JPS6261076B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fresh red pigment preparation without paprika odor. More specifically, the present invention relates to a paprika pigment preparation that exhibits excellent water dispersibility and stability, can be colored in a wide range of desired color tones ranging from light to dark, and is free from paprika odor.

In particular, the present invention relates to paprika pigment isolated from paprika oleoresin and non-hydrophilic lipophilic _C6 ~
The present invention relates to a paprika pigment preparation characterized by mixing and emulsifying a mixed system containing a triglyceride of a _C12 saturated fatty acid and an aqueous system containing a surfactant and/or a protective colloid.

Conventionally, so-called "paprika oleoresin" is produced by removing the solvent from the extract obtained by extracting paprika (capsicum annum L.) fruits and their dried products with solvents such as ketones, alcohols, and halogenated hydrocarbons.
It is known, for example, to use it as a food coloring agent. This paprika oleoresin contains paprika odor and paprika pigment, and is useful for coloring and flavoring foods, but has poor water dispersibility and problems such as discoloration and off-odor formation over time.

In order to avoid such troubles, carbon number 6
A proposal has been made to mix triglycerides of ~12 saturated fatty acids and paprika oleoresin, and add an emulsifier selected from pectin, gelatin, gum arabic, gum tragacanth, etc. to emulsify the mixture to produce a water-dispersible paprika preparation. (Tokuko Akira)
48-43850).

According to this proposal, the color value is approximately 100,000 to approximately
Emulsified formulations are manufactured using so-called paprika oleoresin (usually with a color value of about 10,000 to 150,000). However, although such paprika oleoresin preparations have improved water dispersibility and stability, further improvements are desired, and
Since the problem of paprika odor cannot be avoided, its use is restricted. Further, there are disadvantages such as difficulty in emulsification operation and inability to provide preparations with a deep color tone.

The inventors of the present invention have proposed a method that exhibits further improved water dispersibility and stability, and is essentially free from the trouble of paprika odor, and can be used in a wide range of applications including food and beverages, cosmetics, health and hygiene products, pharmaceuticals, feeds, feedstuffs, etc. We conducted research to provide a paprika pigment preparation that can be used in various fields.

As a result, a mixed system containing paprika pigment separated from paprika oleoresin and triglycerides of non-hydrophilic and lipophilic _C6 - _C12 saturated fatty acids,
The paprika pigment preparation obtained by mixing and emulsifying an aqueous system containing a surfactant and/or a protective colloid is easier to mix and emulsify, exhibits better water dispersibility and stability, has a deep color, and has paprika color. It has been discovered that this is an excellent paprika pigment preparation that is essentially free from odor troubles.

Furthermore, as the paprika pigment, a paprika pigment-containing phase obtained by subjecting paprika oleoresin to paprika flavor component removal treatment is treated with an alkali, and then the pH of the system is adjusted to the acidic side. It is even better to use a paprika pigment obtained by treating the fatty acids contained in the system with a salt-forming agent that can convert them into poorly water-soluble or insoluble salts, and extracting the resulting treated product with an organic solvent. It has been found that it is possible to provide a paprika pigment preparation having the above-mentioned improved effects.

Therefore, an object of the present invention is to provide a paprika pigment preparation that is free from paprika odor and has the above-mentioned improvement effects.

The above objects and many other objects and advantages of the present invention will become more apparent from the following description.

As the paprika color separated from the paprika oleoresin used in the present invention, a paprika color obtained by removing the paprika flavor component from the paprika oleoresin can be preferably used. Paprika pigment obtained by steam distillation treatment with or without addition of oil to the obtained product (Special Publication No. 52-3741 and Japanese Patent Publication No.
No. 52-3809) and paprika pigment obtained by steam distilling paprika oleoresin, then treating it with an alkaline aqueous solution, and then with an organic solvent (Special Publication No. 52
-3742) are also available. The paprika pigment separated from the paprika oleoresin by these known methods is that the treated product formed by treatment with the aqueous alkaline solution contains fatty acids in the form of a water-soluble saponified product, and the paprika pigment is added to these saponified products. Because it is a soap-like solid that is adsorbed or encapsulated, there is a problem that when washed with water, the saponified product dissolves and the pigment is washed away, and the extraction efficiency is poor when extracting with an organic solvent. There are problems such as mixing of parts into the solvent phase.

