JPS6152184B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to pigments, and an object of the present invention is to industrially advantageously produce carotenoid pigments that are stable, highly pure, and odorless.

Carotenoid pigments are obtained by extraction from animals and plants containing high concentrations of carotenoid pigments (eg, carrots, bell peppers, tomatoes, etc.), and are usually obtained in the form of oleoresin.

Although this product is widely used in foods, luxury goods, medicines, and other products, oleoresin has its own drawbacks. Specifically, it has a unique odor derived from wild animals and plants, and its uses are limited.

As a method for removing such defects, a method of steam distilling oleoresin to remove odor components is also used. Although this operation temporarily deodorizes, it has the disadvantage that the odor returns in a short period of time. The reason for this is thought to be due to residual fatty acids contained in the oleoresin. That is, the main fatty acids are polyunsaturated fatty acids such as linoleic acid and linolenic acid, which are likely to be easily oxidized and polymerized in the air, causing rancid odor.

In order to eliminate this drawback, a method of treating oleoresin in an alkaline aqueous solution to form a fatty acid salt, extracting the pigment contained therein with an organic solvent, and then deodorizing it by steam distillation gives good results, but it requires a large amount of organic solvent. Therefore, the manufacturing process becomes complicated, which is industrially disadvantageous.

The inventors have created a method for producing carotenoid pigments that does not have these drawbacks, ie, the present invention. The gist of this invention is to treat the lipids contained in oleoresin with an aqueous alkaline solution to convert them into free fatty acids, and then to remove the resulting free fatty acids along with the odor substances by molecular distillation. The details will be explained below.

The raw material to be treated is carotenoid pigment-containing oleoresin (hereinafter referred to as oleoresin). First, in order to remove the fat contained in this oleoresin, it is saponified with an alkali. First, an aqueous alkaline dispersion of the oleoresin is prepared. Instead of the alkaline aqueous dispersion, an alkali-containing hydrous lower aliphatic alcohol (for example, methanol, ethanol, etc.) may be used. As the alkali component, caustic soda, caustic potash, etc. are used. These treatment conditions cannot be determined unambiguously because they vary greatly depending on the type of oleoresin to be treated, the type of alkali used, and the alkali concentration and amount.
20 to 30% (by weight, the same below) of caustic soda or caustic potassium aqueous solution of about 0.5 to 30% (by weight, the same below)
5 parts may be added and treated at about 10 to 110°C for about 0.5 to 24 hours. During this time, in order to complete the reaction industrially advantageously, it is better to homogenize the system by stirring. In addition, when processing at low temperatures near room temperature, a small amount of salt (e.g., common salt,
It is desirable to add potassium bromide, etc.). After the system is cooled to around room temperature, a mineral acid is added to convert the fatty acid salt produced by the saponification reaction into free fatty acid. Any mineral acid can be used, but dilute sulfuric acid, hydrochloric acid, phosphoric acid, etc. are usually used. At this time, the amount of mineral acid added may be the amount required to neutralize the alkali used.

By this operation, the carotenoid pigment is obtained in a state dissolved or dispersed in the fatty acid.
Then, odor substances and generated fatty acids are removed from this system. One method for removing carotenoid pigments is vacuum steam distillation at high temperatures (for example, about 230 to 250 degrees Celsius), but carotenoid pigments are usually
Although it is relatively stable at temperatures below 100°C, it decomposes in a short time at temperatures above about 150°C, causing changes in hue, brightness, and saturation, as well as a decrease in color value, and the resulting product loses its commercial value. Since it is characterized by a significant decrease in the amount of water, molecular distillation is employed as a method to eliminate this drawback.

As the molecular distillation method, a centrifugal thin film molecular distillation apparatus or a falling film molecular distillation apparatus may be used. Among these, it is desirable to adopt a centrifugal thin-film molecular distillation apparatus in consideration of distillation efficiency and shortening of the contact time between the sample and the high-temperature evaporation surface. Prior to molecular distillation, the oleoresin hydrolyzate is degassed to remove water and low boiling volatiles. The usual degassing method is
That is, a spray method, a falling film method, etc. are employed.
The degassed system is then subjected to molecular distillation. Molecular distillation operating conditions cannot be defined unambiguously because they vary depending on the distillation equipment, the type of raw material oleoresin, etc. To give a specific example, when carrot oleoresin is used, a centrifugal thin film molecular distillation equipment is used. The vacuum level may be approximately 0.005 mmHg and the evaporation surface temperature may be approximately 120 to 220°C, with a temperature of approximately 150 to 200°C being particularly desirable.

