JP2019010106A - Aqueous transparent oil-in-water-type emulsion containing emulsified carotenoid - Google Patents

Abstract

To provide an aqueous carotenoid emulsion capable of exhibiting improved color on carotenoid which is extremely hard to be emulsified since it has low oil solubility and low water solubility, on the other hand, of which a ratio of cis to trans isomer is finely adjusted to achieve a stable system for inhibiting recrystallization, especially at high concentration of the carotenoid.SOLUTION: There is provided an aqueous transparent oil-in-water type emulsion containing processed starch and/or at least one surfactant protein as a water soluble antioxidant, and emulsified carotenoid at a concentration of 0.025 to 2000 ppm.SELECTED DRAWING: None

Description

  The present invention relates to an aqueous transparent oil-in-water emulsion containing a carotenoid and a method for producing the emulsion.

Emulsions containing carotenoids are well known in the prior art. Carotenoids are used as coloring materials and as active substances for the human food and animal feed industry and in the pharmaceutical field. In this field, carotenoids are also known as “Southampton Six” (Sunset Yellow (E110), Quinoline Yellow (E104), Carmoisine (E122), Allura Red (E129), Tartrazine (E102) and Ponceau 4R (E124 In recent years it has been used to replace the synthetic azo dyes known as)). These synthetic azo dyes can have adverse effects, particularly side effects on children's activities and attention.
In the past, it was difficult to replace azo dyes with carotenoids and maintain the same product color match as those using azo dyes.
Carotenoids are insoluble in water. Furthermore, carotenoids are very susceptible to oxidation. Therefore, it is difficult to use carotenoids in a crystalline form that is not stable during storage. In general, many additives are needed to obtain a stable carotenoid emulsion with carotenoids protected from oxidation and having improved coloration.

One means of overcoming the problems in carotenoid handling is the production of microemulsions. These microemulsions exhibit the taste of soap due to the emulsifier used.
Emulsifiers, especially esters of ascorbic acid and long chain fatty acids, in particular ascorbyl palmitate, have also been used in accordance with the teachings of US 4,844,934 to obtain creaming-stable emulsions.

To form a small emulsion, prepared by dispersing a liquid oil such as vitamin E acetate in an aqueous phase using an emulsifier, followed by homogenization at high pressure, the oil phase is liquid at room temperature. , Because the interfacial tension between vitamin E acetate oil and aqueous phase is lower than normal vegetable oils (eg sunflower oil), it requires high amounts of energy along with high amounts of emulsifiers (these materials form emulsions) Is a common tool used for).
On the other hand, emulsifying carotenoids is very difficult due to the low oil solubility and very low water solubility of carotenoids. Furthermore, to prevent recrystallization of carotenoids, the ratio of cis to trans isomers needs to be finely adjusted to achieve a stable system. Thus, emulsions containing carotenoids are actually a different system than emulsions containing pure vitamin E acetate. Finally, emulsion droplets containing only oil-soluble vitamins (eg vitamin E acetate) cannot be used as colorants.

It is an object of the present invention to provide an aqueous carotenoid emulsion that exhibits improved color, preferably at high carotenoid concentrations, with improved bioavailability of carotenoids. Furthermore, the emulsion needs to be clear and transparent, which means very low turbidity. A further object of the present invention is to use exclusively natural renewable raw materials or natural raw materials. Furthermore, the emulsion needs to be manufacturable in a simple and efficient manner within just a few steps.
A further object of the present invention is to provide a carotenoid-containing aqueous emulsion or carotenoid-containing powder as a colorant that replaces the azo dye and reproduces the appearance of the final product colored with the azo dye. In addition, it is an object of the present invention to provide an aqueous carotenoid emulsion that does not contain any azo dyes, but reproduces the appearance of products colored with azo dyes.

  These problems are solved by the emulsion of the present invention and the method for producing the emulsion of the present invention.

In one embodiment, the emulsion of the present invention is 0.025 to 2000 ppm (preferably 0.025 to 300 ppm, 0.1 to 200 ppm, 0.1 to 100 ppm, 1 to 50 ppm, 1 to 30 ppm, 3 to 30 ppm, 3 to 20 ppm, more preferably 1 to It is an aqueous transparent oil-in-water emulsion containing emulsified carotenoids at a concentration of 15 ppm, 3-15 ppm, especially 3-6 ppm. In one embodiment, the concentration of emulsified carotenoid is 5 ppm.
In one embodiment, 1 ppm is 1 part by weight per million parts by weight.
For the purposes of the present invention, an oil-in-water emulsion containing an emulsified carotenoid means an emulsion with oil droplets in water, where the carotenoid is present in the droplets and dissolved in the oil. .

