WATER-DISPERSIBLE COLORING COMPOSITION

Abstract

Coloring agents comprising carotenoid natural pigments in the form of solid particles being dispersed in an aqueous phase comprising polysorbate as a water-soluble emulsifier, use of the coloring agents, edible products comprising the coloring agents and a method for preparing the coloring agents.

Claims

1. A water-dispersible composition comprising a dispersion of at least 2% (w/w) of carotenoid natural hydrophobic pigment in the form of solid particles of an average size of at the most 10 m, said solid particles being dispersed in an aqueous phase comprising polysorbate as a water-soluble emulsifier and wherein the ratio (w/w) of polysorbate emulsifier:carotenoid pigment is in the range of 1:10 to 4:1; and wherein the carotenoid natural hydrophobic pigment is at least one pigment selected from the group consisting of: bixin, -carotene, -carotene, apocarotenals, canthaxanthin, saffron, crocin, capsanthin, capsorubin, lutein, astaxanthin, rubixanthin, violaxanthin, rhodoxanthin and lycopene.

2. The water-dispersible composition according to claim 1, wherein the carotenoid natural hydrophobic pigment is at least one pigment selected from the group consisting of: bixin and -carotene.

3. The water-dispersible composition according to claim 1, wherein the solid particles have an average size of at the most 2 m.

4-5. (canceled)

6. The water-dispersible composition according to claim 1, wherein the ratio (w/w) of polysorbate emulsifier:carotenoid pigment is in the range of 1:4 to 3:1.

7-9. (canceled)

10. The water-dispersible composition according to claim 1, wherein the carotenoid natural hydrophobic pigment is a water-insoluble pigment.

11. The water-dispersible composition according to claim 1, wherein the water-dispersible composition comprises a dispersion of at least 8% (w/w) of carotenoid natural hydrophobic pigment in the form of solid particles of an average size of at the most 10 m.

12-13. (canceled)

14. The water-dispersible composition according to claim 1, wherein the polysorbate is polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 65, polysorbate 80 or a mixture of these.

15. (canceled)

16. The water-dispersible composition according to claim 1, wherein the polysorbate water-soluble emulsifier is present in the composition in an amount of at least 5% (w/w).

17. The water-dispersible composition according to claim 1, wherein the polysorbate water-soluble emulsifier is present in the composition in an amount of at the most 35% (w/w).

18-19. (canceled)

20. The water-dispersible composition according to claim 1, wherein the pH of the water-dispersible composition is a pH from 2 to 5.

21. The water-dispersible composition according to claim 1, wherein the water-dispersible composition also comprises an antioxidant.

22. The water-dispersible composition according to claim 1, wherein the solid particles are being dispersed in the aqueous phase in the absence of a hydrocolloid.

23. The water-dispersible composition according to claim 22, wherein the hydrocolloid is gelatin, gum arabic, beet pectin or starch octenyl succinate derivative.

24. The water-dispersible composition according to claim 1, wherein the solid particles comprise carotenoid crystals covered with polysorbate and comprise less than 0.5% (w/w) of fat, oil or wax.

25. The water-dispersible composition according to claim 24, wherein the carotenoid crystals are bixin and/or -carotene crystals.

26. The water-dispersible composition according to claim 24, wherein the solid particles comprise 0% (w/w) of fat, oil or wax.

27-36. (canceled)

37. An edible product comprising a water-dispersible composition according to claim 1.

38. A method for preparing a water-dispersible pigment composition according to claim 1, the method comprising preparing a dispersion of at least 2% (w/w) of carotenoid natural hydrophobic pigment in the form of solid particles by comminuting the pigment in an aqueous phase comprising polysorbate as a water-soluble emulsifier, to obtain a dispersion comprising the pigment in the form of solid particles of an average size of at the most 10 m.

39. The method according to claim 38, wherein the comminuting is done by milling.

40. The method according to claim 38, wherein the pigment is comminuted in an aqueous phase in the absence of a hydrocolloid.

41. The method according to claim 38, wherein the polysorbate emulsifier is present in an amount of at least 5% (w/w).

42. The method according to claim 38, wherein the ratio of polysorbate emulsifier:carotenoid pigment is in a range of 1:10 to 4:1.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0054] The inventors of the present invention have found that a water-dispersible composition of the first aspect and herein relevant embodiments thereof provides a coloring agent with a very high tinctorial power and acid stability compared to conventional coloring agents currently on the market.

