JP2009165498A - Beverage containing chlorogenic acid - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a beverage containing chlorogenic acid having physiological effects such as a hypotensive effect etc., a good taste and excellent storage stability. <P>SOLUTION: The beverage comprises following components (a), (b) and (c), wherein (a) 0.1-5 wt.% of a mixture of chlorogenic acids including isochlorogenic acids, (b) 0.2-20 wt.% based on the beverage of oligosaccharides comprising mannose as a main component and at least two time by weight of the component (a), and (c) 30-99.7 wt.% of water based on the total weight of the beverage. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a chlorogenic acid-containing beverage having physiological effects such as a blood pressure lowering effect, good taste, and good storage stability.

  Heart diseases such as angina pectoris, myocardial infarction, heart failure or cerebrovascular diseases such as cerebral infarction, cerebral hemorrhage, and subarachnoid hemorrhage are said to be closely related to hypertension. Antihypertensive measures include antihypertensive drugs such as diuretics, sympathomimetic drugs, and vasodilators, which are mainly applied to patients with severe hypertension. On the other hand, the importance of general therapy aimed at improving lifestyle such as diet therapy, exercise therapy, restriction of drinking and smoking is recognized. In particular, improvement of eating habits is important, and many separation and identification of active ingredients having a blood pressure lowering action derived from foods have been made.

On the other hand, plant-derived chlorogenic acids have been known to have an antioxidative effect since long ago (Patent Documents 1 and 2). In recent years, physiologically effective effects in plants such as chlorogenic acid and catechin have attracted attention, and their use in foods and beverages has been studied. Recently, it has been known that chlorogenic acids have an excellent blood pressure lowering effect (Patent Documents 3 and 4). In order to enjoy the physiological effects of these chlorogenic acids, it was necessary to ingest 10 to 5000 mg daily for a certain period of time.
JP-B-59-001465 JP-B 61-30549 JP 2002-53464 A JP 2002-87977 JP2001-149041 JP 2001-070385 A JP2001-07410 JP 2001-073598 A JP 2001-117796 A

  Since chlorogenic acids generally have a peculiar taste accompanied by bitterness and astringency, there has been a problem of causing bitterness and astringency when blended in foods and drinks, particularly beverages. In particular, isochlorogenic acid remains as an aftertaste with a metal-like astringency (coffee roasting chemistry and technology, Toshiro Nakabayashi et al., Hirogaku Publishing, 1995). It was an obstacle to drinking. In addition, a blood pressure lowering effect could not be expected at a trace amount that did not affect the taste. Accordingly, an object of the present invention is to obtain a beverage containing a high concentration of chlorogenic acids having a blood pressure lowering effect, which can be drunk daily and has a good flavor.

  The inventors have been diligently researching and researching the use of chlorogenic acid-containing extracts obtained by extraction from plants such as green coffee beans and mate tea and their effects on flavor. As a result, it has been found that by adding a certain amount of oligosaccharide mainly composed of mannose to chlorogenic acids, astringency and bitterness can be suppressed, and a refreshing and easy-to-drink beverage can be obtained.

That is, the present invention comprises the following components (a), (b) and (c):
(A) 0.1 to 5% by weight of a chlorogenic acid mixture containing isochlorogenic acids,
(B) An oligosaccharide mainly composed of mannose is at least 2 times by weight of the component (a) and 0.2 to 20% by weight in the beverage, and (c) 30 to 99.7% by weight of water ( However, the weight% is a ratio based on the weight of the beverage)
A beverage containing the above is provided.

