Vitamin preparations containing propyl gallate

Abstract

The present invention relates to a powdered vitamin preparation in which the vitamin has a particle size substantially smaller than 0.7 μm and contains an effective amount of propyl gallate. The invention also relates to methods for producing such a preparation, to preparations obtainable according to these methods, and to their use as animal feed, food, a food supplement, personal care products, or pharmaceutical agents. Preparations according to the invention exhibit improved stability compared to the prior art.

Description

[0001] The present invention relates to a preparation with antioxidant properties, its manufacture and use.

[0002] One difficulty in the production of vitamin-containing preparations is that they are often unstable during the manufacturing process, as well as during subsequent storage or further processing in premixes, pellets, or feeds, and are susceptible to damage from oxidative processes. This damage can be caused by reactions with atmospheric oxygen, interactions with heavy metals, or the absorption of UV radiation. As a result of this damage, the vitamins can, for example, change color and / or lose their effectiveness.

[0003] One well-known way to treat the problems described is to add antioxidants to the preparations.

[0004] According to CD Römpp Chemie Lexikon 10th edition version 1.3, Stuttgart / New York: Georg Thieme Verlag, antioxidants are compounds that inhibit or prevent undesirable changes in the substances to be protected caused by oxygen exposure, including oxidative processes.

[0005] Ethoxyquin has antioxidant properties and thus a protective effect against vitamins. Toxicological data on ethoxyquin are insufficient, and ethoxyquin itself is considered non-genotoxic. However, the European Food Safety Authority (EFSA) has determined that one of its metabolites, ethoxyquin imine, could be genotoxic (i.e., damaging to DNA), raising potential safety concerns.

[0006] As a result of the ethoxyquin manufacturing process, the feed additive also contains an impurity, p-phenetidine, which may be a mutagen. Mutagens are substances that cause mutations in the genetic material of animals and humans.

[0007] Due to the current lack of data, EFSA cannot make a decision on the safety of ethoxyquin as a feed additive for the target animals, nor can it make a final assessment of its safety for consumers or the environment.

[0008] Due to these safety concerns, there is an urgent need for antioxidants suitable for use as additives in animal feed, food, dietary supplements, personal care products or pharmaceuticals, and which can replace ethoxyquin in its preparations in the short term.

[0009] EP 0065193 discloses a process for the production of finely divided, powdered carotenoid or retinoid preparations. It is known that antioxidants can be added to either the aqueous or the active ingredient-containing solvent phase during the production of active ingredient preparations, but that they are preferably premixed together with the active ingredient and optionally surfactant-like stabilizers in the solvent phase.

[0010] EP 0807431 (eq. DE 69728206) discloses a process for producing a powder wherein the mean particle size of the substance embedded in the powder is 0.1 to 0.5 µm. Preferably, the embedded substance is a carotenoid.

[0011] The object of the invention is therefore to provide a preparation that achieves or exceeds the stability of formulations containing ethoxyquin without raising the safety concerns that exist for ethoxyquin.

[0012] It was surprisingly found that a powdered vitamin preparation, in which the vitamin essentially has a particle size of less than 0.7 µm and which contains an effective amount of propyl gallate, is ideally suited to solving the given problem. The effective amount of propyl gallate is 3.5 to 9.5% by weight of the total amount of the preparation, with the weight ratio of propyl gallate to vitamin during production ranging from 0.21 to 2.63.

[0013] According to the invention, the effective amount of propyl gallate is understood to be the amount of propyl gallate that is suitable to stabilize the vitamin in the preparation in such a way that after 4 weeks in the stress test at least 20 wt% vitamin, preferably at least 25 wt% and particularly preferably at least 30 wt% of the vitamin content determined at the beginning of the stress test is still retained.

[0014] The stress test for the vitamins is designed so that samples of 100 mg each of the prepared product and 4 g of premix mixture are weighed into glass containers. The premix mixture consists of 50 wt% fine lime (particle size <1000 µm), 20 wt% wheat middlings bran (particle size <1000 µm), 20 wt% 50% choline chloride supported on silica (particle size <1000 µm), and 10 wt% trace element mixture (particle size 100–500 µm). The trace element mixture consists of 46.78 wt% FeSO₄·7H₂O (100–500 µm), 37.43 wt% CuSO₄·5H₂O (100–500 µm), 11.79 wt% ZnO (<500 µm), 3.61 wt% MnO, and 0.39 wt% CoCO₃. After adding all ingredients, the samples are carefully mixed, either mechanically or manually, and these samples (A) are stored in a climate chamber at 40°C and 70% relative humidity for 4 weeks. The vitamin content of the samples is determined before and after storage.The retention (A2 / A1) of the samples, i.e. the vitamin content still contained in the samples, is calculated from the ratio of the contents after (A2) and before storage (A1).

[0015] An effective amount of propyl gallate is understood to be 3.5 to 9.5 wt% propyl gallate, preferably 4 to 9 wt%, particularly preferably 7 to 9 wt% and particularly 8 to 9 wt% propyl gallate based on the total amount of the preparation in the manufacturing step, wherein the sum of the wt% values ​​of the components equals 100 wt% and wherein the wt ratio of propyl gallate to vitamin in the manufacturing process is between 0.21 and 2.63.

[0016] According to the invention, the term manufacturing step includes all process steps a1 to c1 or a2 to c2 or a3 to c3 until the desired process product is obtained.

[0017] It should be explicitly emphasized that in this application all quantity and concentration data and ratios to each other, regardless of whether they relate to the powdered preparation, the solution or dispersion, refer to the quantities used in the manufacturing step, since both propyl gallate and tocopherol or butylhydroxytoluene (BHT) as antioxidants are subject to a continuous degradation process during manufacturing, storage or further processing, and their content in the preparation can therefore only be reliably quantified at the beginning of the manufacturing process, at the time of weighing.

[0018] Within the scope of the present invention, the term dispersion refers to both emulsion and suspension.

[0019] The term "essentially" within the meaning of this invention means or includes in particular that greater than or equal to 80 percent, more preferably greater than or equal to 85 percent, further preferably greater than or equal to 90 percent and most preferably greater than or equal to 95 percent of the particles formed when the powdered vitamin preparations are dissolved have a particle size of less than 0.7µm.

[0020] The particle size is determined using a Malvern Zetasizer Nano ZSP.

[0021] Preferred vitamins according to the invention are vitamins selected from the group consisting of vitamins D, E, K or vitamin Q or their derivatives, for example vitamin E esters such as tocopherol acetate, tocotrienol, vitamin K1, vitamin K2, coenzyme Q10 as well as carotenoids such as β-carotene, canthaxanthin, citranaxanthin, astaxanthin and ester derivatives, zeaxanthin and ester derivatives, lutein and ester derivatives, lycopene, apocarotenic acid and ester derivatives, apocarotenal and mixtures thereof.

