Preparation in the form of a powder containing at least one carotenoid, at least one modified starch, and sucrose

Abstract

A preparation in the form of a powder containing: (a) at least one carotenoid, (b) at least one modified starch, and (c) sucrose; wherein the at least one carotenoid is present in the powder in an amount of 1 to 25% by weight, based on the weight of the powder; and wherein the at least one carotenoid and the sucrose are present in the powder in a ratio by weight of 1:2 to 1:80.

Claims

1. A preparation in powder form comprising: (a) β-carotene, (b) at least one modified starch, and (c) sucrose; wherein the at least one carotenoid is present in the powder in an amount of 1 to 25% by weight, based on the weight of the powder; and wherein the at least one carotenoid and the sucrose are present in the powder in a ratio by weight of 1:2 to 1:80 and said at least one modified starch is present in an amount from 5 to 30% by weight, based on the powder, and wherein the β-carotene has a degree of crystallinity in the range from 90 to 99% determined by X-ray diffraction.

2. The preparation according to claim 1, which further comprises component d) from 0.1 to 10% by weight of an antioxidant based on the total mass of the preparation in powder form.

3. A composition comprising: an additive amount of the preparation according to claim 1; and a component selected from the group consisting of human foods, dietary supplements, animal feeds, pharmaceutical preparations and cosmetic preparations.

4. The preparation according to claim 1, wherein the β-carotene is present in the powder in an amount of 2 to 20% by weight, based on the weight of the powder; and wherein the α-carotene and the sucrose are present in the powder in a ratio by weight of 1:3 to 1:40.

5. The preparation according to claim 1, wherein the β-carotene is present in the powder in an amount of 5 to 15% by weight, based on the weight of the powder; and wherein the β-carotene and the sucrose are present in the powder in a ratio by weight of 1:4 to 1:18.

6. A preparation in powder form comprising: (a) at least one carotenoid, (b) at least one modified starch, and (c) sucrose; wherein the at least one carotenoid is present in the powder in an amount of 1 to 25% by weight, based on the weight of the powder; and wherein the at least one carotenoid and the sucrose are present in the powder in a ratio by weight of 1:2 to 1:80 and said at least one modified starch is present in an amount from 5 to 30% by weight, based on the powder, and wherein the carotenoid has a degree of crystallinity in the range from 90 to 99% determined by X-ray diffraction, wherein the at least one carotenoid is present in the powder in an amount of 8 to 13% by weight, based on the weight of the powder; and wherein the at least one carotenoid and the sucrose are present in the powder in a ratio by weight of 1:5 to 1:10.

7. The preparation according to claim 1, wherein the β-carotene is present in the powder in an amount of 8 to 13% by weight, based on the weight of the powder; and wherein the β-carotene and the sucrose are present in the powder in a ratio by weight of 1:5 to 1:10.

8. The preparation according to claim 1, wherein said at least one modified starch is present in an amount from 8 to 26% by weight.

9. The preparation according to claim 7, which further comprises component d) from 1 to 2% by weight of an antioxidant based on the total mass of the preparation in powder form and said at least one modified starch is present in an amount from 8 to 26% by weight.

10. The preparation according to claim 1, which further comprises component d) from 1 to 2% by weight of an antioxidant based on the total mass of the preparation in powder form.

11. A composition comprising: an additive amount of the preparation according to claim 9; and a component selected from the group consisting of human foods, dietary supplements, animal feeds, pharmaceutical preparations and cosmetic preparations.

12. The preparation according to claim 9, wherein the β-carotene and the sucrose are present in the powder in a ratio by weight of 1:6.6 to 1:7.2.

13. The preparation according to claim 12, wherein the β-carotene has a degree of crystallinity in the range from 95 to 99% determined by X-ray diffraction.