In addition, in the case of oleoresins such as paprika oleoresin, which contain particularly high concentrations of carotenoid pigments and have few unsaponifiables, the fluidity of the distilled product becomes poor due to the distillation of fatty acids, etc., resulting in decomposition of the pigment components due to burning. A phenomenon occurs.

To avoid this phenomenon, it is desirable to add any refined edible oil (eg, olive oil, coconut oil, etc.) prior to distillation. The amount added may be arbitrary as long as it is an amount that maintains fluidity of the distilled product.

The desired product, carotenoid pigment, is obtained by removing volatile substances by molecular distillation.

The carotenoid pigment obtained by this invention is
It has the following effects:

Does not have a specific odor. There is almost no odor that changes over time.

It has excellent color development and is stable over time in terms of hue, brightness, and saturation.

Manufacturing operations are safe and simple.

High manufacturing yield.

Example 1 Carrot oleoresin (color value 10000) 200Kg
400 kg of 20% (w/w) aqueous sodium hydroxide solution was added and mixed with stirring at 95°C for 3 hours. After the saponification reaction was completed, the mixture was cooled to room temperature, neutralized by adding 6.53 kg of 15% (w/w) dilute sulfuric acid, and allowed to stand overnight to separate into an oil layer and an aqueous layer. After removing the aqueous layer, the resulting oil was subjected to a thin film distillation apparatus to remove low-boiling substances and water under reduced pressure (5 mmHg) to obtain 1.91 kg of pigment-containing oil. Next, using a centrifugal molecular distillation device, the vacuum level was 0.003 mmHg and the evaporating dish temperature was
Molecular distillation was carried out at 180°C to obtain 176 g of almost odorless carrot pigment (color value 108,000).

This product was left at room temperature for one month, but the hue, brightness, and chroma did not change, and although the smell did not return, the product did not return.

Example 2 Paprika oleoresin (color value 100000) 5.00Kg
7.50 kg of 20% (w/w) aqueous sodium hydroxide solution and 0.30 kg of sodium chloride were added and stirred at 20°C for 8 hours. Then, while stirring, 18.4 kg of 10% (w/w) dilute sulfuric acid was added to neutralize the mixture, which was then allowed to stand overnight to separate into a pigment-containing oil layer and an aqueous layer. Water and low-boiling volatile substances contained in the oil layer are removed using a thin film distillation device, reducing the oil content to 4.77
Got Kg. 1.00Kg of refined olive oil to the obtained oil
and then reduce the vacuum using a centrifugal molecular distillation device.
Almost odorless paprika pigment is produced by molecular distillation at 0.003mmHg and 175℃ to remove odor components and fatty acids.
2.06Kg (color value 225000) was obtained.

This product was left at room temperature for one month, but the hue, brightness, and saturation did not change, and the odor did not return.

Example 3 Paprika oleoresin (color value 100000) 5.00Kg
7.50 kg of 20% (w/w) aqueous caustic potassium solution was added and stirred at 80°C for 4 hours. Then, while stirring, add 15% (w/
w) 8.75 kg of diluted sulfuric acid was added and allowed to stand overnight to separate into a pigment-containing oil layer and an aqueous layer. Remove the aqueous layer, then
Water and low-boiling volatile substances contained in the oil layer were removed using a thin film distillation apparatus to obtain 4.77 kg of oil. Add 1.00 kg of refined olive oil to the obtained oil and use a centrifugal molecular distillation device to reduce the vacuum to 0.003 mm.
Molecularly distilled Hg at 180℃ to remove odor components and fatty acids, and 1.91 kg of odorless paprika pigment (color value)
249,000).

This product was left at room temperature for one month, but the hue, brightness, and saturation did not change, and the odor did not return.

Claims (1)

[Scope of Claims] 1. A method for producing a carotenoid pigment, which comprises distilling an alkali-treated oleoresin when purifying the carotenoid-containing oleoresin by molecular distillation. 2. A method for producing carotenoid pigments, which comprises, in carrying out molecular distillation purification of a carotenoid-containing oleoresin, distilling a mixture of the oleoresin treated with an alkali and purified edible oil homogeneously added thereto. 3. A method for producing carotenoid pigments, which comprises adding a mineral acid to an alkali-treated oleoresin containing a carotenoid, adding a refined edible oil homogeneously thereto, and distilling the same. .