[0022] As a coherent phase, the vitamin preparation according to the invention contains at least one colloid selected from the group consisting of plant gums, modified plant gums, gelatin, modified gelatin, modified starch, lignosulfonate, chitosan, carrageenan, casein, caseinate, whey protein, zein, modified cellulose, pectin, modified pectin, plant proteins and modified plant proteins or mixtures thereof.

[0023] According to the invention, plant gums are to be understood as agar, alginic acid, alginate, chicle, dammar, marshmallow extracts, gellan, guar gum, gum arabic, gum from plantain husk, gum from spruce sap, locust bean gum, karaya, konjac flour, mastic, tara gum, tragacanth, xanthan gum.

[0024] According to the invention, gelatin and / or plant gums and / or modified plant gums are preferably used as the coherent phase.

[0025] Surprisingly, it was also found that the addition of tocopherol or BHT to the preparation synergistically supports or enhances the antioxidant protective effect of propyl gallate in the preparation. According to the invention, tocopherol refers to both natural and synthetic tocopherol. Natural tocopherol refers to the naturally occurring α-, β-, γ-, and λ-tocopherols, which are also collectively known as mixed tocopherols and marketed by BASF under the brand name Covi-OX. Synthetic tocopherol, also called DL-α-tocopherol, contains a statistical mixture of the eight α-diastereomers. According to the invention, the addition of natural tocopherol to the preparation is preferred.

[0026] Preparations in which propyl gallate and tocopherol are present in a weight ratio of 9:1 to 1:2 are preferred according to the invention, with a ratio of the two antioxidants to each other of 2:1 to 1:1 being particularly preferred.

[0027] Preparations in which the antioxidant protective effect of propyl gallate is supported or increased by the addition of butylhydroxytoluene (BHT) are preferred according to the invention if they are in a weight ratio of propyl gallate to BHT of 8:1 to 1:4, and particularly preferred if they are in a weight ratio of 2:1 to 1:3 to each other.

[0028] The advantage of the preparation according to the invention lies in particular in its antioxidant effect, which, in comparison with preparations containing ethoxyquin or other conventional antioxidants, is reflected in a comparable, and in particular improved, stability of the vitamins in the preparations according to the invention.

[0029] The comparable or improved stability of the vitamin preparations according to the invention can be demonstrated by means of a stress test. For this purpose, samples of 100 mg each of the prepared formulation and 4 g of premix mixture are weighed into glass containers (50 ml glass vials). The premix consists of 50 wt% fine lime (particle size <1000µm), 20 wt% wheat middlings (particle size <1000µm), 20 wt% 50% silica-supported choline chloride (particle size <1000µm) and 10 wt% trace element mixture (particle size 100-500µm), the trace element mixture being composed of 46.78 wt% FeSO₄·7H₂O (100-500µm), 37.43 wt% CuSO₄·5H₂O (100-500µm), 11.79 wt% ZnO (<500µm), 3.61 wt% MnO and 0.39 wt% CoCO₃. After adding all ingredients, the samples are carefully mixed, either mechanically or by hand, and these samples (A) are stored in a climate chamber at 40°C and 70% humidity for 4 weeks.An identical test is performed with a reference sample (B) of the same composition, but containing the same amount of ethoxyquin instead of propyl gallate. The vitamin content of the samples is determined before and after storage. The retention (A2 / A1) and (B2 / B1) of the samples is calculated from the ratio of the contents after (A2), (B2) and before storage (A1) and (B1). For the preparations according to the invention, a ratio (A2 / A1):(B2 / B1) of at least 0.75 is determined. Preferably, a ratio of at least 1 is obtained for the preparations according to the invention.

[0030] To improve the manufacturing and application properties of the vitamin preparation, it may be advantageous to add further components, such as plasticizers and other excipients and additives. Preferred excipients and additives include emulsifiers, oils, water-soluble salts, and / or release agents.

[0031] To adjust the mechanical stability of the coherent phase of the vitamin preparation, it is advisable to add at least one plasticizer to the colloid, such as polyols, sugars, or sugar alcohols, e.g., sucrose, glucose, glucose syrup, starch hydrolysates, fructose, fructose syrup, lactose, maltose, xylose, arabinose, ribose, trehalose, invert sugar, sorbitol, mannitol, dextrin, maltodextrin, glycerol, polyether glycols, or isomalt. The term isomalt refers to a sugar substitute also marketed under the brand name Palatinit® (Südzucker, Germany). Isomalt is a hydrogenated isomaltulose consisting of approximately equal parts of 6-O-α-D-glucopyranosyl-D-sorbitol and 1-O-α-D-glucopyranosyl-D-mannitol. Preferred plasticizers are sucrose, glucose syrup and lactose.

[0032] Furthermore, emulsifiers can be used as auxiliary and additive substances to stabilize the phases during the production of the vitamin preparation according to the invention, for example mono- and diglycerides, monoglycerol fatty acid esters, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, monoglycerol citric acid esters, sugar fatty acid esters or lecithin. Mono- and diglycerides, monoglycerol fatty acid esters and lecithin are preferred emulsifiers.

[0033] In certain circumstances, it may also be advantageous to additionally use a physiologically approved oil of animal or vegetable origin, such as sesame oil, corn oil, cottonseed oil, soybean oil, peanut oil, sunflower oil, rapeseed oil, coconut oil, palm oil, olive oil, safflower oil, animal fats, lard, tallow, or oils or mixtures modified by hydrogenation, fractionation, or transesterification. Preferred oils are corn oil, sunflower oil, and rapeseed oil. Additionally, metal chelators such as EDTA and citric acid can be added to the vitamin preparation according to the invention.

[0034] Furthermore, water-soluble inorganic and / or organic salts can advantageously be added to the coherent phase of the vitamin preparation, such as sodium ascorbate, potassium ascorbate, calcium ascorbate, sodium erythorbate, potassium erythorbate, sodium benzoate, potassium benzoate, sodium citrate, potassium citrate, alkali phosphates, alkali acetates, alkali phytates, and mixtures thereof. Preferred salts are sodium benzoate and disodium hydrogen phosphate.

[0035] To prevent unwanted clumping and improve flowability, it is advantageous to add poorly water-soluble, fine-particulate anti-caking agents with average particle sizes of less than or equal to 10 µm (x50.3 according to DIN ISO 9276-2:2006-02), which adhere to the surface of the powdered vitamin preparation. The preferred anti-caking agent is selected from the group consisting of silicon dioxide, hydrophobically modified silica, tricalcium phosphate (TCP), calcium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, dicalcium diphosphate, calcium silicate, magnesium silicate, magnesium trisilicate, sodium aluminum silicate, talc, kaolin, calcium stearate, magnesium stearate, starches of various botanical sources, cellulose, or mixtures thereof. Silicon dioxide, tricalcium phosphate (TCP), hydrophobically modified silica, and corn starch are particularly preferred.

