DE1190314B - Process for the production of water-dispersible carotenoid preparations for coloring food and feed - Google Patents

Description

Process for the production of water-dispersible carotenoid preparations for coloring food and feed carotenoids, such as ß-carotene, Lycopene, Bixin, Zeaxanthin, Cryptoxanthin, Luthein, Cänthaxantin, ß-Apo-8'-carotenic acid alkyl ester, like the ethyl ester, ß-apo-8'-carotinal, ß-apo-12'-carotinal, and esters of hydroxyl or carboxyl-containing members of this group, have as coloring substances a attained particular importance in technology. Carotenoids are yellow to red pigments; as a result of their relationship or identity with those present in the plant or animal kingdom Pigments are particularly valuable as a substitute for artificial dyes, e.g. B. for food. All carotenoids are insoluble in water and melt when relatively high temperature; they are also very sensitive to oxidation. These properties prevent the crystallized substances from being used directly for coloring of food or feed; in this form they are difficult to absorb and give bad color effects. Those mentioned have a particularly disadvantageous effect Properties when coloring from liquid media; due to insolubility in water With the carotenoids, it is difficult to achieve a homogeneous color effect. This insolubility in water therefore prevents the direct use of the carotenoids for coloring water-based foods such as fruit juices, mineral waters based on fruit juices or with a fruit flavor, frozen, etc .; Dry products, which with water again returned to their original form or prepared with water before consumption become, such as B. custard powder, soup powder, egg powder, tomato concentrates; cheese and dry beverage ingredients such as soda powder.

The invention now relates to a new method for the production of water-dispersible carotenoid preparations for coloring food and feed. This method consists in having a solution of a carotenoid in a volatile organic carotenoid solvent along with a salt of a higher one Fatty acid ester of ascorbic acid or a mixture of the higher fatty acid ester of ascorbic acid with a basic reacting alkali salt or an amino acid and optionally in the presence of water at least until the volatile is removed concentrates organic solvent and, if necessary, dries.

The addition of ascorbyl palmitate has already been proposed several times due to its effect as an antioxidant in carotenoid preparations. Ascorbyl palmitate has also been used as an antioxidant in carotenoid preparations which are dispersible in water. On the basis of the prior art, however, it could not be expected that a salt of this fatty acid ester would have an influence on the degree of dispersity. Specifically, attention is drawn to the German Patents 1,054,317 and 1,038 893 and Swiss Patent 245,659. The final product according to German Patent Specification 1,054,317 is a fat preparation and therefore not water-dispersible. The ascorbyl palmitate present in the preparation can therefore only develop an antioxidant effect. The preparation according to German patent specification 1038 893 is water-dispersible, but the carotenoid used is dissolved in oil. This oil content means that an assumed dispersing effect of ascorbyl palmitate added as an antioxidant is no longer effective. This dispersing effect does not actually exist, because ascorbyl palmitate, as a free acid, has a certain water-in-fat emulsifying effect, but no fat-in-water emulsifying effect. Swiss Patent 245 659 describes a carotenoid preparation in which the solubility of the carotenoids in a fat-soluble solvent is increased by adding a partial ester of a polyhydric alcohol with a higher fatty acid. It is stated that these partial esters exert a certain influence on the emulsifiability of the preparation in water. However, there is no closer relationship with the subject matter of the invention. The method according to the invention can be used, for example, for processing the natural or synthetically accessible representatives of this class of substances mentioned at the beginning. Ss-carotene, which occurs widely in nature and can be produced synthetically, is particularly suitable. Aqueous solutions of the ß-carotene coloring preparations obtainable by the present process are yellow-orange with a dye concentration of 15 mg ß-carotene per liter. The color depends on the ratio of the isomers present. Solutions with predominantly cis-ß-carotene are yellow, and solutions with the trans isomer are orange.

