US20140377435A1 - Lipophilic Antioxidant - Google Patents

Lipophilic Antioxidant Download PDF

Info

Publication number
US20140377435A1
US20140377435A1 US14/479,533 US201414479533A US2014377435A1 US 20140377435 A1 US20140377435 A1 US 20140377435A1 US 201414479533 A US201414479533 A US 201414479533A US 2014377435 A1 US2014377435 A1 US 2014377435A1
Authority
US
United States
Prior art keywords
composition
oil
emulsifier
fatty acids
group
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US14/479,533
Inventor
Michael Müller
Peter Horlacher
Katja Beck
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cognis IP Management GmbH
Original Assignee
Cognis IP Management GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cognis IP Management GmbH filed Critical Cognis IP Management GmbH
Priority to US14/479,533 priority Critical patent/US20140377435A1/en
Publication of US20140377435A1 publication Critical patent/US20140377435A1/en
Assigned to COGNIS IP MANAGEMENT GMBH reassignment COGNIS IP MANAGEMENT GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HORLACHER, PETER, Müller, Michael, BECK, KATJA
Abandoned legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/005—Edible oil or fat compositions containing an aqueous phase, e.g. margarines characterised by ingredients other than fatty acid triglycerides
    • A23D7/0053—Compositions other than spreads
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3544—Organic compounds containing hetero rings
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23B—PRESERVING, e.g. BY CANNING, MEAT, FISH, EGGS, FRUIT, VEGETABLES, EDIBLE SEEDS; CHEMICAL RIPENING OF FRUIT OR VEGETABLES; THE PRESERVED, RIPENED, OR CANNED PRODUCTS
    • A23B9/00—Preservation of edible seeds, e.g. cereals
    • A23B9/16—Preserving with chemicals
    • A23B9/24—Preserving with chemicals in the form of liquids or solids
    • A23B9/26—Organic compounds; Microorganisms; Enzymes
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23C—DAIRY PRODUCTS, e.g. MILK, BUTTER OR CHEESE; MILK OR CHEESE SUBSTITUTES; MAKING THEREOF
    • A23C9/00—Milk preparations; Milk powder or milk powder preparations
    • A23C9/152—Milk preparations; Milk powder or milk powder preparations containing additives
    • A23C9/1528—Fatty acids; Mono- or diglycerides; Petroleum jelly; Paraffine; Phospholipids; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D7/00—Edible oil or fat compositions containing an aqueous phase, e.g. margarines
    • A23D7/01—Other fatty acid esters, e.g. phosphatides
    • A23D7/011—Compositions other than spreads
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/007—Other edible oils or fats, e.g. shortenings, cooking oils characterised by ingredients other than fatty acid triglycerides
    • A23D9/013—Other fatty acid esters, e.g. phosphatides
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23D—EDIBLE OILS OR FATS, e.g. MARGARINES, SHORTENINGS, COOKING OILS
    • A23D9/00—Other edible oils or fats, e.g. shortenings, cooking oils
    • A23D9/06—Preservation of finished products
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0014—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0028—Carboxylic acids; Their derivates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0021—Preserving by using additives, e.g. anti-oxidants containing oxygen
    • C11B5/0035—Phenols; Their halogenated and aminated derivates, their salts, their esters with carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11B—PRODUCING, e.g. BY PRESSING RAW MATERIALS OR BY EXTRACTION FROM WASTE MATERIALS, REFINING OR PRESERVING FATS, FATTY SUBSTANCES, e.g. LANOLIN, FATTY OILS OR WAXES; ESSENTIAL OILS; PERFUMES
    • C11B5/00—Preserving by using additives, e.g. anti-oxidants
    • C11B5/0092—Mixtures
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
    • A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs

