![]() liquid formulations for application in the manufacture of beverages, process for their preparation a
专利摘要:
FORMULATIONS OF CLEAR LIQUID CAROTENOIDS AND CLEAR DRINKS CONTAINING THE SAME. The present invention is directed to a clear liquid formulation comprising: a) at least one carotenoid, and b) at least one modified food starch, and c) at least one saccharide, and d) water, especially for a clear liquid formulation comprising a) of 0.1 to 10% by weight, (preferably from 0.5 to 5.0% by weight, more preferably 0.5 to 3.0% by weight, more preferably 1.0 to 3, 0% by weight) of at least one carotenoid, and b) 20 to 60% by weight (preferably 30 to 50% by weight) of at least one modified food starch, and c) 0.5 to 60% by weight (from preferably 0.5 to 30% by weight, more preferably 0.5 to 20% by weight, more preferably 1.0 to 10% by weight) of at least one saccharide, and d) 35 to 75% by weight. weight (preferably 45 to 65% by weight) of water, all amounts based on the total weight of the liquid formulation, with all amounts adding up to 100% by weight. The present invention is further directed to a process for the manufacture of such liquid formulations, as well as drinks containing them. These drinks are also clear and color stable. 公开号:BR112014024331B1 申请号:R112014024331-0 申请日:2013-03-27 公开日:2020-12-08 发明作者:Gabriela Badolato Bönisch;David Schaffner;Thomas Zwick;André Hunziker 申请人:Dsm Ip Assets B.V; IPC主号:
专利说明:
[01] The present invention relates to formulations of carotenoids, clear, stable, liquid, which - when used in a liquid, especially in a drink such as a soft drink, allows to obtain transparent liquids (even after pasteurization and also at low pH), that is, clear drinks. [02] Carotenoids can be used as dyes. Carotenoids can be obtained from a natural source, by fermentation or by chemical synthesis. [03] The use of carotenoids in beverages is well known. But, to provide liquid aqueous formulations that comprise at least one carotenoid, at least one modified food starch and at least one saccharide, which allows to prepare a stable liquid by pasteurization (especially drinks, such as soft drinks) clear (not opaque, not cloudy) is not yet achieved satisfactorily. [04] Usually, after the pasteurization stage, these drinks become very cloudy, so that they are no longer transparent. For use in many drinks (eg soft drinks) a transparent form is desired for marketing reasons. [05] Therefore, the aim of the present invention was to find a liquid formulation, which does not have the disadvantages mentioned above. Another objective of the present invention is to replace azo dyes in drinks. Thus, in the liquid formulations of the present invention no azo dye such as disclosed in US 2010/0028444 is present. [06] The usual process for the production of drinks (for example, soft drinks) is one in which a carotenoid is emulsified in a first stage. This emulsion is then incorporated into a drink. [07] Surprisingly, it has been found that when a carotenoid is emulsified with certain amounts of at least one modified food starch and certain amounts of at least one saccharide so that the carotenoid is incorporated into a matrix of this modified food starch and the saccharide, a liquid formulation is obtained, which can be used in (aqueous) liquids, which are then transparent and stable by pasteurization (after pasteurization and also at low pH); that is, they are suitable for the manufacture of transparent drinks, especially suitable for the manufacture of clear soft drinks. This is especially surprising, since only these two components of the matrix (modified starch and saccharide) are necessary to achieve the desired result. [08] Therefore, the present invention relates to a clear liquid formulation comprising: a) at least one carotenoid; b) at least one modified food starch; c) at least one saccharide; and d) water. [09] By this means, the carotenoid is incorporated into a matrix of this modified food starch and saccharide. [10] The expression "at least one" means in the case of compound a), for example, that only one carotenoid, but also a mixture of two or more carotenoids, may be present. The same applies in accordance with compound b) and c). [11] The term "clear liquid formulation" in the context of the present invention means that if the liquid formulation according to the present invention is diluted with deionized water so that the carotenoid concentration is 10 ppm, the initial turbidity is ≤ 30 NTU, preferably, the initial turbidity is ≤ 25 NTU, more preferably, the initial turbidity is ≤ 20 NTU, more preferably, the initial turbidity is ≤ 15 NTU. This applies especially if the carotenoid is β-carotene or 8'-apo-β-caroten-8'-al. [12] The term "clear drink" in the context of the present invention means that if the liquid formulation according to the present invention is added to a drink so that the concentration of the carotenoid in the drink is 10 ppm, the turbidity initial turbidity is ≤ 30 NTU, preferably the initial turbidity is ≤ 25 NTU, more preferably, the initial turbidity is ≤ 20 NTU, more preferably, the initial turbidity is ≤ 15 NTU. Advantageously the drink's turbidity after a storage period of 3 months is ≤ 50 NTU. This applies especially if the carotenoid is β-carotene or 8'-apo-β-caroten-8'-al and the drink is a soft drink as prepared according to the example given below. [13] In a preferred embodiment of the present invention, the clear liquid formulation according to the present invention is used in soft drinks, which generally have a pH in the range of 2.5 to 5.0. Such refrigerants containing the clear liquid formulation according to the present invention in a concentration such that the concentration of the carotenoid in the refrigerant is 10 ppm show an initial turbidity of ≤ 30 NTU. Preferably, the initial turbidity is ≤ 25 NTU, more preferably, the initial turbidity is ≤ 20 NTU, more preferably, the initial turbidity is ≤ 15 NTU. Advantageously, the turbidity of the refrigerant after a storage time of 3 months is ≤ 50 NTU. This applies especially if the carotenoid is β-carotene or 8'-apo-β-caroten-8'-al. [14] The present invention relates in particular to a clear liquid formulation, comprising: a) 0.1 to 10% by weight (preferably 0.5 to 5% by weight, more preferably 0.5 to 3.0% by weight, more preferably 1.0 to 3.0% by weight) of at least one carotenoid; b) 20 to 60% by weight (preferably 30 to 50% by weight) of at least one modified food starch; c) 0.5 to 60% by weight (preferably 0.5 to 30% by weight), more preferably, 0.5 to 20% by weight, even more preferably, 0.5 to 10% by weight, more preferably, from 1.0 to 10% by weight) of at least one saccharide; d) 35 to 75% by weight (preferably 45 to 65% by weight) of water; all quantities based on the total weight of the liquid formulation; and where all quantities add up to 100% by weight. [15] Here the carotenoid / s is / are incorporated into a matrix of modified food starch / s and saccharide / s. In a preferred embodiment of the liquid formulation according to the present