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1. (WO2018108438) COMPOSITION CONTENANT DE L'HUILE VÉGÉTALE
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

COMPOSITION CONTAINING VEGETABLE OIL

FIELD OF THE INVENTION

The present invention relates to a composition comprising vegetable oil, caramel and one or more phenolic compounds. The invention also relates to a method to prepare the composition. Finally the invention relates to use of caramel and one or more phenolic compounds to decrease the oxidation of vegetable oil.

BACKGROUND TO THE INVENTION

Vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids in food products are prone to oxidation during storage of the food product. This causes rancidity, and leads to rejection of the food product by consumers. Therefore food products often contain antioxidants to prevent oxidation of the vegetable oil, in particular food products which are stored for a relatively long time. A common antioxidant is EDTA (ethylene-diamine-tetra-acetic acid), which binds metal ions which generally promote oxidation of the triglycerides in the vegetable oil. These metal ions may be present as part of common food ingredients. EDTA however is regarded to be chemical and artificial by consumers, therefore there is a need for alternatives which are natural. Within the food industry an increasing effort is made to remove artificial ingredients from food products and to replace them with natural alternatives. Owing to its effectiveness, reasonable cost, and lack of viable alternatives, however, EDTA has so far been one of the more difficult artificial ingredients to replace. Many compounds are known for their antioxidative properties, however not all compounds are sufficiently effective.

WO 96/34535 A1 relates to a dry chocolate flavored beverage mix and a process for making it.

EP 1 446 020 B1 relates to a process for manufacturing a drink, more specifically a soft drink, which is obtained from a mixture of coffee extract with fluid extract of Kola Nut (Cola nitida).

Takenaka Tetsuo et al. (Bulletin of the Faculty of Agriculture Tamagawa University, vol.0, no.36, 1996, p.1 -9 (abstract accessible via Biosis database) relates to caramels which are prepared by melting glucose with sodium citrate.

G. Sengar et al. (Journal of Food Science and Technology, 51 (9), 2014, p.1686-1696) describe caramels and their anti-oxidant properties.

D. Tagliazucchi et al. (European Food Research and Technology, 227(3), 2008, p.835-843) describes the antioxidant activity of traditional balsamic vinegar, due to

compounds synthesized during cooking of must.

WO2017/001 154 discloses compositions containing caramel and phenolic compounds. WO 2013/189709 A1 relates to EDTA-free mayonnaise, containing reduced grape juice.

JPH10150949 A2 discloses the use of caramel as an antioxidant for whipped cream, and buttercream. The caramel is prepared using pentoses and/or hexoses as the base raw material. The caramel is prepared by heat treatment for 1 to 10 hours at 120 to 150°C.

CN 101708062 relates to the use of modified tea polyphenols in fatty foods, to improve antioxidant activity.

X. Zhang et al. (Food Chemistry, 141 , p. 3451 -3458, 2013) investigated the impact of six dietary polyphenols (phloretin, naringenin, quercetin, epicatechin, chlorogenic acid and rosmarinic acid) on fructose caramelization in thermal model systems at either neutral or alkaline pH. Combination of polyphenol and fructose upon preparation of caramel leads to the formation of antioxidants.

P.J. Tsai et al. (Abstracts of Papers, 234th ACS National Meeting, Boston, MA, USA, August 19-23, 2007, AGFD-191 ) disclose that a combination of polyphenol and sugars upon preparation of caramel leads to the formation of antioxidants.

C. Severini et al. (Italian Journal of Food Science, 10(2) p.147-153, 1998) disclose that Maillard reaction products decrease the oxidation rate of soybean oil in an emulsion. These were prepared by heating a combination of lysine and glucose at 90°C during a time period ranging from 1 to 120 hours. Caramelisation products prepared from glucose at 90°C during a time period ranging from 1 to 120 hours did not decrease the oxidation rate of soybean oil in an emulsion.

M.L. Chen et al. (International Journal of Food Engineering, vol.8, iss.2, art.15, 2012) relates to the colour development during the caramelisation of acidic glucose solutions at a temperature ranging from 75 to 95°C, during time periods ranging from 500 to 2500 hours. The longer the heating time, the higher the antioxidative activity of the heated sugar.

P.J. Tsai et al. (Food Research International, 42(3), p.380-386, 2009) also study the formation of coloured compounds during caramelisation of fructose, xylose, glucose, and sucrose at 90°C during time periods ranging from 4 to 24 hours. The darker the caramel, the stronger the antioxidant activity.

J.S. Kim et al. (Food Science and Biotechnology, 17(5), p. 931 -939, 2008) relates to the antioxidative activity of caramelisation products obtained by browning of glucose and fructose solutions at pH 7.0-12.0 and 80-180°C.

