JPS60176562A - Production of water-soluble food dye - Google Patents

Abstract

PURPOSE:To produce a water-soluble food dye having high discoloration resistance, in high efficiency, by treating a raw material of the dye with a liquid of supercritical state. CONSTITUTION:A raw material containing a water-soluble and non-oleophilic dye such as anthocyanin dye, quinone dye, flavone dye, etc. is put into an extraction tank. Gas such as carbon dioxide gas, ethylene, propane, etc. is pressed into the tank to keep the extraction tank to the state of closed system having a temperature and pressure above the critical point. The oil or fat components, flavor components and a part of water, etc. are extracted and removed from the dye raw material, and the remaining liquid or solid is added with water, alcohol or an aqueous solution of an organic acid to elute the dye remaining in the residue.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigments, and an object of the present invention is to advantageously obtain food pigments of excellent quality.

Food coloring is divided into two types: water-soluble and oil-soluble. This invention relates to the former, that is, water-soluble dyes.

Methods for obtaining water-soluble pigments include solvent extraction methods, etc.
, all of these methods have significant drawbacks.

Disadvantages include, for example, a low yield of solid products, a low rate of removal of impurities, and occasional discoloration of the obtained pigment.

The present invention is free from such drawbacks.

This invention will be explained below.

First, the target dye raw material is generally one that is water-soluble and contains a non-lipophilic dye. It includes flavonoids,
Examples include anthocyanin-based, quinone-based, betacyanin-based, flavone-based, azaphilone-based, phycocyanin-based, and some carotenoid-based ones. Plant leaves, violet, pulp,
Roots, skin of fish and shellfish, meat, blood, etc. are raw materials containing these pigments. Kowara oleoresin can also be used as a raw material. Either raw or dried kowara may be used.

These can be treated singly or in combination of two or more.

Next, the process of obtaining the dye will be explained.

These dye raw materials are placed under a temperature and pressure higher than the critical pressure of a specific liquid. This is a feature of this invention.

The specific liquid is generally hydrophobic or non-lipophilic. These include inert gases such as carbon dioxide, nitrogen, methane, argon, helium, etc. Active gas e.g.
Sulfur dioxide gas, ammonia gas, methane and others can also be used. The boiling points of these liquids are well known, but just to be sure, nitrogen is 195.8°C, argon is -185, 7°C, methane is -116]5°C, ethylene is -103, 9°C1 carbon dioxide is 1567°C
(5.2 atmospheres).

A system in which an appropriate amount of dye raw material is dispersed in a single type of liquid is placed in a closed system under temperature and pressure above the critical level. At this time, the equipment used is basically a closed system that connects a liquid supply source, heat exchanger, compressor, extraction tank, and separation tank.

As long as such a device exists, it can be employed regardless of its format. In this way, impurities contained in the raw material, such as oil, fat, moisture, and volatile matter, are led to the separation tank. In the separation tank, these are discharged from the system by changing the temperature or pressure. Therefore, liquid or solid matter remains in the extraction tank. This residual portion is a mixture of pigments, fibers, proteins, some carbohydrates, ash, etc.

When the desired removal rate of fats and oils and volatiles from the pond is reached, the operation is stopped and the residual liquid or solids are removed from the extraction tank. Water is added to the extracted material, and only a solution made by dissolving the dye in water is taken out, and this is concentrated under reduced pressure, or concentrated using an ion exchange membrane, reverse osmosis, ultrafiltration, or other conventional method to remove the dye. Collect only the amount.

Through the above, the purpose of this invention can be achieved.

Some of the features of this invention are as follows. ■Extremely little discoloration of pigments. This is because since a liquid with a low boiling point is used, it can be produced at a temperature below the inherent discoloration temperature of the dye.

■Product yield rate is extremely high. This is because the color component contained in the raw material does not vaporize and escape, but remains in the extraction tank in its entirety, and almost all of it can be collected using water. ■Productivity is extremely high because the manufacturing process is extremely simple. ■Almost all of the vaporized portion of the liquid used can be recovered and reused, resulting in extremely low wastage.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 Red cabbage 1 '500? A mixture of 1 kg of the juice and a carbon dioxide liquid was refluxed, and the refluxed carbon dioxide was heated under equal pressure to remove the extracted oil and volatile components.

