JP5684310B2 - White clay treated food and drink - Google Patents

Description

  The present invention relates to a clay-treated food / beverage product, and more particularly to a clay-treated food / beverage product in which the content of an imidazole derivative is reduced.

  Imidazole derivatives are included in various foods such as coffee, caramel pigment, malt, or soy sauce. Among these imidazole derivatives, humans ingested a large amount of 4-methylimidazole (4MI), 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole (THI), and the like. There are concerns about the undesired effects of the case.

  For example, 4MI is produced in the production process of caramel color, coffee, dark beer, soy sauce, etc. produced by adding a sulfite compound or ammonium compound to sugar, but it is the largest in the European Food Safety Authority (EFSA). It is regulated to 250 mg / kg or less.

  Various methods aimed at suppressing the amount of 4MI produced when producing foods and drinks containing 4MI have been studied so far (see, for example, Patent Document 1 and Patent Document 2). However, in these 4MI production | generation suppression methods, when 4MI already exists in food-drinks, it had the subject that it was difficult to reduce.

  In order to solve this problem, methods for reducing 4MI have been proposed from foods and drinks containing 4MI (see, for example, Patent Document 3 and Patent Document 4). However, the 4MI reduction method using these ultrafiltration membranes and activated carbon may impair the appearance and the flavor of foods and drinks containing 4MI.

  Therefore, there is still a need for a method for reducing the imidazole derivative by a simple method without losing the appearance and flavor even after storage.

JP 62-48371 A JP 62-48372 A Japanese Patent Publication No. 2-18054 International Publication No. 2011/126752

  An object of the present invention is to provide a method capable of reducing an imidazole derivative, a food / beverage product with reduced imidazole derivative, and a method for producing the food / beverage product by a simple method without losing the appearance and flavor even after storage. .

  The present inventors have found that the content of the imidazole derivative in the food or drink can be reduced by bringing the food or drink containing the imidazole derivative into contact with the clay.

That is, the present invention relates to the following (1) to (8).
(1) A method for reducing an imidazole derivative, comprising bringing a food or drink containing the imidazole derivative represented by the following formula (I) into contact with clay.
Wherein R ¹ is hydrogen or —COR ³ (where R ³ represents a C _1-5 alkyl group), and R ² is a C _1-5 alkyl group or a hydroxy C _1-5 alkyl group. is there).
(2) The reduction method according to (1), wherein the imidazole derivative is 4-methylimidazole or 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole.
(3) The reduction method according to (1) or (2), wherein the food or drink containing the imidazole derivative is coffee, caramel color, caramel color-containing food or drink, beer manufactured from malt, or soy sauce.
(4) A caramel dye, which is a caramel dye formed by a clay treatment, and the imidazole derivative represented by the formula (I) described in (1) is contained in an amount of 1 to 200 ppm based on the solid matter of the caramel dye.
(5) The caramel dye according to (4), wherein the imidazole derivative is 4-methylimidazole or 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole.
(6) A container-packed beverage containing a caramel pigment formed by white clay treatment, and 1 to 100 ppb of the imidazole derivative represented by the formula (I) described in (1) is contained with respect to the beverage. , Caramel color-containing container-packed beverages.
(7) It is a caramel dye containing an imidazole derivative and an iron ion, and the imidazole derivative represented by the formula (I) described in (1) is contained in an amount of 1 to 200 ppm based on the solid matter of the caramel dye, A caramel dye containing 10 to 500 ppm of ions based on the solid matter of the caramel dye.
(8) A method for producing a food or drink in which the imidazole derivative is reduced, comprising a step of bringing the food or drink containing the imidazole derivative represented by the formula (I) described in (1) into contact with white clay.

  ADVANTAGE OF THE INVENTION According to this invention, the new method which can reduce the imidazole derivative represented by the said Formula (I) can be provided by a simple method, without impairing an external appearance and flavor after storage.

