JP2007054053A - Containerized coffee beverage - Google Patents

Abstract

The present invention provides a containerized coffee beverage having a blood pressure lowering action that suppresses the production of hydroxyhydroquinone after heat sterilization.
The following components (A) and (B):
(A) Chlorogenic acids 0.03-1% by mass,
(B) Caffeine 0.015-0.3 mass%
A caffeine / chlorogenic acid of 0.07 (mass ratio) or more and a hydroxyhydroquinone / chlorogenic acid of 5/10000 (mass ratio) or less.
[Selection figure] None

Description

  The present invention relates to a packaged coffee beverage having a blood pressure lowering action and a method for producing the same, which suppresses the production of hydroxyhydroquinone after heat sterilization.

  Antihypertensive drugs include various neuroleptic agents that act on the regulatory system of neural factors, ACE inhibitors that act on the regulatory system of humoral factors, AT receptor antagonists, and regulatory systems of vascular endothelium-derived substances Drugs such as Ca antagonists and antihypertensive diuretics related to the body fluid regulation system in the kidney can be mentioned, and these are mainly used in medical institutions for patients with severe hypertension. However, drugs currently used for the purpose of antihypertensive disease are satisfactory in terms of effectiveness, but the burden on patients is large due to the side effects that are present.

  Moreover, general therapies based on lifestyle improvements such as diet therapy, exercise therapy, and restrictions on drinking and smoking are widely applied to those with normal hypertension including those with mild to severe hypertension. With the increasing awareness of the importance of general therapy, it has been said that improving dietary habits is particularly important. Many foods having a blood pressure lowering action have been extensively searched for food-derived antihypertensive materials, and many active ingredients have been separated and identified.

Among these, it has been reported that chlorogenic acid, caffeic acid, ferulic acid and the like contained in foods such as coffee show 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 packaged coffee beverage having an excellent antihypertensive effect.

  The present inventor has paid attention to the fact that coffee beverages do not show sufficient blood pressure lowering action despite containing chlorogenic acid, and as a result of various studies on the relationship between blood pressure lowering action and coffee beverage ingredients, Was found to inhibit the blood pressure lowering action of chlorogenic acids. The inventors have found that a coffee composition having an excellent blood pressure lowering effect can be obtained by maintaining the amount of chlorogenic acids in a certain range and lowering the hydroxyhydroquinone content to a certain amount or less sufficiently smaller than the amount normally contained.

  However, when the coffee composition is a packaged beverage, it has been found that even if the hydroxyhydroquinone content is reduced, hydroxyhydroquinone increases in the heat sterilization treatment step. As a result of further investigation, it was found that the production of hydroxyhydroquinone by heat sterilization treatment can be suppressed by setting the weight ratio of caffeine and chlorogenic acids in the beverage within a certain range.

That is, the present invention includes the following components (A) and (B),
(A) Chlorogenic acids 0.03-1% by mass,
(B) Caffeine 0.015-0.3 mass%
A caffeine / chlorogenic acid of 0.07 (mass ratio) or more and a hydroxyhydroquinone / chlorogenic acid of 5/10000 (mass ratio) or less.
Moreover, this invention carries out activated carbon process of the coffee extract, and the following component (A) and (B),
(A) Chlorogenic acids 0.03-1% by mass,
(B) Caffeine 0.015-0.3 mass%
The caffeine / chlorogenic acids are 0.07 (mass ratio) or more, and
Hydroxyquinone / chlorogenic acids 5/10000 (mass ratio) The following composition is prepared, and the manufacturing method of the container-packed coffee drink which heat-sterilizes this is provided.

  The container-packed coffee beverage of the present invention has an excellent antihypertensive effect, that is, a blood pressure lowering action or a blood pressure rise inhibiting action, and can be taken for a long time.