Therefore, in the present invention, the paprika pigment-containing phase obtained by removing paprika flavor components from paprika oleoresin is treated with an alkali, and then the pH of the system is adjusted to the acidic side to remove the water-soluble fatty acids contained. Once the alkali salt is in the form of free fatty acids, this pH-adjusted system is treated with a salt-forming agent, such as calcium hydroxide, which can convert the fatty acids contained in the system into poorly water-soluble or insoluble salts. Contrary to the above-mentioned known means, the use of paprika pigment obtained by converting these fatty acids into poorly water-soluble or insoluble salts and extracting the resulting treated product with an organic solvent solves the problem of pigment runoff, extraction efficiency, and This is particularly preferable because troubles in the extraction operation and further troubles in the contamination of the saponified product into the organic solvent phase (pigment-containing phase) can be avoided, and the paprika pigment is obtained from which the paprika odor is removed.

In addition, as the above-mentioned paprika flavor component removal treatment,
Although steam distillation means, reduced pressure distillation means, etc. can be used, it is more preferable to extract paprika oleoresin with a lower aliphatic alcohol or its hydrated product from the viewpoint of removal effect, operation, and equipment.

Therefore, in the present invention, paprika oleoresin is extracted with a lower aliphatic alcohol or its water content, and the paprika pigment-containing phase separated from the alcohol layer (paprika flavor component-containing phase) is treated with an alkali, and then the pH of the system is adjusted. Adjusting to the acidic side, treating the PH-adjusted system with a forming agent that can convert fatty acids contained in the system into poorly water-soluble or insoluble salts, and extracting the obtained treated product with an organic solvent. It is recommended to use paprika pigment obtained by

As is well known, paprika oleoresin is produced by adding an organic solvent such as acetone, n-pentane, n-hexane, methylene chloride, or ethylene dichloride to a dried and crushed paprika fruit and extracting it. It can be obtained by separating the phases and distilling off the organic solvent under normal pressure to reduced pressure.

According to a particularly preferred embodiment of the paprika pigment separated from paprika oleoresin used in the present invention, paprika oleoresin as described above is mixed with a lower aliphatic alcohol such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol. It can be extracted with C ₁ -C ₃ aliphatic alcohols such as. Preferably ethanol can be used.

These aliphatic alcohols can also be used in a hydrous system, for example with a water content of about 1 to about 30%.

Various extraction operations and extraction conditions can be selected, but for example, about 0.5 to about 20 times the weight of aliphatic alcohol is added to paprika oleoresin, and the mixture is heated at room temperature or the boiling point temperature of the lower aliphatic alcohol used for about 5 minutes to about
This can be done by stirring for 10 hours.

After performing the extraction operation in this manner, the alcohol phase and the paprika pigment-containing phase can be separated, for example, by allowing the mixture to stand still. Centrifugation or other liquid-liquid separation means may also be used. If necessary,
Furthermore, the paprika odor of the paprika pigment-containing phase can be further sufficiently removed by adding an aliphatic alcohol to the separated paprika pigment-containing phase and repeating the same operation.

Further, when a steam distillation means is employed, pressurized or reduced pressure conditions may be employed in addition to atmospheric pressure conditions.

In a preferred embodiment of the paprika pigment used in the present invention, the paprika pigment-containing phase obtained as described above is treated with an alkali. Examples of the alkali used in this treatment include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium alcoholate, potassium alcoholate, and combinations thereof. The paprika pigment-containing phase may be used as it is, or it may be used after distilling off the alcohol that may be contained in a small amount.
Further, the alkali may be added in a solid state, or in the form of water, alcohol, or a mixed solution thereof. It is preferable to adopt alkaline conditions such that the alkaline concentration in the alkaline treatment system is about 5% to about 30%.

The above alkali treatment operation and alkali treatment conditions may be selected as appropriate. For example, add about 0.5 to about 5 times the weight of an aqueous sodium hydroxide solution (for a concentration of about 20%) to the paprika pigment-containing phase to give a solution of about 50 to about 100%.
This can be carried out by stirring at a temperature of about 30 minutes to about 12 hours.

After the alkali treatment, the pH of the treatment system is adjusted to the acidic side, preferably about 4 to about 6.5.
Examples of PH regulators include inorganic or organic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, lactic acid, and citric acid.

Through this PH adjustment treatment after the alkali treatment, the fatty acids contained in the paprika pigment-containing phase were
The water-soluble alkali salt form is once converted into free fatty acids. This pH-adjusted system is then treated with a salt-forming agent that can convert the fatty acids contained in the system into poorly water-soluble or insoluble salts. By this treatment, fatty acids that have been once converted into free fatty acids are converted into their sparingly water-soluble or insoluble salts.

