution measured by a CPA method using a C00 type sensor is 5 µV/ppm or higher in terms of the concentration of the unpolymerized catechins, it can be provided as a catechin composition with less unpleasant bitterness although containing unpolymerized catechins at a high concentration.

Description

Description 'Catechin composition and its manufacturing method'

Technical field

The present invention relates to a catechin composition having a low bitter taste derived from a polyphenol component and a method for producing the same, despite containing a high concentration of non-polymeric techins. '' Background Technology ...

'Tea catechins abundantly contained in tea leaves are a kind of polyphenol compounds, including (1) one-epicatechin (EC, (-)-epigalocatechin (E GC), and gallate esters thereof. There are four main types: (1) one-pipe force tinga 'rate (EC g) .. and (-) —epiro-force teking gallate (EGC g). Tea catechins are contained in 10 to 15 w.t% and are the main astringent taste of tea (tea as tea infusion).

These tea catechins are known to have various chemical and physiological activities such as an antioxidant action, an antibacterial action, a deodorizing action, an inhibitory action on blood cholesterol, and an _α -amylase activity inhibiting action. However, in order to develop such physiological effects of tea catechins, it is necessary to consume a large amount of tea power techins. At this time, a catechin composition containing high strength techins is blended in foods and beverages. However, if it is in a form that makes it easy to ingest strong techins, it will be possible to ingest more powerful techins more efficiently than drinking tea (tea as tea infusion). Become. '' ■ '

In order to produce a catechin composition containing such strong techins at a high concentration from tea leaves, impurities coexisting with the catechins in the tea leaves, such as purine bases, sugars, amino acids, organic acids, 'inorganic salts Therefore, it is necessary to purify the catechin oxidation polymer and the like so as to separate and remove as much as possible to obtain a force techin composition containing catechins at a higher concentration.

Conventionally, as a method for obtaining this kind of catechin composition, that is, a force-textile composition containing force-techins at a high concentration, a technique using a liquid extraction method using an organic solvent or a chromato-separation method. Was known. For example, in Japanese Patent No. 1 5 6 1 0 4 3, a method of industrially producing a natural antioxidant by removing caffeine with a black mouth foam and extracting tea tannins with ethyl acetate. Is disclosed. '

In addition, in Patent No. 2 7 0 3 2 4 1 and Patent No. 3 0 5 2 1 7 5, tea force techins are selectively adsorbed on a filler by using kuto mat separation, and adsorbed components are A method for purifying tea power techins by elution with a hydrophilic organic solvent is disclosed.

Furthermore, in Japanese Patent Application Laid-Open No. 1 1 1 2 2 8 5 6 5, the tea extract is brought into contact with a cation exchange resin to remove caffeine, and then ethanol is added to cause precipitation. A method for purifying tea tannins by producing a product and removing the precipitate by filtration is disclosed.

However, the catechin composition obtained by the conventional technology as described above has a large difference between the total polyphenols and the content of non-polymeric power techins. It was shown to contain a lot of polyphenols. In other words, polyphenols other than non-polymer catechins tend to exhibit unpleasant bitterness, and therefore, when blended into foods and beverages, there is a high possibility of adversely affecting the flavor of the foods and beverages. In order to improve such problems, the ability to perform further purification, the ability to use raw materials with a small difference in the content of total polyphenols and non-polymer catechins, or cyclodextrins It was necessary to consider other measures such as adding sweeteners.

'' Disclosure of the invention

Accordingly, the object of the present invention is to reduce the unpleasant bitterness derived from polyphenol components other than non-polymer catechins, preferably with low astringency even though they contain non-polymeric strength catechins at high concentrations. It is to provide a composition. The present inventor, despite containing non-polymeric power catechins at high concentrations, by controlling the content of non-polymer catechins, gallate-type catechins, flavonol aglycones, and purine bases (especially caffeine), Unpleasant bitterness The present inventors have found that a low strength Tekin composition can be obtained and have conceived the present invention based on such knowledge.

'In the present invention, (A) gallate-type catechins and (B) non-polymer catechins have a weight ratio [(A) to (B)] of 0.50 to 0.75, The weight ratio [(B) / (C)] of the polymer catechins to (C) total polyfuninols is 0.80 to 0.97, (D) flavonol aglycone and (B) non-polymeric power The weight ratio [(D) / (C)] is less than 0.002, and the weight ratio [(E) / CC)] of (E) caffeine and (B) non-polymer catechins is 0. Less than 1 ', and its bitterness is obtained by adding the catechin composition to ion-exchanged water to prepare an aqueous solution with a non-polymer catechin concentration of 300 ppm, and using a C 00 type sensor, CPA (Change The CPA value of the aqueous solution when measured by the measurement method is 5 μν ρ pm or more per non-polymer catechin concentration, and preferably the astringency of the catechin composition The aqueous solution of the non-polymer catechins 300 p pm prepared in addition to the on-exchanged water, using AE 1 type sensor, CPA (Change of membrane

Potential cause by Adsorption) CPA value (potential difference) measured by the measurement method 力 Proposed a force-technine composition characterized by exhibiting 1 125 μV / ppm or more per non-polymer catechin concentration To do.

The present inventor also provides a fractionation operation of a tea extract component (a component contained in a tea extract or tea extract) as a method for producing a catechin composition, particularly a catechin composition of the present invention. In the present invention, it was found that by using a structure having an N-alkylglucamine group as an adsorbent, non-polymeric strength techins can be selectively separated from polyphenols, and caffeine can be simultaneously reduced. Based on this knowledge, a new manufacturing method was conceived. That is, the present invention brings a tea extract or tea extract into contact with a structure having an N-alkylglucamine salt, preferably after washing the structure with water, and then recovering the components adsorbed on the structure. The present invention also proposes a method for producing a force-technical composition characterized by Brief description of the drawings.

