JPS5991155A - Method for obtaining carotenoid pigment - Google Patents

Abstract

PURPOSE:To obtain stable and odorless carotenoid pigment, by enzymatically converting chemically bonded unsaturated fatty acids in a carotenoid-contg. oleoresin into satd. fatty acid esters and then carrying out molecular distillation. CONSTITUTION:An oleoresin contg. carotenoid pigment, such as carrot oleoresin or paprika oleoresin, is dissolved in a nonpolar solvent such as benzene or hexane. Enzyme lipase and a satd. fatty acid, such as palmitic or stearic acid, and/or an unsaturated fatty acid are added to the resulting soln. If necessary, a small quantity of water, a polyhydric alcohol or a dispersion aid is added thereto. The mixture is stirred to subject chemically bonded unsaturated fatty acids in the oleoresin to an ester exchange reaction enzymatically, thus converting them into satd. fatty acid esters. Molecular distillation is then carried out to obtain the desired carotenoid pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigments, and its object is to industrially advantageously produce stable and odorless pigments.

Carotenoid pigments are high f! kFi is obtained by extracting carotenoid-containing organisms (for example, carrots, paprika, tomatoes, shrimp, crabs, etc.) using an organic solvent, and is usually obtained in the form of oleoresin. Although this product is widely used in foods, luxury goods, medicines, etc., it has the drawback of having a characteristic odor originating from a driving substance, which limits its use.

As a method to eliminate all of these drawbacks, a method is known in which the oleoresin is completely steam distilled to remove odor components, but this method has the drawback of causing the return of the odor in a short period of time. . This is due to free fatty acids contained in oleoresin and fatty acids constituting fats and oils. That is, the main fatty acids are linau/L' acid,
These unsaturated acids such as lyric acid are unstable in the air and easily undergo oxidation, causing rancid odor of lipids.

As a method to completely remove this drawback, a method is known in which oleoresin is heated in an alkaline aqueous solution, an organic solvent is added, and steam distillation is carried out, but this method requires a large amount of organic solvent and the pigment carotenoid In the case of products containing fatty acid ester /L/ as a main component, the ester undergoes hydrolysis, and when a rich pigment is produced, the pigment component precipitates, which adversely affects hue, brightness, and other properties.

The inventor has created a method for producing carotenoid pigments that does not have these drawbacks, ie, the present invention. - The main point of this invention is to carry out an ester cross-reaction of unsaturated fatty acids chemically bonded in oleoresin to saturated fatty acid esters using an enzyme, and then to convert the unsaturated fatty acids chemically bonded into oleoresins into saturated fatty acid esters, and then to convert the unsaturated fatty acids chemically bonded into oleoresins into saturated fatty acid esters. Gin is subjected to molecular distillation to remove odor components and at the same time remove all free unsaturated fatty acids and excess fatty acids produced by exchange reactions. less than,
The details will be explained below.

The starting material is an oleoresin rich in carotenoid pigments. First, this oleoresin e [polar solution A (e.g., t.
diluted with chloride, pentane, hexane, cyclohexane, petroleum ether, benzene, etc.). The amount used may be such that the oleoresin, the enzyme described below, the laminar fatty acid and/or the unsaturated fatty acid or their ester are homogeneously mixed.
(same hereinafter) may be about 1 part to 10 parts.

Any kind of fatty acid or its ester can be used. In other words, it can be used regardless of the number of carbon atoms, but in most cases, capric acid, lauric acid, myristic acid, palmitic acid, stearin t7'
4=-8. In the case of esters, the alcohol content is q, glycerin, aliphatic alcohol), v hirogamegera (L), and these can be used singly or in combination of two or more types.・Amounts used in 7 may be 10 parts or more per 1 part of oleoresin, and the amount corresponding to the amount of unsaturated fatty acids contained in the oleoresin within this range may be used. Saturated fatty acids such as oleic acid, elaidic acid, etc. are used.

In order to promote the transesterification reaction, the enzyme lipase is used as an auxiliary agent. The amount to be used cannot be univocally defined because it varies depending on the origin of the lipase, the amount of fatty acid or fatty acid ester, and the amount of fatty acid ester. To give a specific example, for example, Candid
a cylindracea origin lipase (titer a
o, o o ol unit) 7? That's fine.

In order to complete the reaction industrially more favorably, a small amount of water and/or polyhydric alcohol-LV (e.g., glycerin, propylene glyco-μ, sono, etc.) and a dispersion aid (
For example, quartz clay, bentonite, etc.) may be completely added.

At this time, the amount of water added is approximately 0.0 per part of oleoresin.
The amount of alcohol added may be about 0.01 part per part of oleoresin, and the amount of dispersion aid added may be about 0.01 to 1 part per 71 parts of oleoresin.

In order to carry out the reaction uniformly, it is desirable to homogenize the system by stirring and to keep it at a temperature close to the optimum temperature for lipase.

This reaction is an equilibrium reaction, and substitution with unsaturated fatty acids can be determined by fatty acid analysis.

The confirmation method follows a conventional method (eg, gas chromatography method).

If necessary, the dispersion aid is removed from the reaction-completed system, and the nonpolar solvent is removed by a conventional method such as distillation or other method.

The resulting system has an odor typical of oleoresin and contains unsaturated fatty acids produced by the exchange reaction and excess saturated fatty acids. A step is then required to remove these substances from the mixed system. The removal method is under high temperature (for example, about 230
A steam distillation method is also considered, but normally carotenoid pigments are relatively stable at temperatures below about 100 degrees Celsius, but at temperatures above about 150 degrees Celsius they decompose in a short period of time, resulting in color change. , the brightness and chroma change, and the product obtained with a decrease in color value has a marked decrease in its commercial value.

