JP6334843B2 - Method for producing fruit soaked liquor - Google Patents

Description

  The present invention relates to a method for producing a fruit soaked liquor containing a cyan glycoside that achieves both a reduction in the content of ethyl carbamate (hereinafter referred to as “CAE”) and a sense of ripening.

CAE is said to increase carcinogenicity when taken in excess. Alcoholic beverages (alcoholic beverages) are also known to contain trace amounts of CAE.
As a typical CAE production mechanism in alcoholic beverages, a pathway in which CAE is produced by a reaction between urea and ethanol produced during brewing is known. Also, especially in alcoholic beverages using drupes such as plums and peaches, cyan glycosides contained in fruits are decomposed into hydrogen cyanide by enzymatic reaction, then oxidized to cyanic acid, and cyanic acid and ethanol react. The path | route which CAE produces | generates is also known (nonpatent literature 1). It is desired to produce an alcoholic beverage with a low CAE content.

  Heat treatment as a method to reduce the CAE content of alcoholic beverages (for example, fruit-immersed liqueurs such as plum wine) made from fruits (plums such as plum, apricot, peach, loquat, plum, and cherry) containing cyan glycosides A method using a processed fruit as a raw material (Patent Document 1), a method of adding a substance having an antioxidant effect such as sulfite gas, sulfite, polyphenol, ascorbic acid in addition to the fruit raw material (Patent Document 2), under low oxygen conditions (Patent Document 3), and a method of using the fruit as it is or after adding water or a low-concentration alcohol solution and leaving it for 3 days or more (Patent Document 4).

JP 2008-306973 A JP 2008-306975 A JP 2009-17877 A JP 2009-296941 A

The EFSA Journal (2007) 551, 1-44

  However, in these methods, the oxidation reaction that is considered necessary for the flavor formation of the fruit soaked liquor is suppressed, the ripening of the soaked liquor does not progress, the mellow flavor cannot be obtained, and the color tone becomes thin. I found it to happen.

  Therefore, this invention makes it a subject to make the reduction | restoration of CAE content and provision of sufficient ripening feeling compatible in fruit immersion liquor.

  As a result of earnestly examining the above problems, the present inventor can reduce the CAE content of the soaking liquor by treating with means for capturing metal ions, and is considered to be an oxidation reaction that is necessary for the progress of aging. It has been found that a sufficient aging feeling can be imparted to the soaked liquor without inhibiting the above.

The present invention is as follows.
(1) A method for producing a fruit-immersed liquor comprising immersing a fruit containing a cyan glycoside in an aqueous alcohol solution,
The said manufacturing method further including processing alcohol aqueous solution and / or fruit immersion liquor using the means to capture | acquire a metal ion.
(2) The means for capturing the metal ions is a chelating agent, and the treatment includes adding the chelating agent to an alcohol aqueous solution and / or fruit soaked liquor, and the alcohol aqueous solution and / or fruit soaking liquor to the chelating agent. The manufacturing method as described in said (1) including at least 1 of making it contact.
(3) The manufacturing method as described in said (1) or (2) with which the said process is performed with respect to fruit immersion liquor.
(4) The manufacturing method according to any one of (1) to (3), wherein the means for capturing the metal ions is a chelate resin, and the treatment includes contacting with the chelate resin.
(5) The production according to any one of (1) to (4) above, wherein the fruit comprising cyan glycoside is one or more kinds of fruit selected from the group consisting of ume, peach and apricot. Method.
(6) Fruit soaked liquor obtained by the production method according to any one of (1) to (5) above.
(7) A method for reducing the content of ethyl carbamate in fruit-immersed liquor obtained by immersing a fruit containing cyan glycoside in an aqueous alcohol solution, and advancing ripening, comprising means for capturing metal ions The method as described above, comprising treating an aqueous alcohol solution and / or fruit soaked liquor.
(8) The method as described in said (7) the said process is performed with respect to fruit immersion liquor.

  In the production of fruit soaking liquor containing cyan glycosides, a reduction in the CAE content and a rich ripening sensation can be achieved by performing treatment using means for capturing metal ions.

3 is a graph showing the measurement result of the amount of CAE in Example 1.

  In this specification, unless otherwise specified, alcohol means ethyl alcohol (ethanol). Further, the alcohol content refers to the volume% of alcohol in the aqueous alcohol solution.

