DK170088B1 - A spreadable water-in-oil emulsion - contains as emulsifier only distilled mono:glyceride(s) and 12-30 wt. of emulsion with aq. phase free of added protein and hydrocolloid - Google Patents

Abstract

A spreadable water-in-oil emulsion contains as emulsifier only distilled monoglycerides or monodiglycerides of edible fatty acids contg. 12-22C atoms. The fatty phase constitutes 12-30 wt.% of the emulsion and the emulsifier has an iodine value of 50-150 and is present in an amt. corresp. to an amt. of monoglyceride of 0.35-4 wt.% of the emulsion and the aq. phase is free of added protein and hydrocolloid.

Description

DK 170088 B1

The present invention relates to a spreadable water-in-oil emulsion which, as an emulsifier, contains only distilled monoglycerides or mono-diglycerides of edible 2 to 22 Fe <3 acids. The emulsifier is present in the fat phase of the emulsion.

By the term "spreadable" is meant that the emulsion must be non-liquid at room temperature and temperatures up to 30 ° C, so as to have a consistency similar to butter, margarine and the low fat, margarine-like products commonly sold under the term minarine. By the term "monoglycerides" is meant, in accordance with conventional terminology, mixtures of esters of fatty acids with glycerol, in which substantially only one of the hydroxyl groups of the glycerol is esterified, while with monodiglycerides, also according to usual terminology is meant mixtures of esters of fatty acids. with glycerol, wherein one and partly two of the glycerol hydroxyl groups are esterified. Distilled monoglycerides usually contain at least 90% monoglyceride.

20 Butter and usual margarine usually contain approx. 80% fat or oil (in this description no distinction will be made between "fat" and "oil"), mainly consisting of triglycerides, ie. glycerol wherein all three hydroxyl groups are esterified with fatty acids which may be 25 saturated or more or less unsaturated. Skinny margarine incl. minarine generally contains approx. 40% fat or oil, basically the same as used in usual margarines.

Minarine has been on the market in Europe since the 1930s, and although the product can now be considered accepted by the public, fat consumption in most countries and not least in Denmark must still be considered too high, from a health policy point of view.

2 DK 170088 B1

However, it is technically difficult to prepare water-in-oil emulsions with substantially lower fat content than the usual minarin products and in particular it is difficult to prepare them in such a way that they are stable at temperatures substantially above refrigerator temperature, especially at room temperature. such as 22 ° C, and the water-in-oil emulsion will not be perceived as buttery or margarine-like.

The patent literature contains various information on margarine or minarine products 10 with lower fat content than minarines.

Thus, European Patent Application No. 256,712 discloses a spreadable water-in-oil emulsion with 18-35% fat in the continuous phase; the discontinuous phase, i.e. the aqueous phase, contains at least 8% by weight of milk proteins and 0.1-1.2% by weight modified, in particular pre-gelatinized starch. These ingredients are stated to allow for the low fat content and are believed to act as stabilizers.

From European published patent application no.

No. 20,237,120 discloses a spreadable water-in-oil emulsion containing from 10 to 35% by weight fat phase and whose aqueous phase has a viscosity of at least 20 mPa.s at a shear rate of 17090 see. and one temperature of 5 ° C; this is achieved by the mixture comprising the aqueous (discontinuous) phase containing a hydrocolloid as a gelling component in an amount of 1-25% by weight. The hydrocolloid may, for example, be a hydrolyzed starch derivative, gelatin, carrageenan or mixtures thereof, and in addition, non-gelling components such as non-gelling starch hydrolyzate or maltodextrin may be included in the aqueous phase.

From UK published patent application no.

2,150,585 is known a spreadable water-in-oil emulsion having a fat phase of 20-90% by weight and containing in the aqueous phase 1-25% (of the total weight of the emulsion) separate grains of natural, crystalline starch or agglomerates of which 80-100% have a diameter of less than 15 µm.

3 DK 170088 B1

The thus-known spreadable water-in-oil emulsions thus contain protein and / or hydrocolloid in the aqueous phase. However, it would be desirable to avoid such microbiologically degradable material in the aqueous phase because it may give rise to microbiological growth, whereas known fat-based emulsifiers in the fat phase rarely give rise to such problems.