14. The preparation according to claim 1, wherein the preparation is prepared by the process which consists essentially of: i) suspending said β-carotene a) in an aqueous molecular dispersed or colloidal solution of said at least one modified starch b), ii) grinding the suspended particles, iii) mixing the ground suspension with said sucrose c), and iv) subsequently converting the suspension optionally in the presence of a coating material into a dry powder, where the suspension comprises after process step iii), based on the dry matter of the aqueous suspension, from 1 to 25% by weight of β-carotene, and the ratio of β-carotene a) to sucrose c) is from 1:2 to 1:80 by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) Suitable carotenoids in the context of the present invention include α- and β-carotene, lycopene, lutein, astaxanthin, zeaxanthin, capsanthin, capsorubin, α- and β-cryptoxanthin, citranaxanthin, canthaxanthin, bixin, β-apo-4-carotenal. β-apo-8-carotenal and β-apo-8-carotenoic esters or mixtures thereof. Preferred carotenoids are β-carotene, β-cryptoxanthin, lycopene, lutein, astaxanthin, zeaxanthin and canthaxanthin. Particularly preferred carotenoids are those selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof, with very particular preference for β-carotene, lycopene and lutein or mixtures thereof, especially β-carotene.

(2) Modified starch means chemically or enzymatically produced starch transformation products. Possibilities in this connection are starch ethers, starch esters or starch phosphates. Preferred representatives of this group are starch esters, especially octenylsuccinate starch, e.g. Capsul® (sodium octenylsuccinate starch) supplied by National Starch.

(3) The content of modified starch is, based on the dry matter of the aqueous suspension, from 5 to 50% by weight, preferably from 5 to 30% by weight, particularly preferably from 8 to 26% by weight.

(4) A preferred embodiment of the aqueous suspension of the invention comprises at least one carotenoid as nanoparticles.

(5) Nanoparticles mean particles having an average particle size D[4.3] determined by Fraunhofer diffraction of from 0.02 to 100 μm, preferably from 0.05 to 50 μm, particularly preferably from 0.05 to 20 μm, very particularly preferably from 0.05 to 5 μm, especially from 0.05 to 1.0 μm. The term D[4.3] refers to the volume-weighted average diameter (see handbook for Malvern Mastersizer S, Malvern Instruments Ltd., UK).

(6) A further preferred embodiment of the aqueous suspension of the invention comprises as component d) in addition from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, particularly preferably from 0.8 to 2.5% by weight, very particularly preferably from 1 to 2% by weight, of one or more antioxidants, based on the dry matter of the aqueous suspension. Examples of suitable antioxidants include α-tocopherol, t-butyl-hydroxytoluene, t-butylhydroxyanisole, citric acid, sodium citrate, ascorbic acid, sodium ascorbate, ascorbyl palmitate or ethoxyquin or mixtures thereof. Preferred antioxidants are α-tocopherol, ascorbic acid, sodium ascorbate, ascorbyl palmitate or mixtures thereof.

(7) To increase the stability of the active substance against microbial degradation, it may be expedient to add preservatives such as, for example, methyl-4-hydroxybenzoate, propyl 4-hydroxybenzoate, sorbic acid or benzoic acid or salts thereof to the preparation.

(8) The aqueous suspension of the invention comprises a solids content of from 10 to 80% by weight, preferably from 30 to 75% by weight, particularly preferably from 50 to 75% by weight.

(9) Besides the modified starch, the aqueous suspensions of the invention and the preparations in powder form produced therefrom may comprise further protective colloids. Examples of suitable substances for this purpose are the following:

(10) bovine, porcine or fish gelatin, especially acid- or base-degraded gelatin having Bloom numbers in the range from 0 to 250, very particularly preferably gelatin A 100, A 200, A 240, B 100 and B 200, and low molecular weight, enzymatically degraded gelatin types having Bloom number 0 and molecular weights of from 15 000 to 25 000 D, such as, for example, Collagel A and Gelitasol P (from Stoess, Eberbach), and mixtures of these gelatin types.

(11) Starch, dextrin, pectin, gum arabic, ligninsulfonates, chitosan, polystyrene sulfonate, alginates, casein, caseinate, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose or mixtures of these protective colloids.

(12) Vegetable proteins such as soybean, rice and/or wheat proteins, it being possible for these vegetable proteins to be in partially degraded or in undegraded form.

(13) The invention also relates to a process for producing an aqueous carotenoid-containing suspension, which comprises

(14) i) suspending one or more carotenoids a) in an aqueous molecular dispersed or colloidal solution of at least one modified starch b) and sucrose c), and

(15) ii) comminuting the suspended particles,

(16) where the suspension comprises after process step ii), based on the dry matter of the aqueous suspension, from 1 to 25% by weight of at least one carotenoid, and the ratio of carotenoid a) to sucrose c) is from 1:2 to 1:80 by weight.

