JP4667317B2 - Method for producing coffee composition - Google Patents

Description

  The present invention relates to a method for producing a coffee composition and a method for producing soluble coffee.

It has been reported that chlorogenic acid, caffeic acid, ferulic acid and the like exhibit excellent blood pressure lowering action (Patent Documents 1 to 3). However, coffee beverages known to contain a large amount of chlorogenic acids do not have a clear blood pressure lowering effect, and there is a report that blood pressure is increased (Non-patent Document 1).
JP 2002-363075 A JP 2002-22062 A JP 2002-53464 A Eur. J. Clin. Nutr., 53 (11), 831 (1999)

  An object of the present invention is to provide a coffee composition that has an excellent blood pressure lowering action and can be taken in the same manner as ordinary coffee, and a method for producing soluble coffee.

  Therefore, the present inventor has paid attention to the fact that coffee beverages do not show sufficient blood pressure lowering action despite containing chlorogenic acids, and as a result of various studies on the relationship between blood pressure lowering action and coffee beverage ingredients, It has been found that hydroxyhydroquinone contained in beverages inhibits the blood pressure lowering action of chlorogenic acids. As a result of further investigation, a porous adsorbent whose pore radius is 0.7 nanometer (nm) or less and whose pore volume is 30% or more of the entire pore volume of the porous adsorbent is washed with an aqueous solvent. After that, by bringing the coffee extract into contact with the porous adsorbent, the hydroxyhydroquinone content is lowered to a level that does not inhibit the blood pressure lowering action of chlorogenic acid while maintaining the amount of chlorogenic acids in the coffee composition within a certain range. I found that I can do it.

That is, according to the present invention, a porous adsorbent having a pore radius of 0.7 nanometer (nm) or less is 30% or more of the total pore volume of the porous adsorbent is washed with an aqueous solvent. Then, the manufacturing method of the coffee composition which makes a coffee extract liquid contact the said porous adsorbent is provided.
In the present invention, the porous adsorbent having a pore radius of 0.7 nanometer (nm) or less and a volume of pores of 30% or more of the whole is washed with an aqueous solvent, and then the coffee extract is removed from the porous extract. A method for producing a coffee composition comprising 0.01 to 1% by mass of chlorogenic acids and having a hydroxyhydroquinone content of less than 0.1% by mass of the amount of chlorogenic acids Is to provide.
In the present invention, the porous adsorbent having a pore radius of 0.7 nanometer (nm) or less and a volume of pores of 30% or more of the whole is washed with an aqueous solvent, and then the coffee extract is removed from the porous extract. A coffee liquor containing 0.01 to 1% by mass of chlorogenic acids and having a hydroxyhydroquinone content of less than 0.1% by mass of the amount of chlorogenic acids, and then bringing the coffee liquor into contact with the adsorbent The present invention provides a method for producing soluble coffee, characterized by spray drying or freeze-drying. By dissolving this soluble coffee in warm water or the like, a coffee liquid containing 0.01 to 1% by mass of chlorogenic acids and having a hydroxyhydroquinone content of less than 0.1% by mass of the amount of chlorogenic acids can be easily prepared. can do.

  According to the production method of the present invention, a coffee composition having an excellent blood pressure lowering effect can be obtained.

The coffee extract used in the method of the present invention can be prepared from an extract from coffee beans, an aqueous solution of instant coffee, or the like.
In the present invention, the type of coffee beans used to obtain the coffee extract is not particularly limited, and examples thereof include Brazil, Colombia, Tanzania, mocha, kilimangelo, mandelin, and blue mountain. Coffee beans include Arabica and Robusta. One kind of coffee beans may be used, or a plurality of kinds may be blended. There is no particular limitation on the method of making coffee beans by roasting coffee beans, and there are no restrictions on the roasting temperature and roasting environment, but the preferred roasting temperature is 100 to 300 ° C., more preferably 150-250 ° C. Preferred roasting methods include a direct fire method, a hot air method, and a semi-hot air method, and a type having a rotating drum is more preferable. Moreover, it is preferable to cool to 0-100 degreeC within 1 hour after roasting from a viewpoint of flavor, More preferably, it is 10-60 degreeC.

  As roasting degree of roasted coffee beans, there are light, cinnamon, medium, high, city, full city, french and italian, and light, cinnamon, medium, high and city are preferred. The L value obtained by measuring the roasting degree with a color difference meter is usually 10 to 30, preferably 15 to 25. Note that coffee beans having different roasting degrees may be mixed.