(Fruit soaked liquor)
Fruit soaked liquor is sake obtained by immersing fruits in an aqueous alcohol solution and storing them for a certain period of time. In the present specification, both sake in a state where the fruit is soaked, and alcohol in a state where the soaking is completed after the fruit is removed because the desired quality has been obtained are both referred to as “fruit soaked liquor”. To be included.

  The storage period from the start of immersing the fruit in the aqueous alcohol solution to the end thereof is referred to as “immersion period” in the present specification. Fruit components such as saccharides, organic acids, amino acids, etc. leached from the fruit during the soaking period in the soaking liquor undergo various chemical reactions, including oxidation reactions, between the ingredients and / or alcohol. Forms the special flavor of sake. After the soaking period, an additional storage period may be added to further increase this aged flavor.

  In the present invention, a fruit containing cyan glycoside is used as a raw material fruit for fruit soaked sake. A cyan glycoside is a glycoside in which a sugar is bonded to the hydroxyl group of α-hydroxynitrile (cyanhydrin), and is also referred to as cyanide glycoside or cyanhydrin glycoside. Specific examples of cyan glycosides contained in fruits include amygdalin (apricot, ume, peach, plum, almond, loquat, cherry, etc.), which is abundant in the seeds of the fruits of the Rosaceae genus Sakura. Amygdalin and prunasin are known.

  The fruit used in the present invention may be a fruit containing a cyan glycoside, and examples thereof include, but are not limited to, apricot, plum, peach, plum, almond, loquat, and cherry. As long as it is an edible fruit, the variety, production area, and maturity are not particularly limited.

In the present invention, a means for capturing metal ions is used. The means for capturing metal ions refers to technical means for inactivating at least one of metal ions, and is not particularly limited as long as such an effect is recognized. Examples of such technical means include an ion exchange resin that can capture at least one of metal ions and a chelating agent. Here, the chelating agent is a compound that can coordinate to a metal ion to form a chelate (complex), and a functional group that can coordinate to a metal ion to form a chelate (complex) (chelate forming group). ) Resin (chelate resin). Examples of the compound that can form a chelate by coordinating with a metal ion include ethylenediaminetetraacetic acid (EDTA), ethylenediamine-N, N′-disuccinic acid (EDDS), and the like. Examples of the chelate resin include N—O, S—N, N—N, and O—O types. Among them, a resin having an iminodiacetic acid type (—N (CH ₂ COO—) ₂ ) chelate-forming group is preferable because it has a high effect of reducing the amount of CAE.

  In the present invention, the alcohol aqueous solution and / or the fruit soaked liquor is treated using a means for capturing metal ions. Here, “alcohol aqueous solution” refers to liquor (alcohol aqueous solution) before soaking the fruit, and “fruit soaked liquor” is sake in a state where the fruit is immersed as described above, Or the liquor from which the fruit has been removed (after soaking).

  Examples of the “treatment” include, but are not limited to, adding a means for capturing metal ions to an aqueous alcohol solution and / or fruit-immersed liquor, or bringing them into contact with each other by passing them through. Specifically, an ion exchange resin, a chelate resin, and / or a compound having a chelate-forming ability are added to an aqueous alcohol solution and / or fruit soaked liquor (including removing these if necessary) Examples include filling an alcohol container and / or fruit soaked liquor with a container such as a column.

  The timing of performing the “treatment” can be freely set according to the means for capturing the metal ions to be used, and may be performed on the alcohol aqueous solution before immersing the fruit, or after immersing the fruit. Although it may be performed on the fruit soaked liquor, it is preferably performed on the fruit soaked liquor. Specifically, when a compound having a chelate-forming ability is added to an alcohol aqueous solution and / or fruit-immersed liquor, it can be carried out at any time without any restriction. In view of the effect, it is preferable to perform the treatment after lapse of 2 months or more, more preferably 3 months or more after the start of immersion. Here, as described above, “fruit soaked liquor” includes both sake in a state where the fruit is soaked and liquor that has been soaked. The CAE content of the fruit soaked liquor tends to increase slightly after removing the fruit from the soaked liquor as well as the period of soaking the fruit (not shown experimental results).