  The chlorogenic acid mixture (component (a)) used in the beverage of the present invention includes chlorogenic acids such as isochlorogenic acid, neochlorogenic acid, cryptochlorogenic acid, and derivatives thereof. Here, chlorogenic acid is 5-caffeoylquinic acid in which caffeic acid is ester-bonded to the 5-position hydroxyl group of quinic acid, and cryptochlorogenic acid is 4 in which caffeic acid is ester-bonded to the 4-position hydroxyl group of quinic acid. -Caffeoylquinic acid, neochlorogenic acid is 3-caffeoylquinic acid in which caffeic acid is ester-bonded to the hydroxyl group at the 3-position of quinic acid. Isochlorogenic acid is dicaffeoylquinic acid in which caffeic acid is ester-bonded to two of the hydroxyl groups at positions 3, 4 and 5 of quinic acid (for example, 3,4-dicaffeoylquinic acid, 3, 5-dicaffeoylquinic acid, 4,5-dicaffeoylquinic acid). As other chlorogenic acids, ferryl quinic acid (for example, 5-ferryl quinic acid) in which ferulic acid is ester-bonded to one of hydroxyl groups at positions 3, 4 and 5 of quinic acid, 3-position of quinic acid, For example, ferryl caffeoylquinic acid (for example, 3-ferryl-4-caffeoylquinic acid) in which caffeic acid and ferulic acid are ester-bonded to two of the 4- and 5-position hydroxyl groups. Examples of derivatives such as isochlorogenic acids and chlorogenic acids include physiologically acceptable salts such as salts and sugar esters. Among these, examples of the salt of isochlorogenic acids, chlorogenic acids, and the like include alkali metal salts such as sodium salt, potassium salt, calcium salt, and magnesium salt, and alkaline earth metal salts.

It is preferable that the isochlorogenic acid content weight ratio in a component (a) is 5 to 33 weight%.
The component (a) is preferably a plant extract, and can be extracted from either a single plant or a mixture of multiple types of plants. Examples of plants that can be used include bitter tea, mate tea, aohada, kuroganemochi, tarayou, fresh coffee beans, and southern leaves. is there. A chlorogenic acid mixture (component (a)) extracted with fresh L-ascorbic acid, citric acid-containing aqueous solution, hot water or ethanol-containing aqueous solution from fresh coffee beans that are seeds of Rubiaceae coffee (Arabica variety, Robusta variety) is particularly preferable. .

  The content of the component (a) in the beverage of the present invention is 0.1 to 5.0% by weight, preferably 0.1 to 2.0% by weight, based on the weight of the beverage. If the amount is less than 0.1% by weight, a sufficient physiological effect cannot be obtained. If the amount exceeds 5.0% by weight, the astringency due to the component (a) may be strongly recognized as an aftertaste.

The oligosaccharide mainly composed of mannose used in the beverage of the present invention (component (b)) means an oligosaccharide mainly composed of mannose, which is a monosaccharide. Here, the term “oligosaccharide” generally refers to a substance that is located between a monosaccharide and a polysaccharide and consists of a glycosyl bond of a certain minor amount of a monosaccharide molecule. That is, it is a polymer with a relatively small number of monosaccharides bound thereto. The term “oligosaccharide” refers to a composition containing a plurality of oligosaccharides having various constituent monosaccharides. The oligosaccharide “class” mainly composed of mannose refers to a composition containing a plurality of oligosaccharides having various types and numbers of constituent monosaccharides. In the present specification, the term “mannooligosaccharide” is used in the same meaning as the term “oligosaccharide mainly composed of mannose”. In the present specification, the term “oligosaccharide mainly composed of mannose” specifically means an oligosaccharide in which 1 to 10 molecules of monosaccharide mainly composed of mannose are bonded. Specifically, mannose is composed of glucose and galactose. It means an oligosaccharide mainly composed of mannose in which 1 to 10 molecules of at least one monosaccharide is bonded. In the present specification, the phrase “mainly composed of mannose” indicates that the constituent ratio of the mannose residue in the oligosaccharide is 70% by weight or more, and particularly preferably 80% by weight or more.

  Oligosaccharides mainly composed of mannose can be produced by hydrolyzing mannan. Here, the raw material mannan can be obtained by extraction from, for example, copra meal obtained from coconut coconut, fuchs, South African coconut plants Huacal Palm, tsukunei manmann, and yam mannan. Mannan thus obtained is treated by one or more methods selected from acid hydrolysis, high-temperature heat hydrolysis, enzyme hydrolysis, and microbial fermentation, preferably activated carbon treatment, adsorption resin treatment, ion A sugar mixture can be obtained by purification by a method such as an exchange resin treatment or an ion exchange membrane treatment. In addition, the oligosaccharide mainly composed of mannan which is the component (a) of the present invention is an acid hydrolysis of galactomannan contained in glucomannan, locust bean gum, guar gum and the like contained in konjac potato, lily, narcissus, and ganbana. , Treated with one or more methods selected from high temperature heat hydrolysis, enzyme hydrolysis, microbial fermentation, and separated by methods such as activated carbon treatment, adsorption resin treatment, ion exchange resin treatment, ion exchange membrane treatment It may be produced by purifying and increasing the ratio of mannose as a constituent sugar.