There is no limitation on the extraction method from coffee beans, for example, using roasted coffee beans or pulverized products thereof using an extraction solvent such as water to hot water (0 to 100 ° C.) or steam, or pressurized steam of 100 ° C. or higher. The method of extracting for 2 seconds-120 minutes is mentioned. The extraction temperature is preferably 50 to 100 ° C., particularly preferably 80 to 100 ° C., and particularly preferably 90 to 100 ° C. from the viewpoint of the amount of chlorogenic acids recovered. The degree of pulverization is as follows: extra fine grinding (0.250-0.500 mm ), fine grinding (0.300-0.650 mm ), medium fine grinding (0.530-1.000 mm ), medium grinding (0.650-1.500 mm ), medium coarse grinding, coarse grinding (0.850- 2.100 mm ), ultra-coarse grind (1.000-2.500 mm ), and cut products having an average particle diameter of 3 mm, 5 mm, and 10 mm. Examples of the extraction method include a boiling type, an espresso type, a siphon type, and a drip type (paper, flannel, etc.).

Examples of the extraction solvent include water, alcohol-containing water, milk, carbonated water, and the like. The pH of the extraction solvent is usually 4 to 10, and 5 to 7 is preferable from the viewpoint of flavor. In addition, a pH adjuster such as sodium bicarbonate, sodium bicarbonate, L-ascorbic acid, and L-alcorbic acid Na may be contained in the extraction solvent, and the pH may be adjusted as appropriate.
The amount of extraction solvent is preferably 0.1 to 100 times the amount of 1 part by weight of coffee beans, and preferably 1 to 30 times the amount from the viewpoint of the amount of chlorogenic acids recovered.

  The extractor includes paper drip, non-woven drip, siphon, nel drip, espresso machine, coffee machine, percolator, coffee press, ibrick, water drip, boiling, coffee or a bag-like non-woven bag structure that can be suspended in a coffee cup. Body, a drip extractor having a structure (such as mesh or punching metal) capable of substantially separating coffee beans from the spray nozzle at the top, and substantially separating coffee beans from the top and / or bottom. Examples include a column extractor having a structure (such as a mesh or punching metal). The extractor may have a structure that can be heated or cooled (for example, an electric heater, a jacket through which hot water, steam, or cold water can flow).

  Examples of the extraction method include a batch extraction method, a semi-batch extraction method, and a continuous extraction method. The extraction time of the batch extraction method or the semi-batch extraction method is preferably 10 seconds to 120 minutes, and more preferably 30 seconds to 30 minutes, from the viewpoint of flavor.

  The coffee extract used in the present invention is one in which coffee beans are used in an amount of 1 g or more, preferably 2.5 g or more in terms of green beans per 100 g of coffee extract. More preferably, 5 g or more of coffee beans are used.

  The coffee extract used in the present invention contains 0.01 to 1% by mass of chlorogenic acids and about 1% by mass of hydroxyhydroquinone in the amount of the chlorogenic acids. Here, as the chlorogenic acids, there are known three types of monocaffeoylquinic acid, ferlaquinic acid, and dicaffeoylquinic acid, and the content of chlorogenic acids is represented by the total amount thereof. Examples of monocaffeoylquinic acid include one or more selected from 3-caffeoylquinic acid, 4-caffeoylquinic acid, and 5-caffeoylquinic acid. Further, examples of ferulquinic acid include one or more selected from 3-ferlaquinic acid, 4-ferlaquinic acid, and 3-ferlaquinic acid. Examples of dicaffeoylquinic acid include one or more selected from 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid, and 4,5-dicaffeoylquinic acid.

  The content of the chlorogenic acids can be measured by high performance liquid chromatography (HPLC). As a detection means in HPLC, UV detection is generally used, but it can also be detected with higher sensitivity by CL (chemiluminescence) detection, EC (electrochemical) detection, LC-Mass detection, or the like.

  The hydroxyhydroquinone content can be measured by HPLC. As a detection means in HPLC, UV detection is generally used, but it can also be detected with higher sensitivity by CL detection, EC detection, LC-Mass detection, or the like. In addition, in measuring the hydroxyhydroquinone content by HPLC, it can also measure after concentrating a coffee solution, However, It is preferable to adjust to pH 3 or less beforehand by addition, such as phosphoric acid or hydrochloric acid.

  In addition, chlorogenic acids extracted from raw coffee beans and / or finely roasted beans having an L value of 30 to 60 can be added to the raw coffee extract of the present invention as necessary.