This salt formation treatment can be performed, for example, under the following operations and conditions. For example, about 0.2 to about 3 of the amount of raw material oleoresin used in the PH-adjusted product
This can be done by gradually adding twice the weight of the salt former. The reaction can be carried out at room temperature, and if desired, cooling or heating conditions can be employed, such as temperatures of 0 to about 100°C. Preferred examples of such salt-forming agents include alkaline earth metal hydroxides such as calcium hydroxide, magnesium hydroxide, and barium hydroxide. In addition, hydroxides of other metals such as Al, Fe, Zn, and Cu can also be used. The solid phase of the system treated with the salt-forming agent is collected by solid-liquid separation means such as filtration or centrifugation, and
If desired, after washing with water, dehydration, etc., extraction with an organic solvent can be performed.

As described above, the solid phase subjected to the pH adjustment treatment and the salt formation treatment is much easier to perform organic solvent extraction than the soap-like solid phase proposed in the past, and has excellent extraction efficiency. ing. As the solvent used for this extraction, a wide variety of organic solvents can be used since triglycerides that interfere with smooth and efficient dye extraction are sufficiently removed. Examples of such organic solvents include ketones such as acetone and methyl ethyl ketone; esters such as methyl acetate and ethyl acetate; alcohols such as methanol, ethanol, and isopropanol;
-pentane, iso-pentane, cyclohexane,
Examples include hydrocarbons such as n-hexane, benzene, and toluene; halogenated hydrocarbons such as methylene chloride, ethylene dichloride, carbon tetrachloride, and chloroform; ethers such as diethyl ether and isopropyl ether; and arbitrary mixtures thereof. can do.

The extraction operation and extraction conditions can be selected as appropriate. For example, about 0.5 to about 20 times the weight of an organic solvent is added to the obtained solid phase and the mixture is heated at room temperature to the boiling point of the solvent used for about 15 minutes to about 15 minutes. This can be done by extracting the temporal pigment component. The extraction can be carried out by flowing the organic solvent down through the solid phase formed into a column.

After the organic solvent extraction operation, the organic solvent phase (paprika pigment-containing phase) and solid residue are separated, and the organic solvent phase is further distilled under atmospheric pressure or reduced pressure to remove the solvent. Paprika pigments with approximately 600,000 color variations can be obtained.

In the present invention, paprika color separated from paprika oleoresin as described above, preferably paprika oleoresin, is subjected to a treatment for removing paprika flavor components, such as steam distillation, extraction with a lower alcohol or a water-containing substance thereof, and the like. The resulting paprika pigment-containing phase, particularly preferably the paprika pigment-containing phase obtained by extraction with a lower alcohol or its hydrate, is treated with an alkali, and then the pH of the system is adjusted to the acidic side, and further, the pH adjustment is performed. The resulting system is treated with a salt-forming agent that can convert the fatty acids contained in the system into poorly water-soluble or insoluble salts, and the resulting treated product is extracted with an organic solvent. Oily C ₆ ~
A mixed system containing triglyceride of C ₁₂ saturated fatty acid and an aqueous system containing a surfactant and/or protective colloid are mixed and emulsified.

Specific examples of the saturated fatty acids belonging to the triglycerides of non-hydrophilic and lipophilic C ₆ to _{C 12} saturated fatty acids include caproic acid, caprylic acid, capric acid, and lauric acid. Those having less than 6 carbon atoms tend to decompose over time and are unstable, and those having more than 12 carbon atoms are difficult to use due to the mixing and emulsification operation. Mono- and di-fatty acid esters cannot be used in the present invention because it is difficult to form the above-mentioned mixed system and the mixed emulsion with the above-mentioned aqueous system becomes unstable.

The appropriate amount of triglyceride of _C6 to _C12 saturated fatty acids to be used is about 0.5 to about 30 times the weight of paprika pigment, preferably about 1 to about 15 times the weight.
There are no particular restrictions on the temperature when forming a mixed system containing the paprika pigment and a non-hydrophilic lipophilic C ₆ - _{C 12} saturated fatty acid triglyceride.
For example, temperatures from room temperature to about 150°C can be exemplified,
A homogeneous mixed solution may be obtained while stirring. The mixed system can further contain natural animal and vegetable oils, essential oils, sucrose, acetate, isohexabutyrate (SAIB), and the like.

As the surfactant used in the present invention, for example, nonionic surfactants such as sucrose fatty acid ester, sorbitan fatty acid ester, soybean phospholipid, propylene glycol fatty acid ester, glycerin fatty acid ester, etc. can be preferably used. Furthermore, anionic surfactants, cationic surfactants, or amphoteric surfactants can also be used. The amount of _these surfactants to be used is, for example _, about
Examples include amounts used in the range of 0.5 to about 150% by weight, more preferably about 1 to about 70% by weight.