[0036] According to the invention, the proportion of auxiliary and additive substances is 0.1 to 60 wt.%, preferably 1 to 50 wt.% and particularly preferably 5 to 30 wt.% based on the total amount of the preparation in the manufacturing step, wherein the sum of the wt. percent values ​​of all components of the preparation equals 100 wt.%.

[0037] A further object of the invention is a method for producing the powdered preparation described above, comprising a1) Dissolving the vitamin in a volatile, water-miscible organic solvent or in a mixture of water and a water-miscible organic solvent at temperatures between 50°C and 200°C, optionally at increased pressure between 20 and 100 bar, within a time of less than 10 seconds; b1) Rapidly mixing the solution obtained according to a1) with an aqueous or colloidally dispersed solution of a colloid at temperatures between 0°C and 80°C, whereby the vitamin is precipitated in colloidally dispersed form; c1) Converting the dispersion formed into a dry powder by separating the main quantity of solvent and subsequent drying.

[0038] The process is carried out in the presence of propyl gallate as an antioxidant, which is added in an effective amount according to the invention. According to the invention, 3.5 to 9.5 wt% propyl gallate, based on the total amount of the preparation, is added to the manufacturing process, wherein the weight ratio of propyl gallate to vitamin during production is between 0.21 and 2.63. The propyl gallate can be added to process steps a1) and / or b1) and / or c1), with the addition of the propyl gallate to process steps a1) and / or b1) being preferred and the addition to process step b1 being most preferred. It is preferred that the pH of the water / organic solvent system be adjusted to a value of 4.5 to a maximum of pH 8.5, since a significant degradation of the propyl gallate is observed at higher pH values. A pH value of 6.5 to a maximum of pH 8.5 is particularly preferred for the system.

[0039] Preferred embodiments with regard to the vitamins can already be found in the explanations given at the beginning.

[0040] The organic solvents used in step a1) of the process according to the invention are primarily water-miscible, thermally stable, volatile solvents containing only carbon, hydrogen, and oxygen, such as alcohols, ethers, esters, ketones, or acetals. It is advantageous to use solvents that are at least 10% water-miscible.

[0041] The solvents must have a boiling point below 200°C and / or fewer than 10 carbon atoms. Methanol, ethanol, n-propanol, isopropanol, 1,2-butanediol-1-methyl ether (1-methoxy-butanol-2), 1,2-propanediol-1-n-propyl ether (1-propoxy-propanol-2), tetrahydrofuran, acetone, or mixtures thereof are particularly preferred.

[0042] The colloids used in the process include plant gums, modified plant gums, gelatin, modified gelatin, starch, modified starch, lignosulfonate, chitosan, carrageenan, casein, caseinate, whey protein, zein, modified cellulose, pectin, modified pectin, plant proteins and modified plant proteins or mixtures thereof.

[0043] According to the invention, plant gums are to be understood as agar, alginic acid, alginate, chicle, dammar, marshmallow extracts, gellan, guar gum, gum arabic, gum from plantain husk, gum from spruce sap, locust bean gum, karaya, konjac flour, mastic, tara gum, tragacanth, xanthan gum.

[0044] According to the invention, gelatin and / or plant gums and / or modified plant gums are preferred.

[0045] To increase the mechanical stability of the dry product, it is advantageous to add a plasticizer to the colloid, such as polyols, sugars, or sugar alcohols, e.g., sucrose, glucose, glucose syrup, starch hydrolysates, fructose, fructose syrup, lactose, maltose, xylose, arabinose, ribose, trehalose, invert sugar, sorbitol, mannitol, dextrin, maltodextrin, glycerol, polyether glycols, or isomalt. The term isomalt refers to a sugar substitute also marketed under the brand name Palatinit® (Südzucker, Germany). Isomalt is a hydrogenated isomaltulose consisting of approximately equal parts of 6-O-α-D-glucopyranosyl-D-sorbitol and 1-O-α-D-glucopyranosyl-D-mannitol. Preferred plasticizers are sucrose, glucose syrup, and lactose.

[0046] The powdered vitamin preparation according to the invention optionally also contains emulsifiers, which in selected cases are preferably used in the production of the dispersion to stabilize the phases during the manufacture of the active ingredient preparation according to the invention. Examples are mono- and diglycerides, monoglycerol fatty acid esters, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, monoglycerol citric acid esters, sugar fatty acid esters, or lecithin. Preferably used emulsifiers are mono- and diglycerides, monoglycerol fatty acid esters, and lecithin.

[0047] In some cases, it may also be advantageous to use an additional physiologically approved oil of animal or vegetable origin, such as sesame oil, corn oil, cottonseed oil, soybean oil, peanut oil, sunflower oil, rapeseed oil, coconut oil, palm oil, olive oil, safflower oil, animal fats, lard, tallow, oils modified by hydrogenation, fractionation, or transesterification, or mixtures thereof. Preferred oils are corn oil, sunflower oil, and rapeseed oil.

[0048] Additionally, it can be advantageous to add metal chelators, such as EDTA and citric acid, to the process.

[0049] The ratio of colloid and plasticizer to carotenoid solution is generally chosen to obtain a dry product containing between 2 and 25 wt% of a vitamin, 10 to 50 wt% of a colloid, 20 to 70 wt% of a plasticizer, and 3.5 to 9.5 wt% propyl gallate, optionally corresponding amounts of tocopherol or BHT, as well as 0.1 to 60 wt% excipients and additives, the sum of the percentages of all components of the preparation being 100 wt%.

[0050] The tocopherol is preferably added to the organic solvent in process step a1), wherein, according to the invention, the ratio of propyl gallate to tocopherol is 9:1 to 1:2, preferably 2:1 to 1:1. When adding tocopherol, natural tocopherol is preferably used according to the invention.

[0051] If BHT is added, according to the invention, the addition preferably takes place at the point of dispersion, i.e., in process step c1, after separation of the solvents. According to the invention, the ratio of propyl gallate to BHT is 8:1 to 1:4, preferably 2:1 to 1:3.

[0052] According to the invention, in step c1) of the process, the dispersion formed is converted into a dry powder by separating the solvent or mixture and subsequent drying. It is advantageous to lower the pH of the dispersion formed with sulfuric acid to a range of 6.5 to 7, particularly to pH 6.8, before separating the solvent or solvent mixture. Subsequently, the conversion into a dry powder can be carried out, among other methods, by spray drying, spray cooling, modified spray drying, freeze-drying, or fluidized bed drying, optionally also in the presence of a separating agent.The preferred separating agent is selected from the group consisting of silicon dioxide, hydrophobically modified silica, tricalcium phosphate (TCP), calcium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, dicalcium diphosphate, calcium silicate, magnesium silicate, magnesium trisilicate, sodium aluminum silicate, talc, kaolin, calcium stearate, magnesium stearate, starches of various botanical sources, cellulose, or mixtures thereof. Silicon dioxide, tricalcium phosphate (TCP), hydrophobically modified silica, and corn starch are particularly preferred.

