Natural water-insoluble encapsulation compositions and processes for preparing same

Abstract

The present invention relates to dry particulate encapsulation compositions comprising a water-insoluble matrix comprising at least 70% by weight of proteins, based on the total weight of the matrix and a moisture content of about 5 to 10% by weight, based on the total weight of the matrix and an encapsulate encapsulated in the matrix, wherein the matrix once wetted in a clear colorless aqueous solution or in mineral oil has a lightness value (L*) greater than about 40, a color vividness or Chroma (C*) lower than about 33 and a hue angle between about 70 and 90. The encapsulation compositions of the present invention are useful in encapsulating dyes, medications and vitamins. Fine particulate encapsulation compositions comprising natural dyes can be used in lieu of artificial lakes in confectionery, cosmetics and caplets color coatings.

Claims

1. A process for extrusion encapsulation, the process comprising: (i) providing an agent to be encapsulated and a water-insoluble protein-rich mixture; (ii) mixing said agent, said water-insoluble protein-rich mixture, and water in an extruder at high shearing and pressure to raise the temperature, thereby enabling the formation of a melt; and (iii) cooling the melt and extruding at low temperature and high moisture sufficient to minimize browning of the water-insoluble protein by the Maillard reaction, thereby encapsulating said agent in a water-insoluble protein-rich matrix.

2. The process of claim 1, further comprising: (iv) drying the extruded mixture to a moisture content of between 5 to 10% by weight, based on the total weight of said dried extruded mixture, wherein said dried extruded mixture comprises at least 70% by weight of water insoluble protein, based on the total weight of said matrix.

3. The process of claim 2, further comprising: (v) milling or grinding said dried extruded mixture to form a dry particulate extrudate.

4. The process of claim 3, wherein said dried extruded mixture is milled or ground to particles having an average size smaller than 150 microns.

5. The process of claim 1, wherein said water-insoluble protein-rich mixture is a plant-derived water-insoluble protein-rich mixture.

6. The process of claim 5, wherein said water-insoluble plant protein-rich mixture is or comprises a rice protein and/or a soy protein.

7. The process of claim 5, wherein said water-insoluble plant protein-rich mixture is or comprises a rice protein concentrate having a rice protein content above 77% by weight, based on the dry weight of said rice protein concentrate; or wherein said water-insoluble plant protein-rich mixture is or comprises a soy protein isolate having a soy protein content above 87% by weight, based on the dry weight of said soy protein isolate.

8. The process of claim 5, wherein the water-insoluble plant protein-rich mixture is a rice protein concentrate, and wherein said extrusion is performed at a moisture content of 30 to 50% by weight, based on the total weight of said rice protein concentrate and water.

9. The process of claim 5, wherein the water-insoluble plant protein-rich mixture is a soy protein isolate, and wherein said extrusion is performed at a moisture content of 45 to 70% by weight, based on the total weight of said soy protein isolate and water.

10. The process of claim 1, wherein the temperature of the extruder during extruding is set to a temperatures between 10° C. and 35° C.

11. The process of claim 1, wherein said agent to be encapsulated is a labile agent, a heat-sensitive agent, and/or a light-sensitive agent.

12. The process of claim 1, wherein said agent is a coloring agent or a labile coloring agent.

13. The process of claim 2, wherein said agent is a coloring agent or a labile coloring agent.

14. The process of claim 3, wherein said agent is a coloring agent or a labile coloring agent.

15. The process of claim 1, wherein said agent is: a natural dye, a nature-identical dye, an artificial dye, a lake of a natural dye, a synthetic dye, a synthetic lake, or any combination thereof.

16. The process of claim 15, wherein said natural dye is an anthraquinone, a betalain, caramel, a carotenoid, a curcuminoid, a flavin, a flavonoid, a porphyrin, geniposide, sandalwood, sepia, or vegetable black.

17. The process of claim 16, wherein: (a) said flavonoid is obtained from at least one of: red cabbage, sweet potato, red radish, elderberry and grape; (b) said betalain is beet red; (c) said anthraquinone is carminic acid or carmine; (d) said carotenoid is: annatto, apocarotenal, apocarotenal ester, canthaxanthin, beta-carotene, lycopene, lutein, paprika, saffron, bixin, norbixin or crocin; (e) said porphyrin is chlorophyll or chlorophyllin; (f) said curcuminoid is turmeric; and (g) said flavin is riboflavin.

18. The process of claim 1, wherein said water-insoluble protein-rich matrix, once wetted in a clear colorless aqueous solution or in mineral oil, has a lightness value (L*) greater than 40, a color vividness or Chroma (C*) lower than 33 and a hue angle between 70° and 90° , according to the CIE Lch color space developed by the Commission Internationale d'Éclairage.

19. The process of claim 1, wherein the melt in (ii) further comprises: (a) an organic acid, an inorganic acid, a calcium salt, or any combination thereof; and/or (b) a stabilizer or preservative agent which is: alpha-tocopherol, ascorbic acid, benzoic acid, isoascorbic acid, butylated hydroxyanisole, butylated hydroxytoluene, sodium citrate, sorbic acid, potassium, sodium bisulphate, or any combination thereof.

20. The process of claim 3, further comprising enrobing the dry particulate extrudate in a non-polar coating comprising: waxes, oils, fats, long chain fatty acid, an acacia, gelatin, lecithin, cholesterol, sulfates or sulfonates, gums, zein, an emulsifier, or any mixture thereof.

21. The process of claim 3, wherein said dried extruded mixture is milled or ground to particles having an average size smaller than 50 microns.

