JP2009500151A - Emulsifier systems, emulsions and their use - Google Patents

Abstract

  The present invention relates to an emulsifier system comprising a) whey protein and / or whey protein hydrolysate and b) a sucrose fatty acid ester having an HLB value of 10-18. The invention further relates to emulsions prepared using the emulsifier system.

Description

  The present invention relates to an emulsifier system comprising a) whey protein and / or whey protein hydrolysate and b) a sucrose fatty acid ester having an HLB value of 10-18.

  The invention further relates to an emulsion comprising α) a dispersed phase comprising at least one fat-soluble substance, β) water as a continuous phase, and γ) an emulsifier system according to the invention.

  The invention further relates to a process for the preparation of the emulsion according to the invention and its use in the human nutrition, animal nutrition, cosmetics or pharmaceutical industry. Further embodiments of the invention will be apparent from the claims. It will be understood that the above-described arrangements of the inventive subject matter described below can be used not only in the specific combinations specified, but also in other combinations without departing from the scope of the invention.

  German Patent No. 2 363 534 describes the production of liquid vitamin and carotenoid products containing sugar. For emulsification, physiologically acceptable emulsifiers such as lecithin and ascorbyl palmitate are used. One disadvantage of such products is that sugars or sugar alcohols tend to crystallize, for example, while the products are stored at low temperatures. This tendency to crystallize results in undesirable inhomogeneities.

  EP 551 638 relates to stabilizing liquid products of fat-soluble substances over the longest possible storage period (> 6 months). For this purpose, long-chain fatty acid esters of ascorbic acid have been proposed as emulsifiers. However, this emulsion must be stored under chilled conditions, which increases transportation costs and is cumbersome to handle.

  Japanese Patent No. 2000 212 066 discloses the use of polyoxyethylene sorbitan fatty acid esters or sugar fatty acid esters as emulsifiers for emulsions of fat-soluble substances.

  Japanese Patent No. 08 120 187 discloses the use of sorbitan fatty acid esters and sucrose fatty acid esters as emulsifiers for carotenoid emulsions.

  Korean Patent No. 20 020 018 518 discloses the use of sucrose fatty acid esters or sorbitan fatty acid esters as emulsifiers for carotenoid emulsions. A β-carotene concentration of up to 3% is achieved.

  European Patent No. 1 095 986 addresses the problem of preventing solidification of the dispersed phase. This problem is solved by providing a method for stabilizing an aqueous liquid product of a fat soluble material. In this case, an oil-in-water emulsion without protective colloid is mixed with a fat-soluble substance containing protective colloid and the preparation is blended with the aqueous phase. Protective colloids are high molecular weight stabilizers.

  EP 361 928 discloses very fine emulsions containing a glycerol / water mixture as dispersion medium and a fat-soluble drug as dispersion phase. As the stabilizer, a nonionic stabilizer having a molecular weight of 1000 or more is used. In this case, the average particle size of the dispersed phase is 10 to 70 nm. The emulsions described in the examples show a change after only 3 months.

  US Patent Application Publication No. 2002/0107292 A1 describes a preparation comprising a lipophilic bioactive substance together with whey protein.

  One of the objects of the present invention is to provide an emulsifier system intended for the widest possible use possibilities. In particular, the emulsifier system is intended to be usable for the preparation of physiologically acceptable emulsions. The emulsifier system is intended to provide such an emulsion, in particular where the active substance exhibits high bioavailability.

  This object is achieved according to the invention by the emulsifier system described at the beginning of the specification or by the emulsion described at the beginning.

  Emulsifiers are auxiliary agents for preparing and stabilizing the emulsion. Emulsion means a dispersion of two or more mutually immiscible liquids. Stabilization means that the dispersed phase α) and the dispersion medium β) are prevented from becoming inhomogeneous, resulting in a thermodynamically stable final state. In the context of the present invention, the dispersed phase means the finely dispersed phase of the emulsion. The continuous phase of the emulsion represents the dispersion medium in the context of the present invention. The emulsifier system of the present invention is utilized as a dispersant.

  The emulsifier system according to the invention comprises whey protein and / or whey protein hydrolyzate as component a). The whey protein preferably used is a spray-dried whey protein having a protein content of at least 80%, particularly preferably a protein content of at least 95%.

  In the case of a whey protein hydrolyzate, use a purified whey protein that has been enzymatically degraded and has a hydrolysis degree of 3 to 20, particularly preferably a hydrolysis degree of 4 to 16 (measured by the OPA method). Is preferred.

