Solid formulations comprising carotene derivatives

Abstract

The present invention relates to a solid formulation comprising carotene derivatives, not including β-carotene, with a high amount of a specific stereochemical form. Furthermore, the present invention relates to a process of production of such a specific formulation.

Description

[0001] Solid Formulations Comprising Carotene Derivatives

[0002] The present invention relates to a solid formulation comprising carotene derivatives such as p-zeacarotene, lycopene, apo-carotenal and esters of apo- carotenoic acid (hereinafter called apo-ester), citranaxanthin, rhodoxanthin, but not including p-carotene, wherein the carotenes as defined herein are present in a high amount of a specific stereochemical form (all-E form). Furthermore, the present invention relates to a process of production of such a specific formulation.

[0003] P-zeacarotene, which is the compound of formula (I), lycopene, which is the compound of formula (II), apo-carotenal, which is the compound of formula (III), and esters of apo-carotenoic acid, which is the compound of formula (IV), wherein X is alkyl, such as methyl, ethyl, isopropyl, are important and useful compounds. The compound for formulae (I) to (IV) are as shown in the “all-E’ stereochemical form, also called “all-trans” stereochemical form.

[0004] Due to the carbon-carbon double bonds, which are part of the structure of the formulae (I) to (IV), there is a variety of stereochemical forms of the compounds according to formulae (I) to (IV).

[0005] Very desired is for all of them the all-E form (as shown above). This stereochemical form is known to be a good bioavailable form of the carotene derivatives as described hereinabove.

[0006] Lycopene, apo-ester, and apo-carotenal are crucial carotenoids, each with unique roles in promoting health and enhancing the color of food and beverage products.

[0007] Lycopene is known for its potential in reducing the risk of chronic diseases and cancer, primarily due to its strong antioxidant activity. Apo-ester and apo- carotenal also exhibit antioxidant properties that may offer protective health benefits and also contribute to the vibrant spectrum of food colors from yellow to red. These carotene derivatives can be derived from various natural sources or synthesized for inclusion in dietary supplements and food products, covering the increasing consumer demand for natural ingredients and the added health advantages they may provide.

[0008] Lycopene is naturally abundant, with tomatoes being a significant source with antioxidant capacity. It exhibits significant health benefits, including reduced risk of chronic diseases like heart conditions and cancer, thanks to its antioxidant properties.

[0009] Apo-carotenal stands out in the carotenoid family for imparting vivid yellow to orange colors, making it a key ingredient for coloration in food and beverage products such as cheese and beverages. Apo-carotenal may also exhibit antioxidant properties which may play a role in safeguarding against chronic diseases, although research into apo-carotenal's specific health impacts is ongoing.

[0010] Apo-ester is identified for its coloration capability, offering a range of color hues from yellow to red. While not as widely recognized as some other carotenoids, apo-ester plays a critical role in the pigmentation of egg yolk and skin in poultry. Apo-ester exhibits antioxidant properties that may support the body's defense against certain chronic conditions.

[0011] 0-Zeacarotene, a less commonly known carotenoid, plays a significant role in imparting a yellow to orange hue in a variety of natural sources. This compound is known for its vivid color hues, serving as an essential ingredient in the food, feed, and pharmaceutical industries. 0-Zeacarotene exhibits antioxidant properties, hinting at potential health benefits.

[0012] Due to the fact that the carotene derivatives such as 0-zeacarotene, lycopene, apo-carotenal and apo-ester, citranaxanthin, rhodoxanthin, not including 0- carotene, can be used for a variety of applications, they need to be formulated. This means that said carotene derivatives are put in a formulation, which is suitable for that specific application.

[0013] Said carotene derivatives as described hereinabove can be formulated as liquid emulsions as well as solid formulations, such as spray-dried powders, granules, beadlets, or similar dried product formulations. These formulations can then be used as such, or they can be further formulated into the final product form.

[0014] The present invention relates to specific solid formulations. The solid formulations of the present invention can be implemented in a food product, a beverage, an animal feed product, a consumer product, or a health product.

[0015] To produce solid formulations, usually in a first step an emulsion / dispersion comprising said carotene derivatives as described hereinabove is produced, which is then in a second step transformed into a solid formulation using commonly known technologies, such as drying, spray drying, etc.

[0016] A problem, which occurs when producing formulations comprising carotene derivatives as described hereinabove such as 0-zeacarotene, lycopene, apo- carotenal and apo-ester, not including 0-carotene, is that they can easily isomerize into the various stereochemical forms.

[0017] Another problem that arises is that the higher the temperature used during the manufacturing process of the formulation the more isomerization to more cis or Z stereoisomers occurs. Thus, it is usually favourable to use low boiling solvents. However, low boiling solvents such as halogenated solvents may be more harmful to the environment. Thus, it is a goal of the present invention to provide a process, and a corresponding solid formulation, comprising said carotene derivatives as described hereinabove without the use of halogenated solvents, and wherein the content of said carotene derivatives having the important all-E form is at least 40 wt-% (based on the total content of the said carotene derivatives).

