JPH0453908B2 - - Google Patents

Description

[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing paprika pigment.

[Problems that the prior art and invention attempt to resolve]

Paprika pigment is produced by Capsicum, a plant in the Solanaceae family.
An extract of the pericarp of L. annuum, the main pigment is said to be capsanthin. After treating the peel with water,
The product obtained by extracting with petroleum ether and 90% ethanol and concentrating the pigment liquid is usually called paprika oleoresin.

These paprika pigments are orange-yellow to orange-red oil-soluble pigments, and because they are derived from natural products, they are used as coloring agents for foods, feed, cosmetics, etc.
For example, salad dressing, sauce for rice crackers, agar for honey beans, sea urchin kneaded, tsukudani, moromi pickled fish, jelly,
It is used as an additive in Kabayaki sauce, bread crumbs, mochi sweets, etc.

Conventionally, to extract pigments from paprika, paprika pigments are obtained by treating paprika pigment-containing substances with an aqueous alkali solution, then extracting with an organic solvent or vegetable oil, and post-processing (Japanese Patent Publication No. 52-3742, 52 −3809
No. 52-8741, JP-A-57-190051, No. 59-
33259 etc.). Another method, which is essentially the same as the above method, is to saponify the paprika pigment-containing material with an alkali and then convert the fatty acid into an insoluble salt before extracting the pigment (see JP-A-56-11960).
In these conventional methods, since the saponification step and the extraction step are separated, the number of steps is long, for example, four steps, and operations such as saponification, post-treatment, centrifugation, vacuum drying, and organic solvent extraction are required. Therefore, the operation is complicated and the processing time is long, so there is a risk that the quality may deteriorate due to oxidation of the paprika pigment.

The present inventors investigated a method for obtaining highly pure paprika pigment by carrying out the complicated saponification and extraction steps of paprika pigment-containing materials in one step, which are the disadvantages of these conventional methods, and as a result, they discovered the present invention.

[Means for solving problems]

That is, the present invention relates to a method for producing paprika pigment in which a paprika pigment extract is treated with an aqueous caustic alkali solution in the presence of acetone or methyl ethyl ketone, insoluble materials are separated, and the resulting liquid is concentrated to obtain a highly pure paprika pigment.

In the present invention, by simultaneously saponifying and desalting with a caustic alkali in acetone or methyl ethyl ketone, it is possible to remove fatty acid derivatives such as triglycerides in the paprika pigment-containing material and concentrate the unsaponifiable pigment. I can do it.

The paprika pigment extract used in the present invention may be any extract obtained by treating a paprika pigment-containing plant with an organic solvent (eg, acetone, hexane, chloroform, ether, etc.).

This paprika pigment extract is treated with an aqueous caustic solution in the presence of acetone or methyl ethyl ketone. If a ketone other than acetone or methyl ethyl ketone is used in this case, the concentration of the dye may be insufficient, or the dye may be slightly altered, resulting in a decrease in the absorption ratio. In addition, alcohols cause decomposition of the pigment and cannot be concentrated at all. With ethers and hydrocarbons, the concentration of the dye is insufficient and post-treatments such as filtration are difficult. The amount of acetone or methyl ethyl ketone used is approximately 5
~10 times (v/w) or more is preferred. If the amount is less than this, the reaction tends to be difficult. Add an aqueous caustic solution to acetone or methyl ethyl ketone containing the paprika pigment extract. Examples of the caustic alkali include sodium hydroxide and potassium hydroxide. And the concentration is about 20 to 50
Weight%. The amount used is about 1-1.5 times (v/w) for paprika pigment extract. The ratio of the aqueous caustic alkali solution to acetone or methyl ethyl ketone is about 0.3 or less, preferably about 0.2 or less; if it is more than this, the reaction is often adversely affected. The treatment is preferably carried out under stirring at a temperature from room temperature to boiling temperature, but is not particularly limited. If the treatment temperature is low, the reaction time will be long, but it will be about 1 hour to several hours. After the reaction is completed, the objective can be achieved by separating the insoluble fatty acid salt and concentrating the liquid.

Other known treatment methods such as deodorization, removal of flavor components, etc. can be added to the method of the present invention as needed to increase its effectiveness.

〔Example〕

Next, examples and reference examples will be shown. Reference examples 1 to 3
shows an example of producing a paprika pigment extract used in the present invention, and Reference Examples 4 and 5 show examples of removing pungency from the product obtained in the present invention.

Reference Example 1 1.5 kg of acetone was added to 1 kg of ground paprika (produced in Poland), heated at 55°C for 1 hour, and then allowed to cool to room temperature. The extract was filtered, the residue was washed with fresh acetone 1.0, and the liquid and washings were combined and concentrated under reduced pressure to obtain an oily paprika pigment extract.
I got g.

Reference Example 2 150 ml of methanol was added to 100 g of crushed paprika (produced in India), heated at 55° C. for 30 minutes, and then allowed to cool to room temperature. The extract was then filtered and the residue was washed with 100 ml of fresh acetone. The residue was heated for 1 hour at 55° C. with 150 ml of fresh acetone, filtered in the same manner and washed with 100 ml of fresh acetone. Combine all liquids and washing liquid and concentrate under reduced pressure.
7.7 g of paprika pigment extract was obtained.

Reference Example 3 750 ml of acetone was added to 500 g of crushed paprika (produced in India) and heated to 55°C. After heating for 30 minutes while stirring occasionally, heating was stopped and the mixture was allowed to cool to room temperature, and the paprika was removed.