  In the present specification, the term “mannan” is not limited to mannan which is a polysaccharide having only d-mannose as a structural unit, but also galactomannan and glucomannan which are polysaccharides having mannose and galactose or glucose as structural units. Shall be included. In addition, d-mannose is aldohexose and the configuration of the hydroxyl group bonded to the carbon adjacent to the carboxyl group in d-glucose is reversed.

  The component (a) of the present invention is obtained by treating green coffee beans or roasted coffee beans with one or more methods selected from acid hydrolysis, high-temperature heat hydrolysis, enzyme hydrolysis, and microbial fermentation. It can be obtained by purification by a method such as activated carbon treatment, adsorption resin treatment, ion exchange resin treatment, ion exchange membrane treatment. Alternatively, an aqueous solution obtained by solubilizing a used coffee residue by one or more methods selected from acid hydrolysis, high-temperature heat hydrolysis, enzyme hydrolysis, and microbial fermentation is activated carbon treatment, adsorption resin treatment, It can also be obtained by purification by a method such as ion exchange resin treatment or ion exchange membrane treatment (Patent Documents 5-9).

  Generally, when roasted and ground coffee is extracted with a commercial extractor under high temperature and high pressure, galactose and arabinogalactan which are side chains of galactomannan contained in the roasted coffee are solubilized by hydrolysis. Therefore, the coffee extraction residue contains mannan, cellulose, arabinogalactose and the like as polysaccharides. Although cellulose is hardly decomposed and remains as a residue, an oligosaccharide mainly composed of mannose can be obtained by appropriately selecting conditions for specifically hydrolyzing mannan without decomposing cellulose.

Examples of the method for decomposing the coffee extraction residue include, but are not limited to, a method of hydrolyzing with an acid and / or high temperature, a method of decomposing with an enzyme, and a method of decomposing by microbial fermentation. Methods for hydrolyzing with an acid and / or high temperature are disclosed in JP-A Nos. 61-96947 and 2-200147. It is possible to hydrolyze spent coffee residue that comes out in a commercial coffee multistage extraction system by adding an acid catalyst in a reaction vessel or by treating it at a high temperature for a short time without adding an acid catalyst. It can also be obtained by decomposing. Although it is convenient to use a tubular plug flow reactor, good results can be obtained with any reactor that is suitable for carrying out a reaction at a relatively high temperature for a short time. By adjusting the reaction time and reaction temperature, solubilizing and hydrolyzing, mannan having a polymerization degree (DP) of 10 to 40 is decomposed into manno-oligosaccharides having DP of 1 to 10, and then separated from coffee residues to obtain manno-oligosaccharides. be able to.

  As a method for decomposing the coffee extraction residue with an enzyme, for example, the coffee extraction residue may be suspended in an aqueous medium, and for example, commercially available cellulase and hemicellulase may be added thereto and suspended while stirring. There are no particular problems with the amount of enzyme, the temperature at which it acts, and other conditions as long as it is the amount, temperature, and conditions used in normal enzyme reactions, depending on the optimum amount of enzyme used, temperature, conditions, and other factors. What is necessary is just to select suitably.

  The reaction solution containing a composition containing an oligosaccharide in which 1 to 10 molecules of a monosaccharide mainly composed of mannose obtained by the above method is bound is purified as necessary. As a purification method, decolorization is performed by bone charcoal, activated carbon, carbonation saturation method, adsorption resin, magnesia method, and the like, and desalting and deoxidation are performed by ion exchange resin, ion exchange membrane, electrodialysis and the like. The combination of the purification methods and the purification conditions may be appropriately selected according to the amount of the dye, salt, acid, etc. in the reaction solution containing the manno-oligosaccharide having 1 to 10 molecules of mannose bonded thereto and other factors. A composition prepared by hydrolyzing the coffee extraction residue with acid and / or heat and containing oligosaccharides with high purity can be used as it is added to beverages such as liquid coffee and instant coffee. Accordingly, a beverage having a richer flavor and aroma of coffee can be provided by adding the product purified by the above method.