[0018] Therefore, the present invention relates to a solid formulation (SF) comprising

[0019] (i) At least one carotene derivative not including 0-carotene, and

[0020] (ii) at least one hydrocolloid, and

[0021] (iii) optionally at least one antioxidant such as a tocopherol, and

[0022] (iv) optionally water

[0023] (v) optionally at least one additional ingredient,

[0024] (vi) optionally an additional coating layer, characterised in that at least 40 weight-% (wt-%) of said carotene derivatives as described hereinabove (based on the total weight of each of said carotene derivatives) is in the all-E form, preferably wherein the solid formulation is essentially free from a halogenated solvent.

[0025] Essentially free from shall mean that no halogenated solvent is used for the manufacturing of the solid formulation, or that the solid formulation does not contain such halogenated solvent in an amount of more than 100 ppm.

[0026] The carotene derivatives as described hereinabove used in the formulation according to the present invention can be from any source. This means that said carotene derivatives can be from a natural source as well as be produced via chemical synthesis or biotechnological processes.

[0027] It is also possible to use a mixture of natural and nature-identical carotene derivatives as described hereinabove from the above-mentioned production processes.

[0028] For the present invention the source of said carotene derivatives is not critical. Essential for the present invention is that the content of said carotene derivatives as described hereinabove in the all-E form is at least 40 wt-%, based on the total weight of each of said carotene derivatives.

[0029] Preferably, the content of said carotene derivatives as described hereinabove in the all-E form is at least 50 wt-%, based on the total weight of each of said carotene derivatives; more preferably the content of each of said carotene derivatives in the all-E form is at least 60 wt-%, based on the total weight of said carotene derivative, especially preferred the of the content of said carotene derivatives in the all-E form is at least 62 wt-%, based on the total weight of each of said carotene derivative.

[0030] Preferably, the solid formulation (SF) has been obtained by using spraygranulation, preferably by using a spray-granulation step starting from a liquid emulsion comprising at least the ingredients of said solid formulation (i) through (ii), and optionally ingredients (iii) through (v).

[0031] Preferably, the solid formulation is essentially free from a halogenated solvent. Therefore, the present invention relates to a solid formulation (SF1 ), which is formulation (SF), wherein the content of said carotene derivatives as described hereinabove in the al \-E form is at least 50 wt-%, based on the total weight of each of said carotene derivative.

[0032] Therefore, the present invention relates to a solid formulation (SFT), which is formulation (SF), wherein the content of said carotene derivatives as described hereinabove in the al \-E form is at least 60 wt-%, based on the total weight of said carotene derivatives.

[0033] Therefore, the present invention relates to a solid formulation (SF1 ”), which is formulation (SF), wherein the content of said carotene derivatives as described hereinabove in the al \-E form is at least 62 wt-%, based on the total weight of each of said carotene derivative.

[0034] The overall content of said carotene derivatives as described hereinabove in the solid formulation according to the present invention is 0.5 to 30 wt-%, based on the total weight of the solid formulation.

[0035] Preferably, the overall content of said carotene derivatives as described hereinabove in the solid formulation according to the present invention is 1 to 25 wt-%, based on the total weight of the solid formulation.

[0036] More preferably, the overall content of said carotene derivatives as described hereinabove in the solid formulation according to the present invention is 1 to 20 wt-%, based on the total weight of the solid formulation.

[0037] Especially preferred, the overall content of said carotene derivatives as described hereinabove in the solid formulation according to the present invention is 1 to 15 wt-%, based on the total weight of the solid formulation.

[0038] Most preferred, the overall content of said carotene derivatives as described hereinabove in the solid formulation according to the present invention is 2 to 15 wt-%, based on the total weight of the solid formulation. Therefore, the present invention relates to a solid formulation (SF2), which is formulation (SF), (SF1 ), (SFT) or (SF1 ”), wherein the content of said carotene derivatives as described hereinabove in the solid formulation is 0.5 to 30 wt-%, based on the total weight of the solid formulation.

[0039] Therefore, the present invention relates to a solid formulation (SF2’), which is formulation (SF), (SF1 ), (SFT) or (SF1 ”), wherein the content of said carotene derivatives as described hereinabove in the solid formulation is 1 to 25 wt-%, based on the total weight of the solid formulation.

[0040] Therefore, the present invention relates to a solid formulation (SF2”), which is formulation (SF), (SF1 ), (SFT) or (SF1 ”), wherein the content of said carotene derivatives as described hereinabove in the solid formulation is 1 to 20 wt-%, based on the total weight of the solid formulation.

[0041] Therefore, the present invention relates to a solid formulation (SF2’”), which is formulation (SF), (SF1 ), (SFT) or (SF1 ”), wherein the content of said carotene derivatives as described hereinabove in the solid formulation is 1 to 15 wt-%, based on the total weight of the solid formulation.

[0042] Therefore, the present invention relates to a solid formulation (SF2””), which is formulation (SF), (SF1 ), (SFT), (SF1 ”) or (SFT”), wherein the content of said carotene derivatives as described hereinabove in the solid formulation is 2 to 15 wt-%, based on the total weight of the solid formulation.