Definitions

  • the present invention relates to a composition containing a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, and also to the use of this mixture as lipophilic antioxidant.
  • a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, and also to the use of this mixture as lipophilic antioxidant.
  • tocopherols and ascorbyl palmitate are used in order to protect, for example, oils containing fatty acids having at least one double bond from oxidation.
  • Catechins are natural substances which occur in nature as plant components. They are hydrogenated flavones. Catechins include, in particular, catechin, epicatechin, gallocatechin and epigallocatechin. In the sense of the present invention, “catechin” or “a catechin” always means a compound selected from the group of catechins. “Catechin” is not the catechin meant in the narrow sense. If the catechin in the narrow sense is meant, then this will be also designated “catechin in the narrow sense”. Catechins occur, for example, in green tea and can be extracted from this. Dried leaves of green tea can contain, for example, 8.5 to 20.6% by weight of catechins.
  • catechins and catechins in green tea may be found, e.g., in Renapp Online, Version 3.0, published by Georg Thieme Verlag, under the headwords “Catechine” [Catechins] and “Tee” [Tea].
  • Catechins are active antioxidants and also have other beneficial properties. However, catechins are hydrophilic and therefore cannot readily be used as antioxidants in lipophilic media. It is therefore desirable to make catechins available as antioxidants for lipophilic media.
  • Catechins are highly water soluble but very sparingly oil-soluble antioxidants. Recent scientific studies verify in addition health-promoting properties of catechins such as, e.g., accelerated fat combustion, anticarcinogenic activity etc.
  • the oil insolubility restricts the formulation ability of catechins to aqueous systems which prevents their use as additives for oils or a mixture of oils.
  • polyphenols in general in particular those having antioxidant properties, are also usable as antioxidants. It is therefore desirable to be able to use not only catechins, but polyphenols in general, as antioxidants in lipophilic media also.
  • the formulations should be free from short-chain and medium-chain alcohols.
  • Diterpenes are natural substances having 20 carbon atoms which are made up of four isoprene units. They belong to the terpene group. Compounds designated diterpenes are not only hydrocarbons, but also derivatives of the corresponding hydrocarbons. Phenolic diterpenes are those diterpenes which contain at least one phenolic OH group. Carnosolic acid belongs to the phenolic terpenes.
  • WO 94/22321 discloses solutions of catechins in nonionic solvents. These solutions can be used as antioxidants in fats and oils.
  • solvents in particular nonionic surfactants are disclosed, in particular lecithin and fatty alcohols having 8-18 carbon atoms are disclosed.
  • lecithin and fatty alcohols having 8-18 carbon atoms are disclosed.
  • glycerol monooleate is disclosed as solvent.
  • KR 2001079020 and JP-A 63135483 likewise disclose lipophilic antioxidants which contain catechins.
  • the object of the present invention was to provide substances which are usable as lipophilic antioxidants.
  • compositions containing a first component selected from the group consisting of at least one polyphenol (in particular a polyphenol having antioxidant properties, preferably at least one catechin), at least one phenolic diterpene (preferably carnosolic acid) and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, wherein the hydrophilic emulsifier is selected from the group consisting of DATEM, CITREM, LACTEM, ACETEM and a sugar ester.
  • a first component selected from the group consisting of at least one polyphenol (in particular a polyphenol having antioxidant properties, preferably at least one catechin), at least one phenolic diterpene (preferably carnosolic acid) and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, wherein the hydrophilic emulsifier is selected from the group consisting of DATEM,
  • a particular embodiment of the present invention is the composition according to the invention, wherein the first component is a catechin or a mixture of catechins and wherein this is preferably in the form of an extract of the leaves of green tea.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the first component is a phenolic diterpene or a mixture of phenolic diterpenes, preferably carnosolic acid.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the glyceride is a triglyceride, the three fatty acids of which each have 6 to 18 carbon atoms.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the hydrophilic emulsifier is selected from the group consisting of DATEM, CITREM, LACTEM and ACETEM.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the compositions mentioned in the paragraphs hereinbefore, wherein the hydrophilic emulsifier is a sugar ester.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the hydrophobic emulsifier is selected from the group consisting of a polyglycerol polyricinoleate, a polyglycerol ester of fatty acid and glycerol monoester of fatty acid (i.e. a monoglyceride; in particular such a monoglyceride having a fatty acid having 10 to 30 carbon atoms, in particular glycerol monooleate or glycerol monostearate).
  • a polyglycerol polyricinoleate a polyglycerol ester of fatty acid and glycerol monoester of fatty acid
  • glycerol monoester of fatty acid i.e. a monoglyceride; in particular such a monoglyceride having a fatty acid having 10 to 30 carbon atoms, in particular glycerol monooleate
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, additionally containing water.
  • a further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, containing 1 to 20% by weight, in particular 5 to 15% by weight, of the first component, 2 to 70% by weight, in particular 20 to 50% by weight of glyceride, 3 to 60% by weight, in particular 15 to 35% by weight of hydrophilic emulsifier, 3 to 60% by weight, in particular 15 to 35% by weight, of hydrophobic emulsifier and 0 to 30% by weight, in particular 0 to 1% by weight, of water.
  • the present invention further relates to a process for producing the composition according to the invention or one of the compositions mentioned in the paragraphs hereinbefore which comprises providing a mixture containing the hydrophilic emulsifier and the hydrophobic emulsifier, optionally warming this mixture to a temperature of at least 50° C., adding the first component to this mixture (optionally with stirring) and thereafter adding the glyceride.
  • the present invention further relates to a use of the composition according to the invention or of one of the particular compositions mentioned in the paragraphs hereinbefore as antioxidant for lipophilic media, wherein the lipophilic medium preferably contains an oil or fat and in particular is a food.
  • the present invention further relates to a second composition containing oil or fat and, based on the mass of the oil or fat, 0.05 to 3% by weight of the composition according to the invention or of one of the particular compositions mentioned in the paragraphs hereinbefore.
  • a further particular embodiment of the present invention is said second composition, wherein the oil or fat is selected from the group consisting of a fat or oil which contains unsaturated fatty acid radicals (in particular radicals of linoleic acid, linolenic acid or oleic acid), fish oil, sunflower oil, borage oil, a glyceride which contains acyl radicals of conjugated linoleic acid and a triglyceride, the acyl radicals of which have 6 to 24 carbon atoms.
  • unsaturated fatty acid radicals in particular radicals of linoleic acid, linolenic acid or oleic acid
  • fish oil in particular radicals of linoleic acid, linolenic acid or oleic acid
  • sunflower oil in particular radicals of linoleic acid, linolenic acid or oleic acid
  • borage oil a glyceride which contains acyl radicals of conjugated linole
  • a further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is an oil-in-water emulsion.
  • a further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is granules or a powder.
  • Powders for the purposes of the present invention are also all further formulations having a solids character, such as, e.g., granules.
  • a further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is a food, in particular one such selected from the group consisting of an oil, a fat, olive oil, butter, margarine, milk, a milk product, cheese, yogurt, a chocolate bar and a muesli bar.
  • the hydrophilic emulsifier can be selected, in particular, from the group consisting of DATEM, CITREM, LACTEM and ACETEM.
  • DATEM is a composition of matter containing mono- and diacetyl tartaric esters of mono- and diglycerides of edible fatty acids
  • DATEM is a composition of matter which contains substituted glycerol molecules which are esterified at at least two OH groups and which bear at least one fatty acid radical (more than 50 mol % of the fatty acid radicals have 16 or 18 carbon atoms) and which bear at least one tartaric acid radical which in turn is monoacetylated or diacetylated.
  • CITREM is a composition of matter containing citric esters of mono- and diglycerides of edible fatty acids.
  • LACTEM is a composition of matter containing lactic esters of mono- and diglycerides of edible fatty acids.
  • ACETEM is a composition of matter containing acetic esters of mono- and diglycerides of edible fatty acids.
  • Edible fatty acids have, in particular, 6 to 24 carbon atoms.
  • a hydrophobic emulsifier has an HLB value of less than 8
  • a hydrophilic emulsifier has an HLB value of at least 8.
  • the HLB value can be determined for nonionic emulsifiers in accordance with Griffin, and for ionic emulsifiers in accordance with Davies. For determination of HLB values see: Tensid-Taschenbuch [Surfactant Handbook], 2nd edition, edited by H. Stache, Carl Hanser Verlag, 1981.
  • PGPR polyglycerol polyricinoleate
  • Ricinoleic acid is 12-hydroxyoleic acid and can form a polyester with itself.
  • Esters of polycondensed castor oil fatty acids with polycondensed glycerol are permitted as a food additive in Germany under the designation E 476.
  • Polyglycerol fatty acid esters can, for example, have the composition of the commercial product Polymuls® 2G from Cognis GmbH, Monheim, Germany.
  • a sugar ester for the purposes of the present invention is, in particular, an ester of a molecule of a sugar selected from the group consisting of sucrose, fructose, glucose and trehalose (sucrose is preferred) and one to three molecules of edible fatty acid (preferably a fatty acid having 6 to 24 carbon atoms).
  • a glyceride for the purposes of the present invention is an ester of glycerol with 1, 2 or 3 fatty acids.
  • a monoglyceride here is an ester of glycerol with one fatty acid
  • a diglyceride is an ester of glycerol with two fatty acids
  • a triglyceride is an ester of glycerol with three fatty acids.