In the present invention, in order to reduce the hydroxyhydroquinone content, the pore volume with a pore radius of 0.7 nanometer (nm) or less is 30% or more with respect to the total pore volume of the porous adsorbent. Adsorbent is used. Furthermore, the pore volume with a pore radius of 0.7 nanometer (nm) or less, preferably 0.2 to 0.7 nm, is 30 to 99%, more preferably 30 to 99% with respect to the total pore volume of the porous adsorbent. It is preferably 95%, more preferably 50 to 95%, particularly preferably 70 to 90%. A porous adsorbent having a pore radius of less than 0.7 nanometers (nm) and a pore volume of less than 30% of the total pore volume of the porous adsorbent has a low selectivity for removing hydroxyhydroquinone. Therefore, it is not preferable. Here, the pore radius and the capacity of the porous adsorbent are values measured by the MP method in the region where the pore radius is 1 nanometer (nm) or less, and in the region where the pore radius exceeds 1 nanometer (nm). Is a value measured by the KJH method, and whether or not the pore volume with a pore radius of 0.7 nanometer (nm) or less is 30% or more with respect to the total pore volume of the porous adsorbent Can be determined from pore distribution curves obtained by the MP method and the KJH method.
MP method pore radius 1 nanometer (nm) or less Total pore volume: VM (cm ³ / g)
Total pore volume in excess of 1 nanometer (nm) by the KJH method: VK (cm ³ / g)
Pore radius by MP method 0.7 nanometer (nm) or less Pore volume: V7 (cm ³ / g)
Ratio of pore volume having a pore radius of 0.7 nanometer (nm) or less to the total pore volume of the porous adsorbent: V% = V7 / (VM + VK) × 100%

  The MP method is a pore measurement method described in a literature (Colloid and Interface Science, 26, 46 (1968)), and the KJH method is a literature (J. Amer. Chem. Soc., 73, 373 (1951)). The pore measuring method described in 1. It can be measured at Sumika Analysis Center, Inc., Toray Research Center, etc. As a pore measuring device, there is BELSORP-mini and the like, which can be measured using a nitrogen adsorption method.

  The porous adsorbent has an average pore radius in the micropore region of 0.5 nanometer (nm) or less, more preferably 0.2 to 0.5 nanometer (nm), particularly 0.3 to 0.00. It is preferably in the range of 5 nanometers (nm). Here, the micropore region indicates 1 nanometer (nm) or less, and the average pore radius is a value of the pore radius indicating the peak top of the pore distribution curve obtained by the MP method.

  As the kind of porous adsorbents, the carbonaceous adsorbent described in the adsorption technology handbook-process, material, design- (issued on January 11, 1999, NTS, supervisor: Atsushi Takeuchi) Silica / alumina-based adsorbent, polymer adsorbent, chitosan resin, etc. can be used. From the viewpoint of leaving the coffee flavor, a carbonaceous adsorbent is preferred.

As the carbonaceous adsorbent, powdered activated carbon, granular activated carbon, and activated carbon fiber are preferable from the viewpoint of selective adsorption of hydroxyhydroquinone. Furthermore, activated carbon fiber is preferable because the flavor of the extract is good and the amount of chlorogenic acids recovered is large.
As raw materials for powdered and granular activated carbon, there are sawdust, coal, coconut husk, etc., but coconut husk activated carbon derived from coconut husk is preferable. Industrial Co., Ltd.), Kuraray Coal GL (Kuraray Chemical Co., Ltd.) and the like can be used. In particular, activated carbon activated by a gas such as water vapor is preferable.
Activated carbon fibers include polyacrylonitriles such as Fineguard (manufactured by Toho Rayon), pitches such as ador (manufactured by Unitika), phenols such as krativ (manufactured by Kuraray), and K filters (manufactured by Toyobo). Such cellulose type, other phenol type, and cotton type.
In addition, the shape of the porous adsorbent is not particularly limited. In addition to ordinary powder and granular materials, the adsorbent is kneaded into fibers, molded with each porous adsorbent, cellulose, nonwoven fabric, and binder. It may be molded.

  The particle size of the porous adsorbent is not particularly limited, but if it is too large, the contact area with the adsorbent becomes small and the adsorption speed becomes slow. From the above points, the average particle size is preferably 0.01 μm or more and 2 mm or less, more preferably 50 μm or more and 400 μm or less, and particularly preferably 50 μm or more and 200 μm or less.

