Dye for Foods, Nutritional Supplements, Cosmetic or Pharmaceutical Products

Abstract

For coloring foods, nutritional supplements, cosmetic or pharmaceutical products, the invention provides a dye, which contains at least one pigment in the form of a water-insoluble sulfate, carbonate, or phosphate of at least one alkaline earth metal, which is selected from the group consisting of calcium sulfate, magnesium phosphate, calcium phosphate, and magnesium carbonate.

Claims

1.-11. (canceled)

12. A dye for coloring foods, nutritional supplements, cosmetic or pharmaceutical products, comprising: at least one pigment in the form of a water-insoluble sulfate, carbonate or phosphate of at least one alkaline earth metal, which is selected from the group consisting of magnesium phosphate, calcium phosphate, magnesium carbonate, and calcium sulfate anhydrite having a mean particle size (d[4,3]) from 1.0 to 5.0 μm.

13. The dye according to claim 12, wherein a suspension of the dye in an aqueous solution of 7% by weight of sugar at pH 3 has a turbidity which is twice to five-times higher than a pigment mixture of 95% by weight of tricalcium phosphate and 5% by weight of calcium carbonate or of 85% by weight of tricalcium phosphate and 15% by weight of calcium carbonate.

14. The dye according to claim 12, wherein a turbidity of a suspension of the dye in an aqueous solution of 7% by weight of sugar at pH 3 decreases over a period of time of 40 minutes by 2% to 5% calculated as difference of the turbidity at 40 minutes and at 0 minutes, based on an initial value.

15. The dye according to claim 12, further comprising at least one soluble colorant.

16. A method for whitening foods, nutritional supplements, cosmetic or pharmaceutical products, comprising: mixing a foodstuff, nutritional supplement, cosmetic product or pharmaceutical product with a dye comprising at least one pigment in the form of a water-insoluble sulfate, carbonate, or phosphate of at least one alkaline earth metal, which is selected from the group consisting of magnesium phosphate, calcium phosphate, magnesium carbonate, and calcium sulfate anhydrite having a mean particle size (d[4,3]) from 1.0 to 5.0 μm.

17. A method for coloring foods, nutritional supplements, cosmetic or pharmaceutical products, comprising: mixing a foodstuff, nutritional supplement, cosmetic product or pharmaceutical product with a dye comprising at least one pigment in the form of a water-insoluble sulfate, carbonate, or phosphate of at least one alkaline earth metal, which is selected from the group consisting of magnesium phosphate, calcium phosphate, magnesium carbonate, and calcium sulfate anhydrite with the anhydrite having a mean particle size (d[4,3]) from 1.0 to 5.0 μm, wherein a suspension of the dye in an aqueous solution of 7% by weight of sugar at pH 3 has a turbidity which is 2 to 5-times higher than a pigment mixture of 95% by weight of tricalcium phosphate and 5% by weight of calcium carbonate or of 85% by weight of tricalcium phosphate and 15% by weight of calcium carbonate.

18. A product of the food, pharmaceutical, or cosmetics industry, comprising the dye according to claim 12.

19. The product according to claim 18, wherein a quantity of the at least one pigment is between 0.1 to 5% by weight, based on a total weight of the product.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0048] The invention will be described in more detail below with reference to the enclosed figures and on the basis of exemplary embodiments. The features of the different exemplary embodiments can be combined with one another in varying combination, in which:

[0049] FIG. 1 shows photographs of gelatin-based fruit gummies with pigments according to the invention according to a first and second embodiment of the invention as well as for comparison with titanium dioxide and resistant maize starch on a black background,

[0050] FIG. 2 shows photographs of hard caramels with white color according to a third and fourth embodiment of the invention compared with white color with titanium dioxide,

[0051] FIG. 3 shows photographs of chocolate-covered hazelnuts, which are sugar-coated with white color according to a fifth and sixth embodiment of the invention, compared to white color with titanium dioxide,

[0052] FIG. 4 shows a comparative illustration of the optical effect of individual sugar-coating layers on the basis of a chocolate-covered hazelnut, which is sugar-coated with a 5% sugar-coating solution with calcium sulfate particles in 20 layers, with the sugar coating of a chocolate-covered hazelnut with a 1% sugar-coating solution with titanium dioxide,

[0053] FIG. 5 shows a volume density distribution of a pigment according to a preferred embodiment of the invention, and

[0054] FIG. 6 shows illustrations of samples of two dyes according to the invention and of two pigment mixtures of tricalcium phosphate and calcium carbonate with turbidity measuring values measured directly after the production as well as 10, 20, and 40 minutes thereafter.