[0053] Preferably in process step c1), the dispersion formed is concentrated to a solids concentration of about 25 to 50 wt.% by distillative separation of the main amount of the solvent or mixture, and this concentrated dispersion is then converted into a dry powder in a spray dryer.

[0054] Particularly preferred in process step c1) of the process according to the invention is the drying in a spray dryer with an integrated and / or downstream external fluidized bed. A powdery preparation with agglomerated particles is preferably formed.

[0055] An alternative method for producing the preparation according to the invention is to dissolve the vitamin in process step a2) in a volatile, water-immiscible organic solvent at temperatures of 30 to 150°C, optionally under increased pressure, and then to emulsify this solution in process step b2) in an aqueous solution of a colloid. In process step c2), the volatile organic solvent is then removed from the resulting emulsion in a manner known per se, e.g., by distillation, optionally under reduced pressure, yielding a dispersion which can be converted into a dry powder by separating the water and subsequent drying.

[0056] For the purposes of the present invention, the term "an immiscible organic solvent" refers to an organic solvent with a water solubility of less than 10% at normal pressure. Possible solvents include, among others, halogenated aliphatic hydrocarbons such as methylene chloride, chloroform, and carbon tetrachloride; carboxylic acid esters such as dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl formate, methyl, ethyl, or isopropyl acetate; and ethers such as methyl tert-butyl ether and mixtures thereof.

[0057] If the vitamin is already in liquid form due to its low melting point at room temperature (20°C) under normal pressure, or has a melting point below 100°C, or is present as a solution in an oil, a further embodiment of the process allows the vitamin to be emulsified directly or after melting or dissolved in oil (process step a3) in an aqueous solution of a colloid without the use of organic solvents (process step b3) and subsequently converted into a dry powder by separating the water and subsequent drying (c3).

[0058] The addition of propyl gallate is also advantageous in these two alternative processes. Analogous to the descriptions given for processes a1-c1, it is added in a quantity of 3.5 to 9.5 wt% based on the total amount of the preparation, with the weight ratio of propyl gallate to vitamin being between 0.21 and 2.63. In the first-mentioned alternative process, the propyl gallate can be added to the aqueous colloidal phase (i.e., in process step b2), to the vitamin-containing organic solvent (in process step a2), and / or to the dispersion (process step c2). Adding the propyl gallate to the aqueous colloidal phase and / or to the vitamin-containing organic solvent is preferred, and adding it to process step b2 is most preferred.

[0059] If the vitamin is present as an oil, melted, or dissolved in an oil, the propyl gallate is added to the vitamin (process step a3) and / or the aqueous colloidal phase (process step b3) and / or the dispersion (process step c3). Adding the propyl gallate to the aqueous colloidal phase is preferred.

[0060] Regarding pH adjustment, it should be noted that if the propyl gallate is added to the organic solvent or the vitamin in oil form, melted or dissolved in oil, this pH adjustment is carried out in the aqueous colloid phase.

[0061] Suitable oils for dissolving the vitamins are those physiologically approved oils of animal or vegetable origin listed in the application. Preferred oils for this purpose are corn germ oil, sunflower oil, and rapeseed oil.

[0062] The colloids used in the process include plant gums, modified plant gums, gelatin, modified gelatin, starch, modified starch, lignosulfonate, chitosan, carrageenan, casein, caseinate, whey protein, zein, modified cellulose, pectin, modified pectin, plant proteins and modified plant proteins or mixtures thereof.

[0063] To increase the mechanical stability of the vitamin preparation, it is advisable to add a plasticizer to the colloid during the process. Suitable plasticizers include polyols, sugars, or sugar alcohols, such as sucrose, glucose, glucose syrup, starch hydrolysates, fructose, fructose syrup, lactose, maltose, xylose, arabinose, ribose, trehalose, invert sugar, sorbitol, mannitol, dextrin, maltodextrin, glycerol, polyether glycols, or isomalt. The term isomalt refers to a sugar substitute also marketed under the brand name Palatinit® (Südzucker, Germany). Isomalt is a hydrogenated isomaltulose consisting of approximately equal parts of 6-O-α-D-glucopyranosyl-D-sorbitol and 1-O-α-D-glucopyranosyl-D-mannitol. Preferred plasticizers are sucrose, glucose syrup and lactose.

[0064] Furthermore, emulsifiers can be used to stabilize the phases during the production of the active ingredient preparation according to the invention, for example mono- and diglycerides, monoglycerol fatty acid esters, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, monoglycerol citric acid esters, sugar fatty acid esters, or lecithin. Preferably used emulsifiers are mono- and diglycerides, monoglycerol fatty acid esters, and lecithin.

[0065] In some cases, it may also be advantageous to use an additional physiologically approved oil of animal or vegetable origin, such as sesame oil, corn oil, cottonseed oil, soybean oil, peanut oil, sunflower oil, rapeseed oil, coconut oil, palm oil, olive oil, safflower oil, animal fats, lard, tallow, oils modified by hydrogenation, fractionation, or transesterification, or mixtures thereof. Preferred oils are corn oil, sunflower oil, and rapeseed oil.

[0066] Additionally, it can be advantageous to add metal chelators, such as EDTA and citric acid, to the process.

[0067] The ratio of colloid and plasticizer to carotenoid solution is generally chosen in the process such that a dry product is obtained containing between 2 and 25 wt% of a vitamin, 10 to 50 wt% of a colloid, 20 to 70 wt% of a plasticizer and 3.5 to 9.5 wt% propyl gallate, optionally corresponding amounts of tocopherol or BHT, as well as 0.1 to 60 wt% excipients and additives, wherein the sum of the percentages of all components of the preparation equals 100 wt%.

[0068] The tocopherol is preferably added to the organic solvent in process step a), wherein, according to the invention, the ratio of propyl gallate to tocopherol is 9:1 to 1:2, preferably 2:1 to 1:1. When adding tocopherol, natural tocopherol is preferably used according to the invention.

[0069] If BHT is added, according to the invention, the addition preferably takes place at the point of dispersion, i.e., in process step c, after separation of the solvents. According to the invention, the ratio of propyl gallate to BHT is 8:1 to 1:4, preferably 2:1 to 1:3.