US5013575 relates to a process for producing a product made of a mixture of sugar and an ingredient including nuts in a heated screw extruder includes the steps of feeding the sugar into the screw extruder at a first intake zone, caramelizing the sugar by conveying the sugar through several caramelization zones which are heated, feeding the nuts to the screw extruder through a second intake zone, and mixing the caramelized sugar with the nuts by conveying the caramelized sugar and the nuts through one or more mixing zones. During the mixing steps, the nuts can be roasted. Sengar Garima et.al. Food caramels: a review, journal of food science and technology, springer (India) private Ltd, India, vol. 51 , no.9, 9 February 2012 (2012-02-09), pages 1686-1696 provides an overview of the classification, physicochemical nature, formulations, coloring properties, antioxidant properties, and toxicity of caramel in different food systems.

Luna Maria Paz et al.: "Kinetics of colour development of molten glucose, fructose and sucrose at high temperatures", Food Biophysics, Springer US, Boston, vol. 9, no. 1 , 17 August 2013 (2013-08-17), pages 61 -68 evaluates colour development in pure sugar melts at temperatures above 160°C, as a function of time.

SUMMARY OF THE INVENTION

Generally an anti-oxidant is required to prevent oxidation of the triglycerides in vegetable oil in food products, in particular in products which are often stored for a long time. Consumers are more and more interested in food products which are free from ingredients which are perceived to be chemical or artificial. Hence one of the objectives of the present invention is to provide an antioxidant system which can be regarded to be a natural or known ingredient, and is not considered to be an artificial chemical by the consumer. Another objective of the present invention is to provide food products containing vegetable oil containing such antioxidant system, and which are free or nearly free from EDTA. Moreover, oxidation of the triglycerides in the vegetable oil in such food products during storage should nevertheless be as low as possible, therefore it is another objective of the present invention to provide food products having that property. The food product may contain an antioxidant system, and such system should not negatively influence the food products. The prior art indicates that caramel is being used as an antioxidant, in particular when the caramel has been heated a long time, and has a dark colour. However, such dark caramel is not suitable to be used in many light coloured food products, as the food product would become too dark. Moreover, the caramel may make the food product too sweet or give the product a too strong caramel or burnt sugar taste. Such tastes are often not desired in food products.

Therefore it is an objective of the present invention to provide an antioxidant system that does not give an undesired colour, and neither an undesired taste, to the food product. Additionally it should be a natural compound or perceived to be a natural and/or common ingredient, and fitting to the food product with regard to taste and colour. More in particular it is an objective of the present invention to provide a mayonnaise which is free or nearly free from EDTA, and that contains an antioxidant system that does not give an undesired colour and taste to the food product, and that is regarded to be a natural ingredient by the consumer.

We have found a solution to these problems by providing a food product containing vegetable oil, wherein the food product comprises caramel and one or more phenolic compounds. The caramel has been prepared by heating a mixture containing one or more monosaccharides and/or one or more disaccharides in the absence of phenolic compounds under mild and controlled conditions, in order to prevent that the colour of the caramel is (too) dark and to prevent that the taste of the caramel becomes too pronounced and burnt sugar-like. The caramel prepared by the method described herein has the advantage that it does not have the dark brown colour of normal caramel and neither the typical burnt caramel taste, while it still provides sweetness. It has a bland colour and taste, and is therefore very suitable to be used in a wide range of food products without interference with colour, taste, and appearance of that food product.

Accordingly in a first aspect the invention provides a composition comprising vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, wherein the concentration of the vegetable oil ranges from 2% to 85% by weight of the

composition,

further comprising caramel and one or more phenolic compounds,

wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to

120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds,

and wherein a 10% by weight solution of the caramel in water has a colour value L* ranging from 50 to 67, and an a* value ranging from -5 to 10, and a b* value ranging from 5 to 60.

The second aspect of the invention provides a method for preparation of a composition according to the first aspect of the invention, comprising the steps:

(i) providing caramel, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to

45 minutes, in the absence of phenolic compounds;

(ii) providing one or more phenolic compounds;

(iii) providing vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids; and

(iv) mixing the caramel from step (i) and the one or more phenolic compounds from step (ii) with the vegetable oil from step (iii).

In a third aspect the invention provides the use of caramel and one or more phenolic compounds in a composition comprising vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids, to reduce the oxidation rate of the vegetable oil, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds.

DETAILED DESCRIPTION OF THE INVENTION

All percentages, unless otherwise stated, refer to the percentage by weight (wt%). D4,3 is the volume weighted mean diameter of a set of droplets or particles. The volume based diameter equals the diameter of a sphere that has the same volume as a given particle (M. Alderliesten, Particle & Particle Systems Characterization 8 (1991 ) 237-241 ).

"Spoonable" means that a composition is semi-solid but not free-flowing on a time scale typical for eating a meal, meaning not free-flowing within a time period of an hour. A sample of such substance is able to be dipped with a spoon from a container containing the composition.

Except in the operating and comparative examples, or where otherwise explicitly indicated, all numbers in this description indicating amounts or ratios of material or conditions of reaction, physical properties of materials and/or use are to be understood as modified by the word "about".

In a first aspect the invention provides a composition comprising vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, wherein the concentration of the vegetable oil ranges from 2% to 85% by weight of the

composition,

further comprising caramel and one or more phenolic compounds,

wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to

120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds,

and wherein a 10% by weight solution of the caramel in water has a colour value L*

ranging from 50 to 67, and an a* value ranging from -5 to 10, and a b* value ranging from 5 to 60.

