Patent Application
20190313659
The present invention relates to food compositions containing vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, further containing a mixtures with stabilising properties. The invention further relates to use of that mixture to reduce the oxidation of vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids.
Generally vegetable oils that are used in food compositions contain mono-unsaturated or poly-unsaturated fatty acids. In particular the double bonds in these fatty acids leads to sensitivity for oxidation. This may lead to the generation of oxidation products which may negatively affect the food composition, as these products may lead to unpleasant or undesired sensorial impressions, like bad smell and bad taste. These oxidation processes may be promoted by long storage of food products, the use of sensitive ingredients, metal content of certain ingredients which may promote oxidation, etcetera. The oxidative degradation of vegetable oil therefore often leads to decreasing value of food products. A common ingredient to reduce the oxidation of vegetable oil often is EDTA, ethylene diamine tetra acetic acid. This compound chelates metal ions, like iron, and therewith prevents that the metal ion can catalyse the oxidation process of the fatty acid in the vegetable oil. EDTA is very effective, however it is also perceived by the consumer to be chemical. As consumers strive to eat natural food products, there is a strive among food producers to remove compounds which are considered to be chemical from food products.
WO 2013/189709 A1 relates to a method of production of an EDTA-free mayonnaise by means of using a combination of reduced grape juice, acetic acid and proteins, whereby tartaric acid and malic acid as well as glucose and fructose are disclosed as components of the reduced grape juice. This described combination serves as EDTA-substitute and has oxidation-stabilising properties.
K. A. Woijtunik et al. (Journal of Agriculture and Food Chemistry, 2014, 62, p. 9088-9094) discloses monoterpenes as antioxidants, particularly pulegone, citral, gamma-terpinene, myrcene and alpha-phellandrene.
Common methods for counteracting oxidative degradation processes and autoxidative processes, in particular in food products containing vegetable oils with mono- or polyunsaturated fatty acids, therefore are often based on the use of EDTA or antioxidants. Since the use of EDTA is regulated and only possible conditionally, there is an ongoing strong interest in alternative solutions to decrease or to avoid the oxidative degradation processes and autoxidative processes, respectively, and thereby the formation of substances causing undesired flavours and/or tastes and/or other disadvantageous effects. Moreover, consumers are more and more interested in food products which do not contain compounds which can be considered to be chemical or artificial.
Therefore the primary objective of the invention is to provide food products containing vegetable oil, which contain one or more compounds that decrease oxidation rate of vegetable oil, and therewith avoid or slow-down the formation of undesired flavours and/or tastes that are formed or have formed during oxidative degradation processes. More in particular it is an objective of the present invention to provide a food composition which is free or nearly free from EDTA, and that contains one or more compounds that do not give an undesired colour or flavour or taste to the food composition, and that do not have negative chemical perception of the consumer.
These objectives have been met by using a combination of compounds which can be obtained from natural sources and which can be used to at least partly replace EDTA, and which lead to reduced oxidation of vegetable oils in food compositions.