[0070] In the process according to the invention, in process step c2), the emulsion formed is converted into a dispersion by separating the organic solvent or mixture and subsequently into a dry powder by separating the water followed by a drying step. It is advantageous to lower the pH of the dispersion formed to a range of 6.5 to 7, particularly to pH 6.8, with sulfuric acid before separating the water. The conversion into a dry powder can then be carried out, among other methods, by spray drying, spray cooling, modified spray drying, freeze-drying, or fluidized bed drying, optionally also in the presence of a coating material. Suitable coating materials include, among others...Corn starch, silica, modified silica, tricalcium phosphate (TCP), calcium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium oxide, magnesium oxide, dicalcium diphosphate, calcium silicate, magnesium silicate, magnesium trisilicate, sodium aluminum silicate, talc, kaolin, calcium stearate, magnesium stearate, starches from various botanical sources, cellulose, or mixtures thereof. Silicon dioxide, tricalcium phosphate (TCP), hydrophobically modified silica, and corn starch are particularly preferred.

[0071] Preferably in process step c2) the dispersion formed is concentrated to a solids concentration of about 25 to 50 wt% by distillative separation of the main amount of the solvent or mixture and then this concentrated dispersion is converted into a dry powder in a spray dryer.

[0072] Particularly preferred in process step c2) of the process according to the invention is the drying in a spray dryer with an integrated and / or downstream external fluidized bed. A powdery preparation with agglomerated particles is preferably formed.

[0073] With the exception of the separation of the organic solvent, which is not necessary in process step c3), the process measures c2) with the aforementioned preferences shall also apply to process step c3).

[0074] The powdered preparation according to the invention is suitable, among other things, as an additive to food preparations, for example for coloring foods such as beverages, as an agent for the manufacture of pharmaceutical and cosmetic preparations, and for the manufacture of food supplement preparations, for example multivitamin preparations for humans and animals.

[0075] Another object of the present invention is the use of the above-described powdered formulation according to the invention as an additive to animal feed, food, food supplements, personal care products or pharmaceuticals.

[0076] The invention is explained by the following examples, which in no way limit the invention: Examples Example 1 (Example 7 from Table 1)

[0077] 30 g of citranaxanthin were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C was maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution was mixed in mixing chamber B with a solution of 32 g of gelatin, 71.4 g of sucrose, and 50 g of glucose syrup in 4000 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, a drug dispersion was obtained, to which 8 g of sunflower oil and 8 g of propyl gallate were added. The propyl gallate was pre-dissolved in 200ml of water and adjusted to pH 7 with NaOH.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 386 nm (standard deviation 142.5, polydispersity index PDI 0.185, D(95): 660 nm) was measured by photon correlation spectroscopy (PCS) (Malvern Zetasizer Nano ZSP). Stability study for citranaxanthin

[0078] The stability of the particles produced in this way was tested in a stress test. For this purpose, samples of 100 mg each of the produced particles and 4 g of premix mixture were weighed into 50 ml glass vials. The premix mixture consisted of 50 wt% fine lime (particle size <1000µm), 20 wt% wheat middlings (particle size <1000µm), 20 wt% 50% silica-supported choline chloride (particle size <1000µm) and 10 wt% trace element mixture (particle size 100-500µm), the trace element mixture consisting of 46.78 wt% FeSO₄·7H₂O (100-500µm), 37.43 wt% CuSO₄·5H₂O (100-500µm), 11.79 wt% ZnO (<500µm), 3.61 wt% MnO and 0.39 wt% CoCO₃. After adding all ingredients, the samples were carefully mixed by hand. These samples were stored in a climate chamber at 40°C and 70% relative humidity for four weeks. The citranaxanthin content of the samples was determined before and after storage.The retention was calculated from the ratio of citranaxanthin contents before and after storage.

[0079] The retention values ​​of the examples are summarized in the following table: Table 1 Active ingredient antioxidant Antioxidant [wt.%] Addition site Antioxidant Active ingredient retention after 4 weeks test [%] 1 Citranaxanthin - 0 Dispersion 7,9 2 Citranaxanthin Ethoxyquin 4 Added as a solid to the dispersion, no pH adjustment required. 52,6 3 Citranaxanthin BHA 4 Molten BHA was stirred into the dispersion with Ultraturrax for 2 minutes at 10,000 rpm, and this was then dispensed 5 times through the microfluidizer at 1,000 bar. 8,2 4 Citranaxanthin Sodium ascorbate 4 Added as a solid to the dispersion, no pH adjustment required. 2,4 5 Citranaxanthin Methylhydroquinone 4 Added as a solid to the dispersion, no pH adjustment required. 10,2 6 Citranaxanthin Vitamin E TPGS 4 Added to the dispersion as a 10% solution without pH adjustment 2,2 7 Citranaxanthin Propyl gallate 4 Dissolved in water pH 7 (4 wt% solution) and added to the dispersion 47,8 8 Citranaxanthin Lauryl gallate 4 Addition to the active ingredient phase, no pH adjustment 15,9 9 Citranaxanthin Green tea extract 4 Dissolved in pH 7 water and added to the dispersion 19,4 10 Citranaxanthin Rosemary acid 4 Added to the dispersion as a 10% solution without pH adjustment 14

[0080] The higher the retention, the better the stability of the particles or their preparation. Example 2 Influence of pH value on propyl gallate activity

[0081] The experiments show that the optimal pH range for adding propyl gallate is between pH 4.5 and pH 8.5 inclusive. Even short residence times at pH values ​​above 8.5 or pre-dissolving the propyl gallate at such pH values ​​were sufficient to significantly reduce its activity. Table 2a. Influence of pH value in the propyl gallate-containing dispersion on the stability of citranaxanthin. Active ingredient Propylene gallate [wt.%] Addition site propylgallate pH value of the sprayed dispersion Retention (Active component after 4 weeks in the test [%] Citranaxanthin 4 Dispersion 4,5 42,2 Citranaxanthin 4 Dispersion 6 39,1 Citranaxanthin 4 Dispersion 7 47,8 Citranaxanthin 4 Dispersion 8 49,4 Citranaxanthin 4 Dispersion 9 28,2 Citranaxanthin 4 Dispersion 10 36,4 Citranaxanthin 4 Dispersion 11 14,7

[0082] This result is also confirmed when the propyl gallate is not added to the vitamin-containing dispersion, but rather to the protective colloid phase (Table 2b). A very good result is obtained when the propyl gallate is added to the protective colloid phase, which is then adjusted with NaOH from a pH of 5 to 7 to a pH of 7, and only raised to 8 to 8.5 with NaOH 15 to 30 minutes before precipitation. Table 2b. Influence of the pH value in the propyl gallate-containing protective colloid phase on the stability of citranaxanthin. Active ingredient Propyl gallate [wt%] Addition site propylgallate pH value of the colloidal phase Active ingredient retention after 4 weeks test [%] Citranaxanthin 4 Colloidal phase Preset to 7; then adjust to pH 8.5 maximum. 44,1 Citranaxanthin 4 Colloidal phase 8.5-9.5 13,4