Fig. 1 shows the results of Comparative Example 1 when the concentration of each sample was adjusted so that the concentration of non-polymer catechins was 300 pp in the measurement of bitterness and astringency using a taste sensor. Figure showing the bitterness and astringency distribution of each Example and Comparative Example based on

' is there. ,, '',

Fig. 2 shows that each sample concentration was adjusted to 100 ppm as EGC g in the measurement of bitterness and astringency using the same taste sensor. 6 is a graph showing the distribution of bitterness and astringency in Examples and Comparative Examples.

(D) Flavonol aglycone and (B) Non-polymer catechins content weight ratio "(D) / (B)" is plotted on the horizontal axis and non-polymer measured by C 0 0 type sensor It is the graph which plotted the value of the Example and the comparative example in the coordinate which took the CP A value (unit: μVZp Pm) per concentration of catechins on the vertical axis.

'' (A) Ester-type catechins and (B) Non-polymer catechins The weight ratio “(A) / (B)” is plotted on the horizontal axis and FIG. 5 is a graph in which values of examples and comparative examples are plotted on a coordinate with the CPA value per concentration (unit: μV / ppm) on the vertical axis. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, the term “total polyphenols” means components that can be quantified by a method for obtaining an equivalent amount of gallic acid using ethyl gallate as a standard product in the iron tartrate colorimetric method. “Total weight of polyphenols” refers to the value calculated as the equivalent amount of gallic acid using ethyl gallate as the standard product in the iron tartrate colorimetric determination method (for details, see Examples) See).

In the present invention, the term “non-polymer catechins” means (1) one-epigalocatechin (EGC), (1) -epigalocatechin gallate (EGC g), (1) epicatechin (EC), (1) Gepatechin gallate (EC g), (Sat)-Gallocatechin (GC), (1)-Gallocatechin gallate (GC g), (Sat) One strength techin (C), (One) One strength techin gallate (C g ) Or In the present invention, the “weight of non-polymer catechins” means the total of all non-polymer catechins contained in the catechin composition. It means the content weight, and the content weight of each non-polymeric force can be quantified by separation analysis by HPLC (for details, see Examples).

In the present invention, “gallate-type catechins” are: (1) Epepigachin catechin gallate (EGC g), (1) 'Epicatechin gallate (EC g), (1)' -Gallocatechin gallate (GC) , g), (1) One-strength techin gallate (C g) is intended to include a mixture of any one or a combination of two or more of these. The `` category weight of catechins '' means the total weight of all gallate-type catechins contained in the catechin composition, and the content of each gallate-type catechin is determined by separation analysis by HPLC. Can be quantified (see examples for details).

In the present invention, the term “flavonol aglycone” is intended to encompass any force of Kenhue roll, quercetin, and myricetin, or a mixture comprising a combination of two or more of these. “Flavonol adalicone content” means the total content of all flavonol adalicons contained in the catechin composition, and the content of each flavonol aglycone can be quantified by separation analysis by HPLC. See Examples). In this specification, “Χ to Υ” (X and Υ are arbitrary numbers) means “X or more and Υ or less” unless otherwise specified.

'' Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

The catechin composition of this embodiment is a catechin composition derived from tea, in other words, a catechin composition obtained from a tea extract obtained by extracting tea leaves and the like, and at least other than techchins and catechins Polyphenols, caffeine, 'purine bases such as theophylline and xanthine (methyl derivatives of the purine ring),' catechin composition containing flavonol aglycone, which has the following characteristics: . '

However, the catechin composition of the present invention is not limited to a catechin composition derived from tea.

(Galate-type catechins / non-polymer catechins)

The catechin composition of the present embodiment is characterized in that the content weight ratio [(A) / (Β)] of (Α) gallate catechins to (と) non-polymer catechins is 0.50 to 0.75. And preferably 0.5 to 0.7, and particularly preferably 0.5 to 0.6.

(Non-polymer catechins / total polyphenols)

Further, the catechin composition of the present embodiment has a weight ratio [(Β) / (C)] of (Β) non-polymer catechins and (C) total polyphenols of 0.80 to 0.9. 7 and preferably 0.88 to 0.97, particularly preferably 0.90 to 0.97.

(Flavonol aglycone Z non-polymer catechins) ''

In the catechin composition of the present embodiment, (D) Flavonol aglycone and (B) 'content weight ratio of non-polymer catechins' [(D) Z (B)] is less than 0.002 With features, preferably less than 0.001 and particularly preferably less than 0.0005.

(Caffeine Z non-polymer catechins) '-Not yet' The catechin composition of the present embodiment comprises (E). Force fin and (B) non-polymer force. ) / (B)] is your comprise the features is less than ^0.1: is, preferably less than 0.05, particularly 'preferably less than 0.02.

(Bitter ingredients)

In addition, the force techin composition of the present embodiment is prepared by adding a force tekin composition to ionic exchange water to prepare an aqueous solution having a non-polymer catechin concentration of 300 ppm, and using a C 00 type sensor. CPA value measured by CPA (Change of membrane Potential caused by Adsorption) measurement method has a bitter taste showing 5 μV / ppm or more per non-polymer catechin concentration, in other words, it contains such a bitter component. In particular, those exhibiting 6 IX V / p pm or more, particularly 7 VZp pm or more are preferable.

