JPS58173163A - Production of carotenoid coloring matter - Google Patents

Abstract

PURPOSE:To obtain industrially the titled coloring matter useful for food, pharmaceutical preparations, etc. as a stable, high-purity and odorless natural coloring matter, by replacing unsaturated fatty acids contained in an oleoresin with a satd. fatty acid by utilizing an ester exchange reaction. CONSTITUTION:One pt.wt. oleoresin contg. carotenoid is dissolved in 1-10pts. wt. nonpolar solvent such as hexane. Then lipase is used as an auxiliary in a quantity of 50-500 units (international unit) per pts.wt. oleoresin. A satd. fatty acid such as lauric acid or a satd. fatty acid ester such as ethyl myristate is added to the above homogeneous system. Usually, the fatty acid is used in a quantity of no more than 10pts.wt. per pt.wt. oleoresin. To complete the reaction industrially advantageously, small quantities of water and a polyhydric alcohol such as glycerol are added.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigments and aims to industrially advantageously produce stable, highly pure, odorless pigments.

Carotenoid pigments are obtained by extraction using organic solvents from plants and animals containing high concentrations of carotenoid pigments (eg, carrots, bell peppers, tomatoes, and ponds), and are usually obtained in the form of oleoresin. This thing is widely used in food,
It is used for luxury goods and medicines. Oleoresins have their own drawbacks. Specifically, it has a unique odor derived from plants and animals, which limits its use.

As a method to remove such defects, a method of steam distilling the oleoresin to remove odor components is also used, but although this operation temporarily deodorizes, the disadvantage is that the odor returns in a short period of time. There is. This is due to the 111e fatty acids contained in oleoresin.

That is, the main fatty acids are unsaturated acids such as linoleic acid and lilunic acid, and these unsaturated fatty acids are unstable in the air and easily undergo oxidation, causing the rancid odor of the lipid.

In order to eliminate this drawback, a method in which oleoresin is heat treated in an aqueous alkaline solution, the pigment contained therein is treated with a solvent, and then steam distilled has also yielded good results.

However, when treated with alkali, the color tone changes, and pigments whose main component is caronanoid fatty acid esters are subject to hydrolysis, and when producing rich pigments, the pigment components precipitate, resulting in changes in hue, brightness, etc. The disadvantage is that it can have a frightening effect.

The inventors have created a process for producing carotenoid pigments that does not have these drawbacks, ie, the present invention. The gist of this invention is to replace unsaturated fatty acids contained in oleoresin with saturated fatty acids using transesterification. The details will be explained below.

The raw material to be treated is oleoresin containing the pigment carotenoid or chili pepper fruit containing carotenoid. First, this oleoresin is dissolved in a nonpolar solvent.

Examples of non-polar solvents include common ones, such as benzine, hexane, heptane, nonane, petroleum ether, petroleum benzine, benzene, and the like. These may be used alone or in combination of two or more. The amount used is sufficient as long as the oleoresin, the enzymes described below, the saturated fatty acids, the Oki filter aid, etc. are homogeneously mixed, and usually, industrially, it is about 1 part (by weight, the same applies hereinafter) of oleoresin. Parts to 10 parts may be enough.

The enzyme lipase is used as an auxiliary agent to promote the fatty acid exchange reaction. The amount used may be about 50 to 50 international parts per part of oleoresin. By the way, the application range and efficacy of lipase differs depending on its origin and the amount and type of partner fatty acid or fatty acid ester, and cannot be defined unambiguously.To give a specific example, for example, carrot oleoresin 90% (
weight, the same applies hereafter)] Candida C per 1 kg
ylindacca origin lipase, titer 80,000 units, 7 g is sufficient.

A saturated fatty acid or a saturated monofatty acid ester is added to this homogeneous system. Any saturated fatty acid can be used, regardless of the number of carbon atoms, but in most cases, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, etc. may be used. These may be used alone or in combination of two or more. Although saturated fatty acid esters (eg, methyl laurate, ethyl myristate, etc.) can be used in place of saturated fatty acids, saturated fatty acids are usually used for ease of operation. The amount used may be 10 parts or less per 1 part of oleoresin, and within this range, the amount corresponding to the amount of unsaturated fatty acids contained in the oleoresin may be used. As an additional note, use monounsaturated fatty acids instead of saturated fatty acids. For example, oleic acid,
Elaidic acid and others may also be used. 1 Unsaturated fatty acids are substances that have the same effect as saturated fatty acids for L].

0 total amount of saturated fatty acids may be replaced with 1 unsaturated fatty acid.

If this homogeneous system is allowed to stand still at room temperature, the fatty acid exchange reaction will occur naturally, but in order to complete the reaction industrially advantageously, a small amount of water and/or polyhydric alcohol, such as
Glycerin, propylene glycol, and others may be added. The amount of water removed may be approximately 0,601 parts per part of oleoresin, and the amount of polyhydric alcohol added may be approximately 0.01 parts per part of oleoresin.

In order to carry out the reaction uniformly, it is better to stir the system to make it homogeneous and to keep it at a temperature close to the optimum temperature for the lipase enzyme. This reaction is an equilibrium reaction, and the substitution of unsaturated fatty acids with saturated fatty acids can be determined by fatty acid analysis. The method of confirmation shall be in accordance with the conventional method.

The nonpolar solvent is removed from the reaction system by a conventional method such as distillation, and the remaining liquid is neutralized with an alkali or alkaline earth metal to form unsaturated fatty acid salts.

It is better to add filter aid before salt formation.

Examples of filter aids include diatomaceous earth and bentonite. Here, the filter aid is considered to act as a dispersion adsorption agent for enzymes and oleoresin dye molecules in the above-mentioned homogeneous dissolving solvent.