The measurement result of the ultraviolet absorption spectrum of 4-methylimidazole (4MI) is represented. The calibration curve based on the measurement result of the ultraviolet absorption spectrum of 4-methylimidazole (4MI) is represented. The removal effect of 4-methylimidazole (4MI) by acid clay treatment is shown. In FIG. 3, “control” is a group to which no acid clay is added, “0.5%” is a group in which 0.5% by mass of acid clay is added to a solution containing 4 methylimidazole (4MI), and “1%”. Represents a group in which 1% by mass of acid clay is added to a solution containing 4 methylimidazole (4MI).

Detailed description of the invention

Method for reducing imidazole derivative in food or drink The method for reducing an imidazole derivative of the present invention comprises bringing a food or drink containing an imidazole derivative into contact with white clay, and containing the imidazole derivative contained in the food or drink. This is a method of reducing the amount.

The imidazole derivative reduced by the reduction method of the present invention is an imidazole derivative represented by the following formula (I):
Wherein R ¹ is hydrogen or —COR ³ (where R ³ represents a C _1-5 alkyl group), and R ² is a C _1-5 alkyl group or a hydroxy C _1-5 alkyl group. is there).

Here, the "C _1-5" as referred to as "C _1-5 alkyl group", the number of carbon atoms in the alkyl group is meant to be a 1-5. The “C _1-5 alkyl group” is, for example, a straight chain such as methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, cyclopropyl, cyclobutyl, cyclopentyl and the like. , Branched chain, cyclic, or a combination thereof, preferably linear or branched, and more preferably methyl.

The hydroxy C _1-5 alkyl group is not particularly limited as long as one or more hydrogen atoms of a linear, branched or cyclic alkyl group are substituted with a hydroxyl group. , Preferably linear or branched, and more preferably 1,2,3,4-tetrahydroxybutyl.

According to a preferred embodiment of the imidazole derivative reduced by the reduction method of the present invention, in the compound represented by the above formula (I), imidazole in which R ¹ is hydrogen and R ² is a C _1-5 alkyl group. Derivatives are provided.

More preferably, the imidazole derivative reduced by the reduction method of the present invention is an imidazole derivative (4-methylimidazole (4-MI)) represented by the following formula.

According to another preferred embodiment of the imidazole derivative reduced by the reduction method of the present invention, in the compound represented by the formula (I), R ¹ is —COR ³ (where R ³ is C _1-5 alkyl). An imidazole derivative is provided wherein R ² is a hydroxy C _1-5 alkyl group.

More preferably, the imidazole derivative reduced by the reduction method of the present invention is an imidazole derivative represented by the following formula (2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole ( THI)).

  The imidazole derivative reduced by the reduction method of the present invention is one or more selected from the group consisting of 4-methylimidazole and 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole. More preferably, it contains 4-methylimidazole (4MI).

  The food and drink used in the method for reducing an imidazole derivative of the present invention is not particularly limited as long as it is a food or drink containing even a small amount of an imidazole derivative, but preferably a coffee bean extract (coffee) or malt. Beer, soy sauce, sauce, caramel color, or caramel color-containing food or drink (preferably cola). The types of coffee beans and malt used in coffee and beer are not particularly limited, but coffee beans and malt having a low L value are more preferable. This is because coffee beans and malt having a low L value contain a relatively large amount of 4MI. Examples of malt having a low L value include malt used as a raw material for black beer.

Caramel dye (caramel) is a solution containing a brown polymer dye obtained by heating and polymerizing saccharides, and is obtained using various polymerization catalysts (for example, ammonium compounds and sulfite compounds). The solution containing the brown pigment is also included in the caramel pigment contained in the food and drink used in the reduction method of the present invention. The caramel color is classified into the following four types according to the production method thereof, but the caramel color produced by any production method may be included in the food or drink.
Caramel I: Starch hydrolyzate, molasses or sugar edible carbohydrates obtained by heat treatment or heat treatment with addition of acid or alkali, without using sulfite and ammonium compounds thing.
Caramel II: A product obtained by heat-treating starch hydrolyzate, molasses or saccharide edible carbohydrate with sulfite compound added or acid or alkali added thereto and not using ammonium compound.
Caramel III: A product obtained by heat-treating starch hydrolyzate, molasses or saccharide edible carbohydrate by adding an ammonium compound, or adding an acid or alkali thereto, and not using a sulfite compound.
Caramel IV: A product obtained by heat-treating a starch hydrolyzate, molasses or sugar edible carbohydrate with a sulfite compound and an ammonium compound or an acid or alkali added thereto.