invention, only compounds a) to d), especially in the amounts given above, are present. This means that the present invention preferably relates to a clear liquid formulation consisting of: a) at least one carotenoid; b) at least one modified food starch; c) at least one saccharide; and d) water. [16] Thus, preferably, no other compounds are present. Such compounds that are not present are the following: - Acacia gum; Gum arabic; also modified as described in WO 2008/110225; - Gum Ghatti as, for example, described in WO 2009/147158; - Proteins, such as gelatine (fish, pigs, bovine gelatine); - Vegetable proteins; - Milk proteins; - Ligninsulfonate; - Conjugates of vegetable gums and modified food starch, especially those as disclosed in WO 2011/039336; - Sodium lauryl sulphate and other sodium alkyl sulphates. [17] This applies, preferably, to all liquid formulations of the present invention. DETAILED DESCRIPTION [18] The liquid formulation according to the present invention is now described in more detail. Compound a) - Carotenoid [19] The term "carotenoid" as used herein comprises a natural or synthetic carotene or a structurally related polyene compound, which can be used as a functional health ingredient or food coloring, such as α-carotene, β- carotene, 8'-apo-β-carotene (8'-apo-β-carotene-8'-al), alkyl esters of 8'-apo-β-carotenoic acid, such as the ethyl ester of (ethyl-8 ' -apo-β-caroten-8'-oate), canthaxanthin, astaxanthin, (di) astaxanthin esters, such as astaxanthin disuccinate, lycopene, lutein, zeaxanthin or crocetin, or mixtures thereof. Preferred carotenoids are β-carotene, 8'-apo-β-carotenal and mixtures thereof, especially β-carotene or -8'-β-apo-carotenal alone, more preferably 8'-apo-β-carotenal. [20] Therefore, a preferred embodiment of the present invention relates to a liquid formulation, as described above, in which at least one carotenoid is chosen from the group consisting of α-carotene, β-carotene, 8'-apo -β-carotene (8'-apo-β-carotene-8'-al), alkyl esters of 8'-apo-β-carotenoic acid, such as the ethyl ester of (ethyl-8'-apo-β-caroten -8'-oato), canthaxanthin, astaxanthin, (di) astaxanthin esters, such as astaxanthin disuccinate, lycopene, lutein, zeaxanthin and crocetin, preferably β-carotene and 8'-apo-β-carotenal, with more preferably, 8'-apo-β-carotenal. Compound b) - "Modified Food Starch" [21] A modified food starch is a food starch that has been chemically modified by methods known to have a chemical structure that provides it with a hydrophilic and a lipophilic portion. Preferably, the modified food starch has a long hydrocarbon chain as part of its structure (preferably, C5-C18). [22] At least one modified food starch is preferably used to make a liquid formulation of the present invention, but it is possible to use a mixture of two or more types of modified food starches in a liquid formulation. [23] Starches are hydrophilic and therefore have no emulsification capacity. However, modified food starches are made from starches replaced by known chemical methods, with hydrophobic moieties. For example, starch can be treated with cyclic dicarboxylic acid anhydrides, such as succinic anhydrides substituted with a hydrocarbon chain (see Amidos OB Wurzburg (editor), "Modified Starches: Properties and Uses, CRC Press, Inc. Boca Raton, Florida, 1986, and later editions.) A particularly preferred modified food starch of the present invention has the following formula (I) where St is a starch, R is an alkylene radical and R 'is a hydrophobic group. Preferably, R is a lower alkylene radical, such as dimethylene or trimethylene. R 'may be an alkyl or alkenyl group, preferably having 5 to 18 carbon atoms. A preferred compound of formula (I) is an "OSA-starch" (sodium starch octenyl succinate). The degree of substitution, that is, the number of hydroxyl groups esterified with the number of free non-esterified hydroxyl groups generally varies in a range of 0.1% to 10%, preferably in a range of 0.5% and 4 %, more preferably, in a range of 3% to 4%. [24] The term "OSA-starch" denotes any starch (from any natural source, such as maize, waxy maize corn, waxy corn, wheat, tapioca and potatoes or synthesized) that has been treated with octenyl succinic anhydride (OSA ). The degree of substitution, that is, the number of hydroxyl groups esterified with OSA for the number of free non-esterified hydroxyl groups generally varies within a range of 0.1% to 10%, preferably within a range of 0.5% and 4%, more preferably, in a range of 3% to 4%. OSA-starches are also known under the term "modified food starch". [25] The term "OSA-starches" also includes such starches that are commercially available, for example, from National Starch under the trade names HiCap 100, Capsul (octenylbutanedioate amylodextrin), Capsul HS, Purity Gum 2000, Clear Gum Co03, UNI -PURE, HYLON VII; National Starch and Roquette Freres, respectively; CereStar under the trade name C * EmCap or Tate & Lyle. [26] In a preferred embodiment of the present invention, a commercially available modified food starch, such as HiCap 100 (from National Starch) and ClearGum Co03 (from Roquette Freres) is used. It is especially advantageous if such a starch or an OSA starch in general is further improved according to a process as disclosed in WO 2007/090614, especially according to a procedure as described in examples 28, 35 and / or 36 of WO 2007/090614. [27] Thus, in another improved embodiment of the present invention, such a commercially available starch was centrifuged as an aqueous solution or suspension prior to use. Centrifugation can be carried out at 1000 to 20000 g, depending on the dry matter content of the modified polysaccharide in the aqueous solution or suspension. If the dry matter content of modified polysaccharide in the aqueous solution or suspension is high, the force applied to centrifugation is also high. For example, for an aqueous solution or suspension with a modified dry weight content of 30% by weight, a centrifugation force of 12,000 g may be adequate to achieve the desired separation. [28] Centrifugation can be performed at dry matter levels in the range of 0.1-60% by weight, preferably in the range of 10-50% by weight, more preferably in the range of 15-40% in weight, at temperatures in the range of 2-99 ° C, preferably in the range of 10-75 ° C, more preferably, in the range of 40-60 ° C. Compound c) - "Saccharide" [29] The term "saccharide" in the context of the present invention includes mono, di, oligosaccharides and polysaccharides, as well as any mixtures thereof [30] Examples of monosaccharides are fructose, glucose (= dextrose), mannose, galactose, sorbose, as well as any mixtures thereof. [31] Preferred monosaccharides are glucose and fructose, as well as any mixture of them. [32] The term "glucose" in the context of the present invention not only means the pure substance, but also a glucose syrup with an ED ≥ 90 This also applies to the other monosaccharides. [33] The term "dextrose equivalent" (DE) indicates the degree of hydrolysis, and is a measure of the