Accordingly in a first aspect the invention provides a food composition comprising vegetable oil comprising mono-unsaturated and/or poly-unsaturated fatty acids, wherein the concentration of the vegetable oil ranges from 5% to 85% by weight of the composition, further comprising a mixture comprising or consisting of:
a) one or more monocyclic monoterpenes of formula (I)
with R1=hydrogen, hydroxy group or carbonyl group, R2=hydrogen, hydroxy group or carbonyl group, R3=0, hydrogen or hydroxy group (according to one alternative, R3 is not present) and R4=isopropyl group, isopropenyl group or isopropylidene group as well as without or with one, two or three double bonds in the cyclic system, preferably selected from the group consisting of gamma-terpinene, alpha-terpinene, beta-terpinene, beta-phellandrene, limonene, thymol, pulegone, carvacrol and alpha-phellandrene,
b) one or more benzoic acid derivatives of formula (II)
with R1, R2 and R3 independently of each other selected from the group consisting of hydrogen, hydroxy group and methoxy group,
c) a first 3-phenylpropenoic acid derivative of formula (IV)
with R1=1-carboxy-2-(3,4-dihydroxyphenyl)ethyl, R2=hydrogen and R3=hydrogen, optionally a second 3-phenylpropenoic acid derivative of formula (IV) with R1=5-carboxy-2,3,5-trihydroxycyclohexyl, R2=hydrogen and R3=hydrogen, and
optionally a third 3-phenylpropenoic acid derivative of formula (IV) with R1=hydrogen, R2=hydrogen and R3=hydrogen,
d) tartaric acid (formula (V))
D-(−)-form, and/or L-(+)-form, and/or meso-form
e) citric acid (formula (VI)) and/or malic acid (formula (VII))
f) glucose, fructose and/or sucrose,
g) 1,2-propanediol and/or 1,3-propanediol and/or propane-1,2,3-triol,
h) water,
i) optionally gallocatechin (Formula (III))
(2R,3S)-3,4-dihydro-2-(3,4,5-trihydroxyphenyl)-2H-1-benzopyran-5 3,5,7-triol
j) optionally one or more further flavouring substances, and
k) optionally one or more further solvents, preferably selected from the group consisting of triacetin (TRI), isopropanol (iPr), isopropyl myristate (IPM), ethanol, dipropylene glycol (DPG) and triethyl citrate (TEC).
In a second aspect, the present invention provides the use of a mixture as defined in the context of the first aspect of the invention in a composition comprising vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids, to reduce the oxidation rate of the vegetable oil.
Such mixture used in the composition of the invention demonstrates particularly advantageous stabilizing properties and oxidation-decelerating, oxidation-inhibiting or anti-autoxidative effects, respectively, according to the studies carried out within the scope of the present invention. The mixtures according to the invention are particularly well suited to reduce or to avoid altogether undesired flavours and/or tastes that are formed or have formed by oxidative degradation and autoxidation, respectively, or to slow down their formation. Thereby, advantageously a better sensorial durability and stabilization of the preparation containing such substances can be achieved. Additionally, the mixtures according to the invention are thereby widely applicable, particularly as component of specific preparations containing one or more oxidation-sensitive compounds (as described herein). The individual substances of the mixture according to the invention are not able to slow down or to avoid altogether the formation of undesired flavours and/or tastes by oxidative degradation and autoxidation, respectively, over a longer period to the same extent as mixtures according to the invention are able to, so that less undesired degradation products are formed, that can produce unpleasant or undesired sensorial impressions.
All percentages, unless otherwise stated, refer to the percentage by weight (wt %). D3,3 is the volume weighted geometric mean particle or droplet diameter. D3,2 is the surface-weighted mean diameter (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 food composition comprising vegetable oil. An edible or a food product in the context of the present invention encompasses, but is not limited to, food products including spreads, salad dressings, dairy products, beverages, dietetic foods, dietary supplements, and others. The products may contain ingredients common in the art and may be made by methods common in the art.
Triacylglycerols (TAG) are the major constituents of natural fats and oils and are esters of glycerol and fatty acids. The chemical structure of the fatty acid and the distribution of the fatty acids over the glycerol backbone determine (at least partly) the physical properties of a fat. The physical properties of fats, like for example the solid fat content (SFC) expressed as N-value, can be modified by altering the chemical structure of the fat. Well known techniques that are widely used include hydrogenation and interesterification.