(Astringent ingredient) Further, the catechin composition of the present embodiment is not essential, but a preferable feature is that the strength of the techchin composition is added to the ionic exchange water and

A 300 ppm aqueous solution was smoked, and the CPA value measured by the CPA (Change of membrane Potential caused by Adsorption) measurement method using an AE type 1 sensor was 1 1 2 5 per non-polymer catechin concentration. It has a bitter taste showing μV / ppm or more '', in other words, it has the characteristics of containing such astringency components, especially 1 1 1 5 V / pm or more, especially 1 1 1 0 V / ppm Those having the above are preferred.

In addition, in the present invention, if bitterness and astringency are measured by a taste sensor, for example, a taste recognition device “SA 4 0 2 J” of Intelligent Sensor Technology Co., Ltd. is used as a sensor for detecting bitterness. `` 0 type sensor '' and `` AE 1 type sensor '' as a sensor to detect astringency, can be performed by CPA (Change of membrane '· Potential caused by Adsorption) measurement method, especially aftertaste objectively Can be evaluated.

In this case, the “measured value by the taste sensor” refers to a potential difference called a CP A value measured by the above-mentioned method, and means that the sensed taste is weaker as the potential difference is higher.

In addition, the measurement may be performed in a concentration range where the potential difference is linear with respect to the concentration of the non-polymer catechins. Non-polymer strength as a guide The concentration of tekins is 2 0 0 p ρ π! It is preferable to measure at ~ 500 ppm. In the case of the present invention, the degree of bitterness and astringency is specified by the CPA value when the concentration of non-polymer catechins is adjusted to 300 ppm. '

(Other contents)

The power tekin ancestral product of the present embodiment is a component that does not depart from the above range in bitterness and astringency, ie, components other than ¾), that is, catechins, polyphenols other than catechins (Frapono

It may contain components other than purine bases such as caffeine, theophylline and xanthine. In particular, 'tea extraction components other than the above components may be added.

: (Form):

The form of the force textile composition according to the present embodiment is not limited, and for example, it can be prepared in various forms such as a solid form, a powder form, a liquid form, and a viscous liquid form.

(Use)

Since the catechin composition of the present embodiment has less caffeine and reduced bitterness or astringency, it can be formulated without concern about the negative effects of caffeine, so the original action of tea catechins, For example, physiologically active functions such as blood cholesterol suppression and α-amylase activity inhibition can be sufficiently imparted. Therefore, the catechin composition of the present embodiment can be used to prepare drugs such as pharmaceuticals and quasi drugs using this as an active ingredient. Specifically, oral administration ^ can be prepared, and at that time, formulation and dosage form may be prepared based on common general technical knowledge.

Speaking of the dosage form, it can be prepared in the form of solution, tablet, powder, granule, dragee, capsule, suspension, emulsion, pill.

In terms of formulation (formulation), commonly used excipients, extenders, binders, wetting agents, disintegrants, surfactants, lubricants, dispersants, buffers, preservatives, solubilizing aids Can be produced by conventional methods using preservatives, preservatives, flavoring agents, soothing agents, stabilizers, and the like. Also, for example, lactose, fructose, glucose, starch, gelatin, magnesium carbonate, synthetic silicate, talc., Magnesium stearate, methylcellulose, carboxymethylsenololose or its salts, gum arabic, polyethylene gum, syrup, Non-toxic additives such as petrolatum, glycerin, ethanol, 'propylene glycol, citrate, sodium chloride, sodium sulfite and sodium phosphate can also be added.

In addition, health foods, health drinks, foods for specified health use, functional foods, food additives, and other drugs, baits, and baits for animals other than humans, which have the catechin composition of this embodiment as an active ingredient and have a pharmacological effect Additives and the like can also be prepared. In particular, since the strength tekin composition of this embodiment has reduced bitterness and astringency, it is added to food and drink materials and food and drinks, health foods, health drinks, foods for specific health use, functional foods, In addition, food (including feed) for animals other than human can be suitably prepared.

“Food and drink materials” to be blended at this time include water, carbonic acid, excipients (including granulating agents), diluents, or even sweeteners, flavors, flour, starch, sugars, oils and fats, etc. One type or two or more types selected from the group of foods and beverages such as various proteins, carbohydrate raw materials, vitamins, and minerals can be mentioned. For example, it can be dissolved in a desired concentration such as purified water or physiological saline to obtain a catechin-containing beverage. ■

In addition, currently known foods and drinks such as sports drinks, fruit drinks, milk drinks, tea drinks, vegetable juices, dairy drinks, alcoholic drinks, jelly, jelly drinks, carbonated drinks, chews Examples include ingum, chocolate, candy, biscuits, snacks, bread, dairy products, fish paste products, livestock products, frozen confectionery, confectionery, dried foods, various foods, processed foods, and supplements.

Furthermore, the catechin composition of the present embodiment is added to various oral hygiene products such as toothpaste, lipstick, lip balm, internal medicine, troche, mouth freshener, mouthwash, etc., and its flavor. And this greatly impairs the taste In addition, the physiological effects of tea cadekins can be added to increase the added value.

Manufacturing method) '' ''

The catechin composition of the present embodiment includes, for example, a tea extract or a tea extract brought into contact with a structure having an N-alkylglucamine group, and the structure is washed with water as necessary. It can be obtained by collecting the adsorbed components.

At this time, the tea extract or tea extract can be obtained by extracting the tea as a raw material, preferably green tea with a suitable solvent. .

The green tea used as a raw material is not limited to its variety, production area, harvest time, plucking method, cultivation method, etc., as long as it is a leaf or stem plucked from a tea tree (scientific name: Camell ia sinensis). Can be used. For example, sencha, pot roasted tea, kabusecha, gyokuro, tencha, matcha, bancha, roasted tea, steamed ball green tea, pot roasted ball green tea, or a mixture of two or more of these It can be used as a fee. Also, a finished tea obtained by subjecting the above tea to a currently known finishing process can be used as a raw material.