amount of reducing sugar calculated as D-glucose based on dry weight; the scale is based on native starch which has an ED of about 0 and glucose with an ED of 100. [34] Examples of disaccharides are sucrose, isomaltose, lactose, maltose and nigerose, as well as any mixture thereof. [35] An example of an oligosaccharide is maltodextrin. [36] An example of a polysaccharide is dextrin. [37] An example of a mixture of mono and disaccharides is inverted sugar (glucose + fructose + sucrose). [38] Mixtures of mono and polysaccharides, for example, are commercially available under the trade name TI Glucidex 47 (from Roquette Freres), Dextrose ST Monohydrate (from Roquette Freres), Sirodex 331 (from Tate & Lyle) and Glucamyl F 452 (by Tate & Lyle). [39] In one embodiment of the present invention, saccharide c) is a mixture of a glucose syrup with an ED of 95 and a glucose syrup with an ED of 47 at a weight ratio of 1: 1. [40] Such mixtures of glucose syrups are preferred examples of saccharide c). Quantities of compounds a) to d) Amount of compound a) [41] A liquid formulation according to the present invention preferably comprises 0.1 to 10% by weight, more preferably 0.5 to 5.0% by weight, even more preferably 0.5 to 3.0% by weight, more preferably 1.0 to 3.0% by weight, of at least one carotenoid based on the total weight of the liquid formulation, where the most preferred carotenoids are β-carotene and 8'- apo-β-carotenal. Amount of compound b) [42] A liquid formulation according to the present invention preferably comprises 20 to 60% by weight, more preferably 30 to 50% by weight, of modified food starch based on the total weight of the liquid formulation, in that the commercially available preferred modified food starch is OSA-starch, which is preferably further improved by separating the insoluble parts, as disclosed, for example, in WO 2007/090614 (examples of centrifugation and microfiltration). If a mixture of two or more modified food starches is present the total amount is also in the ranges as indicated above. Amount of compound c) [43] A liquid formulation according to the present invention preferably comprises 0.5 to 60% by weight, more preferably 0.5 to 30% by weight, even more preferably 0.5 to 20% by weight and 0.5 to 20% by weight, more preferably 1.0 to 10% by weight, of a saccharide based on the total weight of the liquid formulation. [44] In the case of saccharide c) is a mixture of glucose and a glucose syrup with an ED ≤ 60 the amount of glucose is preferably in the range 0 to 30% by weight, more preferably in the range from 0 to 10% by weight, based on the total weight of the liquid formulation, and / or (and preferably,) the amount of glucose syrup with an ED ≤ 60 is preferably in the range of 1 to 30% in weight, more preferably, in the range of 0.5 to 10% by weight, based on the total weight of the liquid formulation. Amount of compound d) [45] A liquid formulation according to the present invention preferably comprises 35 to 75% by weight, more preferably 45 to 65% by weight, of water, based on the total weight of the liquid formulation. [46] In the most preferred embodiment of the present invention, all preferred amounts for each of compounds a) to d) are carried out. [47] If, however, the additional compounds are presented as for example compounds e) and / or compounds f) and / or compounds g) as described below, the amount of water is reduced accordingly. [48] In preferred embodiments of the liquid formulations of the present invention, no other compound than compounds a) to g) is present, wherein compounds e), f) and g) are, independently of each other, optional. This means that the preferred embodiments of liquid formulations of the present invention are as follows: - a liquid formulation consisting only of compounds a) to d); - a liquid formulation consisting only of compounds a) to e); - a liquid formulation consists only of compounds a) to f); - a liquid formulation consisting only of compounds a) to g). [49] In other preferred embodiments of the liquid formulations of the present invention, none of the following compounds are present: - Gum arabic; Acacia gum; Gum Ghatti; - Any protein, such as gelatin (fish, pork, beef); - Any vegetable protein; - Any milk protein; - Ligninsulfonate; - Plant gum and modified food starch conjugates as, for example, disclosed in WO 2011/039336 - No emulsifier (sodium lauryl sulfate). [50] In addition, such clear liquid formulations are preferred according to the present invention, in which the modified food starch b) has been centrifuged prior to use. [51] Advantageously the particle size of the internal phase of the liquid formulation is evident in the range of 100 to 250 nm, preferably in the range of 110 to 210 nm, more preferably, in the range of 130 to 190 nm. Additional compounds of the liquid formulation according to the present invention [52] Suitably, the liquid formulations of the present invention (additional) contain one or more additional compounds selected from the group consisting of water-soluble antioxidants (compounds e)), fat-soluble antioxidants (compounds f)) and MCT ( medium chain triglycerides) (compound g)). Compound e): Water-soluble antioxidants [53] Suitable water-soluble antioxidants are known to the person skilled in the art. Preferably, water-soluble antioxidants are used which are approved for use in food and beverages. [54] Preferred water-soluble antioxidants are selected from the group consisting of citric acid, citric acid salts, ascorbic acid, ascorbic acid salts (preferably sodium ascorbate), as well as any mixture thereof. [55] Preferred water-soluble antioxidants are ascorbic acid, sodium ascorbate and citric acid. [56] Preferably, the total amount of water-soluble antioxidants, relative to the liquid formulation according to the present invention is in the range of 0.1 to 4.0% by weight, more preferably, is in the range of 0 , 1 to 2.0% by weight, based on the total weight of the liquid formulation. Compound f): Fat-soluble antioxidants [57] Suitable fat-soluble antioxidants are known to the person skilled in the art. Preferably, fat-soluble antioxidants are used which are approved for application in food and drinks [58] Preferred fat-soluble antioxidants are selected from the group consisting of tocopherols, for example, dl-α-tocopherol (for example, synthetic tocopherol), d-α-tocopherol (for example, natural tocopherol), β- or γ- tocopherol, or a mixture of two or more of these. [59] The most preferred fat-soluble antioxidant is dl-α-tocopherol. [60] Preferably, the total amount of fat-soluble antioxidants in relation to the liquid formulation according to the present invention is in the range of 0 to 1.5% by weight, more preferably, in the range of 0.01 to 1.0% by weight, more preferably, is in the range of 0.1 to 0.5% by weight, based on the total weight of the liquid formulation. Compound g) [61] A preferred liquid formulation according to the present invention contains MCT (medium chain triglycerides), preferably in an amount ranging from 0 to 5.0% by