Method for obtaining a stable form of fatty acid esters, a stable form of fatty acid esters and a composition comprising a stable form of fatty acid esters

Abstract

The present invention relates to a method for obtaining a stable form of fatty acid esters, comprising steps of: providing a fatty acid esters in liquid form, introducing the fatty acid esters in liquid form into powdered silica, mixing the fatty acid esters with the powdered silica for obtaining the stable form of fatty acid esters. The present invention also relates to a stable form of fatty acid esters comprising fatty acid esters and powdered silica, with at least partially adsorbed particles of fatty acid esters being present on the surface of the powdered silica particles, and wherein the stable form of fatty acid esters being in the form of powder. The present invention also relates to a pharmaceutical, cosmetic or food composition comprising the stable form of fatty acid esters.

Description

[0001] Method for obtaining a stable form of fatty acid esters, a stable form of fatty acid esters and a composition comprising a stable form of fatty acid esters

[0002] The present invention relates to a method for obtaining a stable form of fatty acid esters, a stable form of fatty acid esters and a composition comprising a stable form of fatty acid esters. The objects of the invention are applied in the food, cosmetic, animal feed and pharmaceutical industries, as an additive to compositions, enriching them among others with the essential polyunsaturated fatty acids.

[0003] Ingesting omega-3, omega-6 and omega-9 fatty acids is important for maintaining health for many reasons. These three types of fatty acids are key diet components, which have an important role in various physiological processes of the organism. A diet rich in various sources of these acids, such as fish, nuts, seeds, olive oil and vegetable oils, allows the demand of the organism for these fatty acids to be met to some an extent, but it is estimated that usually only within the range of 60% of the daily demand. The beneficial properties of a well-balanced ratio of omega-3, omega-6 and omega-9 fatty acids have an influence on ensuring a healthy heart and improving brain functions, prevent inflammations, regulate blood pressure, allow the preservation of healthy skin and of an appropriate lipid profile which is important in the prevention of cardiovascular diseases. Omega-3 acid, particularly alpha-linolenic acid (ALA), helps reduce the level of bad cholesterol (LDL) and increase the level of good cholesterol (HDL), which contributes to the maintenance of a healthy cardiovascular system. Omega-3 acid, particularly docosahexaenoic acid (DHA) is a key structural component of brain tissues. Regularly ingesting omega-3 acids may enhance cognitive functions, improve memory and concentration, and protect against neurodegenerative diseases. Both omega-3 and omega-6 are precursors of substances known as eicosanoids, which regulate inflammatory processes in the organism. Omega-9 acid, also known as oleic acid, aids the regeneration of skin cells, the maintenance of its elasticity, and may contribute to mitigating skin inflammatory conditions. In recent years, linseed oil has become popular in the supplementation of omega-3 and omega-6 fatty acids, mainly owing to a high content of essential fatty acids, which exceeds 50%. Prolonged use of linseed oil may, however, be dangerous to human organism, as linseed oil comprises many harmful substances, heavy metals, cyanogenic compounds and pesticides. Moreover, during production many linseed oils are subject to oxidation, which lowers their pharmacological activity and introduces toxic properties.

[0004] In response to the above problems, an increasingly frequent replacement has been to use esters of polyunsaturated fatty acids, such as ethyl esters obtained from vegetable oils or fish oils, particularly from linseed oil, which have high purity and high bioavailability with a very high concentration of essential unsaturated fatty acids.

[0005] Due to the specific character of the particles forming fatty acid esters, which are naturally liquid, the challenge still remaining is to store esters using such a method that ensures no oxidation. Due to the size of the particles, fatty acid esters are typically stored in glass, polypropylene, or PET containers and they cannot be stored in packages made of other plastics, such as commonly used containers made on the basis of polyethylene or its variants, which they penetrate with time. Moreover, the adverse effect of UVA and UVB radiation on the structure of fatty acid esters necessitates their storage in colored containers, additionally complicating their distribution process. Additionally, esters of polyunsaturated fatty acids, including linseed oil esters or fish oil esters, have relatively intensive flavor and odor, which is frequently a limitation to their usage, in particular by people with hypersensitivity to taste and smell. As products having oil characteristics, polyunsaturated fatty acid esters are insoluble or slightly soluble in water, which limits the range of their potential applications, particularly in the food sector.

[0006] Document PL218552B1 discloses a nutritional additive comprising derivatives of fatty acids, the derivatives of fatty acids being active substances - essential polyunsaturated fatty acids, i.e. alpha-linolenic acid and linoleic acid in the form of concentrated ethyl esters of essential unsaturated fatty acids having a minimum concentration of 55% by volume of alpha-linolenic acid and a minimum concentration of 17% by volume of linoleic acid, the acids being isolated in particular from linseed oil. Ethyl esters of higher fatty acids isolated from linseed oil and / or another vegetable oil having a high content of essential unsaturated fatty acids are nutritional additives added to food or animal feed. In turn, a method for manufacturing esters of higher fatty acids from linseed oil and / or another vegetable oil disclosed in document PL218552B1, allows the preservation of the healthpromoting properties of essential polyunsaturated fatty acids, i.e. alpha-linolenic acid and linoleic acid.

