EP2601221A1

EP2601221A1 - Stabilizer

Info

Publication number: EP2601221A1
Application number: EP11740647.0A
Authority: EP
Inventors: Christian KÖPSEL
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2010-08-05
Filing date: 2011-08-03
Publication date: 2013-06-12
Also published as: WO2012017012A1; AU2011287566A1

Abstract

The present invention relates to a stabilizer comprising starch which contains at least one ester group as shown in formula (I), where M⁺ is an alkali metal, M²⁺ is an alkaline earth metal, R is an alkylene radical and R' is an alkyl or alkenyl group having 5 to 18 carbon atoms, and contains less than 0.1% by weight free alkyl- or alkenyl-dicarboxylic acid compounds or mixtures of these, based on the total weight of the starch, to a process for its preparation, and to its use for increasing the stability of a substance to be stabilized.

Description

stabilizer

The present invention relates to a stabilizer comprising starch which comprises at least one ester group corresponding to formula (I)

contains,

M ⁺ an alkali, M ²⁺ an alkaline earth metal,

R is an alkylene radical and

R 'is an alkyl or alkenyl group having 5 to 18 carbon atoms and

contains less than 0.1% by weight of free alkyl or alkenyl dicarboxylic acid compounds or mixtures thereof, based on the total weight of the starch,

a process for its preparation, and its use for increasing the stability of a substance to be stabilized.

Moreover, the present invention relates to the use of at least one such stabilized substance in animal feeds, foods, food supplements, cosmetics or pharmaceuticals. Furthermore, the invention relates to substances which contain a composition comprising the stabilizer according to the invention and a substance to be stabilized. N-octenyl succinate starch is used as an emulsifier in a number of oil-in-water emulsions in the food, pharmaceutical and industrial sectors (Trubiano, 1986: Succinate and substituted succinate derivatives of starch.) In OB Wurzburg (author) Modified starches: Properties and uses, pages 131-147, CRCPress, Inc. Boca Raton, Florida).

For the food industry, an n-octenyl succinate starch with a maximum degree of substitution with n-octenyl succinic acid of 3% and free, non-covalently bound n-octenyl succinic acid of less than 0.3% is permitted (PhD thesis by Yanjie Bai, Kansas State University, 2008).

WO2007 / 090610 describes the use of n-octenyl succinate starch in a composition containing β-carotene. WO2007 / 090614 describes an n-octenyl succinate starch in which substances having a molecular weight between 150 Da and 500 KDa are separated, and their use as an additive in animal and human nutrition as well as in cosmetics and pharmaceuticals. Drusch et al. (J. Agric. Food Chem., 2007, 55, 1 1044-1 1051) describe a study to determine the oxidation stability of microencapsulated fish oil. The microcapsules containing, inter alia, n-octenyl succinate starch were exposed to hydroperoxide and propanal. The object of the present invention was to provide a new starch-based stabilizer. This should be particularly suitable for products that are needed in animal or human nutrition, or are used in the field of cosmetics and pharmaceuticals. The focus was mainly on a stabilizer, the stability of various

should be able to increase to stabilizing substances.

Furthermore, the stabilizer should be suitable for rendering a substance to be stabilized inert to other materials. In particular, a storage of such a stabilized substance in aluminum containers should be made possible.

Accordingly, the stabilizer described above was found.

The stabilizer according to the invention can improve the stability of a substance to be stabilized, e.g. of a solid or a liquid. For the purposes of the present invention, "stability" is understood to mean the chemical stability of a liquid substance to be stabilized, which may increase the stability of one or more parameters, for example color characteristics or particle size and / or distribution is also the inertizing effect which the stabilizer according to the invention can have on a substance to be stabilized, that is to say the stabilizer thus stabilized

Substance does not react or only to a minor extent with other materials. These may be metals, for example. It is preferably rendered inert to aluminum or iron or the corresponding alloys or mixtures thereof, particularly preferably to aluminum or aluminum alloys, as contained for example in an aluminum container.