weight, more preferably, in an amount ranging from 0.01 to 1.0% by weight, more preferably, in an amount in the range of 0.5 to 1.0% by weight, based on the total weight of the liquid formulation. [62] Another preferred liquid formulation according to the present invention contains only a small amount of oil. The term "oil" in the context of the present invention does not include MCT. [63] Preferably, the liquid formulation according to the present invention contains only an amount of oil of a maximum of 3% by weight, more preferably an amount of oil of a maximum of 2% by weight, even more preferably, an amount of oil of at most 1% by weight, based on the total weight of the liquid formulation. In the most preferred embodiment of the present invention, the liquid formulation does not contain any oil except MCT. [64] The term "oil" in the context of the present invention encompasses glycerol and any triglycerides, such as oils or vegetable fats such as corn oil, sunflower oil, soybean oil, safflower oil, rapeseed oil, peanut oil, palm oil, palm kernel oil, cottonseed oil, olive oil or coconut oil, except that the term "oil" does not include MCT. [65] Oils can be of any origin. They can be natural, modified or synthetic. If the oils are natural they can be vegetable or animal oils. The term "oil" in the context of the present invention, therefore, also encompasses canola oil, sesame oil, hazelnut oil, almond oil, cashew oil, macadamia oil, mongongo nut oil, pracaxi oil, nuts, pine nut oil, pistachio oil, Inchi weed oil (Plukenetia volubilis), walnut oil or polyunsaturated fatty acids (= "PUFAs") (for example, arachidonic acid, eicosapentaenoic acid, docosahexaenoic acid and γ -linolenic acid), as well as PUFA triglycerides and PUFA esters, for example, PUFA ethyl esters. [66] Clear, liquid formulations according to the present invention are used for the enrichment, fortification and / or coloring of drinks; said use being a further aspect of the invention. In addition, the invention relates to drinks containing such clear, liquid formulations. Especially, suitable drinks are soft drinks. Such refrigerants generally have a pH in the range of 2.5 to 5.0, preferably a pH in the range of 3.0 to 3.5. Process for the manufacture of the compositions according to the invention [67] The present invention is also related to a process for the manufacture of a clear liquid formulation according to the present invention comprising the following steps: i) forming a solution of carotenoid a) in an organic solvent, optionally adding an antioxidant fat-soluble f) and / or MCT (compound g)); ii) dissolving the modified food starch b), and the saccharide c) and, optionally, the water-soluble antioxidant e), in water to obtain a matrix; iii) emulsifying the solution obtained in step i) to the matrix obtained in step ii) to obtain an emulsion, iv) removing the organic solvent from the emulsion obtained in step iii). [68] The steps are described in more detail below. Step i) [69] An oil can also be added, but it is preferable not to add one, except MCT. If, however, it is added, the amount is chosen so that the final amount of the oil in the resulting liquid formulation, after having performed all the steps is as described above. [70] The same applies to the other compounds: the amounts of carotenoid a), the soluble antioxidant soluble f) and the MCT are chosen so that the final amounts of these compounds in relation to the resulting liquid formulation, after having performed all steps are as described above. [71] The amount of the solvent and the dissolution temperature are chosen to dissolve the carotenoid a), the fat-soluble antioxidant f), the MCT, if present, and the oil, if present, completely. Normally, it is necessary to heat the suspension obtained by mixing all the compounds present in this step to obtain a solution. Preferably, the temperature to which the suspension is heated is in the range of 40 to 90 ° C, more preferably, the temperature is in the range of 40 to 86 ° C. After obtaining the solution, it is usually kept at the temperature it was before being heated. Step ii) [72] Preferably, this step is carried out at a temperature in the range of 50 to 70 ° C, more preferably, at a temperature in the range of 55 ° C to 67 ° C, even more preferably, at a temperature of about 60 ° C. [73] The matrix obtained after performing step ii) is then preferably kept at a temperature in the range of 25 to 65 ° C, more preferably at a temperature in the range of 29 ° C to 66 ° C, even more preferably, at a temperature in the range of 29 to 56 ° C. [74] Depending on the temperature step ii) has been performed, it may be necessary to cool the matrix to such a temperature or to heat it to such a temperature. In most cases, the temperature at which step ii) is carried out and the temperature at which the matrix is maintained are chosen in such a way that a cooling phase is necessary. Step iii) [75] Preferably, this step is carried out at a mixing temperature in the range of 25 to 100 ° C, more preferably, at a temperature of the mixture in the range of 30 to 80 ° C, even more preferably, at a temperature mixing in the range of 35 ° C to 75 ° C to obtain an emulsion. [76] Emulsification can be achieved by means of a rotor-stator device or a high pressure homogenizer, or both. Other devices known to the person skilled in the art can also be used. [77] If the rotor-stator device and / or a high pressure homogenizer is used, a pressure drop in the range of 100 to 1000 bar (10 to 100 MPa), more preferably, in the range of 150 to 300 bar (15 to 30 MPa) is preferably applied. Step iv) [78] The organic solvent can, for example, be removed using a cascade of thin film evaporator (preferred). Other methods known to the person skilled in the art are also applicable. [79] The resulting clear liquid formulations, after having performed steps i) to iv) are advantageously used as such an option (preferred). They can, however, also be dried by any method known to the person skilled in the art, for example, spray drying, spray drying in conjunction with fluidized bed granulation or by a powder capture technique, in which the droplets of emulsified sprays are captured in an absorbent bed, such as starch, and subsequently dried. These dry (powdered) forms can then also be added to drinks, especially soft drinks. [80] Other aspects of the invention are drinks that contain a liquid formulation as described above. [81] Drinks in which the liquid formulations of the present invention can be used as a colorant or a functional ingredient can be carbonated drinks, for example, flavored Seltzer waters, soft drinks or mineral drinks, as well as non-carbonated drinks, for example, waters flavored, fruit juices, fruit punch and concentrated forms of these drinks. They can be based on natural fruit or vegetable juices or artificial flavors. Alcoholic beverages are also included. In addition, beverages containing sugar, diet drinks with non-caloric and artificial sweeteners are also included. Especially preferred