The term "oil" as used herein refers to lipids selected from triglycerides, diglycerides, monoglycerides and combinations thereof. Preferably the oil in the context of this invention comprises at least 90 wt% of triglycerides, more preferably at least 95 wt%. Preferably the oil contains less than 20 wt% of solid oil at 5°C, preferably less than

10 wt% solid oil. More preferred the oil is free from solid oil at 5°C. Most preferred the

011 is liquid at 5°C. Preferred oils for use in the context of this invention are vegetable oils which are liquid at 5°C. Preferably the oil comprises sunflower oil, rapeseed oil, olive oil, soybean oil, and combinations of these oils. Therefore preferably the vegetable oil is an edible oil. The mono-unsaturated fatty acids as comprised in the oil preferably comprises oleic acid. The poly-unsatu rated fatty acids as comprised in the oil preferably comprise linoleic acid and linolenic acid.

Preferably the composition of the invention comprises from 5% to 82% by weight of vegetable oil, preferably from 10% to 80% by weight, preferably from 15% to 78% by weight of oil. Preferably the amount of oil is at least 20% by weight, preferably at least 30% by weight, preferably at least 35% by weight. Preferably the concentration of vegetable oil is maximally 75% by weight, preferably maximally 70% by weight, preferably maximally 65%. Any combination of ranges using these mentioned end points are considered to be part of the invention as well.

The composition of the invention may be present in the form of a water-in-oil emulsion, like a margarine. Preferably the composition is in the form of an oil-in-water emulsion. Preferably the composition is an edible emulsion. Examples of oil-in-water emulsions encompassed by the present invention include mayonnaise, dressings, salad dressings, and sauces. Preferably, the oil-in-water emulsion is a mayonnaise or a dressing or a salad dressing, most preferably a salad dressing or a mayonnaise.

Generally a mayonnaise is spoonable, while a salad dressing is pourable.

Mayonnaise is generally known as a thick, creamy sauce that can be used as a condiment with other foods. Mayonnaise is a stable water-continuous emulsion of

vegetable oil, egg yolk and either vinegar or lemon juice. In many countries the term mayonnaise may only be used in case the emulsion conforms to the "standard of identity", which defines the composition of a mayonnaise. For example, the standard of identity may define a minimum oil level, and a minimum egg yolk amount. Also mayonnaise-like products having oil levels lower than defined in a standard of identity can be considered to be mayonnaises. These kind of products often contain thickeners like starch to stabilise the aqueous phase. Mayonnaise may vary in colour, and is generally white, cream-coloured, or pale yellow. The texture may range from of light creamy to thick, and generally mayonnaise is spoonable. In the context of the present invention "mayonnaise" includes emulsions with vegetable oil levels ranging from 2% to 85% by weight of the product. Mayonnaises in the context of the present invention do not necessarily need to conform to a standard of identity in any country.

In case the composition of the invention is an oil-in-water emulsion, then the

composition comprises an oil-in-water emulsifier. The emulsifier serves to disperse oil droplets in the continuous aqueous phase. Preferably the preferred oil-in-water emulsion of the invention comprises an oil-in-water emulsifier originating from egg yolk. Preferably the composition comprises egg yolk as an ingredient which also provides the water-in-oil emulsifier. The presence of egg yolk may be beneficial for taste, emulsification and/or stability of the oil droplets in the composition of the invention. Egg yolk contains phospholipids, which act as emulsifier for the oil droplets. Preferably the concentration of egg yolk in the composition of the invention ranges from 1 % to 8% by weight of the emulsion, more preferred from 2% to 6% by weight of the emulsion. The egg yolk may be added as egg yolk component, meaning largely without egg white. Alternatively, the composition may also contain whole egg, containing both egg white and egg yolk. The total amount of egg yolk in the composition of the invention includes egg yolk that may be present as part of whole egg. Preferably the concentration of phospholipids originating from egg yolk ranges from 0.05% to 1 % by weight, preferably from 0.1 % to 0.8% by weight of the emulsion.

Part or all of the egg yolk may have been subjected to an enzymatic conversion process using phospholipase. Preferably the phospholipase that is used to treat egg yolk is phospholipase A2. This process leads to split off of fatty acid chains from the phospholipid molecules, and yields enzyme-modified egg yolk. The reaction products of this enzymatic process are retained in the enzyme-modified egg yolk, meaning that the enzyme-modified egg yolk contains fatty acids split off from the phospholipids. A suitable source of enzyme modified egg yolk is "Heat stabilised egg yolk (92-8)", supplied by Bouwhuis Enthoven (Raalte, the Netherlands). Preferably the

concentration of egg yolk which has been modified by treatment with phospholipase ranges from 0.5% to 4% by weight of the composition, preferably from 1 % to 4% by weight of the composition.

