JP2011125284A - Packed coffee beverage - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a packed coffee beverage in which the generation of hydroxyhydroquinone is suppressed. <P>SOLUTION: The packed coffee beverage containing a neutral amino acid of 0.005-1 mass% and the packed coffee beverage containing creatine are provided. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a packaged coffee beverage.

  Coffee beverages contain chlorogenic acids such as chlorogenic acid, caffeic acid, and ferulic acid, which are polyphenols, and these chlorogenic acids are known to have excellent physiological activity. However, it has been reported that the physiological activity by chlorogenic acids is inhibited by hydroxyhydroquinone contained in coffee beverages.

  Therefore, in order to effectively express the physiological activity due to chlorogenic acids, it is advantageous to reduce the amount of hydroxyhydroquinone in the coffee beverage. In view of this, there has been proposed a coffee beverage in which the amount of chlorogenic acids in a coffee beverage is maintained within a certain range and the hydroxyhydroquinone content is reduced to a certain amount or less that is sufficiently smaller than the amount normally contained (Patent Document 1).

  However, even if the amount of hydroxyhydroquinone in the coffee beverage is reduced, hydroxyhydroquinone is generated again during the heat sterilization process when the container is packed and during distribution and storage. Therefore, the amount of chlorogenic acids in the coffee drink is maintained within a certain range, and the hydroxyhydroquinone content is reduced to a certain amount or less, which is sufficiently smaller than the amount normally contained, and then the pH is kept within a certain range, or the coffee solids content is reduced. Container-packed coffee drinks in which the ratio of chlorogenic acids in the water is above a certain level have been proposed (Patent Documents 2 and 3). In other words, these are technologies that control the liquidity of coffee beverages and the concentration of specific components to suppress the production of hydroxyhydroquinone in packaged coffee beverages, and any additive that can inhibit the production of hydroxyhydroquinone has been studied. Not.

  On the other hand, although coffee milk beverages containing neutral amino acids have been proposed (Patent Documents 4 and 5), quality deterioration such as deterioration odor, precipitation and separation of fat content due to milk components is suppressed, and taste is improved. Therefore, there is no description that neutral amino acids are effective in suppressing the production of hydroxyhydroquinone.

JP 2006-204192 A JP 2007-54061 A JP 2006-54062 A JP 2009-055802 A JP 2009-254307 A

Therefore, the subject of this invention is providing the container-packed coffee drink which suppressed the production | generation of hydroxyhydroquinone.
Another object of the present invention is to provide a hydroxyhydroquinone production inhibitor for containerized coffee beverages and a method for inhibiting the production of hydroxyhydroquinone in containerized coffee beverages.

  The present inventor has made various studies to suppress the production of hydroxyhydroquinone (hereinafter also referred to as “HHQ”) in a packaged coffee beverage. Among amino acids, a specific amino acid is used to inhibit the production of HHQ in the packaged coffee beverage. It was found that it is effective and has little flavor change before and after storage.

  That is, this invention provides the container-packed coffee drink containing 0.005-1 mass% of neutral amino acids, and the container-packed coffee drink containing creatine.

  The present invention also provides a hydroxyhydroquinone production inhibitor for packaged coffee beverages containing a neutral amino acid as an active ingredient.

  The present invention further provides a method for suppressing the production of hydroxyhydroquinone in a packaged coffee beverage, comprising the step of adding the hydroxyhydroquinone production inhibitor to a coffee extract.

  The container-packed coffee beverage of the present invention contains a neutral amino acid having an HHQ production-inhibiting action, so that the heat sterilization step when packaging the container and the production of HHQ during distribution and long-term storage are suppressed, Little change in flavor before and after storage. Therefore, the container-packed coffee beverage of the present invention is not easily inhibited by HHQ due to the physiological activity due to chlorogenic acids, can sufficiently expect the physiological effect due to chlorogenic acids, and has high palatability.