Add this crushed paprika twice more to 500ml of acetone.
After extracting in the same manner, the liquids were combined and the acetone was distilled off under reduced pressure to obtain 37.6 g of paprika pigment extract [E1% 1 cm
32.3 (460 nm in chloroform), absorbance ratio (absorbance at 470 nm/absorbance at 454 nm) 0.9659].

Example 1 Paprika pigment extract obtained in Reference Example [E1% 1cm
32.1 (460nm in chloroform) 5.01g in acetone
The solution was dissolved in 34 ml, heated to 50°C under nitrogen atmosphere, and stirred. 5.7 ml of 26% caustic soda water was gradually added dropwise to the mixture, and stirring was continued for 2 hours at the same temperature, resulting in the precipitation of solid matter. Stirring and heating were stopped, and the mixture was allowed to cool to room temperature, and then the solid matter was separated. Wash the solid matter with a small amount of acetone, combine the washing liquid and the liquid, and distill off the acetone under reduced pressure to obtain 0.72 g of paprika pigment with little paprika odor [E1% 1 cm222.3 (460 nm chloroform)]
I got it. In addition, this paprika pigment was diluted with acetone and the absorbance ratio (absorbance at 470 nm/absorbance at 454 nm) was determined using a spectrophotometer, and it was found to be 0.9980 compared to 1.0008 of the raw paprika pigment extract.

Example 2 4.99 g of the paprika pigment extract [E1% 1 cm28.9 (in 454 nm acetone) obtained in Reference Example 2] was dissolved in 50 ml of methyl ethyl ketone, heated to 40° C. under nitrogen atmosphere, and stirred. To this, 6 ml of 25% caustic soda water was gradually added dropwise, and stirring was continued at 40°C for 3 hours, and solid matter began to precipitate. Stirring and heating were stopped, and the mixture was allowed to cool to room temperature, and then the solid matter was separated. Next, the solid matter was washed with a small amount of methyl ethyl ketone, the washing liquid and the liquid were combined, and the methyl ethyl ketone was distilled off under reduced pressure. 1.18 g of paprika pigment with little paprika odor [E1% 1 cm
115.8 (454 nm, in acetone)]. The absorbance ratio of this paprika pigment (absorbance at 470 nm/absorbance at 454 nm) is 1.0008 for the raw paprika pigment extract.
It was 0.9874.

Example 3 The same operations as in Example 1 were carried out except that the reaction was carried out under heating to reflux, to obtain 0.69 g of paprika pigment. [E1% 1cm220.6 (460nm, in chloroform)], absorption ratio 0.9955.

Example 4 The same procedure as in Example 1 was carried out except that the reaction temperature was 16°C to 18°C and the reaction time was 20 hours to obtain 0.75 g of paprika pigment. [E
1% 1cm215.4 (460nm, in chloroform)], extinction ratio
0.9982.

Example 5 21.70 g of the paprika pigment extract of Reference Example 3 was treated in the same manner as in Example 1, and 3.12 g of paprika pigment [E1% 1 cm215.4 (460 nm, in chloroform), extinction ratio
0.9660].

Example 6 18 ml of 20% caustic soda aqueous solution was added to 10.23 g of paprika pigment extract [E1% 1 cm32.1 (460 nm, in chloroform)], and the mixture was heated and stirred at 100°C for 3 hours. After cooling, 150 ml of acetone was added to the reaction mixture, stirred for 15 minutes, and then filtered, and the solid matter was washed with a small amount of acetone.
Combine the liquid and washing liquid and distill off the acetone under reduced pressure.
Paprika pigment with little paprika smell 1.54g [E1% 1cm
208.8 (460 nm, in chloroform)] was obtained.

Example 7 10.04g of paprika pigment extract [E1% 1cm28.9 (460nm, in chloroform)] was added to isopropyl ether20
ml, add 15 ml of 26% caustic soda aqueous solution,
Stirred at 50°C for 2 hours. Add acetone to the reaction solution after cooling.
130 ml was added and the precipitated solid matter was filtered, and the solid matter was washed with a small amount of acetone.

The solution and washing solution were combined and the solvent was distilled off under reduced pressure to obtain 1.30 g of paprika pigment [E1% 1 cm220.5 (460 nm, in chloroform)].

Reference example 4 50ml of 2.05g of paprika pigment obtained in Example 5
of n-hexane and 5 ml of 95% methanol.
was added, shaken, left to stand, and the separated lower layer was removed. After repeating this operation once, the n-hexane layer was separated and the n-hexane was distilled off under reduced pressure to remove the flavor component with an E1% of 1 cm224.0 (460 nm, in chloroform) and an absorption ratio of 0.9651. 1.65 g of almost odorless paprika pigment was obtained.

〔effect〕

According to the present invention, since the concentration of paprika pigment is performed in one step, the operation is simple and the cost is low. Moreover, the effect is that, for example, a raw material with a CV of 100,000 can be dramatically purified into a product with a CV of 500,000 to 700,000 without changing the absorption ratio at all. Furthermore, the saponification conditions are mild, and no alteration of the pigment (decomposition of paprika pigment ester) occurs. In addition, because the process is short and one step, there is little deterioration of the dye due to air oxidation.

Moreover, the characteristic odor of paprika pigment is extremely reduced.

Because of these advantages, the utility of paprika pigment as a natural coloring agent is enhanced by the present invention.

Claims (1)

[Claims] 1. A method for producing paprika pigment in which a paprika pigment extract is treated with an aqueous caustic alkali solution in the presence of acetone or methyl ethyl ketone, insoluble matter is separated, and the resulting liquid is concentrated to obtain a high-purity paprika pigment.