are soft drinks, preferably with a pH in the range of 2.5 to 5.0, more preferably, with a pH in the range of 3.0 to 3.5. [82] The final concentration of carotenoid, especially β-carotene and 8'-apo-β-carotenal, which is added by means of the liquid formulations of the present invention for drinks can be from 0.1 to 50 ppm, in particular, from 1 to 30 ppm, more preferably from 3 to 20 ppm, based on the total weight of the drink and, depending on the particular drink, to be colored or fortified and to the desired degree of coloring or reinforcement. [83] For the coloring or reinforcement of a drink, a liquid formulation of the present invention can be used according to methods known per se for the application of emulsions or suspensions. Advantageously, the drinks containing the liquid formulations according to the present invention are also clear and / or stable in color, preferably they are clear and stable in color. "Stable color", in the context of the present invention, means that the DE * of color difference between the initial color and the color after a storage period of 3 months must be less than 10 (DE * <10). An ED * <10 means that the color difference cannot be seen with the naked eye, that is, without the use of a device such as a colorimeter. [84] The present invention relates to formulations of clear, stable liquid carotenoids, which - when used in a liquid, especially in a drink such as a soft drink, allows the obtaining of transparent liquids (even after pasteurization and also to low pH), that is, clear drinks. [85] The following non-limiting examples further illustrate the invention. EXAMPLE Examples 1-16: Manufacture of clear liquid formulations according to the present invention [86] The examples were performed according to the following general procedure, with the amounts of the compounds (carotenoid, modified food starch, saccharide, antioxidants, water) and the process parameters as given in detail in Table 1-1 and Table 1 -two. The solvent used was an organic solvent selected from the group consisting of dimethyl carbonate, ethyl formate, ethyl acetate, isopropyl acetate, methyl tert-butyl ether and methylene chloride. The amount of the solvent and the dissolution temperature were chosen in order to dissolve the carotenoid and the fat-soluble antioxidant and the MCT, if present, completely. [87] The modified modified starch used was centrifuged before use. General procedure [88] The amount of carotenoids and fat-soluble antioxidant, as shown in Table 1-1 or Table 1-2, is dispersed in the amount of organic solvent, as shown in Table 1-1 or Table 1-2, respectively . [89] The matrix phase consisting of modified food starch (= OSA starch), saccharide and water-soluble antioxidant, as shown in Table 1-1 / Table 1-2 is dissolved in an amount of water, as as shown in Table 1-1 / table 1-2 at 60 ° C. After dissolution, the matrix is cooled to temperature, as shown in Table 1- 1 / Table 1-2. [90] The suspension is heated to temperature, as shown in Table 1-1 / Table 1-2 to dissolve the entire amount of carotenoid. This solution is then kept at the temperature indicated in Table 1-1 / Table 1-2 in a holding vessel. The emulsification process consists of two stages and is carried out under pressure. [91] Both phases are continuously fed to a rotor stator device in which the solution is emulsified in the matrix phase. The rotation speed is 5000 rpm (revolutions per minute) and the temperature of the mixture is as indicated in Table 1-1 / Table 1-2. The next step involves a second micronization step and consists of a sapphire hole. The orifice diameter is as indicated in Table 1- 1 / Table 1-2 and the pressure drop applied over the orifice is as indicated in Table 1-1 / Table 1-2 in temperature, as shown in Table 1-1 / Table 1-2. 10 theoretical pass numbers are applied over this hole. [92] The organic solvent is then removed from the emulsion by means of a cascade of fine evaporator. [93] The results of the examples are summarized below. The particle size of the internal phase was measured by Photo Staining Spectroscopy (Beckman Coulter N4 Plus Submicron Particle Sizer). Example 1 [94] The final product has an 8'-apo-β-carotenal content of 2.8%, E1 / 1 = 1625, an internal phase particle size of 198 nm and a turbidity of 26.7 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 25.6 NTU (measured in a refrigerant as prepared according to the instructions below). Example 2 [95] The final product has an 8% -apos; β-carotenal content of 1.9%, E1 / 1 = 1460, the internal phase particle size of 159 nm and a turbidity of 10.9 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) 11.0 NTU (measured in a refrigerant as prepared according to the instructions below). Example 3 [96] The final product has an 8'-apo-β-carotenal content of 1.7%, E1 / 1 = 1531, the internal phase particle size of 155 nm and a turbidity of 7.6 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 8.4 NTU (measured in a refrigerant as prepared according to the instructions below). Example 4 [97] The final product has an 8'-apo-β-carotenal content of 3.9%, E1 / 1 = 1587, the internal phase particle size of 158 nm and a turbidity of 10.9 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 12.8 NTU (measured in a refrigerant as prepared according to the instructions below). Example 5 [98] The final product has a β-carotene content of 1.9%, E1 / 1 = 1513, the internal phase particle size of 118 nm and a turbidity of 11.9 NTU (measured in water with a concentration β-carotene of 10 ppm) and 14.0 NTU (measured in a refrigerant as prepared according to the instructions below). Example 6 [99] In this example also a lipophilic liquid, that is, 18 g of MCT (medium chain triglycerides), was added. [100] The final product has a β-carotene content of 2.2%, E1 / 1 = 1473, the particle size of the internal phase of 146 nm and a turbidity of 14.9 NTU (measured in water with a concentration β-carotene of 10 ppm) and 21.2 NTU (measured in a refrigerant as prepared according to the instructions below). Example 7 [101] In this example, a fat-soluble antioxidant was used, but as an auxiliary agent, 4 g of MCT (medium chain triglycerides), a lipophilic liquid. [102] The final product has a β-carotene content of 1.9%, E1 / 1 = 1423, the internal phase particle size of 136 nm and a turbidity of 22.7 NTU (measured in water with a concentration β-carotene of 10 ppm) and 31.3 NTU (measured in a refrigerant as prepared according to the instructions below). Example 8 [103] The final product has a 2.8% 8'-apo-β-carotenal content, E1 / 1 = 1371, the internal phase particle size of 183 nm and a turbidity of 12.1 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 13.4 NTU (measured in a refrigerant as prepared according to the instructions below). Example 9 [104] The final product has a content of 2.1% 8'-apo-β-carotenal, E1 / 1 = 1519, the internal phase particle size of 160 nm and a turbidity of 9.9 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 7.5 NTU (measured in a refrigerant as prepared