The container-packed coffee beverage of the present invention contains 0.03 to 1% by mass of (A) chlorogenic acids in terms of blood pressure lowering action, blood pressure rise inhibiting action, and taste, but preferably 0.04 to 0.8. It is contained by mass%, more preferably 0.1-0.6 mass%, further preferably 0.13-0.5 mass%, particularly preferably 0.15-0.4 mass%. (A) The chlorogenic acids include (A ¹ ) monocaffeoylquinic acid, (A ² ) ferulaquinic acid, and (A ³ ) dicaffeoylquinic acid. Here, (A ¹ ) monocaffeoylquinic acid includes at least one selected from 3-caffeoylquinic acid, 4-caffeoylquinic acid and 5-caffeoylquinic acid. Examples of (A ² ) ferulquinic acid include one or more selected from 3-ferlaquinic acid, 4-ferlaquinic acid and 5-ferlaquinic acid. (A ³ ) 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 container-packed coffee beverage of the present invention contains (B) caffeine in an amount of 0.015 to 0.3% by mass or more, preferably 0.016 to 0.25% by mass, more preferably 0.02 to 0.0. The content is 2% by mass, more preferably 0.025 to 0.17% by mass, particularly preferably 0.027 to 0.15% by mass, and most preferably 0.03 to 0.12% by mass. If the caffeine is less than 0.015% by mass, the original flavor of coffee is impaired, and if it is 0.3% by mass or more, the flavor is impaired by the bitter taste of caffeine.

  In the container-packed coffee beverage of the present invention, the ratio of (B) caffeine and (A) chlorogenic acids in the beverage, that is, the mass ratio of caffeine / chlorogenic acids is 0.07 or more, preferably 0.08 to 1. 0.0, more preferably 0.1 to 0.8, still more preferably 0.12 to 0.6, particularly preferably 0.14 to 0.5, and most preferably 0.15 to 0.4. When this ratio is less than 0.07, production of hydroxyhydroquinone by heat sterilization is not sufficiently suppressed.

  In the container-packed coffee beverage of the present invention, the hydroxyhydroquinone (B) is 5/10000 (mass ratio) or less, preferably 1/100000 to 5/10000, more preferably 1/100000 to 4/10000, relative to the amount of chlorogenic acids. More preferably, 1 / 100,000 to 3/10000 is contained. If the amount of hydroxyhydroquinone is 5/10000 (mass ratio) or less with respect to the amount of chlorogenic acids, the blood pressure lowering effect of chlorogenic acids is sufficiently exhibited. Here, the hydroxyhydroquinone content in the beverage of the present invention may be zero.

  The hydroxyhydroquinone content 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. In particular, EC (electrochemical) detection is preferable in that a trace amount of hydroxyhydroquinone can be measured. In addition, in measuring the hydroxyhydroquinone content by HPLC, it can also measure after concentrating a container-packed coffee drink.

Further, the hydroxyhydroquinone content can be directly measured by HPLC, but it can also be quantified by concentrating hydroxyhydroquinone from a packaged coffee beverage by various chromatography and measuring the amount of the concentrated fraction.
In the measurement of the amount of chlorogenic acids, immediately after opening the packaged coffee beverage, for example, in a 5% acetonitrile solution containing 50 mM acetic acid, 10 mM sodium acetate, 0.1 mM 1-hydroxyethane-1,1-diphosphonic acid. 10-fold diluted solution or 4-5 (V / V)% containing 40-50 mM acetic acid, 9-10 mM sodium acetate, 0.09-0.1 mM 1-hydroxyethane-1,1-diphosphonic acid It is preferable to measure with an acetonitrile solution system. Furthermore, in the measurement of hydroxyhydroquinone, immediately after opening the packaged coffee beverage, 5 (V / V)% phosphoric acid, 0.5 mM 1-hydroxyethane-1,1-diphosphonic acid containing 5 (V / V) a solution diluted twice with a methanol solution, or 0.25 to 0.5 (W / V)% phosphoric acid, 0.25 to 0.5 mM 1-hydroxyethane-1,1-diphosphone It is preferable to measure in a 2.5 to 5 (V / V)% methanol solution system containing an acid.