  The reason why the aging feeling can be imparted while reducing the CAE content of the fruit soaked liquor according to the present invention is not clear, but the present inventor presumes as follows. The oxidation reaction from hydrogen cyanide to cyanic acid involves the hydroxyl radicals generated by the electron transfer between metal ions in alcoholic water solution or fruit-immersed liquor and trace amounts of hydrogen peroxide. It is estimated that the generation of hydroxy radicals from hydrogen peroxide is suppressed and the oxidation reaction from hydrogen cyanide to cyanic acid is suppressed. When the generation of cyanic acid is suppressed, the generation of CAE using cyanic acid as a precursor is also suppressed. On the other hand, capture of these ions suppresses generation of hydroxy radicals, but does not capture oxygen itself. Therefore, it is considered that a certain oxidation reaction that is considered to be involved in aging proceeds. The present inventor presumes that a certain oxidation reaction is necessary for the flavor formation of fruit soaked liquor, and the soaked liquor of the present invention is presumed to be a soaked liquor with a sense of ripening because the oxidation reaction is not suppressed. The

  In the present invention, the type of the aqueous alcohol solution in which the fruit containing the cyan glycoside is immersed is not particularly limited as long as it is drunk as a normal alcoholic beverage. Distilled liquor such as whiskey, vodka, rum, shochu, spirits, brewed liquor such as Japanese sake, wine and beer, and mixed liquor such as liqueur can be used. In order to enjoy the characteristic flavor of fruits, liquors that do not have a strong flavor are preferred, and continuous distillation spirits obtained by distilling alcohol-containing products with a continuous distillation machine and continuous distilled alcohol are more preferably used. be able to. Specific examples of such continuous distillation spirits and continuous distillation alcohols include low-scented spirits such as vodka stipulated by the Japanese liquor tax law, alcohol for raw materials such as neutral spirits and grains spirits, and continuous And so-called distillate shochu (so-called shellfish shochu). Depending on the quality of the target fruit soaked liquor, a single type of alcohol aqueous solution may be used, or a plurality of types of alcohol aqueous solution may be used for the purpose of changing the flavor characteristics of the extract.

  The alcohol content of the aqueous alcohol solution when immersing the fruit is not particularly limited. In normal fruit soaked liquor, it is often immersed in an alcohol aqueous solution having an alcohol content of 20 to 40%, but it can be carried out at higher or lower alcohol content.

  The alcohol content in the present invention can be measured by the method described in the National Tax Agency Predetermined Analysis Method (Heisei 19 National Tax Agency Instruction No. 6, revised on June 22, 2007). Specifically, it can measure with the following method about what added saccharide | sugar and what did not add.

  When the sample containing the target alcohol is not added with a saccharide such as sucrose and there is no risk of burning: 100 to 150 mL of a sample is accurately collected at 15 ° C. using a measuring flask. This is transferred to a 300-500 mL flask, each of the volumetric flasks is washed twice with 15 mL of water, and the cleaning solution is also transferred into the flask. Perform direct-fire distillation using the volumetric flask used for sample collection as the receiver. After 70% or more of the sample is distilled, add water to the distillate and return to the original volume at 15 ° C. A sample.

  In the case of a sample that may be burnt to which a saccharide such as sucrose is added: An analytical sample is prepared by a steam distillation method. That is, 100 to 150 mL of sample is accurately collected at 15 ° C. using a volumetric flask. This is transferred to a 500 mL double flask, each of the volumetric flasks is washed twice with 15 mL of water, and the cleaning solution is also transferred into the flask. Steam distillation is performed using the volumetric flask used for collecting the sample as a receiver, and after 98% or more of the collected amount is distilled, water is added to the distillate to return to the original volume at 15 ° C. And

  The density at 15 ° C. of the analysis sample prepared as described above was measured with a vibration-type densitometer, and “Table 2 Alcohol content and density (15 ° C.) and specific gravity (15/15), which is an appendix to the National Tax Agency prescribed analysis method. The alcohol content can be obtained by conversion using the “° C.) conversion table”. In the present specification, a vibration density meter DA-310 manufactured by Kyoto Electronics Industry Co., Ltd. was used as the vibration density meter.

