JPS61281159A - Production of orange pigment - Google Patents

Abstract

PURPOSE:To obtain an odorless pigment having bright orange color with stable color tone and free of after-smell, by extracting krill with a solvent, hydrogenating and hydrolyzing the unsaturated lipid other than the pigment in the extract, adding urea to the isolated fatty acid and removing the component by molecular distillation. CONSTITUTION:Dried krill is extracted with an organic solvent such as n- hexane. A catalyst (preferably palladium oxide) is added to the resultant crude pigment liquid, and the unsaturated lipid other than the pigment in the crude liquid is selectively hydrogenated and then hydrolyzed with lipase. The isolated fatty acid is removed by the addition of urea and/or by the molecular distillation to obtain the objective orange pigment. The staining power of the pigment can be improved by concentrating and purifying the obtained pigment by column chromatography. USE:Coloring of foods, cosmetics, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing an orange pigment of improved quality.

For more information, see Krill (Euphusia 5upper)
For the solvent extract of ba), after selectively hydrogenating contaminating unsaturated lipids other than pigments using a catalyst, lipase is added to hydrolyze the lipids, and free fatty acids are removed by urea addition and/or molecular distillation. By doing so, there is provided an industrially advantageous manufacturing method for producing a bright orange pigment with excellent color stability, which is odorless and does not generate any back-odor, and furthermore, the orange pigment thus obtained is concentrated by column chromatography. The present invention relates to a manufacturing method for industrially advantageously obtaining, by purification, an orange pigment having the above properties and high tinting power.

[Conventional technology]

Krill contains the orange pigment astaxanthin and can be caught in large quantities, so it is used as a raw material for pigments, but the commercially available pigments have drawbacks such as a characteristic off-odor and poor coloring power.

As a method to improve this point, JP-A-60-4558 discloses that after making the pH of the solvent extract of krill neutral, lipase or alkali is added to decompose fatty acids and other impurities to form a liquid system. proposed a method of molecular distillation or washing using dilute alkali.

[Problem to be Solved by the Invention 1] However, even with this purification method, unsaturated fatty acids cannot be removed efficiently, so a peculiar odor remains, and furthermore, it oxidizes over time, producing a return odor. Therefore, the use of krill pigments is limited to foods that are consumed in a relatively short period of time and whose unique odor is not a problem, such as kamaboko and fish roe, and cannot be applied to other foods or cosmetics. It had

[Means for solving problems]

In view of these circumstances, the present inventors have conducted extensive research to solve the above drawbacks, and have found that unsaturated lipids contaminating krill pigments and unsaturated fatty acids liberated by hydrolyzing the same oxidize over time. However, unsaturated fatty acids cannot be sufficiently removed by molecular distillation, and in order to sufficiently remove unsaturated lipids, it is necessary to selectively remove only unsaturated lipids at a stage prior to purification methods such as molecular distillation. We discovered that hydrogenation is necessary and that lipids cannot be removed sufficiently, resulting in only a low concentration of pigment being obtained, which causes a lack of coloring power.Based on this knowledge, we developed the present invention. I was able to complete it.

In other words, the present invention uses a solvent extract of krill to selectively hydrogenate contaminating unsaturated lipids other than pigments using a catalyst, then add an enzyme to hydrolyze the lipids, and then add urea and/or A manufacturing method for industrially advantageously obtaining a bright orange coloring pigment which is odorless, does not produce a return odor, has poor color stability, and is further obtained in this manner by removal by molecular distillation. This is an industrially advantageous manufacturing method for obtaining an orange dye having high coloring power in addition to the above characteristics, which is obtained by concentrating and purifying an orange dye by column chromatography.

Hereinafter, the configuration of the present invention will be explained in detail.

The raw material used is a crude pigment liquid extracted from dried krill with an organic solvent such as n-hexane or acetone.

Purification of the crude dye solution is achieved through four steps: three steps of hydrogenation of lipids, their decomposition, and removal of fatty acids, and further removal of residual lipids by column chromatography.

Fatty acids can be removed using a distillation method using molecular distillation or a chemical method using urea addition.

First is the hydrogenation of lipids, but is it crude pigment? ? Approximately 0.001 part of catalyst (weight, same hereinafter) or 2 to 10 parts of ethanol is added to 1 part of ff, and at 30 to 70°C the hydrogen absorption amount is 10 to 4011 per IKg of total dye e, preferably Shikuha 20 to 20.
The reaction is carried out under the conditions of 301. When ethanol is added, the ethanol is distilled off under reduced pressure to recover the dye solution. Examples of the catalyst used in the present invention include palladium oxide, stabilized nickel, and platinum oxide. Among these, palladium oxide is the most preferred because it causes less decomposition of dyes and can selectively hydrogenate unsaturated lipids. As shown in Figure 1, if hydrogen absorption is carried out under the above conditions, hydrogenation can be carried out efficiently, but if the hydrogen absorption is less than this, a large amount of unsaturated lipids will remain and will not return even if further purified. An odor will be generated, and if the amount is more than 100%, the decomposition of the dye will be significant, which is not preferable.