The container-packed coffee beverage of the present invention has a H ₂ O ₂ (hydrogen peroxide) content of 1 ppm or less, more preferably 0.1 ppm or less, further 0.05 ppm or less, and particularly 0.01 ppm or less. It is preferable in terms of the original flavor. The measurement of hydrogen peroxide can be performed using a commonly used hydrogen peroxide meter. For example, a high-sensitivity hydrogen peroxide meter Super Orientor Model 5 (SUPER ORITECTOR MODEL 5) manufactured by Central Science Co., Ltd. can be used. . In particular, H ₂ O ₂ is lost by sterilization before opening of the can, but when it comes into contact with air by opening the can, it tends to gradually increase with time, so it is described in Japanese Patent Nos. 37322782 and 3706339. Analyze quickly and promptly after opening the can according to the measurement conditions.

  Although the kind of coffee bean used for the container-packed coffee drink of this invention is not specifically limited, For example, Brazil, Colombia, Tanzania, mocha etc. are mentioned. Examples of coffee types include Arabica and Robusta. One kind of coffee beans may be used, or a plurality of kinds may be blended. There are no particular restrictions on the roasting method of roasted coffee beans, and ordinary methods can be employed for the roasting temperature and roasting environment. Furthermore, there is no restriction | limiting also about the extraction method from the bean, For example, the method of extracting from a roasted coffee bean or its ground material using water-hot water (0-100 degreeC) for 10 second-120 minutes is mentioned. Examples of the extraction method include a boiling type, an espresso type, a siphon type, and a drip type (paper, flannel, etc.).

  Moreover, raw milk, cow's milk, whole milk powder, skim milk powder, fresh cream, concentrated milk, skim milk, partially skimmed milk, condensed milk, etc. can be blended in the container-packed coffee beverage of the present invention.

  The container-packed coffee beverage of the present invention refers to one using 1 g or more of coffee beans per 100 g in terms of green beans, preferably 2.5 g or more of coffee beans, and more preferably 5 g of coffee beans. It is what is used above. The container-packed coffee beverage is preferably single-strength. Here, “single strength” means that after opening a packaged beverage, it can be taken as it is without being diluted.

It is important for the coffee composition used for the container-packed coffee beverage of the present invention to reduce the hydroxyhydroquinone content by treating the roasted coffee bean extract with an adsorbent. Examples of the adsorbent include activated carbon and reverse phase chromatographic carrier. More specifically, after adding an adsorbent to an aqueous solution of a roasted coffee bean extract or a dried product of the roasted coffee bean extract and stirring at 0 to 100 ° C. for 10 minutes to 5 hours, the adsorbent is removed. Good. Here, the adsorbent is preferably used in an amount of 0.02 to 1.0 times in the case of activated carbon and 2 to 100 times in the case of a reverse phase chromatographic carrier with respect to the weight of roasted coffee beans. As the activated carbon, the average pore radius in the micropore region is preferably 5 angstroms (Å) or less, more preferably in the range of 2 to 5 angstroms, and particularly preferably in the range of 3 to 5 angstroms. In the present invention, the micropore region indicates 10 angstroms 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 measurement by the MP method. The MP method is a pore measurement method described in the literature (Colloid and Interface Science, 26, 46 (1968)), and is a method adopted by Sumika Chemical Analysis Center, Inc. and Toray Research Center, Inc. .
Moreover, as a kind of activated carbon, coconut shell activated carbon is preferable, and also water vapor activated coconut shell activated carbon is preferable. As a commercial product of activated carbon, Shirakaba (Nippon Enviro Chemicals), Taiko CW (Nikamura Chemical), Kuraray Coal GW (Kuraray Chemical), etc. can be used. Examples of the reverse phase chromatographic carrier include YMC • ODS-A (YMC), C18 (GL Science) and the like.
Among these adsorbent treatment methods, adsorbent treatment methods using specific activated carbon can not only reduce the amount of chlorogenic acids selectively but also reduce the amount of hydroxyhydroquinone, and are also industrially advantageous. Further, from the viewpoint of not lowering the potassium content (maintaining 1/5 or more, particularly 1/2 or more in mass ratio), it is preferable in terms of the original flavor of coffee.