  Although any caramel color can be used as the food or drink used in the reduction method of the present invention, it is preferably a caramel color produced by the above-mentioned production method of caramel III or IV, more preferably production of caramel IV. Caramel color produced by the method. These production methods are production methods in which 4-methylimidazole (4MI) is more easily generated.

According to a preferred embodiment of the method for reducing an imidazole derivative of the present invention, it is selected from the group consisting of 4-methylimidazole and 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole. A food and drink containing one or more imidazole derivatives and white clay, wherein the food or drink is made from coffee, caramel pigment, caramel pigment-containing food (preferably cola), and malt Or a method for reducing imidazole derivatives, which is soy sauce. The caramel pigment-containing food or drink is not particularly limited, but preferably includes processed soy sauce such as cola, soy sauce, miso and soy sauce, sauce, soup, seasoning, liqueur, or beer. .

The clay used in the method for reducing an imidazole derivative of the present invention may be either acidic clay or activated clay, but more preferably acidic clay. As a general chemical component of clay, it has SiO ₂ , Al ₂ O ₃ , Fe ₂ O ₃ , CaO, MgO, etc., but when used in the reduction method of the present invention, the SiO ₂ / Al ₂ O ₃ ratio is Although it does not specifically limit, it is 3-12, Preferably it is 4-9. Further, in an acidic clay and active clay, Fe ₂ O ₃ 2 to 5 wt%, CaO 0 to 1.5 mass%, having composition containing such MgO 1 to 7 wt% preferred. The activated clay used in the present invention is obtained by treating a naturally occurring acidic clay (montmorillonite clay) with a mineral acid such as sulfuric acid, and is a compound having a porous structure having a large specific surface area and adsorbing ability. In addition, it is known that the activated clay used in the present invention is obtained by further acid-treating acidic clay, its specific surface area is changed, decolorization ability is improved, and physical properties are changed.

The specific surface area of the acid clay or the activated clay is preferably 50 to 350 m ² / g, although it varies depending on the degree of acid treatment. For example, as the acid clay, commercially available products such as Mizuka Ace # 20, Mizuka Ace # 200, Mizuka Ace # 400, Mizuka Ace # 600, and Mizrite (manufactured by Mizusawa Chemical Co., Ltd.) can be used. For example, as the activated clay, commercially available products such as Galeon Earth NVZ, Galeon Earth V2, Galeon Earth NF2, and NFX (manufactured by Mizusawa Chemical Co., Ltd.) can be used.

  According to a preferred embodiment of the present invention, in the reduction method of the present invention, the pH of the food or drink when the food or drink containing the imidazole derivative is in contact with the clay is preferably 1 to 10, more preferably. pH is 1.5-7.

  According to another preferable aspect of the present invention, in the reduction method of the present invention, the food / beverage product containing the imidazole derivative and the pH of the food / beverage product when the acid clay is in contact are preferably 1-10, More preferably, it is pH 2-7, More preferably, it is pH 2-5.

  According to another preferable aspect of the present invention, in the reduction method of the present invention, the food / beverage product containing the imidazole derivative and the activated clay in contact with the activated clay preferably have a pH of 1-10, More preferably, the pH is 1.5 to 6.5.

  The food / beverage products containing the imidazole derivative used for the reduction method of this invention may be made to contact the clay containing both acid clay and activated clay, and may be made to contact any one. A plurality of types of acid clay and activated clay may be mixed and used. Preferably, it is an aspect made to contact with acid clay.

  The amount of white clay to be brought into contact with the food or drink containing the imidazole derivative used in the reduction method of the present invention is appropriately determined based on the amount of the imidazole derivative contained in the food or drink, the adsorption ability of the white imidazole derivative, etc. Those skilled in the art can appropriately determine the type of material used in the food or drink, the type of clay, and the like. For example, when caramel pigment is used as a food or drink containing an imidazole derivative, the amount of clay (preferably acidic clay) to be contacted is 0.1 to 10% by mass, more preferably 1 to 8% by mass, and still more preferably. It can be 3-8 mass%, More preferably, it can be 5-8 mass%.