Lubricable water-in-oil emulsions also known as the sole emulsifier contain monoglycerides 10 or mono-diglycerides.

Thus, published European Patent Application No. 98,664 relates to a process for preparing a low fat water-in-oil emulsion, defined as less than 60%, which is characterized in that an emulsion is formed from a fat phase and an aqueous phase. which are then subjected to shear forces for phase switching by means, for example, a Votator A or C unit coated internally or made of a hydrophobic material, preferably polytetrafluoroethylene, thereby crystallizing the fat. According to Example 1 of the specification, a stable (not specified in what temperature range) water-in-oil emulsion is produced having a fat phase of 21% of the weight of the emulsion and composed of fats with specified dilation values. The only emulsifier 25 is 0.55% monoglyceride, "Hymono" Sf 44. It has an iodine number of probably approx. 40 and a monoglyceride content of maybe 90%. This emulsion requires the specific preparation technique specified in the script.

Another method for preparing low-calorie, spreadable water-in-oil emulsions without a special stabilizing agent and having a fat content of 30-60% is known in West German Patent Specification No. 2,345,798, where monoglyceride mixtures containing (obviously only) emulsifying agent are used. unsaturated and saturated fatty acids 35 in a weight percent of 1.5: 1 to 10: 1, preferably 4, 1.6: 1 to 8: 1, further imposing special restrictions on the ratio of the amount of stearic acid to the amount of saturated fatty acids and with respect to the ratio of the amount of linoleic acid to the amount of unsaturated 5 fatty acids having a number multiplied by 100 is * at least 110. Thus, in this known process, margarine or minarine-like products having a fat content less than 30% cannot be produced. .

It is an object of the invention to provide a water-in-oil emulsion of the type initially specified which has a fat content lower than 30% and which can be prepared using conventional equipment in the margarine industry and without including microbiological growth substrates in the water phase. in that it is not necessary to ensure any special balancing of the fatty acids in the mono- or mono-diglycerides.

It has surprisingly been found in the invention that this can be done by the fat phase being 12-30% by weight of the emulsion and the emulsifier having an iodine number 20 of 50-150 and present in an amount corresponding to distilled monoglyceride of 0.35 -4.0% by weight of the emulsion, knowing that the aqueous phase is free of added protein and hydrocolloid.

There are no special restrictions with regard to the composition of the fats (triglycerides) in the fat phase, which may contain both saturated and unsaturated fatty acids and be composed as is usual for margarine and minarine. Thus, fat blends containing animal and / or vegetable oils and fats, partial and / or full cured oils and fats, or butter oil may be used.

According to the invention, the fat phase may conveniently comprise 16-25% of the weight of the emulsion. Even if the above conditions are met, it may be difficult to maintain a product with less than 16% fat phase stable at temperatures of, for example, 30-35 ° C.

Conveniently, as the fatty acid residues, the emulsifier contains mainly residues of fatty acids having 5 to 16 carbon atoms. The fatty acid residues, as shown in the aforementioned iodine numbers, are both saturated and unsaturated. Distilled monoglyceride and mono-diglyceride of this kind are industrially prepared in large quantities and are readily available.

According to the invention, there may conveniently be so much emulsifier present in the fat phase that it corresponds to an amount of distilled monoglyceride of 0.4-3.5%, preferably 0.75-1.5%, of the weight of the emulsion. Lower amounts of monoglyceride may in some cases result in water withdrawal of the emulsion and higher amounts will only lead to improved stability of the emulsion in specific cases.

The iodine number of the emulsifying agent according to the invention may advantageously be 90-120 and particularly conveniently 100-110, which has been found to give the emulsion particularly good stability.