[0043] The solid formulation according to the present invention comprises at least one hydrocolloid. The hydrocolloids according to the present invention have emulsifying properties.

[0044] In the context of the present invention, hydrocolloids are polysaccharides, gelatin of low bloom, having a bloom value of 30 to 150, medium bloom, having a bloom value of 150-225, or high bloom, having a bloom value of 225-325, from fish, pork, or bovine, caseins / caseinates, plant- or animal-based protein, other proteinaceous hydrocolloids, lignin derivatives, and lignosulfonate. Preferred hydrocolloids according to the invention are polysaccharides.

[0045] In the context of the present invention, the term polysaccharide as used herein includes xanthan gum, gum acacia, pectin, guar gum, caroub gum, alginates, celluloses, cellulose derivatives, such as starch and starch derivatives. Preferred polysaccharides according to the present invention are gum acacia, starch, starch derivatives, more preferred are gelatinized starch and modified food starch and especially preferred are modified food starches.

[0046] In the context of the present invention, the term "modified food starch" as used herein relates to modified starches that are made from starches substituted by known chemical methods with hydrophobic moieties. For example, starch may be treated with cyclic dicarboxylic acid anhydrides such as succinic and / or glutaric anhydrides, substituted with an alkyl or alkenyl hydrocarbon group.

[0047] A very common and preferred modified starch is starch sodium octenyl succinate (OSA-starch). OSA-starch as used herein denotes any starch (from any natural source such as corn, wheat, tapioca, potato or synthesized) that was treated with octenyl succinic anhydride. The degree of substitution, i.e. , the number of esterified hydroxyl groups with regard to the total number of hydroxyl groups usually varies in a range of from 0.1 percent to 10 percent, preferably in a range of from 0.5 percent to 5 percent, more preferably in a range of from 2 percent to 4 percent.

[0048] OSA-starches are commercially available e.g., from Ingredion under the trade names HiCap 100, Capsul HF, Capsul HS, Purity Gum 2000, UNI-PURE, HYLON VII from Roquette Freres; from Cargill under the trade name C*EmCap or from Tate and Lyle.

[0049] The content of the at least one hydrocolloid is usually from is from 40 to 90 wt-%, based on the total weight of the solid formulation, preferably from 45 to 90 wt-%, more preferably from 50 to 90 wt-%, based on the total weight of the solid formulation. Therefore, the present invention relates to a solid formulation (SF3), which is the solid formulation (SF), (SF1 ), (SFT), (SF1”), (SF2), (SF2’), (SF2”), (SF2’”) or (SF2””), wherein the at least one hydrocolloid is chosen from the group consisting of polysaccharides, gelatin of low bloom, having a bloom value of 30 to 150, medium bloom, having a bloom value of 150-225, or high bloom, having a bloom value of 225-325, from fish, pork or bovine, caseins / caseinates, planter animal-based protein, other proteinaceous hydrocolloids, lignin derivatives, and lignosulfonate.

[0050] Therefore, the present invention relates to a solid formulation (SF3’), which is the solid formulation (SF), (SF1 ), (SF1’), (SF1”), (SF2), (SF2’), (SF2”), (SF2’”) or (SF2””), wherein the at least one hydrocolloid is chosen from the group consisting of xanthan gum, gum acacia, pectin, guar gum, caroub gum, alginates, celluloses, cellulose derivatives, such as starch and starch derivatives.

[0051] Therefore, the present invention relates to a solid formulation (SF3”), which is the solid formulation (SF), (SF1 ), (SF1’), (SF1”), (SF2), (SF2’), (SF2”), (SF2’”) or (SF2””), wherein the hydrocolloid is modified food starch.

[0052] Therefore, the present invention relates to a solid formulation (SF3’”), which is the solid formulation (SF3”), wherein the modified food starch is starch sodium octenyl succinate.

[0053] Therefore, the present invention relates to a solid formulation (SF4), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”) or (SF3’”), wherein the content of the at least one hydrocolloid is 40 to 90 wt-%, based on the total weight of the solid formulation.

[0054] Therefore, the present invention relates to a solid formulation (SF4’), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”) or (SF3’”), wherein the content of the at least one hydrocolloid is 45 to 90 wt-%, based on the total weight of the solid formulation.

[0055] Therefore, the present invention relates to a solid formulation (SF4”), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”) or (SF3’”), wherein the content of the at least one hydrocolloid is 50 to 90 wt-%, based on the total weight of the solid formulation.

[0056] The solid formulation according to the present invention comprises tocopherol. In the context of the present invention the term “tocopherol” encompasses any of its 8 stereoisomers, i.e. , all-rac-a-tocopherol, including mixed tocopherol.

[0057] The content of the tocopherol is from 0.1 to 5 wt-%, based on the total weight of the solid formulation, preferably from 0.1 to 4 wt-%, more preferably from 0.5 to 3 wt-%, based on the total weight of the solid formulation.