  In addition, caffeine present in the coffee is almost lost in the normal adsorption treatment. Therefore, it is important to keep the caffeine / chlorogenic acids in the coffee composition at 0.07 (mass ratio) or more while removing the hydroxyhydroquinone. For that purpose, the coffee extract is passed through the column. Liquid activated carbon treatment is conceivable, but in that case, it is necessary to strictly control. Further, once all caffeine is removed, caffeine may be blended. Caffeine / chlorogenic acids are 0.07 to 1.0, more preferably 0.08 to 0.8, still more preferably 0.1 to 0.5, and particularly preferably 0.14 to 0.3. It is preferable at the point which can suppress the increase in this.

  In addition, although the increase mechanism of the hydroxyhydroquinone by heat sterilization treatment is not elucidated, if the presence of the precursor of hydroxyhydroquinone is assumed, the precursor may receive and generate | occur | produce by a hydroxyl radical etc. On the other hand, since caffeine has a radical scavenging ability, the presence of caffeine is considered to reduce the concentration of hydroxy radicals and the like in the system, thereby suppressing the increase in hydroxyhydroquinone.

  Moreover, the container-packed coffee beverage in the present invention has a hydroxyhydroquinone peak in the time region of a relative retention time of 0.54 to 0.61 when gallic acid is used as a standard substance in analysis by high performance liquid chromatography. Is preferably not observed. In order to confirm that there is substantially no peak in the time domain, general HPLC can be used. For example, a gradient of 0.05 M acetic acid aqueous solution and 0.05 M acetic acid 100% acetonitrile solution is used as an eluent. It can be confirmed by using an ODS column and detecting with an ultraviolet absorptiometer or the like.

  In the present invention, the fact that the relative retention time with respect to gallic acid does not substantially have a peak in the time region of 0.54 to 0.61 means that the area value at the time of analysis of a 1 ppm solution of gallic acid is S1, and the container is used under the same conditions. When the sum of the peak areas derived from the components eluted in the specific region when analyzing the stuffed coffee beverage is S2, it means that S2 / S1 <0.01.

  The hydroxyhydroquinone content 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. In particular, EC (electrochemical) detection is preferable in that a trace amount of hydroxyhydroquinone can be measured. In addition, in measuring the hydroxyhydroquinone content by HPLC, it can also measure after concentrating a coffee drink etc.

  Sugar, glucose, fructose, xylose, fructose glucose solution, sugar alcohol and other sugars, antioxidants, pH adjusters, emulsifiers, fragrances and the like can be added to the packaged coffee beverage of the present invention. The container-packed coffee beverage of the present invention is preferably a coffee beverage substantially free of milk components, so-called black.

Containers such as PET bottles, cans (aluminum, steel), paper, retort pouches, bottles (glass) and the like can be used for the container-packed coffee beverage of the present invention. In this case, the container can be 50 to 2500 mL. The pH of the container-packed coffee beverage is preferably 5 to 7, more preferably 5.4 to 6.5, and particularly preferably 5.6 to 6.3. As a constituent ratio of monocaffeoylquinic acid in the container-packed coffee beverage, a mass ratio of 4-caffeoylquinic acid / 3-caffeoylquinic acid is 0.6 to 1.2, and 5-caffeoylquinic acid / It is preferable that 3-caffeoylquinic acid mass ratio is 0.01-3. As the container, a container having a low oxygen permeability is preferable from the viewpoint of preventing changes in the components in the coffee. For example, a can made of aluminum or steel, a glass bottle, or the like may be used. In the case of cans and bottles, resealable ones that can be recapped are also included. Here, the oxygen permeability is an oxygen permeability (cc · mm / m ² · day · atm) measured in an environment of 20 ° C. and 50% relative humidity with a container / film oxygen permeability measuring device. Hereinafter, it is more preferably 3 or less, particularly 1 or less.

  When making a container-packed coffee beverage, the sterilization process is usually performed, but if the sterilization process can be heat-sterilized after filling into a container like a metal can, it is performed under the sterilization conditions stipulated in the Food Sanitation Law. Is called. For items such as PET bottles and paper containers that cannot be sterilized by retort, sterilization conditions equivalent to those stipulated in the Food Sanitation Law in advance, such as high-temperature and short-time sterilization using a plate heat exchanger, are cooled to a certain temperature. A method such as filling the container is adopted. In addition, after sterilization under heat, the pH may be returned to neutral under aseptic conditions, or after sterilization under heat under neutral conditions, the pH may be returned to acidity under aseptic conditions.