DETAILED DESCRIPTION

Exemplary Embodiments

[0055] The “%” specifications mentioned in the exemplary embodiments represent percentages by weight (wt.-%), whereby all wt.-% are based on the total weight of a corresponding composition. The proportions of the respectively mentioned components of the recipes add up to 100% by weight in each example.

Example 1: Coloring of Gelatin-Based Fruit Gummies

[0056] The following components were used for the recipe:

[0057] 44.0% by weight of glucose syrup,

[0058] 32.0% by weight of sucrose,

[0059] 7.0% by weight of gelatin,

[0060] 1.0% by weight of citric acid, and

[0061] water

[0062] Weigh gelatin in a heat-resistant bowl and dissolve it with hot water (ratio 2:1). Provide in a heating cabinet (approx. 60° C.) until use.

[0063] Dissolve sugar (sucrose and glucose syrup) in little water, and boil in a pot to approx. 120° C. Cool down sugar mass to below 100° C. and slowly stir in dissolved gelatin. Slowly stir in pigment (e.g. calcium sulfate, titanium dioxide, or maize starch).

[0064] Pour colored fruit gummy mass into prepared starch molds and allow to cool down for at least 24 h.

[0065] A gelatin-based fruit gummy is in each case shown on a black background in FIG. 1, namely in the illustration as pigment on the bottom left with 0.2% by weight of titanium dioxide (E171) and on the bottom right with 20% by weight of resistant maize starch, as well as on the top with a dye according to the invention, namely calcium sulfate with the preferred particle size distribution, that is, with D.sub.50=4 □m, in a content of 1.3% by weight on the top left and 1.8% by weight on the top right. Compared to the resistant maize starch, a significantly improved whitening can be seen due to the use of the dye according to the invention, namely already at a concentration in the end product of 1.3% by weight.

Example 2: Coloring of Foamed Pectin-Based Fruit Gummies

[0066] The following components were used for the recipe:

[0067] 76% by weight of glucose syrup,

[0068] 5% by weight of gelatin,

[0069] 1.6% by weight of critic acid,

[0070] 1% by weight of pectin,

[0071] 0.01 to 2% by weight of calcium sulfate or titanium dioxide, and

[0072] water

[0073] Dissolve gelatin in water (ratio 2:1). Mix pectin and sugar (glucose syrup), dissolve in little water, and boil to approx. 120° C. Cool down sugar/pectin mass and slowly stir in dissolved gelatin. Whip at high speed in a suitable mixer (for example Hobart, universal food processor). Slowly stir in color pigment (e.g. calcium sulfate or titanium dioxide) and whip again at high speed (Hobart—speed 3). Deposit the mass in prepared starch molds by means of a piping bag.

Example 3: Coloring of Hard Caramels

[0074] The following components are used for the recipe:

[0075] 90 to 92% by weight of isomalt

[0076] 6% by weight of maltitol

[0077] 1.7% by weight of citric acid,

[0078] 0.01 to 2% by weight of calcium sulfate or titanium dioxide, and

[0079] water

[0080] Boil isomalt, maltitol, and in little water (>170° C.). Allow temperature to cool down to 140° C. and add citric acid. Allow temperature to cool down to 110° C. and add pigment (e.g. calcium sulfate or titanium dioxide). Pour hot caramel mass into molds and allow to cool down.

[0081] Photographs of hard caramels with white color are shown in FIG. 2. From left to right, three hard caramels can be seen, colored with 0.01% by weight of titanium dioxide, three hard caramels colored with 1.00% by weight of calcium sulfate in the preferred particle size distribution, and three hard caramels colored with 2.00% by weight of calcium sulfate in the preferred particle size distribution with D.sub.50=1.15 μm, D.sub.97=4.00 μm, D.sub.max=21.20 μm, and the smallest particle is >100 nm, whereby the mean particle size of the pigment (d[4,3]) is 1.5 μm. A whitening, which is very close to the result of titanium dioxide as pigment for the use in hard caramels, is attained by means of the dosage of 2% by weight of the dye according to the invention with calcium sulfate as pigment.

Example 4: Hard Sugar Coating of Chocolate Drops, Use of the Pigment in the Sugar-Coating Solution

[0082] The following components were used for the recipe of the sugar-coating solution:

[0083] 68% by weight of sugar,

[0084] 25 to 30% by weight of water,

[0085] 2% by weight of maltodextrin, and

[0086] up to 5% by weight of calcium sulfate or 1% by weight of titanium dioxide.