The pH of the aqueous phase can be excellent as the usual pH of margarines and minarines, i.e. from 4 to the neutral point. Advantageously, it is at least 5.5, especially approx. 6.0. Due to the absence of hydrocolloids or proteins in the aqueous phase, the preservative effect which is usually obtained by the acid addition is not required, and the very low fat content means that the fresh taste of the acid can be obtained with a low amount of acid. As an acid, they may be used in margarine 30 and minarine customarily, for example lactic acid or especially citric acid. In some countries, a rather acidic taste of margarine and similar lubricants is appreciated, and then a pH of the aqueous phase of approx. 4 be helpful. Experiments with a minarine containing 40% fat phase 35 have shown that pH does not affect its stability when the aqueous phase contains no protein. The same applies to the very low fat emulsion of the present invention.

6 DK 170088 B1

The present emulsion is generally used only as a substitute for margarine or minarine and therefore contains adjuvants that are customary for such products. Thus, it may contain salt (i.e., sodium chloride) in a quantity usual for such products, i.

0-2.5% by weight of the emulsion. In the fat phase, for example, carotene may be included in a known manner. It works such as provitamin, and both the aqueous phase and the fat phase may additionally contain vitamins in conventional amounts.

10 Known margarines and minarines contain flavoring and flavoring substances, whose specific nature and composition are usually considered manufacturing secrets and are therefore not disclosed. They are most frequently present in the fat phase.

Because of the very limited amount of fat phase in the pre-emulsifying emulsion, it is contemplated by the invention that both the aqueous phase and the fat phase contain aromatizers of species useful in margarine and minarine.

20 Experiments

The emulsion according to the invention will now be elucidated in some experiments.

In these, a laboratory system was used with 2 alternating emulsion tanks with a volume of 25 every 6 liters and each provided with a propeller stirrer whose speed can be varied continuously from 0 to 2400 rpm. minute (rpm). To pump the emulsion through the plant's cooling and kneading unit, a test high pressure pump type 2-30-4 with a continuously variable 30 output of 0.98 kg / hour was used from Gerstenberg & Agger A / S, Frederiksberg, Denmark. The default capacity of the pump is 50 kg / hour? when capacity is mentioned in connection with the tests described below, this means the amount of emulsion that was actually pumped per unit. hour at the 35 given trial. The cooling and kneading unit was a 3-tube so-called experimental perfector manufactured by Gerstenberg & Agger A / S.

DK 170088 B1 7

This type of apparatus is well known in the margarine industry and is generally called surface scraping heat exchangers. The refrigerant is liquid ammonia, where the evaporation temperature and thus the cooling effect can be varied. In all five experiments, 2 cooling tubes were used and the rotor speed in the cooling tubes was approx. 970 opm.

The fat blends used in the experiments can be characterized as follows by NMR analysis, carried out on a Bruker "Minispec" P 20 apparatus with parallel tempering of the fat blends before analysis:

Temperature NMR values (Solid fat content) 5 ° C 15-60% 15 10 ° C 10-50% 20 ° C 5-25% 30 ° C 0-7% 35 ° C 0-4% 40 ° C 0 -2% 20

For each test, 3 or 4 kg of emulsion was used and all percentages are for test portions of these sizes. In the experiments, all percentages are based on the weight of the entire emulsion and "parts" are weight-25 parts with the entire fat blend set to 100 parts. The emulsification takes place alternately in the two 6 liter tanks and the speed of rotation decreases as the emulsification tank is emptied.

It is known from other experiments and from the production of 30 minarine that the viscosity of the emulsion increases with decreasing emulsification temperature, with intensification of stirring and with increased dosage of monoglyceride of unsaturated fatty acids. In all the experiments, a water-in-oil emulsion was sought and obtained, but the tests have also shown that too high a stirring rate, especially with low dosage of distilled monoglyceride of unsaturated fatty acids, can cause a phase-shift to an oil-in-oil. water emulsion.

However, it has been able to return to a water-in-oil emulsion either by using even higher stirring rates or in the experimental perfector.

t In all experiments, 4 ppm carotene (based on the weight of the emulsion) is included in the fat phase.