As raw materials, in addition to the above green tea, semi-fermented tea such as oolong tea and black tea, and fermented tea can also be used as raw materials. However, in these fermented teas, the polymerization of non-polymer strength techins progresses due to fermentation, and the non-polymer strength techins decrease, so that the non-polymer strength techins intended in the present invention are concentrated. As a raw material 1 It is hard to say that it is appropriate. Therefore, it is preferable to use green tea which is non-fermented tea as a raw material. '

'For tea extraction, water, warm water,' hot water, or an organic solvent such as ethanol, methanol, or acetone, or a mixed solution of the organic solvent and water (eg, 30 to 80% ethanol aqueous solution, 30 to 8 0% methanol aqueous solution, 30 to 80% aqueous acetone solution, etc.). The liquid to be extracted is not limited to these. '' 'When extracting with an organic solvent or water-containing organic solvent, whether the organic solvent is distilled off from the resulting tea extract, or whether it is suspended in water and dissolved after drying. It is desirable to reduce the concentration of the organic solvent in the tea extract as much as possible. Therefore, the extraction is preferably performed with hot water or hot water, particularly hot water from the viewpoint of extraction efficiency.

The extraction method may be a normal method. For example, a column is filled with raw materials, and an extraction solvent such as hot water is sequentially sent to the column, or an extract is obtained, or an extraction kettle is filled with raw materials and fixed with a predetermined amount of extraction solvent such as hot water Select a suitable extraction device according to the amount of raw material to be processed, such as an extraction device called a kneader that is immersed in time, and perform solid-liquid separation by a normal method. There is no particular restriction on the method, and it can be selected as desired or desired. The tea extract thus obtained generally contains 25 to 50% by weight of total polyphenols, 20 to 40% by weight of non-polymer catechins, and 5 to 1 in terms of dry weight. Contains 5% by weight caffeine. The weight ratio of the non-polymer catechins to the total polyphenols is 0.6 to 0.9, and the weight ratio of caffeine to the non-polymer catechins is 0.2 to 0.5.

Next, the tea extract (including tea extract dissolved in water) obtained as described above is selectively contacted with a structure having an N-alkyltalcamine group. The non-polymer strength techins can be adsorbed and separated, and a component containing the non-polymer strength techins at a high concentration can be obtained. .

The above structure refers to a resin in which an N-alkylglucamine group is bonded to a cross-linked resin serving as a substrate such as polystyrene or a styrene-divinylbenzene copolymer. For example, cross-linked polystyrene (a copolymer of a monobula aromatic compound and polybutene aromatic compound) or a cross-linked polymethacrylic acid ester (a copolymer of a metatalyl ester and a polybula aromatic compound) is used as a base, The force S that can introduce an N-alkylglucamine group and the like, and the structure of the substrate are not limited to these.

In order to produce a structure having an N-alkyldalkamine group, for example, (1) after introducing a haloalkyl group into the substrate by a known method, the haloalkyl group and N-alkylglucamine are reacted; (2) Monovinyl aromatic compounds constituting the cross-linked polystyrene include chloromethylstyrene and chloroethyl Norestyrene, promomethylol styrene, promobutinole styrene, etc., roanolalkyl styrene, etc., and a cross-linked copolymer obtained by copolymerizing this with a polybutyl aromatic compound such as divinylbenzene are N- And a method of reacting alkylglucamine.

As a more specific example, any of the above methods is applied to a styrene-dibutylbenzene copolymer.

A method for producing a structure having an N_alkylglucamine group by reacting N-alkylglucamine with a haloalkyl group introduced in step 1 can be mentioned. In this case, as a method for introducing a haloalkyl group into the styrene-dibutenebenzene copolymer, for example, chloromethyl methyl ether is added to the styrene dibutene benzene copolymer and Lewis chloride such as zinc chloride or iron chloride is added. The reaction may be performed in the presence of an acid catalyst. The amount of chloromethyl methyl ether may be an amount that allows the styrene-divinylbenzene copolymer to swell and maintain a slurry state. Depending on the reaction conditions and the amount of the reactants, it is usually from room temperature. The reaction may be performed at a temperature up to 0 ° C for 30 minutes to 20 hours.

As the structure having an N-alkylglucamine group, a commercially available product can be used. For example, Diaion CRB 0 2 (manufactured by Mitsubishi Chemical Corporation), Amberlite IRA 7 4 3 (Rohm and Haas) ), Duolite ES 37 1 N (Rohm 'and' Haas) and the like can be used. The method for bringing the tea extract into contact with such a structure having an N-alkylglucamine group is not particularly limited. For example, the structure is packed in a column and the extract is passed through the column. What is necessary is just to liquid. In addition, it is possible to employ a patch-type contact method in the tank, or other contact methods. ,

The contact amount of the tea extract is preferably 10 to 10 times, especially 3 ^ 7 times the volume of the structure. '

Next, in order to elute polyphenols other than non-polymer catechins, purine bases, and water-soluble components such as amino acids, proteins, and sugars from the structure, 1 to 20 times the volume of the structure, preferably 5 It is preferred to wash the structure thoroughly using ~ 15 times the amount of water. ''

The temperature of the water used for washing is not particularly limited as long as it is lower than the heat resistance temperature of the structure. In particular, normal water (5 to 30 ° C) that is neither cooled nor heated should be used. However, if hot water at 30 to 60 ° C., particularly 30 to 40 ° C. is used, the caffeine can be reduced more sufficiently.