[0083] The method of adding propyl gallate (as a solid or dissolved in water pH 7) to the vitamin-containing dispersion, however, has no influence on the citranaxanthin stability (Table 2c). Table 2c. Investigation of the method of propyl gallate addition on retention Active ingredient Propyl gallate [wt%] Addition site propylgallate Addition type of the PG Active ingredient retention after 4 weeks test [%] Citranaxanthin 4 Dispersion Dissolved in water pH 7 47,8 Citranaxanthin 4 Dispersion Dissolved in water pH 7 46 Citranaxanthin 4 Dispersion Dissolved in water pH 7 49,4 Citranaxanthin 4 Dispersion Fixed bonus without advance payment 47,2 Citranaxanthin 4 Dispersion Fixed bonus without advance payment 44,9 Example 3:

[0084] Influence of propyl gallate concentration on drug stability a) Increasing the propyl gallate concentration increases the stability of the active ingredient citranaxanthin. However, surprisingly, a sharp decrease in stability is observed when the propyl gallate concentration in the preparation is increased to 10 wt%. A very good stabilizing effect was observed with 4 to 9 wt% propyl gallate in the preparation, preferably 7 to 9 wt%, with an optimum at 8 to 9 wt% (Table 3a). Table 3a. Influence of propyl gallate concentration on the drug stability of citranaxanthin Active ingredient Propyl gallate [wt%] Addition site propylgallate Active ingredient retention after 4 weeks test [%] Citranaxanthin 0 Dispersion 7,9 Citranaxanthin 2 Dispersion 20,2 Citranaxanthin 3 Dispersion 26,7 Citranaxanthin 4 Dispersion 47,8 Citranaxanthin 5 Dispersion 45,7 Citranaxanthin 6 Dispersion 45,9 Citranaxanthin 7 Dispersion 49,5 Citranaxanthin 8 Dispersion 55,9 Citranaxanthin 8,5 Dispersion 51,9 Citranaxanthin 9 Dispersion 57,4 Citranaxanthin 10 Dispersion 19,6

[0085] The positive effect of propyl gallate, such as the optimum concentration, can also be confirmed for other carotenoids (Tables 3b-e).

[0086] b) 30 g of canthaxanthin were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C was maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution was mixed in mixing chamber B with a solution of 32 g of gelatin and 121.4 g of sucrose in 4000 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion was obtained, to which 8 g of sunflower oil and the amounts of propyl gallate specified in Table 3b (wt%) were added. The propyl gallate was pre-dissolved in 200ml of water and adjusted to pH 7 with NaOH.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 290 nm (standard deviation 140, polydispersity index PDI 0.193, D(95): 594 nm) was measured using PCS (Malvern Zetasizer Nano ZSP). Table 3b. Influence of propyl gallate concentration on the drug stability of canthaxanthin Active ingredient Propyl gallate [%] Addition site propylgallate Active ingredient retention after 4 weeks premix test [%] Canthaxanthin 4 Dispersion 61,2 Canthaxanthin 6 Dispersion 77,9 Canthaxanthin 8 Dispersion 83,3 Canthaxanthin 9 Dispersion 82,4 Canthaxanthin 10 Dispersion 69,8 Canthaxanthin 12 Dispersion 47,2

[0087] c) 30 g of C30 ester were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C was maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution was mixed in mixing chamber B with a solution of 32 g of gelatin and 121.4 g of sucrose in 4000 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion was obtained, to which 8 g of sunflower oil and the amounts of propyl gallate specified in Table 3c (wt%) were added. The propyl gallate was pre-dissolved in 200ml of water and adjusted to pH 7 with NaOH.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 280 nm (standard deviation 120, polydispersity index PDI 0.181) was measured using a PCS (Malvern Zetasizer Nano ZSP). Table 3c. Influence of propyl gallate concentration on the drug stability of C30 esters Active ingredient Propyl gallate [wt%] Addition site propylgallate Active ingredient retention after 4 weeks premix test [%] C30 esters 0 Dispersion 6,7 C30 esters 2 Dispersion 13,83 C30 esters 4 Dispersion 42,7 C30 esters 6 Dispersion 57,7 C30 esters 8 Dispersion 64,1 C30 esters 10 Dispersion 58,5 C30 esters 12 Dispersion 54,3

[0088] d) 30 g of β-carotene were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C was maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution was mixed in mixing chamber B with a solution of 32 g of gelatin, 71.4 g of sucrose, and 50 g of glucose syrup in 4000 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion was obtained, to which 8 g of sunflower oil and 8 g of propylene gallate were added. The propyl gallate was pre-dissolved in 200ml of water and adjusted to pH 7 with NaOH.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 262 nm (standard deviation 182, polydispersity index PDI 0.268) was measured using a PCS (Malvern Zetasizer Nano ZSP). Table 3d. Comparison of the stabilities of ethoxyquin and propyl gallate on β-carotene. Active ingredient antioxidant Antioxidant [wt%] Addition site Antioxidant Active ingredient retention after 4 weeks test [%] β-Carotene Ethoxyquin 4 Dispersion 22,2 β-Carotene Propyl gallate 4 Dispersion 30,3

[0089] e) 30 g of C30 ester were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C was maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution was mixed in mixing chamber B with a solution of 32 g of gelatin and 121.4 g of sucrose in 4000 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion was obtained, to which 8 g of sunflower oil and the amounts of propyl gallate specified in wt% in Table 3e were added. The propyl gallate was pre-dissolved in 200ml of water and adjusted to pH 7 with NaOH.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 373 nm (standard deviation 165, polydispersity index PDI 0.203, D(95): 683 nm) was measured using PCS (Malvern Zetasizer Nano ZSP). Table 3e. Comparison of the stabilities of ethoxyquin and propyl gallate on C-30 esters. Active ingredient antioxidant Antioxidant [wt.%] Addition site Antioxidant Active ingredient retention after 4 weeks test [%] C30 ester Ethoxyquin 4 Dispersion 28,6 C30 ester Propyl gallate 4 Dispersion 33,4 C30 ester Propyl gallate 4 Dispersion (pH value adjustment before spraying from pH 8.5 to pH 6.8 with H₂SO₄) 39,8 C30 ester Propyl gallate 6 Dispersion 44,4 C30 ester Propyl gallate 8 Dispersion 43,4 Example 4

