JP2873518B2 - Method for producing gardenia red dye - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a gardenia red dye, and more particularly to a method for producing a robust and safe red dye having an excellent color tone.

[0002]

BACKGROUND OF THE INVENTION Gardenia red pigment is used in various processed foods as a robust and safe pigment, and its production method is, as described in Japanese Patent Publication No. 55-5778, a gardenia fruit extract. And tibusano tree (Genipa Ameri
cana Linn.) obtained by reacting an aglycone, a compound having a carboxyl group at the 4-position among the iridoid compounds contained in the fruit extract and the like, and a primary amino group-containing substance under acidic conditions. However, the pigment obtained by the production method has a purple-red color, and is therefore rarely used alone.Other yellow pigments, such as gardenia yellow, safflower yellow, riboflavin, red malt yellow, etc. It was often used by mixing to reduce the apparent blueness. However, the color tone improvement by mixing the yellow pigment and the gardenia red pigment differs in the fastness and physical properties of each pigment, so the change that occurs during the processing of food, the distribution process, and the display of the product becomes large, Various problems have occurred during use.

[0003]

The object of the present invention is to improve the color tone of the gardenia red pigment itself from reddish purple to vermilion without affecting the physical properties, thereby necessitating the use of a mixture of yellow pigments. It is an object of the present invention to provide a method for producing a gardenia red dye that is safe, robust and has a different color tone that can be used for a wide range of applications without any problem.

[0004]

Means for Solving the Problems The present inventors have disclosed Japanese Patent Publication No.
As a measure to reduce the bluish tint of a gardenia red pigment obtained by the method described in JP-A-5-5778, as a result of examining the color tone improving effect by adding various synthetic and natural products at the time of preparing a gardenia red pigment, it is also effective for ascorbic acid. However, it was found that ribose was the most effective, and that other pentoses such as arabinose and xylose had the same effect. The present invention allows these pentoses to be used alone or in combination when preparing a gardenia red pigment,
The heating is based on the finding that the bluish color can be arbitrarily reduced without impairing the characteristics of a safe and robust gardenia red pigment.

That is, the present invention is characterized in that a substance having a carboxyl group at the 4-position of the iridoid skeleton and a substance having a primary amino group in an iridoid compound are reacted under acidic conditions in the presence of pentose. To provide a method for producing a gardenia red pigment. The iridoid compound used in the present invention is a glycoside containing geniposidic acid as a main component represented by the formula (I) and an aglycone of the compound (I) represented by the formula (II).

[0006]

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Preferred basic conditions for the production method of the present invention are represented by amino acids in an acidic substrate solution containing 2 to 20% by weight (hereinafter referred to as%), more preferably 4 to 15%, of geniposide acid. The primary amino group-containing substance is added in an amount of 0.5 mol or more, preferably 1 to 1 mol per geniposidic acid.
Add 2 molar equivalents and adjust the pH at which β-glucosidase can act.
(For example, pH 3 to 6) and an enzyme treatment at a temperature. The pentose is added to the substrate solution in an amount of 1 to 20%, preferably 3 to 10%. When the residual amount of geniposidic acid becomes 50% or less, preferably 20% or less, the enzyme-treated solution to which the pentose is added is 70 ° C. or more, preferably 80 to 80%.
Heat to 100 ° C. In this method, the acid is
Citric, malic, tartaric, adipic, fumaric,
It is preferable that one or more organic acids such as succinic acid be present in an amount of at least 2 mole equivalents, more preferably 3 to 6 mole equivalents, per mole of geniposidic acid. It is preferred to carry out by the method described in -77618. As the primary amino group-containing substance, it is preferable to use arginine, lysine, aspartic acid, DL-alanine, glutamic acid or a salt thereof. As the pentose, one or a mixture of two or more pentoses such as xylose, arabinose, ribose and ribulose can be used.

The dye obtained by the production method of the present invention is
The greater the amount of pentose added, the higher the enzyme treatment and subsequent heating temperature, and the longer the heating time, the greater the effect of reducing blueness. Further, the iridoid compound represented by the formula (I) is hydrolyzed in advance with β-glucosidase to obtain (I
It is also possible to obtain an aglycone represented by the formula (I) and use it as a raw material and subject it to various conditions other than the enzyme treatment in the above-mentioned production method.