The stabilizer of the invention contains starch as described above. The starch may also be a mixture of various such starches. Particularly suitable according to the invention is starch based on a polysaccharide of the formula (C 6 H 2 C> 5) n. It generally consists of D-glucose units that are linked by glycosidic linkages. The macromolecular complex can consist of two components: amylose and amylopectin. Amylose is a linear chain with helical (screw ben-) structure, which are linked only a-1, 4-glycosidically. Amylopectin has a highly branched structure with a-1, 6-glycosidic and a-1, 4-glycosidic linkages. The level of amylopectin and amylose in the starch varies and depends on the botanical source from which the starch is isolated.

Starch can be isolated from any botanical source such as wheat, maize, kale, cereals, sago, rice or tapioca. The starch can also be a mixture of starches from different botanical sources. Preference is given to tapioca starch or waxy maize starch or a mixture thereof. Very particular preference is waxy Stäke.

The starch can also be isolated from genetically modified botanical sources. In the same way, starch can come from a mixture of genetically modified and non-genetically modified sources.

The stabilizer according to the invention contains starch which has at least one ester group corresponding to formula (I)

wherein M ^{+ is} an alkali metal, M ^{2+ is} an alkaline earth metal, R is an alkylene radical and R 'is an alkyl or alkenyl group of 5 to 18 carbon atoms.

If more than one ester group is contained, they may be the same type or have different structures. Preferably, the starch contains more than one ester group. These preferably each have the same structure.

Suitable counterions M ⁺ are, in particular, those alkali metals which are derived from lithium, sodium or potassium or, if more than one ester group is present, from a mixture thereof.

Preferred counterions M ^{2+ are} derived from magnesium or calcium or, when more than one ester group is included, a mixture thereof. In the presence of more than one ester group, it is also possible that a mixture of alkali and alkaline earth metal ions are contained as counterions. Preferably, the or the counterions are either M ⁺ or M ²⁺ . Particularly favored counterion is Na ⁺ . Preferred alkylene radicals R have only R 'as a side chain. In general, the chain length of the alkylene radicals can vary within wide limits. It is usually from 1 to 8 carbon atoms. It is preferably in the range from 1 to 5 carbon atoms, more preferably from 2 to 4, especially preferably 2 carbon atoms.

Both the alkyl and the alkenyl group R 'may be branched or unbranched, preferably it is in each case unbranched. The chain length of the alkyl or alkenyl group is preferably 5 to 10 carbon atoms, preferably 6 to 8 carbon atoms, more preferably 8 carbon atoms.

The degree of substitution of the starch useful in the present invention, i. the number of esterified hydroxyl groups compared to the number of free non-esterified

Hydrxoyl groups varies in the range of 0.1 to 3% based on the total number of hydroxyl groups present in the starch. The starch which is suitable according to the invention can also be a mixture of different degrees of substitution.

In a preferred embodiment, the starch useful in this invention is an n-octenyl succinate starch. To prepare the octenyl succinate starch, starch can be treated with cyclic n-octenyl succinate anhydride. A production process is described, inter alia, in US Pat. No. 2,661,349.

In a most preferred embodiment, the starch useful in the present invention is a sodium n-octenyl succinate starch. Currently commercially available octenyl succinate starches are, for example, Capsul ^® (Natriumoctenylsuccinat strength) from the Fa. National Starch, CLEARGUM CO 01 by Roquette or Puri- ty ^® Gum 2000 (Natriumoctenylsuccinat strength) from the Fa. National Starch, in particular a Natriumoctenylsuccinat Starch such as ^Purity® Gum 2000. The starch which is suitable according to the invention may have, in addition to the esterification, further modifications. The further modifications may take place before or after the esterification. The further modifications can be made by chemical reactions, enzymatic or physical modifications or a combination of these methods. For example, the starch may be partially (partially) hydrolyzed enzymatically. The enzymatic partial hydrolysis can be carried out by known methods with enzymes, for example with glycosylases and / or hydroxylases. In addition to the enzymatic partial hydrolysis, a partial chemical hydrolysis can also take place. Methods for this are known to the person skilled in the art.

The stabilizer according to the invention contains less than 0.1% by weight of free alkyl or alkenyl dicarboxylic acid compounds or mixtures thereof, based on the total weight of the starch contained in the stabilizer. Alkyl- or alkenyl-dicarboxylic acid compounds are preferably understood as meaning alkyl- or alkenyl-dicarboxylic acids, their salts and their anhydrides. These can be in both dissociated and undissociated form.