[0090] Influence of mixed tocopherol and D,L α-tocopherol on stabilities

[0091] Due to their poor water solubility, tocopherols from both synthetic and natural sources are dissolved in the phase containing the active ingredient. If only natural or synthetic tocopherol is added, both do not differ in their protective effect as antioxidants or in their stabilization of carotenoids or retinoids. Table 4a. Influence of synthetic and natural tocopherols on stability Active ingredient antioxidant Antioxidant [wt.%] Addition site Antioxidant Active ingredient retention after 4 weeks test [%] Canthaxanthin Mixed Tocopherol 4 Active ingredient phase 48,7 Canthaxanthin D,L-α Tocopherol 4 Active ingredient phase 45,7

[0092] The situation is different when propyl gallate is added to the tocopherols as an antioxidant. In this case, the stabilization in the premix test is significantly more pronounced for the mixed tocopherol / propyl gallate combination than for the combination of D,L-alpha tocopherol with propyl gallate (Table 4b). Table 4b. Influence of the combination of synthetic or natural tocopherols with propyl igallocate on the stability of vitamins. Active ingredient antioxidant Antioxidant [wt.%] Active ingredient retention after 4 weeks test Canthaxanthin Mixed tocopherol (in active ingredient phase) + propyl gallate (in protective colloid phase) 4 78,1 4 Canthaxanthin D,L-α Tocopherol (in active ingredient phase) + Propyl gallate (in protective colloid phase) 4 57,2 4 C30 esters Mixed tocopherol (in active ingredient phase) + propyl gallate (in protective colloid phase) 4 57,5 4 C30 esters D,L-α Tocopherol (in active ingredient phase) + Propyl gallate (in protective colloid phase) 4 29,2 4 Citranaxanthin Mixed tocopherol (in active ingredient phase) + propyl gallate (in protective colloid phase) 4 67,5 4 Citranaxanthin D,L-α Tocopherol (in active ingredient phase) + Propyl gallate (in protective colloid phase) 4 21,3 4 Example 5 a) Synergistic effect between propyl gallate and tocopherol

[0093] For the combination of propyl gallate and tocopherol, it was found that the total concentration of antioxidant in the preparation can be reduced without compromising stability. Comparing the stability of the preparation containing 4% propyl gallate (61.2%) with that containing 4% mixed tocopherol (48.7%), propyl gallate is clearly the superior antioxidant for this system. However, when mixing 4% propyl gallate with 4% mixed tocopherol and comparing its stability (80.3%) with that of the preparation containing 8% propyl gallate (83.3%), a synergistic effect is evident that would not have been expected from the individual values. This becomes even more apparent when the concentration of mixed tocopherol is reduced from 4% to 2% while maintaining the same propyl gallate content. This system exhibits a stability of 80.6%, while a system containing 6% propyl gallate only achieves a stability of 71.3%.This clearly demonstrates that only a specific concentration of mixed tocopherol is required to achieve a significant increase in stability with a reduced antioxidant content in the preparation. Table 5a. Combination of mixed tocopherol with propyl gallate. Active ingredient Propyl gallate [wt.%] mixed tocopherol [wt%] Canthaxanthin retention after 4 weeks test [%] Canthaxanthin 4 0 61,2 Canthaxanthin 6 0 71,3 Canthaxanthin 8 0 83,3 Canthaxanthin 0 4 48,7 Canthaxanthin 4 4 80,3 Canthaxanthin 4 2 80,8

[0094] 2 wt% mixed tocopherol in combination with 4 wt% propyl gallate almost reach the stability value of 4 wt% mixed tocopherol in combination with 4 wt% propyl gallate. However, if the proportion of mixed tocopherol is reduced to 1 wt%, again in combination with 4 wt% propyl gallate, the stability values ​​begin to decrease (Table 5b). Table 5b. Combination of mixed tocopherol with propyl gallate. Active ingredient Propyl gallate [wt%] mixed tocopherol [wt%] Canthaxanthin retention after 4 weeks test [%] Canthaxanthin 4 (in protective colloid phase pH7) 2 (in active ingredient phase) 76 Canthaxanthin 4 (in protective colloid phase pH7) 4 (in active ingredient phase) 80,6 Canthaxanthin 4 (in protective colloid phase pH7) 1 (in active ingredient phase) 72,8 Table 5c. Combination of mixed tocopherol with propyl gallate Active ingredient Propyl gallate [wt%] mixed tocopherol [wt%] Canthaxanthin retention after 4 weeks test [%] C30 Ester 4 0 42,7 C30 Ester 0 4 11 C30 Ester 4 4 61,7 Citranaxanthin 4 0 39,1 Citranaxanthin 0 4 10,8 Citranaxanthin 4 4 66,5 Experimental procedure for the addition of 4 wt% propyl gallate and 4 wt% tocopherol

[0095] 30 g of citranaxanthin were suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and 9 g of mixed tocopherol. With the pressure relief valve set to 30 bar, the mixture was continuously blended with 390 g of isopropanol in mixing chamber A. A mixing temperature of 170°C was maintained in mixing chamber A at a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side. After a residence time of 0.3 seconds, the molecularly dispersed solution was blended in mixing chamber B with a pH-adjusted solution of 32 g of gelatin, 71.4 g of sucrose, 50 g of glucose syrup, and 9 g of propyl gallate in 4100 g of water at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion was obtained to which 9g of sunflower oil were added.The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 280 nm (standard deviation 142.5, polydispersity index PDI 0.185) was measured using a PCS (Malvern Zetasizer Nano ZSP). b) Synergistic effect between propyl gallate and BHT

[0096] Table 5d. Combination of BHT with propyl gallate. Active ingredient Propyl gallate [wt%] BHT [wt.%] Citranaxanthin retention after 4 weeks test [%] Citranaxanthin 4 0 61,2 Citranaxanthin 4 4 82,3 Citranaxanthin 0 4 56,1 Citranaxanthin 0 4 65,5 Citranaxanthin 0 4 67,9 Citranaxanthin 4 wt% ethoxyquin 79,3 Experimental procedure for the addition of 4 wt% propyl gallate and 4 wt% butylhydroxytoluene

[0097] 30 g of citranaxanthin are suspended in 240 g of isopropanol together with 1.1 g of ascorbyl palmitate and, with the pressure relief valve set to 30 bar, continuously mixed with 390 g of isopropanol in mixing chamber A. At a dosing rate of 6 l / h on the suspension side and 9 l / h on the solvent side, a mixing temperature of 170°C is maintained in mixing chamber A. After a residence time of 0.3 seconds, the molecularly dispersed solution is mixed in mixing chamber B with a solution of 32 g gelatin, 71.4 g sucrose, 50 g glucose syrup, and 9 g propyl gallate in 4100 g water, adjusted to pH 9, at a flow rate of 100 l / h. After separating the solvent under reduced pressure in a distillation apparatus, an active ingredient dispersion is obtained, to which 9g of sunflower oil and 9g of dissolved BHT are added.