according to the instructions below). Example 10 [105] The final product has a β-carotene content of 2.4%, E1 / 1 = 1470, the internal phase particle size of 138 nm and a turbidity of 8.1 NTU (measured in water with a concentration of β-carotene of 10 ppm) and 9.0 NTU (measured in a refrigerant as prepared according to the instructions below). Example 11 [106] The final product has a 2.5% β-carotene content, E1 / 1 = 1322, the internal phase particle size of 207 nm and a turbidity of 19.4 NTU (measured in water with a concentration of β-carotene of 10 ppm) and 18.8 NTU (measured in a refrigerant as prepared according to the instructions below). Example 12 [107] The final product has a 2.0% β-carotene content, E1 / 1 = 1288, the internal phase particle size of 193 nm and a turbidity of 11.1 NTU (measured in water with a concentration of β-carotene of 10 ppm) and 1 1.7 NTU (measured in a refrigerant as prepared according to the instructions below). Example 13 [108] The final product has a β-carotene content of 2.1%, E1 / 1 = 1326, the particle size of the internal phase of 184 nm and a turbidity of 10.3 NTU (measured in water with a concentration β-carotene of 10 ppm) and 10.5 NTU (measured in a refrigerant as prepared according to the instructions below). Example 14 [109] The final product has a content of 2.1% 8'-apo-β-carotenal, E1 / 1 = 1446, the internal phase particle size of 183 nm and a turbidity of 15.1 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 17.7 NTU (measured in a refrigerant as prepared according to the instructions below). Example 15 [110] In this example, a fat-soluble antioxidant was used, but as an auxiliary agent, 5 g of MCT (medium chain triglycerides), a lipophilic liquid. [111] The final product has a content of 8'-apo-β-carotenal of 3.0%, E1 / 1 = 1505, the particle size of the internal phase of 157 nm and a turbidity of 16.4 NTU (measured in water with a concentration of 8'-apo-β-carotenal of 10 ppm) and 10.4 NTU (measured in a refrigerant as prepared according to the instructions below). Example 16 [112] The final product has a β-carotene content of 2.1%, E1 / 1 = 1314, the internal phase particle size of 145 nm and a turbidity of 34.1 NTU (measured in water with a concentration β-carotene of 10 ppm) and 32.8 NTU (measured in a refrigerant as prepared according to the instructions below). Application tests with liquid formulations according to Examples 1-7 [113] Liquid formulations according to examples 1-7 were applied to soft drinks with a concentration of carotenoid, ie 8'-apo-β-carotenal or β-carotene, of 10 ppm. The purpose of these tests was to evaluate the performance of these samples for their application in clear drinks. For clear drinks, the liquid formulation must provide very low turbidity values (as low as possible) and the turbidity must be stable over the storage time. In addition, the liquid formulation has to provide good color stability and good appearance performance (no ring formation, no surface particles and no sedimentation). Application tests with liquid formulations according to Examples 8-16 [114] Liquid formulations according to Examples 8-16 were also applied to soft drinks with a concentration of carotenoid, i.e. 8'-apo-βcarotenal or β-carotene, 10 ppm. Here, however, only the initial turbidity was measured. The results are as indicated above Preparation of soft drinks [115] Soft drinks had the following composition: * From each liquid formulation according to Examples 1 to 7 and 8 to 16 a stock solution was prepared, whereby the liquid formulation was diluted with water so that the stock solution had a concentration of carotenoid (8 ' -apo-β-carotenal or β-carotene) of 0.1% by weight (= 10 ppm). [116] The soft drinks were prepared as follows. [117] Potassium sorbate 1) was dissolved in water, the other ingredients 2) were added, one after the other, while the mixture was stirred gently. Then, the resulting soda syrup was diluted with water in an amount that results in 1000 ml of soda. The pH of the soft drinks was in the range of 3.0 to 3.5. [118] The soft drinks were filled in glass bottles and the bottles were closed with a metallic lid. Some of these bottles were pasteurized and others were not. The bottles were stored at room temperature (temperature in the range of 18 to 27 ° C) and under exposure to light. Color and turbidity measurements were performed immediately after the preparation of drinks (time = 0), as well as after a storage period of 2 weeks, 30 days, 60 days and 90 days. Pasteurization [119] The pasteurization of the soft drinks was carried out in a water bath. A reference bottle containing water and a thermometer was used to control the temperature during pasteurization. The bottles (glass / 200 ml bottles) were placed in a hot water bath with a temperature of 85 ° C. When the bottle temperature reached 80 ° C, the bottles remained in the water bath for an additional 1 minute. After pasteurization, the bottles were quickly cooled (using cold water) to room temperature. Color measurements [120] Color measurements for food applications are performed with a colorimeter (Hunter Lab Ultra Scan Pro) which, unlike a spectrophotometer, can express color values according to the psychophysical perception of color by the human eye. [121] Color measurements are carried out using the guidelines of the CIE (International Commission of Eclairage). Quantities can be expressed either as plane coordinates L * a * b * with L * being the brightness measurement value, with a * being the value on the red-green axis and with b * being the value on the yellow-blue axis. Instrument settings: • Color scale: CIE L * a * b * / L * C * h *; • Definition of light source: equivalent to daylight D65; • Geometry: diffuse / 8 °; • Wavelengths: scanning from 350 to 1050 nm in 5 nm optical resolution; • Diameter of sample measurement area: 19 mm (large); • Calibration mode: Transmission / white tile. [122] The DE * color difference is calculated using the following equation: where L is yellow; = lightness, a = red value, and b = AL value * = Lx * -L0 *; 0 = initial value; x = measurement time; Aa * = ax * -a0 *; 0 = initial value; x = measurement time; Ab * = bx * -b0 *; 0 = initial value; x = measurement time. [123] To obtain good color stability, DE * must be less than 10 (DE * <10); this means that the color difference cannot be seen with the naked eye, that is, without the use of a device such as a colorimeter. Turbidity measurements [124] Suspended solids (or particles) are responsible for the cloudy appearance of drinks containing juice. This cloudy appearance can be assessed by measurements of turbidity. Turbidity depends on the light scattering properties of such particles: their size, shape and refractive index. [125] In this work, turbidity measurements were performed using a turbidimeter (Hach 2100N IS®, USA) and the amounts of turbidity were given in NTU (nephelometric turbidity units). The neophelometer measures the light scattered over a 90 ° sample from the path of the incident light (Fig. 