Edible fats contain a large number of different triacylglycerols (TAGs) with varying physical properties. The TAGs in edible fats are composed of fatty acids with an even number of carbon atoms in the chains, generally varying between 4 and 24 in number. Common fatty acids from vegetable origin are C10, C12, C14, C16, C18, C20 and C22, and most common TAGs are composed of these fatty acids. Moreover each fatty acid can contain up to three double bonds at certain positions in the chain. The terms ‘triacylglycerols’, ‘TAGs’, and ‘triglycerides’ may be used interchangeably in here. The term ‘oil’ as used herein refers to lipids selected from triglycerides, diglycerides, monoglycerides and combinations thereof. The terms ‘oil’ and ‘fat’ may be used interchangeably herein, and should be regarded to be synonyms. Where applicable the prefix ‘liquid’ or ‘solid’ is added to indicate if the fat or oil is liquid or solid at ambient temperature as understood by the person skilled in the art. The term ‘structuring fat’ refers to a fat that is solid at ambient temperature. The term ‘liquid oil’ refers to an oil that is liquid at ambient temperature.
The mixture used in the composition of the invention, leads to reduced oxidation of the vegetable oil, and therefore the amount of EDTA that is added to the composition can be reduced. Therefore 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, more preferred the concentration of EDTA is lower than 0.0005% by weight, and most preferred EDTA is absent from the composition of the invention.
Mixture Used in the Composition of the Invention
The mixture used in the composition of the invention consists of or comprises the compounds mentioned herein before.
Preferably the mixture has an ORAC value of greater than 200 μmol TE/g, with respect to the dry weight of the mixture, preferably of greater than 500 μmol TE/g, particularly preferably of greater than 1000 μmol TE/g, especially preferably of greater than 2000 μmol TE/g.
ORAC stands for Oxygen Radical Absorption Capacity. The ORAC value determines the antioxidative ability or capacity of a substance or a mixture and is given in ORAC units (μmol TE/g) within the scope of the present text. The ORAC value therefore represents a characteristic measure of the antioxidative potential as is described in more detail in WO 2014/147112 A1.
Preferably the mixture has a polyphenol content according to Folin-Ciocalteu of greater than 5%, with respect to the dry weight of the mixture, preferably of greater than 10%, particularly preferably of greater than 15%.
The determination of the ORAC value and of the polyphenol content according to Folin-Ciocalteu took place during studies within the scope of the present invention and therefore also takes place within the scope of the present text generally following “Standardized Methods for the Determination of Antioxidant Capacity and Phenolics in Food and Dietary Supplements” by R. L. Prior et al., Journal of Agriculture and Food Chemistry, 2005, 53, 4290-4302.
Preferably the mixture comprises or consists of, with regard to the total weight of the mixture, respectively,
0.0001 to 80 wt % of component a), preferably 0.001 to 10 wt %, particularly preferably 0.01 to 5 wt %, especially preferably 0.1 to 1 wt %,
0.0001 to 1.5 wt % of component b), preferably 0.001 to 1 wt %, particularly preferably 0.005 to 0.25 wt %, especially preferably 0.01 to 0.1 wt %
0.0001 to 3 wt % of component c), preferably 0.001 to 1.5 wt %, particularly preferably 0.005 to 1 wt %, especially preferably 0.01 to 0.7 wt %
0.005 to 10 wt % of component d), preferably 0.0075 to 5 wt %, particularly preferably 0.01 to 3 wt %, especially preferably 0.01 to 0.5 wt %
0.005 to 10 wt % of component e), preferably 0.0075 to 8 wt %, particularly preferably 0.01 to 5 wt %, especially preferably 0.01 to 3 wt %
0.000005 to 25 wt % of component f), preferably 0.0000075 to 15 wt %, particularly preferably 0.00001 to 10 wt %, especially preferably 0.00005 to 5 wt %
0.0001 to 98 wt % of component g), preferably 0.0005 to 65 wt %, particularly preferably 0.001 to 45 wt %, especially preferably 0.1 to 35 wt %
0.0005 to 95 wt % of component h), preferably 0.005 to 65 wt %, particularly preferably 0.01 to 50 wt %, especially preferably 0.05 to 35 wt %
0.0001 to 1 wt % of component i), preferably 0.001 to 0.7 wt %, particularly preferably 0.005 to 0.5 wt %, especially preferably 0.01 to 0.15 wt %
0.005 to 95 wt % of component j), preferably 0.0075 to 50 wt %, particularly preferably 0.01 to 25 wt %, especially preferably 0.05 to 15 wt %
0.01 to 95 wt % of component k), preferably 0.05 to 65 wt %, particularly preferably 0.1 to 45 wt %, especially preferably 1 to 35 wt %.