The container-packed coffee beverage of the present invention contains (A) a neutral amino acid. Thereby, the production | generation of HHQ in a container-packed coffee drink can be suppressed. As used herein, the term “neutral amino acid” refers to an amino acid having an amino group-containing basic group such as an amino group or a guanidyl group and one carboxyl group in each molecule. It may be a single optically active substance or a racemate. In the present specification, an amino acid having more carboxyl groups than the amino group-containing basic group in one molecule is an acidic amino acid, and an amino acid having more amino group-containing basic groups than a carboxyl group in one molecule. Basic amino acid.
Specific examples of neutral amino acids include glycine, sarcosine, α-alanine, β-alanine, N-methyl-β-alanine, glutamine, asparagine, isoleucine, epsilon-aminocaproic acid, γ-aminobutyric acid, glycylglycine, cysteine Cystine, creatine, serine, tyrosine, tryptophan, threonine, valine, phenylalanine, proline, hydroxyproline, methionine, leucine and the like. Of these, cystine and creatine are preferable, and creatine is particularly preferable from the viewpoint of suppressing HHQ production.

  The content of the neutral amino acid (A) in the container-packed coffee beverage of the present invention is 0.005 to 1% by mass, but the upper limit is 0.8% by mass, particularly 0. The lower limit is preferably 0.008% by mass, more preferably 0.01% by mass, and particularly preferably 0.02% by mass. In addition, when creatine is contained as a neutral amino acid, the content of creatine in the container-packed coffee beverage is not particularly limited, but is preferably the same content as described above from the viewpoint of suppressing HHQ production and flavor.

  The container-packed coffee beverage of the present invention contains chlorogenic acids, and the content of (B) chlorogenic acids in the container-packed coffee beverage of the present invention has an upper limit of 5% by mass from the viewpoint of physiological activity and flavor. It is preferably 3% by mass, more preferably 2% by mass, in particular 1.5% by mass, while the lower limit is preferably 0.08% by mass, furthermore 0.1% by mass, in particular 0.12% by mass. The content of chlorogenic acids is a value measured by “Analysis of chlorogenic acids” described in Examples below. In this specification, “chlorogenic acids” means 3-caffeoylquinic acid, 4-caffeoylquinic acid and mono-caffeoylquinic acid of 5-caffeoylquinic acid, 3-ferlaquinic acid and 4-ferlaquina. Acid and 5-ferlaquinic acid monoferlaquinic acid and 3,4-dicaffeoylquinic acid, 3,5-dicaffeoylquinic acid and 4,5-dicaffeoylquinic acid dicaffeoylquinic acid It is a general term. The chlorogenic acid content is defined based on the total amount of the above nine types.

  Further, the content mass ratio [(A) / (B)] of (A) neutral amino acid and (B) chlorogenic acids in the container-packed coffee beverage of the present invention has an upper limit from the viewpoint of physiological activity and flavor. It is preferably 5, 4.5, further 4, particularly 3.5, while the lower limit is preferably 0.01, further 0.03, further 0.05, especially 0.1.

  Although the container-packed coffee beverage of the present invention may contain HHQ, it is preferable that the HHQ content is sufficiently reduced from the amount usually contained. Specifically, the content of the (C) hydroxyhydroquinone in the packaged coffee drink is less than 0.000059% by mass, more preferably less than 0.000058% by mass, from the viewpoint of inhibiting bioactivity inhibition and production efficiency. Further, it is preferably less than 0.000057% by mass, particularly less than 0.000055% by mass, and the lower limit is not particularly limited, but is preferably 0.00001% by mass. The content of hydroxyhydroquinone is a value measured by “analysis of hydroxyhydroquinone” described in Examples below, but is detected with high sensitivity because an electrochemical detector is used as a detection means. Moreover, in HHQ analysis by HPLC, you may measure after concentrating a container-packed coffee drink.

In addition, the content mass ratio [(C) / (B)] of (C) hydroxyhydroquinone and (B) chlorogenic acids in the container-packed coffee beverage of the present invention is 4.1 from the viewpoint of suppressing physiological activity inhibition. × 10 ⁻⁴ or less, further 4.0 × 10 ⁻⁴ or less, further 3.8 × 10 ⁻⁴ or less, and particularly preferably 3.5 × 10 ⁻⁴ or less, while the lower limit is not particularly limited. It is preferably 5 × 10 ⁻⁴ .

  Such a packaged coffee beverage can be obtained, for example, by blending (A) a neutral amino acid in a coffee extract and adjusting the concentrations of (B) chlorogenic acids and (A) neutral amino acid.