1). [126] Fig. 1 illustrates the nephelometric turbidity measurement principle; Instrument definitions: Light source: 860 ± 10 nm LED. Results for soft drinks containing 8'-apo-β-carotenal (liquid formulations according to examples 1-4) a) Color difference [127] The results for measuring the color difference during storage are shown in Figs. 2 and 3. [128] Fig. 2 shows the color difference (DE *) in unpasteurized soft drinks over a storage period of up to 3 months. X-axis: Storage time in days; y-axis: Color difference (DE *) (dimensionless); 1 = refrigerant containing a liquid formulation according to example 1; 2 = refrigerant containing a liquid formulation according to example 2; 3 = refrigerant containing a liquid formulation according to example 3; 4 = refrigerant containing a liquid formulation according to example 4. [129] All samples were very good (DE * <10) and with similar color stability. [130] Fig. 3 shows the color difference (DE *) in pasteurized refrigerants for up to 3 months. x-axis: Storage time in days; y-axis: Color difference (DE *) (dimensionless); 1 = refrigerant containing a liquid formulation according to example 1; 2 = refrigerant containing a liquid formulation according to example 2; 3 = refrigerant containing a liquid formulation according to example 3; 4 = refrigerant containing a liquid formulation according to example 4. [131] All samples were very good (DE * <10) and with similar color stability. b) Turbidity [132] The results regarding the measurement of turbidity during storage are shown in Figs. 4 and 5. [133] Fig. 4 shows the turbidity of non-pasteurized refrigerants for up to 3 months. X-axis: storage time in days; y-axis: turbidity in NTU; 1 = refrigerant containing a liquid formulation according to example 1; 2 = refrigerant containing a liquid formulation according to example 2; 3 = refrigerant containing a liquid formulation according to example 3; 4 = refrigerant containing a liquid formulation according to example 4 [134] Turbidity increased slightly over time, but in an acceptable range for clear drinks. [135] Fig. 5 shows the turbidity of pasteurized refrigerants for up to 3 months. X-axis: storage time in days; y-axis: turbidity in TU; 1 = refrigerant containing a liquid formulation according to example 1; 2 = refrigerant containing a liquid formulation according to example 2; 3 = refrigerant containing a liquid formulation according to example 3; 4 = refrigerant containing a liquid formulation according to example 4 [136] Turbidity increased slightly over time, but in an acceptable range for clear drinks. c) Physical appearance [137] After 3 months of storage, non-pasteurized and pasteurized soft drinks were visually evaluated for their physical appearance. In this way, samples were examined visually if they show a ring on the neck of the bottle, if there are particles on the surface and if they present white sediments. The following scheme of notes was applied: Ring on the neck of the bottle: 6 = no ring 5 = ring almost imperceptible 4 = recognizable ring 3 = recognizable light thin ring 2 = recognizable strong ring 1 = recognizable wide ring Particles on the surface: 6 = no particles 5 = 1 to 10 particles 4 = more than 10 particles 3 = not more countable 2 = half of the covered surface 1 = more than half of the covered surface White sediment: 6 = no sediment 5 = light matte reflection 4 = sediment fine matte 3 = matte sediments 2 = strong matte sediments 1 = very strong matte sediments [138] For good performance, the score must be ≥ 3. [139] Table 2 shows the results obtained for the evaluation of the appearance of unpasteurized soft drinks. [140] All samples performed very well with respect to their appearance attributes. [141] Table 3 shows the results obtained for the evaluation of the appearance of pasteurized soft drinks. [142] Also in pasteurized beverages, all samples performed very well with respect to their appearance attributes. Results for soft drinks containing β-carotene (liquid formulations according to examples 5-7) a) Color difference [143] The results for measuring the color difference during storage are shown in Figs. 6 and 7. [144] Fig. 6 shows the color difference (DE *) in unpasteurized soft drinks over a storage period of up to 3 months. X-axis: Storage time in days; y-axis: Color difference (DE *) (dimensionless); 5 = refrigerant containing a liquid formulation according to example 5; 6 = refrigerant containing a liquid formulation according to example 6; 7 = refrigerant containing a liquid formulation according to example 7; [145] All samples showed good color stability (DE * <10). [146] Fig. 7 shows the color difference (DE *) in pasteurized refrigerants for up to 3 months. X-axis: Storage time in days; y-axis: Color difference (DE *) (dimensionless); 5 = refrigerant containing a liquid formulation according to example 5; 6 = refrigerant containing a liquid formulation according to example 6; 7 = refrigerant containing a liquid formulation according to example 7; [147] All samples showed good color stability (DE * <10). b) Turbidity [148] The results relating to the measurement of turbidity during storage are shown in Figs. 8 and 9. [149] Fig. 8 shows the turbidity of non-pasteurized refrigerants for up to 3 months. X-axis: storage time in days; y-axis: turbidity in NTU; 5 = refrigerant containing a liquid formulation according to example 5; 6 = refrigerant containing a liquid formulation according to example 6; 7 = refrigerant containing a liquid formulation according to example 7; [150] Turbidity increased slightly over time, but in an acceptable range for clear drinks. [151] Fig. 9 shows the turbidity of pasteurized refrigerants for up to 3 months. X-axis: storage time in days; y-axis: turbidity in NTU; 5 = refrigerant containing a liquid formulation according to example 5; 6 = refrigerant containing a liquid formulation according to example 6; 7 = refrigerant containing a liquid formulation according to example 7; [152] Turbidity increased slightly over time, but in an acceptable range for clear drinks. c) Physical appearance [153] After 3 months of storage, non-pasteurized and pasteurized soft drinks were visually evaluated for their physical appearance. In this way, the samples were examined visually if they have a ring on the neck of the bottle, if there are particles on the surface and if have white sediments. The following scheme of notes was applied: Ring on the neck of the bottle: 6 = no ring 5 = ring almost imperceptible 4 = recognizable ring 3 = recognizable light thin ring 2 = recognizable strong ring 1 = recognizable wide ring Particles on the surface: 6 = no particles 5 = 1 to 10 particles 4 = more than 10 particles 3 = no more countable 2 = half of the covered surface 1 = more than half of the covered surface White sediment: 6 = no sediment 5 = light matte reflection 4 = sediment fine matte 3 = matte sediments 2 = strong matte sediments 1 = very strong matte sediments [154] For good performance, the score must be> 3. [155] Table 4 shows the results obtained for the evaluation of the appearance of unpasteurized soft drinks. [156] All samples performed very well with respect to their appearance attributes. [157] Table 5 shows the results obtained for the evaluation of the appearance of pasteurized soft drinks. [158] All samples performed very well with respect to their appearance attributes. [159] Table 1-1: In this table A = 8'-apo-β-carotenal, B = β-carotene, D = dl-α-tocopherol; H = HiCap 100; MCT = Medium chain triglycerides; S = sodium ascorbate. [160] Table 1-2: In this table A = 8'-apo-β-carotenal, B = β-carotene, D = dl-α-tocopherol; H = HiCap 100;