[0007] Document US6234464B1 discloses microencapsulated unsaturated fatty acids or their mixtures comprising an omega-3 fatty acid or an omega-6 fatty acid or their ethyl ester or glyceride. Particles of the compounds are provided with capsule walls composed of two layers. The inner layer is composed of gelatin A, gelatine B, casein or an alginate, or of a derivative or salt of one of these polymers. The outer layer is composed of gelatin B, gum arabic, pectin or chitosan or a derivative or salt of one of these polymers.

[0008] Document WO2013175253A1 discloses compositions and methods comprising powdered green tea extract and powdered preparations comprising polyunsaturated fatty acids. The document discloses different forms of powdered preparations comprising polyunsaturated fatty acids, including powdered emulsions based on gelatin, agar and cellulose preparations, substances saturated with polyunsaturated fatty acids and microcapsules comprising polyunsaturated fatty acids formed by shells made of various materials.

[0009] Document PL228401B1 discloses a health-promoting food agent containing ethyl esters of fatty acids especially linseed oil or linseed oil and fish oil being microcapsules in the form of powder which contain, in the protein-carbohydrate matrix, a nutraceutical with bioactive ethyl esters of acids ALA, LA or ALA, LA, DHA, EPA, with an addition of not more than 4% by weight of ethanol per at least 99.8% anhydrous pharmaceutical ethanol in the form of drops less than 2 pm in diameter. Document PL228401B1 also discloses a method for the preparation of a health-promoting food agent by mixing, homogenization and drying of the components. In this method, after obtaining a liquid protein-carbohydrate matrix, a nutraceutical containing bioactive ethyl esters of acids ALA, LA or ALA, LA, DHA, EPA is introduced into it, followed by carrying out dispergation of ester phase by mechanical agitation until a stable form of emulsion is obtained, which is then treated with two-steps and two-stages pressure homogenization, i.e.: in stage 1 - at a pressure of at least 20 MPa in step 1 and 4 MPa in step 2, and in stage 2 - at a pressure of at least 30 MPa in step 1 and 10 MPa in step 2. The homogenization during stage 1 is carried out in a process coupled with thermal processing of the emulsion, which is then spray dried in air having a temperature of 160-190°C at the inlet to the drying chamber, and the powder is dispensed and packaged in inert atmosphere.

[0010] The technical problem of the present invention is to provide such a method for obtaining a stable form of fatty acid esters, which would lead to obtaining a stable form of fatty acid esters, which would have an increased resistance to the oxidation of fatty acid esters, a limited tendency for fatty acid esters to penetrate through plastics, and an increased resistance to UVA and UVB radiation. It is expected to obtain a stable form of fatty acid esters, which can be stored in commonly used plastic containers, such as containers based on polyethylene, particularly in the form of pallet tanks, PE containers, plastic bags etc., thus eliminating the need to use highly specialist seals, such as seals based on acrylonitrile butadiene rubber (NBR). It is also expected that the stable form of fatty acid esters has reduced flavor and odor intensity, while demonstrating an increased capability of forming stable suspensions in liquids, particularly in water solutions used in the food and animal feed industries. In addition, it is expected that the stable form of fatty acid esters ensures even mixing of fatty acid esters in water solutions etc., especially those having low fat content. Importantly, fatty acid esters in liquid form, being lighter than water, precipitate faster and float on the surface of water solutions. It is expected that the method for obtaining the stable form of fatty acid esters is a method easy to perform, does not require complicated apparatus, limits the necessary materials, and can be performed by personnel without specialist training. The technical problem of the present invention is to provide a composition comprising a stable form of fatty acid esters, which can be used in the food, cosmetic, animal feed, or pharmaceutical industries, allowing simple adjustment within a broad concentration range of the provided fatty acids, particularly essential polyunsaturated fatty acids. It is also important to provide a composition comprising a stable form of fatty acid esters which is industrially applicable in existing installations, for example those which deliver animal feed and milk premixes, dedicated to powdered products. It is moreover expected to provide a stable form of fatty acid esters which is safe for use in metering pump systems in installations mixing or metering the components of the composition, and which limits or eliminates damage to the pump components.

[0011] According to a first aspect of the invention, there is provided a method for obtaining a stable form of fatty acid esters, characterized in that the method includes: a) providing fatty acid esters in liquid form, b) introducing the fatty acid esters in liquid form into powdered silica, c) mixing the fatty acid esters with the powdered silica for obtaining a stable form of fatty acid esters.

[0012] Preferably, the powdered silica is precipitated silica or pyrogenic silica.

[0013] Preferably, the particle size of the powdered silica is within the range from 1 pm to 350 pm.