22. The process of claim 3, wherein said dried extruded mixture is milled or ground to particles having an average size smaller than 20 microns.

23. The process of claim 3, wherein said dried extruded mixture is milled or ground to particles having an average size smaller than 10 microns.

24. The process of cam 19, wherein the organic acid is tannic acid, ascorbic acid, or a combination thereof.

Description

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS

(1) It is thus an object of the present invention to provide a composition and a process to encapsulate a wide range of active agents including but not limited to dyes, vitamins and medicinal compounds inside a water-insoluble matrix in a particulate form. In one particular embodiment, the resulting particulate composition which contains natural dyes can be used in lieu of artificial lakes in confectionery, cosmetics and caplets color coatings where a natural coloring composition is preferred.

(2) The encapsulation compositions of the present invention have improved shelf life and are useful in the preparation of products such as foods, cosmetics and medications. The present invention further relates to dry edible, natural color pigments that at the present time do not require certification by regulatory agencies since they utilize natural ingredients. The natural dye pigments of the present invention can be used as substitutes for artificial FD&C and D&C lakes that are commonly used for coloring food, drugs and cosmetics.

(3) The process used to make the particulate composition is based on the use of melt extrusion under conditions that limit the formation of undesirable Maillard reaction's brown pigments and thus decrease the alteration of the color of the natural dyes. The present invention is particularly useful in the encapsulation of labile natural dyes. The process can be applied to either water-soluble dyes or water-insoluble dyes. Non-limiting examples of natural dyes that can be encapsulated by the methods of the present invention are presented in Table 1.

(4) TABLE-US-00001 TABLE 1 Natural and nature-identical dyes used in foods, cosmetics and medicine color coating Group Names of coloring Source anthraquinones cochineal (carminic Dactylopus coccus acid, carmine) betalains beet red (betacyanins, Beetroot (Beta vulgaris) betaxanthins) caramel caramel sugar and reactants carotenoids annatto (bixin, norbixin) seeds of Bixa orellana apocarotenal nature identical apocarotenal ester nature identical canthaxanthin nature identical β-carotene Blakeslea trispora (natural) β-carotene nature identical lycopene tomato fruit lutein alfalfa, marigold petals paprika (capsanthin, fruits of Capsicum capsorubin) annuum saffron (crocin) stigmas of Crocus sativus cucurminoids turmeric (curcumin) rhizome of Curcuma longa flavins riboflavin flavonoids anthocyanins various fruits and vegetables porphyrins chlorophyll and spinach, other chlorophyllin other vegetable black plant material

(5) The present invention is not limited to the encapsulation of natural dyes. Artificial dyes may also be used in accordance with the present invention. Non-limiting examples of artificial dyes that may be used include Allura Red, Amaranth, Erythrosine, Indigotine, Sunset Yellow, Brilliant Blue FCF, Fast Green FCF and Tartrazine. Artificial dyes encapsulated in the encapsulation compositions of the present invention become totally water-insoluble and do not migrate making them useful in a variety of applications such as in cosmetic compositions since they do not stain the skin. Of course, the skilled artisan to which the present invention pertains, when choosing an artificial dye, will choose same according to the use, desired utility and characteristics which are to be satisfied. Of course, mixtures of natural and artificial dyes (or mixtures of other encapsulates) are encompassed by the present invention. Similarly, mixtures of natural and nature identical dyes as well as mixtures of natural, nature identical and artificial dyes are encompassed by the present invention.

(6) The encapsulation matrix in which an active agent of the present invention is encapsulated, comprises at least more than 69% protein by weight (70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 97, 98, 99, 100%), more preferably at least 75% and even more preferably at least 80%. The process of the present invention can make use of both water-soluble and water-insoluble protein with minor adjustments to the process, e.g., assembly of extruder elements, operation parameters, ratio of liquids to solids, etc. The manufacturing process yields a water-insoluble matrix from water-soluble protein. Non-limiting examples of proteins that can be used in accordance with the present invention include proteins from milk or whey, wheat (gluten), soy, mays (zein), rice or mixtures thereof. Examples of mixture of proteins that may be used include 50:50, 25:75, 75:25, 90:10, 10:90, 40:60, 60:40 soy:rice or any other combination thereof. Mixtures of more than 2 proteins (e.g., 3, 4, 5 or more) may also be used in accordance with the present invention. For example, one non-limiting advantage of using a mixture of soy and rice proteins as a matrix would be to change the properties of the matrix as to render it more or less impermeable to water. By increasing the proportion of rice extracts relatively to soy proteins, the matrix becomes more resistant to moisture and thus retains the encapsulated material (e.g., dye, medicine, vitamin, food supplement, etc) better.

(7) Consequently, by altering the composition of the matrix and by taking advantage of the different properties of proteins, one skilled in the art can easily adjust the impermeability of the encapsulated material. In addition, different proteins are digested to different rates in the gastro-intestinal tract. The time at which a medicine is released in the body may thus be adjusted by changing the composition of the matrix used to encapsulate it as well as the number of coating layers applied to the active ingredient. Thus, by changing the matrix composition or by increasing the number of layers (or thickness) of the encapsulation composition of the present invention, one can easily control the time and location (e.g., intestine vs stomach) at which the active ingredient is released. Of course the compositions can be adapted to take into account the particular animal to which the composition is administered.

(8) Various additives can be added to the encapsulation matrix in accordance with the present invention namely, acids (e.g., organic or inorganic acids), salts, a calcium salt, e.g., calcium chloride, vitamins, to improve retention or the stability of the active agent or to modify the hue of an encapsulated dye. Other examples of stabilizers or preservative agents include α-tocopherol, ascorbic acid, benzoic acid, isoascorbic acid, butylated hydroxyanisole, butylated hydroxytoluene, sodium citrate, sorbic acid, or potassium or sodium bisulphate.