The term "free" is understood in the context of the present invention is not covalently bound.

In a preferred embodiment, the stabilizer according to the invention contains less than 0.1% by weight of free n-octenyl succinic acid compounds, in particular n-octenyl

Succinic acid, n-octenyl succinic acid sodium salt or n-octenyl succinic anhydride, based on the total weight of starch contained in the stabilizer.

In a further preferred embodiment, the stabilizer according to the invention contains no free alkyl or alkenyl-dicarboxylic acid compounds.

In the context of the present invention, the term "none" is understood to mean that the stabilizer according to the invention contains alkyl or alkenyl-dicarboxylic acid compounds or mixtures thereof below the detection limit The detection of the alkyl- or alkenyl-dicarboxylic acid compounds is described in the examples of the present application via a methanol extraction of the starch and a subsequent determination of the content of free alkyl or alkenyl dicarboxylic acid compounds or mixtures thereof by means of liquid chromatography In a particularly preferred embodiment, the stabilizer according to the invention contains no free n-octenyl succinic acid compounds.

The stabilizer may contain, in addition to the starch according to the invention, one or more further stabilizing compounds. These stabilizing compounds are preferably compounds which are authorized for the corresponding field of use, depending on the use of the stabilizer according to the invention. According to your approval these stabilizing compounds are divided into different categories.

The stabilizing compounds may be fat-soluble or water-soluble.

These stabilizing compounds may include compounds for oxidative stability such as ascorbic acid, its esters or their salts, water-soluble polyphenols such as hydroxytyrosol and oleuropein, aglycone, epigallocatechin gallate (EGCG), t-butylhydroxytoluene, t-butylhydroxyanisole, citric acid, ethoxyquine, propyl gallate, tertiary Butylhydroxyquinoline or 6-ethoxy-1,2-dihydroxy-2,2,4-trimethylquinoline (EMQ) or mixtures thereof. Furthermore, the stabilizer according to the invention may also contain stabilizing compounds for microbial stability, for example methyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, sorbic acid or benzoic acid or salts thereof or mixtures thereof. Furthermore, the stabilizer according to the invention may also contain emulsifiers. Examples of emulsifiers are ascorbyl palmitate, polyglycerol fatty acid esters, such as polyglycerol-3-polyricinoleate (PGPR 90), sorbitan fatty acid esters, such as sorbitan monostearate (span 60), PEG (20) sorbitol monooleate, propylene glycol fatty acid esters or phospholipids, such as lecithin, or mixtures from that.

Stabilizing compounds which can act as a protective colloid can be present in the stabilizer according to the invention. For example, the following gelantines are suitable: bovine, porcine or fish gelatin, in particular acidic or basic 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 with the Bloom number 0 and molecular weights of 15,000 to 25,000 Dal such as Collagel ^® A and Gelitasol ^® P (Stoess, Eberbach) and mixtures of these types of gelatin. Further, dextrin, pectin, gum arabic, ligninsulfonates, chitosan, polystyrenesulfonate, alginates, casein, caseinate, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose or mixtures thereof may be used as the protective colloid.

The protective colloids may also include plant proteins, such as soybean, rice and / or wheat proteins, these vegetable proteins being able to be partially degraded or in undecomposed form.

In the stabilizer according to the invention, the weight ratio of the starch suitable according to the invention to at least one further stabilizing compound is 10: 1 to 1:10, preferably 4: 1 to 1: 4, in particular 3: 1 to 1: 1.

In addition to the starch according to the invention, the stabilizer according to the invention preferably also contains native starch, modified starch, dextrin, pectin, gum arabic, ligninsulfonates, chitosan, polystyrenesulfonate, alginates, casein, caseinate, methylcellulose, carboxymethylcellulose, hydroxypropylcellulose, vegetable proteins such as soya, Rice and / or wheat proteins, which plant proteins may be partially degraded or present in undegraded form.

Modified starches are starches with chemical, enzymatic and / or physical modifications which have no ester group corresponding to the starch contained according to the invention. The starches may have one or more modifications.