  The ratio of the fruit containing cyan glycoside to be immersed and the alcohol aqueous solution to be immersed can be freely adjusted depending on the quality to be obtained, but it is preferably 100 to 1000 g of fruit with respect to 1 L of alcohol aqueous solution, and 1 L of alcohol aqueous solution On the other hand, 130 to 800 g of fruit is preferable because the flavor balance of the extract is improved.

  In the fruit soaked liquor of the present invention, sugars such as sucrose may be added at the start of fruit soaking. In addition to improving the taste by imparting sweetness, the extraction efficiency is increased by osmotic pressure, and the effect of shortening the immersion period can be expected. The saccharide is not particularly limited, and oligosaccharide, sucrose, fructose, maltose, glucose and the like can be used. High sweetness sweeteners such as sucralose and acesulfame K, honey and the like can also be used. When adding said saccharide | sugar etc. to immersion liquor, the addition amount is not specifically limited, Generally, it is about 30-80g with respect to 100g of fruits.

  The soaking period in the soaking liquor of the present invention can be freely adjusted depending on the quantity ratio between the fruit and the aqueous alcohol solution and the desired quality. As an example of the immersion period, although it depends on the quantity ratio between the fruit and the aqueous alcohol solution, it is preferably 2 months or longer, more preferably 3 months or longer. If the soaking period is long, the umami component contained in the fruit is excessively extracted, and the quality of the soaking liquor is impaired.

  The temperature of the soaked liquor during the soaking period will deteriorate if the temperature is low, and if the temperature is high, the extraction efficiency will increase, but chemical changes such as oxidation and Maillard reaction will proceed excessively and the quality will deteriorate. About 10-40 degreeC is preferable, 15-35 degreeC is more preferable, and 20-30 degreeC is still more preferable. In addition, it is preferable that the temperature at the time of immersion measures the temperature of the immersion liquid in the contact part of immersion liquid and immersion container, and it is preferable to measure the depth near the center part of immersion liquid.

  After the soaking period, the fruits and optionally insoluble solids are removed. As the means for removing the insoluble solid content, an appropriate means may be selected according to the degree of generation of the insoluble solid content. For example, if the amount of insoluble solids produced is small, it can be removed by means such as orientation removal, and if the amount produced is large, the insoluble solids can be removed using solid-liquid separation means. As the solid-liquid separation means, specifically, usual separation means such as centrifugation, membrane filtration, diatomaceous earth filtration, filter paper filtration can be carried out. In order to improve working efficiency, a plurality of solid-liquid separation means may be combined.

  From another point of view, the present invention can be understood as a method of reducing the CAE content of fruit-immersed liquor while not stopping (maintaining) ripening. That is, according to the present invention, it is possible to impart a rich flavor with a sense of maturity and a color with an appropriate intensity to fruit soaked liquor while suppressing the generation of CAE. Specifically, in the method of the present invention, the fruit is a fruit containing cyan glycoside, and the alcohol aqueous solution before the fruit immersion and / or the liquor after the fruit immersion is treated with a means for capturing metal ions. including. The ripening feeling includes a mellow and rich flavor that can be obtained when a fruit is immersed for a long period of time, and a light yellow to brown color tone.

[Example 1] Efficacy of chelating agent with respect to the prior art A soup liquor (plum liquor) was produced by using the Minamitakaume fruit in the following manner. 621 g of plum fruit, 416 g of sucrose type liquid sugar (Brix 68 degrees), 420 mL of neutral spirits (alcohol content 95%) and 377 mL of ion-exchanged water were placed in a 2 L container. At this time, the volume of plum wine was about 1700 mL, the alcohol content was about 23.5%, the sugar content was 17 degrees as Brix, and the pH was 3.2 to 3.5.

  The plum wine samples produced in this manner were subjected to various CAE reduction means and immersed for 3 months at room temperature, and then the amount of CAE produced in each plum wine sample was analyzed. Similarly, the amount of CAE produced from a normal plum wine sample (control) without CAE reduction was analyzed. In addition, oxygen was bubbled into the plum wine to increase the dissolved oxygen in the plum wine, and the CAE production amount of the sample that promoted the oxidation reaction by replacing the head space of the container with oxygen was also analyzed.