(17) The invention likewise relates to a process for producing an aqueous carotenoid-containing suspension, which comprises

(18) i) suspending one or more carotenoids a) in an aqueous molecular dispersed or colloidal solution of modified starch b),

(19) ii) comminuting the suspended particles, and

(20) iii) mixing the fine-particle suspension with sucrose c),

(21) where the suspension comprises after process step iii), based on the dry matter of the aqueous suspension, from 1 to 25% by weight of at least one carotenoid, and the ratio of carotenoid a) to sucrose c) is from 1:2 to 1:80 by weight.

(22) The active substance [one or more carotenoids] is in this case suspended before the comminution, preferably in crystalline form, in the abovementioned protective colloid solution.

(23) The comminution of the suspended particles can take place in the context of the present invention inter alia with the aid of a high-pressure homogenizer or preferably by grinding.

(24) The grinding in process steps ii) can moreover take place in a manner known per se, e.g. using a ball mill. This entails, depending on the type of mill used, grinding until the particles have an average particle size D[4.3] determined by Fraunhofer diffraction of from 0.02 to 100 μm, preferably from 0.05 to 50 μm, particularly preferably from 0.05 to 20 μm, very particularly preferably from 0.05 to 5 μm, especially from 0.05 to 1.0 μm. The term D[4.3] refers to the volume-weighted average diameter (see handbook for Malvern Mastersizer S, Malvern Instruments Ltd., UK).

(25) Further details on the grinding and the apparatuses used therefore are to be found inter alia in Ullmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000, Electronic Release, Size Reduction, Chapter 3.6.: Wet Grinding, and in EP-A-0 498 824.

(26) The degree of crystallinity of the ground carotenoid particles after the grinding process is greater than 80%, preferably greater than 90%, particularly preferably greater than 98%.

(27) Preferred embodiments in relation to components a) to c) and the amounts thereof employed are to be found in the explanations made at the outset.

(28) A particularly preferred embodiment of the process of the invention for producing an aqueous carotenoid-containing suspension comprises

(29) i) suspending one or more carotenoids a) selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof in an aqueous molecular or colloidal solution of sodium octenylsuccinate starch b),

(30) ii) grinding the suspended particles, and

(31) iii) mixing the ground suspension with sucrose c),

(32) where the suspension comprises after process step iii), based on the dry matter of the aqueous suspension, from 8 to 13% by weight of at least one carotenoid a) selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof, and the ratio of carotenoid a) to sucrose c) is from 1:5 to 1:10 by weight.

(33) The invention further relates to a process for producing a preparation in powder form, comprising at least one carotenoid, which comprises

(34) i) suspending one or more carotenoids a) in an aqueous molecular dispersed or colloidal solution of at least one modified starch b) and sucrose c),

(35) ii) grinding the suspended particles, and

(36) iii) subsequently converting the suspension if appropriate in the presence of a coating material into a dry powder,

(37) where the suspension comprises in process step ii), based on the dry matter of the aqueous suspension, from 1 to 25% by weight of at least one carotenoid, and the ratio of carotenoid a) to sucrose c) is from 1:2 to 1:80 by weight.

(38) The invention additionally relates to a process for producing a preparation in powder form, comprising at least one carotenoid, which comprises

(39) i) suspending one or more carotenoids a) in an aqueous molecular dispersed or colloidal solution of modified starch b),

(40) ii) grinding the suspended particles,

(41) iii) mixing the ground suspension with sucrose c), and

(42) iv) subsequently converting the suspension if appropriate in the presence of a coating material into a dry powder,

(43) where the suspension comprises after process step iii), based on the dry matter of the aqueous suspension, from 1 to 25% by weight of at least one carotenoid, and the ratio of carotenoid a) to sucrose c) is from 1:2 to 1:80 by weight.

(44) Conversion into a dry powder can moreover take place inter alia by spray drying, spray cooling, modified spray drying, freeze drying or drying in a fluidized bed, if appropriate also in the presence of a coating material. Suitable coating agents include corn starch, silica or else tricalcium phosphate.

(45) Further details of spray cooling and of modified spray drying are to be found in WO 91/06292 (pages 5 to 8).

(46) Preferred embodiments in relation to components a) to c) and the amounts thereof employed are to be found in the explanations made at the outset.