(9) Optionally, the dry particulate composition can be enrobed inside a non-polar coating to provide a barrier to water. Non-limiting examples of non-polar coating that may be used include mixtures of waxes, oils, fats, long chain fatty acids, emulsifiers of natural origin (e.g., acacia, gelatin, lecithin, cholesterol) or of synthetic origin (e.g., sulfates or sulfonates), gums or zein. Additional non-limiting examples of emulsifying agents and other non-polar coatings that may be used in accordance with the present invention may be found in Remington (2000), The Science and Practice of Pharmacy, 20.sup.th edition, pp: 318-334; and Rowe et al., Handbook of Pharmaceutical Excipients, 2003, 4th edition, Pharmaceutical Press, London UK.

(10) Generally, the dyes/pigments or other encapsulated material of the present invention are obtained by extrusion of: 1) a protein extract (e.g., soy, rice, gluten, whey etc, or mixture thereof) which serves as a matrix; 2) an active agent or encapsulate (e.g., natural pigment either dissolved in a liquid or in a powdered form which can be directly mixed with the protein extracts, medicine etc.); 3) water; and 4) optionally, various stabilizers, preservative agents and, in the case of a pigment, various substances that serve to adjust the hue of the coloring agent (e.g., CaCl.sub.2, acids, salts, etc). During this process, all ingredients are mixed together to form a homogenous paste. The extrusion is performed at low temperature and high moisture (approximately 30-50%) which reduce degradation of pigment and the alteration of its color by the Maillard reaction. The extrudate is then dried to a final moisture content of 5 to 10%. When dried, the extrudate is very brittle and can easily be milled to a fine powder of desired size. Particle size of less than 20 μm may be obtained with the extrudate of the present invention.

(11) Thus, the process of the present invention is based on melt extrusion of a protein matrix combined with an extrudate such as dyes/pigments, medicines, vitamins or food supplements. While the precise apparatus to be used in achieving melt extrusion is not critical it has been found that a Baker-Perkin co-rotating twin-screw extruder (model MPF-50) is efficacious.

(12) In one embodiment, elements of the extruder e.g., conveying screw, single-lead screw and kneading blocks, are aligned as to provide mixing, kneading and pressure buildup. The size of orifices at the exit also contributes to pressure buildup inside the extruder. Speed of rotation, alignment of elements of the extruder, i.e., kneading blocks and single-lead screws, and moisture content of the extrudate are determining factors of the amount of heat that is generated through shear force. Overheating of the mixture of protein, coloring and additive is prevented by circulation of chilled water in the extruder outer casing.

(13) In another embodiment, where the encapsulation matrix comprises rice protein concentrate, the amount of moisture that may be used during the extrusion process ranges from about 30% to 50% (30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49 and 50%) more particularly about 38% by weight, based on the total weight of the rice protein concentrate and water. In another embodiment, where the encapsulation matrix comprises soy protein isolate, the amount of moisture that may be used during the extrusion process ranges from about 45% to 70% (45, 50, 55, 60, 65 and 70%), more particularly about 55% by weight, based on the total weight of soy protein isolate and water. At moisture contents above the upper limit, the heat generated by shearing is not sufficient to enable proper protein texturization. At moisture contents under the lower limit, shear-induced heat is such that undesirable browning and coloring degradation occur.

(14) In a particular embodiment, the selection of a suitable amount of a natural dye to be added to the protein matrix depends on the particular type of dye, the particular hue desired and the particular intended application. In a further embodiment, the encapsulated material contains an amount of coloring between 10 and 16,000 color units by weight (determined at the respective maximal absorbency wavelength of the colorings). In another embodiment, the encapsulated material contains an amount of coloring between 10 and 200 color units. In addition, several pigments may be added together in order to achieve a wide array of color that could not be achieved using a single dye. The selection of a suitable amount of the natural dye for the encapsulation process of the present invention depends on the particular type of pigment, on the particular intended application and on the desired appearance of the finished product. The relative amount of each dye depends on the particular color to achieve and thus any combination of dyes may be used in accordance with the present invention to suit particular needs. The achievement of particular colours by the mixture of colours is well known in the art.

(15) In an embodiment, natural coloring preparations of very diverse color hues are obtained by varying the composition of dyes and additives. In a particular embodiment, fine powders of encapsulated natural dyes are dispersed in a media used in candy panning operations and dried to form opaque colored layers and are thus useful in candy coating, dragees coating or the like. Dragees or candy coating constitute a particular type of edible multilayered product where one or more coating layers, typically consisting of sugar, are applied onto a center of an edible ingredient. Non-limiting examples of such centers to be coated include, chewing gum, sugar tablets/granulates and chocolate. Coloring of such edible center is typically carried out in one or more panning steps where the centers are coated with sugar syrup containing the coloring agent. It is normally necessary to apply several coating layers to obtain a sufficient covering with color.

(16) In one particular embodiment, the color intensity of the coloring compositions of the present invention (e.g., natural lakes) is proportional to the concentration of the encapsulated dye. Thus, It has been demonstrated that the amount of pigment required for coloring surfaces with the same color intensity is proportional to the concentration of the encapsulated dye present in the compositions of the present invention. It was discovered that the natural pigments of the composition of the present invention can comprise a high concentration of dye/natural pigment to produce thinner color coats with high color intensities. By allowing a lower application dosage relative to the actual amount of dye while producing brighter color, the encapsulated dyes of the present invention permit significant manufacturing savings. In other embodiments of the invention, the colorings were retained inside the encapsulation matrix to become non-staining. The encapsulated colorings could thus be used in applications where staining is a problem, such as in the field of cosmetics. In still another embodiment, powders of encapsulated colorings that leached coloring when in contact with water, are made impermeable by coating with a non-polar phase. Such compositions could also be used in applications where staining is a problem. In a further embodiment of the present invention, labile natural dyes become more stable once they are encapsulated.

