JPH0730259B2 - Carsamine purification method - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for purifying cursamine, which is capable of obtaining high-purity cursamine from a cursamine-containing raw material such as safflower. More specifically, it relates to a method for isolating and purifying carsamine from a pigment component of a carsamine-containing raw material.

(Prior Art) The red pigment of safflower (carsamine) has been used for dyeing textiles since ancient times as one of the traditional crafts. The method is to elute cursamine with alkaline water, add vinegar to this, and dye the fiber with an acidified liquid.

As a method improved on this traditional method, for example, a method of separating cursamine from safflower using a water-containing organic solvent (Japanese Patent Publication No. Sho 30-8943), extracting cursamine from a safflower with a water-containing organic solvent, and removing the solvent , A method of precipitating carsamine at −10 ° C. and separating carsamine with a mixed solvent of tetrahydrofuran, benzene and water (Japanese Patent Publication No. 47-50762) has been proposed. These methods have the drawback that impurities are also extracted and that the separation of these impurities is difficult.

In addition, a method of insolubilizing an alkaline solution obtained by extracting cursamine from safflower with an acid and then adsorbing it to chitosan and / or cellulose to obtain cursamine extracted with an alkali and an organic solvent (JP-A-63-117069) and safflower Silica gel is added to an alkaline solution in which carsamine is extracted from the solution to adsorb carsamine, and insolubilization with acid is followed by extraction with hydrous acetone to obtain purified carsamine (JP 62-5337A).
No. 5) is proposed.

(Problems to be Solved by the Invention) However, the above-mentioned adsorbents such as chitosan and / or cellulose and silica gel have low adsorption selectivity for carsamine, and have a pH of 2 to 2 in order to remove impurities such as safflower yellow. The process was extremely complicated, for example, it was necessary to lower the amount to 3 to insolubilize the carsamine, further to dry the adsorbent adsorbing the carsamine and then to extract it with a water-soluble organic solvent. Moreover, even with these methods, it was still insufficient to obtain carsamine with high purity.

An object of the present invention is to solve the above-mentioned conventional drawbacks and to provide a novel method for obtaining a highly pure cursamine having a clear color tone in an industrially advantageous manner by an easy procedure.

(Means for Solving the Problems) According to the present invention, after treating a cursamine-containing raw material with an alkaline aqueous solution and adjusting the obtained extract to pH 8 to 9,
The dye is adsorbed by contacting with a porous polymerized resin, the resin is washed with water and / or hydrous alcohol having a water content of 70% or more, and then treated with a water-containing organic solvent having a water content of 50% or less to elute cursamine. A method for purifying carsamine is provided.

It is already known that water-soluble anthocyan pigments such as grape skin pigments and hibiscus pigments are treated with a porous resin adsorbent and collected (JP-A-48-66128 and JP-B-59-50262). Gazette). However, water-insoluble cursamine, which is a safflower crimson dye, is contacted with a porous polymer resin under slightly alkaline conditions to adsorb cursamine, and the water-soluble dye is washed off with water and then eluted with a water-containing organic solvent to collect cursamine. Is not known.

Examples of the cursamine-containing raw material used in the present invention include safflower, dried safflower, and mochi. If desired, these raw materials may be cut into appropriate sizes. The cursamine-containing raw material is washed with water by a conventional method, a part of the yellow pigment is removed in advance, and then treated with an alkaline aqueous solution to extract cursamine.

The alkaline aqueous solution is, for example, about 0.1 to 10% by weight, preferably about 0.5 to 10% by weight of a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide or a carbonate of an alkali metal such as sodium carbonate or potassium carbonate. An aqueous solution of about 5.0% by weight is used.

The amount of the alkaline aqueous solution used is, for example, 1 dried safflower petal.
An amount such as about 10 to 20 parts by weight can be exemplified.

The method for extracting cursamine is to add the cursamine-containing raw material to an alkaline aqueous solution and stir at about 0 to 30 ° C. for about 10 minutes to 2 hours. After the extraction treatment, solid-liquid separation is performed by filtration, centrifugation, etc., and the extract is collected.

The cursamine extract is adjusted to pH 8-9 with acid. pH
Examples of the acids used for the adjustment include inorganic acids such as hydrochloric acid, phosphoric acid and carbonic acid; organic acids such as acetic acid, citric acid, malic acid and tartaric acid.