[0058] Therefore, the present invention relates to a solid formulation (SF5), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’) or (SF4’), wherein the content of the tocopherol is 0.1 to 5 wt-%, based on the total weight of the solid formulation.

[0059] Therefore, the present invention relates to a solid formulation (SF5’), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’) or (SF4’), wherein the content of the tocopherol is 0.1 to 4 wt-%, based on the total weight of the solid formulation.

[0060] Therefore, the present invention relates to a solid formulation (SF5”), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’) or (SF4’), wherein the content of the tocopherol is 0.5 to 3 wt-%, based on the total weight of the solid formulation.

[0061] The solid formulation according to the present invention can comprise some water (residual water). The content of the residual water can vary depending on the kind and properties of drying, which is used to dry the solid formulation.

[0062] The water content of the solid formulation according to the present invention is less than 8 wt-%, based on the total weight of the solid formulation.

[0063] Preferably, the water content of the solid formulation according to the present invention is less than 7 wt-%, more preferably less than 6 wt-%, especially preferred less than 5 wt-%, based on the total weight of the solid formulation.

[0064] Therefore, the present invention relates to a solid formulation (SF6), which is the solid formulation (SF), (SF1 ), (SFT), (SF1”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’) or (SF5”), wherein the content of water is less than 8 wt-%, based on the total weight of the solid formulation.

[0065] Therefore, the present invention relates to a solid formulation (SF6’), which is the solid formulation (SF), (SF1 ), (SFT), (SF1”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’) or (SF5”), wherein the content of water is less than 7 wt-%, based on the total weight of the solid formulation.

[0066] Therefore, the present invention relates to a solid formulation (SF6”), which is the solid formulation (SF), (SF1 ), (SFT), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’) or (SF5”), wherein the content of water is less than 6 wt-%, based on the total weight of the solid formulation. Therefore, the present invention relates to a solid formulation (SF6’”), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’) or (SF5”), wherein the content of water is less than 5 wt-%, based on the total weight of the solid formulation.

[0067] The solid formulation according to the present invention can comprise optionally at least one further ingredient. Such ingredients can be starch hydrolysates (such as dextrins, maltodextrins and glucose syrup), vegetable oils, dyestuffs, such as other carotenoids, preferably not already in the formulation, such as said carotene derivatives, fillers, binders, flavours, etc.

[0068] By vegetable oil it is understood that it is an oil extracted from a plant and which is used as a carrier for emulsification of said carotene derivatives. Examples of suitable vegetable oils are rapeseed oil, corn oil, sunflower oil, safflower oil, cotton seed oil, palm oil, coconut oil, MCT oil, or any other, explicitly not meant by vegetable oil is a liquid oily substance having a different function than that of a carrier for emulsification of the said carotene derivatives. Such liquid oily substance may be e.g. tocopherols, such as all-rac-a-tocopherol, which are typically used as antioxidant.

[0069] Preferably the solid formulation does not comprise a vegetable oil as defined hereinabove.

[0070] The content of these additional ingredients can be up to 15 wt-%, based on the total weight of the solid formulation.

[0071] Therefore, the present invention relates to a solid formulation (SF7), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”) or (SF6’”), wherein the solid formulation comprises at least one additional ingredient chosen from the group consisting of starch hydrolysates (such as dextrins, maltodextrins and glucose syrup), vegetable oils, dyestuffs, such as other carotenoids, preferably not already in the formulation, such as said carotene derivatives, fillers, binders and flavours. Therefore, the present invention relates to a solid formulation (SF8), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”) or (SF7), wherein the content of the at least one additional ingredient is up to 15 wt-%, based on the total weight of the solid formulation.

[0072] The solid formulation according to the present invention can be coated, which means it can have an additional coating layer.

[0073] The additional coating layer can be any commonly known coating layer. It could also be a powder coating layer. Such a powder coating can be made from starch (such as com starch).

[0074] The additional coating layer can be up to 45 wt-% of the solid formulation, based on the total weight of the solid formulation.

[0075] Therefore, the present invention relates to a solid formulation (SF9), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7) or (SF8), wherein solid formulation is coated with an additional coating layer.

[0076] Therefore, the present invention relates to a solid formulation (SF9’), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7) or (SF8), wherein solid formulation is coated with a powder coating layer.

[0077] Therefore, the present invention relates to a solid formulation (SF10), which is the solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9) or (SF9’), wherein the coating is up to 45 wt-% of the solid formulation, based on the total weight of the solid formulation. It is clear, that for one embodiment of the present invention the amounts always add up to 100 %.

[0078] The solid formulation according to the present invention can be powderous, in the form of a granule, or in the form of a beadlet.

[0079] The particle size of the solid formulation can be form 50 pm to 1000pm.

[0080] The particle size distribution of the powderous formulation according to the mean Sauter diameter D(3,2) is measured by a laser diffraction instrument Mastersizer 3000 (Malvern Instruments, Malvern, United Kingdom), applying the Fraunhofer model.

[0081] The size can vary. It can depend on a variety of factors, such as the production process, the intended use, etc.

[0082] The solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9), (SF9’) or (SF10) according to the present invention can be used as such or further formulation into a final product.