5 In the first test series, an * emulsification temperature of approx. 50 ° C and moderate stirring. The quantitative composition of the finished emulsion was:

Test Distilled Mono- Grease Blend - Water Phase 1n No. glyceride, iodine number approx. 105 1 0/5% 24.5% a) 2 0.8% 24.2% a) 3 1.0% 24.0% a) 15 4 1.3% 23.7% a) 5 2.0 % 23.0% a) 6 0.5% 19.5% b) 7 0.8% 19.2% b) 8 1.0% 19.0% b) 20 9 1.3% 18.7% b) 10 2.0% 18.0% b)

Fat blend: 25 parts hardened soybean oil, m.p. 41 ° C 75 parts liquid soybean oil 25

Aqueous phase a: 73.0% water "2.0% salt J pH 6.0

b: 78.0% water "I

2.0% saline pH 6.0

Flavor: 100 ppm flavor for the water phase + 100 ppm flavor for the fat phase k 35 9 DK 170088 B1

The ammonia temperature of the experiments was -10 ° C and the capacity 40 kg / hour.

Assessment after storage at 5 ° C for 3 days when smeared with a knife on a piece of cardboard gave the following results: 5

Emulsion from experiment no.

1 separates in water and grease phase 2 quite good, differs slightly • yes 3 extremely stable 4 extremely stable 5 extremely stable, slightly soft 6 separates slightly 7 extremely stable • J5 8 extremely stable 9 extremely stable 10 extremely stable

The assessment method used is very critical. gives the impression of the appearance of the product (color, smoothness, graininess, uniformity, whether it is coherent or distinct in the water and fat phase, etc.), its consistency (hard or soft, greasy) and spreadability. Although this product proves to be separable in water-25 and grease phase during lubrication, it can very well be a stable water-in-oil emulsion in the package and behave like a normal margarine or minarine and can even be used to spread bread. . The products are usually tested after storage at 5 ° C; if the product appears stable by smearing on cardboard after storage at 5 ° C, it will also be stable after storage at higher temperature. A product that differs in the water and grease phase upon lubrication after storage at 5 ° C may be stable after storage at higher temperature, e.g., 10 ° C or 20 ° C. This is because a larger amount of crystals is melted at increased storage temperature than otherwise, thereby making the fat phase softer. The products that during the test proved to "separate" 10 DK 170088 B1 or "separate a little" are stable in the package and usable and spreadable on bread.

In the taste assessment, the stable samples were found to be well aromatic and to give a good mouthfeel. The water distribution assessed by microscope showed fine, uniform distribution of the water droplets; the vast majority had a diameter of less than c 10 µm.

A second series of experiments was conducted to test the products after storage at 5 ° C, 10 ° C and 20 ° C. The emulsifier was the same as in Experiments 1-10 and aqueous phase a) was used. The amount of distilled monoglyceride was:

Experiment No. Menace emulsifier 11 0.8% 15 12 0.5% 13 0.4% 14 0.3%

The product of Experiment # 14 separated the Experiment Perfector. The others were tested in the described test by smearing on cardboard after 3 days of storage. The results were:

Egrs.nrt Storage at 5 * C Storage at 10 * C Storage at 20 * C

25 11 excellent stable excellent stable superbly stable 12 separates a little well stable good stable 13 separates a little differs a little

The product tested in experiment # 12 was satisfactory after storage at 10 ° C and 20 ° C; that in experiment no.

Thirteen tested were less satisfactory at the lubrication, but had satisfactory appearance in the package.

In addition, in these experiments, the same distilled monoglyceride was also tested at high concentrations and in * 35 otherwise in the manner described.

11 DK 170088 B1

Fors. Distilled monoglyceride Fat mixture Water phase no. 105 15 3.0% 22.0% a) 5 16 4.0% 16.0% b)

After storage for 3 days at 5 ° C, the product tested in Experiment 15 proved extremely stable by smearing on cardboard. The product tested in Experiment 16 differed after 10 storage for 3 days at 5 ° C, was extremely stable in the lubrication sample after storage for 3 days at 10 ° C; and was slightly too soft after storage at 20 ° C for 3 days; then a few drops of oil were present on the surface.

A further test series was conducted to elucidate the importance of the capacity and the ammonia temperature. The water phases a) and b) from experiments 1-16 were used; emulsifier corresponding to 1.0% distilled monoglyceride with iodine number was used approx. 105 and 24 and 19% fat blending, respectively, and aroma as used in Experiments Nos. 1-10. The portion size 20 was 4 kg.