The pH-adjusted extract then adsorbs the cursamine treated with the porous polymerized resin. As the porous polymer resin,
Examples thereof include a styrene-divinylbenzene copolymer or a methacrylic acid ester polymer, crosslinked polystyrene, and acrylonitrile-divinylbenzene copolymer. All of these porous polymer resins are commercially available, for example, DIAION (HP10,20,30,40,50; S
P-207, SP-206: Mitsubishi Kasei Co., Ltd .; Amber Light (X
AD-2, XAD-4: manufactured by Rohm and Haas Co.); Chromosorb cetury 101-108 (Johns
Manyville, Inc.) and the like.

The method of adsorption treatment to the porous polymer resin is carried out by bringing the extract solution into contact with the porous polymer resin, and, for example, by passing the extract solution through a column filled with the porous polymer resin, the cursamine is removed. Adsorb to the porous polymer resin.

The amount of the porous polymer resin used with respect to the extract varies depending on the concentration of carsamine in the extract.
About 0.01 to 1 part by volume of the resin is used with respect to parts by weight.
The porous polymerized resin packed in the column is preliminarily moistened by flowing water, and the cursamine extract solution is used to e.g.
It is carried out by passing the liquid at the flow rate of. After the adsorption treatment, the column is filled with water and / or a water content of about 70 to 95% by weight,
It is preferably washed with water-containing methanol having a water content of about 70 to 80% by weight or water-containing methanol to remove safflower yellow and other impurities.

Then, the cursamine adsorbed on these resins is eluted with a water-containing organic solvent. Examples of such a water-containing organic solvent include water-miscible organic solvents such as methanol, ethanol, and acetone having a water content of about 50% by weight or less.
For elution treatment, these organic solvents are used, for example, SV about 0.5 to 5
Through the column at a flow rate of.

By removing the solvent from the obtained eluate, it is possible to obtain extremely high-purity carsamine in a high yield.

Next, the embodiments of the present invention will be described more specifically by way of examples.

(Example) Example 1 100 g of dried safflower petals were washed with 200 ml of water to remove yellow pigment. Next, 1,200 g of a 4% sodium carbonate solution was added to the washed safflower petals to extract the cursamine. After adjusting the pH to 8.5 by adding 6N hydrochloric acid to the obtained cursamine extract, it was passed through a column filled with 150 ml of porous polymer resin SP-20 (Mitsubishi Kasei) at SV of about 1 to adsorb cursamine. Then, the mixture was washed successively with 300 ml of water and 300 ml of 20% methanol to remove residual salts and yellow dye. Next, 600 ml of 80% methanol was poured to desorb the cursamine, and methanol was removed from the resulting solution by distillation under reduced pressure to obtain 150 mg of high-purity cursamine.

Example 2 500 g of safflower petals were crushed and then washed with water to remove yellow pigment. 4% potassium carbonate solution on washed safflower petals 1,
500 g was added and stirred to extract the carsamine. The pH of the obtained extract was adjusted to 8.5 as in Example 1, and then SV1 was applied to a column packed with 200 ml of a porous polymer resin HP-20 (Mitsubishi Kasei).
The solution was passed through the column to adsorb the cursamine. The resin adsorbing the cursamine was washed with 400 ml of water and 400 ml of 25% ethanol to remove impurities such as residual salts and yellow pigment. Then, the cursamine was desorbed using 800 ml of 95% ethanol, and ethanol was removed by distillation under reduced pressure to obtain 230 mg of high-purity cursamine.

(Effects of the Invention) According to the method of the present invention, by using a porous polymerized resin having excellent adsorption selectivity for carthamine, the cursamine in the alkaline extract of safflower adsorbed on the resin is adjusted to pH 2 to 3. PH8 ~ without lowering and insolubilizing treatment
It was possible to wash with water under the slightly alkaline condition of 9.

As a result, it is possible to eliminate impurities other than carthamine, which were conventionally included together when insolubilizing carsamine, and it is possible to easily remove impurities such as safflower yellow by washing with water under the slightly alkaline condition, which makes a leap. Highly pure and high quality cursamine can be industrially extremely advantageously obtained.

Claims (1)

[Claims] 1. A cursamine-containing raw material is treated with an alkaline aqueous solution, the obtained extract is adjusted to pH 8 to 9, and then contacted with a porous polymerized resin to adsorb a dye, and the resin is mixed with water and / or water-containing water. A method for purifying cursamine, which comprises washing with hydrous alcohol having a rate of 70% or more and then treating with a water-containing organic solvent having a water content of 50% or less to elute cursamine.