[0083] The solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9), (SF9’) or (SF10) can be used in food products, in feed products, in dietary supplements, in pharmaceutical products and / or in personal care products.

[0084] Furthermore, the present invention relates to food products, feed products, dietary supplements, pharmaceutical products and personal care products comprising at least one solid formulation (SF), (SF1 ), (SFT), (SF1 ”), (SF2), (SF2 ), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9), (SF9’) or (SF10). The solid formulation according to the present invention as described hereinabove are produced by commonly known methods.

[0085] Generally, the solid formulation (SF), (SF1 ), (SFT), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4 ), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9), (SF9’) or (SF10) according to the present invention is produced as follows:

[0086] Step (I): dissolving and emulsifying / dispersing of any of said carotene derivatives as described hereinabove or mixtures thereof, and

[0087] Step (II): producing a solid form out of the emulsion / dispersion of step (I).

[0088] Therefore, the present invention relates to a process (P) for a producing solid formulation (SF), (SF1 ), (SF1 ’), (SF1 ”), (SF2), (SF2’), (SF2”), (SF2’”), (SF2””), (SF3), (SF3’), (SF3”), (SF3’”), (SF4), (SF4’), (SF4’), (SF5), (SF5’), (SF5”), (SF6), (SF6’), (SF6”), (SF6’”), (SF7), (SF8), (SF9), (SF9’) or (SF10), comprising step (I): dissolving and emulsifying / dispersing of any of said carotene derivatives as described hereinabove, or mixtures thereof, and step (II): producing a solid form out of the emulsion / dispersion of step (I).

[0089] In the following the steps are discussed in more details.

[0090] Step (I)

[0091] Any of said carotene derivatives as described hereinabove or mixtures thereof are dissolved in a solvent and / or a mixture of solvent.

[0092] Suitable solvents are organic solvents which have preferably a boiling point of less than 150°C, more preferably less than 140°C, especially less than 120°C at 1013.25 hPa.

[0093] Suitable solvents are halogenated solvents, such as dichloromethane, chloroform; or non-halogenated solvents such as, carboxylate ester such as dimethyl carbonate, diethyl carbonate, propylene carbonate; methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl formate, methyl ethyl ketone, isobutyl methyl ketone, isobutanol (2-Methyl-1 -propanol), or mixtures thereof.

[0094] Preferred solvents are non-halogenated solvents.

[0095] More preferred solvents are ethyl acetate, isobutyl acetate, isopropyl acetate, or mixtures thereof.

[0096] Especially preferred solvents are isobutyl acetate or isopropyl acetate.

[0097] Most preferred solvent is isobutyl acetate.

[0098] In the context of the present invention, a “dispersion" may be an emulsion, i.e. the particle’s core may be liquid. Alternatively, the dispersion may be a suspension, i.e. the particle’s core may be solid. In a typical embodiment of the present invention, however, the particle’s core of the dispersion comprises both, liquid and solid compounds.

[0099] The “particles" of dispersion are too small to be seen with the naked eye. In a preferred embodiment of the invention, the particles have an average size in the range from 50 to 1000 nm, more preferably from 100 to 800 nm and more preferably from 100 to 500 nm [Average diameter of particle sizes, measured by Dynamic Light Scattering (Anton Paar, Litesizer 500)]. The particles are water-dispersible despite of having a lipophilic core. This is achieved by surrounding the core with the at least one hydrocolloid having emulsifying properties (ingredient (ii)). Said surrounding is referred to as the shell of the particle.

[0100] An aqueous solution is prepared as well, which comprises water and at least one hydrocolloid (ingredient (ii)).

[0101] It is clear, that all preferences for the hydrocolloid as stated above apply here as well.

[0102] Preferably, the at least one hydrocolloid is chosen from the group consisting of xanthan gum, gum acacia, pectin, guar gum, caroub gum, alginates, celluloses, cellulose derivatives, such as starch and starch derivatives.

[0103] More preferably, the hydrocolloid is modified food starch. Most preferably, the hydrocolloid is starch sodium octenyl succinate.

[0104] Finally, these two phases are combined usually under vigorous stirring and / or high-pressure homogenization to obtain the dispersion / emulsion.

[0105] It is clear, that the phase containing any of said carotene derivatives as well as the water phase could also comprise further (non-essential) ingredients, such as starch hydrolysates (such as dextrins, maltodextrins and glucose syrup), vegetable oils, dyestuffs, such as other carotenoids, preferably not already in the formulation, such as said carotene derivatives, fillers, binders, and flavours. By vegetable oil it is understood that it is an oil extracted from a plant and which is used as a carrier for emulsification of said carotene derivatives. Examples of suitable vegetable oils are rapeseed oil, corn oil, sunflower oil, safflower oil, cotton seed oil, palm oil, coconut oil, MCT oil, or any other, explicitly not meant by vegetable oil is a liquid oily substance having a different function than that of a carrier for emulsification of the said carotene derivatives. Such liquid oily substance may be e.g. tocopherols, such as all-rac-a-tocopherol, which are typically used as antioxidant.