Preferably the composition has a pH ranging from 3 to 5, preferably ranging from 3 to 4.6, more preferred from 3.5 to 4. Preferably this pH of the composition is obtainable, preferably obtained by using acetic acid or vinegar. Preferably the composition comprises vinegar selected from apple vinegar, white wine vinegar, red wine vinegar, and malt vinegar, and any combination of these. These vinegars naturally contain phenolic compounds, and therefore these preferred vinegars serve not only to acidify the composition of the invention, but also as the source of the one or more phenolic compounds. Suitable suppliers of such vinegars are for example Kuhne (Hamburg, Germany), Mizkan Euro Ltd. (London, UK), and J.R. Sabater S.A. (Murcia, Spain).

As the combination of caramel and one or more phenolic compounds serve as antioxidant system, preferably the concentration of EDTA is lower than 0.005% by weight, preferably lower than 0.002% by weight of the composition. More preferred the concentration of EDTA is lower than 0.001 % by weight, and most preferred EDTA is absent from the composition of the invention. The advantage of the combination of the caramel and the one or more phenolic compounds is that it can at least partly, or even completely replace EDTA, and serve as an antioxidant for the vegetable oil in the composition.

This way the EDTA can be replaced by natural compounds and/or compounds which are common food ingredients. Caramel is considered to be a common food ingredient, as it is prepared by heating natural sugars, and is normally used as ingredient in many food products. Therefore many consumers regard caramel to be natural. Normally caramel is used to provide colour and taste to the food products. In here however, the caramel prepared by the method described herein has the advantage that it does not have the dark brown colour of normal caramel and neither the typical caramel taste. It has a bland colour and taste, and is therefore very suitable to be used in a wide range of food products without interference with colour, taste, and appearance of that food product.

Preferably the one or more monosaccharides that is heated to obtain the caramel comprises fructose or glucose, or a combination of the two. In case a combination is used, then preferably fructose and glucose are present at a weight ratio ranging from 10:1 to 1 :10.

Preferably the one or more disaccharides that is heated to obtain the caramel comprises sucrose. Preferably the caramel is prepared from sucrose as the only disaccharide, preferably without monosaccharide. The reason is that sucrose is easily available, is known to consumers as the basis of caramel, and provides a good quality caramel for use in the present invention.

The mixture comprising one or more monosaccharides and/or one or more

disaccharides is heated to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes to obtain the caramel. This has to be interpreted as that the mixture is within the required temperature range during the indicated time period. Any time required to for example heating the mixture from room temperature to 160°C is not included in the indicated time period. At a temperature below 160°C generally the caramelisation reaction proceeds only very slow, therefore the temperature rise to 160°C does not have much influence on the final end product (the caramel).

Preferably the mixture comprising one or more monosaccharides and/or one or more disaccharides is heated during a time period ranging from 20 minutes to 45 minutes at a temperature ranging from 180°C to 200°C to obtain the caramel. More preferred the mixture is heated from more than 30 minutes to 45 minutes at a temperature ranging from 180°C to 200°C to obtain the caramel, more preferred from 31 minutes to

40 minutes at a temperature ranging from 180°C to 200°C to obtain the caramel, more preferred from 31 minutes to 40 minutes from 180°C to 190°C to obtain the caramel.

Alternatively and preferably the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides during a time period ranging from 45 minutes to 100 minutes at a temperature ranging from 160°C to less than 180°C to obtain the caramel. More preferred the mixture is heated from 45 minutes to 90 minutes at a temperature ranging from 160°C to less than 180°C to obtain the caramel. Preferably the heating is done from 45 minutes to 60 minutes at a temperature ranging from 170°C to less than 180°C to obtain the caramel. Alternatively and preferably the heating is done from 60 minutes to

120 minutes from 160°C to less than 170°C to obtain the caramel, preferably from 60 minutes to 100 minutes.

In another preferred embodiment the heating is done at a temperature ranging from 175°C to 185°C during a time period ranging from 25 minutes to 35 minutes, even more preferred from more than 30 minutes to 35 minutes, even more preferred from 31 minutes to 35 minutes. Therefore in a preferred embodiment the invention provides a composition comprising vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, wherein the concentration of the vegetable oil ranges from 2% to 85% by weight of the composition,

further comprising caramel and one or more phenolic compounds,

wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides at a temperature ranging from 175°C to 185°C during a time period ranging from 25 minutes to

35 minutes, even more preferred from more than 30 minutes to 35 minutes, even more preferred from 31 minutes to 35 minutes, in the absence of phenolic compounds, and wherein a 10% by weight solution of the caramel in water has a colour value L* ranging from 50 to 67, and an a* value ranging from -5 to 10, and a b* value ranging from 5 to 60.

The temperatures and time periods as defined herein relate to atmospheric conditions.

Preferably the heating step is done by transferring the one or more monosaccharides and/or one or more disaccharides to an oven which is set at the required temperature, and perform the heating step inside that oven. This way overheating of the mono-and/or disaccharides in the oven can be prevented and the formation of the caramel can be well controlled. As compared to a method where mono- and/or disaccharides are heated in a pan with a heat source at the bottom, better temperature control is achieved. Heating in a pan may lead to local overheating of the mono- and/or disaccharides, in particular at the bottom of the pan. This way the caramel may become too dark, or may generate a too high burnt taste, although it may seem that the temperature of the caramel in the pan as a whole has achieved the temperature as desired.