From the viewpoint of the effect of reducing the hydroxyhydroquinone content, the pore volume of the porous adsorbent by the MP method is preferably 0.5 cm ³ / g or more, more preferably 0.5 to ² cm ³ / g, and further preferably 6-1 cm < ³ > / g is preferable.

  These porous adsorbents are used after washing with an aqueous solvent. By washing with an aqueous solvent, the removal rate of hydroxyhydroquinone from the coffee extract by the porous adsorbent treatment is improved. Examples of the aqueous solvent used for washing include water, tap water, ion-exchanged water, pure water, ethanol aqueous solution, and saline. The temperature of the aqueous solution used is preferably 5 to 95 ° C, more preferably 15 to 90 ° C, and particularly preferably 40 to 85 ° C.

  The amount of the aqueous solvent used for washing is preferably 100 to 20000 parts by mass, more preferably 200 to 2000 parts by mass, and particularly preferably 400 to 1000 parts by mass with respect to 100 parts by mass of the porous adsorbent. Examples of the washing means include a method of adding a porous adsorbent to an aqueous solvent and stirring for 1 minute to 2 hours, a method of introducing an aqueous solvent into a column packed with the porous adsorbent, and the like. The pressure for washing with an aqueous solvent is preferably 0 to 1 MPa. As a method for applying pressure at this time, there are a method using a gas, preferably an inert gas (nitrogen, argon gas, etc.), a method using a pressure kettle (heat), and a method of applying pressure to an extract in a column flow method. Can be mentioned.

  Next, the coffee extract is brought into contact with the washed porous adsorbent. The amount of the porous adsorbent used is preferably 10% by mass or more, more preferably 10 to 200% by mass, based on the solid content of the raw coffee extract. The soluble solid content of the raw coffee extract can be measured using a digital differential densitometer DD-7, a digital refractometer RX-5000, a digital refractometer RX-5000α (Atago Co., Ltd.) and the like.

Examples of the contact treatment means include a batch method and a column flow method.
As a batch method, a porous adsorbent may be removed after adding a porous adsorbent to a liquid containing a coffee extract and stirring at −10 to 100 ° C. for 0.5 minutes to 5 hours. Examples of the atmosphere during the treatment include air and inert gas (nitrogen gas, argon gas, helium gas, carbon dioxide, carbon dioxide gas), but inert gas is preferred from the viewpoint of flavor.

  In the column passing method, a porous adsorbent is filled in an adsorption column, a liquid containing a coffee extract is passed from the lower or upper part of the column, and discharged from the other. The ratio L / D of the adsorbent filling height L and D (diameter) is usually 0.1 to 10. The amount of the porous adsorbent packed in the column may be an amount that can be packed in the adsorption column before passing the liquid. It is sufficient that at least one of the upper and lower stages of the adsorption column has a separation structure which has a mesh (net) or punching metal and does not substantially leak the porous adsorbent. The opening diameter of the separation structure may be smaller than the average particle diameter of the porous adsorbent, preferably an opening of 1/2 or less, particularly preferably 1/3 or less of the average particle diameter of the porous adsorbent. A specific opening diameter is 0.1 to 1000 μm. The adsorption treatment temperature of the liquid containing the coffee extract is −10 to 100 ° C., and preferably 0 to 40 ° C. from the viewpoint of flavor. The residence time (K / QC) of the liquid flow rate (QC [g / min]) containing the coffee extract with respect to the porous adsorbent amount (K [g]) in the adsorption column is 0.5 to 300 minutes.

  It is possible to remove the fine powder of the porous adsorbent from the coffee composition by a solid-liquid separation process. As a method for removing the fine powder of the porous adsorbent, a method selected from a centrifugal separator, filter paper, zeta potential filter, filter press, diatomaceous earth filtration and the like can be selected. From the viewpoint of flavor and texture, it is usually preferable to remove fine powder of 1 μm or more, preferably 0.5 μm or more, particularly preferably 0.1 μm or more, by the solid-liquid separation step.

  By the contact treatment, hydroxyhydroquinone in the raw coffee extract is remarkably removed. Accordingly, the coffee composition obtained by the method of the present invention contains 0.01 to 1% by mass of chlorogenic acids, but preferably 0.05 to 1% by mass in terms of blood pressure lowering action and taste.