[0014] Preferably, the specific surface area of the powdered silica particles is within the range from 100 m2 / g to 250 m2 / g.

[0015] Preferably, step b) is performed by dropwise addition or spraying.

[0016] Preferably, steps b) and c) are performed simultaneously.

[0017] Preferably, step c) is performed in a temperature within the range from 15 °C to 30 °C.

[0018] Preferably, in step a) the fatty acid esters in liquid form are selected from a group comprising: fatty acid esters, fatty acid monoesters, fatty acid ethyl esters.

[0019] Preferably, the fatty acid esters include ethyl esters of polyunsaturated fatty acid esters based on fish oils or vegetable oils or their combinations, preferably ethyl esters of polyunsaturated fatty acids based on linseed oil.

[0020] Preferably, in step b) the fatty acid esters in liquid form are introduced into powdered silica in an amount from 30% by weight to 80% by weight.

[0021] Preferably, step b) and / or step c) are performed in protective atmosphere.

[0022] Preferably, prior to step c) air is evacuated and protective gas is introduced in its place. According to a second aspect of the invention, there is provided a stable form of fatty acid esters characterized in that it comprises fatty acid esters and powdered silica, with at least partially adsorbed particles of fatty acid esters being present on the surface of the powdered silica particles, and wherein the stable form of fatty acid esters being in the form of powder.

[0023] Preferably, the powdered silica is precipitated silica or pyrogenic silica.

[0024] Preferably, the particle size of the powdered silica is within the range from 1 pm to 350 pm.

[0025] Preferably, the specific surface area of the powdered silica particles is within the range from 100 m2 / g to 250 m2 / g.

[0026] Preferably, the fatty acid esters are selected from a group comprising: fatty acid esters, fatty acid monoesters, fatty acid ethyl esters.

[0027] Preferably, the fatty acid esters include ethyl esters of polyunsaturated fatty acid esters based on fish oils or vegetable oils or their combinations, preferably ethyl esters of polyunsaturated fatty acids based on linseed oil.

[0028] Preferably, the content of fatty acid esters is within the range from 30% by weight to 80% by weight.

[0029] According to a third aspect of the invention, there is provided a pharmaceutical, cosmetic or food composition comprising a stable form of fatty acid esters as defined in the second aspect of the invention.

[0030] The stable form of fatty acid esters of the present invention, owing to the use of powdered silica, with particles of fatty acid esters at least partially adsorbed to the surface thereof, takes the form of a powder, which allows it to be used in many applications of pharmaceutical, food and cosmetic compositions (including in animal care products). Owing to the phenomenon of fatty acid esters adsorption on the surface of the powdered silica particles, the obtained stable form of fatty acid esters has a reduced tendency to oxidize and is more resistant to the adverse effect of UVA and UVB radiation. Moreover, the stable form of fatty acid esters of the invention can be stored in containers made of plastics (mainly due to the limited penetration degree of fatty acid ester particles through the pores of plastic materials) which are also transparent, increasing its application and distribution possibilities. Owing to their powdered form, fatty acid esters can be used in food industry as ingredients of instant products stored in the loose form of powder and requiring the addition of water or water solutions prior to their ingestion. The stable form of fatty acid esters can be thus used in supplement mixes for humans and animals, in particular to enrich food for humans, as well as in supplements, supplementary feed mixes and premixes for household and farm animals, with the powdered form enabling the use of automated mix production, as well packaging and delivery systems, which were difficult or even impossible to provide in the case of fatty acid esters in liquid form. The stable form of fatty acid esters also has a reduced degree of releasing odors and flavors, which makes the product easier to serve for ingestion, particularly by children and animals, as part of supplementation of essential polyunsaturated fatty acids omega-3, omega-6 and omega-9. The stable, powdered form of fatty acid esters of the invention also allows a broad application in cosmetic industry and does not require the use of additional technical means to introduce them to the base of ointments or gels, because silica is frequently used in these products as a filling or anti-agglomeration agent. Due to the possibility of using pharmaceutical grade silica as powdered silica, the stable form of fatty acid esters of the invention can be also successfully used in pharmaceutical industry, independently or as a component of more complex pharmaceutical compositions. Importantly, in water solutions, the stable form of fatty acid esters forms a stable suspension which can hold for a longer time, increasing the application capabilities particularly in the area of instant products and milk premixes for animals. This property of the stable form of fatty acid esters also allows them to be combined with substances, such as water solutions of vitamins and other active agents, which could not be mixed with the esters due to their oily characteristics. Owing to the high content of fatty acid esters, which in turn have a high concentration particularly of essential unsaturated fatty acids, it is possible to provide a broad range of regulation to the target concentration of fatty acids in the final mixes and compositions comprising the stable form of fatty acid esters of the invention. Also, the method of obtaining the stable form of fatty acid esters of this invention is uncomplicated and can be implemented with the use of basic technical means and by personnel without specialist training. The use of dropwise addition or a precise spraying technique allows in turn the precise metering of fatty acid esters to the powdered silica, influencing the accuracy of the method expressed by a uniform adsorption of the particles of fatty acid esters on the surface of powdered silica particles. Additionally, owing to its powdered form, the stable form of fatty acid esters of this invention can be used in installations which meter or deliver components of the prepared composition. Moreover, owing to the use of powdered silica with small-size particles, on the order of several pm, the stable form of fatty acid esters is safe to use in metering pump systems in installations mixing or metering the components of the composition, limiting or eliminating damage to the pump components. Moreover, the product obtained by using powdered silica with small-size particles on the order of single micrometers can be metered with the use of aerosol systems, which additionally increase the scope of potential applications of the stable form of fatty acid esters of this invention.