  • Fatty acids in this case are preferably carboxylic acids having 2 to 30, in particular 2 to 20, in particular 6 to 18, in particular 8 to 10, carbon atoms.
  • Triglycerides are glycerides which are preferred according to the invention.
  • CLA is an abbreviation for conjugated linoleic acid, that is for an octadecadienoic acid, wherein the two double bonds are not separated by one or more saturated carbon atoms, but start at carbon atoms no. n and n+2 (n is a natural number from 2 to 15).
  • the double bonds are situated either at positions 9 and 11 (9,11-octadecadienoic acid) or at positions 10 and 12 (10,12-octadecadienoic acid).
  • E-Z isomerism is possible at each double bond.
  • CLA isomers possible for CLA are designated by the symbols c for cis and t for trans and by quoting the numbers for the position of the double bonds, that is to say, e.g., c9,t11-CLA.
  • CLA is c9,t11-CLA or t10,c12-CLA.
  • composition according to the invention has numerous advantages over the prior art.
  • the composition according to the invention must contain no alcohols. It must not contain glycerol monooleate; this is advantageous in some cases, since glycerol monooleate in some cases has a tendency to form ⁇ -phases which can become noticeable as unwanted deposits in formulations.
  • ⁇ -phases in glycerol monooleate see “Emulgatoren für Struktur” [Emulsifiers for Foods], published by Gregor Schuster, Springer-Verlag, 1985, pages 82 to 87.
  • compositions according to the invention contain the catechin only in a concentration of 2.7% by weight.
  • the compositions according to the invention can have a catechin content which is up to approximately four times higher. That means approximately four times less (frequently undesired) auxiliaries are also introduced into the final formulation (at comparable catechin concentrations in the end formulation).
  • the compositions according to the invention are flexible to a certain extent in the choice of glyceride (auxiliary oil). Fish oil, for example, can be used as such. The introduction of auxiliary into the end formulation can be reduced still further.
  • composition according to the invention exhibits a significantly better antioxidant activity than conventional antioxidants.
  • the very good antioxidant activity leads to an improved long-term stability and improved sensory stability of the stabilized products.
  • the products stabilized by the composition according to the invention have good sensory properties. For instance, they do not have, e.g., an unpleasant bitter taste as is the case with, e.g., the emulsifier polysorbate 60 (commercially available as Tween 60).
  • composition according to the invention does not require any alcohols and may be formulated not only with water but also without water.
  • the water-containing concentrates then, after dissolution in oil, preferably give a W/O microemulsion.
  • the antioxidant activity of the composition according to the invention surpasses that of the conventional oil-soluble antioxidants at comparable concentration manyfold. This is confirmed by the stability tests which are conventional for unsaturated oils such as the Rancimat test and determination of the peroxide value.
  • composition according to the invention may be incorporated into the most varied triglycerides such as, e.g., fish oils, sunflower oil, conjugated linoleic acids and medium-chain triglycerides, which enables their use in numerous foods and food supplements.
  • triglycerides such as, e.g., fish oils, sunflower oil, conjugated linoleic acids and medium-chain triglycerides, which enables their use in numerous foods and food supplements.
  • the resultant solutions generally show either no additional turbidity or, at higher concentrations, a slight additional turbidity of the oil (compared with the oil without composition according to the invention).
  • composition according to the invention into lipophilic media which are to be protected against oxidation can be illustrated schematically and for an example formulation as follows: dissolve, e.g., a green tea extract in water; glycerol monooleate and tartaric esters are heated with stirring (50° C.); the green tea extract/water mixture is stirred into the glycerol monooleate/tartaric ester mixture, thereafter a short-chain triglyceride is added. The resultant water can if required be removed (e.g. by freeze drying).
  • the composition according to the invention is (preferably without heating) stirred into the corresponding oil phase or fat phase.
  • the amount of composition which is stirred in depends on the use. If the composition principally acts as antioxidant, the amount is calculated in such a manner that the concentration of the composition in the final oil formulation or fat formulation is in the range 500-1000 ppm (coarse guide value). With other applications the concentrations are correspondingly higher.
  • the composition according to the invention contains, as auxiliary for solubilization, a mixture of hydrophilic and hydrophobic emulsifiers, and preferably also an auxiliary oil.
  • the hydrophilic emulsifier is preferably the tartaric ester of mono- and diglycerides, the hydrophobic emulsifier preferably glycerol monooleate.
  • auxiliary oil preferably, medium-chain triglyceride (C8/C10 triglyceride) is used.
  • a water-containing concentrate is produced, since this has a better absorption capacity for the first component than the corresponding water-free mixture.
  • the water can, if required, be removed again (e.g. by freeze drying).
  • the water-free concentrates especially have a tendency to give a clear solution in oil.
  • compositions contain the components in the following quantitative ranges (all figures in percent by mass):
  • Green tea extract 5-20% (contains approximately 70% catechins)
  • C8/C10 triglyceride 10-50% Water 0-10%
  • compositions according to the invention are preferably introduced into the second compositions according to the invention at concentrations such that the first component of the composition according to the invention, based on the oil or fat in the second composition, is present in a concentration of 20 to 1000 ppm, preferably 30-500 ppm, particularly preferably 30-300 ppm.
  • the second composition according to the invention can be, in particular, a food.
  • compositions were produced:
  • Fish oil 18/12 is fish oil containing 18% EPA (eicosapentaenoic acid) and 12% DHA (docosahexaenoic acid)
  • the table hereinafter makes clear the stabilizing activity of catechin compared with conventional antioxidants and mixtures thereof based on the induction periods (as a measure of oxidative stability) determined using the Rancimeter.
  • the sample is exposed to an airstream at temperatures of 50-220° C.
  • the high-volatility oxidation products (the majority formic acid) are transferred by the airstream into the measurement vessel and there absorbed in the measurement solution (distilled water).
  • the measurement solution distilled water
  • oxidation curves are obtained, the inflection point of which is designated induction time, and is a good characteristic value for oxidation stability.
  • the Rancimat method was developed as an automated variant of the extremely complex active oxygen method (AOM) for determining the induction time of fats and oils. In the course of time, the method has established itself and found use in various national and international standards, for example AOCS Cd 12b-92 and ISO 6886.
  • the catechin mixture described hereinbefore was stirred into the fish oil in an appropriate amount.
  • the catechin-containing oil was mixed with the water phase and corresponding amounts of emulsification aids and homogenized.
  • the resultant emulsion was then freed from the water by a suitable process (e.g. spray-drying) so as to arrive at a powder/granules.
  • a suitable process e.g. spray-drying
  • Example formula of a fish oil-containing cereal bar Fish oil or fish oil powder contained the amounts of catechin mentioned in examples hereinbefore.
  • Step 1 Production of the syrup mixture:
  • Step 2 Production of the fat mixture:
  • Step 3 Add the fat mixture to the syrup mixture and heat the mixture to 90-95° C.
  • Step 4 Production of the cereal mixture:
  • fish oil powder 1.90 g of fish oil powder with the cereals and optionally with further components (such as flavorings/aroma substances, vitamins, minerals).
  • further components such as flavorings/aroma substances, vitamins, minerals.
  • the fish oil can be added directly to the fat mixture.
  • Step 5 Add the cereal mixture to the syrup mixture
  • Step 6 Feed to the roller compacter
  • Step 7 Cooling and cutting of the bars
  • PUFA polyunsaturated fatty acid
  • PUFA polyunsaturated fatty acid
  • phenols and/or polyphenols are water-in-oil emulsions of PUFA-containing oils or fats, e.g. fish oil.
  • emulsions display significantly better sensory properties and oxidative stability than conventionally stabilized emulsions, even after thermal stress such as, e.g., pasteurization.
  • An o/w emulsion was produced using a high-pressure homogenizer and emulsification aids (emulsifiers).
  • the oil-soluble components are charged for this in the oil phase, the water-soluble components in the water phase.
  • a heating of the phases can accelerate the solution process.
  • the two phases are combined and homogenized using the homogenizer.
  • Addition of the phenols/polyphenols proceeds, according to their solubility, either to the water phase or oil phase.
  • addition is via the oil phase
  • the addition is via the water phase or, if the catechin was appropriately preformulated, also via the oil phase.
  • a typical formulation is the following:
  • a further typical formulation is the following:
  • the viscosity of the emulsions is below 5000 mPas, preferably below 3000 mPas, particularly preferably below 1500 mPas.
  • a trained test panel rated the PUFA emulsions stabilized with phenols/polyphenols as superior compared with non-stabilized emulsions or emulsions stabilized in a conventional manner.
  • emulsions can be used in the following food matrices:
  • a 500 g Omevital ® 18/12 TG Gold 30 g modified starch HI-CAP 100 450 g water 20 g whey protein hydrolysate 2 g anhydrous citric acid 125 mg catechin ( 250 ppm based on water phase)
  • B 500 g Omevital ® 18/12 TG Gold 30 g modified starch HI-CAP 100 450 g water 20 g whey protein hydrolysate 2 g anhydrous citric acid 125 mg carnosolic acid ( 250 ppm based on oil phase)
  • Example D Use of the emulsion in milk
  • Example C Use of the emulsion in yogurt
  • Example A The product according to Example A was added according to Example D to milk. After homogenization at 200 bar, the milk was cooled to 45° C. 50 g of bacterial starter culture for yogurt (YC 180 from Chr. Hansen) were added to 450 g of the milk dispersion. For the fermentation, various samples were placed in an incubator at 45° C. After reaching a pH of 4.5 to 4.6, the samples were cooled, 7% sugar was added with stirring (to obtain a stirred yogurt) or they were homogenized at 80 to 100 bar (to obtain a drinking yogurt).
  • bacterial starter culture for yogurt YC 180 from Chr. Hansen