As the coffee extract, a coffee extract extracted from roasted coffee beans, an aqueous solution of instant coffee, or the like can be used.
The coffee extract used in the present invention preferably uses 1 g or more of coffee beans in terms of green beans per 100 g of the coffee extract, 2.5 g or more, particularly 5 g or more of coffee beans. The extraction method and extraction conditions are not particularly limited, and can be performed by known methods and conditions. For example, the method and conditions described in JP-A-2009-153451 can be employed. The obtained coffee extract may be concentrated or diluted with water as necessary.

Examples of coffee bean species used for extraction include Arabica, Robusta and Revelica. There are no particular restrictions on the coffee beans' production area, but examples include Brazil, Colombia, Tanzania, Mocha, Kilimangelo, Mandelin, and Blue Mountain. One kind of coffee beans may be used, or a plurality of kinds may be blended.
It is preferable to use roasted coffee beans as the coffee beans, and examples of the roasting degree include light, cinnamon, medium, high, city, full city, French and Italian. Among these, light, cinnamon, medium, high, and city are preferable because they contain a large amount of chlorogenic acids and are easy to drink.
There are no particular restrictions on the method of roasting coffee beans, and there are no restrictions on the roasting temperature and roasting environment, and ordinary methods can be employed.

In the present invention, a coffee extract having a sufficiently reduced HHQ content is preferably used. In order to obtain a coffee extract with a reduced HHQ content, the coffee extract may be treated with an adsorbent.
As the adsorbent, activated carbon, reverse phase chromatographic carrier, or the like can be used. As a treatment method, an adsorbent is added to a coffee extract or an aqueous solution of instant coffee and stirred at 0 to 100 ° C. for 10 minutes to 5 hours, and then the adsorbent is removed. The amount of adsorbent used is preferably 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 mass of coffee beans.

  As the kind of activated carbon, coconut shell activated carbon is preferable, and steam activated coconut shell activated carbon is more preferable. As a commercial product of activated carbon, Shirakaba WH2C (Nippon Enviro Chemicals Co., Ltd.), Taiko CW (Nikamura Chemical Co., Ltd.), Kuraray Coal GW (Kuraray Chemical Co., Ltd.) and the like can be used. Examples of the reverse phase chromatographic carrier include YMC • ODS-A (YMC Corporation), C18 (GL Science Corporation) and the like.

  The Brix value of the container-packed coffee beverage of the present invention is preferably 1 to 3, particularly 1.5 to 2.5. A Brix value within the above range is preferred because of excellent flavor and difficulty in forming a precipitate. Here, the “Brix value” is a value measured by “Measurement of Brix” described in Examples described later.

  In addition, the container-packed coffee beverage of the present invention includes, as necessary, milk components, sweeteners, bitterness inhibitors, antioxidants, fragrances, organic acids, organic acid salts, inorganic acids, inorganic acid salts, inorganic salts, and pigments. , One or more additives such as emulsifiers, preservatives, seasonings, acidulants, amino acids, pH adjusters, and quality stabilizers may be blended.

  The container-packed coffee beverage of the present invention may be a black coffee beverage or a milk coffee beverage, but a black coffee beverage substantially free of milk components is preferred. The container-packed coffee beverage is preferably single-strength. Here, “single strength” refers to a beverage that can be used as it is without being diluted after the container-packed coffee beverage is opened.

  The pH (20 ° C.) of the packaged coffee beverage of the present invention is preferably 5 to 7, more preferably 5.4 to 6.5, and particularly preferably 5.6 to 6.3, from the viewpoints of stability and flavor.

The container-packed coffee beverage of the present invention is filled into a normal packaging container such as a molded container (so-called PET bottle) mainly composed of polyethylene terephthalate, a metal can, a paper container combined with a metal foil or a plastic film, or a bottle. Can be provided.
Container-packed coffee beverages, for example, can be sterilized under the sterilization conditions stipulated in the applicable regulations (Food Sanitation Law in Japan) if they can be sterilized by heating after filling in containers such as metal cans. Can be manufactured. For PET bottles and paper containers that cannot be sterilized by retort, sterilize under the same conditions as above, for example, after sterilizing at high temperature and short time with a plate heat exchanger, etc. The method can be adopted.

  As mentioned above, although the container-packed coffee drink of this invention was demonstrated, the structure similar to the above is employ | adopted also in the hydroxyhydroquinone production | generation inhibitor of the container-packed coffee drink of this invention, and the production | generation suppression method of the hydroxyhydroquinone of a container-packed coffee drink. be able to.