According to the invention, the term “aqueous clear oil-in-water emulsion” means a clear emulsion with low turbidity. Turbidity is measured in NTU, which is nephelometric turbidity units, measured using any standard turbidimeter, in one embodiment of the present invention, a 2100AN turbidimeter manufactured by HACH.
For the purposes of the present invention, a clear emulsion is defined as an aqueous emulsion containing 5 ppm carotenoid with an NTU value of 35 or less.
In one embodiment of the invention, an aqueous emulsion comprising 5 ppm carotenoids has a turbidity value of 1 to 35 NTU (preferably 10 to 35 NTU, more preferably 15 to 30 NTU, especially 15 to 25 NTU, 15 to 20 NTU). ).
In a further embodiment of the invention, the aqueous emulsion comprising 5 ppm carotenoid has a turbidity value selected from the group consisting of 15, 16, 17, 18, 19, 20, 21, 22, 23, 24 and 25 NTU.

In another embodiment of the present invention, the carotenoid is a group consisting of canthaxanthin, astaxanthin, lutein, zeaxanthin, beta-zeacaroten, lycopene, apocarotenal, bixin, paprika oleoresin, capsanthin and capsorbin And is preferably apocarotenal, more preferably β-apo-8-carotenal.
In an embodiment of the invention, the carotenoid is β-carotene.
In a further embodiment, the oil-in-water emulsion of the present invention does not contain β-carotene.

In the context of the present invention, the characteristic “free” refers to known state-of-the-art analytical methods for the qualitative and / or quantitative detection of carotenoids, such as spectroscopy (UV / VIS), chromatographic methods (HPLC), NMR methods and Means that the relevant compound cannot be detected in the composition of the invention using mass spectrometry.
All carotenoids can be natural products or natural products. Naturally equivalent carotenes are synthetic carotenes that have exactly the same chemical structure as natural carotenes found in nature.

  In another embodiment, the emulsion of the present invention has an oil droplet diameter (using a dynamic light scattering method) of 50 to 400 nm (preferably 80 to 300 nm, more preferably 100 to 150 nm, especially 130 to 140 nm). .

  According to the present invention, the oil droplet size is the z-average size and is measured in one embodiment using Malvern's zetasizer nano-s (serial number MAL500613).

The emulsion of the present invention, in another form, has a polydispersity index (PDI) between 0.01 and 0.4 (preferably between 0.01 and 0.3, more preferably between 0.01 and 0.2, especially between 0.01 and 0.1). Have. The polydispersity index (PDI) defines the width of the oil droplet size distribution and is specified in Part 8 of ISP13321.
The emulsion of the present invention, in another form, has 70% of the oil droplets between 0 and 200 nm (preferably 80% of the oil droplets are between 0 and 200 nm, more preferably 90% of the oil droplets are between 0 and 200 nm. Especially 95% of the oil droplets are between 0 and 200 nm).

In one embodiment, the emulsion is 140-280 (preferably 140-250, 150-250, more preferably 150-230, 150-220, more preferably 160-230, 180-215, especially 205-215). Color intensity value (E 1/1).
The color intensity value (E 1/1) of the aqueous solution is defined as the absorbance of light (different for each carotenoid) at maximum absorbance through a 1 cm cuvette containing 1% carotenoid emulsion. When measuring the color intensity value (E 1/1) at a density lower than 1%, it is necessary to correct the measured color intensity value using a dilution factor.
E1 / 1 = (A _max x 20) / (Sample weight (g))

  In one embodiment of the invention, the carotenoid is a triacylglycerol oil (eg MCT oil (medium chain fatty acid triacylglycerol), olive oil, corn oil, sunflower oil, peanut oil, soybean oil or other alternative vegetable oil, preferably MCT oil) is melted and / or dissolved and / or isomerized from the trans form to the cis form.

  Therefore, the emulsion of the present invention, in one embodiment, is MCT oil (medium chain fatty acid triacylglycerol), olive oil at a concentration of 0.1 to 150 ppm (preferably 1 to 75 ppm, more preferably 5 to 50 ppm, especially 15 to 30 ppm). , A triacylglycerol oil selected from the group consisting of sunflower oil, peanut oil, soybean oil and vegetable oil, preferably MCT oil.

The triacylglycerol oil used in the present invention is in one embodiment an ester of glycerol, where the glycerol is esterified with a fatty acid, the fatty acid having a carbon chain length of 4-22 and any carbon. Can have a double bond in the position.
Preferably, MCT oil is used, where the MCT is esterified with glycerol with fatty acid, the fatty acid is saturated and has a carbon chain length of 6-10 (preferably 8-10 carbon chain length) , An ester of glycerol.
Isomerization is at a temperature of 100-200 ° C. (120-180 ° C., more preferably 130-160 ° C.) with a trans isomer content between 30 and 100% (preferably between 30 and 90%). More preferably between 35 and 80%, in particular between 40 and 75%).

  Isomerization can be carried out in the presence of an oil-soluble antioxidant.