[0031] The solution according to the present invention has been shown in the embodiments below and illustrated in the drawing, in which Fig. 1 shows a bar chart illustrating the creaming index for mixtures comprising an embodiment of the stable form of fatty acid esters, while Fig. 2 shows a bar chart illustrating the creaming index for mixtures comprising an embodiment of the stable form of fatty acid esters in the time points of 3 minutes and 5 minutes after manual mixing.

[0032] Example 1 -method of obtaining the stable form of fatty acid esters

[0033] The embodiment of the method of obtaining the stable form of fatty acid esters of this invention comprises the first step of providing fatty acid esters in liquid form. In this embodiment, fatty acid esters are used in the form of concentrated ethyl esters of essential unsaturated fatty acids having a minimum concentration of 55% by volume of alpha-linolenic acid and a minimum concentration of 17% by volume of linoleic acid, the acids being isolated from linseed oil. The characteristics of the used fatty acid esters and the method for obtaining them are disclosed in detail in the document PL218552B1, which is by reference incorporated in this disclosure. Importantly, the type and characteristics of the fatty acid esters are not limited to this embodiment, and in alternative embodiments of this invention it is possible to use any fatty acid esters, including in a non-limiting manner: fatty acid esters, fatty acid monoesters, fatty acid ethyl esters. Preferably, the embodiments of the invention include methods for obtaining the stable form of fatty acid esters using ethyl esters of polyunsaturated fatty acid esters based on fish oils or vegetable oils (including algae oils) or their combinations, preferably ethyl esters of polyunsaturated fatty acids based on linseed oil.

[0034] After obtaining and providing fatty acid esters in liquid form, they are introduced into the powdered silica. In this embodiment, the powdered silica is precipitated silica with the particle size within the range from 16 pm to 20 pm and with the specific surface area of the particles within the range from 170 m2 / g to 210 m2 / g, which is the commercially available product PERKASIL® SM 660, manufactured by W. R. Grace & Co. -Conn. As above, the type and parameters of the used powdered silica are not limited to those disclosed in this embodiment, and alternatively one can use powdered silica obtained in pyrogenic or precipitation technology, with the particle size within the range from 1 pm to 350 pm and with the specific surface area of the particles within the range from 100 m2 / g to 250 m2 / g. Other non-limiting examples of powdered silica which meets the above criteria include the precipitation silica MFIL-P(U) DF having the particle size within the range from 250 pm to 350 pm and the specific surface area of the particles with the range from 160 m2 / g to 200 m2 / g, manufactured by Konimpex Chemicals Sp. z o.o. and the precipitation silica MFIL-P(S) (3.0 Microns) having the particle size within the range from 2 pm to 4 pm and the specific surface area of the particles not smaller than 180 m2 / g, manufactured by MADHU SILICA PVT. LTD. In turn, powdered silica with the particle size of 1 pm is exemplified by the silica under the trade name MSS001 manufactured by Whitehouse Scientific Ltd.

[0035] In this embodiment, fatty acid esters in liquid form are preferably introduced into powdered silica by dropwise addition, which allows a precise control of the amount of fatty acid esters introduced into powdered silica. Alternatively, fatty acid esters in liquid form can be introduced into powdered silica with different techniques, for example by pouring the metered volume of fatty acid esters or by using spraying techniques.

[0036] In this embodiment, 60 g of fatty acid esters were introduced into 40 g of powdered silica. During the introduction process, the mixture was subjected to mixing. The entire step of introducing fatty acid esters in liquid form into powdered silica was performed at a temperature of 20 °C, but in alternative embodiments this step can be performed at a temperature within the range from 15 °C to 30 °C. In this embodiment, fatty acid esters were introduced into powdered silica for obtaining the stable form of fatty acid esters comprising 60% by weight of fatty acid esters. Importantly, the scope of this invention is not limited to the indicated content of fatty acid esters in the final stable form of fatty acid esters, and in alternative embodiments it is possible to select such a ratio of fatty acid esters in liquid form to powdered silica that the obtained stable form of fatty acid esters comprises from 30% by weight to 80% by weight of fatty acid esters.