(17) In one particular embodiment, the dry particulate encapsulation composition of the present invention comprises (a) an encapsulate, encapsulated in a water-insoluble matrix comprising at least 70% by weight of protein, based on the total weight of the matrix, and a moisture content of about 5 to 10% by weight, based on the total weight of the matrix. In a particular embodiment, the matrix, once wetted in a clear colorless aqueous solution or in mineral oil has a lightness value (L*) greater than 40, a color vividness or Chroma (C*) lower than 33 and a hue angle between 70° and 90°.

(18) In a further embodiment, the composition of the present invention is prepared by a process comprising:

(19) (i) mixing an encapsulate (A), a matrix (B) and water in an extruder, to obtain a melted mixture which comprises encapsulate (A), matrix (B) and water;

(20) (ii) extruding the melted mixture, to obtain an extruded mixture;

(21) (iii) cutting the extruded mixture in small pieces (e.g., smaller than 10 mm, 8 mm, 6 mm, 5 mm, 4 mm);

(22) (iv) drying the pieces of extruded mixture to a moisture content between 5 and 10% by weight, based on the total weight of dried extruded mixture; and

(23) (v) grinding the dried extruded mixture.

(24) In an embodiment, the protein matrix retains completely or partially the encapsulate when the encapsulation composition of the present invention is dispersed into an aqueous solution.

(25) The present invention is further illustrated by the following non-limiting examples.

Example 1

(26) Colour Characteristics of an Extruded Soy Protein Isolate

(27) A soy protein isolate was extruded without an encapsulate under conditions which enable the formation of a melt while minimizing undesirable Maillard reactions (see Table 3). The main impact on the color of the protein matrix was on lightness (L* value). The difference in the lightness of the dry powder prior to (Table 2) and after extrusion, i.e., ΔL*=−10.2, indicates a darkening of the soy protein isolate. Darkening was more apparent when the powder was immersed in a syrup or in oil, i.e., ΔL*=−30.9 and −25, respectively. Nevertheless, as seen in examples 2 through 8, the matrix of extruded soy protein isolate is adequate for the encapsulation of dyes while enabling the expression of colors.

(28) TABLE-US-00002 TABLE 2 Color characteristics of the soy protein isolate and of the rice protein concentrate Sample preparation prior Colorimeter to colorimeter readings readings L* C* H soy protein none 89.0 14.1 87° isolate immersed in syrup 73.8 22.4 81° immersed in oil 69.8 25.6 81° rice protein none 83.2 20.1 87° concentrate immersed in syrup 58.5 30.6 81° immersed in oil 55.9 29.1 80°

(29) TABLE-US-00003 TABLE 3 Examples of natural colorings and vitamin encapsulated in soy protein isolate by extrusion Extruder feed Sample preparation Colorimeter composition prior to colorimeter readings Ingredient (g/min) readings L* C* H Example 1: none 78.8 20.2  84° soy protein isolate 240 immersed in syrup 42.9 24.0  76° water 300 immersed in oil 44.8 26.1  76° Example 2: soy protein isolate 240 none 51.5 10.4 254° red cabbage color 24 immersed in syrup 4.9 8.0 263° water 276 immersed in oil 5.7 6.0 267° Example 3: soy protein isolate 240 none 34.1 14.0 274° red cabbage color 24 calcium chloride 24 immersed in syrup 1.0 3.4 283° water 252 immersed in oil 2.1 3.8 274° Example 4: soy protein isolate 240 none 41.5 9.3 328° red cabbage color 24 tannic acid 2.4 immersed in syrup 5.4 7.7 299° water 273.6 immersed in oil 4.7 4.7 315° Example 5: soy protein isolate 240 none 43.1 28.4  9° beet red 24 ascorbic acid 6 immersed in syrup 5.1 14.9  10° water 270 immersed in oil 7.2 20.3  15° Example 6: soy protein isolate 240 none 41.2 28.3  23° beet red 24 turmeric 1 ascorbic acid 6 immersed in syrup 4.7 11  21° water 269 immersed in oil 5.4 14.3  21° Example 7: soy protein isolate 240 none 73.2 44.1  66° norbixine 0.48 immersed in syrup 31.8 53.5  63° water 299.5 immersed in oil 39.2 62.3  62° Example 8: soy protein isolate 240 none 71.8 54.6  83° saffron 2.4 immersed in syrup 41.5 56.7  78° water 297.6 immersed in oil 33.0 50.4  73° Example 9: soy protein isolate 240 none 75.1 65.0  88° turmeric 4.8 immersed in syrup 38.8 53.8  79° water 288 immersed in oil 40.6 59.2  76°

Example 2

(30) Red Cabbage Coloring Encapsulated in a Soy Protein Isolate

(31) A fine powder of red cabbage color encapsulated in a soy protein isolate matrix was produced (see Table 3). The red cabbage color was diluted in the extruder liquid feed, extruded with soy protein isolate, the resulting extrudate was dried and ground. The dry powder, which possesses a tarnished appearance, takes on an appealing intensely dark, predominantly blue color, once wetted in syrup or oil. Observations of the powder suspended in oil and in syrup were made using an optical microscope. The 10× eye piece had a scale which was calibrated using a calibration slide with a 100 micron marking. The appearance of powder particles suspended in oil and in syrup was identical. Particles were irregular, vitreous (translucent) and uniformly stained. A vast majority of particles measured about 25 microns. The smallest particles measured 5 to 10 microns while very few particles were around 50 microns. The amount of anthocyanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 40% of the total amount of encapsulated anthocyanin. This composition is suitable for use as a predominantly blue coloring in low moisture and/or non-polar products.