The mixture is prepared by dissolving the solid ingredients in the solvents water and propylene glycol. If necessary, this preparation can be slightly heated to maximally 40° C. until all compounds are dissolved. Then the other ingredients can be added after cooling to room temperature. All ingredients can be obtained from natural sources, and therefore it does not have the negative impression of a chemical that EDTA has.
Preferably the total amount of mixture in the composition ranges from 0.05 to 5 wt %, preferably from 0.1 to 3 wt %, preferably from 0.2 to 1 wt %.
Oil-in-Water Emulsion
Preferably the composition of the invention is in the form of an oil-in-water emulsion. Examples of oil-in-water emulsions encompassed by the preferred invention include mayonnaise, dressings, salad dressings, and sauces. Preferably, the oil-in-water emulsion is a mayonnaise or a sauce, most preferably a mayonnaise. Preferably the composition of the invention is a low-fat mayonnaise.
Preferably the oil in the context of this oil-in-water emulsion 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 oil 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. The mono-unsaturated fatty acids as comprised in the oil preferably comprise oleic acid. The poly-unsaturated fatty acids as comprised in the oil preferably comprise linoleic acid and linolenic acid.
The concentration of the vegetable oil ranges from 5% to 85% by weight of the composition. Preferably the composition of the invention comprises from 10% to 80% by weight of vegetable oil, preferably from 15% to 75% 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 70% by weight, preferably maximally 65%, preferably maximally 60%. Any combination of ranges using these mentioned end points are considered to be part of the invention as well.
In case the preferred oil-in-water emulsion is a low-fat mayonnaise, the amount of oil preferably ranges from 20% to 60% by weight, preferably from 30% to 55% by weight preferably from 35 to 50% by weight of the composition. Generally such a mayonnaise or low-fat mayonnaise is spoonable. In another preferred embodiment, the oil-in-water emulsion is a salad dressing. Generally such salad dressing is a pourable liquid. In such case the amount of oil preferably ranges from 5% to 60% by weight, preferably from 10% to 55% by weight preferably from 15 to 50% by weight of the composition. The preferred emulsions typically are pourable or spoonable as opposed to solid. In case the preferred emulsion is non-pourable, it is preferred that the consistency of the emulsion is such that it cannot be cut in two as the parts of the emulsion that have been divided by the cutting will confluence after the cutting.
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 5% 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 preferably the composition comprises an oil-in-water emulsifier. The emulsifier serves to disperse oil droplets in the continuous aqueous phase. The preferred oil-in-water emulsion of the invention comprises egg yolk. 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 preferred oil-in-water emulsion has a pH ranging from 3 to 5, preferably ranging from 3 to 4.6, preferably from 3 to 4. This pH preferably is measured at 20° C. Suitable acids to obtain that pH are selected from acetic acid, citric acid, lactic acid, malic acid, phosphoric acid, hydrochloric acid, glucono-delta-lactone and combinations thereof. Preferably, the emulsions comprise acetic acid, citric acid or combinations thereof.
Preferably oil droplets dispersed in the preferred oil-in-water emulsion have a surface weighted mean diameter D3,2 of less than 10 micrometer, preferably from 0.3 to less than 10 micrometer, preferably from 0.5 to 8 micrometer, preferably less than 6 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). Typically, 80 to 100% of the total volume of the oil droplets contained in the composition of the invention have a diameter of less than 15 micrometer, more preferably a diameter ranging from 0.5 to 10 micrometer.