Next, an organic solvent such as ethanol, methanol, and acetone, or a mixed solution of the organic solvent and water (for example, 30 to 80% ethanol aqueous solution, 30 to 80% methanol aqueous solution, ■ 30 to 80 % Aqueous solution of the like) is brought into contact with the above structure to elute the adsorbed fraction containing the non-polymeric strength techins, thereby recovering the tea strength technic concentrate containing the catechin composition of the present embodiment. 9 At this time, the organic solvent or the mixed solution of the organic solvent and water has a capacity of the structure.

It is preferable to use 1 to 20 times, particularly 3 times or more. ·

According to the above production method, it is possible to obtain a tea strength Tekin concentrate with a low caffeine content and reduced astringency and bitterness, and this concentrate can be used as it is as a catechin composition of the present embodiment. However, it can be further concentrated and dried to be used as the force textile composition of this embodiment.

(Examples)-Examples and comparative examples will be described below, but the scope of the present invention is not limited to the following examples. '

First, a method for dividing the strengths obtained in Examples and Comparative Examples 1 and 2 and control green tea extracts 1 to 7 (hereinafter also referred to as “sample” or “analytical sample”) About ¾.

^ Determination of total polyphenols>

The total weight of polyphenols in the catechin compositions 1 and 2 and the control green tea extracts 1 to 7 obtained in Examples and Comparative Examples (hereinafter referred to as “content”) is described in “Tea Industry Research Report, Vol. 7 1, p. 4 3-7 4, 1990 ”, in accordance with the iron tartrate colorimetric determination method, and using ethyl gallate as a standard product as a converted amount of gallic acid ( table 1 ) .

Specifically, the content of total polyphenols was quantified under the following conditions. • Preparation of iron tartrate reagent: Ferrous sulfate 'heptahydrate 10 Omg' and potassium sodium tartrate 50 Omg were dissolved in distilled water to make 10 OmL.

, 'Preparation of Phosphate Buffer: A mixture of 1/15 M aqueous sodium hydrogen phosphate solution and 1-15 M aqueous potassium dihydrogen phosphate solution was adjusted to pH 7.5.

· Preparation of standard solution: 50, 100, 1 50, 200, 250 ppm aqueous solutions of ethyl gallate were prepared. .

• Preparation of analytical sample solution: The analytical sample solution was prepared by dissolving the analytical sample in ion-exchanged water so that the concentration of each analytical sample in the aqueous solution was 250 ppm. In the case of control green tea extract 1, since the component content was low, the analysis sample solution was prepared so that the concentration of the analysis sample in water was 50,0 ppm.

(Measuring method) . · '

To 5 niL of the standard solution or analysis sample solution, 5 mL of iron tartrate reagent was added, mixed to a constant volume of 25 mL with phosphate buffer, and the absorbance at UV 540 nm was measured. .

A calibration curve was created from the measured values of the standard solution, and was used to determine the equivalent amount of ethyl gallate in the analytical sample. The 1.5-fold amount was taken as the total polyphenol content. <Quantification of non-polymer catechins and caffeine>

The s of the catechin compositions 1 and 2 and the control green tea extracts 1 to 7 obtained in the examples and comparative examples is “Jou; rnal of Food Composition and Analysis, Vol. 1 2.1

7, p. 6 75 to 6 85, 2004 ”(Table 1).

• 'Preparation of standard solution: Weigh 10 mg each of EGC, EGC g, EC, EC g, GC, GC g, C, C g, and caffeine into a 100 mL volumetric flask and add 0.5% Ascorbic acid was dissolved in an aqueous solution of 0 '. 0 1% EDTA disodium, and the volume was determined. This solution was further diluted 2-fold or 5-fold. Prior to analysis, it was passed through a 0.45 μιη Versapore filter.

• Preparation of analytical test solution: Analytical samples are dissolved in ION-exchanged water, and analytical sample solutions are prepared so that the concentration of each analytical sample in the aqueous solution is 250, ppm. In the case of the control green tea extract 1, since the component content was low, the analysis sample solution was prepared so that the concentration of the analysis sample in the aqueous solution was 500 ppm.

' (Measuring method) ..

Using HP, undiluted, 2-fold diluted, and 5-fold diluted standard solutions under the following conditions, create a calibration curve with the peak area and growth rate of each component of the chromatogram obtained. Using this, the concentration of each component in the analysis sample solution was determined.

(HP L C condition)

HP LC system: Shimadzu LC—10 0AD two-component high pressure gradient system Column: Wa kosil— II 5 C 1 8 HG (3.0 mm I. D. X 1 50 mm) Column temperature: 40 ° C '

Mobile phase A: Water monomethanol monophosphate (85: 15.5: 0.1)

'Mobile phase B: water-ethanol monoethyl acetate-phosphoric acid (85: 1/5: 1: 0: 1)

Detection: UV 280 nm

Injection volume 5 μL

Gradient program: The mobile phase was 100%, and the flow rate was 0.3 mLZ for 1 to 12 minutes from the start of the analysis, then the flow rate was linearly increased to 0.45 mLZ for 1 minute. The flow rate was maintained until 19 minutes after dropping, and then the flow rate was increased to 1.0 mLZ in 1 minute, and mobile phase B was increased from 0% to 100%. After that, the flow rate was maintained until 40 minutes. '

The content of flavonol aglycone contained in the catechin compositions 1 and 2 and the control green tea extracts 1 to 7 obtained in Examples and Comparative Examples is “Tea Industry Research Report, Vo l. 69, p. 45 to 50, 1 98 6 ”and measured by the following HP LC method (Table 2).