Example 3

(32) Hue Alteration of Red Cabbage Coloring Encapsulated in a Soy Protein Isolate by Calcium Chloride

(33) A similar experiment to that shown in Example 2 (see Table 3) was performed, except that calcium chloride was added to the extruder liquid feed in order to alter the color of the extrudate. The resulting powder once wetted in syrup or oil takes on an appealing intensely dark predominantly purple color. The amount of anthocyanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 15% of the total amount of encapsulated anthocyanin.

(34) Thus, calcium chloride contributes to retaining anthocyanins inside the encapsulation matrix and to altering the color to a more purple shade. This composition is suitable for use as a predominantly purple coloring in low moisture and/or non-polar products.

Example 4

(35) Hue Alteration of Red Cabbage Coloring Encapsulated in a Soy Protein Isolate by Tannic Acid

(36) A similar experiment to that shown in Example 2 (see Table 3) was performed, except that tannic acid was added to the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing dark predominantly mauve color. The amount of anthocyanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 43% of the total amount of encapsulated anthocyanin.

(37) Thus, tannic acid does not help in retaining anthocyanins inside the encapsulation matrix but shifts the color to a redder hue. This composition is suitable for use as a predominantly mauve coloring in low moisture and/or non-polar products.

Example 5

(38) Beet Red Encapsulated in a Soy Protein Isolate

(39) A fine powder of beet red encapsulated in a soy protein isolate matrix was produced (see Table 3). Beet red and ascorbic acid were dissolved in the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing moderately dark predominantly purplish-red color. Ascorbic acid serves as a stabilizer of beet red. The amount of betanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 46% of the total amount of encapsulated betanin. This composition is suitable for use as a predominantly purplish red coloring in low moisture and/or non-polar products.

Example 6

(40) Beet Red and Turmeric Mixture Encapsulated in a Soy Protein Isolate

(41) A similar experiment to that shown in Example 5 (see Table 3) was performed, except that turmeric was also added to the extruder liquid feed by dispersion with a commercial blender. The resulting powder once wetted in syrup or oil takes on an appealing moderately dark predominantly red color. This composition is suitable for use as a predominantly red coloring in low moisture and/or non-polar products.

Example 7

(42) Norbixin Encapsulated in a Soy Protein Isolate

(43) A fine powder of norbixin encapsulated in a soy protein isolate matrix was produced (see Table 3). Norbixin was diluted in the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing bright predominantly orange color. The amount of norbixin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 9% of the total amount of encapsulated norbixin. This composition is suitable for use as a predominantly orange coloring in low moisture and/or non-polar products.

Example 8

(44) Saffron Encapsulated in a Soy Protein Isolate

(45) A fine powder of saffron (which contains crocin) coloring encapsulated in a soy protein isolate matrix was produced (see Table 3). Saffron was diluted in the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing bright predominantly golden-yellow color. The amount of crocin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 37% of the total amount of encapsulated crocin. This composition is suitable for use as a predominantly golden-yellow coloring in low moisture and/or non-polar products.

Example 9

(46) Turmeric Encapsulated in a Soy Protein Isolate

(47) A fine powder of turmeric encapsulated in a soy protein isolate matrix was generated (see Table 3). Turmeric was dispersed in the extruder liquid feed using a commercial blender. The resulting powder once wetted in syrup or oil takes on an appealing bright predominantly yellow color. Turmeric is known to be very light-sensitive. However, there were no differences in colorimetry measurements after 20 days of exposure of the encapsulated turmeric to light. The amount of curcuminoids released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 6% of the total amount of encapsulated curcuminoids. This composition is suitable for use as a predominantly yellow coloring in low moisture and/or non-polar products.

(48) TABLE-US-00004 TABLE 4 Examples of natural colorings and vitamin encapsulated in rice protein concentrate by extrusion Extruder feed Sample preparation Colorimeter composition prior to colorimeter readings Ingredient (g/min) readings L* C* H Example 10: none 82.8 17.8  87° rice protein concentrate 250 immersed in syrup 57.6 28.5  81° water 200 immersed in oil 48.8 29.8  79° Example 11: rice protein concentrate 250 none 40.2 13.3 307° red cabbage color 25 immersed in syrup 8.0 13.1 306° water 175 immersed in oil 3.2 6.6 301° Example 12: rice protein concentrate 250 none 45.4 12.5 301° red cabbage color 25 calcium chloride 25 immersed in syrup 7.0 12.7 301° water 150 immersed in oil 3.9 7.8 295° Example 13: rice protein concentrate 250 none 46.9 29.0 354° beet red 25 ascorbic acid 6.25 immersed in syrup 13.4 31.9  4° water 168.75 immersed in oil 8.2 25.3  9° Example 14: rice protein concentrate 250 none 33.6 18.4  8° carminic acid 3.7 Immersed in syrup 2.9 9.5  8° water 196.3 Immersed in oil 2.1 5.7  11° Example 15: rice protein concentrate 247.5 none 42.9 52.8  38° bixin 2.5 immersed in syrup 30.4 57.8  42° water 200 immersed in oil 29.4 51.5  39° Example 16: rice protein concentrate 250 none 79.5 58.1  90° turmeric 5 immersed in syrup 53.6 68.1  83° water 195 immersed in oil 45.1 63.5  79°

Example 10

(49) Color Characteristics of an Extruded Rice Protein Concentrate

(50) A rice protein concentrate was extruded without an encapsulate under conditions which enable the formation of a melt while minimizing undesirable Maillard reactions (see Table 4). Darkening due to the extrusion process was much less intense than with the soy protein isolate. In fact, differences in the lightness of the dry powder prior to (Table 2) and after extrusion, i.e., ΔL*=−0.4, was almost negligible. The same holds for extruded powder after immersion in a syrup or in oil, i.e., ΔL*=−0.9 and −7.1, respectively.