Another object of the invention is a process for the preparation of the stabilizer according to the invention. The preparation process involves the separation of free alkyl or alkenyl Dicarboxylic acid compounds or mixtures thereof of starch containing at least one ester group of the formula (I)

contains,

M ⁺ an alkali, M ²⁺ an alkaline earth metal,

R is an alkylene radical and

R 'is an alkyl or alkenyl group having 5 to 18 carbon atoms

by reprecipitation to a residual content of less than 0.1 wt.% Based on the total weight of the starch and optionally the addition of one or more further stabilizing compounds. For a more detailed description of the starch and the other stabilizing compounds, reference is made to the preceding text. The reprecipitation is generally carried out with a medium in which either the starch suitable according to the invention or the free alkyl- or alkenyl-dicarboxylic acid compounds are not soluble.

The reprecipitation is preferably carried out with a medium in which the starch present in the stabilizer according to the invention is not soluble, but the free alkyl or alkenyl-dicarboxylic acid compounds are dissolved. In a preferred embodiment, the reprecipitation is carried out with at least one alcohol or a mixture of at least one alcohol and water. In a particularly preferred embodiment, the reprecipitation is carried out with ethanol from water. In a further preferred embodiment, the separation of the free alkyl or alkenyl dicarboxylic acid compounds or mixtures is carried out below their detection limit, i. after separation no residual content is present in the stabilizer according to the invention.

For the reprecipitation of starch with alcohol, the person skilled in the art has in principle methods available which he can apply in the present case.

Another object of the invention is a composition comprising the stabilizer of the invention and a substance to be stabilized. A "substance to be stabilized" may be a single substance or a mixture of substances to be stabilized.

In a preferred embodiment of the invention, the substance to be stabilized comprises a fat-soluble substance or a mixture thereof. In the context of the present invention, the term "fat-soluble" is understood to be lipophilic (fat-loving) Fat-soluble substances are easily dissolved in fats and oils In a preferred embodiment of the invention, the fat-soluble substance is a carotenoid, a fat-soluble vitamin and / or a PUFA (polyunsaturated fatty acid).

As carotenoids are generally understood the known, accessible from natural or synthetic sources representatives. Examples of these are alpha-carotene, beta-carotene, gamma-carotene, lycopene, lutein, astaxanthin, zeaxanthin, cryptoxanthin, citranaxanthin, canthaxanthin, echinenone, bixin, β-Αρο-4-carotenal, β-Αρο-8-carotenal, β -Apo-4-carotenoic acid ester, singly or as a mixture. Preferably, a carotenoid is selected from the group consisting of alpha-carotene, beta-carotene, gamma-carotene, astaxanthin, canthaxanthin, citranaxanthin, lycopene and lutein. Very particular preference is given to beta-carotene.

The fat-soluble vitamins generally include vitamins A, E, D and K including their derivatives, for example vitamin A esters such as vitamin A acetate, vitamin A propionate or vitamin A palmitate and vitamin E esters such as tocopheryl acetate. Within the scope of the invention, they can be used in the form of vitamin solutions in oils, as provitamins, or as pure vitamins of natural or synthetic origin. Preference is given to vitamin A and E and their derivatives. Particularly preferred are vitamin A acetate, vitamin A propionate and vitamin A palmitate or vitamin E acetate and mixtures thereof, most preferably vitamin A acetate and / or vitamin E acetate. The PUFAs (polyunsaturated fatty acids) include polyunsaturated fatty acids, preferably having a chain length of 18, 20 or 22 carbon atoms with 2 to 6 double bonds in cis conformation. Biologically relevant are the omega-3 fatty acids and omega-6 fatty acids. In the case of omega-3 fatty acids, the last double bond in the polyunsaturated carbon chain is the third-most C-C bond from the carboxyl end. Omega-3 fatty acids include alpha-linolenic acid (ALA, 18: 3ω-3), eicosapentaenoic acid (EPA, 20: 5ω-3) and docosahexaenoic acid (DHA, 22: 6ω-3). For omega-6 fatty acids, the last double bond in the polyunsaturated carbon chain is at the sixth-most C-C bond seen from the carboxyl end. Examples of omega-6 fatty acids are linoleic acid (18: 2 ω-6, 9Z, 12Z-octadecadienoic acid), gamma-linolenic acid (18: 3 ω-6, 6Z, 9Z, 12Z-octadecadienoic acid), and arachidonic acid (20: 4 ω-6, 5Z, 8Z, 1 1Z, 14Z-