  Sucrose fatty acid esters having an HLB value of 10-18 as component b) include sucrose stearate, sucrose palmitate, sucrose myristate, sucrose laurate, or sucrose oleate. The proportion of monoesters (eg sucrose monostearate) is in each case greater than 55%, preferably in the range 70-85%. A preferred sucrose fatty acid ester is sucrose laurate having a HLB value of 16 comprising sucrose monolaurate in a proportion of 75-85%.

  In a preferred embodiment of the emulsifier system according to the invention, the weight ratio of component a) to component b) is in the range 0.01: 1 to 100: 1, preferably in the range 0.1: 1 to 10: 1, particularly preferably 0.9: The range is 1 to 1.1: 1.

In addition to the sucrose fatty acid ester, the emulsifier system further comprises one or more low molecular weight emulsifiers in an amount of 0.01 to 70% by weight, preferably 0.1 to 50% by weight, particularly preferably 0.5 to 20% by weight, based on the total amount of the emulsifier system. % Concentration. Particularly suitable as such are amphiphilic compounds or mixtures of said compounds. In principle, any surfactant with an HLB value of 5 to 20 is suitable. Examples of suitable corresponding surfactants are: esters of long chain fatty acids such as C ₁₀ -C ₂₀ -alkyl esters with ascorbic acid, mono- and diglycerides of fatty acids and their ethoxylated products, fatty acids Esters of monoglycerides with acetic acid, citric acid, lactic acid or diacetyltartaric acid, polyglycerol fatty acid esters (eg monostearate of triglycerol), sorbitan fatty acid esters, propylene glycol fatty acid esters, and lecithin. It is preferable to use ascorbyl palmitate.

  The emulsifier system of the present invention is particularly noteworthy in that emulsions of fat-soluble active substances prepared using it exhibit a high bioavailability effect.

The invention also relates to an emulsion comprising α) a dispersed phase comprising at least one fat-soluble substance α ₁ ), β) water as a continuous phase, and γ) an emulsifier system according to the invention. However, further components may be present. The total components of the emulsion of the present invention are 100% by weight based on the weight of the emulsion.

The fat-soluble substance α ₁ ) present in the emulsion according to the invention can in principle be any fat-soluble substance. Preferably, the fat-soluble substance α ₁ ) is physiologically acceptable, ie is acceptable in the context of human and animal physiology. However, it may be acceptable from the viewpoint of plant physiology. Suitable examples are fat-soluble vitamins A, D, E or K, or derivatives thereof, such as vitamin A and vitamin E esters (such as retinyl acetate, tocopherol acetate), tocotrienol, vitamin K ₁ , vitamin K ₂ , and Carotenoids such as β-carotene, canthaxanthin, astaxanthin and its ester derivatives, zeaxanthin and its ester derivatives, lutein and its ester derivatives, lycopene, and apocarotenal. Carotenoids are pigments that are widespread in nature and exist in finely dispersed forms in many foods, giving them a characteristic color. In addition to the well-known provitamin A effect of some carotenoids, for this reason, carotenoids are also of interest as colorants in the human food and animal feed industry and the pharmaceutical industry. The colors obtained with relatively high concentrations of carotenoid emulsions usually cover the range from orange to red. In contrast, the relatively high concentration β-carotene-containing emulsions of the present invention are distinguished by vivid yellow color and color intensity, which is desirable for many human foods.

  Carotenoids are also commonly used in the cosmetic field to protect the skin.

In addition, fat-soluble substances α ₁ ) that can be used in the context of the present invention are polyunsaturated fatty acids such as arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid, linoleic acid, linolenic acid (both free and triglyceride forms) And aromatic oils such as orange oil, peppermint oil or citrus oil.

Further suitable fat-soluble substances α ₁ ) are glycerides of polyunsaturated fatty acids such as wheat oil, sunflower oil, corn oil or medium chain length triglycerides or mixtures of said oils.

Finally, any of the most common fat-soluble substances α ₁ ) that play a physiological role in the human or animal body but are usually processed as emulsions due to their water insolubility are suitable as components of the emulsion. ing.

Preferred fat-soluble substances α ₁ ) in the context of the present invention are in particular from the group consisting of the fat-soluble vitamins listed above, for example vitamins A, D, E, K and their derivatives; astaxanthin, lycopene, β-carotene and lutein Carotenoids selected; as well as polyunsaturated fatty acids. Astaxanthin, lycopene, β-carotene and lutein are particularly preferred.