The combination of ingredients in the preferred oil-in-water emulsion has a very significant effect on the rheological properties of the emulsion, e.g. in that it provides an elastic modulus G′, measured at 20° C., within the range of 100 to 1,000 Pa, most preferably in the range of 300 to 700 Pa at a strain (deformation) of 1%.
The dynamic viscosity of the preferred oil-in-water emulsion preferably ranges from 0.5 to 30 Pa·s, more preferably from 1 to 10 Pa·s at a shear rate of 50 s−1 and 20° C. The viscosity can be determined using an AR1000 controlled stress rheometer ex TA Instruments (New Castle, Del., USA).
The preferred oil-in-water edible emulsion may suitably contain one or more additional ingredients. Examples of such optional ingredients include thickeners like starches or gums, salt, sugar, spices, vitamins, flavouring, colouring, mustard, herbs and pieces of meat, vegetable or cheese. Such optional additives, when used, collectively, do not make up more than 40%, more preferably not more than 20%, preferably not more than 10% by weight of the composition.
The preferred oil-in-water emulsion may be prepared by any common method in the art. Preferably such method includes the following steps:
The dispersion obtained in step (ii) is further homogenised to create a fine dispersion of oil droplets. The optional homogenisation step (iii) is done during a time period long enough that the dispersed oil phase typically has a mean diameter D3,2 of less than 10 micrometer, preferably from 0.3 to less than 10 micrometer, preferably from 0.5 to 8 micrometer. Preferably the oil droplets of the emulsion obtained in step e) have a volume weighted geometric mean droplet size D3,2 of less than 6 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, N.Y., USA).
Preferably in the final optional homogenisation step the homogenisation is performed using a colloid mill operating at a rotation rate ranging from 2,000 to 14,000 rpm. In such step the emulsion is pumped through the head of the colloid mill, to be contacted with the rotating elements of that head. The oil droplets are finely dispersed after such homogenisation step having the required size, and a homogeneous emulsion is obtained. The emulsion may be recirculated once or twice over the colloid mill head in order to create the required oil droplet size.
Water-in-Oil Emulsion
Preferably the food composition of the invention is in the form of a water-in-oil emulsion. Such fat continuous food products are well known in the art and include preferably shortenings comprising a fat phase and margarine comprising a fat phase and an aqueous phase. Margarine traditionally contains about 80% of an edible fat phase, and 20% of an aqueous phase, that is dispersed as small droplets in the continuous edible fat phase. Other examples of water-in-oil emulsions are low-fat spreads, in which the proportion of edible fat phase is lower and aqueous phase is higher than margarine, for example about 10 to 40% edible fat phase and about 60 to 90% aqueous phase. For the purpose of the present invention, margarine includes water-in-emulsions containing from 10 to 80% by weight of fat.
The fat phase of margarine and similar edible fat continuous spreads is often a mixture of liquid oil and structuring fat. The structuring fat serves to structure the fat phase (for example in a shortening as well as in a water-in-oil emulsion) and helps to stabilize the aqueous phase, if present, by forming a fat crystal network. For a margarine or spread, ideally the structuring fat has such properties that it melts or dissolves at mouth temperature upon consumption.
The liquid oil preferably has the same preferred features and preferred origin as disclosed in the context of the preferred oil-in-water emulsion.
The structuring fat may be a single fat or a mixture of different fats. The structuring fat may be of vegetable, animal (e.g. dairy fat) or marine origin. Preferably at least 50 wt % of the structuring fat (based on total amount of structuring fat) is of vegetable origin, more preferably at least 60 wt %, even more preferably at least 70 wt %, still more preferably at least 80 wt %, even still more preferably at least 90 wt % and even still more further preferably at least 95 wt %. Most preferably the structuring fat essentially consists of structuring fat of vegetable origin.