[0055] The water-dispersible composition according to the invention comprises at least one carotenoid natural pigment.

[0056] As discussed aboveoccasionally, food grade or pharmaceutically acceptable colorings agents are provided that contain coloring substances in the form of synthetic or artificial compounds having substantially the same chemical composition as natural occurring coloring agents. These types of coloring agents are also referred to in the art as nature identical colors.

[0057] In the present context, the expressions naturally occurring coloring agents and natural pigments also include nature identical colors.

[0058] As known in the art-carotene is an example of a pigment that may be obtained directly from a natural source and/or be a so-called nature identical color.

[0059] The natural pigment can be any food grade or pharmaceutically acceptable coloring matter derived from a natural source. Thus, the pigment may either be in a substantially pure form or it may be contained in the material where it occurs naturally such as a plant or animal material, optionally in combination with a food grade and/or pharmaceutically acceptable carrier.

[0060] It is essential that the pigments used in the current composition are solid water insoluble pigments.

[0061] Hydrophobic pigments are not soluble in water at any pH value.

[0062] Carotenoids which have yellow, orange or red colors occur widely in nature and important sources are plants including grasses, the annatto tree, citrus species, Capsicum annum, Crocus sativus flowers and marigold flowers, marine algae, yeast and some animals.

[0063] Carotenoids can be divided into the following classes: carotenoid hydrocarbons, xanthophylls and apocarotenoids.

[0064] As discussed above in relation to the first aspectthe carotenoid natural hydrophobic pigment is at least one pigment selected from the group consisting of: bixin, -carotene, -carotene, apocarotenals, canthaxanthin, saffron, crocin, capsanthin, capsorubin, lutein, astaxanthin, rubixanthin, violaxanthin, rhodoxanthin and lycopene.

[0065] The water-dispersible composition as described herein may comprise two or more different carotenoidsfor instance 3% (w/w) of bixin and 6% (w/w) -carotene, which give a composition with 9% (w/w) of carotenoid natural hydrophobic pigment.

[0066] Preferably, the carotenoid natural hydrophobic pigment is at least one pigment selected from the group consisting of: bixin and -carotene.

[0067] The present invention relates to a water-dispersible composition comprising a dispersion of at least 2%, such as at least 3%, such as at least 4%, such as at least 5%, such as at least 6%, such as at least 7%, such as at least 8%, such as at least 9%, such as at least 10% (w/w) of carotenoid natural hydrophobic pigment as described above in the form of solid particles of an average size of at the most 10 m or even less, said particles being dispersed in an aqueous phase comprising at least one water-soluble polysorbate emulsifier.

[0068] It may be preferred that the water-dispersible composition as described herein is comprising a dispersion of less than 50% (w/w), such as less than 40% (w/w) of carotenoid natural hydrophobic pigment.

[0069] In preferred embodiments, the average size of the solid particles is at the most 9 m, such as at the most 8 m, such as at the most 7 m, such as at the most 6 m, such as at the most 5 m, such as the most 4 m, such as at the most 3 m, such as at the most 2 m, such as at the most 1.9 m, such as at the most 1.8 m, such as at the most 1.7 m, such as at the most 1.6 m, such as at the most 1.5 m, such as at the most 1.4 m, such as the most 1.3 m, such as at the most 1.2 m, such as the most 1.1 m, such as the most 1.0 m, such as at the most 0.9 m, such as at the most 0.8 m, such as at the most 0.7 m, such as at the most 0.6 m, such as at the most 0.5 m, such as at the most 0.4 m, such as at the most 0.3 m.

[0070] In relation to measurement of size of the particlesin working examples herein were used Malvern MasterSizer and there was measured D(4,3). As known in the artD(4,3) relates to mean diameter by volume (i.e. the same as mass).

[0071] Accordingly and as understood by the skilled person in the present contextthe average size of the particles relates to D(4,3) measured Malvern MasterSizer.

[0072] Polysorbates are a class of emulsifiers used in some pharmaceuticals and food preparation. Polysorbates are oily liquids derived from ethoxylated sorbitan (a derivative of sorbitol) esterified with fatty acids. Common brand names for polysorbates include Scattics, Alkest, Canarcel, and Tween.