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Food Science & Technology (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Zoology (AREA)
  • Nutrition Science (AREA)
  • Biophysics (AREA)
  • Biochemistry (AREA)
  • Fats And Perfumes (AREA)
  • Edible Oils And Fats (AREA)

Abstract

The present invention relates to a composition containing a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, and also to the use of this mixture as lipophilic antioxidant.

Description

  • The present invention relates to a composition containing a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, and also to the use of this mixture as lipophilic antioxidant.
  • Conventionally tocopherols and ascorbyl palmitate are used in order to protect, for example, oils containing fatty acids having at least one double bond from oxidation.
  • Catechins are natural substances which occur in nature as plant components. They are hydrogenated flavones. Catechins include, in particular, catechin, epicatechin, gallocatechin and epigallocatechin. In the sense of the present invention, “catechin” or “a catechin” always means a compound selected from the group of catechins. “Catechin” is not the catechin meant in the narrow sense. If the catechin in the narrow sense is meant, then this will be also designated “catechin in the narrow sense”. Catechins occur, for example, in green tea and can be extracted from this. Dried leaves of green tea can contain, for example, 8.5 to 20.6% by weight of catechins. Information on catechins and catechins in green tea may be found, e.g., in Renapp Online, Version 3.0, published by Georg Thieme Verlag, under the headwords “Catechine” [Catechins] and “Tee” [Tea].
  • Catechins are active antioxidants and also have other beneficial properties. However, catechins are hydrophilic and therefore cannot readily be used as antioxidants in lipophilic media. It is therefore desirable to make catechins available as antioxidants for lipophilic media.
  • Catechins are highly water soluble but very sparingly oil-soluble antioxidants. Recent scientific studies verify in addition health-promoting properties of catechins such as, e.g., accelerated fat combustion, anticarcinogenic activity etc. The oil insolubility restricts the formulation ability of catechins to aqueous systems which prevents their use as additives for oils or a mixture of oils.
  • In addition to catechins, polyphenols in general, in particular those having antioxidant properties, are also usable as antioxidants. It is therefore desirable to be able to use not only catechins, but polyphenols in general, as antioxidants in lipophilic media also.
  • If there were a way to incorporate polyphenols, in particular catechins, in a corresponding amount in a stable manner in oils, not only would the very good antioxidant power of polyphenols be usable for oils, but also the health-promoting activity of polyphenols would be able to be combined with those of oils and/or oil formulations. Preferably, the formulations should be free from short-chain and medium-chain alcohols.
  • Diterpenes are natural substances having 20 carbon atoms which are made up of four isoprene units. They belong to the terpene group. Compounds designated diterpenes are not only hydrocarbons, but also derivatives of the corresponding hydrocarbons. Phenolic diterpenes are those diterpenes which contain at least one phenolic OH group. Carnosolic acid belongs to the phenolic terpenes.
  • WO 94/22321 discloses solutions of catechins in nonionic solvents. These solutions can be used as antioxidants in fats and oils. As solvents, in particular nonionic surfactants are disclosed, in particular lecithin and fatty alcohols having 8-18 carbon atoms are disclosed. In example 7, inter alia, also glycerol monooleate is disclosed as solvent.
  • However, this has the disadvantage that catechins are only soluble therein at a low concentration and that frequently cloudy oils are obtained.
  • KR 2001079020 and JP-A 63135483 likewise disclose lipophilic antioxidants which contain catechins.
  • The object of the present invention was to provide substances which are usable as lipophilic antioxidants.
  • This object is achieved by a composition containing a first component selected from the group consisting of at least one polyphenol (in particular a polyphenol having antioxidant properties, preferably at least one catechin), at least one phenolic diterpene (preferably carnosolic acid) and mixtures of both, at least one glyceride, at least one hydrophilic emulsifier and at least one hydrophobic emulsifier, wherein the hydrophilic emulsifier is selected from the group consisting of DATEM, CITREM, LACTEM, ACETEM and a sugar ester. This composition according to the invention is subject matter of the present invention.
  • A particular embodiment of the present invention is the composition according to the invention, wherein the first component is a catechin or a mixture of catechins and wherein this is preferably in the form of an extract of the leaves of green tea.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the first component is a phenolic diterpene or a mixture of phenolic diterpenes, preferably carnosolic acid.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the glyceride is a triglyceride, the three fatty acids of which each have 6 to 18 carbon atoms.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the hydrophilic emulsifier is selected from the group consisting of DATEM, CITREM, LACTEM and ACETEM.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the compositions mentioned in the paragraphs hereinbefore, wherein the hydrophilic emulsifier is a sugar ester.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, wherein the hydrophobic emulsifier is selected from the group consisting of a polyglycerol polyricinoleate, a polyglycerol ester of fatty acid and glycerol monoester of fatty acid (i.e. a monoglyceride; in particular such a monoglyceride having a fatty acid having 10 to 30 carbon atoms, in particular glycerol monooleate or glycerol monostearate).
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, additionally containing water.
  • A further particular embodiment of the present invention is the composition according to the invention or one of the particular compositions mentioned in the paragraphs hereinbefore, containing 1 to 20% by weight, in particular 5 to 15% by weight, of the first component, 2 to 70% by weight, in particular 20 to 50% by weight of glyceride, 3 to 60% by weight, in particular 15 to 35% by weight of hydrophilic emulsifier, 3 to 60% by weight, in particular 15 to 35% by weight, of hydrophobic emulsifier and 0 to 30% by weight, in particular 0 to 1% by weight, of water.
  • The present invention further relates to a process for producing the composition according to the invention or one of the compositions mentioned in the paragraphs hereinbefore which comprises providing a mixture containing the hydrophilic emulsifier and the hydrophobic emulsifier, optionally warming this mixture to a temperature of at least 50° C., adding the first component to this mixture (optionally with stirring) and thereafter adding the glyceride.
  • The present invention further relates to a use of the composition according to the invention or of one of the particular compositions mentioned in the paragraphs hereinbefore as antioxidant for lipophilic media, wherein the lipophilic medium preferably contains an oil or fat and in particular is a food.
  • The present invention further relates to a second composition containing oil or fat and, based on the mass of the oil or fat, 0.05 to 3% by weight of the composition according to the invention or of one of the particular compositions mentioned in the paragraphs hereinbefore.
  • A further particular embodiment of the present invention is said second composition, wherein the oil or fat is selected from the group consisting of a fat or oil which contains unsaturated fatty acid radicals (in particular radicals of linoleic acid, linolenic acid or oleic acid), fish oil, sunflower oil, borage oil, a glyceride which contains acyl radicals of conjugated linoleic acid and a triglyceride, the acyl radicals of which have 6 to 24 carbon atoms.
  • A further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is an oil-in-water emulsion.
  • A further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is granules or a powder.
  • Powders for the purposes of the present invention are also all further formulations having a solids character, such as, e.g., granules.
  • A further particular embodiment of the present invention is the second composition according to any of the paragraphs hereinbefore, wherein the second composition is a food, in particular one such selected from the group consisting of an oil, a fat, olive oil, butter, margarine, milk, a milk product, cheese, yogurt, a chocolate bar and a muesli bar.
  • According to the present invention the hydrophilic emulsifier can be selected, in particular, from the group consisting of DATEM, CITREM, LACTEM and ACETEM. In this case DATEM is a composition of matter containing mono- and diacetyl tartaric esters of mono- and diglycerides of edible fatty acids, in particular DATEM is a composition of matter which contains substituted glycerol molecules which are esterified at at least two OH groups and which bear at least one fatty acid radical (more than 50 mol % of the fatty acid radicals have 16 or 18 carbon atoms) and which bear at least one tartaric acid radical which in turn is monoacetylated or diacetylated. CITREM is a composition of matter containing citric esters of mono- and diglycerides of edible fatty acids. LACTEM is a composition of matter containing lactic esters of mono- and diglycerides of edible fatty acids. ACETEM is a composition of matter containing acetic esters of mono- and diglycerides of edible fatty acids. Edible fatty acids have, in particular, 6 to 24 carbon atoms.
  • A hydrophobic emulsifier has an HLB value of less than 8, a hydrophilic emulsifier has an HLB value of at least 8. The HLB value can be determined for nonionic emulsifiers in accordance with Griffin, and for ionic emulsifiers in accordance with Davies. For determination of HLB values see: Tensid-Taschenbuch [Surfactant Handbook], 2nd edition, edited by H. Stache, Carl Hanser Verlag, 1981.
