JPS5827753A - Purification of yellow pigment from "kuchinashi" (japanese jasmine) - Google Patents

Abstract

PURPOSE:A yellow pigment solution extracted from fruits of KUCHINASHI is passed through a nonpolar porous polymer resin to effect the adsorption of the pigment, then iridoid glycosides and polyphenols are removed to obtain the titled yellow pigment free from changing to green as well as in color tone. CONSTITUTION:Fruits of KUCHINASHI are extracted with water or an aqueous solvent and the resultant yellow pigment solution is passed through a column filled with a nonpolar porous polymer resin to effect the adsorption of the yellow pigment, then the column is washed with water. Then, an alcohol such as ethanol is passed through to elute iridoid glycoside for removal. Then, the eluate is concentrated to remove the alcohol and passed through a resin that adsorbs only polyphenols, such as polyamide resin, to effect the separation of the polyphenols, thus giving the objective yellow pigments (crosin, crosetin). EFFECT:The product is free from change to green and to dull tone. USE:Coloring of chinese noodles.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a solution of a dark colored pigment extracted from a gardenia fruit through water or a water-soluble solvent, either of a substance that changes the color or a substance that changes the color to a dull color, or The present invention relates to a method for purifying a gardenia yellow pigment, which is characterized in that it is possible to remove both pigments and thereby obtain a gardenia yellow pigment with extremely good attractability.

Yellow pigments obtained from gardenia fruits are widely used as pigments in the food field in many countries such as Japan, Taiwan, and the United States, and in Japan, they are especially used actively for coloring Chinese noodles.

However, Chinese noodles using this dye often turn green, and as a result of investigating the cause of this, the causative agent was found to be an iridoid complex, as shown in Japanese Patent Publication No. 13971/1983. It is currently confirmed to be a glycoside (zeeboside 1).

On the other hand, the inventors speculated that the cause of greening may be influenced by the freshness of the gardenia fruit, and performed the following results.

First, we use fresh gardenia fruits that have just been harvested and old gardenia fruits that have passed through the summer and have been faked the year before.
We produced yellow pigments using the same method for each, made two sets of noodles using these, and conducted the seven green discoloration tests. It was originally confirmed that gardenia fruits cause green discoloration.
The yellow pigment of Ktena 7 is a mixture, and its absorption curve shows that it contains an iridoid glycoside (zeniboside) that has a maximum absorption at -233n+n, a polyphenol (chlorogenic acid) that has a maximum absorption at 325nm, and 440nl1.
It turns out that it consists of three components: a yellow pigment substance (crocin, crocetin) that has maximum absorption at 1. When the absorption curves of both dye solutions used in the above-mentioned experiment were taken and changes in each of the three components mentioned above were examined, changes in the contents of clodino and crocetin were found to be similar to KIi.

It is known that this component has been reduced to less than half in old gardenias, and no significant changes have occurred in the other two components. From this result, the cause of the green discoloration of noodles is iridoid glycosides (due to a decrease in crocin and crocetin, which are yellow pigment substances, a relative increase in iridoid glycosides & green discoloration occurs, which is explained above). Experiments have shown that $ J -t&-
11! It is believed to cause discoloration of noodles.
Therefore, we conducted the following experimental research on a method for removing iridoid glycosides and c1clgenic acid, and based on these results, we completed the present invention.

Gardenia yellow pigment is made into non-polar and porous polymer resin (manufactured by Mitsubishi Kasei, Diaion HP-203) and boriacid resin (manufactured by Wako Junka, %0) which adsorbs only polyphenols.
-200), and three divisions according to column cI'v togelahui: iridoid glycoside division with 238fltu K maximum absorption, chlorogenic acid division with 325nm K maximum absorption, and 44υnm K
It is divided into three categories, crocin and crocodile, which have the highest absorption, and each is used to investigate the green discoloration of Chinese noodles as shown below.
went on strike. However, although ``kansui'' is usually used for Chinese noodles, in one test, ``kansui'' was not added in order to shorten the time required for greening due to non-alkalinization and to make the reaction more sensitive. The following tests were conducted using Chinese noodles.