(1) Analysis of chlorogenic acids HPLC was used as an analytical instrument. The model numbers of the constituent units of the apparatus 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 Co.).

The analysis conditions are as follows.
Sample injection volume: 10 μL,
Flow rate: 1.0 mL / min,
UV-VIS detector setting 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%

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)
(B ¹ ) Monocafe oil quinic acid: 5.3, 8.8, 11.6, total 3 points (B ² ) Monoferlaquinic acid: 13.0, 19.9, 21.0, total 3 points ( B ³ ) Dicaffeoylquinic acid: 36.6, 37.4, 44.2 in total.
From the area values of the nine types of chlorogenic acids determined here, the content (mass%) of chlorogenic acids was determined using 5-caffeoylquinic acid as a standard substance.

(2) Analysis of hydroxyhydroquinone by HPLC-electrochemical detector The analytical instrument used was a Couloarray system (model 5600A, manufactured by ESA, USA) 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 C: 0.1 (W / V)% phosphoric acid, 0.1 mM 1-hydroxyethane-1,1-diphosphonic acid, 5 (V / V)% methanol solution,
Eluent D: 0.1 (W / V)% phosphoric acid, 0.1 mM 1-hydroxyethane-1,1-diphosphonic acid, 50 (V / V)% methanol solution.

  For preparing the eluents C and D, 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 C Eluent D
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 and the supernatant was used as an analysis sample. 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, hydroxyhydroquinone (Wako Pure Chemical Industries, Ltd.) was used as a standard substance, and the content (mass%) of hydroxyhydroquinone was determined.

(3) Measurement of creatine The creatine content was calculated by multiplying 1.159 by the value obtained by subtracting the creatinine content from the total creatinine content. Analysis was requested from the Japan Food Analysis Center.

(Measurement of creatinine)
A sample was collected, extracted with water, and filtered to obtain a creatinine test solution. Next, a picric acid reagent was added to the test solution and allowed to stand at room temperature for 60 minutes, and then a predetermined amount was measured and an absorbance measurement (wavelength 520 nm) was performed.

(Measurement of total creatinine)
Hydrochloric acid was added to a test solution of creatinine obtained by the same operation as described above, heated to dryness and then watered, and a test solution was obtained by filtration. A picric acid reagent was added to the test solution and allowed to stand at room temperature for 60 minutes, and then a predetermined amount was measured and absorbance was measured (wavelength 520 nm).

(4) Measurement of neutral amino acids other than creatine The analytical instrument used was Hitachi High-Technologies L-8800A type high-speed amino acid analyzer. The analysis conditions are as follows.
In the amino acid analyzer, 1 mL of the sample and 1 mL of 0.2 M hydrochloric acid were mixed and then made up to 10 mL with ion-exchanged water, and filtered with a membrane filter (GL Chromatodisc 25A, pore size 0.45 μm, GL Sciences Inc.). It was used for analysis later.
The measurement mode of the amino acid analyzer was PH mode.
Neutral amino acid retention time (minutes)
(A ¹ ) Glycine: 11.8
(A ² ) Alanine: 13.2
Using the amino acid mixed standard solution (manufactured by Wako Pure Chemical Industries, Ltd.) H type as the standard substance, the content (mass%) of the neutral amino acid was determined from the area values of the two neutral amino acids determined here.

Sample injection volume: 20 μL,
Flow rate: PUMP A 0.40 mL / min, PUMP B 0.35 mL / min
UV-VIS detector setting wavelength: 440 nm, 570 nm
Column oven set temperature: 57 ° C.

Here, PUMP A used the following eluent, and PUMP B used the following reaction solution.
Eluent: PH-1, PH-2, PH-3, PH-4, PH-RG (manufactured by Mitsubishi Chemical Corporation),
Reaction solution: ninhydrin reagent R1 (manufactured by Wako) and buffer R2 (manufactured by Wako).

(5) Measurement of Brix The refractometer reading for sugar (Brix) at 20 ° C. of the sample was measured using a sugar meter (Atago RX-5000, manufactured by Atago).