The carotenoid as the fat-soluble substance α ₁ ) generally exists in a state dissolved in oil. It is common to use carotenoids dissolved in oil with oil as the dispersed phase. Examples of suitable oils are any physiologically acceptable oils, especially peanut oil, coconut oil, sunflower oil, olive oil, or other triacylglycerides. The amount of oil used is determined by the solubility of the particular carotenoid in the corresponding oil. Generally, the carotenoid is dissolved in the oil at a temperature in the range of 120-220 ° C, preferably in the range of 160-200 ° C.

  In the case of astaxanthin, the weight ratio of oil to carotenoid can be in the range of 50 to 1000, preferably 100 to 500, particularly preferably 200 to 400. For other carotenoids, this weight ratio may exceed 1000, depending on the solubility of the carotenoid used.

The fat-soluble substance α ₁ ) mainly means a single fat-soluble substance. However, it is also possible to combine several fat-soluble substances, for example two or three fat-soluble substances α ₁ ). Preferably, only one type of fat-soluble substance α ₁ ) is used.

The fat-soluble substance α ₁ ) according to the invention is usually present in an amount of 0.01 to 50% by weight, based on the total weight of the emulsion. In a preferred embodiment, the proportion of fat-soluble substance α ₁ ) is 2 to 40% by weight, particularly preferably 2 to 20% by weight and most preferably 5 to 15% by weight, based on the total weight of the emulsion.

When carotenoids are used as fat-soluble substances α ₁ ), they are usually 0.01-5% by weight, preferably 0.01-2% by weight, particularly preferably 0.05-1% by weight, most preferably, based on the total weight of the emulsion. Is present at a concentration of 0.1-0.5% by weight.

  The average particle size of the dispersed phase α) of the emulsions according to the invention is generally 900 nm or less. In a further embodiment of the invention, the average particle size of the dispersed phase α) is from 50 nm to 850 nm. In a preferred embodiment of the invention, the particle size of the dispersed phase α) is from 150 nm to 500 nm. In this context, the average particle size of the emulsions of the invention can be measured by weight distribution based on mass, for example, using a photon correlation spectrometer at a wavelength of 632.8 nm.

  The emulsifier system γ) is 0.2 to 20% by weight, preferably 0.5 to 10% by weight, particularly preferably 0.5 to 5% by weight and most preferably 1 to 3% by weight, based on the total weight of the emulsion.

  Depending on the field of application, further ingredients or additives may be added to the emulsions of the present invention. The components α), β), γ) and any possible components add up to 100% by weight with respect to the emulsion.

  In addition to whey protein and sucrose fatty acid esters, the emulsions of the present invention can further comprise at least one other protective colloid.

  Suitable and advantageous additional colloids are water-soluble or water-swellable protective colloids, such as, for example: bovine, porcine or fish gelatin, in particular acid-degraded or with a bloom strength in the range of 0 to 250 Base-degraded gelatin, particularly preferably gelatin A 100, A 200, B 100 and B 200, and enzyme-degraded low molecular weight gelatin with a Bloom strength of 0 and a molecular weight of 15000-25000 D such as Collagel A and Gelitasol P (Eberbach, Stoess) ), And mixtures of these gelatin types, as well as starch, dextrin, pectin, gum arabic, lignin sulfonic acid, chitosan, polystyrene sulfonic acid, alginate, casein, caseinate (such as sodium caseinate), methylcellulose, carboxymethylcellulose , Hydroxypropyl cellulose, modified starch (octet Sodium succinate starch (Capsul, from National Starch, etc.), plant proteins such as soybean, rice and / or wheat proteins (these plant proteins may be in a partially degraded or undegraded form) . Suitable synthetic hydrocolloids are, for example, polyvinyl alcohol and polyvinyl pyrrolidone.

  Suitable protective colloids are modified starch, casein and / or sodium caseinate, soy protein, and gelatin, with casein and / or sodium caseinate being particularly preferred.

  The amount of protective colloid used additionally is 0.1-50% by weight, preferably 1-30% by weight, particularly preferably 2-20% by weight, most preferably 3-10% by weight, based on the dry content of the emulsion It is.

  Additional protective colloids are preferably used in addition to the emulsifier system of the present invention when adding the emulsion of the present invention to beverages and other aqueous liquids to stabilize the dispersed phase. Thus, preferably high molecular weight stabilizers are added, especially when using the emulsions of the invention (eg adding the emulsions of the invention to formulations in the field of human food and animal feed).