Experiment Capacity Ammonia- Water phase No._ ~ _ temperature_ 25 17 50 kg / hour -10eC a) 18 50 - -10 * C b) 19 20 - -10eC a) 20 20 - -10eC b) 30 21 20 - 0eC a) 22 20 - 0 * C b) 23 50 - 0eC a) 24 50 - 0eC b) 35

Assessment by lubrication with pinch on cardboard after storage at 5 * C showed: 12 DK 170088 B1

Experiments Nos. 17-19 and 21-24: Extremely stable and greasy. Experiment Nos. 20: Slightly loose water on the surface, slightly separated appearance, but the loose water can be reworked into the product.

Λ

Taste assessment of the emulsions 17-24 showed that they were well aromatic and gave quite good mouthfeel. At 18 ° C the products were a bit softer, but also gave the same results.

10 This series of experiments shows that the technological conditions in the preparation of the emulsion have no significant effect on the properties of the emulsion.

The next series of experiments was conducted to determine whether the salt content is important for the stability of the emulsion and to find the lower limit of the fat phase's share in the emulsion, which still allows a water-in-oil emulsion to be obtained. The weight of each serving was 3 kg. The salt, sodium chloride, was present dissolved in the water. Emulsifier equal to 1.0% (by weight of emulsion) 20 distilled monoglyceride with iodine number was used approx. 105. As in Experiments Nos. 1-10, the aromatic addition was similar. The capacity was 50 kg / hour and the ammonia temperature -10 ° C. The emulsions were prepared with the following composition: 25 Experiment No._Water_Salt_Fat blend 25 73.0% 2.0% 24.0% 26 74.0% 1.0% 24.0% 27 75.0% 0.0% 24.0 % 30 28 79.0% 1.0% 19.0% 29 80.0% 0.0% 19.0% 30 80.0% 2.0% 17.0% 31 82.0% 2.0% 15.0% in 35 The ratings showed that the emulsions from experiments no.

25-30 were extremely stable when smeared at 5 ° C. The emulsion from Experiment No. 31 had quite a bit of dissolved water, but it could easily be reworked upon smearing.

In yet another test series, the distilled mono-glyceride was replaced with mono-diglycerides containing 60% and 40% monoglyceride, respectively, and dosed in such a way that the amount of emulsifier corresponding to approx. 1% distilled monoglyceride. In these experiments, the fat mixture and water phase were as in Experiments Nos. 1-10 and the preparation itself as in Nos. 25-31.

The composition of the emulsions was as follows:

Fat Blend- Water- Your_ Phase

Experiment No. 32 1.7% 60% s mono-diglyce- 23.3% a) 15 Rid, Iodine 113 - 33 1.7% 60% s Mono-diglyce- 18.3% b) Ride, Iodine 113 - 34 2.5% 40% s mono diglyce 22.5% a) Ride, iodine number 118 20 - 35 2.5% 40% s mono diglyce 17.5% b) Ride, iodine number 118 - 36 2, 5% 43% s mono diglyce 18.5% b) equine, iodine number 128 - 37 1.8% '54% s mono diglyce 18.5% b) 25 equine, iodine number 124

The emulsions formed were finely stable at lubrication at 5 ° C and had good aroma. These experiments show that monoglycerides can be used instead of pure monoglycerides.

In yet another test series, emulsifiers with lower iodine numbers were tested and so that the emulsion was included in an amount of 1% distilled monoglyceride. These emulsifiers were prepared by mixing higher and lower iodine monoglycerides. The iodine numbers of the monoglycerides in 14 DK 170088 B1 Experiment No. 38 were approx. 80, Experiment No. 39 ca. 70 and experiment # 40 approx. 60 5 The composition of the mixtures was otherwise as in Experiment No. 8, however, so that the capacity was 50 kg per liter. hour. e

The emulsions from Experiments Nos. 38-40 were well stable on smearing and had good taste. Thus, these experiments show that emulsifiers with 10 iodine numbers can be used quite well lower than the preferred values of 100-110.