(51) The following examples (11 to 16) demonstrate that the matrix of extruded rice protein concentrate is adequate for the encapsulation of dyes while enabling the expression of colors. In general, after immersion in syrup, dyes are better retained inside the encapsulation matrix of rice protein concentrate than the soy protein isolate matrix.

Example 11

(52) Red Cabbage Coloring Encapsulated in a Rice Protein Concentrate

(53) A fine powder of red cabbage color encapsulated in a rice protein concentrate matrix was created (see Table 4). The red cabbage color was diluted in the extruder liquid feed, extruded with rice protein concentrate, the resulting extrudate was dried and ground. The dry powder which possesses a pastel appearance takes on an appealing intensely dark predominantly purple color once wetted in syrup or oil. The amount of anthocyanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 31% of the total amount of encapsulated anthocyanin. This composition is suitable for use as a predominantly purple coloring in low moisture and/or non-polar products.

Example 12

(54) Hue Alteration of Red Cabbage Coloring Encapsulated in a Rice Protein Concentrate by Calcium Chloride

(55) A similar experiment to that shown in Example 11 was performed, except that calcium chloride was added to the extruder liquid feed (see Table 4). The resulting powder once wetted in syrup or oil takes on an appealing intensely dark color similar to that of Example 11. The amount of anthocyanin released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 27% of the total amount of encapsulated anthocyanin. Calcium chloride had less effect on the improvement of dye retention and on color change with the rice protein concentrate matrix than with the soy protein isolate matrix (Example 2). This composition is suitable for use as a purple coloring in low moisture and/or non-polar products.

Example 13

(56) Beet Red Encapsulated in a Rice Protein Concentrate

(57) A fine powder of beet red encapsulated in a rice protein concentrate matrix was created (see Table 4). Beet red and ascorbic acid were diluted in the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing moderately dark predominantly purplish-red color. Ascorbic acid serves as a stabilizer of beet red. The amount of betanin released from the rice protein matrix in syrup after 15 minutes immersion at room temperature was 27% of the total amount of betanin. This composition is suitable for use as a predominantly purplish-red coloring in low moisture and/or non-polar products.

Example 14

(58) Carminic Acid Encapsulated in a Rice Protein Concentrate

(59) A fine powder of carminic acid encapsulated in a rice protein concentrate matrix was generated (see Table 4). Carminic acid was diluted in the extruder liquid feed. The resulting powder once wetted in syrup or oil takes on an appealing moderately dark predominantly brownish-red color. The amount of carminic acid released from the encapsulation matrix in syrup after 15 minutes immersion at room temperature was 23% of the total amount of carminic acid. This composition is suitable for use as a brownish-red coloring in low moisture and/or non-polar products.

Example 15

(60) Bixin Encapsulated in a Rice Protein Concentrate

(61) A fine powder of bixin encapsulated in a rice protein concentrate matrix was produced (see Table 4). Bixin was blended with the rice protein concentrate and introduced into the extruder through the solids feed port. The resulting powder once wetted in syrup or oil takes on an appealing bright predominantly orange color. Bixin, which is insoluble in water at neutral pH, was encapsulated in a rice protein concentrate without having to use an alkali or an emulsifier. No bixin was released from the encapsulation matrix in syrup even after an extended period (several days). This composition is suitable for use as a predominantly orange coloring in low moisture and/or non-polar products. This example also demonstrates that bixin can be used in color blends wherein pH sensitive colorings are used, e.g., anthocyanins, since no pH-altering agent is used in the manufacturing process.

Example 16

(62) Turmeric Encapsulated in a Rice Protein Concentrate

(63) A fine powder of turmeric encapsulated in a rice protein concentrate matrix was created (see Table 4). Turmeric was dispersed in the extruder liquid feed using a commercial blender. The resulting powder once wetted in syrup or oil takes on an appealing bright predominantly yellow color. No turmeric was released from the encapsulation matrix in syrup even after an extended period (several days). This composition is suitable for use as a predominantly yellow coloring in low moisture and/or non-polar products.

Example 17

(64) Tartrazine Encapsulation in a Rice Protein Concentrate

(65) An artificial dye, namely tartrazine, was dissolved in the extruder liquid feed and encapsulated in a rice concentrate at a concentration of 0.1% based on the weight of the dry rice protein concentrate. The colorimetry measurements of the dry yellow powder were: L*=80.6, C*=43.6 and h=89°. In water, tartrazine was totally retained inside the encapsulation matrix. No tartrazine was released from the encapsulation matrix in syrup. This composition is suitable for use as a predominantly yellow coloring in low moisture and/or non-polar products.

(66) Encapsulated dyes from Examples 2 to 9 and 11 to 17, were not released from their respective encapsulation matrix when submerged in mineral oil.