[0098] The dispersion was then converted into a stable, water-soluble dry powder by spray drying. After dissolving in water, a particle size of 290 nm (standard deviation 140, polydispersity index PDI 0.180) was measured using PCS (Malvern Zetasizer Nano ZSP).

Claims

1. A pulverulent vitamin formulation in which the vitamin essentially has a particle size of less than 0.7 µm, wherein the effective amount used is 3.5% to 9.5% by weight of propyl gallate based on the total amount of the formulation, where the weight ratio of propyl gallate to vitamin in the production is between 0.21 and 2.63.

2. The pulverulent vitamin formulation according to claim 1, wherein the vitamin is selected from the group consisting of vitamins A, D, E, K or Q or derivatives thereof, for example vitamin A esters and vitamin E esters such as retinyl acetate or tocopherol acetate, tocotrienol, vitamin K1, vitamin K2, coenzyme Q10 and carotenoids such as β-carotene, canthaxanthin, citranaxanthin, astaxanthin and ester derivatives, zeaxanthin and ester derivatives, lutein and ester derivatives, lycopene, apocarotenic acid and ester derivatives, apocarotenal and mixtures thereof.

3. The pulverulent vitamin formulation according to claim 1 or 2, wherein the formulation comprises butylhydroxytoluene or synthetic and / or natural tocopherol.

4. The pulverulent vitamin formulation according to claim 3, wherein the tocopherol is natural tocopherol.

5. The pulverulent vitamin formulation according to claim 3 or 4, wherein propyl gallate and tocopherol are present in the formulation in a ratio of 9:1 to 1:2.

6. The pulverulent vitamin formulation according to claim 3, wherein propyl gallate and butylhydroxytoluene are present in the formulation in a ratio of 9:1 to 1:2.

7. The pulverulent vitamin formulation according to any of the preceding claims 1 to 6, wherein the quotient therein of active vitamin (A2 / A1) in relation to a comparative sample that comprises, rather than propyl gallate, the same amount of ethoxyquin (B2 / B1), after 4 weeks in a stress test, is at least 0.75, where the proportion of active vitamin is ascertained by weighing 100 mg in each case of the formulation produced and 4 g of a mixture of 50% by weight of fine lime (< 1000 µm), 20% by weight of wheat bran (< 1000 µm), 20% by weight of 50% silica-supported choline chloride (< 1000 µm) and 10% by weight of trace element mixture (100-500 µm), said trace element mixture consisting of 46.78% by weight of FeSO4x7H2O (100-500 µm), 37.43% by weight of CuSO4x5H2O (100-500 µm), 11.79% by weight of ZnO (< 500 µm), 3.61% by weight of MnO and 0.39% by weight of CoCO3 into 50 mL glass containers, mixing the ingredients and storing them in a climate-controlled chamber at 40°C and 70% humidity for 4 weeks, with determination of the vitamin content (A1) and (B1) prior to commencement of the storage and of the vitamin content (A2) and (B2) on conclusion of the storage, calculating the proportion of active vitamin from the quotient A2 / A1 and B2 / B1.

8. A process for producing finely divided, pulverulent vitamin formulations in which the vitamin essentially has a particle size of less than 0.7 µm, comprising the steps of a1) dissolving the vitamins in a volatile, water-miscible organic solvent or in a mixture of water and a water-miscible organic solvent at temperatures between 50°C and 200°C, optionally under elevated pressure, within a period of less than 10 seconds, b1) rapidly mixing the solution obtained after a) with an aqueous or colloidally dispersed solution of a colloid at temperatures between 0°C and 50°C, with precipitation of the vitamin in colloidally dispersed form, c1) converting the dispersion formed to a dry powder by removing the majority of solvent and then drying, or a2) dissolving the vitamins in a volatile, water-immiscible organic solvent at temperatures of 30 to 150°C, optionally under elevated pressure, b2) mixing the solution obtained after a) with an aqueous or colloidally dispersed solution of a colloid, forming an emulsion, c2) removing the organic solvent from the emulsion and converting the suspension / dispersion formed to a dry powder by removing the water and then drying, or a3) converting the vitamin to a liquid by heating above its melting point or dissolving it in an oil or incubating it at room temperature, b3) mixing the melt obtained after a3) with an aqueous or colloidally dispersed solution of a colloid, forming an emulsion, c3) converting the dispersion formed to a dry powder by removing the water and then drying, wherein the process is conducted in the presence of an effective amount of propyl gallate, where the effective amount used is 3.5% to 9.5% by weight of propyl gallate based on the total amount of the formulation and the weight ratio of propyl gallate to vitamin in the production is between 0.21 and 2.63.

9. The process according to claim 8, wherein the propyl gallate is added to the organic solvent-containing vitamin phase and / or to the colloid-containing aqueous solution and / or to the dispersion formed.

10. The process according to claim 8 or 9, wherein the process is conducted at a pH of pH 4.5 to pH 8.5, more preferably at a pH of 6.5 to 8.5.

11. The process according to claim 10, wherein, after addition of the propyl gallate to the colloid-containing aqueous solution, said solution is adjusted to a pH of 6.5 to 8.5.

12. The process according to any of claims 8 to 11, wherein tocopherol is added to the organic vitamin-containing phase.

13. The process according to claim 12, wherein the tocopherol is natural tocopherol.

14. The process according to claim 12 or 13, wherein propyl gallate and tocopherol are used in a ratio of 9:1 to 1:2.

15. The process according to any of claims 8 to 11, wherein butylhydroxytoluene is added to the dispersion formed.

16. The process according to claim 15, wherein propyl gallate and butylhydroxytoluene are used in a ratio of 9:1 to 1:2.

17. The process according to any of claims 8 to 16, wherein the vitamin is selected from the group consisting of vitamins A, D, E, K or Q or derivatives thereof, for example vitamin A esters and vitamin E esters such as retinyl acetate or tocopherol acetate, tocotrienol, vitamin K1, vitamin K2, coenzyme Q10 and carotenoids such as β-carotene, canthaxanthin, citranaxanthin, astaxanthin and ester derivatives, zeaxanthin and ester derivatives, lutein and ester derivatives, lycopene, apocarotenic acid and ester derivatives and apocarotenal.

18. The process according to any of claims 8 to 17, wherein the colloid is selected from the group consisting of plant gums, modified plant gums, gelatin, modified gelatin, modified starch, lignosulfonate, chitosan, carrageenan, casein, caseinate, whey protein, zein, modified cellulose, pectin, modified pectin, plant proteins and modified plant proteins or mixtures thereof.

19. A pulverulent vitamin formulation produced by a process according to any of claims 8 to 18.

20. The use of the pulverulent vitamin formulation according to any of claims 1 to 7 and 19 as additives in animal feeds, foods, food supplements, personal care products or pharmaceutical compositions.