The raw materials for the Chinese noodles used are 70 g of wheat and 30 g of water.
The plates using the above three categories of dyes were each OD[[2.
t)/g, add this and knead thoroughly to give 37'O
The sample was left in a constant temperature bath for 24 hours, and the discoloration after 9 hours was tested.

As a result, the iridoid glycoside category clearly turned green, the chlorogenic acid category did not cause any green discoloration, but the yellow became dull yellow, and only the crocin and croceti 7 categories showed no discoloration at all. Stay yellow my friend. What? The results measured using the s color difference needle are shown in Table 1 below.

Table 1 Based on this, it was confirmed that iridoid glycosides and polyphenols (chlorogee 51) have a color-changing effect1.
The present invention is characterized in that these substances are removed.

A specific embodiment of the present invention will be described in detail below.

Example 1 Color value 3300, 238rLm (iridoid glycoside)
/44αnIn (crocin, crocetin) ratio is 1.5
Take 60g of the gardenia extract from step 9, dilute it to about three times its volume, filter it through a vial 0 super cell, and pass the filtrate from step 7 through Kara AL3X15aIL filled with 50g of Diamond Ion Hp-20 to extract gardenia. The dyes in the solution were adsorbed, the column was washed with 100 m of distilled water, and then 15 wt of ethanol was added.
00 mJ to remove the iridoid body, and then add 95 wt ethanol to 200 mJ.
ml, dissolve and collect a mixture of crocin, crocetin and polyphenols, and distill the collected liquid to remove the alcohol content to obtain 50 g of purified pigment liquid.

The color value of the nine dye liquid obtained is 3800, -238 nm (iridoid glycoside)/440 nm (crocin, croceti/)
The ratio is 0.36, meaning that the smaller the ratio, the less iridoid shields, and therefore, it can be seen that iridoid glycosides (238 nm) are removed. In addition, when the recovery rate of crocin and croceti was calculated, it was 94.1. This result is illustrated in FIGS. 2(A) and 2(B).

Example 2 60g of the same gardenia extract pigment solution as used in Example 1 was taken and treated in the same manner as in Example 1. Only the polyphenols inside were adsorbed and removed, and the remaining pigments were recovered.The recovery rate of crocin and crocetin was calculated to be 88.71.

This result is illustrated in FIGS. 1(4) and 1(B).

The following two examples are the Northern method in which the methods of Example 1 and Example 2 are combined to enhance the purification effect.

Example 3 The same gardenia extracted pigment solution used in Example IKjIP was treated as in Example 2 to obtain 1.
Remove only the polyphenols from the dye solution to obtain a dye solution. Next, the dye solution was passed through a HP-20 column according to the method of JIHF11, and 1611+ (Wt)
Iridoid glycosides were eluted and removed with ethanol, and then
Dissolve and elute crocin and crocetin with 95% wtl ethanol to obtain a purified pigment solution.

The resulting purified pigment solution had a recovery rate of crocin and crocetin of 88.7% using C-200 and 9'L5% using HP-20, resulting in a total recovery rate of 881%.
It became I (811L game K 99.591: ),
The results are illustrated in Figure 1 (A) to Lot.

Example 4 First, the same gardenia extracted pigment liquid as used in Example I was subjected to the 7 treatments of Example 1.
Iridoid glycosides are removed from the pigment solution to obtain an ophthalmic pigment solution.

Remove ethanol from this dye solution by steaming #IK.
Using this solution, C! according to Example 2! -200 column to remove polyphenols from the purified dye solution. The recovery rate of crocin and croceti/ by this method is 94.1% by HP-20.
The number due to 0 is 87chi, and in the end, the total is 821.
(The result was 94,1 inch x 87 hooks. This result is illustrated in Figure 2 (4) to (0).

The present invention relates to a method for refining the raw pigment using a yellow pigment extracted from gardenia fruits with water or a water-bathable solvent as a raw material, and using two different types of resin. It is. That is, %uK,? ) is of good quality (for example, when fresh Chinese pear fruit is used), H
By using P-20fe, a purified pigment that does not cause green discoloration can be obtained. However, if the pigment material used as the raw material is not of good quality (for example, if old gardenia fruit is used)
, o-2 uυ resin is not used as a pretreatment or post-treatment layer, it is not possible to guarantee a purification result of a pigment that does not cause greening.