Next, a step of obtaining the dye from the harvest is required. An organic solvent treatment is applied to obtain the dye from the mixed system. Examples of organic solvents include common ones such as acetone, ethyl acetate,
Ethanol and others are used. Since the ml dye obtained by recovering the organic solvent from the extract still has the odor characteristic of oleoresin, it is then subjected to a deodorizing process.

As a deodorizing method, there are conventional methods such as pressurized steam distillation method,
Atmospheric pressure steam distillation method, reduced pressure steam distillation method, method of flowing an inert gas (e.g., nitrogen gas, argon gas, etc.) as a carrier gas under reduced pressure, molecular distillation method, water-containing lower aliphatic alcohol/I/ (e.g., methanol) , ethanol, propatool, and its fti treatment are used.Among them, color I
In order to achieve a high yield without any change in the densification, and to obtain a high yield, it is preferable to use an atmospheric steam distillation method, a reduced pressure steam distillation method, or a method in which an inert gas is passed under reduced pressure as a carrier gas.

What is obtained after the deodorization process is the desired product, the pigment carotenoid.

The pigment obtained by this invention has the following advantages as a natural coloring agent.

■It does not have a specific odor. There is almost no odor that changes over time.

(2) Excellent color development and color 8'l is stable over time.

■The tone of the obtained product is the same as that of oleoresin.

■Manufacturing operations are safe and simple.

■The manufacturing yield is high, and the brightness and saturation of the pigment are high.

The pigment of this invention can be used as a natural coloring agent, for food products, luxury goods, etc.
The scope of its use can be expanded to pharmaceuticals, cosmetics, and other fields. This is because it has no unique odor and is excellent in hue, brightness, and saturation.

Example 1 Carrot oleoresin 1 toge, lauric acid 1 k? ,+
1-hexa741. ') Pase [Lipase M, Y manufactured by Meito Sangyo ■ (30,000 units) 37? , glycerin 1
0? , silica earth 100! A mixture consisting of i' from 39 to 41
Stirred at °C for 16 hours. The n-hexane recovered by distillation was neutralized by adding 2 kq of 10% aqueous sodium hydroxide solution and 4 kq of 15% brine, and the resulting solid was separated using a centrifuge. This solid material was air-dried at 50° C. to obtain 2.2 kq of dry material. Add 5 kq of acetone to this
was added and vigorously stirred for 5 hours to extract the pigment. Completely separate the solvent layer and add 4 kq of acetone to the heel extraction residue.
After time extraction, the solvent layers were combined and distilled under normal pressure to recover acetone gold. The obtained dye was steam-distilled for 3 hours under reduced pressure to obtain a dye 8 that does not have the characteristic odor of Caro and Nodo.
60Li' was obtained.

When oleoresin was deodorized by direct steam distillation treatment or hydroalcohol treatment, the odor returned when stored at room temperature for about 2 weeks to 1 month, but the dye produced in Example 1 was deodorized at room temperature for 1 week. Even after storage, no change in hue, brightness, or saturation or a faint odor occurred.

Example 2 Paprika oleoresin 500? and myristic acid 750?
Dissolved in petroleum ether (bp 55-8 (F fraction) 31, diatomaceous earth 502.50% hydrated glycerin 51 and lipase [Meito Sangyo Seisuno (-ze MY' (30,000 units)] 5? and stirred and mixed for 24 hours at 39-41°C. After distilling off the petroleum ether, a 15% aqueous solution of caustic soda t, o
oofi' was added, and 2,000 r of 20% saline solution was added to neutralize the mixture, and the resulting solid was centrifuged. This solid material was vacuum dried at 60'C and photographed at 1,850i.
I got i'. In order to extract the dye 11B, ethyl acetate/V 4 kq was added to this, and after stirring gently for 8 hours, the bath agent layer was separated, and ethyl acetate yv 2 touge was added to the extraction residue and extracted for another 4 hours, and the solvent layer was separated. was distilled under normal pressure to recover ethyl acetate. The obtained dye was steam-distilled for 3 hours under normal pressure to obtain the dye Nokpuriki 4501, which had and did not have the characteristic odor of paprika.

When oleoresin was deodorized by direct steam distillation treatment or hydroalcohol treatment, the odor returned when stored at room temperature for about 2 weeks to 1 month, but the paprika dye produced in Example 2 was kept at room temperature for 1 year. No change in hue, brightness, saturation, or return of odor occurred even when stored in

patent applicant Sanei Chemical Industry Co., Ltd.

Claims (1)

[Scope of Claims] (1) A method for producing carotenoid pigments, which comprises adding lipase and saturated fatty acids to carotenoid-containing oleoresin to replace unsaturated fatty acids in the oleoresin with the saturated fatty acids. The method for producing carotenoid pigments according to claim (1), wherein water and/or polyhydric alcohol is homogeneously added to a solution of carotenoid-containing oleoresin and a nonpolar solvent. (8) 44-free R of carotenoid-containing oleoresin
A method for producing carotenoid pigments, which comprises adding saturated fatty acids, lipase, sandy loam, and other filter aids to a 7-drug solution. (4) Add saturated fatty acids, lipase, and a filter aid to a nonpolar powder solution of carotenoid-containing oleoresin to replace the unsaturated fatty acids in the oleoresin with saturated fatty acids to remove the nonpolar solvent from the solution system. 1. A method for producing a pigment carotenoid, which comprises isolating carotenoids from an organic solvent solution of carotenoids obtained by adding an alkali to the resulting residue to neutralize it, and then adding an organic solvent to elute the carotenoid.