Eicosatetraenoic). The long-chain polyunsaturated fatty acids are preferably alpha-linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, linoleic acid, gamma-linolenic acid, arachidonic acid or a mixture thereof. Particularly preferred are the long-chain polyunsaturated fatty acids eicosapentaenoic acid, docosahexaenoic acid or a mixture thereof.

The composition of the invention may also adjuvants such as thickeners, hard fats, chelating agents, such as alkali or alkaline earth salts of citric acid, phytic acid or Contain phosphoric acid and / or emulsifiers, as far as they are not already included in the stabilizer according to the invention. Examples of emulsifiers are ascorbyl palmitate, polyglycerol fatty acid esters, such as polyglycerol-3-polyricinoleate (PGPR 90), sorbitan fatty acid esters, such as sorbitan monostearate (span 60), PEG (20) sorbitol monooleate, propylene glycol fatty acid esters or phospholipids, such as lecithin ,

The composition according to the invention preferably contains from 5 to 99% by weight of the stabilizer according to the invention and from 5 to 95% by weight of the substance to be stabilized, more preferably from 40 to 99% by weight of the stabilizer according to the invention and from 1 to 60% by weight stabilizing substance, in particular a fat-soluble substance, in each case based on the total weight of the composition.

The composition according to the invention may also contain auxiliaries, such as thickeners, hard fats, chelating agents and / or emulsifiers. Preferably, the composition then contains from 5 to 80% by weight of the stabilizer according to the invention and from 1 to 60% by weight of the substance to be stabilized, more preferably from 30 to 60% of the stabilizer according to the invention and from 5 to 50% by weight of the substance to be stabilized, in particular a fat-soluble substance, in each case based on the total weight of the composition, the sum of the ingredients of the composition giving 100% by weight.

In a further preferred embodiment, the composition according to the invention contains from 1 to 20% by weight carotenoid and from 5 to 99% by weight of the stabilizer according to the invention, particularly preferably from 1 to 20% by weight carotenoid and from 30 to 60% by weight of the stabilizer according to the invention , in each case based on the total weight of the composition. The sum of the ingredients of the composition results in each case 100 wt.%, Wherein the inventive composition may also contain adjuvants and / or another substance to be stabilized.

In a further preferred embodiment, the composition according to the invention contains from 30 to 50% by weight of vitamin A and from 5 to 70% by weight of the stabilizer according to the invention, in particular, in each case based on the total weight of the composition. The sum of the ingredients of the composition is in each case 100% by weight, and the composition according to the invention may also contain adjuvants and / or a further substance to be stabilized, in particular vitamin E.

In a further preferred embodiment, the composition according to the invention contains from 10 to 60% by weight of vitamin E and from 5 to 90% by weight of the stabilizer according to the invention, more preferably from 10 to 60% by weight of vitamin E and from 30 to 60% by weight of Stabilizer according to the invention in each case based on the total weight of the composition. The sum of the ingredients of the composition results in each case 100 wt.%, Wherein the inventive composition may also contain adjuvants and / or another substance to be stabilized. In a further preferred embodiment, the composition according to the invention contains from 1 to 40% by weight PUFA and from 5 to 99% by weight of the stabilizer according to the invention, particularly preferably from 1 to 40% by weight PUFA and from 30 to 60% by weight of the stabilizer according to the invention , in each case based on the total weight of the composition. The sum of the ingredients of the composition results in each case 100 wt.%, Wherein the inventive composition may also contain adjuvants and / or another substance to be stabilized.

Another object of the invention is a method for stabilizing a substance to be stabilized that comprises mixing a stabilizer according to the invention with a substance to be stabilized.

The respective mixing method depends on the components to be mixed. The person skilled in the art selects a suitable mixing method. Among the preferred mixing methods is emulsification.