Specific examples of protective colloids include natural gums such as gum arabic, xanthan gum, guar gum, locust bean gum, and gum tragacanth;
Examples include polysaccharides such as dextrin and cyclodextrin; proteins such as gelatin and casein; and the like. These protective colloids are usually used in the form of an aqueous solution, and the concentration may be any concentration that does not cause any inconvenience to the type of protective colloid used and the drying process, but for example, from about 0.05 to about 50.
An example is a concentration range of % (weight). _The amount of the protective colloid-containing _aqueous system to be used can be arbitrarily selected depending on the type of protective colloid. One example is the amount used. These surfactants and protective colloids may be used alone or in combination of two or more. The aqueous system further includes sorbitol, glycerin,
It may contain polyhydric alcohols such as propylene glycol.

Next, the C ₆ -C ₁₂ fatty acid triglyceride solution of paprika pigment and the aqueous system containing the surfactant and/or protective colloid thus obtained may be mixed and emulsified by a conventional method. Mixing and emulsification may be carried out using, for example, an emulsifier, and if desired, the mixed system may be heated to, for example, about 30 to about 50°C and then emulsified to make the emulsification operation easier. In this way, an emulsified paprika pigment preparation can be obtained. The obtained emulsion has excellent water dispersibility, does not have the odor characteristic of paprika, is stable over time, and can be used in a wide range of food and beverages and other fields.

The paprika pigment preparation of the present invention can be in the form of a powder or granule as well as an emulsion. Drying to obtain the above-mentioned dried product form can be carried out, for example, by spray drying in a spray dryer at any desired temperature and time. As the drying means, vacuum drying, freeze drying, hot air drying, etc. can also be employed. Furthermore, in order to produce a granular paprika pigment preparation, the powdered or emulsified paprika preparation obtained as described above can be easily produced using a known granulator or granulator.

The paprika pigment preparation of the present invention can be used, for example, in foods and drinks,
It is useful in fields of use such as luxury goods, feed, health medicines, and cosmetics.

For example, natural ingredients are used in foods and beverages such as drops, candied, chiyocolate, ice cream, sherbet, milk drinks, yokan, bean paste, porridge, jelly, boiled beans, dried vegetables, seafood, processed meat foods, yakiniku sauce, and pickles. Coloring agents; for example, natural coloring agents for health and pharmaceutical products such as tablets, liquid oral medicines, powdered oral medicines, and poultices; or also for cosmetic products, such as the coloring of soaps, detergents, shampoos, etc. It is useful as a natural source colorant; etc.

Hereinafter, several embodiments of the paprika pigment preparation of the present invention and its production will be illustrated in more detail with reference to Examples.

Reference Example 1 (Manufacture of paprika pigment) Add 1.5 kg of 90% ethanol solution to 500 g of paprika oleoresin and stir at room temperature for 4 hours. The alcohol phase and paprika pigment-containing phase are separated by standing overnight, and 500 g of a 20% aqueous potassium hydroxide solution is added to the paprika pigment-containing phase, followed by heating and stirring at 80°C for 4 hours. Next, 10% hydrochloric acid solution was added to adjust the pH to 6.0, and then 220 g of calcium hydroxide was gradually added.
The mixture was then centrifuged to obtain 1.4Kg of solid material. 8 kg of acetone is added to this solid, and the mixture is stirred at room temperature for 5 hours to extract the pigment component. The solvent phase was separated and distilled under reduced pressure to remove acetone, yielding 105 g of odorless paprika pigment.

Reference Example 2 (Manufacture of paprika pigment) 200g of paprika oleoresin and 1kg of methanol
and stir at 50°C for 6 hours. The paprika pigment-containing phase is separated by cooling, and 450 g of a 25% aqueous sodium hydroxide solution is added thereto, followed by heating and stirring at 65° C. for 5 hours. Then, after adjusting the pH to 6.5 with a 10% hydrochloric acid solution, 150 g of calcium hydroxide was gradually added. Then, it was centrifuged to obtain 730 g of solid material. This solid was packed into a cylindrical column, and 2 kg of acetone was added from the top.
Flow continuously (SV = 0.1) to obtain an acetone dye eluate. This acetone solution was distilled under reduced pressure to remove acetone, yielding 62 g of paprika color without paprika odor.