Although the cause of the reduction in the blue tint of the gardenia red pigment according to the present invention is not yet clear, it is due to the formation of a yellow pigment by the pentose and the primary amino group-containing substance and the pigment. It is considered that the antioxidant property is derived from the high oxidation resistance. According to the production method of the present invention,
Red dye arbitrarily reduced blue color, ultrafiltration method, reverse osmosis method, isoelectric point precipitation method, hydrophilic organic solvent addition method, organic acid by purification method using ion exchange method alone or in combination, It is also possible to remove the pentose, the iridoid compound, the enzyme and the like to obtain a higher-purity dye.
The dye thus produced is a liquid dye,
Alternatively, it can be used as a powdery pigment by spray-drying after adding a saccharide.

[0010]

According to the production method of the present invention, the blue tint of the gardenia red pigment can be efficiently reduced, so that the color tone can be changed from reddish purple to vermilion without separately adding a yellow pigment. Can be improved. Next, the present invention will be described with reference to examples. Example 1 2.5 g of geniposidic acid, 0.9 g of DL-alanine, citric acid
5.0 g and 2.5 g of D-ribose are dissolved in water, and 50%
After adjusting the pH to 4.0 with a NaOH solution, water was further added to bring the total volume to 50 ml. 0.25 g of Cellulase AP-5 (manufactured by Amano Pharmaceutical Co., Ltd.) was added thereto, and the mixture was maintained at 50 ° C. for 24 hours, and then heated at 90 ° C. for 2 hours to inactivate the enzyme to obtain a red dye liquid. .

This dye solution was diluted with water so that the absorbance at the maximum absorption wavelength became 0.5, and the color tone was measured using a color difference meter SZ- # 80 manufactured by Nippon Denshoku Industries Co., Ltd. It was a red-orange pigment represented by L, a, b = 72.7, 32.4, 2.8. Comparative Example 1 The same operation as in Example 1 was carried out except that D-ribose was not added, and the color tone of the obtained red pigment liquid was changed to Example 1.
As a result of measurement in the same manner as above, L, a, b
= 72.5, 35.9, -5.1.

In 50 ml of a red dye solution prepared from DL-alanine prepared in Example 1 and Comparative Example 1, 250 ml of deionized water was added.
ml of ultrafiltration equipment (UF-LM) of Tosoh Corporation.
SII) ultrafiltration membrane cassette (UF
-2CS-10PS). 2 more on the way
50 ml of deionized water was added, and the mixture was concentrated and purified to about 80 ml. Table 1 shows the color tones of the obtained dye solutions.

Table 1 {Hunter display} ──────────────────Lab △ b ─────────────────────────── ─ Example 1 72.2 32.7 0.3 ─ Comparative Example 1 71.0 33.6 -6.3 6.6 ──────────────────── ────────

Example 2 To 6.5 g of a gardenia fruit extract (iridoid content: 52%), 18 ml of water and 1 g of granular NaOH were added, and the mixture was maintained at 60 ° C for 3 hours. 9 g of citric acid was dissolved therein, and geniposide acid 3.1 was dissolved.
g of iridoid solution was obtained. 1.8 g of sodium L-aspartate and 2.5 g of D-xylose were dissolved in this iridoid solution, and the pH was adjusted to 4.5 using a 50% NaOH solution, and water was added to bring the total volume to 50 ml. Next, 0.45 g of Cellulase Onozuka 3S (manufactured by Yakult Honsha Co., Ltd.) was added, and the mixture was heated to 60 ° C. under nitrogen atmosphere at 21 ° C.
The enzyme was inactivated by heating at 90 ° C. for 3 hours. As a result of measuring the color tone of the obtained red dye liquid by the same method as in Example 1, the values by Hunter display were L, a,
The compound was a red-orange pigment represented by b = 72.4, 34.1, -1.0. Comparative Example 2 The same operation as in Example 2 was carried out except that D-xylose was not added. As a result, L, a,
A purple-red pigment liquid represented by b = 72.1, 35.9, -6.7 was obtained.

Example 3 70 ml of water and 4 g of granular NaOH were added to 26 g of a gardenia fruit extract (iridoid content: 52%), and the mixture was maintained at 60 ° C. for 3 hours. To this, 118 ml of an iridoid solution obtained by dissolving 36 g of citric acid was divided into four equal parts, and DL-alanine 1.2 was added to each.
g, 2.3 g of sodium L-aspartate, 2.5 g of sodium L-glutamate and 2.5 g of L-lysine hydrochloride were dissolved. Further, 2.5 g of D-xylose was added, and 50
The pH was adjusted to 4.5 using a% NaOH solution, and water was added to a total volume of 50 ml. Then, 0.35 g of Cellulase AP-5 (manufactured by Amano Pharmaceutical Co., Ltd.) was dissolved. This at 50 ° C
The enzyme reaction was carried out for one hour. 2 at 90 ° C
The enzyme was inactivated by heating for a period of time to obtain a red dye solution.
The color tone was measured in the same manner as described above. The results are shown in Table 2 together with Comparative Example 3. Comparative Example 3 The same operation as in Example 3 was carried out except that D-xylose was not added, and the measured color tone was compared with Example 3 and shown in Table 2.