The carbon dioxide gas used lowers the temperature and returns the rainbow to its original system.
Reused for extraction. After extracting the pigment in this way,
A residual liquid was obtained. This material was pulverized, 500 tnl of 50% ethanol water was added thereto to make a homogeneous system, which was stirred at room temperature for 3 hours, filtered and concentrated under reduced pressure to obtain anthocyanin pigment 201. The obtained pigment had no off-taste or odor, and did not change color or fade.

Example 2 To 2.0 OOIP of dried purple corn seeds, 1 f of citric acid, 50% volume, and 20 g of ethanol water were added, stirred for 3 hours at room temperature, and then filtered. The obtained pigment liquid was concentrated under reduced pressure to obtain approximately 300% of the purple corn crude pigment liquid! i'(E"i' Tsumugi-11) was obtained. This liquid was placed in an extraction tank with liquid nitrogen and heated with water vapor from outside the tank. The temperature was raised to 40°C, the nitrogen solution was refluxed, and the The released oil and volatile components were removed. In the separation tank, the temperature was lowered to 10'C, and nitrogen was further returned to the original system for reuse.

Approximately 701 iL of pigment component remained in the extraction tank. The purple corn pigment thus obtained had no off-taste or odor and melted transparently.

Example 3 Cochineal pigment crude extract 21 and carbon dioxide gas liquid (40-50
°C/100-1.50 kQ/tU) into the extraction tank and countercurrent extraction was performed. A separation tank was filled with 100 g of activated carbon in advance, and the oil and aroma components in the pigment liquid were discharged into the separation tank together with the carbon dioxide gas liquid.

The remaining pigment in the extraction tank is taken out, water is added, and this pigment is filtered through an ultrafiltration membrane (molecular weight cut off, s, ooo) at 10 kg/-
It was further concentrated under the following conditions to obtain a dye concentrate of about 1001.

The obtained dye concentrate was very clear and had no off-taste or odor.

Patent Applicant Tamei Kagaku Kuri Co., Ltd. Procedural Amendment (Voluntary) 1985/1986/1/2 Patent Application No. 33112 1988 2 Invention Title Process for Producing Hydroxy Acidic Food Color 3 Amendment Relationship with the case Patent applicant postal code 561 5. Contents of the amendment As shown in the attached sheet Amended specification Name of the invention Process for producing water-soluble food coloring 2 Claims Water-soluble and non-lipophilic coloring matter For example, pigment raw materials containing anthocyanins, quinones, and others are placed in an extraction tank, and carbon dioxide gas is added to the residual liquid or solidified part, and water, alcohol, or an organic acid water bath is added to the former. 1. A method for producing water-soluble food coloring, which is characterized by transferring the former to the latter.

3. Detailed Description of the Invention The present invention relates to pigments and aims to industrially advantageously obtain food pigments of excellent quality.

Food coloring is divided into two main categories: water-soluble and oil-soluble. This invention relates to the former, that is, water-soluble dyes.

Methods for obtaining water-soluble pigments include solvent extraction methods, etc.
All of these methods have serious drawbacks. Disadvantages include, for example, a low yield of product, a low rate of removal of impurities, and occasional discoloration of the dye obtained.

The present invention is free from such drawbacks.

This invention will be explained below.

First, the target dye raw material is generally one that is water-soluble and contains a non-lipophilic dye. It includes flavonoids,
Examples include anthocyanin-based, quinone-based, betacyanin-based, flavone-based, azaphyron-based, phycocyanin-based, some carotenoid-based, and others. Raw materials containing pigments include leaves, pulp, roots, etc. of M products, skin of fish and shellfish, meat, blood, etc. These oleoresins can also be tossed as raw materials. Either of these fresh or dried products may be used. These can be processed singly or in combination.

Next, the process of obtaining the dye will be explained.

These dye raw materials are treated with a fluid in a supercritical state. This is a feature of this invention.

A fluid such as carbon dioxide gas, ethylene, propane, etc. is brought into contact with an appropriate amount of the dye raw material and placed in a closed system under temperature and pressure above the critical point. At this time, the equipment used is basically a liquid supply source,
It is a closed system that connects a heat exchanger, compressor, extraction tank, and separation tank.