Reference Example 3 (Manufacture of paprika pigment) 1 kg of paprika oleoresin and 10 parts of 85% ethanol
Kg and stirred at 60°C for 1 hour. After standing still, the paprika pigment-containing phase is separated, and 5 kg of 85% ethanol is added thereto, followed by stirring at 60°C for 30 minutes. Add 2 kg of a 20% sodium hydroxide ethanol solution to the similarly separated paprika pigment-containing phase, and heat and stir at 70°C for 5 hours. After cooling, add 10% hydrochloric acid solution to adjust the pH.
6, gradually add 500 g of calcium hydroxide. Then, it was centrifuged to obtain 2.7 kg of solid material. After drying this solid under reduced pressure to remove the water content, 5 kg of ethyl acetate was added to it and the mixture was heated at 50℃ for 2 hours.
The pigment components are extracted by stirring for a period of time. The solvent phase was separated and distilled under reduced pressure to remove ethyl acetate, yielding 248 g of odorless paprika pigment.

Reference Example 4 (Manufacture of paprika pigment) In Reference Example 3, the paprika pigment-containing phase separated from the distillate by steam distillation of paprika oleoresin was used instead of the paprika pigment-containing phase extracted with ethanol. A similar paprika dye was obtained in the same manner as in Example 3.

Reference Example 5 Add 2 kg of 90% ethanol solution to 500 g of paprika oleoresin and stir at 45°C for 3 hours. After cooling, leave to stand to separate the paprika pigment-containing phase, and add to this
Add 600 g of 25% potassium hydroxide in methanol and heat at 60°C for 8 hours. Next, the pH was adjusted to 6.0 with a 5% aqueous hydrochloric acid solution, and methanol was distilled off under reduced pressure. Next, 250g of calcium hydroxide was gradually added to this, and the solids were separated by centrifugation.
Obtained 1.5Kg. Add 10 kg of acetone to this solid and stir at room temperature for 3 hours to extract the pigment component. The solvent phase was separated and distilled under reduced pressure to remove acetone, yielding 93 g of odorless paprika pigment.

Example 1 0.6 parts of paprika pigment (400000CV...Color Value) produced in Reference Example 3, 6.4 parts of triglyceride of saturated fatty acids having 8 to 12 carbon atoms, and 9 parts of SAIB were mixed and dissolved by heating to approximately 50°C. do. 84 parts of a separately prepared 30% gum arabic aqueous solution and the above dye solution (16 parts) were mixed and emulsified using an emulsifier to obtain a paprika dye emulsion preparation. After this product was left at room temperature for one year, it was odorless and had a good emulsified state.

Example 2 1 part of the paprika pigment (300000 CV) produced in Reference Example 2 and 2 parts of the same triglyceride used in Example 1 were mixed and heated to about 100°C to dissolve. 97 parts of a separately prepared 30% gum arabic aqueous solution and the above dye solution (3 parts) were mixed and emulsified using an emulsifier to obtain a paprika dye emulsion preparation. After this product was left at room temperature for one month, it was odorless and had a good emulsified state.

Example 3 0.5 part of the paprika pigment (500000CV) produced in Reference Example 5 is mixed with 2.5 parts of the same triglyceride used in Example 1, and the mixture is heated to about 50°C and dissolved. A mixed aqueous solution of 90 parts of a 30% gum arabic aqueous solution and 20 parts of dextrin prepared separately and the above pigment solution were mixed, emulsified in an emulsifier, and then dried in a spray dryer (hot air temperature 150°C) to form a paprika pigment powder. I got it.

After this product was left at room temperature for one month, it was odorless, and when redispersed in water, it became a stable emulsion with good dispersibility.

Claims (1)

[Scope of Claims] 1. A mixed system containing a paprika pigment separated from paprika oleoresin, a triglyceride of a non-hydrophilic and lipophilic C ₆ to _{C 12} saturated fatty acid, and an aqueous system containing a surfactant and/or a protective colloid. A paprika pigment preparation characterized by being mixed and emulsified with a system. 2 The paprika pigment is obtained by treating the paprika pigment-containing phase obtained by subjecting the paprika oleoresin to paprika flavor component removal treatment with an alkali, and then removing the system from the paprika pigment.
The PH is adjusted to the acidic side, and the PH adjusted system is
Claim 1, which is a paprika pigment obtained by treating the fatty acids contained in the system with a salt-forming agent that can convert into poorly water-soluble or insoluble salts, and extracting the resulting treated product with an organic solvent. Paprika pigment preparation as described. 3. The paprika color preparation according to claim 2, wherein the paprika flavor component removal treatment is performed by extracting paprika oleoresin with a lower aliphatic alcohol or a water-containing substance thereof. 4. The paprika color preparation according to claim 2, wherein the paprika flavor component removal treatment is performed by steam distilling paprika oleoresin. 5. The paprika color preparation according to claim 1, wherein the paprika color preparation is in a dosage form selected from the group consisting of an emulsion, a powdered product, and a granulated product thereof.