[0087] Production of the sugar-coating solution in a pot: Dissolve sugar and maltodextrin in water, and boil (106° C.) until everything is dissolved. Add pigment at 35° C. by stirring. Introduce chocolate drops into coating drum. Build up several layers by alternating powdered sugar and sugar-coating solution and allow to try. Finally seal with brightening agent.

Example 5: Sugar Coating of Chocolate-Covered Hazelnuts with White Color

[0088] The following components were used for the recipe:

[0089] 70 g of sugar,

[0090] 30 g of water, and

[0091] 1% by weight of titanium dioxide or up to 10% by weight of calcium sulfate.

[0092] For the coating of the chocolate-covered hazelnuts according to this example 5, the same sugar-coating solutions as for the nuts shown in FIG. 3 were used, that is, the pigment CaSO.sub.4 was present in the form of particles with the “preferred particle (size) distribution” with D.sub.50=4 μm. A coating, which is comparable to the whitening power of titanium dioxide, was attained with the content of 10% by weight of calcium sulfate as pigment.

[0093] From left to right in FIG. 3, photographs of chocolate-covered hazelnuts are shown, which were coated with sugar-coating solutions according to the above-described recipe, whereby a content of 5% by weight was set for calcium sulfate. In the picture on the left, a chocolate-covered hazelnut can be seen, which is provided with 14 layers of a 1% sugar-coating solution with titanium dioxide as pigment, the particle size distribution of which has a value of D.sub.50=0.25 μm.

[0094] The picture in the middle shows a chocolate-covered hazelnut, which is coated with 20 layers of a 5% sugar-coating solution with calcium sulfate as pigment according to a fifth embodiment of the invention, whereby the pigment is present in the form of particles with the particularly preferred particle size distribution, in the case of which D.sub.50=1.6 μm.

[0095] In the picture on the right, a chocolate-covered hazelnut is shown, which is covered with 20 layers of a 5% sugar-coating solution with calcium sulfate as pigment according to a sixth embodiment of the invention, whereby the pigment is present in the form of particles with the preferred particle size distribution, in the case of which D.sub.50=4 μm. It can be seen that when using the 5% sugar-coating solution according to the invention with calcium sulfate as pigment, a whitening of the chocolate-covered hazelnut is attained in spite of the coarser particles, which is comparable to that of the titanium dioxide-containing sugar-coating solution.

[0096] In connection with the image shown in the right picture in FIG. 3 of a chocolate-covered hazelnut, which is sugar-coated in 20 layers with a 5% sugar-coating solution with calcium sulfate particles according to the sixth embodiment of the invention described here, a comparison of the optical effect, attained when applying one of these layers each compared to a sugar coating of a chocolate-covered hazelnut with a 1% sugar coating with titanium dioxide as pigment is shown in FIG. 4. A chocolate-covered hazelnut is in each case shown in the bottom row after the application of a first pigment layer (left) of a 1% sugar-coating solution with titanium dioxide as pigment, a second layer of this sugar-coating solution (on the right next to the first image), and so on, to a hazelnut after the application of the thirteenth layer of the titanium dioxide-containing sugar-coating solution (on the very right in the top row).

[0097] A chocolate-covered hazelnut is in each case shown in the top row in FIG. 4 after the application of a first pigment layer of the 5% sugar-coating solution with calcium sulfate particles (left), a second pigment layer (on the right next to the first image), and so on, to a hazelnut after the application of the twentieth layer (on the very right in the top row). In comparison, it can be seen that a significant increase of the whitening of the chocolate-covered hazelnut is no longer attained purely optically after approximately the eleventh layer. The person of skill in the art can determine the number of layers, which are required for the respective use case with the used dyes in order to attain the desired optical effect, by means of test or reference series of this type.

[0098] A particle size distribution for a pigment, which is particularly preferred in the context of the invention, is illustrated in FIG. 5. The pigment consists of calcium sulfate anhydrite. The analysis of the data was carried out according to the Mie model for a refractive index of the particles of 1.580 and an absorption index of the particles of 0.010 with a refraction index of the dispersing agent of 1.0 by means of a device of the model Malvern Mastersizer 3000.

[0099] The particle size analysis provided a value for the uniformity of the totality of the particles of 0.599 and a specific surface of 5045 m.sup.2/kg. The Sauter mean diameter d[3,2] is 1.19 □m. The De Brouckere diameter d[4,3] is 1.95 □m. D.sub.10 is 0.593 □m, D.sub.50 has a value of 1.64 □m, and D.sub.90 is 3.78 □m, The smallest detected particles are larger than 128 nm and the largest detected particles are smaller than D.sub.max=7.64 □m.