Preferably in the composition the concentration of the caramel ranges from 0.1 % to 5%, preferably from 0.5% to 3% by weight of the composition. More preferred the concentration ranges from 1 % to 3% by weight of the composition.

The advantage of the caramels used in the present invention, is that they have a relatively bland, light colour, such that they are not very dark and do not give much colour to the composition in which they are incorporated. In particular for use in a mayonnaise this is an advantageous property. The colour of the obtained caramels can be determined by dissolving at 10% by weight in water, and determining the L*, a*, and b* values according to the CIE colour space. Comparison with water provides the colour of the caramel, by determining the ΔΕ* value, which is determined using the following formula:

ΔΕ* = (ΔΖ.*2 + Aa*2 + Ab*2)V2

The higher the L* value, the more translucent a sample. A dark sample has a low L* value. The higher the a* value, the more reddish the sample. Preferably a 10% by weight solution of the caramel in water has a colour value L* ranging from 55 to 65, and an a* value ranging from -5 to 5, and a b* value ranging from 5 to 50. Preferably the value of L* ranges from 56 to 64, preferably the value of a* ranges from -2 to 3; preferably the value of b* ranges from 10 to 48. L* and a* are more important values than the value of b*, as b* only has a minor influence on the final colour of the product. Preferably the value of ΔΕ* as compared to water ranges from 0 to 60, more preferred from 0 to 50.

Phenolic compounds can be found in nature in many types. One or more phenolic compounds used in the composition may be added as separate ingredients. Preferably though the one or more phenolic compounds are added to the composition as an element of another ingredient in the composition of the invention, for example in the vinegars mentioned herein before. Preferably the one or more phenolic compounds comprise one or more compounds from the group consisting of 3,4-dihydroxy-benzoic acid, syringic acid, p-coumaric acid, gallic acid, caffeic acid , trans-ferulic acid, vanillic acid, chlorogenic acid, and DL-catechin hydrate.

A common method to determine the phenolic compounds concentration of a sample, is the concentration in "gallic acid equivalents" (GAE). Whenever reference is made herein to "gallic acid equivalents" what is meant is the amount of gallic acid equivalents as determined by the Folin-Ciocalteu assay. Gallic acid (3,4,5-trihydroxybenzoic acid) is the phenolic acid that is used as a standard for determining the phenol content of various analyses by the Folin-Ciocalteu assay (see V.L. Singleton et al., Analysis of total phenols and other oxidation substrates and antioxidants by means of Folin-Ciocalteu reagent, Methods in Enzymology 299, 152-178, 1999).

Preferably the total concentration of the one or more phenolic compounds in the composition of the invention ranges from 0.0001 wt% to 0.1 wt% GAE. More preferred the concentration of the one or more phenolic compounds ranges from 0.0002 to 0.05 wt% GAE.

If not expressed as gallic acid equivalents, preferably the total concentration of the one or more phenolic compounds ranges from 0.0001 % to 0.1 % by weight of the composition. More preferred the concentration of the one or more phenolic compounds ranges from 0.0002 to 0.05% by weight of the composition.

The composition of the invention may contain a structurant to stabilise the water phase and to thicken the composition, in particular for products with low oil levels, for example less than 60% oil. Many structurants are oligomers or polymers from vegetable, microbial, or animal origin. The structurants can be water-soluble or water-insoluble, and they may be used native or in chemically or physically modified form. Examples of structurants from vegetable origin are water-soluble polysaccharides like native starches, chemically modified starches, carrageenan, locust bean gum, carboxymethyl cellulose, and pectin. Also oligosaccharides and polysaccharides present in corn syrup or glucose syrup may be used as structurant in mayonnaise-type emulsions. Additionally proteins from vegetable origin may be used as structurant in oil-in-water emulsions, for example ground pulse seed may be used to provide structure to an emulsion. Examples of water-insoluble structurants from vegetable origin are cellulosic fibres like citrus fibres and tomato fibres. Examples of structurants from microbial or algae origin are the polysaccharides xanthan gum, agar, and alginate. Examples of polymeric structurants from animal origin are proteins like casein from cow's milk and gelatin.

The composition of the invention may suitably contain one or more additional ingredients. Examples of such optional ingredients include salt, spices, sugars (in particular mono- and/or disaccharides), mustard, vitamins, flavouring, colouring, preservatives, antioxidants, herbs and vegetable pieces. Such optional additives, including the structurants, when used, collectively do not make up more than 40%, more preferably not more than 20% by weight of the composition.

Method for preparation of a composition according to the invention

In a second aspect the present invention provides a method for preparation of a composition according to the first aspect of the invention, comprising the steps:

(i) providing caramel, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to

45 minutes, in the absence of phenolic compounds;

providing one or more phenolic compounds;

providing vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids; and

mixing the caramel from step (i) and the one or more phenolic compounds from step (ii) with the vegetable oil from step (iii).