Due to their extraordinary coloring power, the aldehydes are suitable ß-Apo-8'-carotinal (C30) and ß-Apo-12'-carotinal (C38) for the production of coloring preparations, which produce a red color in aqueous solutions. These aldehydes and ß-carotene together result in mixtures that deliver orange and red-orange solutions that, thanks to their color intensity, especially for coloring drinks based on orange concentrates are economically valuable. A mixture of, for example, 2 parts of ß-carotene and 1 part ß-apo-8'-carotinal (C30) is around three times more extensive than the same amount by weight ß-carotene.

Canthaxanthin produces red in a dilution of 15 mg per liter of water Solutions which, due to their color and luminosity, are ideally suited for Coloring of fruit juices, syrups, jams, confectionery products and the like.

As an ester of ascorbic acid with higher fatty acids, such as those with 12 to 20 carbon atoms, come e.g. B. the esters with myristic acid, palmitic acid, Stearic acid into consideration. The commercially available ascorbyl palmitate is preferred used to form the water-dispersible carotenoid preparations.

The ones used to form the water-dispersible carotenoid preparations suitable amount of the ascorbyl fatty acid ester depends on various factors and can be about 0.1 and especially 0.3 to 10 times the amount of the carotenoid be.

In the case of particularly poorly soluble carotenoids or those with strong The asoorbyl fatty acid ester is expedient with a pronounced tendency to crystallize at least in the same amount, based on the carotenoid, used, preferably in double or higher amount. The tendency of the carotenoid, during evaporation to crystallize out can be reduced by particularly rapid evaporation. Apparatuses in which the material to be evaporated in continuously has proven to be suitable Movement is held, e.g. B. by rotating the evaporation flask or by intensive Stir. The evaporation is preferably carried out in vacuo.

The tendency of the carotenoid to crystallize when it is evaporated Solution in an organic volatile solvent can be further reduced when crystallization-inhibiting substances are added to the solution, such as. B. Lecithin; small amounts of water, glycerine, fatty acids and their esters can also be used (including glycerides) and others have a beneficial effect.

In addition to the alkalis, which are preferred as basic agents, Like sodium hydroxide and sodium carbonate, amino acids can also be used for this purpose be used. The use of basic amino acids, such as arginine and lysine, can also have a crystallization-retarding effect.

The higher fatty acid ester of ascorbic acid or a salt thereof can be partially replaced by other substances with a solubilizing effect. In some cases, mixtures of solubilizers can have a particularly beneficial effect; for example, the addition of sodium tocopherol phosphorus ester allows both the production of particularly weakly opalescent aqueous solutions and at the same time reduce the total amount of solubilizer (based on the carotenoid). Other solubilizers are z. B. sodium taurocholate, salts of p-aminobenzoic acid etc.

The ascorbyl fatty acid ester salt content of the new carotenoid preparations already provides a certain protection against oxidation. By adding phenolic Antioxidants, a further improvement in the protection against oxidation can be achieved; Tocopherol and nordihydroguajaretic acid (NDGA) are particularly effective.

Carotenoid volatile organic solvents come in particular halogenated hydrocarbons into consideration, such as. B. chloroform, carbon tetrachloride and methylene chloride. Other volatile solvents, such as. B. benzene or Carbon disulfide, however, are useful.

In a preferred embodiment of the process for producing the new water-dispersible carotenoid preparations, the solution of the carotenoid and the salt of the higher fatty acid ester of ascorbic acid (or a mixture of the higher fatty acid ester of ascorbic acid with a basic agent) is concentrated to dryness and then taken up in water; or the solution in the volatile organic solvent is distributed in water and the volatile solvent is then distilled off. The liquid carotenoid concentrates obtained by this process variant (carotenoid content about 1 to 5010) are used for direct coloring of solutions, e.g. B. water or fruit juices are suitable.

In mineral water or in hard water with a considerable content calcium occurs as a result of the formation of the poorly soluble calcium salt of the higher Fatty acid esters of ascorbic acid precipitates. These precipitates can be avoided or at least be delayed if protective colloids are added to the aqueous solution be e.g. B. gelatin, dextrin, sucrose esters of higher fatty acids, in particular Sucrose oleate, gum arabic, tragacanth, pectin, etc. Complexing agents such as ethylenediaminetetraacetic acid (EDTA, as disodium salt), have a smaller, but still noticeable effect.