  In addition, in this specification, a coffee extraction residue is what is called coffee extraction mash after extracting the roasting ground coffee in air | atmosphere. The coffee extraction residue used in the present invention may be a coffee extraction residue of any origin and process, whether it is extracted under normal pressure or pressure, as long as it is extracted in a normal liquid coffee or instant coffee manufacturing process. Can also be used.

  Monosaccharides such as glucose, mannose, and arabinose, mannooligosaccharides, cellooligosaccharides, and the like have been confirmed in the hydrolyzate of the coffee extraction residue. Therefore, although this oligosaccharide usually contains glucose, galactose, arabinose, cellooligosaccharide, etc., it can exhibit a sufficient effect for improving the taste of the beverage.

In this specification, the number of repeating bonds of the sugar monomer is referred to as the degree of polymerization and is represented by DP (Degree of Polymerization).
“Oligosaccharide” means a sugar polymer having a relatively small number of monosaccharides as described above. In particular, in the present specification, it refers to a polymer having 10 or less monosaccharides. In this specification, mannose (monosaccharide) is an oligosaccharide of DP1 for convenience, but strictly speaking, an oligosaccharide is composed of two or more monosaccharides. That is, from an academic point of view, a sugar having a polymerization degree of 1 (DP1) is a monosaccharide, not an oligosaccharide. However, since the oligosaccharides used in the present invention may contain monosaccharides, even in such a case, they are collectively referred to as “oligosaccharides”. That is, in the case of “an oligosaccharide mainly composed of mannose”, it should be understood that the sugar composition may contain a monosaccharide having a degree of polymerization of 1.

  “Degree of polymerization” or “DP” means the number of monosaccharides constituting the oligosaccharide. Therefore, for example, a manno-oligosaccharide in which mannose is composed of four monosaccharides has a degree of polymerization of 4, and is described as DP4.

  Of the oligosaccharide compositions, DP1 is mannose, DP2 is mannobiose, DP3 is mannotriose, DP4 is mannotetraose, DP5 is mannopentaose, DP6 is mannohexa, etc. As the DP, DP7 includes mannoheptaose and the like, and it is presumed that these binding modes are β-1,4 bonds.

  Sweetness increases by increasing the mannose content ratio (DP1 ratio) in oligosaccharides mainly composed of mannose, but when it reaches around 50%, the bitterness peculiar to mannose tends to increase and its use as a sweetener is limited. It was seen in the tendency to be. About what adjusted mannose to about 20%, there exists a refreshing feeling of aftertaste with a faint sweetness, and the taste improvement effect is recognized.

  Next, the content of the component (b) in the beverage of the present invention is 2 times or more, particularly preferably 2 to 4 times the weight of the component (a). Moreover, content of a component (b) is 0.2 to 20 weight% on the basis of the weight of a drink, Most preferably, it is 0.2 to 5 weight%. When the content of the component (b) is less than 2 times the weight of the component (a) or less than 0.2% by weight in the beverage, the effect of improving the astringency and aftertaste by the component (b) cannot be obtained, and 20% by weight. On the other hand, the specific bitterness becomes too strong.

  The beverage of the present invention contains water (component (c)) in an amount of 30 to 99.7% by weight, preferably 70 to 98.5% by weight, more preferably 85 to 98.5% by weight based on the weight of the beverage. If the water content is less than 30% by weight, it is not preferable because the taste is too thick.

Examples of the form of the beverage of the present invention include coffee, black tea, green tea, juice drink with fruit juice or vegetable juice addition, carbonated soft drink, soft drink without addition of fruit juice and the like.
The pH of the beverage of the present invention is preferably 3 to 7, particularly 5 to 6 from the viewpoint of storage stability of the component (a) having a physiological effect. Moreover, as for pH in the case of setting it as a carbonated drink, 3-4 are preferable. The pH of the beverage of the present invention is adjusted by adding sodium bicarbonate or organic edible acid. Usable edible organic acids include citric acid, fumaric acid, adipic acid, acetic acid or mixtures thereof. These acids can exist in their undissociated form or as their respective salts.