A first example showing the results of the first to fourth examples shows the above relationship.
The explanation will be as follows with reference to the drawings and FIG.

Figure 2 (4) shows the absorption curve of the raw gardenia pigment liquid, and Figure 82 (B) shows the absorption curve of the pigment obtained by purification according to the method of Example 1 using HP-20 as the resin. In Fig. 2 (4), there is clearly an iridoid structure that exhibits maximum absorption at 238 flm.
In the same figure (B), the peak at 2381m is not seen, indicating that the iridoid glycosides that cause green discoloration have been removed.

@1 Figure (4) shows the absorption curve of the raw gardenia pigment liquid,
Figure 1 shows the absorption curves of nine dyes obtained by purification according to the method of Example 2 above using Bl (C!-2OL as resin); The peak of chlorogenic acid shown in Figure 2 is clearly confirmed, but the figure (box 2) shows that this peak has decreased.

As explained earlier, this substance is not a greening substance, but it is a substance that gives dullness to the bright yellow color of gardenia yellow pigments (crocin, croceti/). By method 3, the absorption curves of nine dyes were pretreated with 0-200 resin and then treated with HP-20 resin. , the same figure (B) shows each absorption curve after the treatment based only on 0-200. Therefore, as can be seen in Fig. 1 (C), the iridoid array exhibits absorption at 23gn+n2 and 325n+n. This clearly shows that 2 and chlorogenic acid were removed by the method of Example 3.

Figure 2 (C) shows the HP-
The absorption curves of 9 dyes pretreated with 0.1-order TTCC-200 resin are illustrated, while %@2
Figure (4) shows the raw dye solution, the same figure (each absorption surface after treatment using only BlriHP-20), and therefore Figure 82 (238 flffl and 325 nm as shown in Cal). It is clearly shown that iridoid glycosides and chlorogenic acids exhibiting absorption were removed by the method of Example 4.

According to the present invention as detailed above, it is possible to provide an extremely excellent gardenia yellow pigment by removing one or both of the substances that cause greening and the substances that cause color change to dull color. Therefore, its utility value as a method for producing dye nI is extremely high.

[Brief explanation of drawings]

FIGS. 1 and 2 are graphs of absorption curves for explaining the dye purification effect according to the present invention. Patent Applicant: Kamoto Headquarters Co., Ltd. No. 1 Prisoner (Fig. 2) - View 3, quiet

Claims (1)

[Claims] (1) A yellow pigment solution extracted from the fruit of a gardenia using a water-soluble solvent is mixed into a non-polar porous one.
1. A method for purifying gardenia yellow pigment, which comprises adsorbing yellow pigment by passing it through tJjl, and removing iridoid glycosides by fractionally eluting the yellow pigment with water and alcohol. (2) From the depths of the gardenia fruit, water is extracted using a water-soluble solvent, and a yellow pigment solution is extracted from the polyamide aI! A method for purifying gardenia yellow pigment, which comprises removing polyphenols from the yellow pigment bath by passing it through a resin that adsorbs only polyphenols. L33 Yellow pigment F1 extracted from Kutenak fruit using water or a water-soluble solvent! A dye solution from which polyphenols are removed is obtained by passing the solution through a polyamide resin that adsorbs only polyphenols, and then the remaining dye is removed by passing the dye solution through a non-polar porous polymer resin. Gardenia yellow as described in the first and second claims, characterized in that the iridoid glycosides are removed by adsorbing the iridoid glycosides by adsorbing the adsorbed 9 remaining pigments with water 2 and alcohol. Pigment purification method. (4) For water-dangerous gardenias, a yellow pigment solution extracted through a water bathing solvent is passed through a non-polar porous polymer resin to adsorb the yellow pigment. A dye solution is obtained from which iridoid bodies are removed by fractional elution with alcohol, and then the dye solution is concentrated to remove alcohol and passed through a resin such as polyamide that only adsorbs polyphenols. The method for purifying gardenia yellow pigment according to claim 4 @ 8 items 1 and 2, characterized in that polyphenols are removed.