Example 18

(67) Usefulness of Encapsulated Dyes for Candy Coatings

(68) The usefulness of encapsulated dyes for candy coatings is presented in examples 18 to 21. A dispersion media similar to those used in candy panning operations, was made by mixing together sucrose, gum acacia and water in a proportion of 60:10:30 by weight and heating to 60° C. Encapsulated dye and the dispersion media were mixed together in a proportion of 5:20 by weight, spread out in plastic Petri dish and dried to form an opaque colored layer similar to that of candy coatings.

(69) A dark predominantly blue layer was obtained from the encapsulated dye of Example 2 (see table 3). Colorimetry measurements were: L*=17.2, C*=7.4 and h=270°.

Example 19

(70) An opaque colored layer was obtained by mixing together the encapsulated dye of Example 11, sucrose and gum acacia as described in Example 18. A dark predominantly purple layer was obtained from the encapsulated dye of Example 11. Colorimetry measurements were: L*=24.9, C*=8.3 and h=307°.

Example 20

(71) An opaque colored layer was obtained by mixing together the encapsulated dye of Example 12, sucrose and gum acacia as described in Example 18. A dark predominantly red layer was obtained from the encapsulated dye of Example 12. Colorimetry measurements were: L*=21.2, C*=19.9 and h=2°.

Example 21

(72) An opaque colored layer was obtained by mixing together the encapsulated dye of Example 15, sucrose and gum acacia as described in Example 18. A dark predominantly yellow layer was obtained from the encapsulated dye of Example 15. Colorimetry measurements were: L*=59.7, C*=51.8 and h=82°.

Example 22

(73) Use of Non Polar Coatings

(74) A demonstration of the use of a non-polar coating to water-proof encapsulated dyes is provided herein. The coating was a mixture of (by weight of coating) 2.01% zein, 11.55% canola oil, 82.48% denatured ethanol, 0.66% calcium chloride and 3.30% Durlac 100 W emulsifier. The coating mixture and encapsulated dye of Example 2 were mixed together in a proportion of 3:1 by weight respectively and the denatured ethanol was evaporated. The amount of red cabbage color released from the coated encapsulated dye in syrup after 15 minutes immersion at room temperature was 4% of the total amount of red cabbage color. Therefore the non-polar coating substantially improved impermeability of the encapsulated dye.

Example 23

(75) Encapsulation of a High Concentration of Dye

(76) In some instances it might be desirable to use an encapsulated dye with a higher dye concentration than those of previous Examples to produce thinner color coats with a high color intensity on candies or in other applications. There could also be some economic benefits since the manufacturing of encapsulated dyes with a high dye concentration would not entail significantly different manufacturing costs (without raw materials) than those of an encapsulated dye at a lower dye concentration. This would hold true if it could be demonstrated that the encapsulated dyes can be used at a dosage level proportionate to the amount of dye in the encapsulate. This is demonstrated herein.

(77) Turmeric was encapsulated in a rice protein concentrate at two concentrations in a fashion similar to that of example 16. To achieve this turmeric was dispersed in the extruder liquid feed using a commercial blender at two concentrations. The resulting powders had a turmeric concentration of 1.96% and 9.1% by weight based on the dry weight of encapsulated turmeric. The encapsulated dyes are hereafter referred to as “low dye encapsulate” and “high dye encapsulate” respectively. The high dye encapsulate contained 4.64-fold more turmeric color that the low dye encapsulate.

(78) The low dye and high dye encapsulates were ground to a very fine powders, i.e., particle size averaging 9 microns, using a commercial blender and a ceramic ball mill. A portion of dispersion media was made by mixing together 3 g icing sugar, 0.05 g gum acacia, 1.25 g medium invert sugar, 0.3125 g low bloom gelatin and 2.3875 g water and by heating lightly in a microwave oven until clear. A portion of the low dye encapsulate of 1.64 g was blended with 3.86 g of confectionery sugar and dispersed in a portion of dispersion media. A portion of the high dye encapsulate of 0.28 g was blended with 5.22 g of confectionery sugar and dispersed in a portion of dispersion media. Hence the quantity of low dye encapsulate in the dispersion media was about 5.9-fold higher than the quantity of high dye encapsulate in the dispersion media. The solids content of both mixtures was identical.

(79) Two-gram portions of dispersed dye encapsulates were applied onto the surface of square (48 mm×48 mm) white ceramic tiles and spread evenly over the entire surface using a spatula. The color coatings were dried at room temperature in the dark and color measurements were made. Tiles coated with the dispersion media that contained the low dye encapsulate and the high dye encapsulate had similar L* values, i.e., 85.7 and 85.4 respectively and h values, i.e., 91° and 90° respectively. However, the color vividness was higher for the tiles coated with the dispersion media that contained the high dye encapsulate than the low dye encapsulate, i.e., 49.9 and 35.6 respectively.

(80) Therefore, technical advantages relating to the encapsulation of a high concentration of dye compared to a low concentration of dye include a lower application dosage relative to the actual amount of dye and a brighter color.

Example 24

(81) Encapsulated Dye with a Very High Color Value

(82) This example serves as a demonstration of an encapsulated dye with a very high color value. Bixin 100% is a food color with a very high color value i.e., about 310,000 (determined by spectrophotometry at 458 nm after dilution in ethanol). Encapsulated bixin was produced as in example 15, except that bixin was blended with rice protein concentrate in a proportion of 5:95 (w/w). The encapsulated dye thus obtained contained c.a. 15,500 color units of bixin.

Example 25

(83) Encapsulation Process

(84) Materials

(85) Proteins:

(86) Soy protein isolate, Pro-Fam 974 (Archer Daniel Midland, Ill., USA), with a protein content of about 90% based on the dry weight of the isolate; Rice protein concentrate, Remypro N80+(Remy Industries, Leuven-Wijgmaal, Belgium), with a protein content of about 80% based on the dry weight of the concentrate.