[0073] As discussed abovepolysorbates are very cost-efficient and this is a herein relevant advantage of the use of polysorbate as emulsifier as discussed herein.

[0074] The polysorbate may e.g. be polysorbate 20, polysorbate 40, polysorbate 60, polysorbate 65, polysorbate 80 or a mixture of these.

[0075] In working examples herein was used polysorbate 80 and it may be a preferred polysorbate.

[0076] Suitable examples of polysorbate include polysorbate with E-numbers: E 431, E 432, E 433, E 434, E 435 or E 436.

[0077] As known in the artE-numbers are codes for substances that can be used as food additives for use within the European Union and the E-numbers are not changed over time and E-numbers therefore directly and unambiguously technically define a food additive of interest.

[0078] In a preferred embodiment the water-soluble emulsifier is present in the composition in an amount of at least 5% (w/w), such as at least 6% (w/w), such as at least 7% (w/w), such as at least 8% (w/w), such as at least 9% (w/w), such as at least 10% (w/w), such as at least 11% (w/w), such as at least 12% (w/w), such as at least 13% (w/w), such as at least 14% (w/w), such as at least 15% (w/w), and such as at least 20% (w/w).

[0079] In a preferred embodiment the water-soluble emulsifier is present in the composition in an amount of at the most 35% (w/w), such as at the most 25% (w/w), such as at the most 24% (w/w), such as at the most 23% (w/w), such as at the most 22% (w/w), such as at the most 21% (w/w), such as at the most 20% (w/w).

[0080] The low concentration of water-soluble emulsifier needed in the coloring composition of the present invention to achieve acid stability as well as high tinctorial power assures that costs of production can be kept at a minimum and the inventors have found that no off-taste from the water soluble emulsifier is detectable in the finished edible product (e.g. a soft drink).

[0081] As discussed above in relation to the first aspectthe ratio (w/w) of polysorbate emulsifier:carotenoid pigment is in the range of 1:10 to 4:1, more preferably in the range of 1:10 to 3:1.

[0082] As discussed aboveworking examples herein show that it is possible to obtain good carotenoid color products even with use of relatively small amounts of polysorbate as emulsifier, which is an advantage of the present invention.

[0083] Preferably there is not used more polysorbate than required in order to make a water-dispersible composition as described herein.

[0084] It may be preferred the ratio (w/w) of polysorbate emulsifier:carotenoid pigment is in the range of 1:4 to 4:1, such as 1:4 to 3:1 or such as 1:3 to 3:1. In a preferred embodiment of the invention the ratio (w/w) of polysorbate emulsifier:carotenoid pigment is in the range of 1:4 to 2:1, such as 1:2.5 to 2.5:1 or such as 1:2 to 2:1.

[0085] The water-dispersible composition as described herein may comprise other types of emulsifier than polysorbate.

[0086] However, it is preferred that at least 80% (w/w) of the total amount of emulsifier in the water-dispersible composition is the polysorbate emulsifier, more preferably that at least 90% (w/w) of the total amount of emulsifier in the water-dispersible composition is the polysorbate emulsifier, even more preferably that at least 97% (w/w) of the total amount of emulsifier in the water-dispersible composition is the polysorbate emulsifier and most preferably that essentially all of the total amount of emulsifier in the water-dispersible composition is the polysorbate emulsifier.

[0087] Preferably, the pH of the water-dispersible composition is a pH from 1 to 7, more preferably a pH from 2 to 5 and even more preferably a pH from 2.5 to 4.

[0088] Preferably, the water-dispersible composition as described herein also comprises an antioxidant (such as tocopherols, rosemary extract, ascorbic acid or ascorbates).

[0089] In one preferred embodiment the solid particles are being dispersed in the aqueous phase in the absence of a hydrocolloid.

[0090] The term hydrocolloid as used herein refers to a protective colloid which prevents agglomeration of the pigments and thus provides wetting and dispersing activity.

[0091] Examples of hydrocolloids include gelatin, gum arabic, beet pectin and starch octenyl succinate derivatives.

[0092] Starch octenyl succinate is the common name given to starch n-octenyl succinate which is made by treating starch with n-octenyl succinic anhydride at pH 8-8.5. This type of starch derivative is anionic due to a carboxyl group and hydrophobic due to the C.sub.8-alkene chain.

[0093] The common E-number of starch sodium octenyl succinate derivatives is E1450 (see EU food additive legislation).