  The coffee composition obtained by the method of the present invention has a hydroxyhydroquinone content of less than 0.1% by mass based on the amount of chlorogenic acids. If the hydroxyhydroquinone content is less than 0.1% by mass with respect to the amount of chlorogenic acids, the blood pressure lowering action of chlorogenic acids is exhibited. The hydroxyhydroquinone content is more preferably 0.02% by mass or less based on the amount of chlorogenic acids. If the hydroxyhydroquinone content is 0.02% by mass or less with respect to the amount of chlorogenic acids, the blood pressure lowering action of chlorogenic acids becomes even more remarkable. Here, the hydroxyhydroquinone content in the composition of the present invention may be zero.

  Moreover, raw milk, cow milk, whole milk powder, skim milk powder, fresh cream, concentrated milk, skimmed milk, partially skimmed milk, condensed milk, etc. can be suitably blended in the coffee composition produced by the method of the present invention.

In the coffee composition obtained by the method of the present invention, the ratio of chlorogenic acids to the coffee solids, that is, the mass ratio of chlorogenic acids / coffee solids is preferably 0.025 or more, more preferably 0.03 to 0.00. 9, particularly preferably 0.08 to 0.4. The coffee solid content here is not based on all the solid content in the beverage or the composition but is defined based on the following calculation formula, and the unit is based on mass.
Coffee solids [mass%]
= Brix-[milk solid content + sugar + dietary fiber + carbohydrate excluding sugar]
Here, each item described above is defined by the following calculation formula.
Milk solid content = lipid + 1.8 x lactose Sugar = glucose + fructose + sucrose + maltose

Here, the measurement method of each item is quantified by the following method.
-Brix: Represented by a refractometer reading for sugar at 20 ° C (° Brix).
For example, it can be analyzed with Atago RX-5000 (manufactured by Atago).
Latest Soft Drinks (issued on September 30, 2003, published by Kosuge Co., Ltd., page 243)
-Lipid: Rosette Gottlieb method-Lactose: High-performance liquid chromatographic method-Sugar: Glucose, fructose, sucrose, maltose: High-performance liquid chromatographic method-Carbohydrate excluding saccharide: High-performance liquid chromatographic method `` Is a saccharide added to the coffee composition, such as oligosaccharides such as trisaccharides and tetrasaccharides, sugar alcohols such as erythritol, xylitol, sorbitol, maltitol, and reduced starch syrup, polysaccharides such as starch, etc. Lactose from sugar-based sweeteners described in the literature (Sweetness genealogy and its science: published on June 20, 1986, published by Korin Co., Ltd., page 90, Table 2-1 Main sugar-based sweeteners) These are defined as monosaccharides, disaccharides, oligosaccharides and sugar alcohols excluding glucose, fructose, sucrose and maltose, which are four types defined as saccharides and sugars.
・ Dietary fiber: High-performance liquid chromatographic method (enzyme-HPLC method)
Here, dietary fiber refers to the nutrition labeling standard system for foods, second edition (issued July 1, 1999, edited by the Japan Health and Nutrition Food Association, Nutrition Food Department, pages 46-51). It refers to the object of analysis by the method.
In addition, the analysis method for each item above is the product test series (12-5) published by Tokyo Metropolitan Consumer Life Center: How much canned coffee-sugar and caffeine is? -Analytical methods described in (issued in November 2001) and notification of the Director of Newly Developed Food Health Countermeasures Office, Food Health Division, Ministry of Health and Welfare, April 26, 1999; Concerning analytical methods for nutritional components, etc.

Moreover, if the coffee composition obtained as described above is spray-dried or freeze-dried, a soluble coffee capable of preparing a coffee composition having the composition can be obtained. Further, by concentrating the coffee composition obtained as described above, a pasty coffee capable of preparing a coffee composition having the composition is obtained. In addition, the coffee composition obtained as described above is appropriately prepared and sterilized and then filled into a container such as a plastic bottle or a cup and then tightened, or filled into a container such as a can and sterilized after being sterilized and then sterilized. A beverage is obtained.
Here, as the spray drying method and the freeze drying method, specifically, in the case of spray drying, for example, the coffee composition is sprayed from a nozzle and is usually in hot air at 150 to 310 ° C., preferably about 210 to 310 ° C. Can be made into a porous, water-soluble coffee powder. On the other hand, in the case of freeze-drying, for example, the coffee composition is frozen in liquid nitrogen or a freezer, pulverized, sieved, and then sublimated in vacuum to reduce the moisture to 3% or less. Can be.