'Preparation of standard solution: lmg each of kaempferol, quercetin, and myricetin was weighed into a 10 OmL volumetric flask, dissolved in methanol, made up to volume, and further diluted 10'. It was passed through a 0.45 m Versapore filter before analysis. • Preparation of analytical sample solution: Dissolve the analytical sample in 25% ethanol to prepare the analytical sample solution so that the concentration of each analytical sample in the solution is 2000 ppm, and pass through a 0.45 μπι Versapore filter. I let you. In the case of Control Green Tea Extract 1, since the component content was low, the analysis sample solution was prepared so that the concentration of the analysis sample in the solution was 5000 ppm.

(Measurement method) '' Apply the standard solution to HP LC under the following conditions, create a calibration curve with the peak and area of each component in the obtained chromatogram, and the concentration of each component in the analysis sample solution. Asked. ■ ■

(HP'LC condition) ·

HP L C Equipment: Shimadzu L C—10 AD Two High Pressure Gradient System Column: & 1 ^ 0 3 1 1—11 550 1 8 HG (4.6 mm I. D. X 250 mm).

Column temperature: 40 ° C

Mobile phase A: Water-acetonitrile sodium dihydrogen phosphate dihydrate (900 mL: 100 mL: 780 mg) was mixed and adjusted to pH 2.3 with phosphoric acid.

Mobile phase B: water-acetonitrile sodium dihydrogen phosphate dihydrate (6

50 mL

35 OmL: 7 8 Omg) and adjusted to pH 2.3 with phosphoric acid Flow rate: 1 m min '

Detection: UV 3 2 5 nm

'Injection volume: 2 0 L'

Gradient program: Mobile phase B was increased from 0% to 100% linearly within 32 minutes from the start of analysis. Thereafter, mobile phase 0 was kept at 100% until 45 minutes. '' '

[Example 1]

15 g of green tea leaves were immersed in 25 OmL of hot water at 80 ° C and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 10 6 m to obtain an extract. After injecting the extract (all) obtained above into a column (φ 2 5 X 6 Omm) packed with 3 OmL of diamond CRB 0 2 which is a structure having an N-alkyldalkamine group, 30 mL of normal temperature water (about 2,0 ° C) was added, and then 15 OmL of 60% aqueous ethanol was allowed to flow, and 15 OmL of "60% aqueous ethanol eluate" was recovered. The “60% water-containing ethanol eluate” was concentrated and freeze-dried to obtain “Tea Power Textile Composition 1” 3400 mg.

[Example 2]

15 g of green tea leaves were soaked in 25 OmL of 80 ° C hot water and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 10 6 μπι to obtain an extract. After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 3 OmL of Diaion CRB 0 2, which is a structure having an N-alkylglucamine group, 45 ° C brine 30 OmL, and then 15 OmL of 60% aqueous ethanol was flowed to collect 15 OmL of "60% aqueous ethanol eluate". The 60% aqueous ethanol eluate was concentrated and freeze-dried to obtain “tea catechin composition 2” 4 S Omg. '

[Comparative Example 1]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C and extracted for 20 minutes, and the extract was obtained by solid-liquid separation with a 106, Aim metal mesh. The extract (all) was concentrated and freeze-dried to obtain 7 mg of “control green tea extract 1” 4.2.

[Comparative Example 2]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C. and extracted for 20 minutes, and solid-liquid separation was performed with a metal mesh having an opening of 10 06 im to obtain an extract.

After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 3 OmL of styrene-divinylbenzene copolymer Diaion HP 20 (manufactured by Mitsubishi Chemical Co., Ltd.), at room temperature (about 20 ° C ), 30 OmL of water, and then 18 OmL of 60% water-containing ethanol, and 15 ml of 60% water-containing ethanol eluate. 26 25454

Collected. The 60% aqueous ethanol eluate was concentrated and freeze-dried to obtain 30 mg of “control green tea extract 2”.

[Comparative Example 3]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C, extracted for 2 minutes, and solid-liquid separated with a metal mesh with an opening of 106 im to obtain an extract.

After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 30 mL¾ of strongly acidic cation exchange resin Dyaion PK 2 1 6 (Mitsubishi Chemical Corporation), at room temperature (about 20 At 1 ° C, 300 mL of water at 60 ° C) and then 80 mL of 60% ice-cold ethanol were flowed to collect 1 50 mL of 60% hydrous ethanol eluate. The “6: 0% aqueous ethanol eluate” was concentrated and freeze-dried to obtain 29 mg of “control green tea extract 3”.

[Comparative Example 4]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 106 µπι to obtain an extract.

After injecting the extract (all) into a column (φ 2 5 X 6 Omm) packed with 3 OmL of strongly basic anion exchange resin Diaion PA 3 1 6 (Mitsubishi Chemical), room temperature (about 20 At 15 ° C., 30 OmL of water and then 18 OmL of 60% aqueous ethanol were flowed to collect 15 OmL of “60% aqueous ethanol eluate”. The “60% aqueous ethanol eluate” was concentrated and lyophilized to obtain 2 mg of “control green tea extract 4”.

[Comparative Example 5] '

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C. and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 106 μπι to obtain an extract.

After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 3 Om L of weakly acidic cation exchange resin Diaion WK 1 1 (Mitsubishi Chemical), at room temperature (about 20 ° C ), 30 OmL _{N and} then 18 OmL of .60% aqueous ethanol were flowed to collect 15 OmL of "60% aqueous ethanol eluate". The “60% aqueous ethanol eluate” was concentrated and freeze-dried to obtain 30 mg of “control green tea extract 5”.

[Comparative Example 6]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C. and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 106 μηι to obtain an extract.