Aqueous carotenoid preparations containing protective colloids can be converted into dry products, which thanks to their extensive tolerance with hard water and other aqueous solutions, their stability and good solubility are particularly preferred. This transfer takes place z. B. in a vacuum drying cabinet, by spray or roller drying, by freeze drying or by drying in a thin film evaporator. Instead of the usual gelatine (with high, medium or low gel strength, d. H. Bloom number) can also be a partially degraded gelatin can be used. This can e.g. B. by treating a aqueous Gelatin solution with papain at 38 ° C for about 10 minutes or with acids such as Tartaric acid, citric acid, ascorbic acid. This treatment diminished the protective colloid effect is not essential, but has the advantage that the preparation is already soluble in cold water.

The carotenoid preparations produced according to the invention are in Water dispersible and form homogeneously colored, translucent in thin layers Solutions. The products containing protective colloids vary according to the type of product used Protective colloids are already soluble in cold or moderately warm water (approx. 35 ° C). The products manufactured according to the method are expedient for use pre-dissolved in at least 10 times the amount of water, if necessary by heating up to to about 85 ° C, and then, if possible, further diluted. In this form are they are suitable for coloring fruit beverages, such as. B. orange drinks, tomato products (Juice and pastes), syrups, canned food, cheese, etc. In contrast to many azo dyes the new carotenoid preparations are not destroyed by ascorbic acid, which z. B. in fruit juices, jams and the like. Is naturally contained. Watery Dispersions of many carotenoids are stabilized by ascorbic acid.

However, the preparations produced can be used for special applications can also be used in dry form, for example for coloring pudding powder, Dry powder, egg powder, dry tomato concentrates, cheese and the like. Example 1 16.5 g trans-ß-carotene, 16.5 g ascorbyl palmitate and 1.1 g a-tocopherol are in 375 g of chloroform dissolved with heating.

This solution is emulsified with a solution of 64.5 g of gelatine, 170 g of water and 1.65 g of sodium hydroxide, then poured onto a metal sheet and dried at about 40 ° C. in a vacuum drying cabinet. Example 2 9.9 g of trans-β-carotene, 6.6 g of cis-β-carotene, 16.5 g of ascorbyl palmitate and 1.1 g of α-tocopherol are dissolved in 375 g of chloroform with heating.

This solution is converted into a solution of 64.5 g of gelatin and 170 g of water and 1.65 g of sodium hydroxide and stirred in the resulting emulsion in vacuo 40 ° C dried.

Example 3 5.5g β-apo-8'-carotinal (C30), 11g cis -β-carotene, 16.5g Ascorbyl palmitate and 1.1 g of a-tocopherol are dissolved in 375 g of chloroform in the heat.

This solution is homogenized with a solution of 64.5 g of gelatin, 170 g of water and 1.65 g of sodium hydroxide and dried at 40 ° C. in vacuo. Example 4 6.05 g of β-apo-8'-carotinal (C30), 2.2 g of canthaxanthin, 8.25 g of ascorbyl palmitate and 0.55 g of ca-tocopherol are dissolved in 190 g of chloroform while hot.

This solution is converted into a solution of 32.25 g of gelatin and 85 g of water and 0.825 g of sodium hydroxide are stirred in, homogenized and dried in vacuo at 40.degree.

Example 5 16.5 g of β-apo-8'-carotenal (C30), 16.5 g of ascorbyl palmitate and 1.1 g of α-tocopherol are dissolved in 375 g of chloroform with heating.

This solution is stirred into a solution of 64.5 g of gelatin, 170 g of water and 1.65 g of sodium hydroxide, homogenized and dried in vacuo at 40.degree. Example 6 16.5 g of cis-β-carotene, 16.5 g of ascorbyl palmitate and 1.1 g of α-tocopherol are dissolved in 375 g of chloroform with heating.