A last series of experiments aimed to investigate the stability of the emulsions at higher temperatures using different fat blends and the following fat blends were tested: A) 25 parts of cured soybean oil, m.p. 41 * C 75 parts liquid soybean oil

20 B) 2 parts full cured palm oil, m.p. 60EC

23 parts hardened soybean oil, m.p. 41 * C 75 parts liquid soybean oil

C) 15 parts hardened soybean oil, m.p. 41'C 30 parts hardened soybean oil, m.p. 35 ° C

25 55 parts liquid soybean oil D) 5 parts hardened soybean oil, m.p. 41 * C 55 parts butter oil 40 parts liquid soybean oil E) 100 parts butter oil 30 In these experiments, water phases a) and b) were used from Experiments Nos. 1-10; the emulsifier was 1% distilled monoglyceride with iodine number approx. 105. The temperature of the ammonia refrigerant was 1010 ° C and the capacity 50 kg / hour.

The fat blends had the following assay values: 15 DK 170088 B1

Fat mixture A ·. · B C D E

Solid fat content at 5 * C 21.9 25.5 36.1 30.3 54.2 5 - 10 ° C 18.2 21.6 30.8 23.8 45.2 - 20 * C 9.2 12.1 15.6 8.5 15.9 30 * C 1.5 4.4 3.3 1.2 3.4 35 "C 0.1 2.9 0.1 0.0 0.4 40 * C 0.0 0.7 0.0 0.0 0.3 Melting point, C 30.0 36.5 30.6 28.0 29.0

Iodine (fat blend) 114 112 104 74 34 and the composition of the emulsions were as follows: Test No. 41 24.0% fat blend A), aqueous phase a) 42 19.0% - A), b) 43 24.0% - B ), - a) 44 19.0% - B), - b) 45 24.0% - C), - a) 20 - 46 19.0% - C), - b) 47 24.0% - D ), a) 48 19.0% - D), b) 49 24.0% - E), - a) 50 19.0% - E), - b) 25

Experimental Emulsions Nos. 41-50 were stored at 5 ° C, 18 ° C, 25 ° C, 30 ° C, and 35 ° C, respectively, to evaluate the extraction of oil from the emulsions. At 25 ° C they were all stable for up to one week without oil withdrawal and upon heating to 35 ° C the emulsions 43, 44, 46, 49 and 50 were stable for at least 25 hours without oil withdrawal.

It is expected that the invention will result in the manufacture of minarine with even lower fat content than has hitherto been commercial practice, thereby helping to improve the general health of the 35 populations.

Claims (9)

A spreadable water-in-oil emulsion containing as the emulsifier only distilled monoglycerides or mono diglycerides of edible fatty acids containing 12-22 carbon atoms, characterized in that the fat phase constitutes 12-30% by weight of the emulsion and that the emulsifier has an iodine number of 50-150 and is present in an amount corresponding to the amount of monoglyceride of 0.35-4.0% by weight of the emulsion and that the aqueous phase is free of added protein and hydrocolloid. Emulsion according to claim 1, characterized in that the fat phase constitutes 16-25% of the weight of the emulsion. Emulsion according to claim 1 or 2, characterized in that the emulsifier as fatty acid residues contains substantially residues of fatty acids having 16-18 carbon atoms. Emulsion according to any one of the preceding claims, characterized in that the emulsifier is present in an amount corresponding to an amount of distilled monoglyceride of 0.4-3.5% by weight of the emulsion. Emulsion according to claim 4, characterized in that the emulsifier is present in an amount corresponding to an amount of distilled monoglyceride of 0.75-1.5% by weight of the emulsion. Emulsion according to any one of the preceding claims, characterized in that the iodine number of the emulsifier is 90-120. 5 Emulsion according to claim 6, characterized in that the iodine number of the emulsifier is * 100 to 100. Emulsion according to any one of the preceding claims, characterized in that the pH of the aqueous phase is DK 170088 B1 4-7. Emulsion according to any one of the preceding claims, characterized in that aromatizers 5 are present in both the aqueous phase and the fat phase.