After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 30 mL of weakly basic anion exchange resin Diaion WA 30 (Mitsubishi Chemical Corporation), room temperature (about 20 ° C) ), 30 OmL of water and then 80 mL of 60% aqueous ethanol were allowed to flow, and 5'0mL of “60% aqueous ethanol eluate” was recovered. The “60% aqueous ethanol eluate” was concentrated and lyophilized to obtain 10 mg of “control green tea extract 6”.

[Comparative Example 7]

15 g of green tea leaves were soaked in 25 OmL of hot water at 80 ° C and extracted for 20 minutes, followed by solid-liquid separation with a metal mesh having an opening of 106 μπι to obtain an extract.

After injecting the extract (all) into a column (φ 25 X 6 Omm) packed with 30 mL of hydrophilic polybule resin Toyopearl HW-40 (manufactured by Tosohichi Co., Ltd.), room temperature (about 20 ° C) Then, 60 mL of water was added, and then 80 mL of 60% aqueous ethanol was passed through, and 15 mL of “60% aqueous ethanol eluate” was recovered. The “60% hydrous ethanol solution” was concentrated and freeze-dried to obtain “control green tea extract 7” 9 10 mg.

(table 1.)

(unit:%) As can be seen from Table 1, in Examples 1 and 2, caffeine is reduced with good selectivity, and non-polymeric strength tekins are recovered evenly. "Non-polymer catechins"

Compared with Comparative Example 1 in which Z total polyphenols show 0.88 4 to 0.94 3 and no resin treatment, the polyphenol components other than non-polymer catechins Was confirmed to be greatly reduced. In Example 2, in which hot water was used for cleaning the structure, caffeine was reduced more efficiently than in Example 1. '

On the other hand, Comparative Example 2 is a structure of only the parent body having no N-alkyldalkamine group, but caffeine was hardly removed. Also, the cation exchange resins of Comparative Example 3 and Comparative Example 5 showed a tendency to condense cuff: In the strong basic anion exchange resin of Comparative Example 4, almost no non-polymeric strength quinones were recovered. However, even with the weakly basic anion exchange resin of Comparative Example 6, the recoverability of EGC g and EC g ester-type catechins was greatly inferior.

In Comparative Example 7, the caffeine removal performance was excellent, but the recoverability of non-polymer catechins was markedly uneven, and EG C and E C non-ester catechins could not be recovered. In addition, “non-polymer strength techins / total polyphenols” was 0.740, suggesting that many polyphenol components other than non-polymer catechins remain.

(Table 2) m Example Comparative example

1 2 1 2 3 5 6 7 Genferrore 6.4 0 8.7 26 32 106.6 13.1 74.1 Quercetis 18.6 28.1 12.3 47.9 36.7 111.5 26.7 114.7 Myricetin 25.7 14.7 25.7 27.8 15.8 59.9 64.5 23.5 Flavonol total (D) 34.1 • 42.8 46.7 101.6 84.5 278 104.3 212.3 Flavonol meter / Non-polymer catechins

4.7X10 " ⁴ 5.7 XIO" ⁴ 2.1 X10 * ³ 2.8 X10 ' ³ 2.2X10. ³ 7.3 X10 " ³ 1.9 X10 * ³ 2.83 X10" ³ [(D) / (B)]

(Unit: mg / l OOg) Based on Table 2, the content of flavonol aglycone was examined.

In 1 and 2, flavonol aglycone, which is a structurally similar component of non-polymer strength techins, is reduced, and the ratio of flavonol aglycone content to non-polymer strength techins [(D) / (B )] for see the. in examples 1 and 2, 4. 7 X 1 0- ⁴ Arure, is 5. 7 X 1 0- 1/1 0 ⁴ as ⁴ (1 0 fourth power portion of 1) Whereas the content is in the order of ■, in the case of Comparative Examples 1 to 7, in the case of 1. 9 X 1 0 1 ³ to 7. 3: X 1 0 ^{-3 1/1} 0 The content was 3 digits (one ^{third of} 1 Ci), and a one-digit difference, that is, a significant difference was observed between the cold-treated example and the comparative example. .

: <Measure bitterness and astringency>

CPA (Change of membrane Potential caused by Adsorption) measurement for catechin compositions 1 and 2 and control green tea extracts 1, 2 and 7 obtained in Examples and Comparative Examples using a taste recognition device equipped with a taste sensor The bitterness and astringency of each sample was examined by measuring the CPA value by the method. The results are shown in Table 3 below. In addition, the control green tea extracts 3 to 6 obtained in Comparative Examples 3 to 6 have the component composition (particularly the composition ratio of catechin), caffeine content, and extract of the above results. In terms of the three-time yield, it was judged that there was no need to show the results from the taste sensor because no superiority to the example was found.

'Ku' taste sensor: C PA measurement method> '

Preparation of sample solution: Ion exchange water was added to each sample, and the sample was dissolved in distilled water so that the non-polymer catechin concentration in the solution was 300 ρ · pm. Separately, the sample was dissolved in distilled water so that the EGCg concentration was lOOppm.

Preparation of Washing Solution 1: A 30% ethanol solution of 100 mM potassium chloride + 10 mM potassium hydroxide was prepared. .

Washing. Preparation of solution 2: An aqueous solution of 30 mM potassium chloride + 0.3 mM tartaric acid was prepared. : '

Cleaning solution 3-5, Stabilizing solution, CPA solution: Same as cleaning solution 2.

Taste recognition device used: “S A 402 J” manufactured by Intelligent Sensor Techno Koji Co., Ltd.

Sensors used: “C 00” as the sensor for measuring bitterness, and “AE 1” as the sensor for measuring astringency.