(6) Sensory test About the presence or absence of the change of the flavor of each container-packed coffee drink before and behind storage at 60 degreeC for 1 week, it evaluated by five panelists, and determined by consultation after that.

Example 1
Arabica coffee beans having a roasting degree of L22 were extracted with ion-exchanged water at 95 ° C. to obtain a coffee extract. Next, the Brix of the coffee extract was measured, and a column (inner diameter: 45 mm, length: 150 mm) filled with activated carbon (Shirakaba WH2C, Nippon Envirochemicals Co., Ltd.) in an amount of 50% by mass with respect to Brix was prepared. Thereafter, the coffee extract was passed through a column filled with activated carbon under conditions of a temperature of 25 ° C. and SV = 3 [h ⁻¹ ] to obtain a coffee extract from which hydroxyhydroquinone had been removed.
Next, the coffee extract from which hydroxyhydroquinone has been removed is diluted with ion-exchanged water, adjusted to pH 6 with sodium bicarbonate, and then blended with creatine so that the creatine content in the coffee beverage is 0.05% by mass. A coffee drink was prepared. The amount of chlorogenic acid and the amount of hydroxyhydroquinone before heat sterilization were analyzed.
Next, after filling the obtained coffee beverage into a 190 g can, it was sealed and subjected to retort sterilization treatment (124 ° C., 21 minutes) to obtain a container-packed coffee beverage. Next, the amount of chlorogenic acid and the amount of hydroxyhydroquinone after heat sterilization were analyzed. Next, after storing the container-packed coffee beverage at 60 ° C. for 1 week, the amount of chlorogenic acid and the amount of hydroxyhydroquinone after storage were analyzed, and a sensory test was performed. The results are also shown in Table 1.

Example 2
A container-packed coffee beverage was obtained by the same operation as in Example 1 except that the blending amount of creatine in the coffee beverage was changed to 0.5% by mass. Next, the packaged coffee drink before and after storage at 60 ° C. for 1 week was analyzed, and a sensory test was performed. The results are also shown in Table 1.

Example 3
A container-packed coffee beverage was obtained by the same operation as in Example 1 except that the blending amount of creatine in the coffee beverage was changed to 0.005% by mass. Next, the packaged coffee drink before and after storage at 60 ° C. for 1 week was analyzed, and a sensory test was performed. The results are also shown in Table 1.

Example 4
A packaged coffee drink was obtained by the same operation as in Example 1 except that cystine was added instead of creatine. Next, the packaged coffee drink before and after storage at 60 ° C. for 1 week was analyzed, and a sensory test was performed. The results are also shown in Table 1.

Comparative Example 1
A container-packed coffee drink was obtained by the same operation as in Example 1 except that creatine was not blended. Next, the packaged coffee drink before and after storage at 60 ° C. for 1 week was analyzed, and a sensory test was performed. The results are also shown in Table 1.

  Table 1 confirms that the formation of hydroxyhydroquinone is suppressed not only at the time of heat sterilization but also at the time of long-term storage in the container-packed coffee beverage containing the neutral amino acid, and the change in flavor before and after storage is suppressed. I understood that. Moreover, it turned out that the container-packed coffee drink which mix | blended creatine as a neutral amino acid is excellent in stability, chlorogenic acids hardly deteriorate.

Claims (8)

  A packaged coffee beverage containing 0.005 to 1% by mass of a neutral amino acid.   Containerized coffee drink containing creatine.   The container-packed coffee drink of Claim 1 or 2 whose content of the chlorogenic acids in the said container-packed coffee drink is 0.01-5 mass%.   The container according to any one of claims 1 to 3, wherein the content mass ratio [(A) / (B)] of (A) a neutral amino acid and (B) chlorogenic acids is 0.01 to 5. Stuffed coffee drink.   A hydroxyhydroquinone production inhibitor for containerized coffee beverages containing a neutral amino acid as an active ingredient.   The hydroxyhydroquinone production inhibitor according to claim 5, wherein the neutral amino acid is creatine.   The hydroxyhydroquinone production inhibitor according to claim 5 or 6, wherein an application amount of the neutral amino acid is 0.005 to 1 mass% with respect to the packaged coffee beverage.   The production | generation suppression method of the hydroxyhydroquinone of a packaged coffee drink including the process of adding the hydroxyhydroquinone production inhibitor of any one of Claims 5-7 to a coffee extract.