  Although the reduction method of this invention will not be specifically limited if content of the imidazole derivative represented by the said formula (I) in food / beverage products reduces, Compared with the food / beverage products before white clay treatment, it is 10 % Is preferably reduced, more preferably 50% or more. In addition, the content of the imidazole derivative represented by the above formula (I) in the food and drink after the clay treatment is not particularly limited. However, when the food or drink is a caramel dye, It is 1-200 ppm (preferably 100 ppm or less) with respect to a solid substance. Moreover, when it is a container-packed drink containing the caramel pigment formed by the clay treatment, the imidazole derivative represented by the above formula (I) is 1 to 100 ppb, more preferably 1 to 30 ppb, Preferably it is less than 30 ppb.

In addition, coffee, caramel dye, caramel dye-containing food and drink (preferably cola), beer produced from malt, or food and drink such as soy sauce are contained in activated carbon. Compared with the case where it is in contact with the clay, the case where it is brought into contact with the white clay is preferable in terms of appearance because the saturation of the food and drink is small compared to the saturation of the food and drink before contact. The saturation of food and drink can be measured, for example, with a color difference meter (manufactured by Konica Minolta, model number: CM-3500d). The L ^* value, a ^* value, and b ^* value can be measured according to the device manual.

Caramel dye According to one embodiment of the caramel dye of the present invention, it is a caramel dye formed by a clay treatment, and the imidazole derivative represented by the above formula (I) is contained in an amount of 1 to 200 ppm based on the solid matter of the caramel dye. Caramel dyes are provided. The imidazole derivative represented by the above formula (I) contained in the caramel dye of the present invention is not particularly limited as long as it is contained in an amount of 1 to 200 ppm relative to the caramel dye solid, but preferably It is 1-100 ppm with respect to solid content of a caramel pigment, More preferably, it is 1-70 ppm, More preferably, it is less than 60 ppm. By treating the caramel color with clay, the content of the imidazole derivative represented by the above formula (I) contained in the caramel color of the present invention can be reduced. The content of the imidazole derivative in the caramel dye can be measured using high performance liquid chromatography (HPLC) as described in the following examples. Moreover, when the iron ion is contained in the caramel color of the present invention in an amount of 10 to 500 ppm based on the solid matter of the caramel color, it can be considered that the caramel color is a clay-treated one.

  According to another aspect of the present invention, the imidazole derivative represented by the above formula (I) is a container-packed beverage containing a caramel pigment formed by white clay treatment. A caramel pigment-containing container-packed beverage is provided that contains ~ 100 ppb. The imidazole derivative contained in the container-packed beverage of the present invention is not particularly limited as long as it is contained in an amount of 1 to 100 ppb with respect to the container-packed beverage. 1-30 ppb, more preferably less than 30 ppb. By treating the caramel color with clay, the content of the imidazole derivative contained in the container-packed beverage of the present invention can be reduced. The content of the imidazole derivative in the container-packed beverage can be measured using high performance liquid chromatography (HPLC) as described in the following examples. Here, examples of the container-packed beverage include beverages packed in transparent containers such as PET bottles and bottles, and sealed containers such as cans and paper containers.

  According to another aspect of the present invention, there is provided a caramel dye containing an imidazole derivative and an iron ion, the imidazole derivative is contained in an amount of 1 to 200 ppm based on the solid matter of the caramel dye, and the iron ion is contained in the caramel. A caramel dye is provided that is present in an amount of 10 to 500 ppm based on the solid matter of the dye. The imidazole derivative contained in the caramel dye is not particularly limited as long as it is contained in an amount of 1 to 200 ppm with respect to the solid of the caramel dye, but preferably 1 to 1 with respect to the solid content of the caramel dye. It is 100 ppm, More preferably, it is 1-70 ppm, More preferably, it is less than 60 ppm. Further, the iron ion contained in the caramel dye is not particularly limited as long as it is contained in an amount of 10 to 500 ppm with respect to the solid substance of the caramel dye. It is 20-300 ppm, More preferably, it is 30-200 ppm. The iron ions contained in the caramel color may be derived from white clay. The content of imidazole derivatives and iron ions in the caramel dye can be measured using high performance liquid chromatography (HPLC) as described in the following examples.