  The container-packed coffee beverage of the present invention contains an effective amount of chlorogenic acids having an antihypertensive effect, and the amount of hydroxyhydroquinone that inhibits the antihypertensive effect of chlorogenic acids is reduced even after heat sterilization treatment. Therefore, it is useful as a blood pressure lowering or blood pressure increase suppressing pharmaceutical composition, a blood pressure lowering beverage, and a blood pressure increase suppressing beverage.

Analytical methods for chlorogenic acids and hydroxyhydroquinone are as follows.
Chlorogenic acid analysis method:
Analysis condition A
The analytical instrument used was HPLC (Shimadzu Corporation). The model numbers of the unit units are as follows.
Detector: SPD-M10A, oven: CTO-10AC, pump: LC-10AD, autosampler: SIL-10AD, column: Inertsil ODS-2 ID 4.6 mm × length 250 mm.
The analysis conditions are as follows.
Sample injection volume: 10 μL, flow rate: 1.0 mL / min, ultraviolet absorption photometer detection wavelength: 325 nm (chlorogenic acids), 290 nm (hydroxyhydroquinone), eluent A: 0.05 M acetic acid 3% acetonitrile solution, eluent B: 0.05M acetic acid 100% acetonitrile solution.

Concentration gradient condition time Eluent A Eluent B
0 minutes 100% 0%
20 minutes 80% 20%
35 minutes 80% 20%
45 minutes 0% 100%
60 minutes 0% 100%
70 minutes 100% 0%
120 minutes 100% 0%

  Retention time of chlorogenic acids (unit: minutes) (A1) Monocaffeoylquinic acid: 17.9, 20.4, 22.0, 3 points in total (A2) Ferlaquinic acid: 22.8, 25.8, 27. 0 total 3 points (A3) dicaffeoylquinic acid: 32.3, 33.0, 35.8 total 3 points From the area determined here, 5-caffeoylquinic acid was used as a standard substance, and mass% was obtained. It was.

Methods for analysis of chlorogenic acids and caffeine:
Analysis condition K
Analyzes of chlorogenic acids and caffeine in a packaged coffee beverage or coffee composition are 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%
70.0 minutes 100% 0%

After precisely weighing 1 g of the sample, it was made up to 10 mL with eluent A, filtered through a membrane filter (GL chromatodisc 25A, pore size 0.45 μm, GL Sciences), and subjected to HPLC 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.
The analysis of caffeine was carried out in the same manner as chlorogenic acids except that UV-VIS detector set wavelength: 270 nm and caffeine was used as a standard substance. Caffeine retention time is 18.9 minutes.

Analysis method B of hydroxyhydroquinone by HPLC-electrochemical detector B
A method for analyzing hydroxyhydroquinone in a packaged coffee beverage or coffee composition 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%

  The analytical sample was prepared by accurately weighing 5 g of the sample, and then adding 0.5 (W / V)% phosphoric acid, 0.5 mM 1-hydroxyethane-1,1-diphosphonic acid, 5 (V / V)% methanol solution. The volume was made up to 10 mL, and this solution was centrifuged to obtain a 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.

  EXAMPLES Next, although an Example is given and this invention is demonstrated in detail, this invention is not limited to this at all.

Example 1
The coffee beans were extracted with 8 times the amount of ion-exchanged water (95 ° C.) with respect to medium-roasted coffee beans. Next, Brix in the obtained coffee extract was measured, and a column (inner diameter: 45 mm, length: 150 mm) filled with activated carbon (birch) in an amount of 50% by weight with respect to Brix was prepared.
Thereafter, a coffee extract was passed through a column filled with activated carbon under the conditions of a temperature of 25 ° C. and SV8, and activated carbon treatment to obtain a coffee composition A from which hydroxyhydroquinone had been removed.
The chlorogenic acid content in the coffee composition from which the hydroxyhydroquinone thus obtained was removed was measured, diluted with ion-exchanged water, and the pH was adjusted with sodium bicarbonate. The hydroxyhydroquinone content before heat sterilization was below the detection limit. Next, the coffee composition thus obtained was filled in a 190 g can, sealed, and subjected to a retort sterilization treatment.
The amount of chlorogenic acid and the amount of caffeine were measured under analytical conditions, and the amount of hydroxyhydroquinone was measured by an analytical method using an HPLC-electrochemical detector.