(Measuring method)

The sensor was washed with cleaning solution 1 for 90 seconds, then cleaning solutions 2 and 3 for 1 20 seconds each. Then, the potential was measured for 30 seconds with the stabilizing solution and then with the sample solution. Cleaning liquid After washing for 3 seconds each with 4 and 5, the potential was measured with CPA solution for 30 seconds.

The potential difference obtained from “Measured potential of CPA solution” and “Measured potential of stable solution” was defined as the C PA value.

The concentration of each sample evaluated was adjusted so that the non-polymer catechin concentration would be 3 OO p pm. Fig. 2 shows the distribution of bitterness and astringency in each Example and Comparative Example based on Comparative Example 1 when prepared so that 'EG C g is lOOppm. Indicated. .

The distribution of _Λ taste was evaluated using the software attached to the taste recognition device “SA402J.”

(Table 3)

(Single 1: μV / ppm,

From Table 3, the bitterness of Example 1 and Example 2 shows that the CPA value per non-polymer catechin concentration (ie, “potential difference Z non-polymer strength textile concentration”) when using a C 00 type sensor was about 8 i The difference from Comparative Examples 1, 2, and 7 was clear, confirming that the bitterness was greatly reduced. On the other hand, the astringent taste of Example 1 and Example '2 shows that the CPA value per non-polymer catechin concentration (ie, “potential difference Z non-polymer catechin concentration”) when using the AE type 1 sensor is −1 1 V / pp ^ 1 100 μV / ppm ”, showing a higher value compared to Comparative Examples 2 and 7, confirming that the astringency is weakened. '

In addition, based on Fig. 1, when compared with Comparative Example 1 in which no resin treatment was performed, the bitter tastes of Examples 1 and 2 were perceived to be significantly attenuated, and the astringency tends to be perceived as weak. Take it. On the other hand, in Comparative Examples 2 and 7, it can be confirmed that both astringency and bitterness are significantly strongly detected from Comparative Example 1.

As can be seen from Fig. 2 ₍ as compared to Comparative Example 1, the astringency of Examples 1 and 2 is not much different, but the bitterness is significantly attenuated. The bitterness is still significantly perceived, although it is weakened to the same extent as in Example 1. In Comparative Example 7, the EGC g concentration compared to other Examples and Comparative Examples as shown in Table 1. Due to the high concentration, the extract concentration when the evaluation sample is prepared based on the EGC g concentration becomes low, so that both astringency and bitterness are attenuated and perceived. The difference in bitterness is obvious.

Consideration of the correlation between the ingredient content ratio and the taste sensor measurement value>

The correlation between the component composition ratios of the examples and comparative examples and the measurement results by the taste sensor was evaluated (FIGS. 3 and 4). As shown in Fig. 3, the CPA value per non-polymer strength techin concentration of COO showing bitterness shows a correlation with the content weight ratio of flavonolglycon and non-polymer strength techins, and the correlation coefficient is R ² = 0.9 8 High correlation with 8 2. This confirms that the bitterness of the tea catechin composition can be reduced by controlling the flavonol aglycone.

On the other hand, looking at Fig. 4, the CPA value per non-polymer catechin concentration of AE 1 showing astringency shows a correlation with the content ratio of non-polymer catechins such as ester-type strength techchins, and the correlation coefficient Showed a relatively high value of R ² = 0.89 0 6. This indicates that the astringency of the catechin composition depends on the composition ratio of the catechin, and even if the concentration of non-combined strength techin is improved, the increase in astringency can be suppressed by maintaining the composition ratio. It's suggested that it be. Industrial use bearability,

According to the present invention, it is possible to provide a force-technine composition with less bitterness despite containing a non-polymer force-tickin at a high concentration.

Claims

Catechin composition satisfying the following requirements (1) to (5).

(1): The weight ratio [(A) Z (B)] of (A) gallate catechins and (B) non-polymer catechins is 0.50 to 0.75.

(2): The weight ratio [(B) / (C)] of (B) non-polymer catechins to (C) total polyphenols is 0.80 to 0.97.

(3): (D) Flavonol aggregon and (B) Non-polymer catechins have a weight ratio [(D) / (B)] of less than 0.002.

(4): The content weight ratio [(E) / (B.)] Of (E) caffeine to (B) non-polymeric power textiles is less than 0.1. '

(5): The bitterness of the catechin composition is determined by adding an aqueous solution with a non-polymer catechin concentration of 300 ppm to the ion exchange water and using a CO 0 type sensor. (Change of membrane potential caused by adsorption) The CPA value of the aqueous solution when measured by the measuring method is 5 μVZp pm or more per non-polymer catechin concentration.

2. For the astringent taste of catechin composition, add the catechin composition to ion-exchanged water to prepare an aqueous solution with a non-polymer catechin concentration of 300 ppm, and use an AE type 1 sensor to adjust the CP A (Change of membrane Potential caused by Adsorption No j¾J The CPA value of the aqueous solution measured by the usual method 2. The catechin composition according to claim 1, wherein the catechin composition is 1 125 / ppm or more.

3. A method for producing a catechin composition, comprising bringing a tea extract or a tea extract into contact with a structure having an N-alkylglucamine group and recovering components adsorbed on the structure.

4. The tea extract or tea extract is brought into contact with a structure having an N-alkyldalkamine group and the structure is washed with water, and then the components adsorbed on the structure are recovered. The method for producing a force fkin composition according to claim 3.

5. The obtained catechin composition was prepared by adding the catechin group to ion-exchanged water to prepare an aqueous solution with a non-heavy, combined catechin concentration of 300 P pm. Change oi membrane Potential caused by Adsorption; The CPA value of the aqueous solution when measured by a measurement method is 1 125 μV / ppm or more per non-polymer catechin concentration. A method for producing a catechin composition according to Tatsumi.