Decomposition of lipids by enzymes is carried out by adding approximately 0.1-5 parts of water to 1 part of the dye solution and adjusting the FA to 0.
In addition to 200,000 units (international units, the same applies hereinafter),
Stir at about 35-40°C for 10-40 hours. Then about 8
The mixture is heated to 0 to 100°C to inactivate the enzyme and left to stand to separate the upper dye liquid layer. Lipids can be decomposed by using alkali in a pond, but this is not preferred because the odor stability of the final dye is poor.

For the removal of separated fatty acids, glycerin and other lipids, molecular distillation is approximately 0.01-0.0 OITorr.
.

If the temperature is around 140-190℃, there will be less decomposition of the dye.
Lipids can be removed efficiently. For urea addition, add about 1 to 5 parts of a saturated urea ethanol solution to 1 part of the dye
After stirring at ℃ for about 10 to 40 hours, cool, filter the crystals, remove ethanol under reduced pressure, add n-hexane and wash with water to remove remaining urea, and remove n-hexane under reduced pressure. Do by doing.

The dye obtained by straining in this way is
Unlike that obtained with No. 58, it was a bright orange pigment with no peculiar odor or back odor, and excellent color stability.

Furthermore, if superior coloring power is desired, residual lipids are removed by column chromatography. That is, carrier 0.5
1 part of the dye solution is adsorbed on a column packed with ~2 parts and 0.5 to 2 parts of Celite, and only the lipids are eluted with a low polar solvent.
Next, the dye is eluted with a mixed solvent of a low polar solvent and a high polar solvent. The column is regenerated by passing through a highly polar solvent. Examples of carriers used in the present invention include silicic acid, activated clay,
Examples include magnesium silicate, activated alumina, activated carbon, and silica gel. Among these, silicic acid is the most preferred because it can retain and elute dyes well and has a high dye recovery rate. Examples of the low polar solvent used in the present invention include n-hexane, petroleum ether, toluene, and benzene. Among these, n-hexane is most preferred because of its high safety and low cost. Examples of the highly polar solvent used in the present invention include methanol, ethanol, acetone, and ethyl acetate. Among these, acetone is the most preferred because it can effectively elute highly polar lipids remaining on the column and is inexpensive. Examples of the mixed solvent of a low polarity solvent and a high polarity solvent used in the present invention include combinations of the various solvents listed above. Among these, a mixed solvent of about 1 to 10 χ acetone-n-hexane is most preferred since it can selectively and efficiently elute the dye.

The dye obtained as described above was an orange dye of excellent quality, which had extremely high tinting power in addition to the above-mentioned properties aimed at by the present invention.

By adding this pigment to food or cosmetics,
These can be colored bright orange. In addition, according to sensory tests, it had no effect on the flavor of foods or the smell of cosmetics, and no odor was observed to return over time.

[Example] Next, the present invention will be specifically clarified with reference to Examples and Comparative Examples. The present invention is not limited to this 4)
.

Example-1 Krill pigment liquid (pigment content 219+++g%) 10
95% ethanol 5001 and palladium oxide 40 in 0kg
．． 1 kg was added and hydrogenation was carried out for 120 minutes at 45° C. and a hydrogen pressure of 4 kg/C+112, and the amount of hydrogen absorbed during that time was 301 per kg of dye liquid. After the reaction was completed, palladium oxide was collected by filtration, and ethanol was distilled off.

The reduced dye solution had an iodine value of 78 and a dye content of 208 mg%.

Add 1,001 liters of water to the reduced dye solution, adjust the pH to 7.0 with dilute sulfuric acid, and add lipase (30,000 units/g) 0.
After adding 5 kg of enzyme solution dissolved in soi water, 3
The mixture was stirred at 8°C for 25 hours. Next, after heating at 90° C. for 30 minutes, the mixture was allowed to stand still and the upper dye liquid layer was separated. This dye liquid is subjected to molecular distillation at 160°C and 0.005 Torr to remove low-boiling point fatty acids, odor components, etc. to obtain purified dye liquid 2.
0.2 kg (dye content 980 mg%) was obtained.

1. Make this purified pigment liquid into candy. When colored with the addition of Oz, it was colored in a very clear orange color, with no unusual taste or odor, and no return odor or fading due to aging was observed.