[0037] In the next alternative embodiment, the steps of introducing fatty acid esters in liquid form to powdered silica and of mixing fatty acid esters with powdered silica are performed preferably in protective atmosphere for the purpose of limiting the negative interaction of oxygen with fatty acid esters. Preferably, oxygen is not present in the protective atmosphere, which is, in a non-limiting example, a nitrogen atmosphere. Preferably, after manufacturing the stable form of fatty acid esters, the next step of dispensing and packaging is also performed in protective atmosphere.

[0038] Preferably, the vessel in which the step of mixing fatty acid esters with powdered silica is performed is a pressure vessel. Directly after fatty acid esters and powdered silica are introduced, air is evacuated from the vessel for limiting the degree of interaction of oxygen with fatty acid esters. The technology of evacuating air from containers is known from the processes of vacuum packaging food products and therefore will not be described in detail for the clarity of this disclosure. Air is evacuated from the vessel until a pressure value within the range from 5 mbar to 50 mbar is reached. Subsequently, inert gas, such as nitrogen, is introduced into the pressure vessel, and the step of mixing fatty acid esters with powdered silica is performed in its atmosphere. Nitrogen is introduced into the pressure vessel until the pressure value approximates the atmospheric pressure. This preferably allows an additional reduction of the impact of oxygen present in air on the degradation process of fatty acid esters, and additionally prolongs the stability of the obtained stable form of fatty acid esters.

[0039] After introducing the entire volume of fatty acid esters into the powdered silica, the stable form of fatty acid esters of this invention was obtained. In this aspect of the invention, the stable form of fatty acid esters thus comprises fatty acid esters and powdered silica, with at least partially adsorbed particles of fatty acid esters being present on the surface of the powdered silica particles, and with the stable form of fatty acid esters being in the form of powder. As regards the type of fatty acid esters and powdered silica, the above discussion applies to the method for obtaining the stable form of fatty acid esters and therefore it will not be repeated for the clarity of this disclosure. In this embodiment, the stable form of fatty acid esters has the content of saturated fatty acids in the form of ethyl esters at 6.2 g / 100 g, the content of monounsaturated fatty acids in the form of ethyl esters at 11.6 g / 100 g, and the content of polyunsaturated fatty acids in the form of ethyl esters at 43 g / 100 g.

[0040] Importantly, in some embodiments the mechanisms related to the sorption of the particles of fatty acid esters to the particles of powdered silica are not limited to adsorption to the external surface of the particles of powdered silica, and in the case when the particles of powdered silica have a sufficiently large size of pores, there are also possible other sorption processes of the particles of fatty acid esters inside the pores of the powdered silica particles, thus filling the inside of the pores and increasing the saturation degree of powdered silica with fatty acid esters.

[0041] Example 2 - stability tests of the suspension of the stable form of fatty acid esters

[0042] In this example, tests were performed into the stability of suspension formation of the stable form of fatty acid esters of this invention, which has a high content of essential polyunsaturated fatty acids omega-3, omega-6 and omega-9. The test utilized the stable form of fatty acid esters comprising 0.86% omega-3 and 1.71% omega-3. The stable form of fatty acid esters was prepared according to the description of Example 1, i.e. with the use of the PERKASIL® SM 660 powdered silica. For the sample comprising 0.86% of omega- 3 acids, 0.86 g of the stable form of fatty acid esters was introduced per 100 g of the solvent, and for the sample comprising 1.71% of omega-3 acids, 1.71 g of the stable form of fatty acid esters was introduced per 100 g of the solvent. The two thus prepared stable forms of fatty acid esters were added to the solvent in the form of water and cow milk with 2% fat content.

[0043] After introducing the stable form of fatty acid esters into water (for both omega-3 concentration values), the samples were mixed for 10 minutes at two different temperatures, i.e. the first mixture at a temperature of 25 °C and the second mixture at a temperature of 37 °C. The step of mixing was performed with the use of a magnetic stirrer at a rotational speed of 400 rpm. The mixture is dispersible in water in both temperature conditions (i.e. 25 °C and 37 °C). The obtained water solution is white and nontransparent. Fifteen minutes after mixing is stopped, sedimentation occurs (for all of the samples) at the bottom of the flask, which results from the used carrier, i.e. powdered silica. After agitation, the sediments again easily become suspended. Also importantly, on the surface of the solution, there is a small oil fraction, significantly smaller than the oil fraction occurring on the surface of the solution when a mixture with liquid fatty acid esters is formed. As a consequence, a significantly reduced emission of characteristic flavor and odor of fatty acid esters is obtained in the formed stable suspension of fatty acid esters in water solutions.