The mixing can be done for example by mixing chamber micronization, emulsification, milling, extrusion or a combination thereof. The mixing chamber micronization can be carried out, for example, according to the method described in EP 0 065 193. The production of finely divided, pulverulent carotenoid preparations can be carried out by dissolving a carotenoid in a volatile, water-miscible organic solvent at elevated temperatures, optionally under elevated pressure, the carotenoid precipitating by mixing with an aqueous solution of the stabilizer according to the invention and then dried.

An emulsification process are described, for example, in DE 12 1 1 91 1 or EP 0 410 236, it being possible for the stabilizer according to the invention to be present in the aqueous solution. In WO 2007/003543, for example, a grinding method is described in which ß-carotene is comminuted as a suspension by grinding in the presence of sucrose or glucose and modified starch to a particle size of about 0.6 μιη and then the carotenoid-containing suspension in a Dry powder is transferred. The grinding process described can also be carried out in the presence of the stabilizer according to the invention.

Extrusion methods are known, for example, from WO 00/21504 and WO 04/009054. In the emulsification process, for example, an emulsion comprising the substance to be stabilized and the stabilizer according to the invention is first formed, which is then extruded with a matrix.

Another object of the invention is the use of the stabilizer according to the invention for increasing the stability of a substance to be stabilized. Thus, the invention proper compositions come readily in contact with aluminum and or iron-containing materials.

By using the stabilizer according to the invention, for example, a storage of a substance to be stabilized in an aluminum container is made possible, since there is no pox formation or pitting. Storage in aluminum containers is of great advantage over, for example, plastic containers, especially in the case of substances that are sensitive to light and / or to oxidation. Storage can reach up to one year. However, it is also possible to store the substance to be stabilized or the composition according to the invention for more than one year in an aluminum and / or iron-containing container, e.g. up to two years. The storage period can also be longer, for example, up to three years.

Furthermore, the clarification (creaming, sedimentation) of the composition according to the invention is improved by the use of the stabilizer according to the invention. Likewise, the use of the stabilizer according to the invention does not lead to any growth of the particles during storage, when the composition is a dispersion. Agglomeration tendency is reduced or agglomeration does not occur.

In a further preferred embodiment, the substance to be stabilized is an additive to an animal feed, food or dietary supplement, as well as cosmetic or pharmaceutical. The composition is suitable inter alia as an additive to an animal feed or to food preparations or compound feed, as an agent for the production of a pharmaceutical and cosmetic preparation and for the production of a dietary supplement in the human or animal sector. Preferably, the composition can be used as a feed additive in animal nutrition, for example by mixing in feed pellets during extrusion or by applying or spraying on feed pellets. The application as a feed additive is effected in particular by direct spraying of the composition according to the invention, for example as a so-called "post-pelleting application." Preferably, the feed pellets are loaded with the compositions under reduced pressure.

Typical applications in the food industry are, for example, the vitaminization and coloring of beverages, dairy products such as yoghurt, milk mix drinks or milk ice cream, as well as pudding powders, egg products, baking mixes and confectionery. In the cosmetics sector, the composition can be used, for example, for decorative personal care products, for example in the form of a cream, a lotion, as a lipstick or make-up. Another object of the invention is a substance containing composition of the invention. Preferably, the substance is an animal feed, a food, a dietary supplement, a cosmetic or a pharmaceutical. The invention is illustrated by the following non-limiting examples:

Examples Detection of free alkyl or alkylene dicarboxylic acids Extraction and provision of the sample solution

Approximately 500 mg of starch was extracted with 15 ml of methanol for 12 h with constant shaking. The extraction mixture was filtered. The starch on the filter was washed with 7 ml of methanol. This was repeated three times. All filtrates are combined. Approximately 80% of the free alkyl or alkylene succinic compounds were extracted. To the filtrates was added 1 ml of a 0.16 N methanolic KOH solution. The filtrates were dried at 30 ° C in a flash evaporator. The residue was dissolved in 2 ml of methanol. 0.5 ml of this residue solution was transferred to another vessel. To this 0.5 ml of the residue solution was added 0.5 ml of a derivatizing solution (2.8 g of 2-p-dibromoacetophenone and 0.28 g of 18-crown-6 in 50 ml of CH ₃ CN). After sealing the vessel, a treatment was carried out at 80 ° C for 30 min. Thereafter, the solution was cooled to room temperature and used within 24 h. Analysis by liquid chromatography