This solution is made with a solution of 64.5 g of gelatin, 170 g of water and 1.65 g of sodium hydroxide and emulsified on a drying roller in vacuo at about 60 ° C dried.

100 mg of this ß-carotene preparation are heated in 2 ml of water dispersed to 35 ° C. The solution is heated to 60 ° C (water bath) and with 8 ml Water diluted. This coloring solution becomes 150 g syrup (simpl.) And 10 g orange concentrate (1: 6) given and mixed well. After adding 2 g of citric acid, dissolved in 2 ml of water, is made up to 11 with carbonated water. An orange table water is obtained which has a beautiful yellow-orange color. Example 7 Solution I: 5 g of β-apo-8'-carotinal (C30), 10 g of cis β-carotene, 10 g of ascorbyl palmitate and 1 g of oc-tocopherol are dissolved in 375 g of chloroform in the heat.

Solution 1I: 80 g gelatin and 10 g sucrose oleate are each in 120 g of water dissolved in the heat and the two solutions mixed.

Solution 111. 1 g of sodium hydroxide is dissolved in 20 g of water. The solution II is placed in a four-necked stirred flask, heated to 60 ° C and evacuated (approx 180 mm HB column). Then the solutions I and III are slowly and in poured in the same amount from two dropping funnels. The vacuum becomes like this regulates that the chloroform is distilled off as completely as possible from the foaming mass. The residue is dried in a vacuum drying cabinet at 45.degree.

40 mg of the ground dye preparation are dispersed in 2 ml of water while warming to 35 ° C. The solution is heated to 60 ° C. (water bath) and diluted with 8 ml of water. This coloring solution is added to 150 g syrup (simpl.) And 10 g orange concentrate (1 : 6) and mixed well. After adding 2 g of citric acid dissolved in 2 ml of water, the mixture is made up to 11 with carbonated water. An orange table water is obtained which has a beautiful yellow-orange color.

Example 8 5 g ß-apo-8'-carotinal (C30), 10 g cis-ß-carotene, 70 g ascorbyl palmitate, 10 g sodium carbonate, 1 g α-tocopherol, 3 g lecithin and 1 g water are heated to boil in 750 g Dissolved or suspended chloroform and evaporated in a rotary evaporator at 45'C bath temperature in a water jet vacuum.

Example 9 9.9 g of trans-β-carotene, 6.6 g of cis-β-carotene, 16.5 g of ascorbyl palmitate and 1.1 g of α-tocopherol are dissolved in 375 g of chloroform with heating.

This solution is emulsified with a solution of 65 g of gum arabic, 150 g of water and 1.65 g of sodium hydroxide. The chloroform is distilled off in vacuo with stirring and the residue is evaporated to dryness in a vacuum drying cabinet. Example 10 3 g of β-carotene, 4.5 g of arginine palmitoyl ascorbate and 0.2 g of α-tocopherol are taken up in 25 g of chloroform with heating and the solution is homogenized with 92.3 g of distilled water. The pH is adjusted to 7 with sodium carbonate solution. The solvent is distilled off from the emulsion by heating it under vacuum. Example 11 Solution I: 3 g of cis-β-carotene; 4.5 g of lysine palmitoyl ascorbinate and 0.35 g of ae-tocopherol are taken up in 25 g of chloroform with heating.

Solution 1I: 5 g of gelatin are added to 85.4 g of distilled water Heating dissolved and the solution cooled to 38'C. This solution becomes 0.75 g of papain added and during. Allowed to act for 5 minutes. Then the solution will come up Heated to 100 ° C and cooled again and added 1 g of ammonia (25%).

Solution I is homogenized with solution II, and from the emulsion the solvent is distilled off by heating under vacuum. Example 12 solution I: 18.2 g cis-ß-carotene, 7 g ascorbyl palmitate, 3; 6 g methane sodium hydroxide solution (1.25%) and 2.2 g of oc-tocopherol are in 360 g of a 5,3% solution of tocopherolphosphorestersaurem Sodium dissolved in methanol and chloroform (1: 1).