[0044] After introducing the stable form of fatty acid esters into milk (for both omega-3 concentration values), the samples were mixed for 10 minutes at two different temperatures, i.e. the first mixture at a temperature of 25 °C and the second mixture at a temperature of 37 °C. The step of mixing was performed with the use of a magnetic stirrer at a rotational speed of 400 rpm. The mixture is dispersible in milk in both temperature conditions (i.e. 25 °C and 37 °C). Fifteen minutes after mixing is stopped, sedimentation occurs (for all of the samples) at the bottom of the flask, which results from the used carrier, i.e. powdered silica. After agitation, the sediments again easily become suspended. Also importantly, on the surface of milk, there is a small oil fraction, significantly smaller than the oil fraction occurring on the surface of milk when a mixture with liquid fatty acid esters is formed. As a consequence, a significantly reduced emission of characteristic flavor and odor of fatty acid esters is obtained in the formed stable suspension of fatty acid esters in milk.

[0045] Due to the oil fraction visible on the surface of the solution, 0.1% by weight of emulsifier in the form of E471 (fatty acid mono- and diglycerides) was added to the mixture. The addition of E471 causes the size of fat drops on the surface of the mixture to decrease and the solution to become more uniform. The use of the emulsifier allows the reduction of the minimum visible washed oil fraction from the stable form of fatty acid esters of this invention.

[0046] The above stability tests, particularly the ease of formation of the dispersed mixture of the stable form of fatty acid esters in water or milk solutions, confirm the possibility to use the object of the invention in instant mixtures, particularly in supplementation mixtures, instant drinks or animal feed prefixes which allow an increase in the content of essential unsaturated fatty acids omega-3, omega-6 and omega-9.

[0047] Example 3 - stability tests of the emulsion of the stable form of fatty acid esters

[0048] In this example, tests were performed into the stability of emulsion formed on the basis of the stable form of fatty acid esters according to the present invention, by identifying the creaming index (%) of milk replacer (MR) for dairy goat kids with the addition of polyunsaturated fatty acids. This experiment was performed for:

[0049] • Sample 1 - reconstituted milk replacer (130 g of MR-1 powder),

[0050] • Sample 2 - reconstituted milk replacer supplemented with linseed oil (130 g of MR-1 powder + 3.75 ml / l of linseed oil),

[0051] • Sample 3 - reconstituted milk replacer supplemented with liquid ethyl esters of polyunsaturated fatty acids on the basis of linseed oil (130 g of MR-1 powder + 3.75 ml / l of fatty acid esters),

[0052] • Sample 4 - reconstituted milk replacer supplemented with the stable form of fatty acid esters according to the present invention (130 g of MR-1 powder + 6.25 g / l of the stable form of fatty acid esters), Sample 5 - reconstituted milk replacer supplemented with the stable form of fatty acid esters according to the present invention (130 g of MR-1 powder + 6.25 g / l of the stable form of fatty acid esters).

[0053] In Sample 3, there were used the fatty acid esters manufactured and characterized in Example 1, i.e. those formed in accordance with the disclosure of patent PL218552B1. In Sample 4, the stable form of fatty acid esters was obtained in a process analogical to that disclosed in Example 1, with the difference being that the powdered silica was the precipitation silica MFIL-P(U) DF. In Sample s, the stable form of fatty acid esters was obtained in a process analogical to that disclosed in Example 1, with the use of the powdered silica PERKASIL® SM 660. In Samples 4 and 5, the stable form of fatty acid esters had the content of fatty acid esters of approx. 60% by weight.

[0054] Each of the above were evaluated directly after being manufactured and at two time points, i.e. 3 minutes and 5 minutes after manual mixing.

[0055] One hundred thirty grams (130 g) of MR powder pre-weighed on a digital scale were introduced into twenty beakers (four beakers per sample) each having a volume of 2000 ml. The water bath was filled with water having a temperature of 39 °C and was carefully monitored with a thermometer in order to ensure a stable temperature. Water was introduced into the breakers with MR up to the volume of 1 liter and a stopwatch was started immediately, and MR was mixed / reconstituted with an electronic kitchen blender (BOSCH Ergomixx, MSM66130, 600W) set to 2000 rev. / min., mixing for 1 minute. In Sample 2 (with the addition of linseed oil) and in Sample 3 (with the addition of fatty acid esters in liquid form), the liquid additives were introduced prior to mixing. On the other hand, in Sample 4 and in Sample 5, the stable form of fatty acid esters in powder form was mixed with MR powder prior to adding water and mixing in the blender. Each time, the final step was manual mixing.

[0056] The creaming index was determined for each sample by measuring the height of the mixture with the use of a caliper with an electronic digital display (Lux; 150 mm) directly after manufacturing and at the two time points (3 and 5 minutes after manual mixing). A measurement was taken of the entire height, and a subsequent measurement was taken of the height of the serum (oil) layer, i.e. the upper layer visible as a circular ring above the reconstituted MR. In order to calculate the creaming index, the following equation was used, in accordance with the publication Hoseini, A., Jafari, S. M., Mirzaei, H. Asghari, A., and Akhavan, S. (2015), Application of image processing to assess emulsion stability and emulsification properties of Arabic gum. Carbohydra. Polym. 126: 1-8, in which

[0057] Ho

[0058] CI = — %100% Ht where Cl is creaming index, Ho is height of oil layers, and Ht is total height of the mixture.