[0094] Preferably, the solid particles of the first aspect comprises carotenoid (preferably bixin and/or -carotene) crystals covered with polysorbate and the solid particles comprise less than 0.5% (preferably 0%) (w/w) of fat, oil or wax.

[0095] In a particular preferred embodiment, the water-dispersible composition of the first aspect and herein relevant embodiments thereof is a water-dispersible composition, wherein the water-dispersible composition comprises a dispersion of at least 10% (w/w) of -carotene as the natural pigment in the form of solid particles of an average size of at the most 10 m, said particles being dispersed in an aqueous phase comprising polysorbate as the water-soluble emulsifier and wherein the ratio (w/w) of polysorbate emulsifier:-carotene pigment is in the range of 1:3 to 3:1.

[0096] In relation to the embodiment immediately aboveit is preferred that: [0097] the composition comprises at least 12% (w/w) of -carotene, more preferably at least 14% (w/w) of -carotene and even more preferably at least 18% (w/w) of -carotene; [0098] the solid particles have an average size of at the most 4 m, more preferably of at the most 2 m, even more preferably of at the most 1.5 m and most preferably of at the most 1.0 m; and/or; [0099] the ratio (w/w) of polysorbate emulsifier:-carotene pigment is in the range of 1:2 to 3:1, more preferably in the range of 1:2 to 2:1 and even more preferably in the range of 1:2 to 1.5:1; and/or [0100] wherein solid particles comprises -carotene crystals covered with polysorbate and the solid particles comprise less than 0.5% (preferably 0%) (w/w) of fat, oil or wax.

[0101] In a particular preferred embodiment, the water-dispersible composition of the first aspect and herein described embodiments thereof is a water-dispersible composition, wherein the water-dispersible composition comprises a dispersion of at least 10% (w/w) of bixin as the natural pigment in the form of solid particles of an average size of at the most 10 m, said particles being dispersed in an aqueous phase comprising polysorbate as the water-soluble emulsifier and wherein the ratio (w/w) of polysorbate emulsifier:bixin pigment is in the range of 1:3 to 3:1.

[0102] In relation to the embodiment immediately aboveit is preferred that: [0103] the composition comprises at least 12% (w/w) of bixin, more preferably at least 14% (w/w) of bixin and even more preferably at least 18% (w/w) of bixin; [0104] the solid particles have an average size of at the most 4 m, more preferably of at the most 2 m, even more preferably of at the most 1.5 m and most preferably of at the most 1.0 m; [0105] the ratio (w/w) of polysorbate emulsifier:bixin pigment is in the range of 1:2 to 3:1, more preferably in the range of 1:2 to 2:1 and even more preferably in the range of 1:2 to 1.5:1; and/or [0106] wherein solid particles comprises bixin crystals covered with polysorbate and the solid particles comprise less than 0.5% (preferably 0%) (w/w) of fat, oil or wax.

[0107] The water-dispersible composition according to the present invention is useful in the manufacture of an edible product or a pharmaceutical product. An edible product may e.g. be a food product or a feed product.

[0108] The water-dispersible composition according to the present invention can be used as a colorant for food, feed and/or pharmaceutical products. The composition is particularly useful in low pH applications such as in application where pH of the product is below 7, such as below 6, such as below 4, or even below a pH of 3. Most food products are in the acidic range and a specific useful application includes coloring of beverage products. In beverage products the pH is typically around 2-3 and the beverage product is therefore preferably a beverage product, wherein the pH is from pH 2 to 3.

[0109] Preferred examples of a food product are beverage, wine gum, marmalade, jam, sugar confectionary, panned chocolate lentils, sausage casings, pasta, macaroni, cheese, prepared food or extruded foods.

[0110] Preferred example of a beverage is soft drink.

[0111] In a specific aspect the present invention relates to a pharmaceutical product comprising a composition according to the above description.

[0112] As discussed abovea fourth aspect of the invention relates to a method for preparing a water-dispersible pigment composition of the first aspect and herein relevant embodiments thereof, the method comprising preparing a dispersion of at least 2% (w/w) of carotenoid natural hydrophobic pigment in the form of solid particles by comminuting the pigment in an aqueous phase comprising polysorbate as a water-soluble emulsifier, to obtain a dispersion comprising the pigment in the form of solid particles of an average size of at the most 10 m.