Preferably the caramel in step (i) is mixed with water first to create a solution of the caramel in water. In step (iv) the mixing of the various compounds in done in no particular order. Other optional ingredients of the composition that is prepared may be mixed with caramel in step (i), or with the one or more phenolic compounds in step (ii), or with the oil in step (iii) before these ingredients are mixed in step (iv). Other optional ingredients may be mixed with the ingredients after step (iv).

The second aspect of the invention also provides a method for preparation of a preferred oil-in-water emulsion according to the first aspect of the invention. Therefore the present invention provides a method for preparation of a composition in the form of an oil-in-water emulsion, comprising the steps:

(i) providing an aqueous mixture comprising an oil-in-water emulsifier,

and comprising caramel, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to

45 minutes, in the absence of phenolic compounds;

(ii) mixing vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids with the mixture from step (i) to prepare an oil-in-water emulsion; and

(iii) providing one or more phenolic compounds and adding these to the mixture from step (ii) and simultaneously or subsequently adding an acid to the mixture from step (ii) to bring the pH of the mixture to a value between 3 and 5.

In step (i), the aqueous mixture may contain other optional water soluble ingredients, like sugars, salt, flavours, mustard. Preferably all caramel present in the composition of the invention is present in the mixture of step (i). The oil-in-water emulsifier preferably comprises phospholipids originating from egg yolk. In step (ii) the oil is dispersed in the aqueous mixture from step (i), and preferably the mixture is homogenised during a time period long enough to create an oil-in-water emulsion wherein the oil droplets have a volume weighted mean droplet size D4,3 of less than 10 micrometer, preferably ranging from 0.3 to 10 micrometer, preferably ranging from 0.5 to 8 micrometer. This mean diameter may suitably be determined using the method described by Goudappel et al. (Journal of Colloid and Interface Science 239, p. 535-542, 2001 ). Preferably, 80 to 100% of the total volume of the oil droplets contained in the present emulsion have a diameter of less than 15 micrometer, more preferably a diameter ranging from 0.5 to 10 micrometer.

The homogenisation may be done using a conventional mixer for preparing oil-in-water emulsions, such as a colloid mill, or another mill as described in WO 02/069737 A2. A suitable supplier of such emulsification equipment is Charles Ross & Son Company, (Hauppauge, New York, USA).

In step (iii) the one or more phenolic compounds are added to the oil-in-water emulsion from step (ii). Preferably all phenolic compounds present in the composition of the invention are added in step (iii). Also acidification to bring the pH of the oil-in-water emulsion to a value between 3 and 5, preferably between 3 and 4.6, is done in this step (iii). In case vinegar is the source of the one or more phenolic compounds, as described herein before, then the addition of one or more phenolic compounds and acidification take place simultaneously.

Alternatively the second aspect provides a method for preparation of a preferred oil-in-water emulsion according to the first aspect of the invention. Therefore the present invention also provides a method for preparation of a composition in the form of an oil-in-water emulsion, comprising the steps:

(i) providing an aqueous mixture comprising an oil-in-water emulsifier;

(ii) mixing vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids and with the mixture from step (i) to prepare an oil-in-water emulsion; (iii) providing a mixture of caramel and one or more phenolic compounds, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising

one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds; and

(iv) mixing the mixture from step (iii) with the mixture from step (ii) and

simultaneously or subsequently adding an acid to the mixture from step (ii) to bring the pH of the mixture to a value between 3 and 5.

In step (i), the aqueous mixture may contain other optional water-soluble ingredients, like sugars, salt, flavours, mustard. The oil-in-water emulsifier preferably comprises phospholipids originating from egg yolk. Similarly as described before, in step (ii) the oil is dispersed in the aqueous mixture from step (i), and preferably the mixture is homogenised during a time period long enough to create an oil-in-water emulsion wherein the oil droplets have a volume weighted mean droplet size D4,3 of less than 10 micrometer, preferably ranging from 0.3 to 10 micrometer, preferably ranging from 0.5 to 8 micrometer. Preferably, 80 to 100% of the total volume of the oil droplets contained in the present emulsion have a diameter of less than 15 micrometer, more preferably a diameter ranging from 0.5 to 10 micrometer.

In step (iii) a mixture of the caramel and the one or more phenolic compounds is prepared. Preferably this is done in an aqueous mixture. Preferably this mixture contains all phenolic compounds and caramel present in the composition of the invention. In case a vinegar is the source of the one or more phenolic compounds as described herein before, the caramel may be added to that vinegar. This mixture is then added to the oil-in-water emulsion from step (ii) in step (iv). Also acidification to bring the pH of the oil-in-water emulsion to a value between 3 and 5, preferably between 3 and 4.6, is done in this step. In case vinegar is the source of the one or more phenolic compounds, then addition of caramel, one or more phenolic compounds and acidification take place simultaneously.

Preparation of this premix in step (iii) may have the advantage that the antioxidant effect of the combination of caramel and one or more phenolic compounds is stronger

than when caramel and one or more phenolic compounds are not added

simultaneously.

Preferably the concentration of EDTA is lower than 0.005% by weight of the composition, preferably lower than 0.002% by weight of the composition. More preferred the concentration of EDTA is lower than 0.001 % by weight, and most preferred EDTA is absent from the compositions prepared according to a method of the second aspect of the invention.