[0106] Preferably the carotene derivative phase does not comprise a vegetable oil as defined hereinabove.

[0107] Preferably the solid formulation does not comprise a vegetable oil as defined hereinabove.

[0108] Preferably the solid formulation does not comprise a vegetable oil as defined hereinabove, and the solvent used in step (I) is isobutyl acetate.

[0109] Depending on step (II), the viscosity of the dispersion / emulsion needs to be in such a range that the granulation step can take place.

[0110] Therefore, the present invention relates to a process (P1 ), which is process (P), wherein said carotene derivatives as described hereinabove is dissolved in at least one solvent which have a boiling point of less than 150°C. Therefore, the present invention relates to a process (PT), which is process (P), wherein said carotene derivatives as described hereinabove is dissolved in at least one solvent which have a boiling point of less than 140°C.

[0111] Therefore, the present invention relates to a process (P1 ”), which is process (P), wherein said carotene derivatives as described hereinabove is dissolved in at least one solvent which have a boiling point of less than 120°C.

[0112] Therefore, the present invention relates to a process (PT”), which is process (P), wherein said carotene derivatives as described hereinabove is dissolved in isopropyl acetate, isobutyl acetate, or ethyl acetate, or mixtures thereof, wherein preferably the carotene derivative is dissolved in isobutyl acetate.

[0113] Therefore, the present invention relates to a process (P2), which is process (P), (P1 ), (PT), (P1”) or (PT”), wherein an aqueous solution is prepared, which comprises water and at least one hydrocolloid.

[0114] Therefore, the present invention relates to a process (P2’), which is process (P), (P1 ), (PT), (P1”) or (PT”), wherein an aqueous solution is prepared, which comprises water and at least one hydrocolloid, wherein the at least one hydrocolloid is chosen from the group consisting of xanthan gum, gum acacia, pectin, guar gum, caroub gum, alginates, celluloses, cellulose derivatives, such as starch and starch derivatives.

[0115] Therefore, the present invention relates to a process (P2”), which is process (P), (P1 ), (PT), (P1”) or (PT”), wherein an aqueous solution is prepared, which comprises water and at least one hydrocolloid, wherein the at least one hydrocolloid is a modified food starch.

[0116] Therefore, the present invention relates to a process (P2’”), which is process (P), (P1 ), (PT), (P1”) or (PT”), wherein an aqueous solution is prepared, which comprises water and at least one hydrocolloid, wherein the at least one hydrocolloid is starch sodium octenyl succinate. Step (II)

[0117] In step (II) a solid form out of the emulsion / dispersion of step (I) is formed. This is done by a granulation process, more preferably in a spray-granulation process.

[0118] Granulation is a process in which powder particles are made by building up larger particles starting from small particles by layering these small particles with the solids-bearing liquid.

[0119] The granulation process via the spraying of emulsion onto the seed particles (made from spray drying of the emulsion) was performed for at least 30 minutes, preferably up to several hours, and subsequent drying phase of at least 30 minutes, preferably up to 2 h, at a product temperature of 70°C - 100°C, preferred 75°C to 90°C, most preferred around 80°C.

[0120] The liquid emulsion is spray-granulated in two-steps:

[0121] I) the preparation of seed material applying spray drying with an air inlet temperature of 160°C to 190°C and an air outlet temperature of 70°C

[0122] - 100°C (preferred 75°C to 90°C, most preferred around 80°C) and

[0123] II) the preparation of granules using a fluid bed processor (such as for example a fluid bed processor type WFP-Mini (DMR Prozess- Technologie GmbH)).

[0124] Therefore, the present invention relates to a process (P3), which is process (P), (P1 ), (PT), (P1”), (P2), (P2’), (P2”) or (P2’”), wherein the liquid emulsion is spray-granulated in two-steps:

[0125] I) the preparation of seed material applying spray drying with an air inlet temperature of 160 to 190 °C and an air outlet temperature of 70°C

[0126] - 100°C and

[0127] II) the preparation of granules using a fluid bed processor. Therefore, the present invention relates to a process (P3’), which is process (P), (P1 ), (PT), (P1”), (P2), (P2’), (P2”) or (P2’”), wherein the liquid emulsion is spray-granulated in two-steps:

[0128] I) the preparation of seed material applying spray drying with an air inlet temperature of 160 to 190 °C and an air outlet temperature of 75°C to 90°C, and

[0129] II) the preparation of granules using a fluid bed processor.

[0130] Therefore, the present invention relates to a process (P3”), which is process (P), (P1 ), (P1 ’), (P1 ”), (P2), (P2’), (P2”) or (P2’”), wherein the liquid emulsion is spray-granulated in two-steps:

[0131] I) the preparation of seed material applying spray drying with an air inlet temperature of 160 to 190 °C and an air outlet temperature of around 80 °C and

[0132] II) the preparation of granules using a fluid bed processor.