  • The designation PGPR (polyglycerol polyricinoleate) summarizes esters of polycondensed castor oil fatty acids with polycondensed glycerol. Ricinoleic acid is 12-hydroxyoleic acid and can form a polyester with itself. Esters of polycondensed castor oil fatty acids with polycondensed glycerol are permitted as a food additive in Germany under the designation E 476. Polyglycerol fatty acid esters can, for example, have the composition of the commercial product Polymuls® 2G from Cognis GmbH, Monheim, Germany. This is a mixture of (% in each case is % by weight) fatty acid monoesters of diglycerol: 65-75%, fatty acid monoesters of glycerol: 15-20%, fatty acid diesters of glycerol: 5-10%, total glycerols: 30-40%, free glycerols: 2-5%.
  • A sugar ester for the purposes of the present invention is, in particular, an ester of a molecule of a sugar selected from the group consisting of sucrose, fructose, glucose and trehalose (sucrose is preferred) and one to three molecules of edible fatty acid (preferably a fatty acid having 6 to 24 carbon atoms).
  • A glyceride for the purposes of the present invention is an ester of glycerol with 1, 2 or 3 fatty acids. A monoglyceride here is an ester of glycerol with one fatty acid, a diglyceride is an ester of glycerol with two fatty acids and a triglyceride is an ester of glycerol with three fatty acids. Fatty acids in this case are preferably carboxylic acids having 2 to 30, in particular 2 to 20, in particular 6 to 18, in particular 8 to 10, carbon atoms. Triglycerides are glycerides which are preferred according to the invention.
  • CLA is an abbreviation for conjugated linoleic acid, that is for an octadecadienoic acid, wherein the two double bonds are not separated by one or more saturated carbon atoms, but start at carbon atoms no. n and n+2 (n is a natural number from 2 to 15). Preferably, the double bonds are situated either at positions 9 and 11 (9,11-octadecadienoic acid) or at positions 10 and 12 (10,12-octadecadienoic acid). In this case, cis-trans isomerism (E-Z isomerism) is possible at each double bond. The isomers possible for CLA are designated by the symbols c for cis and t for trans and by quoting the numbers for the position of the double bonds, that is to say, e.g., c9,t11-CLA. In a preferred embodiment of the present invention, CLA is c9,t11-CLA or t10,c12-CLA.
  • The composition according to the invention has numerous advantages over the prior art. The composition according to the invention must contain no alcohols. It must not contain glycerol monooleate; this is advantageous in some cases, since glycerol monooleate in some cases has a tendency to form β-phases which can become noticeable as unwanted deposits in formulations. For β-phases in glycerol monooleate, see “Emulgatoren für Lebensmittel” [Emulsifiers for Foods], published by Gregor Schuster, Springer-Verlag, 1985, pages 82 to 87.
  • All example formulations in WO 94/22321 contain the catechin only in a concentration of 2.7% by weight. The compositions according to the invention can have a catechin content which is up to approximately four times higher. That means approximately four times less (frequently undesired) auxiliaries are also introduced into the final formulation (at comparable catechin concentrations in the end formulation). In addition, the compositions according to the invention are flexible to a certain extent in the choice of glyceride (auxiliary oil). Fish oil, for example, can be used as such. The introduction of auxiliary into the end formulation can be reduced still further.
  • The composition according to the invention exhibits a significantly better antioxidant activity than conventional antioxidants. The very good antioxidant activity leads to an improved long-term stability and improved sensory stability of the stabilized products.
  • The products stabilized by the composition according to the invention have good sensory properties. For instance, they do not have, e.g., an unpleasant bitter taste as is the case with, e.g., the emulsifier polysorbate 60 (commercially available as Tween 60).
  • The composition according to the invention does not require any alcohols and may be formulated not only with water but also without water. The water-containing concentrates then, after dissolution in oil, preferably give a W/O microemulsion. The antioxidant activity of the composition according to the invention surpasses that of the conventional oil-soluble antioxidants at comparable concentration manyfold. This is confirmed by the stability tests which are conventional for unsaturated oils such as the Rancimat test and determination of the peroxide value.
  • The composition according to the invention may be incorporated into the most varied triglycerides such as, e.g., fish oils, sunflower oil, conjugated linoleic acids and medium-chain triglycerides, which enables their use in numerous foods and food supplements.
  • The resultant solutions generally show either no additional turbidity or, at higher concentrations, a slight additional turbidity of the oil (compared with the oil without composition according to the invention).
  • The production and introduction of the composition according to the invention into lipophilic media which are to be protected against oxidation can be illustrated schematically and for an example formulation as follows: dissolve, e.g., a green tea extract in water; glycerol monooleate and tartaric esters are heated with stirring (50° C.); the green tea extract/water mixture is stirred into the glycerol monooleate/tartaric ester mixture, thereafter a short-chain triglyceride is added. The resultant water can if required be removed (e.g. by freeze drying). The composition according to the invention is (preferably without heating) stirred into the corresponding oil phase or fat phase. The amount of composition which is stirred in depends on the use. If the composition principally acts as antioxidant, the amount is calculated in such a manner that the concentration of the composition in the final oil formulation or fat formulation is in the range 500-1000 ppm (coarse guide value). With other applications the concentrations are correspondingly higher.
  • The composition according to the invention contains, as auxiliary for solubilization, a mixture of hydrophilic and hydrophobic emulsifiers, and preferably also an auxiliary oil. The hydrophilic emulsifier is preferably the tartaric ester of mono- and diglycerides, the hydrophobic emulsifier preferably glycerol monooleate. As auxiliary oil, preferably, medium-chain triglyceride (C8/C10 triglyceride) is used.
  • For production of the composition according to the invention, first, preferably, a water-containing concentrate is produced, since this has a better absorption capacity for the first component than the corresponding water-free mixture. The water can, if required, be removed again (e.g. by freeze drying). The water-free concentrates especially have a tendency to give a clear solution in oil.
  • Typical example compositions contain the components in the following quantitative ranges (all figures in percent by mass):
  •
    Green tea extract  5-20%
    (contains approximately 70% catechins)
    Glycerol monooleate 10-35%
    Tartaric esters 10-35%
    C8/C10 triglyceride 10-50%
    Water  0-10%
  • The compositions according to the invention are preferably introduced into the second compositions according to the invention at concentrations such that the first component of the composition according to the invention, based on the oil or fat in the second composition, is present in a concentration of 20 to 1000 ppm, preferably 30-500 ppm, particularly preferably 30-300 ppm.
  • The second composition according to the invention can be, in particular, a food.
    • EXAMPLES
  • In the examples, proprietary products were used which were all obtained from Cognis GmbH, Monheim, in Germany, unless stated otherwise. The table hereinafter compares the brand names and the chemical composition of the products used.
  • Brand name Chemical composition
    Polymuls ® PGPR a polyglycerol polyricinoleate
    Polymuls ® 2G a fatty ester polyglycerol
    Monomuls ® 90-O18 glycerol monooleate
    Delios ® V a triglyceride, the fatty acids of
    which have predominantly 8 or
    10 carbons atoms
    Lamegin ® DWP 2000 an emulsifier which is one of what
    are termed DATEM (diacetyl tartaric
    ester monoglycerides); this is a
    composition of matter which contains
    glycerol molecules which are
    esterified at at least two OH groups,
    and which bear at least one fatty
    acid radical (chain length of the
    fatty acid radicals: predominantly 16
    and 18 carbon atoms) and which bear
    at least one tartaric acid radical
    which in turn is monoacetylated or
    diacetylated.
    Coviox ® T 90 EU natural tocopherols
    Hi Cap 100 1-octenyl succinic anhydride-
    esterified (OSA) starch
  • All percentage figures in the examples are percent by weight, unless stated otherwise.
  • The following compositions were produced:
  • First Hydrophilic Hydrophobic
    No. component Glyceride emulsifier emulsifier
    1 Catechin solution 37.5% 25% 25%
    (72.73% green Delios ® V Lamegin ® Monomuls ®
    tea powder + DWP 2000 90-O18
    27.27% water):
    12.5%
    2 Catechin solution 30% 25% 25%
    (72.73% green Delios ® V Lamegin ® Monomuls ®
    tea powder + DWP 2000 90-O18
    27.27% water):
    20%
    3 Catechin solution 30% 25% 22.73%
    (72.73% green Delios ® V Lamegin ® Polymuls ®
    tea powder + DWP 2000 PGPR and
    27.27% water): 2.27%
    20% Polymuls ® 2G
    4 Catechin solution 30% 25% 25%
    (72.73% green Delios ® V Lamegin ® Polymuls ®
    tea powder + DWP 2000 PGPR
    27.27% water):
    20%
    5* 9.1% Green Tea 37.5% 25% 25%
    Low Caffeine Dry Delios ® V Lamegin ® Monomuls ®
    Extract DWP 2000 90-O18
    (contained
    approximately
    70% catechins)
    6* 9.4% Green Tea 38.8% 25.9% 25.9%
    Low Caffeine Dry Delios ® V Lamegin ® Monomuls ®
    Extract DWP 2000 90-O18
    (contained
    approximately
    70% catechins)
    *Composition No. 6 was obtained by removing the water from composition No. 5. Composition No. 5 contained 3.4% water.
    • Production of a Polyphenol Mixture Based on Catechin