[0113] Preferably the comminuting is done by milling, preferably wet milling.

[0114] A preferred milling is ball milling.

[0115] As understood by the skilled person in the present contextpreferred embodiments in relation to a water-dispersible composition of the first aspect may imply corresponding evident preferred embodiments in relation to the fourth aspect of the invention (relating to a method for preparing a water-dispersible pigment composition of the first aspect).

[0116] For instance, in relation to the method of the fourth aspect it may be preferred that: [0117] the pigment is comminuted in an aqueous phase in the absence of a hydrocolloid; [0118] the polysorbate emulsifier is present in an amount of at least 5% (w/w); [0119] the ratio of polysorbate emulsifier:carotenoid pigment is in a range of 1:10 to 4:1.

[0120] The invention will now be further illustrated in the following non-limiting examples.

EXAMPLES

Example 1

Composition with Beta-Carotene and Polysorbate

[0121] Composition of Milled Suspension:

TABLE-US-00001 Ingredient % Amount (g) Dem. water 73.8 2952 Polysorbate 80 7.5 300 Ascorbic acid 3 120 K-sorbate 0.1 4 Acetic acid 0.6 24 Beta-carotene crystals 15 600 Citric acid to pH 3.0-3.5

[0122] Ball Milling:

[0123] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0124] The particle size of the milled beta-carotene crystals was measured on a Malvern Mastersizer.

[0125] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0126] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0127] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0128] Milling was continued until a particle size (d(4,3)) of 0.26 microns was obtained.

[0129] After storage for 3 months at 4 C. a mean particle size d(4,3) of 0.28 microns was measured.

[0130] The viscosity of the composition was still very low after milling and this was still the case after storage for 3 months at 4 C.

[0131] Beta-carotene strength was measured: 12.48%.

[0132] 0.032 g of the color formulation was dissolved in 250 ml of a standard soft drink medium with a pH value of 3.0 and measured on a Minolta Chromameter, CT310.

[0133] Chroma was measured at 96.51, which is a high value.

Example 2

Composition with Crystalline Bixin and Polysorbate

[0134] Composition of Milled Suspension:

TABLE-US-00002 Ingredient % Amount (g) Dem. water 73.8 2952 Polysorbate 80 7.5 300 Ascorbic acid 3 120 K-sorbate 0.1 4 Acetic acid 0.6 24 Bixin crystals 90% 15 600 Citric acid to pH 3.0-3.5

[0135] Ball Milling:

[0136] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0137] The particle size of the milled bixin crystals was measured on a Malvern Mastersizer.

[0138] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0139] Milling was continued until a particle size (d (4,3)) of 0.73 microns was obtained.

[0140] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm and a 0.1 mm slit on the mill.

[0141] Milling was continued until a particle size (d (4,3)) of 0.28 microns was obtained.

[0142] After storage for 3 months at 4 C. a mean particle size d(4,3) of 0.28 microns was measured.

[0143] The viscosity of the composition was still very low after milling and this was still the case after storage for 3 months at 4 C.

[0144] Bixin strength was measured: 13.0%.

[0145] 0.0385 g of the color formulation was dissolved in 250 ml of a standard soft drink medium with a pH value of 3.0 and measured on a Minolta Chromameter, CT310.

[0146] Chroma was measured at 90.18, which is a high value.

Example 3

Composition with Beta-Carotene and Polysorbate

[0147] Composition of Milled Suspension:

TABLE-US-00003 Ingredient % Amount (g) Dem. water 66.3 2652 Polysorbate 80 15 600 Ascorbic acid 3 120 K-sorbate 0.1 4 Acetic acid 0.6 24 Beta-carotene crystals 15 600 Citric acid to pH 3.0-3.5

[0148] Ball Milling:

[0149] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0150] The particle size of the milled beta-carotene crystals was measured on a Malvern Mastersizer.

[0151] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0152] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0153] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0154] Milling was continued until a particle size (d (4,3)) of less than 0.30 microns was obtained.

[0155] The viscosity of the composition was after milling still very low.

[0156] Beta-carotene strength was measured: around 12-13%.

Example 4

Composition with Crystalline Bixin and Polysorbate

[0157]

TABLE-US-00004 Ingredient % Amount (g) Dem. Water 63.3 2476 Polysorbate 80 11 440 Ascorbic acid 4 160 K-benzoate 0.1 4 Acetic acid 30% 0.6 80 Bixin crystals 90% 21 840 Citric acid to pH 3.0-3.5

[0158] Ball Milling:

[0159] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0160] The particle size of the milled bixin crystals was measured on a Malvern Mastersizer.