[0059] The test results are shown in bar charts in Fig. 1 and Fig. 2.

[0060] In tests performed directly after the formation of the mixtures (Fig. 1), the used additive was found to have a significant influence on the creaming index. The highest creaming index was observed for Sample 2 and Sample 3, i.e. MR with the addition of liquid fatty acid preparations (linseed oil and ethyl esters of linseed oil polyunsaturated fatty acids). The creaming coefficients of Sample 1 (control) and of Samples 4 and 5 (additives comprising the stable form of fatty acid esters according to the present invention) were not significantly different and were significantly lower than in Sample 2 and Sample 3.

[0061] Moving on to Fig. 2, in which the creaming index is shown at two time points, i.e. 3 minutes and 5 minutes, after manual mixing, it should be noted that similarly the creaming index for Sample 2 and Sample 3 is significantly higher than for the remaining samples, and it should be also stressed that Sample 1, Sample 4 and Sample 5 have high values of the creaming index, with a limited variation at the two time points. The low values of the creaming index indicate that the particles of the stable form of fatty acid esters of this invention easily bind with the reconstituted milk replacer and do not separate over time. The tests clearly demonstrate the long life and stability of the emulsion formed on the base of the stable form of fatty acid esters according to the present invention.

[0062] Example 4 - tests of the stability and flavor and odor release of the stable form of fatty acid esters

[0063] In this example, tests were performed into the stability of a suspension formed on the base of the stable form of fatty acid esters according to the present invention. The stability of the suspension was evaluated by means of the suspension sedimentation time, by identifying the sediment height of the carrier particles of the stable form of fatty acid esters as a function of time. Additionally, the intensity of the odor and flavor of the suspension were evaluated organoleptically after 1 min., 5 min., 10 min., 15 min., and 60 min. The tests were performed on two samples:

[0064] Sample A: a stable form of fatty acid esters comprising 75% by weight of fatty acid esters and powdered silica having a particle size within the range from 2 pm to 4 pm.

[0065] Sample B: a stable form of fatty acid esters comprising 75% by weight of fatty acid esters and powdered silica having a particle size within the range from 250 pm to 350 pm.

[0066] Samples A and B were prepared following the method described in Example 1, with the use of fatty acid esters in the form of the product Leenvit® Omega 3+6+9 Classic manufactured by Leenvit Group Sp. z o.o. In 100 ml, the used fatty acid esters comprise: 50 g of omega-3 alpha-linolenic acid (ALA), 15 g of omega-6 oleic acid (OA), and 12.5 g of omega-9 linoleic acid (LA).

[0067] Sample A was prepared with the use of the MFIL-P(S) precipitation silica (3.0 microns) having the particle size within the range from 2 pm to 4 pm and the specific surface area of the particles not smaller than 180 m2 / g, manufactured by MADHU SILICA PVT. LTD. Sample B was prepared with the use of the MFIL-P(U) DF precipitation silica having the particle size within the range from 250 pm to 350 pm and the specific surface area of the particles within the range from 160 m2 / g to 200 m2 / g, manufactured by Konimpex Chemicals Sp. z o.o.

[0068] Each of the Samples A and B was prepared by dropwise addition of 75 g of the above mentioned fatty acid esters to 25 g of powdered silica (with the particle size appropriate to each of the samples). After the fatty acid esters had been introduced into the powdered silica, the obtained product was mixed for 10 minutes for obtaining the stable form of fatty acid esters (Samples A and B) having a 75% by weight content of fatty acid esters.

[0069] Three 200 ml beakers (4 cm in diameter) were filled with 10 g of the stable form of fatty acid esters (Samples A and B) and with 100 ml of distilled water. The mixtures were intensively mixed for 10 minutes for obtaining a well-dispersed suspension. Subsequently, the forming sediment was observed for each sample in the function of time, with measurements taken of the sediment height for the 1 min., 5 min., 10 min., 15 min., and 60 min. time points. The results are listed in Table A below. Additionally, after each of the mixtures was prepared, the odor and flavor of each of the samples were evaluated organoleptically.

[0070] Table A. Test of the stability and flavor and odor release

[0071] The results shown in Table A demonstrate that the use of powdered silica with the smaller particle size (Sample A) resulted in the formation of a more stable suspension, which is manifested by sedimentation occurring after a longer time (in comparison to the other samples) and in a smaller quantity (as defined by the height of the sediment). In the case of Sample A, the organoleptic tests did not demonstrate the emission of characteristic flavor and odor. Importantly, in the case of Sample B, the formed sediment can be also described as limited, which indicates good properties regarding the stability of the suspension. Moreover, in the case of Sample B, the flavor and odor were also imperceptible or very weak, allowing such solutions to be used in the food or cosmetic industry.