  As CAE reduction means, a conventionally known method (a method of replacing dissolved oxygen in plum wine and the headspace of the container with an inert gas and a method of adding an antioxidant) and a method of the present invention (adding a chelating agent) Method). Samples in which dissolved oxygen and head space in plum wine were replaced with inert gas were used to reduce dissolved oxygen by bubbling argon gas or nitrogen gas into plum wine, and the head space of the plum wine container was replaced with argon gas or nitrogen. A gas-substituted one was used. In addition, an analysis was also conducted on an anemone pack made by Mitsubishi Gas Chemical Co., Ltd. in an umeshu container to maintain the headspace in an anaerobic state (N number of each level = 2). About each plum wine sample and control which carried out gas substitution, the dissolved oxygen concentration at the time of an immersion start was also measured (refer to Table 1. In addition, the thing which enclosed the aneropack was not measured). The dissolved oxygen concentration of the gas-substituted plum wine sample was about 150 to 250% for the oxygen-substituted sample and about 10 to 20% for the argon-substituted or nitrogen-substituted sample with respect to the control.

  Samples added with antioxidants were analyzed for samples added with vitamin C at various concentrations shown in Table 1 and samples added with potassium metasulfite at various concentrations shown in Table 1. As samples to which a chelating agent was added, samples to which EDTA was added at various concentrations described in Table 1 were analyzed. The CAE content of each sample was measured as follows.

(Measurement of CAE content: preparation of analysis sample)
4 mL of pure water was added to 1 mL of plum wine sample and diluted 5 times. To this, 100 μL of 1000 ppb CAE- d (substituted deuterium for part of hydrogen of the ethyl group of CAE) was added as an internal standard. This was applied to a column ChemElut manufactured by VARIAN, and allowed to stand for 5 minutes, and then eluted with 20 mL of dichloromethane. The eluate was further passed through a column BondElutSAX / PSA manufactured by VARIAN to remove contaminants, and a passing solution was used as a sample. Further, the column was washed several times with dichloromethane, and the washing solution was combined with the sample. The sample was concentrated under reduced pressure at 450 mmHg and 35 ° C., and further concentrated to 1 mL through a spitz tube through nitrogen gas to obtain an analytical sample.

(Measurement of CAE content: GC / MS analysis conditions)
Using the analytical sample prepared by the above procedure, the CAE content was measured by GC / MS. The analysis conditions are as follows.

Equipment used: Agilent Technologies 5975C GC / MSD
Column used: HP-INNOWAX (30m x 0.25mm)
Carrier gas: Helium Flow: 1.0 mL / min
Inlet temperature: 200 ° C
Column temperature: raised from 45 ° C. (held for 5 minutes) at a heating rate of 20 ° C./min and held at 230 ° C. for 5 minutes Injection volume: 1.0 μL
Detector: MS
Ion source temperature: 230 ° C
SIM setting: m / z 62 for CAE, m / z 64 for CAE- d (internal standard)
The breakdown of each sample and the measurement results of CAE content are shown in Table 1 and FIG.

(Sensory evaluation and color analysis)
About the said umeshu sample, the sensory evaluation about the presence or absence of the matured flavor was performed by the trained professional panelist. Moreover, it evaluated by measuring the light absorbency of wavelength 500nm about the color tone which aged each sample. The sensory evaluation and color tone analysis results are shown in Table 2.

(result)
The oxygen substituted sample contained about 250-270% CAE relative to the control. On the other hand, those maintaining the anaerobic state and those substituted with argon were suppressed to about 80% and about 90% of the CAE amount of the control, respectively, suggesting that inert gas replacement is effective in suppressing CAE production. In the nitrogen gas replacement sample, the CAE amount slightly increased from about 115 to 120% with respect to the control, but it is estimated that oxygen was slightly involved during nitrogen bubbling. The sample to which the antioxidant was added was suppressed to a CAE amount of about 80% or less with respect to the control although there was variation, and the CAE amount became lower as the added amount of the antioxidant added (350 ppm of potassium metasulfite). Suppressed to about 15% of control with added sample). Even in the chelating agent-added sample, the amount of CAE produced was suppressed, and the production of CAE was not observed at EDTA 100 ppm at about 20% or less relative to the control, EDTA 300 ppm at about 18% or less, and EDTA 1500 ppm.