  The coffee composition and soluble coffee obtained by the present invention contain an effective amount of chlorogenic acids having a blood pressure-lowering action, and the amount of hydroxyhydroquinone that inhibits the blood pressure-lowering action of chlorogenic acids is reduced. It is useful as a pharmaceutical composition for lowering blood pressure and a beverage for lowering blood pressure. In addition, the coffee composition obtained by the present invention is useful as a container-packed coffee beverage because the amount of hydroxyhydroquinone regenerated is small even after heat sterilization.

Example 1
The column was filled with 80 g of activated carbon (WH2CLSS, manufactured by Nippon Enviro), and 4923 g of pure water at 20 ° C. was passed through the column at a flow rate of 164 [g / min]. Thereafter, 533 g of coffee extract was passed through the coffee extract at a flow rate of 21 [g / min], activated carbon treatment was performed, pure water was passed through the passed column, and the coffee extract in the column was recovered. .
The treated activated carbon-containing coffee composition was filtered through a 0.5 μm filter, and the activated carbon was removed to obtain a coffee composition. Baking soda was added to the coffee composition according to the formulation shown in Table 1 until the pH reached a specified value to prepare a coffee beverage composition. The coffee beverage composition was filled into a beverage can and sealed, and then sterilized using a retort sterilizer under the sterilization conditions (temperature x time) shown in Table 1 to obtain a product.

Example 2
A coffee beverage composition was prepared by adding baking soda to the coffee extraction treatment liquid obtained in Example 1 until the pH reached a specified value according to the formulation shown in Table 1. The coffee beverage composition was concentrated to Brix 25% using a vacuum concentrator, and an instant coffee product was obtained using a spray dryer.
2 g of instant coffee was poured into 100 g of hot water at 80 ° C. to obtain a coffee beverage.

Comparative Example 1
The same operation as in Example 1 was performed except that pure water was not passed through the column to obtain a coffee beverage composition.

Comparative Example 2
The same operation as in Example 1 was performed except that KL (manufactured by Nippon Enviro) was used as the activated carbon and the container was not packed and sterilized to obtain a coffee beverage composition.

  In addition, the chlorogenic acid in the coffee solutions of Examples 1 and 2 and Comparative Examples 1 and 2 was measured under analytical condition K, and hydroxyhydroquinone was measured with an HPLC-electrochemical detector.

Analysis method of chlorogenic acids: Analysis condition K
A method for analyzing chlorogenic acids in a packaged coffee beverage or coffee composition is as follows. The analytical instrument used was HPLC. The model numbers of the unit units are as follows. UV-VIS detector: L-2420 (Hitachi High-Technologies Corporation), column oven: L-2300 (Hitachi High-Technologies Corporation), pump: L-2130 (Hitachi High-Technologies Corporation), autosampler: L-2200 (Hitachi High-Technologies Corporation), column: Cadenza CD-C18 inner diameter 4.6 mm × length 150 mm, particle diameter 3 μm (intact Inc.).
The analysis conditions are as follows. Sample injection volume: 10 μL, flow rate: 1.0 mL / min, UV-VIS detector set wavelength: 325 nm, column oven set temperature: 35 ° C., eluent A: 0.05 M acetic acid, 0.1 mM 1-hydroxyethane-1 , 1-diphosphonic acid, 10 mM sodium acetate, 5 (V / V)% acetonitrile solution, eluent B: acetonitrile.

Concentration gradient condition Time Eluent A Eluent B
0.0 minutes 100% 0%
10.0 minutes 100% 0%
15.0 minutes 95% 5%
20.0 minutes 95% 5%
22.0 minutes 92% 8%
50.0 minutes 92% 8%
52.0 minutes 10% 90%
60.0 minutes 10% 90%
60.1 minutes 100% 0%

In HPLC, 1 g of a sample was precisely weighed, made up to 10 mL with eluent A, filtered through a membrane filter (GL chromatodisc 25A, pore size 0.45 μm, GL Sciences Inc.), and subjected to analysis.
Retention time of chlorogenic acids (unit: minutes)
(A ¹ ) Monocafe oil quinic acid: 5.3, 8.8, 11.6, total 3 points (A ² ) Ferlaquinic acid: 13.0, 19.9, 21.0, total 3 points (A ³ ) Dicaffeoylquinic acid: 36.6, 37.4, 44.2 in total. From the area values of the nine types of chlorogenic acids determined here, 5-caffeoylquinic acid was used as a standard substance, and the mass% was determined.