Thus, in one embodiment of the present invention, the emulsions each contain an oil soluble antioxidant at a concentration of 0.001 to 60 ppm (preferably 0.01 to 30 ppm, more preferably 0.1 to 20 ppm, especially 0.5 to 12 ppm).
According to one embodiment of the present invention, the oil-soluble antioxidant is soluble in a non-polar solvent and forms a molecular dispersion.
The oil-soluble antioxidant according to the present invention is
・ Ethoxyquin;
Hindered phenolic antioxidants (eg t-butylhydroxytoluol, t-butylhydroxyaniso, t-butylhydroxyquinone);
Vitamin A, retinoic acid and its esters having a carbon chain length of C1-C20;
Vitamins D2 and D3;
Alpha, beta, gamma and delta tocopherols or a mixture comprising at least two of the tocopherols;
Alpha, beta, gamma and delta tocotrienol, or a mixture comprising at least two of its tocotrienols;
A natural extract comprising at least one of the above compounds, a phenolic diterpene (eg carnosol, carnosic acid);
Cinnamic acid derivatives (2-ethoxyethyl p-methoxycinnamate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyldiisopropyl cinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinna Mino, and BASF products such as Tinogard TT, Tinogard HS, LC-gallates, Eugenol, Thymol, Organosolv lignin (Organosolv- Lignin);
Preferably α-tocopherol;
Selected from the group consisting of
The oil-soluble antioxidant has a concentration of 0.001 to 60 ppm (preferably 0.1 to 30 ppm, more preferably 1 to 20 ppm, particularly 6 to 12 ppm).

By using the method of the present invention, the carotenoids are highly stable in triacylglycerol oil, so no solid particles are present in the droplets. The droplets are a mixture of carotenoids, an optional oil-soluble antioxidant, and triacylglycerol oil.
In one embodiment, the mixture of carotenoid, optionally oil-soluble antioxidant, and triacylglycerol oil is a solution (carotenoid, optionally oil-soluble antioxidant, and molecular dispersion of triacylglycerol oil). Means the body).
In one embodiment of the invention, the carotene can be crystallized or partially crystallized.

In another aspect of the invention, the emulsion is from modified starch and / or gelatin, whey protein, whey protein isolate, sodium caseinate and other milk proteins, soy protein, potato protein. At least one surface active protein selected from the group consisting of: and / or natural polymers such as lignin sulfonate, pectin, fenugreek gum and gum arabic, preferably including modified starch, more preferably octenyl succinate Contains acid starch.
Modified starch and / or at least one surfactant protein has a concentration of 0.5 to 600 ppm (preferably 2 to 300 ppm, more preferably 20 to 200 ppm, especially 60 to 120 ppm). The polymers described above have a molecular weight MW-distribution of 10,000 to 2,000,000 g / mol (preferably 20,000 to 1,000,000 g / mol, more preferably 30,000 to 500,000 g / mol).
In one embodiment, the emulsion of the present invention does not contain octenyl succinic anhydride modified acacia gum (agaca gum is also known as gum arabic).

In a further embodiment, the emulsion is from the group comprising monosaccharides, disaccharides, oligosaccharides, glucose syrup, maltose and trehalose (preferably glucose syrup, maltose and trehalose), preferably glucose syrup, maltose and trehalose (more preferably A carbohydrate selected from the group consisting of (glucose syrup), said carbohydrate having a DE (dextrose equivalent) of between 20 and 50 (preferably between 35 and 50, in particular between 43 and 48). Sugars include glucose, fructose, galactose or mannose.
The carbohydrate has a concentration of 0.5 to 10,000 ppm (preferably 2 to 5000 ppm, more preferably 20 to 3000 ppm, especially 60 to 2000 ppm).

In another embodiment, the emulsion of the present invention is:
-Phenolic OH in the chemical structure, such as hydroxy derivatives of cinnamic acid (for example, hydroxycinnamic acid, hydroxycinnamic acid ester (for example, hydroxyhydrocinnamate) which is a kind of polyphenol having C6-C3 skeleton) Natural compounds that are effective as antioxidants due to the inclusion of groups;
-Esters of caffeic acid, ferulic acid, tyrosol, hydroxytyrosol, cinnamic acid, chlorogenic acid, coumarin, coumarinic acid, sinapinic acid, cinnamic acid, chicory acid and any of these compounds having C1-C20;
An extract of a plant rich in at least one of the above compounds;
Rosmarinic acid, hydroxytyrosol;
Extracts from common spices, in one embodiment, common spices include rosemary, lemon balm, oregano, thyme, peppermint, sage or similar plants containing or rich in at least one of the above compounds Selected from a group;
Any of the flavones extracted from other flavones, flavones, teas, or other plants that contain or are rich in catechins or epicatechins or their derivatives, which are one of the natural compounds with over 5000 compounds, can be used as antioxidants These compounds may be glycosylated with carbohydrates or esterified with C1-C20 fatty acids or gallic acid; plants containing or rich in one or more of the above-mentioned compounds (eg, Extracts from tea, olives, pears, apples);
-Sodium ascorbate, polyphenole, teanova 80, glutathione, lipoic acid, catechin, punicalagin, xanthone, benzotropolones (preferably sodium ascorbate);
Comprising at least one water soluble antioxidant selected from the group consisting of:
The water-soluble antioxidant has a concentration of 0.001 to 60 ppm (preferably 0.1 to 30 ppm, more preferably 1 to 20 ppm, particularly 6 to 12 ppm).