(47) A particularly preferred embodiment of the process of the invention for producing a carotenoid-containing preparation in powder form comprises

(48) i) suspending one or more carotenoids a) selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof in an aqueous molecular or colloidal solution of sodium octenylsuccinate starch b),

(49) ii) grinding the suspended particles, and

(50) iii) mixing the ground suspension with sucrose c), and

(51) iv) subsequently converting the suspension if appropriate in the presence of a coating material into a dry powder,

(52) where the suspension comprises after process step iii), based on the dry matter of the aqueous suspension, from 8 to 13% by weight of at least one carotenoid a) selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof, and the ratio of carotenoid a) to sucrose c) is from 1:5 to 1:10 by weight.

(53) The invention also relates to a preparation in powder form, comprising

(54) a) at least one carotenoid, preferably selected from the group consisting of β-carotene, lutein, zeaxanthin and lycopene or mixtures thereof,

(55) b) at least one modified starch, preferably from 5 to 50% by weight, particularly preferably from 5 to 30% by weight, very particularly preferably from 8 to 26% by weight, of octenylsuccinate starch and

(56) c) sucrose,

(57) wherein the preparation comprises, based on the total mass of the preparation in powder form, from 1 to 25% by weight, preferably from 2 to 20% by weight, particularly preferably from 5 to 15% by weight, very particularly preferably from 8 to 13% by weight, of at least one carotenoid, and the ratio of carotenoid a) to sucrose c) is from 1:2 to 1:80, preferably from 1:3 to 1:40, particularly preferably from 1:4 to 1:18, very particularly preferably from 1:5 to 1:10, by weight.

(58) A further preferred embodiment of the preparation of the invention in powder form comprises as component d) in addition from 0.1 to 10% by weight, preferably from 0.5 to 5% by weight, particularly preferably from 0.8 to 2.5% by weight, very particularly preferably from 1 to 2% by weight, of one or more antioxidants, based on the total mass of the preparation in powder form.

(59) Examples of suitable antioxidants include α-tocopherol, t-butyl-hydroxytoluene, t-butylhydroxyanisole, citric acid, sodium citrate, ascorbic acid, sodium ascorbate, ascorbyl palmitate or ethoxyquin or mixtures thereof. Preferred antioxidants are α-tocopherol, ascorbic acid, sodium ascorbate, ascorbyl palmitate or mixtures thereof.

(60) The degree of crystallinity of the carotenoid particles present in the preparation in powder form—which can be determined for example by x-ray diffraction measurements—is greater than 70%, preferably in the range from 80 to 100%, particularly preferably in the range from 90 to 99%, very particularly preferably in the range from 95 to 99%.

(61) The dry powders of the invention are notable inter alia for being redispersible without difficulty in aqueous systems to achieve a uniform fine distribution of the active substance in the particle size range below 1 μm.

(62) Use of the inventive combination of sucrose and modified starch as formulation aids has the advantage, compared with other sugars, for example lactose or glucose, that the carotenoid formulations produced therewith show particularly high storage stability inter alia in multivitamin tablets (see table).

(63) The carotenoid formulations of the invention are suitable inter alia as additive to human food preparations, for example for coloring human foods such as beverages, as compositions for producing pharmaceutical and cosmetic preparations, and for producing dietary supplement products, for example multivitamin products in the human and animal sector.

(64) Implementation of the process of the invention is explained in detail in the following examples.

Example 1

Production of a β-Carotene Dry Powder with Use of a Mixture of Sucrose and Octenylsuccinate Starch (β-Carotene:Sucrose=1:6.6)

(65) a.

(66) 1160 g of water were heated to 55° C. under protective gas, and 26.5 g of sodium ascorbate, 23.5 g of ascorbic acid and 500 g of octenylsuccinate starch (Capsul®, from National Starch) were added. 500 g of crystalline β-carotene were suspended in this solution by stirring. The suspension was then ground with the aid of a ball mill until the β-carotene particles had an average particle size D[4.3] measured by Fraunhofer diffraction of about 0.6 μm.

(67) b.

(68) 2630 g of this ground suspension were transferred under protective gas into a second reactor and, while stirring, 3207 g of sucrose and a further 469 g of octenylsuccinate starch were added. The temperature of this mixture was kept at 55° C. Addition of 30 g of α-tocopherol was followed by the suspension being homogenized and subsequently being converted by modified spray drying into a dry powder in the form of beadlets. The β-carotene content in the beadlets was 11.1% and had an E1/1.sup.1) of 91. .sup.1) The E1/1 defines in this connection the specific extinction of a 1% strength aqueous dispersion of a 10% by weight dry powder in a 1 cm cuvette at the absorption maximum.