  Moreover, the caramel pigment | dye containing the imidazole derivative represented by the said Formula (I), and the container-packed drink containing a caramel pigment | dye are the ones when it is made to contact with white clay compared with the case where it contacts with activated carbon. Compared with the saturation of the food / beverage products before making it contact, the saturation of goods is especially preferable on an external appearance, and there are few chroma differences. The saturation of the caramel pigment and the container-packed beverage containing the caramel pigment can be measured in the same manner as described above.

Further, the amount of minerals contained in the caramel pigment of the present invention is not particularly limited, but preferably iron ions are 10 to 500 ppm, calcium ions are 200 to 5000 ppm, Aluminum ion is 10 to 1000 ppm, silicon ion is 100 to 1000 ppm, potassium ion is 50 to 1000 ppm, more preferably, iron ion is 20 to 300 ppm, calcium ion is 500 to 3000 ppm, aluminum ion is 100 to 1000 ppm, silicon ion Is 200 to 1000 ppm, and potassium ions are 80 to 500 ppm. The content of these minerals is preferably the content when the caramel color is treated with acid clay.
Further, the amount of minerals contained in the container-packed beverage containing the caramel color of the present invention is not particularly limited, but preferably 0.01 to 1 ppm of iron ions relative to the container-packed beverage, The calcium ion is 0.2 to 10 ppm, the aluminum ion is 0.01 to 2 ppm, the silicon ion is 0.1 to 2 ppm, and the potassium ion is 0.05 to 2 ppm. More preferably, the iron ion is 0.02 to 0 ppm. .6 ppm, calcium ions are 0.5 to 6 ppm, aluminum ions are 0.1 to 2 ppm, silicon ions are 0.2 to 2 ppm, and potassium ions are 0.08 to 1 ppm. The content of these minerals is preferably the content when the caramel color is treated with acid clay.

  The imidazole derivative, white clay, and food / beverage products used in the white clay treatment contained in the caramel color of the present invention and the packaged beverage containing the caramel color are the same as the imidazole derivative, white clay, and food / beverage products used in the reduction method of the present invention. It may be.

Method for Producing Food / Beverage Products with Reduced Imidazole Derivative The production method of the present invention includes the step of bringing food / beverage products containing the imidazole derivative represented by the above formula (I) into contact with clay, containing the imidazole derivative. It is the manufacturing method of the food-drinks by which the quantity was reduced.

  The step of bringing the food / beverage product containing the imidazole derivative represented by the above formula (I) into contact with the acid clay is not particularly limited, but is preferably performed at pH 1 to 10, more preferably pH 2. It is -7, More preferably, it is pH 2-5. By making it contact on such conditions, the imidazole derivative (especially 4MI) represented by the said formula (I) in this food-drinks can be reduced.

  The step of bringing the food / beverage product containing the imidazole derivative represented by the above formula (I) into contact with the activated clay is not particularly limited, but is preferably performed at pH 1 to 10, more preferably pH 1. 5 to 6.5. By making it contact on such conditions, the imidazole derivative (especially 4MI) represented by the said formula (I) in this food-drinks can be reduced.

  The imidazole derivative, white clay, and food and drink used in the production method of the present invention may be the same as the imidazole derivative, white clay, and food and drink used in the reduction method of the present invention.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, the technical scope of this invention is not limited to these illustrations.

Preparation of calibration curve of 4-methylimidazole (4MI) Using a commercially available 4-methylimidazole (4MI), the ultraviolet absorption spectrum was measured. The concentration of 4MI was dissolved in water so as to be 10 ppm, and the ultraviolet absorption spectrum of the solution was measured using a spectrophotometer (U-3310, manufactured by Hitachi, Ltd.). The measurement results are shown in FIG. The absorption maximum wavelength of 4MI was 212 nm.