  Furthermore, the emulsion can also contain at least one low molecular weight stabilizer, such as antioxidants and / or preservatives, to protect the active substance. Examples of suitable antioxidants or preservatives are ascorbic acid, ascorbyl palmitate, tert-butylhydroxytoluene, tert-butylhydroxyanisole, lecithin, ethoxyquin, methylparaben, propylparaben, sorbic acid, or sodium benzoate. Antioxidants or preservatives are in an amount of 0.01-50% by weight, preferably 0.1-30% by weight, particularly preferably 0.5-20% by weight, most preferably 1-10% by weight, based on the dry content of the emulsion. used.

  The antioxidant effect of ascorbyl palmitate can be further increased by mixing tocopherol in addition to the dispersed phase α) in a known manner. The proportion of tocopherol is preferably 0.01 to 4% by weight, preferably 0.05 to 0.5% by weight, based on the total amount of the emulsion of the present invention.

  Compared to conventional emulsions, in particular those described in US 2002/0107292 A1 (using whey protein and ethoxylated sorbitan fatty acid ester (Tween 20) as emulsifier system), the emulsion according to the invention is dispersed in the emulsion The bioavailability improvement of a fat-soluble active substance present as a phase is shown.

  The emulsions of the present invention exhibit even higher color strength. The measure used for color intensity is relative color intensity, which is also called the E1 / 1 value. The E1 / 1 value defines the specific absorption coefficient at the absorption maximum of a 1.0% aqueous emulsion in a 1 cm cuvette. In the context of the present invention, high color intensity means that the relative color intensity is in particular 100 or more. The relative color strength of the emulsion of the present invention is usually 100-200.

In a further embodiment of the present invention, the emulsion of the present invention has an advantageous low turbidity, which is desirable for certain human foods, for example. The turbidity of the emulsion is generally determined as specified in ISO 7027 / DIN EN 27027. The emulsions of the present invention usually have a turbidity of 50 NTU to 1000 NTU, depending on their specific composition. The low turbidity is generally from 50 NTU to 400 NTU, particularly preferably from 50 NTU to 200 NTU. Low turbidity is achieved with the emulsions of the present invention, especially in the β-carotene embodiment, even when using the above-mentioned high proportion of fat-soluble substance α ₁ ).

  In a further embodiment, the applicability of the emulsions of the invention in the human food sector (beverage industry) and in the animal feed sector is good. That is, the promising properties described herein are achieved in each case or in various combinations, especially for applications in the beverage industry.

  When this emulsion is used in the field of human food and animal feed, the desired carotenoid concentration is especially about 5 ppm to 100 ppm.

  When using the emulsion in the beverage industry, it is further possible to have a high content of electrolyte. A high electrolyte content is achieved in particular in critical systems such as concentrates or isotonic drinking water containing a high content of various salts.

  Further, when the emulsion is used in the beverage industry, it is generally at a low pH. In the context of the present invention, low pH means in particular pH 6 or less, such as pH 2 to pH 5, especially pH 2 to 3.

  In a further embodiment of the invention, the emulsions of the invention are distinguished by their bacteriostatic action. This bacteriostatic action means preventing the growth and proliferation of bacteria without killing the bacteria.

  The mixing of the various components of the emulsion of the present invention can be performed directly before adding the emulsion to human food, beverages, animal feed, cosmetics or pharmaceuticals. However, the emulsion of the present invention may be first filled and stored in a container after preparation, and the emulsion may be added to human food, beverages, animal feed, cosmetics or pharmaceuticals only when necessary.

In a preferred embodiment, the emulsion of the invention comprises 0.1 to 0.5% by weight of the fat-soluble substance α ₁ ) of the astaxanthin embodiment, 1.0 to 3.0% by weight of whey protein a) and sucrose laurate having an HLB value of 16. the emulsifier system γ) of the present invention of the embodiment comprising b).

Methods for preparing the emulsions of the present invention are known to those skilled in the art. The emulsions of the present invention can be prepared, for example, in two stages:
A pre-emulsification stage for emulsifying the fat-soluble substance α ₁ ) in the dispersion medium β) to prepare a crude emulsion, and a final emulsification stage for preparing the final emulsion.

  To prepare the emulsions of the present invention, using a rotor / stator system with a diameter D = 10-15 mm, generally emulsifying at a rotational speed of 6000 to 10,000 revolutions / minute, preferably 8000 to 10,000 revolutions / minute, followed by The emulsion is preferably passed through a high-pressure homogenizer once or a plurality of times for emulsification. Further pre-emulsification methods are possible by membrane emulsification methods.

  Final emulsification can be performed by passing the crude emulsion through, for example, a high-pressure homogenizer one or more times (for example, twice or three times). In general, the emulsification is carried out under a pressure of 200 to 1200 bar, preferably 600 to 1000 bar.