  According to one embodiment of the present invention, the water soluble antioxidant forms a molecular dispersion in water.

The subject of the present invention is the following process:
a) Modified starch and / or at least one surfactant protein at a concentration of 0.7-70% (preferably 1-50%, more preferably 5-30%, especially 15-25%), 0.001-80% (preferably Preparing a solution comprising at least one carbohydrate and water at a concentration of 10-70%, more preferably 15-60%, in particular 30-50%) and mixing the components;
b) at least one carotenoid at a concentration of 0.1-15% (preferably 0.5-5%, more preferably 0.5-3%, especially 1-2%) and 1-30% (preferably 3-20%, more Preferably mixed with triacylglycerol oil at a concentration of 3-15%, 3-10%, especially 3-5%), 100-200 ° C (120-180 ° C, more preferably 130-160 ° Preparing a solution by melting the dispersed carotenoid and optionally isomerizing said carotenoid from the trans form to the cis form at the temperature of C),
c) introducing the solution of step b) into the solution of step a);
d) performing at least one step of pre-emulsification by passing the mixture of step c) through a rotor / stator mixer;
e) performing at least one step (preferably at least two steps) of high-pressure homogenization at a pressure of 300 to 2,000 bar;
f) spray drying the emulsion of step e) to obtain a powder;
g-1) preparing an emulsion by introducing the powder of step f) into water;
Including
A process for producing an emulsion in which the percentages are by weight with respect to the emulsions of steps c) to e) and the total amount of all compounds used is 100%.

  Further objects are 5% to 70% (preferably 10% to 70%, preferably 10% to 60%, more preferably, in steps g) above in step a) to f) above and step g-1) Preparing an emulsion by introducing the powder of step f) into water at a concentration of 20% to 50%), wherein the percentage is weight percent relative to the concentration of the powder according to step f) in water It is a manufacturing method of an oil-type emulsion.

  In one embodiment of the method of the present invention, optionally at least one water soluble antioxidant at a concentration of 0.001-10% (preferably 0.001-4%, more preferably 0.01-1.5%, especially 0.5-1.5). Add in step a).

  In one embodiment of the method of the invention, optionally at least one oil-soluble antioxidant at a concentration of 0.001 to 10% (preferably 0.001 to 5%, more preferably 0.01 to 2%, especially 0.1 to 1%). And triacylglycerol oil at a concentration of 1-30% (preferably 3-20%, more preferably 3-15%, 3-10%, especially 3-5%) in step b).

In another aspect, the method of the invention comprises:
Mixing the carbohydrate in the emulsion in step c) or d),
Adding a water-soluble antioxidant after step c), d) or e);
Adding an oil-soluble antioxidant in step a), c) or d);
Including one or more of the alternative means.

In one embodiment, the pre-emulsification is performed until the oil droplet size (z-average particle size) is 200 nm to 20 μm (preferably 250 nm to 10 μm, more preferably 300 nm to 5 μm).
The pre-emulsion is stable for at least 10 hours (with stirring) at 60 ° C. (preferably 5 hours (with stirring) at 60 ° C., more preferably 3 hours (with stirring)) at 60 ° C.

In one embodiment, a two-stage homogenizer is used in the high pressure homogenization process. A two-stage homogenizer consists of two pressure valves, so that each pass through the device consists of two stages. The first stage has 0-3000 bar (preferably 500-2000 bar, more preferably 650-1500 bar, especially 800-950 bar), and the second stage has 0-3000 bar (preferably 50-2000 bar). Bar, more preferably 50-1500 bar, in particular 50-1000 bar).
In another form, the emulsion is passed through a microfluidizer in one stage at 300-2000 bar (preferably 500-1500 bar, more preferably 500-1400 bar).
All steps in the process are performed at a temperature between 0 and 500 ° C (preferably between 20 and 200 ° C, more preferably between 20 and 200 ° C, especially between 50 and 200 ° C). .
The high pressure homogenization step is performed in another form at least 2, 3, 4, 5, 6, 7, 8, 9, 10, 15, 20, 30 or more.