  • 25 g of Monomuls® 90-O18 and 25 g of Lamegin® DWP 2000 were warmed to approximately 50° C. and mixed and melted with stirring. Subsequently 12.5 g of a catechin mixture consisting of “green tea low caffeine dry extract” (caffeine: 0.33%; epigallocatechin gallate: 42.7%; catechins in total: 70.46%) and water were stirred into the emulsifier premix. After homogeneous distribution, 37.5 g of MCT (Delios® V) were added. Subsequently the water was removed by freeze drying.
    • Production of the Catechin-Containing Fish Oil
  • The above-described polyphenol mixture based on catechin was stirred into fish oil:
      • 0.76 g of the polyphenol mixture based on catechin in 99.24 g of fish oil 18/12: concentration therefore 500 ppm
      • 1.52 g of the polyphenol mixture based on catechin in 98.48 g of fish oil 18/12 concentration therefore 1000 ppm.
  • Fish oil 18/12 is fish oil containing 18% EPA (eicosapentaenoic acid) and 12% DHA (docosahexaenoic acid)
  • The table hereinafter makes clear the stabilizing activity of catechin compared with conventional antioxidants and mixtures thereof based on the induction periods (as a measure of oxidative stability) determined using the Rancimeter.
  • Rancimat method for measuring oxidation stability:
  • In the Rancimat method, the sample is exposed to an airstream at temperatures of 50-220° C. The high-volatility oxidation products (the majority formic acid) are transferred by the airstream into the measurement vessel and there absorbed in the measurement solution (distilled water). In continuous recording of the conductivity of this measurement solution, oxidation curves are obtained, the inflection point of which is designated induction time, and is a good characteristic value for oxidation stability. The Rancimat method was developed as an automated variant of the extremely complex active oxygen method (AOM) for determining the induction time of fats and oils. In the course of time, the method has established itself and found use in various national and international standards, for example AOCS Cd 12b-92 and ISO 6886.
  • TABLE
    Rancimat test of fish oil 18/12
    Induction
    Antioxidant period
    Not stabilized 1.08 h
    4400 ppm Coviox ® T 90 EU 2.50 h
    4400 ppm Coviox ® T 90 EU + 500 ppm 4.30 h
    ascorbylpalmitate
    500 ppm catechin 10.8 h
    1000 ppm catechin 16.0 h
  • Conditions: 5 g at 120° C. with 20 l of air per hour
  • Production of a catechin-containing fish oil powder
  • The catechin mixture described hereinbefore was stirred into the fish oil in an appropriate amount. The catechin-containing oil was mixed with the water phase and corresponding amounts of emulsification aids and homogenized.
  • The resultant emulsion was then freed from the water by a suitable process (e.g. spray-drying) so as to arrive at a powder/granules.
    • Example of a Formulation for Removal of the Water
  • Mass/g
    Fish oil 18/12 50.00
    Na Caseinate 10.00
    Glucose DE 29 24.00
    Hi Cap 100 6.00
    Soya protein 10.00
    Antioxidant catechin (1000 ppm catechin in oil)
    Water 150.0
    • Uses of the Catechin-Containing Fish Oil Powder in Milk Products
  • Incorporation of 2.67 g of the powder hereinbefore in 150 ml of milk (optionally with subsequent pasteurization)
  • Incorporation of 2.67 g of the powder hereinbefore into 150 ml of yogurt. The incorporation can proceed
  • a) by using the abovementioned fish oil-containing milk, which is then processed by a corresponding fermentation process to give a yogurt or
  • b) by adding the powder directly into the yogurt or via the fruit phase into a yogurt.
    • Use of a Polyphenol-Containing Fish Oil Powder in a Bar
  • Example formula of a fish oil-containing cereal bar. Fish oil or fish oil powder contained the amounts of catechin mentioned in examples hereinbefore.
  • Composition [%]
    Fish oil powder (15% PUFA) 1.90
    Sugar 12.15
    Glucose syrup solid 18.90
    Sorbitol (powder) 2.70
    Water 11.25
    Sunflower oil 4.85
    Lecithin (liquid) 0.15
    Cornflakes 19.90
    Oat flakes 8.10
    Wheat flakes 8.10
    Raisins (sultanas) 10.50
    Banana chips 1.20
    Apple pieces 0.30
    Total 100.00
    • Production of the B
  • Step 1: Production of the syrup mixture:
  • mix 12.5 g of sugar, 18.9 g of glucose syrup, 2.7 g of sorbitan powder and 11.25 g of water and heat it to approximately 60° C.
  • Step 2: Production of the fat mixture:
  • mix 4.85 g of sunflower oil and 0.15 g of lecithin and heat to approximately 60° C.
  • Step 3: Add the fat mixture to the syrup mixture and heat the mixture to 90-95° C.
  • Step 4: Production of the cereal mixture:
  • mix 1.90 g of fish oil powder with the cereals and optionally with further components (such as flavorings/aroma substances, vitamins, minerals). Alternatively, the fish oil (powder or oil) can be added directly to the fat mixture.
  • Step 5: Add the cereal mixture to the syrup mixture
  • Step 6: Feed to the roller compacter
  • Step 7: Cooling and cutting of the bars
    • Further Examples
  • % always means percent by weight.
  • The following further examples relate to PUFA emulsions (PUFA=polyunsaturated fatty acid) stabilized with phenols and/or polyphenols. These are water-in-oil emulsions of PUFA-containing oils or fats, e.g. fish oil.
  • These emulsions display significantly better sensory properties and oxidative stability than conventionally stabilized emulsions, even after thermal stress such as, e.g., pasteurization.
  • An o/w emulsion was produced using a high-pressure homogenizer and emulsification aids (emulsifiers). The oil-soluble components are charged for this in the oil phase, the water-soluble components in the water phase.
  • A heating of the phases can accelerate the solution process. The two phases are combined and homogenized using the homogenizer. Addition of the phenols/polyphenols proceeds, according to their solubility, either to the water phase or oil phase. In the case of carnosolic acid, addition is via the oil phase, in the case of catechin the addition is via the water phase or, if the catechin was appropriately preformulated, also via the oil phase.
  • A typical formulation is the following:
      • 40-60% fish oil (Omevital® 18/12 TG Gold, obtainable from Cognis GmbH, Monheim, Germany)
      • 0.5-10% modified starch (Hi-Cap 100, obtainable from National Starch)
      • 0.5-10% whey protein hydrolysate
      • pH regulators such as lactic acid and/or citric acid
      • content of phenols/polyphenols (including the corresponding esters) of 20-1000 ppm, preferably 30-500 ppm, particularly preferably 30-300 ppm, based on the oil phase or water phase
      • remainder: water
  • A further typical formulation is the following:
      • 40-60% fish oil (Omevital® 18/12 TG Gold, Cognis)
      • 0.5-10% sucrose ester (Sisterna SP 70, Sisterna)
      • 0.5-10% lecithin (rapeseed lecithin)
      • 0-10% whey protein hydrolysate
      • pH regulators such as lactic acid and/or citric acid preferred
      • content of phenols/polyphenols (including the corresponding esters) of 20-1000 ppm, preferably 30-500 ppm, particularly preferably 30-300 ppm, based on the oil phase or water phase
      • remainder: water
  • The viscosity of the emulsions is below 5000 mPas, preferably below 3000 mPas, particularly preferably below 1500 mPas.
  • A trained test panel rated the PUFA emulsions stabilized with phenols/polyphenols as superior compared with non-stabilized emulsions or emulsions stabilized in a conventional manner.
  • Advantage: high sensory and oxidative stability. Even after thermal stress such as pasteurization.
  • These emulsions can be used in the following food matrices:
      • dairy products (milk, yogurt, drinking yogurt, cheese etc.)
      • drinks in general
      • milk-based fruit drinks and soft drinks
      • soya-based fruit drinks and soft drinks
      • liquid food supplements
  • These emulsions can be produced as follows:
      • charge deionized water into stirring equipment
      • stir in HI-CAP emulsifier at RT
      • heat to 80-85° C. (duration 10 min), at approximately 60° C. add whey protein concentrate
      • hold for 10 min (heating step)
      • cool to 15-20° C. (duration 15 min)
      • dissolve antioxidant in subquantity of fish oil or water, added
      • add fish oil
      • adjust with anhydrous citric acid to pH 4.0
      • stirred for 5 min (emulsification)
      • homogenized 1×at a pressure of 230/30 bar,
      • viscosity: 240 mPas
      • pasteurization (optional)
      • emulsion of experiment 1 heated to 80° C. in the water bath in 100 ml square bottles, duration approximately 15 min
      • heated for 5 minutes further, 85° C.
      • bottles removed from water bath, placed turned over into the refrigerator
      • viscosity: 210 mPas (pasteurized)
  • Further formulation examples:
  •
    A
    500 g Omevital ® 18/12 TG Gold
    30 g modified starch HI-CAP 100
    450 g water
    20 g whey protein hydrolysate
    2 g anhydrous citric acid
    125 mg catechin (=250 ppm based on water phase)
    B
    500 g Omevital ® 18/12 TG Gold
    30 g modified starch HI-CAP 100
    450 g water
    20 g whey protein hydrolysate
    2 g anhydrous citric acid
    125 mg carnosolic acid (=250 ppm based on oil phase)
    C
    500 g Omevital ® 18/12 TG Gold
    30 g modified starch HI-CAP 100
    450 g water
    20 g whey protein hydrolysate
    2 g anhydrous citric acid
    62.5 mg catechin (=125 ppm based on water phase)
    62.5 mg carnosolic acid (=125 ppm based on oil phase)
  • Example D: Use of the emulsion in milk
  • 1 g of emulsion from the above example is added to 99 g of milk (fat content 1.5%) with stirring. Optionally, pasteurization can proceed thereafter.
  • Example C: Use of the emulsion in yogurt
  • The product according to Example A was added according to Example D to milk. After homogenization at 200 bar, the milk was cooled to 45° C. 50 g of bacterial starter culture for yogurt (YC 180 from Chr. Hansen) were added to 450 g of the milk dispersion. For the fermentation, various samples were placed in an incubator at 45° C. After reaching a pH of 4.5 to 4.6, the samples were cooled, 7% sugar was added with stirring (to obtain a stirred yogurt) or they were homogenized at 80 to 100 bar (to obtain a drinking yogurt).