In addition to the components (a), (b) and (c), a sweetener, a fragrance component, a milk component, an emulsifier, an emulsion stabilizer and the like can be added to the beverage of the present invention. Here, examples of the sweetener include sugars such as sucrose, glucose, fructose, xylose, fructose glucose solution, sugar alcohol, and calorie-free sweetener. These sweeteners have a sugar content (Brix) of 0.1 to 10,
It is preferable to mix | blend so that it may become 3-10 especially. If the Brix exceeds 20, it is too sweet to drink. Perfume ingredients include natural or artificial flavors selected from fruit flavors, plant flavors and mixtures thereof. When milk components are used, raw milk, cow milk, whole milk powder, skim milk powder, fresh cream, concentrated milk, skim milk, partially skimmed milk, condensed milk and the like are used. Examples of emulsifiers and emulsion stabilizers are preferably gums, pectins, sucrose fatty acid esters, glycerin fatty acid esters, microcrystalline cellulose, lecithins, sorbitan fatty acid esters, polyglycerin fatty acid esters and the like.

  The beverage of the present invention can be prepared, for example, by mixing the components (a), (b), (c) and other components, filling the container, sterilizing it, and preparing a container-packed beverage. Here, examples of the container include a metal can, a polyethylene terephthalate resin (PET) bottle, a paper pack, a tube pack, and a bottle. The sterilization means is performed under the sterilization conditions stipulated in the Food Sanitation Law if it can be sterilized by heating after filling the container like a metal can. For PET bottles and paper containers that cannot be sterilized by retort, sterilization conditions equivalent to those stipulated in the Food Sanitation Law in advance, for example, UHT sterilization at high temperature and short time with a plate heat exchanger, then cooled to a certain temperature Then, it is adopted as a container-packed beverage that fills the container.

According to the present invention, a chlorogenic acid-containing beverage having physiological effects such as a blood pressure lowering effect, good taste, and good storage stability is obtained.
(Example)

EXAMPLES The present invention will be specifically described below with reference to examples, but it should not be construed that the present invention is limited to the examples.
First, the analysis of oligosaccharides mainly composed of chlorogenic acids and mannose will be described below.
(I) Analytical method of chlorogenic acids Using an ODS-2 reverse phase column, the gradient was measured with eluent A (0.05 M acetic acid 3 vol% acetonitrile aqueous solution) and eluent B (0.05 M acetic acid 100 vol% acetonitrile solution). Elute over time. Compare and identify standard products and retention times. From the area value, the weight% of chlorogenic acids is determined using caffeoylquinic acid in the fifth position as a standard substance.
(Ii) Analyzing oligosaccharides mainly composed of mannose After degreasing and deproteinizing the sample solution with hydrochloric acid, using a column for Dionex sugar analysis, detection and quantification using a differential refractometer by high performance liquid chromatography . Qualitative determination is performed from the retention time using a mixture of mannose and DP2-6 oligosaccharide standards (Nippon Biocon).

Preparation of each component (1) As the component (a), a commercially available green coffee bean extract-P (Oryza Oil Chemical Co., Ltd.) was used. Here, the content of chlorogenic acids in the extract was 45% by weight as measured according to the above-described method for analyzing chlorogenic acids, and the content of isochlorogenic acid was 11% by weight. When dissolved in water at a concentration of 1%, the bitter taste was felt at the same time, and the astringent taste with astringent taste was strongly felt in the aftertaste.
(2) Component (b) was produced by the following method.

  In order to make it easy to send the coffee extraction residue to the reactor, it was first pulverized to a particle size of about 1 mm. Next, a slurry of water and pulverized material having a total solid content of about 14% by weight was prepared and heat-treated in a 4 m hot plug flow reactor. Pumped to the plug flow reactor with high pressure steam at a rate corresponding to a residence time of 8 minutes and maintained at about 220 ° C. using a 6.35 mmφ orifice. Thereafter, the reaction was stopped by spraying under atmospheric pressure. The resulting slurry was filtered to separate a liquid containing soluble solids from insoluble solids. This soluble solid content-containing liquid is decolorized with activated carbon and an adsorption resin, further desalted with an ion exchange resin, and then concentrated and dried to contain an oligosaccharide in which 1 to 10 molecules of monosaccharides mainly composed of mannose are bonded. The product was obtained in 14% yield.