Comparative example-1 Krill pigment liquid (pigment content 219mg%) 100k
A solution prepared by adding 1,001 g of water to 1,001 g of water was adjusted to pH=7.0 with dilute sulfuric acid, and then added with lipase (30,000 units/g) 0.5
After adding 50 kg of enzyme solution dissolved in water, 38 kg
The mixture was stirred at ℃ for 25 hours. Next, after heating at 90°C for 30 minutes,
The upper dye liquid layer was separated. This dye solution was heated to 160°C, 0
．． By molecular distillation at 0.005 Torr, 21.7 kg of purified dye liquid (dye content: 885 mg%) was obtained.

When 1.0% of this purified pigment liquid was added to the candy to color it, it became a bright orange color, but a slight odor was observed over time.

Example-2 Saturated urea ethanol solution 2001 was added to the enzyme-treated dye solution of Example-1, and after mixing and stirring at 75°C for 20 hours,
Cooled. The generated crystals are filtered, ethanol is distilled off under reduced pressure, n-hexane is added and washed with water to remove remaining urea, and n-hexane is distilled off to obtain a purified dye solution 20
．． 8 kg (dye content 911 mg%) was obtained.

When 0.1% of this purified pigment liquid was added to color a soft drink, it was colored in a very vivid orange color, with no strange or unusual odor, and no odor or fading due to aging was observed at all.

Example-3 The purified dye solution of Example-2 was further heated at 160°C, o, oosT.
Purified dye solution by molecular distillation at orr 17.9k
g (dye content 1020111 g%) was obtained.

When chewing gum was colored with O01χ using this purified pigment liquid, it was colored in a very vivid orange color, with no off-taste or odor, and no return odor or fading due to aging was observed.

Example 4 4.0 kg of the purified pigment liquid of Example 3 was adsorbed on a stainless steel column with an inner diameter of 21 cm and a height of 60 cm packed with 3.0 kg of silicic acid and 3° kg of Celite, and the purified dye solution of Example 3 was adsorbed into a stainless steel column packed with 3.0 kg of silicic acid and 3° Okg of Celite. Elutes polar lipids. Next, the dye was eluted and recovered through 3χ acetone-n-hexane mixed solvent 101, and 0.72 kg (dye content 4873 mg%) of purified dye W was obtained.

Add this purified pigment liquid to a lipstick base as shown in Table 1 at a concentration of 1.0%.
When a lipstick was produced by blending the lipstick with the same amount as the lipstick, it was colored in a very vivid orange color and no strange odor was detected.

Furthermore, even when this lipstick was left at 45°C for one month, no return odor or discoloration was observed.

Table - 1% by weight Candelilla wax 9.0 Solid paraffin 8.0 Beeswax
5゜O carnauba wax
5.0 lanolin
11.0 Refined castor oil 5
1.0 Isopropyl myristate ester 10.0
Purified krill pigment 1゜O fragrance
Appropriate amount comparative example-2 Krill pigment liquid (pigment content 219mg%> 100k
g was added to a solution in which 30 kg of caustic potash was dissolved in 95% ethanol 6001, and neutral lipids were decomposed in a centrifugal flow bath for about 2 hours while stirring and blowing nitrogen gas. Then p with dilute sulfuric acid.
After adjusting H=2.5 and adding a large amount of salt water, the pigment oil was extracted with diethyl ether in a conventional manner.

The dye solution from which the ether was distilled off was heated to 180°C and 0.005T.
Concentrated dye M19.1k by molecular distillation with orr
g (dye content 873 mg%) was obtained.

Add this concentrated pigment liquid to the lipstick base shown in Table 1 at 1.0%.
When a lipstick was manufactured by adding % of the lipstick, there was little peculiar odor immediately after, but the color density was too light, and when it was left at 45°C, a strong odor developed after about a week, making it unusable.

[Effects of the Invention] The method for producing an orange dye according to the present invention has a high recovery rate and is an industrially advantageous method. The orange pigment obtained by the present invention is odorless, has excellent odor stability, color stability, and coloring power, and can be incorporated into various foods and cosmetics.

[Brief explanation of the drawing]

Is Figure 1 a krill pigment? l! (Pigment content 219mg%)
100kg was heated to 45℃ using 0.1kg of palladium oxide.
This shows the iodine value and pigment content relative to the amount of hydrogen absorbed when hydrogenated.

Claims (2)

[Claims] (1) For krill solvent extract, unsaturated lipids other than pigments are selectively hydrogenated with a catalyst, then lipase is added to hydrolyze the lipids, and free fatty acids are removed by urea addition and/or molecular distillation. A method for producing an orange pigment characterized by: (2) For krill solvent extract, unsaturated lipids other than pigments are selectively hydrogenated with a catalyst, then lipase is added to hydrolyze the lipids, and free fatty acids are removed by urea addition and/or molecular distillation. A method for producing an orange dye, which comprises further concentrating and purifying it by column chromatography.