Preferred features as described in the context of the first aspect of the invention, are applicable to this second aspect of the invention as well, mutatis mutandis.

Use of caramel and one or more phenolic compounds

In a third aspect the invention provides the use of caramel and one or more phenolic compounds in a composition comprising vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids, to reduce the oxidation rate of the vegetable oil, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds.

In a third aspect the invention provides a method to reduce the oxidation rate of vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids in a composition, by using caramel and one or more phenolic compounds in that composition, wherein the caramel is obtainable, preferably obtained by heating a mixture comprising one or more monosaccharides and/or one or more disaccharides to a temperature ranging from 160°C to less than 180°C during a time period ranging from 45 to 120 minutes or to a temperature ranging from 180°C to 220°C during a time period ranging from 5 to 45 minutes, in the absence of phenolic compounds.

Preferably the concentration of EDTA is lower than 0.005% by weight of the composition, preferably lower than 0.002% by weight of the composition. More

preferred the concentration of EDTA is lower than 0.001 % by weight, and most preferred EDTA is absent from the composition.

Preferred features as described in the context of the first or second aspect of the invention, are applicable to this third aspect of the invention as well, mutatis mutandis.

DESCRIPTION OF FIGURES

Figure 1 : Hexanal concentration (in arbitrary units) in the headspace in accelerated shelf-life test, mayonnaises from example 2. Legend:

· sample 2-1 (with EDTA)

■ sample 2-2 (no EDTA)

▲ sample 2-3 (no EDTA, caramel and cider vinegar)

♦ sample 2-4 (no EDTA, caramel and balsamic vinegar)

Figure 2: Oxygen concentration in the headspace as function of time in mayonnaises from example 2. Legend:

• sample 2-1 (with EDTA)

■ sample 2-2 (no EDTA)

▲ sample 2-3 (no EDTA, caramel and cider vinegar)

♦ sample 2-4 (no EDTA, caramel and balsamic vinegar)

Figure 3: Hexanal concentration (in arbitrary units) in the headspace in accelerated shelf-life test, mayonnaises from example 3. Legend:

• sample 3-1 (with EDTA)

■ sample 3-2 (no EDTA)

▲ sample 3-3 (no EDTA, caramel and cider vinegar)

♦ sample 3-4 (no EDTA, caramel and cider vinegar)

EXAMPLES

The following non-limiting examples illustrate the present invention.

Raw Materials

• Water: demineralised water.

• Soybean oil ex Cargill (Amsterdam, The Netherlands).

• Sugar: sucrose white sugar W4 ex Suiker Unie (Oud Gastel, Netherlands).

• Salt: NaCI suprasel ex Akzo Nobel (Amersfoort, Netherlands).

• EDTA: Ethylenediaminetetraacetic acid, calcium disodium complex, dehydrate;

Dissolvine E-CA-10 ex Akzo Nobel (Amersfoort, Netherlands).

• Egg yolk: ex Bouwhuis Enthoven (Raalte, the Netherlands); contains 92% egg yolk and 8% kitchen salt.

• Vinegar spirit 12% ex. Kijhne (Hamburg, Germany)

• Apple vinegar: Amora Cider Vinegar ex Unilever France (Paris, France).

• Balsamic vinegar: ex. Acetum (Modena, Italy).

• Caramel colour (E150b): ex. Nigay (Feurs, France).

· Burnt sugar powder: ex. Nigay (Feurs, France).

Methods - Accelerated shelf-life test to follow lipid oxidation.

Vegetable oil is subjected to conditions which promote oxidation, without requiring the typical shelf life of 4 to 9 months of mayonnaise.

Mayonnaise samples with various compositions are prepared (as described in the examples below) and 1 g of each sample is filled in a capped glass vial (20ml_ volume) and kept in a temperature controlled oven at 50°C. Oxidation experiments are carried out during a period up to about 30 days and at several time points a sample is picked for headspace-GC-MS measurement of volatile oxidation markers (e.g. hexanal). Usually every data point is measured in triple The measurements are performed on a GC-MS combination of Agilent (7890A/5975C). The GC column used is a DB-Wax (20m-0.18d - 0.3μη"ΐ) from J&W. The injection volume is 500μΙ_ with a split of 40:1 and a column flow of 1 ml/min. Total nine volatiles (mainly aldehydes and alkanes -considered as marker for lipid oxidation) are analysed, of which hexanal is the most important marker, and reported in here. The hexanal response is given in arbitrary units - the higher the response the more hexanal and the more oxidation of triglycerides.

The oxidation of triglycerides occurs in several steps, in which the first step is the most important. This first step is the lag phase, which is the phase where there is not much oxidation, and after this phase the oxidation starts to accelerate. This means that the amount of oxidation products rapidly starts to increase. The longer the lag phase, the slower the oxidation process, and the better the result.