  The components in the coffee oligosaccharide of the composition containing the oligosaccharide thus obtained were in the proportions shown in Table 1. As a result of sensory evaluation using this as a 1% aqueous solution, a refreshing aftertaste sweetness was felt although the bitterness was faintly felt.

Oligosaccharide DP1 as mannose, DP2 as mannobiose, DP3 as mannotriose, DP4 as mannotetraose, DP5 as mannopentaose, DP6 as mannohexaose, etc. As DP7 or higher, DP7 is mannoheptaose or the like, DP8 is mannooctaose or the like, DP9 is mannononaose or the like, DP10 is mannodekaose or the like, and the binding mode is β-1,4 glycoside bond Presumed.
(3) Using commercially available regular coffee (Ajinomoto General Foods Co., Ltd., trade name: MAXIM Special Blend) and using 160 ml of boiling water for 8 g of ground roasted coffee beans, about 100 ml of extracted coffee bean extract (Brix1 .2%) was obtained, and the components (a) and (b) were added to adjust the concentration (% by weight) shown in Table 2. Eight skilled panelists were selected for sensory evaluation of taste. In addition, the score of evaluation in Table 2 is an average score of each panel scored (0 to 4 points) according to the following criteria.
(Scoring criteria) Feel either astringency or astringency very strongly: 4 points, feel astringency or astringency strongly: Feel 3 points, astringency or astringency: 2 points, astringency, Feel either faint or faint: 1 point, no astringency, no nasty taste: 0 points As is clear from Table 2, when component (b) is less than 2 times the weight of component (a), the component (a)
It has a strong astringent taste and astringency. Moreover, if it is 2 weight times or more and 4 weight times or less, the astringency and astringent taste of a component (a) will be suppressed with the increase in quantity. On the other hand, when component (b) exceeds 20 weight%, it turned out that a taste becomes too bitter. Moreover, even if it added sugar twice a weight instead of the oligosaccharide, only the sweetness became strong and the effect which suppresses astringency was not recognized.

  Place 10 kg of roasted coffee beans in a basket-type extraction container, supply hot water at 80 kg / hr under atmospheric pressure, cool immediately after extraction, and insoluble solid with a ball-type centrifuge (Westfalia SA-20) The extracted roasted coffee bean extract with a solid content of 10.4% was obtained. Using this, a coffee drink was prepared with the formulation shown in Table 3, filled into a 250 ml steel can container, and sealed and retort sterilized (110 ° C., 3 minutes).

  In the same manner as in Example 2, an extracted roasted coffee bean extract having a solid content of 10.4% was obtained, and this was used to prepare a coffee drink containing milk (milk is Meiji Dairy ( Co., Ltd., trade name: using Meiji's delicious milk). This beverage was filled in a 250 ml steel can container, sealed and then retort sterilized (120 ° C., 10 minutes).

  Using black tea leaves (manufactured by BBL Japan Co., Ltd.), a black tea extract obtained by extracting 300 g of boiling water with respect to 5 g of the tea leaves (solid content concentration: 0.3%) as shown in Table 3 A black tea beverage was prepared and filled and sterilized in the same manner as in Example 2.

  Using lemon juice (fresh lemon juice), a lemon juice drink was prepared according to the formulation shown in Table 3, and filled and sterilized in the same manner as in Example 2.

Comparative Example 2-5

  As a comparative example, a beverage was prepared with the same formulation as in Example 2-5 except that the oligosaccharide of component (b) of the present invention was not added. The sensory evaluation was performed and scored in the same manner as in the examples. As a result, as is apparent from Table 3, the beverages of the present invention to which oligosaccharides were added and used were greatly improved in astringency and aftertaste, good in flavor, and stable without occurrence of scum. .

Claims (2)

The following components (a), (b) and (c):
(A) 0.1 to 5% by weight of a chlorogenic acid mixture containing isochlorogenic acids,
(B) An oligosaccharide mainly composed of mannose is at least 2 times by weight of the component (a) and 0.2 to 20% by weight in the beverage, and (c) 30 to 99.7% by weight of water ( However, the weight% is a ratio based on the weight of the beverage)
Beverages containing.   The beverage according to claim 1, wherein components (a) and (b) are derived from coffee beans.