  Next, 4MI was dissolved in water so as to be 5, 10, 15, 20 mg / L, and a calibration curve was prepared using a spectrophotometer (manufactured by Hitachi, U-3310). The result is shown in FIG.

Reduction effect of 4-methylimidazole (4MI) by acid clay. Commercially available 4-methylimidazole (4MI) was dissolved in water to a concentration of 10 ppm. Next, acidic clay (Mizuka Ace # 20, manufactured by Mizusawa Chemical Co., Ltd.) was added to this solution so as to be 0.5% and 1%, respectively, and stirred, followed by filtration with a 0.45 μm membrane filter (Millipore). The acid clay was removed. The absorption wavelength was measured using a spectrophotometer, and the 4MI content of this solution was calculated from the calibration curve created above. The result is shown in FIG. It was confirmed that the 4MI content was reduced by bringing the 4MI-containing aqueous solution into contact with the clay.

Reduction effect of 4-methylimidazole (4MI) in caramel color Regarding the commercially available caramel color containing 4-methylimidazole (4MI), the reduction effect of 4MI was examined using acidic clay and activated clay.

  A commercially available caramel pigment (IV) (caramel IV) was diluted with water so that the 4MI content was 25 ppm and dispensed into test tubes in 40 ml aliquots. In these caramel dye aqueous solutions, as shown in Table 1 below, acidic clay (Mizuka Ace # 400, manufactured by Mizusawa Chemical Co., Ltd.), activated clay (Galleon Earth NFX, manufactured by Mizusawa Chemical Co., Ltd.), or activated carbon (CL-K, Ajinomoto Fine Techno) 2, 4 and 6% by mass were added, stirred with a vortex mixer, and contacted at room temperature for 10 minutes. Thereafter, centrifugation was performed at 3000 rpm for 10 minutes, and 30 ml of the supernatant was decanted and collected.

  Next, the collected sample was accurately collected and weighed so as to be in the range of 0.5 to 1 g, and quantified to 50 ml with 0.2 mol / L phosphate buffer (pH 6). 10 ml of this was collected, 10 ml of a 0.1 mol / L di (2-ethylhexyl) phosphate-chloroform solution was added, and the mixture was shaken for 5 minutes. Centrifugation is then performed, and 5 ml of the chloroform layer (lower layer) is collected. After adding 1 ml of 0.1 mol / L phosphoric acid and stirring with a vortex mixer, centrifugation is performed, and the phosphoric acid layer (upper layer) is separated. Then, 4MI analysis was performed by high performance liquid chromatography (HPLC). The HPLC operating conditions were as follows. In addition, Example 7 and the control group 2 are the same as the above except that the pH of the sample solution before the contact treatment between the sample and white clay was adjusted to 5.2 using 1N NaOH (6.6%). Prepared and subjected to analysis.

Model: LC-10AS (manufactured by Shimadzu Corporation)
Detector: UV-visible spectrophotometer SPD-10AV (manufactured by Shimadzu Corporation)
Column: CAPCELL PAK C18 AQ (3 μm), φ4.6 mm × 25 cm (manufactured by Shiseido Co., Ltd.)
Column temperature: 40 ° C
Mobile phase: 0.01 mol / L sodium octane sulfonate, 0.05 mol / L potassium dihydrogen phosphate and acetonitrile (900: 60)
Flow rate: 1.0ml / min
Measurement wavelength: 214 nm
Injection volume: 20 μl

  From Table 1 above, it was confirmed that 4MI can be reduced depending on the amount of white clay added in both acid clay and activated clay. Further, the treatment with acidic clay showed a higher 4MI removal effect compared with the treatment with activated clay, and a higher 4MI reduction effect was confirmed even when treated with the activated carbon of the comparative example. Furthermore, comparison between Example 1 and Example 7 confirmed that the content of 4MI was further reduced when the pH before the contact treatment between the sample and the clay was lower.

4-Methylimidazole (4MI) Reduction Effect and Appearance and Aroma Evaluation in Caramel Colors Commercially available caramel color containing 4-methylimidazole (4MI), 4MI reduction effect, appearance and aroma using acid clay and activated clay The change of was examined.