Preferably the natural fat is selected from the group consisting of palm fat, allan blackia, pentadesma, shea butter, coconut oil, soybean oil, rapeseed oil and dairy fat. More preferably the natural fat is selected from the group consisting of palm oil, palm kernel oil, palm oil fraction, palm kernel fraction, coconut oil and dairy fat fraction. Even more preferably the natural fat is selected from the group consisting of palm oil, palm kernel oil, palm oil fraction, palm kernel fraction and coconut oil.
The various fat sources may be fully hardened by full hydrogenation, they may be fractionated, intra-esterified, and/or inter-esterified.
The structuring fat may comprise minor amounts of other components like for example monoglycerides that are naturally present in the fat.
To optimize the structuring capacity and/or impression of the emulsion in the mouth upon consumption, structuring fats having a certain solid fat content are preferred. Therefore, the structuring fat as present in the solid particles preferably has a solid fat content N10 from 50 to 100%, N20 from 26 to 95% and N35 from 5 to 60%. The N-value expresses the solid fat content (SFC) at a certain temperature (in ° C.).
The structuring fat preferably has a solid fat content N10 selected from the list consisting of 45 to 100%, 55 to 90% and 65 to 85%;
N20 selected from the list consisting of 25 to 80%, 40 to 70% and 45 to 65%;
N35 selected from the list consisting of 0.5 to 60%, 0.5 to 20%, 0.5 to 14%, 15 to 50% and to 45%.
Preferred solid fat content profiles of the structuring fat are:
N10 from 45 to 100%, N20 from 25 to 80% and N35 from 0.5 to 60%;
N10 from 55 to 90%, N20 from 40 to 70% and N35 from 0.5 to 20%;
N10 from 55 to 90%, N20 from 40 to 70% and N35 from 15 to 50%;
N10 from 65 to 85%, N20 from 45 to 65% and N35 from 0.5 to 14%; and
N10 from 65 to 85%, N20 from 45 to 65% and N35 from 30 to 45%.
Generally edible fat continuous food products like for example margarines and similar edible fat continuous spreads are prepared according to known processes that encompass the following steps:
(i) Making a pre-emulsion of an aqueous phase and an edible fat phase. For margarine the fat phase usually contains a mixture of liquid oil (often containing C16-C18 mono- or polyunsaturated fatty acids) and structuring fat (often containing C16-C18 saturated fatty acids).
(ii) The emulsion is heated for pasteurisation, leading to complete melting of the edible fat phase.
(iii) The warm emulsion is cooled under high shear to induce crystallization of the structuring fat to create an emulsion. A fat crystal network is formed to stabilize the resulting emulsion and give the product some degree of firmness. Common equipment in this step is a scraped surface heat exchanger, wherein the wall of the heat exchanger is at a temperature lower than −10° C. The saturated fatty acids crystallise on the cold wall, and these solids are scraped from the wall. The water-in-oil emulsion is formed in this step, leading to a fine dispersion of aqueous phase droplets (size usually smaller than 10 micrometer) in the continuous fat phase. The droplets are stabilised by small saturated fat crystals on the interface of the droplets.
(iv) The crystal network is further modified to produce the desired firmness, confer plasticity and reduce the water droplet size. This step is often done in a tube containing a mixer.
(v) The emulsion is filled in its packaging for further distribution to consumers.
These steps are usually conducted in a process that involves apparatus that allow heating, cooling and mechanical working of the ingredients, such as the churn process or the votator process. The churn process and the votator process are described in the Ullmans Encyclopedia, Fifth Edition, Volume A 16, pages 156-158.
In order to ensure that the structuring fat is liquid when introduced into the mixing apparatus or before being mixed with the liquid oil phase, preferably in step (ii) the melting temperature is at least 50° C., preferably at least 60° C., preferably at least 70° C., and preferably maximally 90° C. At these temperatures all crystals of the triacylglycerols have become liquid, there are no nuclei for solidification any more at these melting temperatures.