In one embodiment, the method of the present invention facilitates the production of a stable emulsion without any surfactant.
In one embodiment, the stable oil-in-water emulsion of the present invention does not contain surfactants and / or emulsifiers in addition to modified starch (preferably starch octenyl succinate). That is, octenyl succinate starch is the only surfactant and / or emulsifier present in the emulsions of the present invention.

A further subject of the present invention is a powder comprising a carotenoid according to step f).
In another form, the powder has a residual moisture content of 0-15% (preferably 0.1-10%, more preferably 3-5%).

In one embodiment, the powder produced according to the method of the invention is
Modified starch and / or at least one surfactant protein at a concentration of 0.7-70% (preferably 1-60%, more preferably 10-50%, especially 20-40%),
Optionally, at least one water soluble antioxidant at a concentration of 0.001-10% (preferably 0.001-4%, more preferably 0.001-2%, especially 1%),
At least one carbohydrate at a concentration of 0.001-80% (preferably 10-80%, more preferably 20-70%, especially 45%),
At least one carotenoid at a concentration of 0.5-20% (preferably 1-5%, more preferably 1-3%, especially 2-3%), preferably with a trans isomer content between 30 and 100% The
Optionally, at least one oil-soluble antioxidant at a concentration of 0.001-10% (preferably 0.001-5%, more preferably 0.01-3%, especially 1%),
Triacylglycerol oil at a concentration of 1-50% (preferably 3-50%, 3-40%, more preferably 3-20%, 3-15%, 7-15%, especially 8%),
Including, the total amount of all compounds used is 100%.

  In one embodiment of the present invention, the powder is at an inlet temperature between 80 ° C and 500 ° C (preferably 100-300 ° C, more preferably 100-200 ° C) and about 40-150 ° C. It is obtained by spray drying at an outlet temperature (preferably 50-100 ° C, more preferably 50-90 ° C).

  Another subject of the invention is a (concentrated) emulsion comprising a carotenoid according to step g-2), prepared by introducing the powder of step f) into water. This (concentrated) emulsion is a storage emulsion that can be further diluted.

  In one embodiment of the present invention, the aqueous clear emulsion, concentrated storage emulsion and / or powder of the present invention is used as a colorant (preferably a natural or natural colorant). The aqueous emulsions, concentrated storage emulsions and / or powders of the present invention are used as colorants in soft drinks, flavored water, fruit juices, beverages such as punches or concentrated forms of these beverages, and alcoholic beverages and instant beverage powders. The

  In a further embodiment, the aqueous emulsion, concentrated storage emulsion and / or powder of the present invention is used in food and / or feed. Typically, the aqueous emulsions, concentrated storage emulsions and / or powders of the present invention are dairy products such as ice cream, cheese, milk drinks or yogurt, soy milk, confectionery products, gums, desserts, candy, puddings, jelly Also used in instant pudding powders, as well as in snacks, cookies, sauces, cereals, salad dressings, soups.

  The aqueous emulsions, concentrated storage emulsions and / or powders of the present invention can also be used in pharmaceutical products such as tablets or capsules, or in cosmetic and dermatological formulations.

  In one embodiment, the aqueous emulsions, concentrated storage emulsions and / or powders of the present invention are used in place of, and instead of, azo dyes. The product of the present invention replaces the azo dye as a food colorant by reproducing the appearance of the final product (meaning that the final product has the same color and transparency).

Example 1. Preparation procedure
a) Modified starch, sodium ascorbate and carbohydrate were dissolved in water having a temperature of 60 ° C.
b) Apocarotenal with tocopherol was dissolved and isomerized in MCT oil for 4 minutes at 130-160 ° C.
c) The solution of step b) was mixed with the solution of step a).
d) The mixture of step c) was pre-emulsified with a laboratory scale rotor / stator mixer for 9 minutes. e) The mixture was further emulsified with a high pressure microfull diizer.
f) The emulsion was spray dried. The inlet temperature was 100-120 ° C. The outlet temperature was about 60 ° C.
g) An emulsion was prepared by introducing the dry powder into water at a carotenoid concentration of 5 ppm.

  The powder had a residual moisture content of 5% concentration.

  In the following example, the E1 / 1 value was measured at a maximum absorbance of 460 nm and the maximum absorbance of 1% apocarotenal in the solvent was 2640. The absorbance at 600 nm is an index of turbidity.

2. Increasing apocarotenal concentration An emulsion according to Example 1 was prepared with the following compounds and concentrations. Here, the mixture of step 1 e) was further emulsified with a high pressure microfull dither (1 pass at 1000 bar).

3. Use of various carbohydrates Emulsions according to Example 1 were prepared with the following compounds and concentrations. Here, the mixture of step 1 e) was further emulsified with a high pressure microfull dither (1 pass at 1000 bar).

4). Use of Various Modified Starch Concentrations Emulsions according to Example 1 were prepared with the following compounds and concentrations. Here, the mixture of step 1 e) was further emulsified with a high pressure microfull dither (1 pass at 800 bar).