[0133] Therefore, the present invention relates to a process (P4), which is process (P), (P1 ), (P1 ’), (P1 ”), (P2), (P2’), (P2”), (P2’”), (P3), (P3’) or (P3”), wherein the granulation process is performed for at least 30 minutes, preferably up to several hours, and subsequent drying phase of at least 30 minutes, preferably up to 2 h, at a product temperature of 70°C - 100°C is carried out.

[0134] Therefore, the present invention relates to a process (P4’), which is process (P), (P1 ), (P1 ’), (P1 ”), (P2), (P2’), (P2”), (P2’”), (P3), (P3’) or (P3”), wherein the granulation process is performed for at least 30 minutes, preferably up to several hours, and subsequent drying phase of at least 30 minutes, preferably up to 2 h, at a product temperature of 75°C to 90°C is carried out.

[0135] Therefore, the present invention relates to a process (P4”), which is process (P), (P1 ), (PT), (P1 ”), (P2), (P2’), (P2”), (P2’”), (P3), (P3’) or (P3”), wherein the granulation process is performed for at least 30 minutes, preferably up to several hours, and subsequent drying phase of at least 30 minutes, preferably up to 2 h, at a product temperature of around 80°C is carried out. The following Example illustrates the invention further without limiting it. All percentages and parts, which are given, are related to the weight and the temperatures are given in °C, when not otherwise stated.

[0136] EXAMPLES

[0137] Example 1 :

[0138] To prepare the solution, 16.5 g lycopene and 1.65 g (all rac)-a-tocopherol are suspended into 210 mL ethyl acetate using a 500 mL three-necked round bottom flask and heated-up to 115 °C until complete dissolution is achieved. For the matrix phase containing the emulsifier, 120 g OSA-modified food starch are dissolved in 260 mL water at room temperature in a 1 L beaker using conventional vertical stirring for 1 h. The solution is added to the matrix phase and emulsified at 50-60 °C for up to 9 min using a rotor stator (IKA G45M) with high shear stirrer (IKA T50) at 10.000 rpm. If required, additional water may be added to adjust viscosity during emulsification.

[0139] After transferring the emulsion into a 2 L three-necked round bottom flask and the addition of 125 mL water, the organic solvent is evaporated at 40 °C under vacuum. Vacuum evaporation and eventual further water addition are continued until reaching a final emulsion with appropriate levels of viscosity and residual moisture for the subsequent drying process.

[0140] The emulsion is spray-granulated in two-steps by I) the preparation of seed material applying spray drying with an air inlet temperature of 180 °C and an air outlet temperature of 80 °C in a GEA Niro spray tower, Mobile Minor 2000 Model D1 -Spezial and II) the preparation of granules using a fluid bed processor type WFP-Mini (DMR Prozess-Technologie GmbH). The granulation process via the spraying of emulsion onto the seed particles is performed for 3 h and a subsequent drying phase for 2 h at a product temperature of 80 °C. The spray granulation process yields an increase of the (all-E)-isomeric ratio, amounting to an (all-E)-isomeric ratio of 46.2 wt-% for lycopene.

[0141] Example 2:

[0142] To prepare the solution, 33 g apo-carotenal and 3.3 g (all rac)-a-tocopherol are suspended into 420 mL isobutyl acetate using a 1 L three-necked round bottom flask and heated-up to 115 °C until complete dissolution is achieved. For the matrix phase containing the emulsifier, 240 g OSA-modified food starch are dissolved in 520 mL water at room temperature in a 2 L beaker using conventional vertical stirring for 1 h. The solution is added to the matrix phase and emulsified at 50-60 °C for up to 18 min using a rotor stator IKA G45M with high shear stirrer IKA T50 at 10.000 rpm. If required, additional water may be added to adjust viscosity during emulsification.

[0143] After transferring the emulsion into a 4 L three-necked round bottom flask and the addition of 250 mL water, the organic solvent is evaporated at 40 °C under vacuum. Vacuum evaporation and eventual further water addition are continued until reaching a final emulsion with appropriate levels of viscosity and residual moisture for the subsequent drying process.

[0144] The liquid emulsion is spray-granulated in two-steps by I) the preparation of seed material applying spray drying with an air inlet temperature of 180 °C and an air outlet temperature of 80 °C in a GEA Niro spray tower, Mobile Minor 2000 Model D1 -Spezial and II) the preparation of granules using a fluid bed processor type WFP-Mini (DMR Prozess-Technologie GmbH). The granulation process via the spraying of emulsion onto the seed particles is performed for 3 h and a subsequent drying phase for up to 2 h at a product temperature of 80 °C. The spray granulation process yields an increase of the (all-E)-isomeric ratio, amounting to an (all-E)-isomeric ratio of 47.5 wt-% for apo-carotenal.

[0145] Example 3:

[0146] The liquid emulsion is prepared according to the workflows as described in the Examples 1 and 2. The liquid emulsion is spray-granulated in two-steps by I) the preparation of seed material applying spray drying with an air inlet temperature of 180 °C and an air outlet temperature of 80 °C in a GEA Niro spray tower, Mobile Minor 2000 Model D1-Spezial and II) the preparation of granules using a fluid bed processor type WFP-Mini (DMR Prozess- Technologie GmbH). The granulation process via the spraying of emulsion onto the seed particles is performed for 1 .5 h and a subsequent drying phase for 1 h at a product temperature of 80 °C. The spray granulation process yields an increase of the (all-E)-isomeric ratio, amounting to an (all-E)-isomeric ratio of 45.8 wt-% for lycopene.