Preferably the weight ratio between structuring fat and liquid oil ranges from 1:100 to 50:100, preferably from 5:100 to 25:100. This means that the total fat phase of the emulsion preferably comprises from 1% by weight to 50% by weight of structuring fat, and from 50% by weight to 99% by weight of liquid oil. More preferably the total fat phase of the emulsion preferably comprises from 5% by weight to 25% by weight of structuring fat, and consequently from 75% by weight to 95% by weight of liquid oil. With these ratios a fat-continuous emulsion can be produced which has the correct hardness and consistency.
An emulsifier may be comprised in the composition to create a good dispersion of aqueous phase in the fat phase. Preferably the composition of the invention comprises a water-in-oil emulsifier. The emulsifier preferably has a HLB value of lower than 7. The HLB value is the hydrophilic-lipophilic balance, and is a measure for the degree of hydrophilicity or lipophilicity. An emulsifier with a HLB value lower than 10 generally is oil soluble, while an emulsifier with a HLB value higher than 10 generally is water-soluble. Hence preferably an emulsifier having a HLB value of 7 or lower, is mixed with the liquid oil prior to mixing with the other ingredients of the composition of the invention. Preferably, the concentration of the emulsifier is maximally 5% based on the weight of the mixture of liquid oil and emulsifier, preferably maximally 1%, preferably maximally 0.1%, preferably maximally 0.01%. A relatively high emulsifier content may lead to the ability to produce low fat or very low fat water-in-oil emulsions, although a relatively high emulsifier content is not necessary to produce low-fat water-in-oil emulsions.
Preferably the emulsifier comprises a monodiglyceride of fatty acid, or a diglyceride of fatty acids. Preferably the emulsifier comprises one ore more of emulsifiers chosen from the group consisting of saturated monoglycerides, unsaturated monoglycerides, and sugar-fatty acid esters (also known as the ‘Spans’, e.g. sorbitan monostearate). Preferably the HLB value of the emulsifier is lower than 5, preferably lower than 3, preferably 1. Another preferred emulsifier is lecithin from soyabean, or egg.
The amount of aqueous phase and fat phase in the preferred water-in-oil emulsion may range widely. The fat phase includes the structuring fat and the liquid oil, and preferably an emulsifier as defined before. Preferably the concentration of the fat phase ranges from 5% to 95% based on the weight of the emulsion, preferably from 15% to 50%. The emulsion may comprise a fat phase as a majority phase (for example, a margarine containing about 70 to 80% by weight of fat phase), preferably the emulsion comprises from 10% to 80%, preferably from 15% to 60% fat phase based on the weight of the emulsion. Most preferably though the produced emulsion is a low fat emulsion with a fat content ranging from 15% to 50% by weight, preferably ranging from 18% to 45% by weight of fat phase, preferably ranging from 25% to 45% by weight of fat phase, preferably ranging from 30% to 45% by weight of fat phase. An advantage of the method of the present invention is that low fat spreads (maximally 50% by weight of fat phase) can be produced in a single step.
The aqueous phase is dispersed in small droplets in the continuous fat phase during the mixing in the mixing apparatus. Preferably the D3,3 value of the dispersed aqueous phase droplets is less than 10 micrometer, preferably less than 8 micrometer, preferably less than 6 micrometer. Preferably the D3,3 value of the dispersed aqueous phase droplets is less than 3 micrometer, or even less than 2 micrometer.
Preferably the preferred water-in-oil emulsion has a pH ranging from 4 to 6, preferably ranging from 4 to 5.5, preferably from 4.5 to 5.5. This pH preferably is measured at 20° C. Suitable acids to obtain that pH are selected from acetic acid, citric acid, lactic acid, malic acid, phosphoric acid, hydrochloric acid, glucono-delta-lactone and combinations thereof.