  The emulsions according to the invention can be used for various purposes, in particular for coloring or vitamin addition (especially provitamin A), or for human food (especially beverages, particularly preferably soft drinks, vitamin juices, sports drinks) It can be used as an antioxidant. Also contemplated for use in the animal nutrition, cosmetics, or pharmaceutical industries.

  The emulsions of the invention colorize beverages (eg lemonade) in the case of β-carotene, for example for adding vitamins to liquid human food or animal feed, for simple and accurate dispensing. Is very suitable for.

  The invention also relates to a human food, animal feed, cosmetic or pharmaceutical comprising the emulsifier system of the invention or the emulsion of the invention.

Astaxanthin-containing O / W emulsion
Composition of O / W emulsion (per 1kg of emulsion)
Continuous phase (60% by weight of emulsion)
580g double distilled water
10 g of sucrose laurate (L-1695, manufactured by Mitsubishi Chemical Foods)
10 g of whey protein (BiPRO (registered trademark), manufactured by Davisco, USA)
Dispersed phase (40% by weight of emulsion)
0.7g α-tocopherol
1.54g astaxanthin
398g medium chain length triglyceride (Miglyol)

This emulsion was prepared as follows:
Crystalline astaxanthin was suspended in medium chain length triglyceride and pulverized with a vibration mill to a particle size of about 20 μm. The finely divided suspension was sent into a heated coil and temporarily raised to a temperature of 160-200 ° C. At this time, astaxanthin was dissolved. The dispersed phase α) was then mixed with the emulsifier system γ), which was added together to the dispersion medium β) and homogenized for about 15 seconds at 10,000 rpm with an Ultra Turrax (diameter D = 12 mm). The temperature of the emulsion was about 70 ° C. Finally, this crude emulsion was emulsified by passing it through a slit at 600 bar, followed by further emulsification at 1000 bar using a Microfluidizer from Microfluidics, and small droplets of a dispersed phase α) with a narrow particle size distribution. This was repeated 3 times to obtain.

Claims (19)

a) whey protein and / or whey protein hydrolysate, and
b) sucrose fatty acid esters with HLB values of 10-18,
An emulsifier system containing   The emulsifier system according to claim 1, wherein the weight ratio of component a) to component b) ranges from 0.01: 1 to 100: 1.   The emulsifier system according to claim 1 or 2, wherein the sucrose fatty acid ester is sucrose laurate having an HLB value of 16.   The emulsifier system according to any one of claims 1 to 3, wherein the whey protein hydrolyzate has a degree of hydrolysis of 3 to 20. α) a dispersed phase comprising at least one fat-soluble substance α ₁ ),
β) water as a continuous phase, and γ) an emulsifier system according to any one of claims 1 to 4,
An emulsion containing 6. The emulsion according to claim 5, wherein the fat-soluble substance α ₁ ) is vitamin A, D, E or K or a derivative thereof, or a glyceride of a polyunsaturated fatty acid. 6. The emulsion according to claim 5, wherein the fat-soluble substance α ₁ ) is at least one carotenoid. The emulsion according to claim 7, wherein the fat-soluble substance α ₁ ) is at least one carotenoid selected from the group consisting of astaxanthin, lycopene, β-carotene and lutein. The emulsion according to claim 5 or 6, wherein the content of the fat-soluble substance α ₁ ) is 0.01 to 50% by weight, based on the total weight of the emulsion.   8. Emulsion according to claim 7, wherein the carotenoid content is 0.01 to 5% by weight, based on the total weight of the emulsion.   11. Emulsion according to any one of claims 5 to 10, wherein the emulsifier system represents 0.2 to 20% by weight, based on the total weight of the emulsion.   The emulsion according to any one of claims 5 to 11, wherein the average particle size of the dispersed phase α) is 900 nm or less.   13. Emulsion according to any one of claims 5 to 12, wherein at least one further emulsifier is present.   14. Emulsion according to any one of claims 5 to 13, wherein at least one further protective colloid is present.   15. Emulsion according to any one of claims 5 to 14, wherein at least one low molecular weight stabilizer is present.   16. A method for preparing an emulsion according to any one of claims 5 to 15 by pre-emulsification followed by final emulsification.   17. The method of claim 16, wherein a rotor / stator system is used followed by emulsification with a high pressure homogenizer.   Use of an emulsion according to any one of claims 5 to 15 in the human nutrition, animal nutrition, cosmetic or pharmaceutical industry.   A human food, animal feed, cosmetic or pharmaceutical comprising the emulsifier system according to any one of claims 1 to 4 or the emulsion according to any one of claims 5 to 15.