[0147] Example 4:

[0148] The liquid emulsion is prepared according to the workflows as described in the Examples 1 and 2. The liquid emulsion is spray-granulated in two-steps by I) the preparation of seed material applying spray drying with an air inlet temperature of 180 °C and an air outlet temperature of 80 °C in a GEA Niro spray tower, Mobile Minor 2000 Model D1-Spezial and II) the preparation of granules using a fluid bed processor type WFP-Mini (DMR Prozess- Technologie GmbH). The granulation process via the spraying of emulsion onto the seed particles is performed for 1 .5 h and a subsequent drying phase for 2 h at a product temperature of 80 °C. The spray granulation process yields an increase of the (all-E)-isomeric ratio, amounting to an all-E isomeric ratio of 42.9 wt-% for apo-carotenal.

[0149] Table 1 - contents of final composition:

Claims

Claims1. Process for the production of a solid formulation comprising(i) At least one carotene derivative, not including 0-carotene, and(ii) at least one hydrocolloid, and(iii) optionally at least one antioxidant, and(iv) optionally at least one additional ingredient,(v) optionally an additional coating layer, characterised in that at least 40 wt-% of said carotene derivative, based on the total weight of said carotene derivative, is in the all-E form, wherein said solid formulation is obtained by spray-granulation from the liquid emulsion formed comprising at least the ingredients of said formulation (i) through (ii), optionally (i) through (iii), in two steps:I) the preparation of seed material applying spray drying to the liquid emulsion with an air inlet temperature of 160 to 190 °C and an air outlet temperature of 70°C - 100°C andII) the preparation of granules using a fluid bed processor.

2. Process according to claim 1 , wherein the granulation process is performed for at least 30 minutes, preferably up to several hours, and subsequent drying phase of at least 30 minutes, preferably up to 2 h, at a product temperature of 70°C - 100°C is carried out.

3. Process according to claim 1 or 2, wherein the solid formulation does not contain a vegetable oil.

4. Process according to any one of the preceding claims, wherein the solvent used in step (I) of the spray-granulation is a non-halogenated solvent, preferably isopropyl acetate or isobutyl acetate.

5. A solid formulation comprising(i) At least one carotene derivative, not including 0-carotene, and(ii) at least one hydrocolloid, and(iii) optionally at least one antioxidant, and(iv) optionally at least one additional ingredient,(v) optionally an additional coating layer, characterised in that at least 40 wt-% of said carotene derivative, based on the total weight of said carotene derivative, is in the all-E form, and wherein said solid formulation is obtained by spray-granulation from the liquid emulsion formed comprising at least the ingredients of said solid formulation (i) through (ii), optionally (i) through (iii).

6. The solid formulation according to claim 5, wherein the content of said carotene derivative in the all-E form is at least 50 wt-%, based on the total weight of said carotene derivative.

7. The solid formulation according to claim 5, wherein the content of said carotene derivative in the all-E form is at least 60 wt-%, based on the total weight of said carotene derivative.

8. The solid formulation according to any of the preceding claims 5 to 7, wherein the content of said carotene derivative in the solid formulation is 0.5 to 30 wt-%, based on the total weight of the solid formulation.

9. The solid formulation according to any of the preceding claims 5 to 7, wherein the content of said carotene derivative in the solid formulation is 1 to 25 wt-%, based on the total weight of the solid formulation.

10. The solid formulation according to any of the preceding claims 5 to 8, wherein the at least one hydrocolloid is chosen from the group consisting of polysaccharides, gelatin of low bloom, medium bloom or high bloom from fish, pork, or bovine, caseins / caseinates, plant- or animal-based1 protein, other proteinaceous hydrocolloids, lignin derivatives, and lignosulfonate.

11. The solid formulation according to any of the preceding claims 5 to 8, wherein the at least one hydrocolloid is chosen from the group consisting of xanthan gum, gum acacia, pectin, guar gum, caroub gum, alginates, celluloses, cellulose derivatives, such as starch and starch derivatives.

12. The solid formulation according to any of the preceding claims 5 to 9, wherein the hydrocolloid is modified food starch.

13. The solid formulation according to any of the preceding claims 5 to 12, wherein the content of the at least one hydrocolloid is 40 to 90 wt-%, based on the total weight of the solid formulation.

14. The solid formulation according to any of the preceding claims 5 to 13, wherein the at least one antioxidant is a tocopherol and wherein the content of the tocopherol is 0.1 to 5 wt.-%, based on the total weight of the solid formulation.

15. A solid formulation obtained by the process according to any of the claims 1 to 4.

16. A food product, a beverage, an animal feed product, a consumer product, or a health product comprising said formulation according to any of the claims 5-15.

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