  A commercially available caramel pigment (IV) (caramel IV) was diluted 5-fold with water and dispensed into test tubes in 40 ml aliquots. In these caramel dye aqueous solutions, as shown in Tables 2 and 3 below, acidic clay (Mizuka Ace # 400 or Mizuka Ace # 200, both manufactured by Mizusawa Chemical Co., Ltd.) or activated carbon (CL-K, Ajinomoto Fine Techno Co., FP) -1, FP-6, manufactured by Nippon Enviro Chemicals Co., Ltd.) was added in an amount of 2 and 4% by mass, stirred with a vortex mixer, and contacted at room temperature for 10 minutes. Thereafter, centrifugation was performed at 4000 rpm for 10 minutes, and 30 ml of the supernatant was decanted and collected. Thereafter, 4MI was analyzed using high performance liquid chromatography (HPLC) under the same conditions as described above.

Regarding fragrance, sensory evaluation was performed by a plurality of panelists. The fragrance point was based on the control group 3, and compared with the fragrance point, a 5-point evaluation was performed with 5 points having the same fragrance unique to caramel and 1 point having a fragrance significantly inferior to the control. The fragrance standard of fragrance is as follows. The evaluation results are shown in Table 4 below.
(Scent evaluation standard)
5 points: Caramel's unique aroma is equivalent to the control 4 points: Caramel's unique aroma is slightly inferior to the control 3 points: Caramel's unique aroma is slightly inferior to the control 2 points: Caramel's unique aroma 1 point: Caramel's unique aroma is significantly inferior to control

The brightness and saturation were measured as follows. For the analysis with the colorimeter, L ^* value, a ^* value and b ^* value were measured using a spectrocolorimeter CM-3500d (manufactured by Minolta Co., Ltd.). A spectrophotometer is a light receiver that selectively receives light transmitted from an object when it is irradiated with light having a specific spectral composition, and obtains the spectral transmission characteristics of the object using a spectrophotometer. The tristimulus value is obtained from the numerical value. The L ^* value represents lightness, and the a ^* value (+ direction: red, − direction: green) and b ^* value (+ direction: yellow, − direction: blue) represent chromaticity. The saturation C ^* is represented by the square root of (a ^* ) ² + (b ^* ) ² . The L ^* value, a ^* value, b ^* value, and C ^* in the colorimeter are shown in Table 4 below.

  For caramel solids, according to the atmospheric pressure heating drying method (official method) in which the sample described in the Food Sanitation Guidelines, Riken, is heated and dried at room temperature under the specified temperature and conditions, and the weight difference before and after drying is moisture, It was measured.

Moreover, about content of the minerals (iron ion (Fe), calcium ion (Ca), aluminum ion (Al), silicon ion (Si), potassium ion (K)) in the caramel pigment aqueous solution after the acid clay treatment, The analysis was performed according to the following procedure.
To 1 ml of caramel dye, 3.5 ml of 70% nitric acid and 0.5 ml of 30% hydrogen peroxide were added and thermally decomposed with a microwave decomposition apparatus. After cooling, the decomposition solution is diluted with ultrapure water, and iron ions (Fe), calcium ions (Ca), aluminum ions (Al), silicon ions (Si), and potassium ions (K) are diluted with an ICP emission spectrometer. Quantified. The equipment and reagents used are as follows.

(apparatus)
ICP emission spectrometer: iCAP 6500 Duo (Thermo Fisher Scientific Co., Ltd.)
Measurement conditions for ICP emission spectrometry
RF power: 1150 W
Nebulizer gas flow rate: 0.65L / min
Auxiliary gas flow rate: 0.5L / min
Plasma gas flow rate: 12L / min
Chamber: Glass cyclone Nebulizer: Glass coaxial type for aqueous solution

Microwave digester: ETHOS PLUS (Milestone General Co., Ltd.)
(reagent)
Nitric acid: PlasmaPURE 67-70% (SCP SCIENCE)
Hydrogen peroxide: Ultra high purity, 30% (Kanto Chemical)
Standard reagent: ICP general-purpose mixture XSTC-22 100ppm (SPEX Certiprep)
Internal standard reagent: Rhodium standard solution for atomic absorption 1000ppm (Wako Pure Chemical Industries, Ltd.)