Table-2 {D-xylose Hunter indication amino acids}有 Yes No Lab △ b ────────────────────────────── ＤＬ DL-alanine no addition 71.8 33.3 -5.9 添 addition 72.2 32.0 0.1 6.0 L-aspartic acid no addition 72.7 37.2 -7.9 ─ sodium addition 72.6 34.9 -0.7 7.2 L-glutamic acid no addition 73.5 37.9 -8.8 ─ Addition of sodium 73.4 36.8 -2.8 6.0 Addition of L-lysine hydrochloride 67.5 25.4 -8.0 7 Addition 70.0 24.5 10.2 18.2 ────────────────────わ か る As can be seen from the above results, the b-value, which shows a bluish color on the Hunter display, greatly changed to the positive side by adding xylose. Has been improved, indicating a decrease in blueness.

Example 4 130 g of water and 7 g of granular NaOH were added to 50 g of a gardenia fruit extract (iridoid content: 52%), and the mixture was maintained at 60 ° C. for 3 hours. Next, 65 g of citric acid was dissolved, and the solution was passed through an adsorption type resin Diaon HP-20 to remove dye impurities, thereby obtaining 200 ml of an iridoid solution containing geniposidic acid as a main component. 12 g of L-lysine was dissolved therein, the pH was adjusted to 4.5 using a NaOH solution, and the mixture was divided into 7 equal parts.
2.5 g of glucose, D-(-)-arabinose, D-xylose, D-(-)-fructose, D-ribose and sucrose were dissolved. No sugar was added to the remaining one. Each was made up to 50 ml by adding water, and 0.5 ml of Cellulase Onozuka 3S (manufactured by Yakult Honsha) was added.
After the addition, the mixture was maintained at 60 ° C. for 22 hours. Then 90
The enzyme was inactivated by heating at 2 ° C. for 2 hours, and the color tone of the obtained red dye solution was measured in the same manner as in Example 1. The results are shown in Table-3.

Table 3 ─────────────────────────────────── Hunter display 表──────────────────────────────── No. type Lab △ b ───────── １ 1 Without addition 67.9 26.1 -5.6 ─ 2 D-(+)-glucose 69.9 29.5 -4.0 1.6 3 D -(-)-Arabinose 69.9 25.9 5.5 11.1 4 D-xylose 69.8 24.0 10.1 15.7 5 D-(-)-fructose 68.1 26.7 -5.2 0.46 D-ribose 70.6 21.5 16.8 22.4 7 sucrose 68.9 28.5 -4.7 0.9 ─── ──────────────────────────────── * Nos. 3, 4, and 6 are the present invention, others are comparative examples . As can be seen from the above results, the coexistence of pentose at the time of the enzyme treatment makes it possible to obtain a red pigment liquid with reduced bluish color.

Example 5 18 g of geniposidic acid, 12 g of DL-malic acid, and L
-The pH was adjusted to 4 after dissolving 7 g of arginine in 120 ml of water. Add water to make the total volume 240 ml and divide it into 4 equal parts.
Xylose was added at 0, 2, 5, 10% (w / v).
Further, each has a cellulase AP-5 (manufactured by Amano Pharmaceutical Co., Ltd.)
Was added at 0.3 g each and maintained at 50 ° C. for 23 hours.
The enzyme was inactivated by heating at 3 ° C. for 3 hours to obtain a red dye solution.

Table 4 shows the color tone of the red dye solution measured by the same method as in Example 1. Table-4 ─────────────────────────────────── D-xylose color tone (Hunter display) ────────────────────────── (w / v%) Lab △ b ───────────── ────────────────────── 0 73.1 37.7 -9.7 ─2 73.0 36.9 -8.0 1.75 773 0.0 36.3 -6.2 3.5 10 73.1 35.3 -4.2 5.5 ────────────────────────わ か る As can be seen from the above results, the blueness of the gardenia red pigment can be arbitrarily reduced by increasing the amount of D-xylose.

Continuation of the front page (56) References JP-A-4-153271 (JP, A) JP-A-55-108464 (JP, A) JP-B-55-5778 (JP, B2) (58) Fields investigated (Int) .Cl. ⁶ , DB name) C09B 61/00 CA (STN) CAOLD (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] 1. Iridoid skeleton 4 in an iridoid compound
A method for producing a gardenia red dye, comprising reacting a substance having a carboxyl group at the 1-position with a substance having a primary amino group under acidic conditions in the presence of pentose.