Analysis method of hydroxyhydroquinone by HPLC-electrochemical detector The analysis method of hydroxyhydroquinone in coffee beverage is as follows. The analytical instrument used was a Couloarray system (model 5600A, development / manufacturing: ESA, USA, import / sales: MC Medical Co., Ltd.) which is an HPLC-electrochemical detector (coulometric type). The names and model numbers of the constituent units of the apparatus are as follows.
Analytical Cell: Model 5010, Couloarray Organizer, Couloarray Electronics Module / Software: Model 5600A, Solvent Delivery Module: Model 582, Gradient Mixer, Autosampler: Model 542, Pulse Damper, Degasser: Degasys Ultimate DU3003, Column Oven : 505. Column: CAPCELL PAK C18 AQ inner diameter 4.6 mm × length 250 mm Particle diameter 5 μm (Shiseido Co., Ltd.).

The analysis conditions are as follows.
Sample injection volume: 10 μL, flow rate: 1.0 mL / min, applied voltage of electrochemical detector: 0 mV, column oven set temperature: 40 ° C., eluent A: 0.1 (W / V)% phosphoric acid, 0. 1 mM 1-hydroxyethane-1,1-diphosphonic acid, 5 (V / V)% methanol solution, eluent B: 0.1 (W / V)% phosphoric acid, 0.1 mM 1-hydroxyethane-1,1 -Diphosphonic acid, 50 (V / V)% methanol solution.

  Eluents A and B were prepared by using distilled water for high performance liquid chromatography (Kanto Chemical Co., Ltd.), methanol for high performance liquid chromatography (Kanto Chemical Co., Ltd.), phosphoric acid (special grade, Wako Pure Chemical Industries, Ltd.) )), 1-hydroxyethane-1,1-diphosphonic acid (60% aqueous solution, Tokyo Chemical Industry Co., Ltd.).

Concentration gradient condition Time Eluent A Eluent B
0.0 minutes 100% 0%
10.0 minutes 100% 0%
10.1 min 0% 100%
20.0 minutes 0% 100%
20.1 minutes 100% 0%
50.0 minutes 100% 0%

  After accurately weighing 5 g of the sample, it was made up to 10 mL with 0.5 (W / V)% phosphoric acid, 0.5 mM 1-hydroxyethane-1,1-diphosphonic acid, 5 (V / V)% methanol solution. The solution was centrifuged to obtain an analytical sample of the supernatant. This supernatant was passed through Bond Elut SCX (solid phase filling amount: 500 mg, reservoir volume: 3 mL, GL Sciences Inc.), and about 0.5 mL of the first passage solution was removed to obtain a passage solution. The passing liquid was filtered through a membrane filter (GL chromatodisc 25A, pore size 0.45 μm, GL Sciences Inc.) and immediately subjected to analysis.

  In the analysis under the above conditions of the HPLC-electrochemical detector, the retention time of hydroxyhydroquinone was 6.38 minutes. From the obtained peak area value, mass% was determined using hydroxyhydroquinone (Wako Pure Chemical Industries, Ltd.) as a standard substance.

The coffee extract and activated carbon used in Examples and Comparative Examples are shown below.
(Activated carbon)

(1) Nippon Enviro-made activated carbon: WH2C 42/80 LSS (particle size 200-400 μm)
Results of pore volume measurement by BELSORP-mini Total pore volume 0.837 mL / g, 0.7 nm or less pore volume 0.651 mL / g
MP70 pore volume 0.670mL / g
Average pore radius in the micropore region 0.35 nm
0.7 nm or less pore volume / total pore volume = 78%
0.2-0.7 nm pore volume / total pore volume = 78%

(2) Nippon Enviro activated carbon: KL (particle size 500-2000 μm)
Results of pore volume measurement by BELSORP-mini Total pore volume 2.051 mL / g, 0.7 nm or less pore volume 0.479 mL / g
Pore volume by MP method 0.771mL / g
Average pore radius in the micropore region 0.6 nm
0.7 nm or less pore volume / total pore volume = 23%
0.2-0.7 nm pore volume / total pore volume = 23%
(Coffee extract)
Coffee extract (manufactured by Takasago Coffee Co., Ltd.) Brix 15% was used as a coffee extract.
Chlorogenic acids: 13500 mg / kg
Hydroxyhydroquinone: 90 mg / kg