[0100] The particles measured with the result as illustrated in FIG. 5 and as described above, were produced by grinding a calcium sulfate anhydrite pigment, the particle size distribution of which was analyzed as follows: The Sauter mean diameter d[3,2] was 2.12 □m. The De Brouckere diameter d[4,3] was 3.27 □m. D.sub.10 was 1.04 □m, D.sub.50 had a value of 2.76 □m, and D.sub.90 was 6.27 □m. The value for D.sub.97 was 8.36 □m. The smallest detected particles were larger than 461 nm, and the largest detected particles were smaller than D.sub.max=11.2 □m.

[0101] A dye with a pigment for whitening consisting of calcium sulfate anhydrite, which has the result of the particle size distribution as illustrated in FIG. 5 and as described above, was used as dye and was analyzed with regard to its pH stability, compared to a mixture of tricalcium phosphate and calcium carbonate (hereinafter “TCP” or “CC”, respectively).

[0102] A first turbidity measurement had the following result, whereby all pigments had a comparable particle size distribution. 2.75 g/L of the pigment or of the pigment mixture were in each case dispersed into a base recipe of demineralized water with 7% by weight of sugar and a quantity of citric acid.

TABLE-US-00002 Pigment or pigment mixture Turbidity/FNU Calcium sulfate anhydrite according to the invention 249 95% by weight of TCP + 5% by weight of CaCO3 190 85% by weight of TCP and 15% by weight of CaCO3) 208

[0103] The turbidity was used as measure for the opacity of the samples. The turbidity was optically determined in accordance with ISO 7027 in the above-reproduced first analysis at a wavelength of the used light 860 nm under scattered light measurement at an angle of 90°, whereby the result is specified in “FNU”, that is, “Formazine Nephelometric Units”.

[0104] Calcium sulfate anhydrite according to the invention results in the highest turbidity. The second highest turbidity is attained by the 85/15 mixture (TCP/CC). This mixture, however, is not sufficiently stable due to the content of calcium carbonate, and the calcium carbonate dissolves after a relatively short time under the acidic conditions, and only the insoluble TCP remains.

[0105] Two variations of the invention compared with the mixtures of TCP and CC were observed in a closer analysis. A sample (“trial”) of a pigment according to the invention consisting of calcium sulfate anhydrite with a particle size D.sub.50 of 1.6 □m or 4 □m, respectively, will hereinafter be identified with “V1” or “V2”, respectively. A sample (“trial”) of a mixture of 85% by weight of TCP+15% by weight of CaCO3 or 95% by weight of TCP+5% by weight of CaCO3, respectively, is identified with “V3” or “V4”, respectively. To set a pH value of 3, 2.75 g/L of the pigment or of the pigment mixture were in each case dispersed in a base recipe of demineralized water with 7% by weight of sugar and a quantity of citric acid. The results are compiled in FIG. 6. The turbidity data is specified in the unit “NTU”. This “Nephelometric Turbidity Unit” (NTU) is a unit used in the water treatment for the turbidity of liquids, which is determined by means of a calibrated nephelometer.

[0106] FIG. 6 shows images of the samples in jars in front of a dark background in the bottom region and in front of black and white striped background in the top region at the beginning of the measurement (image top left in FIG. 6, time specification “0 minutes”) as well as after 10, 20, and 40 minutes. At the beginning of the measurement (“0 minutes”), a 2.6- to 4.9-times higher turbidity of the pigment according to the invention appears in the beverage base recipe than in the case of the pigment mixtures of TCP and CC.

[0107] Over a period of time of 40 minutes, the turbidity of the pigment according to the invention decreases only by 3% to 4.3% (calculated as differences of the turbidity at 40 minutes and at 0 minutes based on the initial value) in the beverage base recipe. In contrast, the turbidity of the pigment mixtures of TCP and CC in the beverage base recipe decreases over a period of 40 minutes by 7.3% to 12.1% and thus by more than double or almost three times, respectively, compared to the pigment according to the invention.

[0108] This data confirms the first measurements according to the above table and show that the pigment according to the invention effects a stable whitening of a beverage even in the case of a low pH value of 3, while the turbidity decreases significantly over time in the case of known pigment mixtures. It can furthermore be seen that the coverage of the black and white striped background remains unchanged over the entire measuring direction when using the dyes according to the invention.

[0109] The person of skill in the art can see that the invention is not limited to the above-described examples, but on the contrary, can be varied in a variety of ways. The features of the individually illustrated examples can in particular also be combined with one another or can be exchanged for each other.