Claims (13)

1.-10. (canceled)
11. A composition comprising:
(a) 1 -20% of a first component selected from the group consisting of at least one polyphenol, at least one phenolic diterpene and combinations thereof,
(b) 2-20% of least one glyceride,
(c) 3-60% of least one hydrophilic emulsifier, and
(d) 3-60% at least one hydrophobic emulsifier, and
(e) 0-30% water
wherein the hydrophilic emulsifier is selected from the group consisting of mono- and diacetyl tartaric mono- and diglycerides of edible fatty acids, citric mono- and diglycerides of edible fatty acids, lactic mono- and diglycerides of edible fatty acids, acetic mono- and diglycerides of edible fatty acids and sugar esters.
12. The composition of claim 11, wherein component (a) is catechin or a mixture of catechins.
13. The composition of claim 11, wherein component (a) is carnosolic acid.
14. The composition of claim 11, which comprises 15 to 35% by weight of the hydrophilic emulsifier, and 15 to 35% by weight of the hydrophobic emulsifier.
15. The composition of claim 11, wherein the hydrophilic emulsifier is a sugar ester.
16. The composition of claim 11, wherein the hydrophobic emulsifier is selected from the group consisting of polyglycerol polyricinoleates, polyglycerol esters of fatty acids, and glycerol monoesters of fatty acids.
17. The composition of claim 16, wherein said hydrophobic emulsifier is a monoglyceride of a fatty acid having about 10 to about 30 carbon atoms.
18. The composition of claim 16, wherein said hydrophobic emulsifier is selected from the group consisting of glycerol monooleate and glycerol monostearate.
19. A process for producing the composition of claim 11 which comprises:
(i) providing a mixture containing the hydrophilic emulsifier (c) and the hydrophobic emulsifier (d);
(ii) adding component (a) to this mixture; and
(iii) thereafter adding the glyceride component (b).
20. A composition comprising:
(a) at least one oil or fat; and
(b) about 0.05 to 3% by weight of the composition of claim 11, based on the weight of the at least one oil or fat.
21. The composition of claim 20, wherein the oil or fat is selected from the group consisting of fats and oils which contain unsaturated fatty acid moieties, fish oil, sunflower oil, borage oil, glycerides which contain acyl moieties of conjugated linoleic acid, and triglycerides having acyl moieties of 6 to 24 carbon atoms.
22. A method for improving the oxidation stability of lipophilic media comprising adding the composition of claim 11 to the lipophilic medium in an amount effective to improve the oxidation resistance over said medium without the added composition.
US14/479,533 2007-12-13 2014-09-08 Lipophilic Antioxidant Abandoned US20140377435A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US14/479,533 US20140377435A1 (en) 2007-12-13 2014-09-08 Lipophilic Antioxidant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07024183 2007-12-13
EP07024183.1 2007-12-13
US12/333,106 US8865024B2 (en) 2007-12-13 2008-12-11 Lipophilic antioxidant
US14/479,533 US20140377435A1 (en) 2007-12-13 2014-09-08 Lipophilic Antioxidant

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US12/333,106 Continuation US8865024B2 (en) 2007-12-13 2008-12-11 Lipophilic antioxidant

Publications (1)

Publication Number Publication Date
US20140377435A1 true US20140377435A1 (en) 2014-12-25

Family

ID=39406032

Family Applications (2)

Application Number Title Priority Date Filing Date
US12/333,106 Expired - Fee Related US8865024B2 (en) 2007-12-13 2008-12-11 Lipophilic antioxidant
US14/479,533 Abandoned US20140377435A1 (en) 2007-12-13 2014-09-08 Lipophilic Antioxidant

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US12/333,106 Expired - Fee Related US8865024B2 (en) 2007-12-13 2008-12-11 Lipophilic antioxidant

Country Status (2)