  On the other hand, regarding the sensory evaluation, both the inert gas substitution group and the antioxidant addition group had a lighter flavor than the control, indicating a lack of aging. Furthermore, the antioxidant-added sample was recognized to have a flavor peculiar to each antioxidant, and it was suggested that the sample might be different from normal plum wine quality. In addition, the color tone (darkness) of the antioxidant addition group is about 90% or less of the control, and the tendency increases as the amount of addition of the antioxidant increases. The color stayed at 60%. It was suggested that the addition of the antioxidant is effective in suppressing the formation of CAE, but is disadvantageous for imparting a sense of ripening, which is important for fruit soaked sake. In addition, the inert gas substitution group also showed a tendency to lack a sense of ripening as in the case of the antioxidant-added sample (color tone unmeasured).

  The chelating agent-added sample had a mellow flavor that was aged, and was comparable to the control. The color tone was as thick as the control and had the appearance of an aged soaking liquor.

  By using a means for trapping metal ions (addition of a chelating agent), it has been clarified that CAE generation is not only extremely suppressed as compared with the conventional method, but also a sufficient aging feeling is imparted. . Moreover, the quality was inferior to that of a control that had undergone a similar immersion period.

[Example 2] Method of contacting with chelate resin For 100 mL of plum wine produced in the same manner as in Example 1 (immersion period 3 months), two types of chelate resins manufactured by Mitsubishi Chemical Corporation: Diaion CR11 (iminodiacetic acid type (- N (CH ₂ COO—) ₂ )) and Diaion CR20 (polyamine type (—NH (CH ₂ CH ₂ NH) _n · H)) were added in an amount of 3 g (= 3 w / v%) and stirred for 30 minutes. And stirred. After stirring, the plum wine from which the resin was removed was stored at 50 ° C. for 12 days in an incubator and subjected to an acceleration test to examine the amount of CAE. The CAE analysis conditions are the same as in Example 1. As a result, assuming that the CAE amount of the control not subjected to the chelate resin treatment was 100 (%), the CR11-treated product was 41%, and the CR20-treated product was 99%.

[Example 3] Timing of chelation treatment The timing of chelation treatment was examined. Plum wine produced in the same manner as in Example 1 was passed through a chelate resin column after a certain period of time (three levels of 1 month / 2 months / 3 months) after the start of soaking, and the resulting liquid was again plum fruit It was returned to the container containing, and immersion was continued. After 6 months of soaking, the amount of CAE in each plum wine sample was examined. What was immersed for 6 months without passing through the chelate resin column was used as a control. As the chelate resin column, 20 g of chelate resin Diaion CR11 (iminodiacetic acid type (—N (CH ₂ COO—) ₂ )) manufactured by Mitsubishi Chemical Corporation was packed in a 1.3 cm × 20 cm inner diameter column. The liquid conditions were a plum wine sample of 1350 mL and a flow rate of 7.5 mL / min.

As a result, the CAE amount of the sample that was chelated after 1 month / 2 months / 3 months after the start of immersion was 95% / 70, assuming that the CAE amount of the control not subjected to the chelating resin treatment was 100 (%). It was revealed that the rate of decrease in the amount of CAE was higher in the sample chelated after 2 months and 3 months from the start of immersion. Thereby, it was suggested that it is more effective to process after a fixed immersion period.

Claims (5)

A method for producing a fruit soaked liquor comprising immersing a fruit containing cyan glycoside in an aqueous alcohol solution,
The manufacturing method further comprising capturing metal ions by treating fruit soaked liquor with an EDTA and / or iminodiacetic acid type chelate resin after two months or more have passed since the start of soaking . The manufacturing method according to claim 1, wherein the treatment includes at least one of adding EDTA to fruit soaked liquor and bringing fruit soaked liquor into contact with EDTA . The manufacturing method according to claim 1, wherein the treatment includes bringing fruit soaked liquor into contact with an iminodiacetic acid type chelate resin.   The manufacturing method of any one of Claims 1-3 whose fruit containing the said cyan glycoside is 1 or 2 or more types of fruit chosen from the group which consists of a plum, a peach, and apricot. A method for reducing the ethyl carbamate content of fruit-immersed liquor obtained by immersing a fruit containing cyan glycoside in an aqueous alcohol solution, and advancing ripening,
The method comprising capturing metal ions by treating fruit soaked liquor with an EDTA and / or iminodiacetic acid type chelating resin after two months or more have passed since the start of soaking .