  From Table 2 above, it was confirmed that 4MI could be reduced depending on the amount of white clay (acid clay) added. Moreover, compared with the case where it processed with multiple types of activated carbon of a comparative example, the higher 4MI reduction effect of acidic clay was confirmed. In addition, the solid content of caramel pigment was hardly decreased by the clay treatment, but decreased by the activated carbon treatment, suggesting that the yield was not good. Furthermore, it was confirmed that the content of various minerals was increased in the caramel pigment treated with acid clay than in the comparative example.

According to Table 4 above, with respect to the saturation (C ^* ), Examples 8 to 11 had a smaller difference Δ than Comparative Examples 4 to 9 compared to the control group. That is, the white clay treatment not only has a higher 4MI removal rate than the activated carbon treatment, but can also reduce the saturation change rate (saturation difference).

  In addition, regarding the fragrance, in Examples 8 to 11, the caramel-specific fragrance almost equivalent to that in the control group 3 was left, whereas in Comparative Examples 4 to 9, almost no fragrance was felt. It is thought that the aroma component peculiar to caramel has been absorbed and removed by the activated carbon treatment.

Appearance and flavor evaluation of beverage containing caramel color treated with clay, using the same amount of caramel color treated with clay in Example 9 or Example 11 or caramel color treated with activated carbon in Comparative Example 5, respectively, An appropriate amount of sweetener, flavor, and caffeine was added to produce a cola beverage. Each sample was stored under conditions of (1) 9000 lux, 10 ° C. for 7 days, or (2) 45 ° C. for 5 days, and evaluated for exposure resistance and heat deterioration resistance, respectively. The criteria for the external viewpoint and the flavor point are as shown below.

(Appearance point evaluation criteria)
5 points: Appearance is equivalent to the control 4 points: Appearance is slightly fading than the control 3 points: Appearance is fading slightly from the control 2 points: Appearance is fading slightly than the control 1 point: Appearance is significantly fading than the control

(Taste point evaluation standard)
5 points: Flavor is equivalent to control 4 points: Flavor is slightly inferior to control 3 points: Flavor is slightly inferior to control 2 points: Flavor is considerably inferior to control 1 point: Flavor is control Significantly worse

(1) Sensory evaluation results of samples stored at 9000 lux at 10 ° C. for 7 days are shown below.

(2) The sensory evaluation results of the sample stored at 45 ° C. for 5 days are shown below.

  From the results of Table 5 above, the food and drink using the caramel pigment treated with the clay is more resistant to exposure and the deterioration of the fragrance can be suppressed compared to the food and drink using the caramel pigment treated with activated carbon. confirmed.

  Moreover, from the result of the said Table 6, the direction of the food / beverage products using the caramel pigment | dye processed with white clay has high tolerance with respect to a heating (long-term storage) compared with the food / beverage products using the caramel pigment | dye processed with activated carbon, and contains sweetness It was confirmed that the deterioration of flavor was also suppressed.

Claims (4)

A method for reducing an imidazole derivative, comprising bringing a food or drink containing an imidazole derivative represented by the following formula (I) into contact with acidic clay:
Wherein R ¹ is hydrogen or —COR ³ (where R ³ represents a C _1-5 alkyl group), and R ² is a C _1-5 alkyl group or a hydroxy C _1-5 alkyl group. is there).   The reduction method according to claim 1, wherein the imidazole derivative is 4-methylimidazole or 2-acetyl-4- (1,2,3,4-tetrahydroxybutyl) -1H-imidazole.   The reduction method according to claim 1 or 2, wherein the food or drink containing the imidazole derivative is coffee, caramel color, caramel color containing food or drink, beer manufactured from malt, or soy sauce. The manufacturing method of the food / beverage products in which this imidazole derivative was reduced including the process which the food / beverage products containing the imidazole derivative represented by Formula (I) of Claim 1 and acidic clay are contacted.