Reference example 1
20 g of commercial instant coffee (Nescafe (registered trademark) Gold Blend Red Label, Nestlé Japan)) was dissolved in 1400 mL of distilled water to obtain a raw coffee solution. As a result of HPLC analysis, the raw coffee solution contained 660 ppm of chlorogenic acid and 5.0 ppm of hydroxyhydroquinone.
To 1400 mL of this raw coffee solution, 30 g of activated carbon white WH2C 28/42 (Nippon Enviro Chemicals Co., Ltd.) was added (150% with respect to the solid content), stirred for 1 hour, and then filtered using a membrane filter (0.45 μm). About 1300 mL of coffee solution was obtained. As a result of HPLC analysis, chlorogenic acid was contained at 590 ppm, but no hydroxyhydroquinone peak was detected.
Further, the obtained filtrate was freeze-dried to obtain 15.8 g of soluble coffee powder.

Reference example 2
Evaluation of blood pressure lowering of coffee powder prepared in Reference Example 1 i) Experimental materials and methods (a) 13-14 weeks old male spontaneously hypertensive rats (SHR) preliminarily commercially available for 5 consecutive days The blood pressure measurement was carried out by using a blood pressure measuring apparatus (manufactured by Softron Co., Ltd.) to sufficiently familiarize the rat with the blood pressure operation, and then the evaluation test was measured. All rats were housed under conditions of 25 ± 1 ° C., 55 ± 10% relative humidity, and 12 hours of illumination (7 am to 7 pm) (rat room breeding room).
(B) Administration method and dose: In the test group, the coffee powder (activated carbon coffee) prepared in Example 1 was used. The control group used commercial instant coffee. Activated carbon-treated coffee and instant coffee were each dissolved in physiological saline, and prepared so that the total amount of chlorogenic acids was 200 mg / kg. The administration method was oral administration using an oral sonde. The dose was 5 mL / kg.
(C) Test method: 4 to 6 SHRs were used per group. The systolic blood pressure of the tail vein before and 12 hours after oral administration was measured, and the blood pressure change rate after 12 hours was calculated from the blood pressure before administration.
(D) Statistical processing method: The measurement results obtained were subjected to Student's t-test representing the mean value and standard error, and the significance level was 5%.

ii) Results As is apparent from Table 2, when the coffee obtained according to the present invention was ingested, a significant decrease in blood pressure was observed as compared with the case of ingesting ordinary instant coffee.

Claims (6)

A porous adsorbent having a pore radius of 0.7 nanometer (nm) or less and 30% or more of the total pore volume of the porous adsorbent is 100 parts by mass with respect to 100 parts by mass of the porous adsorbent. After washing with an aqueous solvent of not less than 200 parts by mass and not more than 20000 parts by mass , the coffee extract is brought into contact with the porous adsorbent, containing 0.01 to 1% by mass of chlorogenic acids, and the content of hydroxyhydroquinone is the chlorogenic acids The manufacturing method of the coffee composition which is less than 0.1 mass% of quantity. Temperature of the aqueous solvent when the porous adsorbent cleaning method according to claim 1 Symbol placement of the coffee composition is 15 to 90 ° C.. The porous adsorbent is a porous adsorbent in which the volume of pores having a pore radius of 0.7 nanometer (nm) or less is 30 to 99% of the total pore volume of the porous adsorbent. Or the manufacturing method of the coffee composition of 2 . A method for producing soluble coffee, wherein the coffee composition according to any one of claims 1 to 3 is obtained, and then the coffee composition is spray-dried or freeze-dried. A porous adsorbent having a pore radius of 0.7 nanometer (nm) or less and 30% or more of the total pore volume of the porous adsorbent is 100 parts by mass with respect to 100 parts by mass of the porous adsorbent. After washing with an aqueous solvent of not less than 2000 parts by mass and not more than 20000 parts by mass , the coffee extract is brought into contact with the porous adsorbent to contain 0.01 to 1% by mass of chlorogenic acids and the content of hydroxyhydroquinone is A method for producing soluble coffee, comprising obtaining a coffee composition that is less than 0.1% by mass of the amount of chlorogenic acids, and then spray drying or freeze drying the coffee composition. A porous adsorbent having a pore radius of 0.7 nanometer (nm) or less and 30% or more of the total pore volume of the porous adsorbent is 100 parts by mass with respect to 100 parts by mass of the porous adsorbent. A method for removing hydroxyhydroquinone from a coffee extract, in which the coffee extract is brought into contact with the porous adsorbent after washing with an aqueous solvent of at least part by mass and not more than 20000 parts by mass .