Example 2
It was produced in the same manner as in Example 1 except that caffeine was added as a raw material. The hydroxyhydroquinone content before heat sterilization was below the detection limit.

Comparative Example 1
It was produced in the same manner as in Example 1 except that coffee composition B obtained from coffee beans from which caffeine was removed was used. The hydroxyhydroquinone content before heat sterilization was below the detection limit.

Comparative Example 2
Extraction was performed with ion-exchanged water (95 ° C.) in an amount eight times that of medium-roasted coffee beans to obtain a coffee composition C. It was manufactured in the same manner as in Example 1 except that the activated carbon treatment was not performed. The hydroxyhydroquinone content before heat sterilization was 0.00131% by mass.

Example 3
A column (inner diameter: 45 mm, length: 150 mm) packed with 50% by weight of activated carbon (Shirakaba WH2C) with respect to Brix, a medium roasted coffee extract, was heated to 25 ° C., SV8 [1 / volume [m ³ ] / The coffee extract was passed under the condition of the flow rate [m ³ / hr].
The activated carbon-treated coffee extract A was pH adjusted using an aqueous solution in which sodium bicarbonate was dissolved, and then diluted with ion-exchanged water so that the chlorogenic acids would be 170 mg / 100 g.
The obtained coffee composition was filled in a 190 g can, sealed, and retort sterilized at 131 ° C. for 100 seconds.

Example 4
A column (inner diameter: 45 mm, length: 150 mm) packed with 50% by weight of activated carbon (Shirakaba WH2C) with respect to Brix, which is a coffee mixed extract with a medium roasting degree and a low roasting degree, is heated at 25 ° C., SV8 [1 Coffee extract was passed under the conditions of / volume [m ³ ] / flow rate [m ³ / hr].
The activated carbon-treated coffee extract B was adjusted with an aqueous solution in which sodium bicarbonate was dissolved, and then diluted with ion-exchanged water so that the chlorogenic acids were 350 mg / 100 g.
The obtained coffee composition was filled in a 190 g can, sealed, and retort sterilized at 131 ° C. for 100 seconds.

Comparative Example 3
A column (inner diameter 45 mm, length 150 mm) packed with 50% by weight activated carbon (Morcybon X2M) with respect to Brix, a coffee extract with a high roasting degree, was heated at 25 ° C., SV8 [1 / volume [m ³ ] / The coffee extract was passed under the condition of a flow rate [m ³ / hr].
The activated carbon-treated coffee extract D was adjusted with an aqueous solution in which sodium bicarbonate was dissolved, and then diluted with ion-exchanged water so that the chlorogenic acids would be 170 mg / 100 g.
The obtained coffee composition was filled in a 190 g can, sealed, and retort sterilized at 123 ° C. for 10 minutes.

  Table 1 shows the sterilization conditions and analytical values after sterilization treatment of the container-packed coffee beverages obtained in Examples 1 to 4 and Comparative Examples 1 to 3. As is clear from Table 1, the container-packed coffee beverage of the present invention in which the ratio of caffeine / chlorogenic acids and the ratio of hydroxyhydroquinone / chlorogenic acids is adjusted is suppressed from increasing in hydroxyhydroquinone due to heat sterilization treatment.

<Specific example of measurement pretreatment of chlorogenic acid>
After opening the canned coffee, 1 g was accurately weighed and then eluent A (5 (V / V)% containing 50 mM acetic acid, 10 mM sodium acetate, 0.1 mM 1-hydroxyethane-1,1-diphosphonic acid) The solution was made up to 10 mL with an acetonitrile solution, filtered through a membrane filter (GL chromatodisc 25A, pore size 0.45 μm, GL Sciences Inc.), and subjected to analysis.