As long as such a device exists, it can be employed regardless of its format. In this way, impurities contained in the raw material, such as fats and oils, part of water, and volatile matter, are led to the separation tank. In the separation tank, these are discharged from the system by changing the temperature or pressure. Therefore, liquid or solid matter remains in the extraction tank. This residual part contains pigments, fibers, proteins, some liquid, ash,
It is a mixture of water, etc.

When the removal rate of fats and oils, volatile matter, etc. reaches the desired level,
Stop operation and remove residual liquid or solids from the extraction tank. Water is added to the extracted material, and only a solution made by dissolving the dye in water is taken out, and this is concentrated under reduced pressure, or concentrated using an ion exchange membrane, reverse osmosis, ultraviolet filtration, or other conventional methods. Collect only the pigment.

Through the above, the purpose of this invention can be achieved.

Some of the features of this invention are as follows. ■Extremely little discoloration of pigments. This is because since the dye is used at a relatively low temperature, it can be produced at a temperature below the inherent discoloration temperature of the dye.

■Product yield rate is extremely high. This is because the color component contained in the raw material does not vaporize and escape, but remains in the extraction tank in its entirety, and almost all of it can be collected using water. ■Productivity is extremely high because the manufacturing process is extremely simple. - Almost all of the vaporized portion of the fluid used can be recovered and reused, resulting in extremely low wear and tear.

Next, the present invention will be explained in detail with reference to Examples.

Example 1 Red cabbage 1500F was ground into juice, 1 kLj of the juice was brought into contact with carbon dioxide gas in a supercritical state, and the contacted carbon dioxide gas was extracted by raising the temperature at equal pressure outside the extraction system. Oil and volatile components were removed.

The used carbon dioxide gas is lowered in temperature and returned to the original system.
Reused for extraction. After extracting and removing impurities in this manner, a residue was obtained. This material was pulverized, 500 ml of 50% ethanol water was added thereto to make a homogeneous system, which was stirred at room temperature for 3 hours, filtered through p-filter, and concentrated under reduced pressure to obtain anthocyanin thread pigment 202. II Also, the obtained dye did not have any off-taste or odor, and did not change color or fade.

Example 2 Dry product of purple corn seeds 2.0005',
Citric acid], Ii', 50 volume Ji%, ethanol water 20
Put g into an extraction tank together with liquid nitrogen, pressurize carbon dioxide gas, heat it with water vapor from outside the extraction tank,
Raise the temperature to 0°C, bring it into contact with the supercritical state, extract,
The volatiles were transferred to the extraction phase and led to a separation tank. The temperature of the separation tank was raised to 50°C, and after separating and removing the extract, the temperature of the carbon dioxide gas was lowered, and the tank was returned to the original system for reuse.

The remaining amount was passed through Oki paper in an extraction tank to obtain about 702 pigment components. The purple corn pigment thus obtained had no off-taste or odor and melted transparently.

Example 3 Cochineal pigment crude extraction throat 2e and carbon dioxide gas were heated in a supercritical state (4.0~50"C/100~15
0 kq/cm). A separation tank was filled with 100 liters of activated carbon, and the aroma components in the dye liquid were adsorbed and removed with the carbon dioxide gas liquid into the separation tank at an outlet for 41 minutes.

The remaining dye in the extraction tank was taken out, and water was added to the dye.
It is further concentrated under the conditions of kQ/- to a dye of approximately 1.00 F.
A condensate was obtained. The obtained dye concentrate was very clear and had no off-taste or odor.

Patent applicant: Sanei Chemical Industry Co., Ltd.

Claims (1)

[Claims] A pigment layer containing water-soluble and non-lipophilic pigments, such as anthocyanins, quinones, and other pigments, is placed in an extraction tank, and carbon dioxide gas, fluoropane gas, etc. under pressure and temperature above the critical pressure are added to the extraction tank. , by bringing other liquids into contact with each other, heating the system to a temperature above criticality, extracting and removing oils and fats, water, aroma components, etc., and adding water, alcohol, or an aqueous solution of an organic acid to the remaining liquid or solid part. A method for producing water-soluble food coloring, which comprises transferring the coloring matter contained in the former to the latter.