Example 2

Production of β-Carotene Dry Powder with Use of a Mixture of Sucrose and Octenylsuccinate Starch (β-Carotene:Sucrose=1:7.2)

(69) 1160 g of water are heated to 55° C. under protective gas, and 26.5 g of sodium ascorbate, 23.5 g of ascorbic acid and 500 g of octenylsuccinate starch (Capsul®, from National Starch) are added. 500 g of crystalline β-carotene are suspended in this solution by stirring, and the suspension is ground with the aid of a ball mill until the β-carotene particles have an average particle size D[4.3] measured by Fraunhofer diffraction of about 0.6 μm.

(70) b.

(71) 2774 g of this ground suspension were transferred under protective gas into a second reactor and, while stirring, 3914 g of sucrose were added. The temperature of this mixture was kept at 55° C. Addition of 32 g of α-tocopherol was followed by the suspension being homogenized and subsequently converted by modified spray drying into a dry powder in the form of beadlets. The β-carotene content in the beadlets was 11.7% and had an E1/1.sup.1) of 89.

Example 3 (Comparative Test)

Production of a β-Carotene Dry Powder with Use of a Mixture of Glucose Syrup and Octenylsuccinate Starch (β-Carotene:Glucose Syrup=1:6.6)

(72) a.

(73) 7.5 kg of water were heated to 55° C. under protective gas, and 0.225 kg of sodium ascorbate, 0.2 kg of ascorbic acid and 4.25 kg of octenylsuccinate starch (Capsul®, from National Starch) were added. 4.25 kg of crystalline β-carotene were suspended in this solution by stirring. The suspension was then ground with the aid of a ball mill until the β-carotene particles had an average particle size D[4.3] measured by Fraunhofer diffraction of about 0.6 μm.

(74) b.

(75) 2445 g of this ground suspension were transferred under protective gas into a second reactor and, while stirring, 3590 g of glucose syrup and a further 419.7 g of octenylsuccinate starch were added. The temperature of this mixture was kept at 55° C. Addition of 26.9 g of α-tocopherol was followed by the suspension being homogenized and subsequently converted by modified spray drying into a dry powder in the form of beadlets. The β-carotene content in the beadlets was 10.9% and had an E1/1.sup.1) of 94.

Example 4 (Comparative Test)

Production of β-Carotene Dry Powder with Use of a Mixture of Glucose Syrup and Octenylsuccinate Starch (β-Carotene:Glucose Syrup=1:7.6)

(76) 2481 g of the ground suspension from Example 3a were transferred under protective gas into a second reactor and, while stirring, 4194 g of glucose syrup were added. The temperature of this mixture was kept at 55° C. Addition of 27.4 g of α-tocopherol was followed by the suspension being homogenized and subsequently converted by modified spray drying into a dry powder in the form of beadlets. The β-carotene content in the beadlets was 10.6% and had an E1/1.sup.1) of 96.

(77) Table: Storage Stability of the β-Carotene Beadlets in Multivitamin Tablets

(78) The stability of the β-carotene beadlets was tested by means of multivitamin mineral tablets having a content of about 3 mg of β-carotene per tablet. The tablets were packed in HDPE containers whose lid was sealed with heat-sealed aluminum foil. The tablets were stored at 40° C. and 75% relative humidity for 6 months. The β-carotene content was analyzed in each case after storage for 3 and 6 months.

(79) TABLE-US-00001 TABLE After 3 months After 6 months Initial β- β- β- Content: carotene carotene carotene BC:sugar β- content per content per Loss content per Loss Ex. Sugar ratio carotene tablet [mg] tablet [mg] (%) tablet [mg] (%) 1 Sucrose 1:6.6 11.1 3.66 3.19 12.8 3.00 18.0 2 Sucrose 1:7.2 11.6 3.86 3.39 12.2 3.46 10.4 3 Glucose syrup 1:6.6 10.9 3.60 2.67 25.8 2.75 23.6 4 Glucose syrup 1:7.6 10.6 3.40 2.57 24.4 2.45 27.9