Oxygen concentration in headspace

To follow oxidation of fatty acids in emulsions in the experiments, the oxygen concentration is measured in the headspace of closed jars in which emulsions are stored to follow oxidation. The lower this concentration, the more oxygen is consumed for oxidation processes. The oxygen content is determined by taking a sample of gas from the headspace with a needle through the closed lid of the jar. The oxygen concentration in the sample is determined by gas analyser.

Example 1 - Preparation of Caramels

For preparation of the caramels A, B, C, and D in Table 1 below, the following procedure was generally applied. Sucrose (200 gram) was added into a round baking mould, and evenly distributed (thin layer) in the mould to ensure a homogeneous thermal treatment. An oven (Miele, type H4250B) was pre-heated to the required temperature and the baking mould with sucrose was placed in the middle position of the oven. The caramel formation was visually inspected by colour change of the sugar mass and at regular time intervals samples were taken for sensorial evaluation.

Caramels G, H, and I were prepared by adding 400 gram sucrose to 300 gram water, at its natural pH (7). The solution was heated in a pan on an induction plate. The solution was stirred with a spoon during heating. After reaction was stopped (when the required temperature was reached), the product was poured out of the pan on a flat plate to cool down. The caramel became solid upon cooling on the plate. This method is the same as the method described in non-prepublished patent application

PCT/EP2016/062861 .

The L*a*b* colour of the various caramels and of water was determined, using a Hunterlab LabScan XE colorimeter. The Δ£* value with water was determined, as described herein before.

Table 1 : L*a*b* colour measurement of caramels at 10 wt% in water and ΔΕ* with water.


Example 2 - Preparation of Mayonnaises, Oxidation, and Sensory Properties Mayonnaises were prepared with and without caramels according to the following recipes.

Table 2: Recipes of mayonnaises.


The mayonnaises were prepared at bench scale (1 kg emulsion) by first preparing an aqueous phase, which was prepared by mixing water, egg yolk, sucrose, salt, caramel, and EDTA, as applicable. Subsequently oil was slowly added to the aqueous phase, while mixing with a high shear mixer (Silverson). The oil was added in about 10 minutes, while the mixing speed was slowly increased from about 1600 to about 7200 rpm. After the oil had been homogenised, and the emulsion had become smooth, acetic acid and/or vinegar were slowly added while the mixer was kept at 7200 rpm. The compositions had a pH of 3.8.

The mayonnaises were subjected to the accelerated oxidation tests as described above. The hexanal amount released by the oxidation process was determined as function as time, as well as the oxygen concentration in the headspace. Results are shown in Figure 1 and Figure 2, showing that the emulsion containing EDTA shows least oxidation. The sample without EDTA and containing caramel and a polyphenol-rich vinegar shows an improved oxidation resistance, with only natural compounds that help to retard oxidation. In particular the onset of oxidation is substantially delayed, as shown in the two figures. Sample 2-2 without EDTA and caramel shows an onset of

oxidation already after about 8 days. Samples 2-3 and 2-4 with caramel show the onset after only about 18 days. This is a substantial difference which improves the shelf-life of the emulsions of the invention containing the caramel.

In addition the these analyses, the mayonnaises from this example were also tasted by 14 members of an expert taste panel. A full sensory evaluation of the mayonnaise samples was carried out by the trained panel. Each sample was evaluated on 25 attributes (which included taste and odour attributes) on a 1 to 15 intensity scale. With intensity 1 a certain attribute is absent or very low, and with intensity 15 such attribute is very pronounced. The evaluation was carried out in duplicate, using a balanced design and a randomized order. When tested, the mayonnaises were 1 week old and stored at 5°C after preparation. They were offered to the panel at 5°C.

The results showed that the 4 samples were not significantly different from each other for any of the 25 tested attributes. Table 3 shows the scores for the attributes typically associated with caramel. The letter next to the score value indicates the statistical significance of that attribute for a specific sample as compared to the other three samples.

Table 3: Sensory scores of mayonnaise from Table 2.


In all cases the four samples do not statistically differ on the attributes connected with caramel. Also visually no difference could be observed between the 4 samples as prepared in this experiment. This means that the compositions of the invention did not have any impact on the sensory properties of the mayonnaise as compared to the reference sample with EDTA and without caramel.

Example 3 - Preparation of Mayonnaises and Oxidation

Mayonnaises were prepared containing caramels according to the following recipes. As comparison mayonnaises containing EDTA were prepared as well, without caramel.

Table 4: Recipes of mayonnaises.


The mayonnaises were prepared at laboratory scale (400g emulsion) in a similar way as in example 2.

The mayonnaises were subjected to the accelerated oxidation tests as described above. The hexanal concentration in the headspace was determined as function as time, shown in Figure 3. Also here the onset of oxidation is substantially delayed.

Sample 3-2 without EDTA and caramel shows an onset of oxidation already after about 8 days. Samples 3-3, and 3-4 with caramel show the onset after only about 17 to 20 days. This is a substantial difference which improves the shelf-life of the emulsions of the invention containing the caramel. Additionally sample 3-3 containing caramel according to the invention and compared to sample 3-4 containing caramel prepared in a pan, shows that the new preparation method of caramel leads to an improved antioxidant effect. Less hexanal is formed in sample 3-3 compared to 3-4.