[0161] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0162] Milling was continued until a particle size (d (v,0.5)) of 0.42 microns was obtained.

[0163] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm and a 0.1 mm slit on the mill.

[0164] Milling was continued until a particle size (d (v,0.5)) of 0.25 microns was obtained. After storage for 3 months at 4 C. a mean particle size d(v,0.5) of 0.28 microns was measured.

[0165] The viscosity of the composition was very low also after milling. This was still the case after storage for 3 months at 4 C.

Example 5

Composition with Beta-Carotene and Polysorbate

[0166] Composition of Milled Suspension (Recipe 20% Beta-Carotene):

TABLE-US-00005 Ingredient % Amount (g) Dem water 54.3 2118 Polysorbate 80 20 800 Ascorbic acid 4 160 K-sorbate 0.1 4 Acetic acid 30% 0.6 80 Crystalline beta-carotene 21 840 Citric acid to pH 3.0-3.5

[0167] Ball Milling:

[0168] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0169] The particle size of the milled beta-carotene crystals was measured on a Malvern Mastersizer.

[0170] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0171] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0172] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0173] Milling was continued until a particle size (d (v,4,3)) of 0.28 microns was obtained.

[0174] After storage for 3 months at 4 C. a mean particle size d(v,4,3) of 0.29 microns was measured.

[0175] The viscosity of the composition was still very low after milling. This was still the case after storage for 3 months at 4 C.

Example A

Composition with Turmeric/Curcumin Powder and Polysorbate (Comparative Example)

[0176] Composition of Milled Suspension:

TABLE-US-00006 Ingredient % Amount (g) Dem. water 68.2 2728 Polysorbate 80 10 400 K-sorbate 0.1 4 Acetic acid 0.6 24 Curcumin powder 95% 21 840 Citric acid to pH 3.0-3.5

[0177] Ball Milling:

[0178] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0179] The particle size of the milled curcumin powder was measured on a Malvern Mastersizer.

[0180] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with a diameter in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0181] Milling was continued until a particle size (d (4,3)) of 0.47 microns was obtained.

[0182] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm. and a 0.1 mm slit on the mill.

[0183] Milling was continued until a particle size (d(v,0.5) of 0.25 microns was obtained.

[0184] The viscosity of the composition was still very low.

[0185] After storage for two weeks at 4 C. in a common fridge viscosity increased dramatically and particle size also increased. D (v,0.5) in this period increased from 0.25 micron to 0.95 micron. This demonstrates that the combination of turmeric as the pigment and polysorbate does not work as it does not lead to stable coloring compositions.

Example B

Composition with Beta-Carotene and Citric Acid Esters of Fatty Acid Mono/Diglycerides (Comparative Example)

[0186] Composition of Suspension:

TABLE-US-00007 Ingredient % Amount (g) Dem. water 79.9 3196 Citric acid ester of fatty acid mono/diglycerides 10.0 400 (citrem N-12) Ascorbic acid 5.0 200 K-sorbate 0.1 4 Acetic acid 0.6 24 Beta-carotene crystals 5.0 200 Citric acid to pH 3.0-3.5

[0187] Ball Milling:

[0188] It was attempted to mill the color suspension on a LabStar ball mill (Netzsch, Germany) equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0189] This turned out to be impossible due to a very high viscosity.

Example C

Composition with Carbo Vegetabilis and Polysorbate (Comparative Example)

[0190] Composition of Milled Suspension (Recipe 5% Carbo):

TABLE-US-00008 Ingredient % Amount g Dem water 50 2000 Acetic acid 1 40 Polysorbate 15 600 Carbo pasta 15% carbo 34 1360 Citric acid to pH 3

[0191] Ball Milling:

[0192] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0193] The particle size of the milled beta-carotene crystals was measured on a Malvern Mastersizer.

[0194] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0195] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0196] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0197] Milling was continued until a particle size (d (v,0.5)) of 0.21 microns was obtained.

[0198] The viscosity of the composition was still very low

[0199] The milled composition was stored at 4 C. for 4 days. The particle size had then increased to d(v,0.5) 1.13 microns.

[0200] This demonstrates that this coloring composition is not stable.

Example D

Composition with Carbo Vegetabilis and Polysorbate (Comparative Example)

[0201] Composition of Milled Suspension (Recipe 5% Carbo):

TABLE-US-00009 Ingredient % Amount g Dem water 22.33 893.3 Acetic acid 1 40 Polysorbate 10 400 Carbo pasta 15% carbo 66.7 2666.7 Citric acid to pH 3

[0202] Ball Milling:

[0203] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0204] The particle size of the milled beta-carotene crystals was measured on a Malvern Mastersizer.

[0205] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0206] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0207] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0208] Milling was continued until a particle size (d (v,0.5)) of 0.20 microns was obtained.

[0209] The viscosity of the composition was still very low

[0210] The milled composition was stored at 4 C. for 4 days. The particle size had then increased to d(v,0.5) 0.90 microns.

[0211] This demonstrates that this coloring composition is not stable.

Example E

Composition with Copper Chlorophyllin and Polysorbate (Comparative Example)

[0212] Cu chlorophyllin/polysorbate: 2/1

TABLE-US-00010 Water phase 1) Ingredient Grams Dem. water 1241 Cu chlorophyllin 520

[0213] Stirred until all Cu chlorophyllin has dissolved

TABLE-US-00011 Water phase 2) Ingredient Grams Dem. water 1875 K sorbate 4 H.sub.2SO.sub.4 conc. 75

[0214] When all had dissolved water phase 1 was added to water phase 2 under stirring.

[0215] When all had been added the suspension was treated for 2 minutes on a Silverson.mixer to stir up lumps of precipitated Cu chlorophyllin

[0216] After this treatment pH was measured at 2.35.

[0217] 260 g polysorbate was then added to the Cu chlorophyllin suspension.

[0218] pH measured at 2.43.

[0219] Stirred for two hours.

[0220] The suspension appeared very viscous, too viscous for ball milling.

[0221] pH raised by the addition of solid KOH.

[0222] After 2.33 g: pH: 2.66.

[0223] After another 7.15 g: pH: 4.06.

[0224] The precipitated suspension still appeared very viscoustoo viscous for milling.

[0225] It was concluded that with this composition it will not be possible to produce a coloring composition according to the invention.

Example F

Composition with Copper Chlorophyllin and Polysorbate (Comparative Example)

[0226] Cu chlorophyllin/polysorbate: 1/2

TABLE-US-00012 Water phase 1) Ingredient Grams Dem. water 1131.9 Cu chlorophyllin 260

[0227] Stirred until all Cu chlorophyllin has dissolved

TABLE-US-00013 Water phase 2): Ingredient Grams Dem. water 937.5 K sorbate 2 H.sub.2SO.sub.4 conc. 37.5

[0228] When all had dissolved water phase 1 was added to water phase 2 under stirring.

[0229] pH was measured at 1.94 in the precipitated Cu chlorophyllin suspension.

[0230] 540 g polysorbate was then added to the suspension.

[0231] When all had been added the suspension was treated for 5 minutes on a Silverson.

[0232] pH was then adjusted to 4.35 with solid KOH.

[0233] The suspension was stored overnight at 4 C for ball milling.

[0234] Viscosity had increased significantly overnight and the mill clogged.

[0235] The suspension was then diluted to a theoretical strength of 6% and milled right after.

[0236] Ball Milling:

[0237] The color suspension was milled on a LabStar ball mill (Netzsch, Germany) in two steps.

[0238] The particle size of the milled Cu chlorophyllin crystals was measured on a Malvern Mastersizer.

[0239] During the first milling step the mill was equipped with 450 ml of beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range 0.6-0.8 mm and a 0.2 mm slit on the mill.

[0240] Milling was continued until all particles with a diameter of above 10 microns had disappeared.

[0241] The beads were then exchanged with 450 ml of smaller beads (SiliBeads ZY, Sigmund Lindner GmbH, Germany) with diameters in the range of 0.3-0.4 mm.

[0242] Milling was continued until a particle size (d (v,0.5)) of 0.13 microns was obtained.

[0243] The viscosity of the composition was still very low.

[0244] The milled composition was stored at 4 C for 4 days. The particle size had then increased to d(v,0.5) 0.44 microns.

[0245] It was concluded that this coloring composition was not stable.