<Specific example of measurement pretreatment of hydroxyhydroquinone>
After opening the canned coffee, 5 g is precisely weighed immediately and then 5 (V / V) containing 0.5 (W / V)% phosphoric acid and 0.5 mM 1-hydroxyethane-1,1-diphosphonic acid. The volume was made up to 10 mL with a% methanol solution, and this solution was centrifuged to obtain a supernatant. The supernatant was passed through Bond Elute JR SCX (solid phase filling amount: 500 mg, GL Sciences Inc.), and about 1.0 mL of the first passage liquid was removed to obtain a passage liquid. 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.

<Specific measurement example of hydrogen peroxide>
Using a hydrogen peroxide analyzer SUPER ORITECTOR MODEL 5 (Central Science Co., Ltd.) and calibrating with a standard calibration solution (hydrogen peroxide 1 ppm), the analyzer measurement cell contains 0.5% potassium bromate. Add 1 mL of 0.2 M phosphate buffer (pH 7.0). When the dissolved oxygen in the cell becomes zero by sending nitrogen, the commercial canned coffee and the test sample that have been allowed to stand in a thermostatic bath at 30 ° C. are opened, and 1 mL is quickly extracted and added to the measurement cell. After that, according to the measurement procedure of the device, the generated oxygen concentration is read from the printer. In the case of removing the data, measurement is made every 15 minutes thereafter, and a straight line is drawn by the least square method using the data obtained after 1 hour. Here, the detection limit of MODEL5 was 0.1 mg / kg.

Reference example 1
After dissolving 20 g of commercial instant coffee (Nescafe (registered trademark) Gold Blend Red Label) in 1400 mL of distilled water (this coffee is referred to as coffee composition P), 30 g of activated carbon white rice cake 28/42 (Nippon Enviro Chemicals) is added, After stirring for a period of time, it was filtered using a membrane filter (0.45 μm) to obtain a filtrate (this coffee is referred to as coffee composition Q). The obtained filtrate was freeze-dried to obtain 15.8 g of a brown powder. This brown powder was dissolved in distilled water, and chlorogenic acids and hydroxyhydroquinone were quantified by HPLC analysis. As a result, 4.12% by mass of chlorogenic acids were contained (according to analysis condition A), and hydroxyhydroquinone was below the detection limit ( Analysis condition B). Moreover, when the potassium content was measured by ICP emission spectroscopic analysis, both the raw instant coffee and the activated carbon-treated coffee were about 4.2% by mass.

Reference example 2
Blood pressure drop evaluation of coffee composition Q prepared in Reference Example 1 Experimental materials and methods (a) 13-14 week old male spontaneously hypertensive rats (SHR) preliminarily commercially available for 5 days for non-invasive blood for rats 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 composition Q (activated carbon-treated coffee) prepared in Reference Example 1 was used. The control group used commercial instant coffee. Activated charcoal-treated coffee and instant coffee were each dissolved in physiological saline to prepare a total chlorogenic acid amount of 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%.
Results: As is clear from Table 2, by taking the coffee composition Q, a significant decrease in blood pressure was observed as compared with the case of taking ordinary instant coffee.

Claims (4)

The following components (A) and (B),
(A) Chlorogenic acids 0.03-1% by mass,
(B) Caffeine 0.015-0.3 mass%
A caffeine / chlorogenic acid of 0.07 (mass ratio) or more and a hydroxyhydroquinone / chlorogenic acid of 5/10000 (mass ratio) or less.   The containerized coffee beverage according to claim 1, wherein the mass ratio of caffeine / chlorogenic acids is 0.1 to 0.8. The container-packed coffee beverage according to claim 1, wherein the container has an oxygen permeability of 5 [cc · mm / m ² · day · atm] or less. The coffee extract is treated with activated carbon, and the following components (A) and (B):
(A) Chlorogenic acids 0.03-1% by mass,
(B) Caffeine 0.015-0.3 mass%
The caffeine / chlorogenic acids are 0.07 (mass ratio) or more, and
Hydroxyquinone / chlorogenic acids 5/10000 (mass ratio) A composition of 5 or less (mass ratio) or less is prepared.