(87) Dyes:

(88) Beet red, Vegetable Juice Color 4015 (Food Ingredient Solutions, New York N.Y., USA), a beet juice concentrate with a minimum betanin content of 1.5%; Bixin, 100% (Food Ingredient Solutions, New York N.Y., USA); Norbixin, AFC WS 4600P (Rhodia, Madison, Wis., USA), an annatto extract dried using potassium carbonate with a norbixin content of 15%; Red cabbage color (Colarome, St. Hubert, QC, Canada), an aqueous concentrate exempt of diluents with a color value attributable to anthocyanins of 1600 (determined by spectrophotometry at 535 nm in pH 3.0 McMaine buffer); Saffron color, Safrante Industrial (Azafran Natural, Malaga, Spain), a saffron extract dried using maltodextrin; Tartrazine, 07799 FD&C Yellow #5, Granular (Sensient, St. Louis Mo., USA); Turmeric powder P8003 (Food Ingredient Solutions, New York N.Y., USA), a curcuma extract dried using gum acacia as the carrier with a curcumin content of 5±0.4%.

(89) Reagents:

(90) Ascorbic acid, fine granulation (Brenntag Canada, Lachine QC, Canada); Calcium chloride 93%, anhydrous (Brenntag Canada, Lachine QC, Canada); Gelatin, low bloom Kosher (VYSE Gelatin Co., Shiller Park Ill., USA); Gum acacia, Arabic gum Type CS (Daminco, Oakville ON, Canada); Denatured alcohol, SDAG-13, anhydrous (Commercial Alcohols, Tiverton ON, Canada), grain ethyl alcohol denatured with 1% ethyl acetate; Durlac 100 W emulsifier (Loders & Croklaan, Channahon Ill., USA); Medium invert sugar (Nealanders Intl., Dorval QC, Canada); Tannic acid (Fleurchem, Middletown N.Y., USA); Zein F4000, regular grade (Freeman Industries, Tuckahoe N.Y., USA).

(91) Methods

(92) Colorimetry Measurements:

(93) Colorimetry measurements were determined using a ColorFlex™ colorimeter (Hunter Associates Laboratory Inc., Reston, Va.) and a quartz sample cup. Calibration was performed using black and white porcelain color standards and performance of the colorimeter was verified by making readings using a green porcelain standard (illuminant D65/10° observer). Direct color measurements of samples were performed by layering a sufficient amount of sample in the sample cup to ensure opacity. Colorimetry measurements of samples were also performed by suspending samples of encapsulated dyes in a liquid media comprised of either a 50% aqueous solution of sucrose (syrup) or mineral oil, pouring the suspension in the sample cup and letting settle to form an opaque layer of wetted sample before making readings.

(94) Melt Extrusion:

(95) Melt extrusion was accomplished utilizing a Baker-Perkin co-rotating twin-screw extruder (model MPF-50) incorporating 9 sections that can be independently electrically-heated and cooled with chilled water. Solids were introduced using a metering screw through an opening located on top of the third section. A metering pump was used to inject liquids through a port located immediately downstream from the solids port. The die was fitted with two 9 mm orifices and was cooled with chilled water (0° C. to 2° C.). For the extrusion of the soy protein isolate, the two parallel screw assemblies were each comprised of (in the direction of the flow): 10.8 cm spacer, 27.9 cm conveying screw, 10.2 cm single-lead screw, 25.4 cm kneading blocks (20 blocks, 30° forward), 10.2 cm single-lead screw, 11.4 cm kneading blocks (9 blocks, 90°) and 20.3 cm single-lead screw. The assembly of extruder elements used with rice protein concentrate was: 10.8 cm spacer, 27.9 cm conveying screw, 10.2 cm single-lead screw, 25.4 cm kneading blocks (20 blocks, 30° forward), 10.2 cm single-lead screw, 11.4 cm kneading blocks (9 blocks, 30° forward), 5.1 cm kneading blocks (4 blocks, 30° reverse) and 15.2 cm single-lead screw. Temperature settings of the third section through the ninth were respectively 30° C., 35° C., 35° C., 35° C., 10° C., 10° C. and 10° C. Cooling of the sections was performed using chilled water (0° C. to 2° C.). Screw speed was 200 RPM. The extrudate was cut using a 4 blade rotating knife operating at about 1,600 RPM. Of course it should be understood that as the general extrusion process is well known in the art, the particular setting described above (e.g., speed of rotating screw and rotating knife, spacer, conveying screw, lead screw, kneading blocs, single lead screw, temperatures settings, etc. . . . ) could be modified in accordance with the desired characteristics of the extrudate. Thus, other melt extrusion parameters as well as other extruder apparatuses may also be used in accordance with the present invention.

(96) Extrudate Drying and Grinding:

(97) Extrudates were dried at room temperature by layering on paper-lined wire racks and circulating air to a moisture content between 5 and 10% by weight. The resulting dried extrudate was ground using a domestic blender and a fine grind mill (Prater, model CLM18) yielding a powder with particles averaging about 20 microns. Fine powders were produced in Examples 1 to 22 inclusively and Example 24.

(98) Alternatively the dried extrudate was ground using a domestic blender and a ceramic ball mill yielding a very fine powder with particles averaging about 9 microns. Very fine powders were produced in Example 23.

(99) Although the present invention has been described hereinabove by way of preferred embodiments thereof, it can be modified, without departing from the spirit and nature of the subject invention as defined in the appended claims.