5. Use of Various Pressures Emulsions according to Example 1 were prepared with the following compounds and concentrations. Here, the mixture of step 1 e) was further emulsified with a high pressure microfull dither (1 pass at 600 or 1000 bar).

6). 1-5 passes through a microfull dizer An emulsion according to Example 1 was prepared with the following compounds and concentrations. Here, the mixture of step 1 e) was further emulsified with a high pressure microfull dither (1000 bar).

(Appendix)
(Appendix 1)
  An aqueous transparent oil-in-water emulsion containing emulsified carotenoids at a concentration of 0.025 to 2000 ppm. (Appendix 2)
  Carotenoids include canthaxanthin, astaxanthin, lutein, zeaxanthin, beta-zeacaroten, lycopene, apocarotenal, bixin, paprika oleoresin, capsanthin and capsorbine (preferably apocarotenal, more preferably β-apo- The emulsion according to claim 1, which is selected from the group consisting of 8-carotenal).
(Appendix 3)
  The emulsion according to appendix 1 or 2, wherein the NTU (turbidity) value at a carotenoid concentration of 5 ppm is 1 to 35 NTU.
(Appendix 4)
  The color intensity value (E 1/1) is 140-280, and the color intensity value (E 1/1) is the absorbance of light at the maximum absorbance passing through a 1 cm cuvette containing 1% carotene dissolved in an organic solvent. The emulsion according to any one of supplementary notes 1 to 3, defined as:
(Appendix 5)
  The emulsion according to any one of supplementary notes 1 to 4, wherein the oil droplet diameter measured using a dynamic light scattering method is 50 to 400 nm.
(Appendix 6)
  Supplementary note 1 comprising triacylglycerol oil selected from the group consisting of MCT oil (medium chain fatty acid triacylglycerol), olive oil, sunflower oil, peanut oil, soybean oil and vegetable oil (preferably MCT oil) at a concentration of 0.1 to 150 ppm The emulsion in any one of thru | or 5.
(Appendix 7)
  The emulsion according to any one of appendices 1 to 6, comprising modified starch and / or at least one surfactant protein having a molecular weight MW distribution of 10,000 to 2,000,000 g / mol at a concentration of 0.5 to 600 ppm.
(Appendix 8)
  Appendix 1 comprising at least one carbohydrate selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, glucose syrup, maltose and trehalose, wherein the carbohydrate has a DE between 20 and 50 at a concentration of 0.5-10000 ppm The emulsion in any one of thru | or 7.
(Appendix 9)
  Natural compounds effective as antioxidants by including phenolic OH groups in the chemical structure;
  Esters of caffeic acid, ferulic acid, tyrosol, hydroxytyrosol, cinnamic acid, chlorogenic acid, coumarin, coumarinic acid, sinapinic acid, cinnamic acid, chicory acid, and any of these compounds having C1-C20;
  Plant extracts rich in at least one of the above compounds;
  Rosmarinic acid, hydroxytyrosol;
  Extracts from common spices;
  Flavones (preferably flavones extracted from plants such as tea or other plants containing catechin or epicatechin or derivatives thereof);
  Extracts from plants (eg tea, olives, pears, apples) containing one or more of the above-mentioned compounds;
  Sodium ascorbate, polyphenol, tinova 80, glutathione, lipoic acid, catechin, panicalagin, xanthone, benzotropolone (preferably sodium ascorbate);
Comprising at least one water soluble antioxidant selected from the group consisting of:
  The emulsion according to any one of supplementary notes 1 to 8, wherein the water-soluble antioxidant has a concentration of 0.001 to 60 ppm.
(Appendix 10)
        Ethoxyquin;
  Hindered phenolic antioxidants (eg, t-butylhydroxytoluol, t-butylhydroxyanisole, t-butylhydroxyquinone);
  Vitamin A, retinoic acid and its esters with C1-C20;
  Vitamins D2 and D3;
  Alpha, beta, gamma and delta tocopherols or a mixture comprising at least two of the tocopherols;