[0072] Example 5 - composition comprising the stable form of fatty acid esters Table 1 shows a pharmaceutical composition in the form of a toothpaste formulation comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in this pharmaceutical composition is the stable form of fatty acid esters as shown in Example 1.

[0073] Table 1. Pharmaceutical composition in the form of a toothpaste formulation Table 2 shows a cosmetic composition in the form of a barrier silicone cream formulation comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in this cosmetic composition is the stable form of fatty acid esters as shown in Example 1.

[0074] Table 2. Cosmetic composition in the form of a barrier silicone cream formulation

[0075] Table 3 shows a food composition in the form of a bakery premix comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in the food composition is the stable form of fatty acid esters as shown in Example 1. Table 3. Food composition in the form of a bakery premix

[0076] Table 4 shows a cosmetic composition in the form of an anti-aging balm comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in this cosmetic composition is the stable form of fatty acid esters as shown in Example 1. Table 4. Cosmetic composition in the form of an anti-aging balm

[0077] Table 5 shows a cosmetic composition in the form of a sun balm comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in this cosmetic composition is the stable form of fatty acid esters as shown in

[0078] Example 1.

[0079] Table 5. Cosmetic composition in the form of a sun balm

[0080] Table 6 shows a cosmetic composition in the form of a hoof care balm comprising the stable form of fatty acid esters according to this embodiment. The stable form of fatty acid esters used in this cosmetic composition is the stable form of fatty acid esters as shown in Example 1.

[0081] Table 6. Cosmetic composition in the form of a hoof care balm

Claims

Claims1. A method for obtaining a stable form of fatty acid esters, characterized in that the method includes: a) providing fatty acid esters in liquid form, b) introducing the fatty acid esters in liquid form into powdered silica, c) mixing the fatty acid esters with the powdered silica for obtaining a stable form of fatty acid esters.

2. The method for obtaining the stable form of fatty acid esters according to claim 1, characterized in that the powdered silica is precipitated silica or pyrogenic silica.

3. The method for obtaining the stable form of fatty acid esters according to claim 1 or 2, characterized in that the particle size of the powdered silica is within the range from 1 pm to 350 pm.

4. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 3, characterized in that the specific surface area of the powdered silica particles is within the range from 100 m2 / g to 250 m2 / g.

5. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 4, characterized in that step b) is performed by dropwise addition or spraying.

6. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 5, characterized in that steps b) and c) are realized simultaneously.

7. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 6, characterized in that step c) is performed in a temperature within the range from 15°C to 30°C.

8. The method for obtaining the stable form of fatty acid esters according to any of claims 1 -7, characterized in that in step a) the fatty acid esters in liquid form areselected from a group comprising: fatty acid esters, fatty acid monoesters, fatty acid ethyl esters.

9. The method for obtaining the stable form of fatty acid esters according to claim8, characterized in that the fatty acid esters include ethyl esters of polyunsaturated fatty acid esters based on fish oils or vegetable oils or their combinations, preferably ethyl esters of polyunsaturated fatty acids based on linseed oil.

10. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 9, characterized in that in step b) the fatty acid esters in liquid form are introduced into powdered silica in an amount from 30% by weight to 80% by weight.

11. The method for obtaining the stable form of fatty acid esters according to any of claims 1 - 10, characterized in that step b) and / or step c) are performed in protective atmosphere.

12. The method for obtaining the stable form of fatty acid esters according to claim 11, characterized in that prior to step c) air is evacuated and protective gas is introduced in its place.

13. A stable form of fatty acid esters, characterized in that it comprises fatty acid esters and powdered silica, with at least partially adsorbed particles of fatty acid esters being present on the surface of the powdered silica particles, and wherein the stable form of fatty acid esters being in the form of powder.

14. The stable form of fatty acid esters according to claim 13, characterized in that the powdered silica is precipitated silica or pyrogenic silica.

15. The stable form of fatty acid esters according to claim 13 or 14, characterized in that the particle size of the powdered silica is within the range from 1 pm to 350 pm.

16. The stable form of fatty acid esters according to any of claims 13 - 15, characterized in that the specific surface area of the powdered silica particles is within the range from 100 m2 / g to 250 m2 / g.

17. The stable form of fatty acid esters according to any of claims 13 - 16, characterized in that the fatty acid esters are selected from a group comprising: fatty acid esters, fatty acid monoesters, fatty acid ethyl esters.

18. The stable form of fatty acid esters according to claim 17, characterized in that the fatty acid esters include ethyl esters of polyunsaturated fatty acid esters based on fish oils or vegetable oils or their combinations, preferably ethyl esters of polyunsaturated fatty acids based on linseed oil.

19. The stable form of fatty acid esters according to any of claims 13 - 18, characterized in that the content of fatty acid esters is within the range from 30% by weight to 80% by weight.

20. A pharmaceutical, cosmetic or food composition comprising the stable form of fatty acid esters as defined in any of claims 13 - 19.

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