The preferred water-in-oil emulsion may suitably contain one or more additional ingredients. Examples of such optional ingredients include thickeners like starches or gums, salt, sugar, spices, vitamins, flavouring, colouring, herbs, spices. Such optional additives, when used, collectively, do not make up more than 40%, more preferably not more than 20%, preferably not more than 10% by weight of the composition.
Use of the Mixture
In a second aspect, the present invention provides the use of a mixture as defined herein in a food composition comprising vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids, to reduce the oxidation rate of the vegetable oil. The invention also provides a method to reduce the oxidation rate of vegetable oil comprising mono-unsaturated or poly-unsaturated fatty acids in a food composition, using a mixture as defined herein before.
Preferred aspects indicated in the context of the first or second aspect of the invention are applicable to the third aspect of the invention, mutatis mutandis.
Legend:
The following non-limiting examples illustrate the present invention.
Raw Materials
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 which is normal for a mayonnaise.
Emulsion 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 (20 mL volume) and kept in a temperature controlled oven at 50° C. Oxidation experiments are carried out during a period up to 42 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 triplo. The measurements are performed on a GC-MS combination of Agilent (7890A/5975C). The GC column used is a DB-Wax (20 m-0.18 d-0.3 μm) from J&W. The injection volume is 500 μL 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 a gas analyser.
Equipment
The mixture can be used in food compositions according to the invention.
These mixtures are prepared by dissolving the solid compounds in the premixed solvents water and propylene glycol. If necessary, these preparations are slightly heated to maximally 40° C. until all compounds are dissolved. Then the other ingredients are added after cooling to room temperature.
Various low-fat mayonnaises were prepared containing EDTA, without EDTA, and containing a mixture containing the compounds of and at concentrations of M1 in example 1. The compositions of these water-in-oil emulsions is given in Table 2.
These mayonnaises were prepared by the following method:
In order to assess oxidation of oil, the oxygen concentration in the headspace in the jars containing the emulsions was followed during a period of about 2 months. The emulsions were stored at a temperature of 20° C. The higher the oxygen concentration, the less the oxidation of the oil. This is shown in
The oxidation of the oil in the emulsions was followed by the accelerated shelf-life test, as described above. Emulsions from Table 2 were stored at 50° C., and samples from the headspace taken as during a time period of about 1.5 months. The hexanal concentration in the headspace is shown in
Various salad dressings were prepared containing EDTA, without EDTA, and containing a mixture containing the compounds of and at concentrations of M1 in example 1. The compositions of these water-in-oil emulsions is given in Table 3.
These salad dressings were prepared by the following method:
In order to assess oxidation of oil, the oxygen concentration in the headspace of the emulsions was followed during a period of about 4 months. The emulsions were stored in at a temperature of 20° C. The oxygen concentration is shown in
Various margarines were prepared containing a mixture containing the compounds of and at concentrations of M1 in example 1 at two concentrations, and without such mixture. The compositions of these water-in-oil emulsions is given in Table 4.
These margarines were prepared using a mini-votator containing an A-unit and a C-unit. First the aqueous phase and fat phase were prepared, and heated for pasteurisation. The phases were mixed to prepare a pre-emulsion, and then the pre-emulsions were pumped through the mini-votator. Before emulsification, the pH of the aqueous phase was adjusted to 5 by addition of lactic acid 20%.
In order to assess oxidation of oil, the oxygen concentration in the headspace of the emulsions was followed during a period of more than 4 months. The emulsions were stored in closed packages at a temperature of 5° C. This is shown in
The light margarine 028 shows the lowest oxygen concentration in the headspace, thus most oxidation of the fatty acids. The sample 030 containing the highest concentration of the mixture containing the compounds of and at concentrations of M1 in example 1 shows least oxidation.
Therefore this mixture of components can be used to decrease oxidation of vegetable oil in a water-in-oil emulsions.
| Number | Date | Country | Kind |
|---|---|---|---|
| 16200705.8 | Nov 2016 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/080328 | 11/24/2017 | WO | 00 |