  Alpha, beta, gamma and delta tocotrienol, or a mixture comprising at least two of the tocotrienol;
  A natural extract comprising at least one of the above compounds;
  Phenolic diterpenes (eg carnosol, carnosic acid);
  Cinnamic acid derivatives (2-ethoxyethyl p-methoxycinnamate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyldiisopropyl cinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinnamate And); and
  LC-gallates, Eugenol, Thymol;
Including an oil-soluble antioxidant selected from the group consisting of:
  The emulsion according to any one of supplementary notes 1 to 9, wherein the oil-soluble antioxidant has a concentration of 0.001 to 60 ppm.
(Appendix 11)
  11. An emulsion according to any one of appendices 1 to 10, wherein the carotenoid has an isomerized trans isomer content between 30 and 100%.
(Appendix 12)
        The following steps:
  a) preparing a solution comprising modified starch and / or at least one surfactant protein at a concentration of 0.7-70%, at least one carbohydrate at a concentration of 0.001-80%, and water and mixing the components;
  b) Mixing at least one carotenoid at a concentration of 0.1-15% with triacylglycerol oil at a concentration of 1-30% and melting the dispersed carotenoid at a temperature of 100-200 ° C. Preparing the step,
  c) introducing the solution of step b) into the solution of step a);
  d) performing at least one step of pre-emulsification by passing the mixture of step c) through a rotor / stator mixer;
  e) performing at least one step of high-pressure homogenization;
  f) spray drying the emulsion of step e) to obtain a powder;
  g-1) preparing an emulsion by introducing the powder of step f) into water;
Including
  The method for producing an emulsion according to any one of appendices 1 to 9, wherein the percentage is% by weight with respect to the emulsion of steps c) to e).
(Appendix 13)
        The following steps:
  a) preparing a solution comprising modified starch and / or at least one surfactant protein at a concentration of 0.7-70%, at least one carbohydrate at a concentration of 0.001-80%, and water and mixing the components;
  b) Mixing at least one carotenoid at a concentration of 0.1-15% with triacylglycerol oil at a concentration of 1-30% and melting the dispersed carotenoid at a temperature of 100-200 ° C. The step of preparing,
  c) introducing the solution of step b) into the solution of step a);
  d) performing at least one step of pre-emulsification by passing the mixture of step c) through a rotor / stator mixer;
  e) performing at least one step (preferably two steps) of high-pressure homogenization;
  Said percentage is the weight percent for the emulsion of steps c) to e),
  f) spray drying the emulsion of step e) to obtain a powder;
  g-2) preparing an emulsion by introducing the powder of step f) into water at a concentration of 5% to 70%, wherein the percentage is weight% relative to the concentration of the powder according to step f) in water A method for producing an oil-in-water emulsion containing an emulsified carotenoid.
(Appendix 14)
        Mixing the carbohydrate in the emulsion in step c) or d);
        Adding the water-soluble antioxidant after step c), d) or e);
        Adding the oil-soluble antioxidant in step a), c) or d);
The manufacturing method according to appendix 12 or 13, including one or more of alternative means including:
(Appendix 15)
  15. A powder containing carotenoid obtained in step f) according to appendix 12 or 14.
(Appendix 16)
  An oil-in-water emulsion containing a carotenoid obtained in step g-2) according to appendix 13 or 14.
(Appendix 17)
  Use of the aqueous emulsion according to appendix 16 or the powder according to appendix 15 as a colorant (preferably a natural or natural colorant in foods, feeds, pharmaceuticals, cosmetics and / or skin preparations).
(Appendix 18)
  Use according to appendix 17 as a replacement for an azo dye.