权利要求:
Claims (11) [0001] 1. Liquid formulation for application in the manufacture of beverages, characterized by the fact that it consists of: a) at least one carotenoid; b) at least one modified food starch; c) at least one saccharide; d) water; e) at least one water-soluble antioxidant; and f) at least one fat-soluble antioxidant, in which the liquid formulation, if diluted with deionized water so that the concentration of the carotenoid is 10 ppm, the initial turbidity will be ≤ 30 NTU. [0002] 2. Liquid formulation according to claim 1, characterized by the fact that carotenoid a) is incorporated in a matrix of modified food starch b), and saccharide c). [0003] 3. Liquid formulation according to claim 1 or 2, characterized by the fact that saccharide c) is present in an amount in the range of 0.5 to 60% by weight, preferably in an amount in the range of 0 , 5 to 30% by weight, more preferably, in an amount in the range of 0.5 to 20% by weight, even more preferably, in an amount in the range of 0.5 to 10% by weight, based on the total weight of the liquid formulation and / or in which carotenoid a) is present in an amount in the range of 0.1 to 10% by weight, preferably in an amount in the range of 0.5 to 5.0% by weight , more preferably, in an amount ranging from 0.5 to 3.0% by weight, even more preferably, in an amount ranging from 1.0 to 3.0% by weight, based on the total weight of the liquid formulation and / or in which the modified starch b) is present in an amount in the range of 20 to 60% by weight, more preferably, in an amount in the range of 30 to 50% by weight, based on the total weight of liquid formulation a, and / or where water d) is present in an amount in the range of 35 to 75% by weight, more preferably, in an amount in the range of 45 to 65% by weight, based on the total weight of the formulation liquid. [0004] 4. Liquid formulation according to any one of claims 1 to 3, characterized by the fact that carotenoid a) is selected from the group consisting of α-carotene, β-carotene, 8'-apo-β-caroten -8'-al, esters of 8'-apo-β-carotenoic acids, canthaxanthin, astaxanthin, (di) esters of astaxanthin, lycopene, lutein, zeaxanthin or crocetin, and mixtures thereof, preferably where the carotenoid is β-carotene or 8'-apo-β-caroten-8'-al, or a mixture thereof. [0005] 5. Liquid formulation for application in the manufacture of beverages, characterized by the fact that it comprises: a) 0.1 to 10% by weight (preferably from 0.5 to 5% by weight, more preferably from 0.5 to 3.0% by weight, more preferably 1.0 to 3.0% by weight) of at least one carotenoid; b) 20 to 60% by weight (preferably 30 to 50% by weight) of at least one modified food starch; c) 0.5 to 60% by weight (preferably 0.5 to 30% by weight, more preferably from 0.5 to 20% by weight, even more preferably from 0.5 to 10% by weight weight, more preferably, from 1.0 to 10% by weight) of at least one saccharide; d) 35 to 75% by weight (preferably 45 to 65% by weight) of water; all quantities based on the total weight of the liquid formulation; and wherein all quantities add up to 100% by weight; where the liquid formulation, if diluted with deionized water so that the concentration of the carotenoid is 10 ppm, the initial turbidity will be ≤ 30 NTU. [0006] 6. Liquid formulation according to any one of claims 1 to 5, characterized by the fact that it further comprises e) water-soluble antioxidants selected from the group consisting of ascorbic acid, sodium ascorbate, citric acid and any mixture of and / or where the total amount of water-soluble antioxidants e) is in the range of 0.1 to 4.0% by weight, preferably in the range of 0.1 to 2.0% by weight, based on in the total weight of the liquid formulation. [0007] Liquid formulation according to any one of claims 1 to 6, characterized by the fact that it further comprises f) fat-soluble antioxidants, additionally comprising dl-α-tocopherol and / or in which the total amount of the fat-soluble antioxidants f) is in the range of 0 to 1.5% by weight, preferably in the range of 0.01 to 1.0% by weight, more preferably in the range of 0.1 to 0.5% by weight, based on the total weight of the liquid formulation. [0008] Liquid formulation according to any one of claims 1 to 7, characterized in that the modified food starch b) has been centrifuged before use. [0009] Liquid formulation according to any one of claims 1 to 8, characterized in that the particle size of the internal phase is in the range of 100 to 250 nm, preferably in the range of 110 to 210 nm, with more preferably in the range of 130 to 190 nm. [0010] 10. Process for the manufacture of a liquid formulation for application in the manufacture of beverages, as defined in any one of claims 1 to 9, characterized by the fact that it comprises the following steps: i) forming a solution of carotenoid a) in a solvent organic, adding a fat-soluble antioxidant f); ii) dissolve the modified food starch b), and the saccharide c) and the water-soluble antioxidant e) in water to obtain a matrix; iii) emulsify the solution obtained in step i) to the matrix obtained in step ii) to obtain an emulsion, iv) remove the organic solvent from the emulsion obtained in step iii) in which the liquid formulation, if diluted with deionized water so that the carotenoid concentration is 10 ppm, the initial turbidity will be ≤ 30 NTU. [0011] 11. Drink, characterized by the fact that it comprises at least one liquid formulation as defined in any one of claims 1 to 9.
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公开号 | 公开日 EP2830443A1|2015-02-04| JP2015512632A|2015-04-30| CN104244735A|2014-12-24| KR20140144722A|2014-12-19| JP2018108088A|2018-07-12| EA034301B1|2020-01-27| IN2014DN08254A|2015-05-15| EA201401068A1|2015-04-30| WO2013144221A1|2013-10-03| CO7121347A2|2014-11-20| US20150064318A1|2015-03-05| JP6492335B2|2019-04-03| EP2644041A1|2013-10-02| CN104244735B|2018-04-03|
引用文献:
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申请号 | 申请日 | 专利标题 EP12162549.5A|EP2644041A1|2012-03-30|2012-03-30|Clear liquid carotenoid formulations and clear beverages containing them| EP12162549.5|2012-03-30| PCT/EP2013/056553|WO2013144221A1|2012-03-30|2013-03-27|Clear liquid carotenoid formulations and clear beverages containing them| 相关专利
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Process for preparation of 7 alpha-carboxyl 9, 11-epoxy steroids and intermediates useful therein an
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