Column: Micro Bondapack C18 (Waters) or an equivalent column

Mobile phase: elution with a gradient of 70% methanol in water to 80% methanol in water within 5 minutes

Flow rate: 1.5 ml / min

Detector: UV at 254 nm, attenuation 0.16 AUFS,

Injection volume: 5 μΙ

Create the calibration curve

A 0.5 M solution of sodium cetenyl succinate was prepared (solution A). 0.25 ml of solution A was transferred to another vessel and diluted with methanol (solution B). Three different calibration standards were prepared by adding 0.5 ml, 1 ml and 2 ml of solution B to the 0.25 ml of solution A. To each of these mixtures was added 1 ml of a 0.16N methanolic KOH solution. Each solution was dried at 30 ° C. The supernatant was dissolved in 2 ml of methanol (solutions C1, C2 and C3). 0.5 ml of these residue solutions were transferred to another vessel. To this 0.5 ml of the residue solutions was added 0.5 ml of a derivatizing solution (2.8 g of 2-p-dibromoacetophenone and 0.28 g of 18-crown-6 in 50 ml of CH ₃ CN). After closing the vessels, treatment was carried out at 80 ° C for 30 minutes. Thereafter, the solutions were cooled to room temperature. 5 μΙ each were used for liquid chromatography. The content of residues in these 5 μΙ was:

For solution C1, 0.2375 μg

For solution C2 0.4750 μg

For solution C3 0.9500 μg

Calculation:

A calibration curve was prepared according to the procedure described above. Based on the height of the peak of the unknown solution in liquid chromatography, the content of free alkyl and alkylene compounds (calculated as octenyl succinic acid) in the injection volume could be determined by means of the calibration curve.

% free alkyl and alkylene compounds: 300 * value of graphene / Weight of starch (mg)

Note: The formula was corrected to 100% yield by dividing by 0.8 (240 / 0.8 = 300)

Example 1 :

Preparation of Composition 1 (Invention): Composition containing no free n-octenyl succinic acid compound

380 g of water were initially charged and heated to 60.degree. To this was added 17 grams of reprecipitated (containing no free alkyl or alkenyl-dicarboxylic acid compounds) Purity Gum 2000 (National Starch), 175 grams of glucose and 5.6 grams of sodium ascorbate. The mixture (solution L4) was allowed to swell at 60 ° C for 60 minutes.

18.7 g of .beta.-carotene dispersion (Lucarotin ^® MCT 20, BASF) were heated on a heated to 180 ° C oil bath until the beta-carotene was completely dissolved. The oil phase was then introduced into the water phase while agitating with a toothed wheel dispersing machine (Ultra Turrax) at 10,000 rpm. After an emulsification time of 15 minutes, the emulsion was applied by means of a

High-pressure homogenizer finely emulsified at 700 bar. After spray-drying, a free-splitting, cold-water-dispersible powder with a β-carotene content of 1.15% was obtained. Preparation of composition 2 (for comparison): Composition with 0.1% by weight of free n-octenyl-succinic acid compounds The preparation corresponds to the preparation of composition 1, to which additional 0.51 g of 23% strength o-tosylsuccinic acid salt were added to the solution L4 has been.

Preparation of Composition 3: Composition with 0.5% by weight of free n-octenyl succinic acid compounds (comparative example)

The preparation corresponds to the preparation of composition 1, wherein in addition to the solution L4 2.55 g of 23% strength Octenylbernsteinsäurenumsumsalz was added.

From Compositions 1, 2 and 3, particle size and clearness were measured before and after storage for 5 hours at room temperature. The measurement of the clearing was carried out by means of a Lumifuge (Dispersion Stability and Particle Characterization by Sedimentation Kinetics in a Centrifuge Field, D. Lerche, Journal of Dispersion Science and Technology Vol. 23, No. 5, pp. 699-709; Rapid Assessment of Sedimentation M. Kuentz, D. Röthlisberger, European Journal of Pharmaceutics 56 (2003) 355-361). The particle size was measured by means of light scattering. The results are shown in Table 1.