Solution 11: 66 g of gelatine are added to 250 g of distilled water Heating dissolved and the resulting solution cooled to 38 ° C. Now 1 g of papain becomes added and allowed to ferment for 8 minutes. The mixture is heated to 100 ° C. and cooled off and mixed with 1.8 g of a 25% ammonia solution.

Solution II is admixed with stirring in a thin stream of the solution I and homogenized therein. A liquid dye preparation is obtained by distilling off the solvent from the emulsion with heating in vacuo.

By drying the emulsion in a vacuum drying cabinet at 40 ° C or A cold water-dispersible dry preparation is obtained in a circulating air drying cabinet at 35 ° C.

Example 13 Solution I: 44.5g rennet casein are distilled in 200g Stirred water, mixed with 50 ml ammonia solution (25%) and about 2 hours kept at 60 ° C. with stirring. Then 0.3 g of sodium taurocholate are added. Solution 1I: 2.2 cis-ß-carotene, 1.9 g trans-ß-carotene, 0.4 g ammonium ascorbyl palmitate, 0.4 g of ascorbyl palmitate and 0.4 g of oc-tocopherol are taken up in 30 g of chloroform and heated to the boiling point of chloroform.

The solution I is homogenized in solution II. the emulsion through Vacuum treatment in heat from the organic solvent and the excess Ammonia is freed and placed in a vacuum drying cabinet at 40 ° C or in a circulating air drying cabinet dried at 35 ° C.

Claims (14)

Claims: 1. Process for the production of water-dispersible Carotenoid preparations for coloring food and feed, d u r c h characterized in that one is a solution of a carotenoid in a volatile organic Carotenoid solvents together with a salt of a higher fatty acid ester Ascorbic acid or a mixture of the higher fatty acid ester of ascorbic acid with a basic alkali salt or an amino acid and optionally in the presence of water at least until the volatile organic material is removed Concentrates solvent and, if necessary, dries. 2. The method according to claim 1, characterized in that the sodium salt of palmitoyl ascorbate is added to the carotenoid solution clogs. 3. The method according to claim 1 and 2, characterized in that one is approximately equimolecular amounts of the basic compound and the fatty acid ester the ascorbic acid used. 4. The method according to claim 1 to 3, characterized in that that approximately equimolar amounts of an alkali metal carbonate are added to the carotenoid solution, in particular sodium carbonate and ascorbyl palmitate are added. 5. The method according to claim 1 to 3, characterized in that the carotenoid solution is approximately equimolar Amounts of an amino acid and ascorbyl palmitate added. 6. The method according to claim 1 to 5, characterized in that the carotenoid solvent is a lower one Halocarbons such as chloroform or methylene chloride are used. 7. Procedure according to claim 1 to 6, characterized in that the organic carotenoid solvent an antioxidant is added. B. Method according to claim 7, characterized in that that tocopherol or ascorbic acid is used as an antioxidant. 9. Procedure according to claim 1 to 8, characterized in that the organic carotenoid solvent an anti-crystallization agent, e.g. B. lecithin adds. 10. Procedure according to claim 1 to 9, characterized in that the carotenoid solution in one aqueous solution of a colloid distributed and the emulsion obtained until it is removed of the volatile organic solvent or to dryness. 11. Procedure according to claim 10, characterized in that the colloidal solution is an aqueous Solution of gelatin, partially degraded gelatin, dextrin, gum arabic, or Sugar- Acid esters, such as sucrose palmitate or sucrose oleate, used. 12. The method according to claim 10 and 11, characterized in that one the emulsion obtained is homogenized before concentration. 13. The method according to claim 1 to 12, characterized in that the carotenoid dye ß-carotene, ß-apo-8'-carotenoic acid alkyl ester, β-apo-8'-carotenal, β-apo-12'-carotenal, canthaxanthin or mixtures thereof used in quantities of at least 5 ° / o. 14. The method according to claim 1 to 13, characterized in that the mixture concentrated to dryness is dispersed in water. Considered publications: German Auslegeschriften No. 1038 893, 1 054 317; Swiss patent specification No. 245 659.