Molecular distillation is employed as a method to eliminate such drawbacks.

The molecular distillation apparatus may be a centrifugal thin film molecular distillation apparatus or a falling type molecular distillation apparatus. Among them, it is desirable to employ a centrifugal molecular distillation apparatus in consideration of distillation efficiency and short contact time between the sample and the high-temperature evaporation surface.

Molecular distillation operating conditions cannot be defined unambiguously because they vary depending on the distillation equipment, the type of raw material oleoresin, etc., and will therefore be shown by specific examples. Carrot oleoresin? When used, the degree of vacuum is approximately 0.00 using a centrifugal thin film molecular distillation device.
Evaporation surface temperatures of 1 to 0.005 Torr and about 120 to 220°C may be used, with temperatures of about 150 to 200°C being preferred. The desired product, carotenoid pigment, is obtained by removing volatile substances by molecular distillation.

The carotenoid pigment obtained by the method of this invention has the following remarkable effects as a natural colorant.

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

■Excellent color development and stable hue over time.

(2) The color tone of the product obtained by the method of the present invention is the same as that of oleoresin.

■Manufacturing operations are safe and simple.

■High manufacturing yield, and high pigment brightness and depth.

Examples Gearlot Oleoresin 5 #4, Lauric Acid 5 kQ,
n-heki ty20j! 1 lipase [(J&ndida
cylindra-cea origin, (ao, ooo units)
] 85F, Glycerin 501, Silica Frozen Earth 500? The mixture was stirred and mixed at a temperature of 39-41°C for 20 hours. The quartz clay was filtered out using a basket type centrifugal separator 14, and the filtrate was then distilled under normal pressure to recover all of the n-hexane.

This thick silk was degassed using a one-way deforming device and then vacuumed to 0.002 Torr using a centrifugal thin film molecular distillation device.
Molecular distillation was carried out under conditions of A@dish humidity temperature of 175°C to remove odor components, fatty acids, etc., and carrot dye 4.4#'i, which had no odor peculiar to oleoresin, was obtained. V-oresin that has been deodorized by direct steam distillation or hydroalcohol treatment will return its odor if stored at room temperature for about 2 weeks to 1 month;
There was no change in hue, brightness, or saturation, and no return of odor occurred.

This remarkable effect is due to the fact that the unsaturated fatty acids in the fatty acid content, which are the cause of the odor of the carrot dye-containing oleoresin, are replaced with saturated fatty acids, and volatile substances are removed by molecular distillation treatment.

Example 2 Paprika oleoresin 5# and myristic acid 7.5 toge were dissolved in petroleum ether (bp 55-80°C fraction) 20E,
Diatomaceous earth 5001.50% hydrated glycerin y50f and lipase ((kndida cylidracea origin,
(80,000 units)) Add 40F and 89~41゛C
The mixture was stirred and mixed for 20 hours at a temperature of . basket type centrifuge
a. Filter the diatomaceous earth using a machine and distill the filtrate under normal pressure.
- Recovered hexane. This concentrate was treated under reduced pressure (4 Torr) using a downstream model deaerator, and then treated at a vacuum degree of 0.001 Torr using a centrifugal thin film molecular distillation device.
Molecular distillation was performed at an evaporating dish temperature of 170° C. to remove odor components, fatty acids, etc., and 4.8 kq of paprika pigment without the odor characteristic of oleoresin was obtained. When oleoresin is deodorized by direct steam distillation or hydroalcohol treatment, the odor returns when stored at room temperature for about 2 weeks to 1 month.However, when this product was stored at room temperature for 6 months, the color, There was no change in brightness or chroma, and no return of odor occurred. This remarkable effect is due to the fact that the unsaturated fatty acids in the fat that cause the odor of the paprika dye-containing oleoresin were replaced with saturated fatty acids, and the volatile substances f were removed by molecular distillation.

Example 3 Carrot oleoresin toor, myristic acid LOO
P,n/'s xane 400g/l lipase (Geo
trichum OandidiumOrigin900,0
00 units] 25 da, glycerin 1? , diatomaceous earth 10? The mixture was stirred and mixed at a temperature of 38 to 4 cf for 20 hours. The filtrate was filtered using a diatomite filter using a basket type centrifugal filter, and then the solvent was distilled off under reduced pressure using a rotary evaporator. This t'fkd product was flowed down using a molecular distillation apparatus at a vacuum degree of 0.001 Torr.

Molecular distillation was carried out under the condition of an evaporating dish temperature of 170° C. to remove odor components, fatty acids, etc., to obtain Carrot Pigment 90F, which does not have the odor characteristic of oleoresin. This product was left at room temperature for six months, but the hue, brightness, and saturation did not change, and the odor did not return. This remarkable effect is due to the fact that the unsaturated fatty acids in the fat component, which are the cause of the odor of the carrot dye-containing oleoresin, are replaced with saturated fatty acids, and the volatile substances are removed by molecular distillation.

patent applicant Sanei Chemical Industry Co., Ltd. 11-

Claims (2)

[Claims] (1) When purifying carotenoid-containing oleoresin by molecular distillation, enzymatic lipase, saturated fatty acids and/or 1 unfiltered fatty acid are added to a ## polar solvent solution of the oleoresin, and all unsaturated fatty acids in the oleoresin are purified. Or, a method for obtaining a pigment carotenoid, which comprises distilling a carotenoid substituted with a monounsaturated fatty acid. (2) The method for obtaining carotenoid pigments according to claim (1), in which a fractional auxiliary agent, a polyhydric alcohol, and/or water are homogeneously added to the distillation system.