Claims (18)

  An aqueous transparent oil-in-water emulsion containing emulsified carotenoids at a concentration of 0.025 to 2000 ppm.   Carotenoids include canthaxanthin, astaxanthin, lutein, zeaxanthin, beta-zeacaroten, lycopene, apocarotenal, bixin, paprika oleoresin, capsanthin and capsorbin (preferably apocarotenal, more preferably β-apo- The emulsion according to claim 1, which is selected from the group consisting of 8-carotenal).   The emulsion according to claim 1 or 2, wherein the NTU (turbidity) value at a carotenoid concentration of 5 ppm is 1 to 35 NTU.   The color intensity value (E 1/1) is 140-280, and the color intensity value (E 1/1) is the absorbance of light at the maximum absorbance passing through a 1 cm cuvette containing 1% carotene dissolved in an organic solvent. 4. Emulsion according to any of claims 1 to 3, defined as   The emulsion according to any one of claims 1 to 4, wherein the oil droplet diameter measured using a dynamic light scattering method is 50 to 400 nm.   A triacylglycerol oil selected from the group consisting of MCT oil (medium chain fatty acid triacylglycerol), olive oil, sunflower oil, peanut oil, soybean oil and vegetable oil (preferably MCT oil) at a concentration of 0.1 to 150 ppm. The emulsion according to any one of 1 to 5.   Emulsion according to any of the preceding claims comprising modified starch and / or at least one surfactant protein having a molecular weight MW distribution of 10,000 to 2,000,000 g / mol at a concentration of 0.5 to 600 ppm.   The method comprising at least one carbohydrate selected from the group consisting of monosaccharides, disaccharides, oligosaccharides, glucose syrup, maltose and trehalose, wherein the carbohydrate has a DE between 20 and 50 at a concentration of 0.5-10000 ppm. The emulsion according to any one of 1 to 7. Natural compounds effective as antioxidants by including phenolic OH groups in the chemical structure;
Esters of caffeic acid, ferulic acid, tyrosol, hydroxytyrosol, cinnamic acid, chlorogenic acid, coumarin, coumarinic acid, sinapinic acid, cinnamic acid, chicory acid, and any of these compounds having C1-C20;
Plant extracts rich in at least one of the above compounds;
Rosmarinic acid, hydroxytyrosol;
Extracts from common spices;
Flavones (preferably flavones extracted from plants such as tea or other plants containing catechin or epicatechin or derivatives thereof);
Extracts from plants (eg tea, olives, pears, apples) containing one or more of the above-mentioned compounds;
Sodium ascorbate, polyphenol, tinova 80, glutathione, lipoic acid, catechin, panicalagin, xanthone, benzotropolone (preferably sodium ascorbate);
Comprising at least one water soluble antioxidant selected from the group consisting of:
The emulsion according to any one of claims 1 to 8, wherein the water-soluble antioxidant has a concentration of 0.001 to 60 ppm. Ethoxyquin;
Hindered phenolic antioxidants (eg, t-butylhydroxytoluol, t-butylhydroxyanisole, t-butylhydroxyquinone);
Vitamin A, retinoic acid and its esters with C1-C20;
Vitamins D2 and D3;
Alpha, beta, gamma and delta tocopherols or a mixture comprising at least two of the tocopherols;
Alpha, beta, gamma and delta tocotrienol, or a mixture comprising at least two of the tocotrienol;
A natural extract comprising at least one of the above compounds;
Phenolic diterpenes (eg carnosol, carnosic acid);
Cinnamic acid derivatives (2-ethoxyethyl p-methoxycinnamate, ethylhexyl p-methoxycinnamate, 2-ethylhexyl 4-methoxycinnamate, methyldiisopropyl cinnamate, isoamyl 4-methoxycinnamate, diethanolamine 4-methoxycinnamate And); and
LC-gallates, Eugenol, Thymol;
Including an oil-soluble antioxidant selected from the group consisting of:
The emulsion according to any one of claims 1 to 9, wherein the oil-soluble antioxidant has a concentration of 0.001 to 60 ppm.   11. Emulsion according to any of claims 1 to 10, wherein the carotenoid has an isomerized trans isomer content between 30 and 100%. The following steps:
a) preparing a solution comprising modified starch and / or at least one surfactant protein at a concentration of 0.7-70%, at least one carbohydrate at a concentration of 0.001-80%, and water and mixing the components;
b) Mixing at least one carotenoid at a concentration of 0.1-15% with triacylglycerol oil at a concentration of 1-30% and melting the dispersed carotenoid at a temperature of 100-200 ° C. Preparing the step,
c) introducing the solution of step b) into the solution of step a);
d) performing at least one step of pre-emulsification by passing the mixture of step c) through a rotor / stator mixer;
e) performing at least one step of high-pressure homogenization;
f) spray drying the emulsion of step e) to obtain a powder;
g-1) preparing an emulsion by introducing the powder of step f) into water;
Including
10. A process for producing an emulsion according to any one of the preceding claims, wherein the percentage is% by weight relative to the emulsion of steps c) to e). The following steps:
a) preparing a solution comprising modified starch and / or at least one surfactant protein at a concentration of 0.7-70%, at least one carbohydrate at a concentration of 0.001-80%, and water and mixing the components;
b) Mixing at least one carotenoid at a concentration of 0.1-15% with triacylglycerol oil at a concentration of 1-30% and melting the dispersed carotenoid at a temperature of 100-200 ° C. Preparing the step,
c) introducing the solution of step b) into the solution of step a);
d) performing at least one step of pre-emulsification by passing the mixture of step c) through a rotor / stator mixer;
e) performing at least one step (preferably two steps) of high-pressure homogenization;
Said percentage is the weight percent for the emulsion of steps c) to e),
f) spray drying the emulsion of step e) to obtain a powder;
g-2) preparing an emulsion by introducing the powder of step f) into water at a concentration of 5% to 70%, wherein the percentage is weight% relative to the concentration of the powder according to step f) in water A method for producing an oil-in-water emulsion containing an emulsified carotenoid. Mixing the carbohydrate in the emulsion in step c) or d);
Adding the water-soluble antioxidant after step c), d) or e);
Adding the oil-soluble antioxidant in step a), c) or d);
The manufacturing method according to claim 12 or 13, comprising one or more of alternative means including:   A powder comprising carotenoids obtained in step f) according to claim 12 or 14.   An oil-in-water emulsion containing a carotenoid obtained in step g-2) according to claim 13 or 14.   Use of an aqueous emulsion according to claim 16 or a powder according to claim 15 as a colorant (preferably a natural or natural colorant in foods, feeds, pharmaceuticals, cosmetics and / or skin preparations).   Use according to claim 17, as an alternative to azo dyes.