Table 1: Results of particle size and elution measurements before and after 5 h storage at room temperature.

Composition 1 Composition 2 Composition 3

(Inventive) (Comparative Example) (Comparative Example)

Particle size 160 157 161

without storage

[Nm]

Particle size 165 168 177

after 5 h storage

at RT [nm]

Δ particle size 5 1 1 16

Clarification without 17.6 14.5 15.9

Storage [%]

Clarification after 5 21, 1 21, 1 33,8

h storage at RT

[%]

Δ Clarification 3.5 6.6 17.9 Example 2:

Storage of a composition comprising the stabilizer according to the invention and .beta.-carotene in an aluminum container.

Compositions according to compositions 3 (comparative example) and 1 (example of the invention) were stored in an aluminum container over a period of 14 days at room temperature. In the comparative example in which no stabilizer according to the invention was used, a change in the aluminum content could be observed after storage. The storage leads to a larger pitting on the aluminum container (2 to 3 mm, see Fig. 1) and a small pox, especially on the side walls of the Alumniumgebindes (see Fig. 2). By contrast, in the composition in which the stabilizer of the present invention was used, no change in the aluminum package was observed.

Claims

claims:

Stabilizer containing starch which contains at least one ester group of the formula (I)

contains,

M ⁺ an alkali metal, M ²⁺ an alkaline earth metal,

R is an alkylene radical and

R 'is an alkyl or alkenyl group having from 5 to 18 carbon atoms and the stabilizer is less than 0.1% by weight of free alkyl or alkenyl dicarboxylic acid compounds or mixtures thereof, based on the total weight of the starch,

contains.

A stabilizer according to claim 1 wherein the stabilizer does not contain free alkyl or alkenyl dicarboxylic acid compounds.

A stabilizer according to any one of claims 1 or 2, wherein the starch is a sodium n-octenyl succinate starch.

Process for the preparation of a stabilizer according to at least one of Claims 1 to 3 comprising the removal of free alkyl or alkenyl

Dicarboxylic acid compounds or mixtures thereof of starch according to any one of claims 1 to 3, by reprecipitation to a residual content of less than 0.1 wt.%, Based on the total weight of the starch.

The method of claim 4, wherein the reprecipitation is carried out with ethanol.

A method according to claim 4 or 5, wherein after separation there is no residual content of free alkyl or alkenyl dicarboxylic acid compounds in the stabilizer.

7. A composition comprising a stabilizer according to any one of claims 1 to 3 or obtainable by a method according to any one of claims 4 to 6 and a substance to be stabilized.

8. The composition of claim 7, wherein the substance to be stabilized comprises a fat-soluble substance.

9. The composition of claim 8, wherein the substance to be stabilized comprises at least one carotenoid, a fat-soluble vitamin, a PUFA (polyunsaturated fatty acid) or a mixture thereof.

10. The composition according to claim 9, wherein the substance to be stabilized comprises astaxanthin, alpha-carotene, beta-carotene, gamma-carotene, vitamin A, vitamin E, PUFA, lutein, lycopene or a mixture thereof.

1 1. A method for stabilizing a substance to be stabilized, according to at least one of claims 7 to 10, comprising mixing at least one stabilizer according to at least one of claims 1 to 3 or obtainable by a process according to at least one of claims 4 to 6, with one to be stabilized Substance according to at least one of claims 7 to 10.

12. Use of a stabilizer according to any one of claims 1 to 3 or obtainable by a process according to any one of claims 4 to 6, for increasing the stability of a substance to be stabilized, according to at least one of claims 7 to 10.

13. Use according to claim 12, wherein the substance to be stabilized is an additive to an animal feed, food, dietary supplement, cosmetic or pharmaceutical.

14. Use according to claim 12, for inerting the substance to be stabilized with respect to iron, aluminum or an iron and / or aluminum-containing alloy.

15. A substance containing a composition according to any one of claims 7 to 10.

A fabric according to claim 15, wherein the fabric is an animal feed, a food, nutritional supplement, a cosmetic or a pharmaceutical.