Country Link
US (2) US8865024B2 (en)
EP (1) EP2070421B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017018654A1 (en) * 2015-07-27 2017-02-02 씨제이제일제당(주) Antioxidant composition for oil, preparation method therefor, cooking oil containing same, and method for preparing cooking oil
WO2020038737A1 (en) 2018-08-23 2020-02-27 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120219647A1 (en) * 2009-08-26 2012-08-30 Harald Breivik Antioxidant composition
PL2585563T3 (en) 2010-06-25 2018-01-31 Castrol Ltd Uses and compositions
US9127232B2 (en) 2010-10-26 2015-09-08 Castrol Limited Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy-carboxylic acids, and uses thereof
HUE044068T2 (en) 2011-02-11 2019-09-30 Clover Corporation Ltd Nutritional compositions and uses thereof
US20120219682A1 (en) * 2011-02-28 2012-08-30 Frank Monteleone Antimicrobial compositions within antioxidant solutions used to protect whole protein foods
BR112014000239A2 (en) 2011-07-07 2017-06-13 Bp Exploration Operating surface finish
FR3007643B1 (en) * 2013-06-28 2015-09-04 Oreal STABLE COSMETIC COMPOSITION CONTAINING MONOGLYCERIDE, TARTARIC MONOGLYCERIDE ESTER AND SEQUESTRING AGENT
GB201501991D0 (en) 2015-02-06 2015-03-25 Castrol Ltd Uses and compositions
GB201502002D0 (en) 2015-02-06 2015-03-25 Castrol Ltd Uses and compositions
JP2019512029A (en) * 2016-02-26 2019-05-09 ディーエスエム アイピー アセッツ ビー．ブイ．Ｄｓｍ Ｉｐ Ａｓｓｅｔｓ Ｂ．Ｖ． New coating system (II)
WO2019185888A1 (en) * 2018-03-29 2019-10-03 Dsm Ip Assets B.V. Novel use of tocopherols

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274574B1 (en) * 1999-02-26 2001-08-14 Kraft Foods, Inc. Use of mesophase-stabilized compositions for delivery of cholesterol-reducing sterols and stanols in food products
US20040013788A1 (en) * 2001-01-19 2004-01-22 The Nisshin Oillio, Ltd. Edible fat/oil composition
US20060105092A1 (en) * 2004-11-12 2006-05-18 Kraft Foods Holdings, Inc. Trans-fatty acid free shortening
US20060121174A1 (en) * 2004-12-08 2006-06-08 Franke William C Compositions and methods to deliver consumable water dispersible phytosterols
US20080311211A1 (en) * 2005-11-22 2008-12-18 Nestec S.A. Easily Dispersible Lipidic Phase

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2452943A (en) 1946-05-18 1948-11-02 Colgate Palmolive Peet Co Catalyzed sulfamic acid sulfation
US2868812A (en) 1955-02-09 1959-01-13 Colgate Palmolive Co Manufacture of fatty acid monoesters of glycerol monosulfuric acid and salts thereof
JPS63135483A (en) 1986-11-26 1988-06-07 Sankyo Co Ltd Antioxidant
US4832876A (en) 1987-09-14 1989-05-23 Colgate-Palmolive Company Process for the manufacture of higher fatty monoglyceride monosulfate detergents
US5117032A (en) 1990-06-06 1992-05-26 Henkel Kommanditgesellschaft Auf Aktien Process for making glycerol ether sulfates
WO1994022321A1 (en) 1993-04-01 1994-10-13 Kalamazoo Holdings, Inc. Lipid-soluble green tea catechin antioxidant solutions
KR0176017B1 (en) 1996-08-05 1999-05-15 이서봉 Water soluble conductive polyaniline composites
US6312753B1 (en) * 1996-09-06 2001-11-06 Mars, Incorporated Cocoa components, edible products having enriched polyphenol content, methods of making same and medical uses
BR9915963B1 (en) * 1998-12-05 2012-07-24 oil or water care emulsion in the form of milk or cream, dry mix emulsion, dry mix emulsion, and use of a polysaccharide combination, a xanthan polysaccharide and a polyglucomannan polysaccharide.
AU784481B2 (en) * 2000-07-11 2006-04-13 Hahntech International Limited Low fat edible emulsions
DE60143753D1 (en) * 2000-08-08 2011-02-10 Kao Corp OIL / GREASE COMPOSITION
JP4995377B2 (en) * 2001-04-26 2012-08-08 花王株式会社 Oil composition
KR100420609B1 (en) 2001-06-05 2004-03-02 주식회사 네오뉴론 Additive complex product of antioxidant and stabilizer to usability and solubilization.
JP4157765B2 (en) * 2002-02-18 2008-10-01 花王株式会社 Powdered oil
US20030215560A1 (en) * 2002-04-08 2003-11-20 Todd Paul H. Labiatae herb extract compositions readily dispersible in cold brine
US9743680B2 (en) * 2005-10-14 2017-08-29 Wild Flavors, Inc. Microemulsions for use in food and beverage products
WO2007060174A1 (en) * 2005-11-23 2007-05-31 Nestec S.A. Oil-in-water emulsion for creating new product consistencies

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6274574B1 (en) * 1999-02-26 2001-08-14 Kraft Foods, Inc. Use of mesophase-stabilized compositions for delivery of cholesterol-reducing sterols and stanols in food products
US20040013788A1 (en) * 2001-01-19 2004-01-22 The Nisshin Oillio, Ltd. Edible fat/oil composition
US20060105092A1 (en) * 2004-11-12 2006-05-18 Kraft Foods Holdings, Inc. Trans-fatty acid free shortening
US20060121174A1 (en) * 2004-12-08 2006-06-08 Franke William C Compositions and methods to deliver consumable water dispersible phytosterols
US20080311211A1 (en) * 2005-11-22 2008-12-18 Nestec S.A. Easily Dispersible Lipidic Phase

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017018654A1 (en) * 2015-07-27 2017-02-02 씨제이제일제당(주) Antioxidant composition for oil, preparation method therefor, cooking oil containing same, and method for preparing cooking oil
EP3329784A4 (en) * 2015-07-27 2019-03-06 CJ Cheiljedang Corporation Antioxidant composition for oil, preparation method therefor, cooking oil containing same, and method for preparing cooking oil
WO2020038737A1 (en) 2018-08-23 2020-02-27 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition
US11248188B2 (en) 2018-08-23 2022-02-15 Klueber Lubrication Muenchen Se & Co. Kg Lubricant composition

Also Published As

Publication number Publication date
EP2070421B1 (en) 2016-09-14
US8865024B2 (en) 2014-10-21
EP2070421A1 (en) 2009-06-17
US20090152502A1 (en) 2009-06-18

Similar Documents

Publication Publication Date Title
US8865024B2 (en) Lipophilic antioxidant
US9301536B2 (en) Antioxidant composition for marine oils comprising tocopherol, rosemary extract, ascorbic acid and green tea extract
Jacobsen Oxidative stability and shelf life of food emulsions
US20150159117A1 (en) Edible fat or oil, food containing same, and process for producing same
US20100260913A1 (en) Oxidative Stabilizing of Sterols and Sterol Esters
US20110236560A1 (en) Food supplementation with phenolic antioxidants in vinegar
JP6664228B2 (en) Emulsified compositions, acidic foods and acidic beverages
US20190223462A1 (en) Premix for preparing emulsion composition, and composition using same
US20170360737A1 (en) Long-chain polyunsaturated fatty-acid-containing fat and food containing same
Jacobsen et al. The use of antioxidants in the preservation of food emulsion systems
JP5786215B1 (en) Antioxidant composition and fats and oils to which it is added
CN113382639A (en) Ice cream containing highly unsaturated fatty acid
US20150282498A1 (en) Powder Containing Polyunsaturated Fatty Acids and Process for Making Same
AU710590B2 (en) A process for protecting fat-based aqueous emulsion products against metal-catalyzed oxidation and a product thus protected
EP3200597B1 (en) Pourable water-in-oil cooking composition
US20240023570A1 (en) Oil-in-water emulsified composition
US20230217946A1 (en) Stabilization of lc-pufas by side stream product from green coffee decaffeination
JP6733837B2 (en) Soymilk drink containing highly unsaturated fatty acids
JP4207515B2 (en) Oil degradation inhibitor
WO2016191433A1 (en) Mono and di-glyceride esters of omega-3 fatty acid emulsions
JP2022088160A (en) Oil-in-water emulsion composition
JP5012709B2 (en) Bulk oil
WO2024090547A1 (en) Oil/fat composition and method for producing same
KR20220053573A (en) oil composition

Legal Events

Date Code Title Description
AS Assignment

Owner name: COGNIS IP MANAGEMENT GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:MUELLER, MICHAEL;HORLACHER, PETER;BECK, KATJA;SIGNING DATES FROM 20160503 TO 20160505;REEL/FRAME:039388/0203

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION