WO2021089970A1

WO2021089970A1 - Method for producing a feed or a feed supplement for livestock animals

Info

Publication number: WO2021089970A1
Application number: PCT/FR2020/052041
Authority: WO
Inventors: Abdeslam El Harrak; César Adrien Claude René CRETEL
Original assignee: Huddle Corp
Priority date: 2019-11-07
Filing date: 2020-11-09
Publication date: 2021-05-14
Also published as: FR3102991A1; FR3102991B1

Abstract

The invention relates to a method for preparing a feed or a feed supplement in the form of modularly stacked objects for the controlled release of nutrients and/or physiologically active substances for monogastric animals, comprising a core having an aqueous phase with water-soluble active substances and a lipid phase with fat-soluble active components, the aqueous phase being dispersed in the lipid phase, and a coating of the core, in which the cores are prepared from a water-in-oil double emulsion followed by a filtration or decantation and in which a coating is then carried out.

Description

Process for manufacturing a feed or feed supplement for farm animals

Field of the invention

The subject of the invention is a process for manufacturing a food or a food supplement for monogastric farm animals, in particular fish. In particular, the invention relates to foods or food supplements allowing controlled release of the active substances which they contain.

State of the art

It is well known to use physiologically active substances to supplement the feed of farm animals to improve their health conditions and accelerate their growth.

Such physiologically active substances can be proteins, lipids, carbohydrates, but also vitamins and any form of food supplementation targeting prebiotics, probiotics, amino acids, antioxidants, or other molecules (ie essential oils) for nutraceutical or therapeutic purposes. direct or indirect.

The diversity of the conditions in which food is ingested and digested requires a response adapted to each species and to each stage of animal maturity.

Aquaculture feeds on the market are often made through the processing and formulation of several raw materials using a process called extrusion. This process imposes strong constraints in temperature (> 140 ° C) and pressure (> 25 bars) for several minutes, which degrades the nutritional qualities of the raw materials and therefore of the food in fine.

In addition, this process impacts and freezes the design of the food: granules. However, these granules are not an optimal format to facilitate absorption by a fish (buoyancy, size, attractiveness, etc.) and the dislocation of the granule, which is not controlled after ingestion, is not optimum for good digestive assimilation by the fish. .

All this results in a low effective conversion rate of the active substances of food and food supplements for the growth and health of farm animals and in particular fish. This also results in poor economic performance of the aquaculturist who has to deal with longer growth cycles and with larger quantities of feed at iso-cycle times, and also fish of less good quality, and therefore less well valued on the market. On the other hand, these phenomena have a direct impact on the environment since reduced food conversion rates lead to an increase in the discharge of undigested organic matter in addition to the ammonia resulting from the digestion of proteins. These discharges destroy the neighboring ecosystem (eutrophication) and increase the risk of infections and pathology on farms through degradation of water quality. This induces an increase in the use of phytosanitary products.

Interest therefore remains in foods or food supplements whose structures and manufacturing processes make it possible to offer a response adapted to each species and to each stage of animal maturity.

And in particular, there is a need for foods and food supplements which allow rapid release of active substances or nutrients but sequenced, that is to say in precise and identified areas of the digestive system of the target animal for better metabolization of these nutrients.

Brief description of the invention The invention relates to the following processes:

1. Process for the preparation of a food or a food supplement in the form of modular stacking objects allowing a controlled release of nutritive and / or physiologically active substances for monogastric animals, comprising a core with an aqueous phase with active substances water-soluble and a lipid phase with liposoluble active components, said aqueous phase being dispersed in said lipid phase, and a coating of the core, comprising the following steps:

(a) preparing said aqueous phase by dispersing said water-soluble active substances in water and adding gelling reagents;

(b) injecting said aqueous phase into an oil to obtain a first emulsion of aqueous particles being gelled in the oil;

(c) allowing said first emulsion to stand or heat to complete the gelation reactions of the aqueous beads and obtain gelled aqueous beads dispersed in the oil;

(d) adding said first emulsion to a mixture of at least one oil and at least one liquid wax;

(e) introducing all of said first emulsion and said mixture of at least one oil and at least one liquid wax into an aqueous solution with stirring to obtaining a second emulsion, said second emulsion comprising gelled aqueous particles dispersed in a lipid matrix, said lipid matrix itself being in the form of particles dispersed in said aqueous solution;

(f) cooling said second emulsion to a temperature below the melting temperature of said at least one wax to stabilize said lipid particles by solidifying said at least one wax;

(g) obtaining said lipid particles, i.e. said nuclei, by filtration or decantation; and

(i) forming the coating of said cores by successive immersions in baths of cationic and anionic polysaccharides.

2. Preparation process according to object 1, in which after having obtained the first emulsion of water particles in oil in step (b), said first emulsion is subjected to high shear, preferably between 2000. and 20,000 s-1, to reduce the size of the aqueous particles in the oil before gelation of said particles of the aqueous phase (step (b ').

3. Preparation process according to one of objects 1 and 2, comprising a final step of drying the products under a flow of air at a temperature below 50 ° C, preferably between 18 and 40 ° C.

4. Preparation process according to any one of the preceding objects, wherein said at least one wax is a crystallizable wax with a melting point of less than 90 degrees Celsius and preferably less than 65 degrees Celsius.

5. Preparation process according to any of the preceding objects, wherein said gelation reagents comprise an anionic polysaccharide such as an alginate, a calcium salt and pyrophosphate. 6. Preparation process according to object 5, wherein the calcium salt is selected from the group of calcium sulphate, carbonate and stearate.

7. Preparation process according to any one of the preceding objects, in which all of the aqueous solutions used comprise a controlled amount of osmotic agent. 8. Preparation process according to object 7, in which said osmotic agent is chosen from the group of sugars, salts, water-soluble polymers, preferably with a molecular mass of less than 150 kg / mole, and their combinations. 9. Preparation process according to any one of the preceding objects, in which, after having obtained said lipid particles in step (f) and before forming the coating in step (g), said lipid particles are dispersed. in a protein phase (stage

(P)

10. Preparation process according to any one of the preceding objects, in which, before injecting said first emulsion into a mixture of oils and liquid waxes, a precise dose is brought into said mixture of oils and liquid waxes. of said liposoluble active substances.

11. Preparation process according to one of the preceding objects, in which, before injecting said first emulsion into a mixture of at least one oil and at least one liquid wax, at least one dispersed in said mixture. an oil and at least one liquid wax a clay phase exfoliated in a lipid medium.

12. Preparation process according to object 11, in which the exfoliation of a clay phase in a lipid medium is carried out in the presence of a surfactant, said surfactant having the characteristic of having a cationic polar head.

13. Preparation process according to object 12, wherein said surfactant is lecithin.

This manufacturing process has the advantage of never bringing all of its constituents to a high temperature which could degrade their properties.

Description of Figures

The invention is described below with the aid of Figures 1 to 14, given by way of illustration only:

[Fig. 1] shows schematically in section and without respecting the respective dimensions a first product of the invention;

[Fig. 2] shows schematically in section a second product of the invention; [Fig. 3] shows schematically in section a third product of the invention; [Fig. 4] shows schematically an embodiment of a coating of the core of a product object of the invention;

[Fig. 5] shows a diagram of a manufacturing process for the first product;

[Fig. 6] shows a diagram of the additional steps for the manufacture of the third product;

[Fig. 7] shows the size distribution of aqueous particles; [Fig. 8] shows the size distribution of lipid particles;

[Fig. 9] shows the change in the iodine number measured during aging in the air free of lipid particles;

[Fig. 10] shows an image of a lipid particle obtained under a scanning electron microscope;

[Fig. 11] presents a curve for monitoring the rheological behavior of a protein layer;

[Fig. 12] shows an example of protein particles obtained after gelation;

[Fig. 13] presents the conductimetric monitoring of metered additions of biopolymers loaded in water; and

[Fig. 14] shows the evolution of the conductivity of lipid particles as a function of metered additions of charged biopolymers.

Detailed description of the invention

Figure 1 shows schematically and in section without any respect for the respective dimensions of each phase a first product that can be produced with a process according to one of the objects of the invention.

This first product 10 comprises a core 12, a protein phase 11 and a coating 14 of the whole of the core 12 and of the protein phase 11. The core 12 comprises an aqueous phase in the form of dispersed spherical (or irregular) gelled particles 16. in a lipid matrix 18. The protein phase 11 surrounds the core 12 and is surrounded by the coating 14.

A first element of this first product is that it contains a gelled aqueous phase containing water-soluble active substances, including in particular nutrients. Advantageously, the size of the gelled particles is between 1 and 200 μm and preferably between 20 and 100 μm.

The gelation of the aqueous phase makes it possible to limit the leakage of nutrients and active substances outside the particles. It also makes it possible to stabilize the size of the particles by limiting coalescence and thus increase the specific surface area of the aqueous phase and therefore accelerate the rate of release of the active substances which it contains in the digestion phase. According to a preferred embodiment, the aqueous phase comprises an anionic polysaccharide such as an alginate with a content of between 1 and 4% by weight relative to the weight of the aqueous phase.

The aqueous phase can advantageously be gelled by reacting the anionic polysaccharide with reagents such as a calcium salt as well as pyrophosphate or deltagluconolactone.

The calcium salt can be chosen from the group of calcium sulphate, carbonate and stearate.

The solubility of the calcium salt is obtained by reaction with protons (acids) released in situ. They can be generated by reactants such as pyrophosphates or deltagalactolactone in contact with water.

Advantageously, the aqueous phase further comprises an osmotic agent.

This osmotic agent can be chosen from the group of sugars, salts, water-soluble polymers, preferably with a molecular mass of less than 150 kg / mole, and their combinations.

A preferred choice of osmotic agent may be sorbitol with a content of less than 5% by weight relative to the weight of the aqueous solution so as not to make the final product indigestible. A content of between 0.8 and 1.5% by weight of sorbitol is optimal. Guérande salt can also be used advantageously, which also makes it possible to provide useful mineral salts.

Preferably, the content of the aqueous phase dispersed in the lipid matrix is between 10 and 50% by volume, and preferably between 15 and 30% by volume relative to the total volume of the aqueous phase and of the lipid matrix. Below 10% by volume, the volume of the aqueous phase is no longer sufficient to easily introduce the water-soluble active substances and have good homogeneity of composition of the cores of the objects.

Beyond 50%, it becomes much more difficult to keep a water emulsion dispersed in the lipid phase.

The gelled aqueous phase can comprise hydrophilic active substances such as amino acids, vitamins, prebiotics, probiotics, anti-oxidants, and their combinations. A second element of this first product 10 is that the aqueous phase 16 is dispersed in a matrix or lipid phase 18.

Advantageously, the lipid matrix 18 comprises at least one vegetable or animal oil, in particular from fish, and at least one crystallizable wax. Waxes can be of animal (beeswax) or vegetable origin.

Preferably, the waxes used are crystallizable waxes with a melting point of less than 90 degrees Celsius and very preferably less than 65 degrees Celsius.

The wax content is advantageously between 5 and 25% by weight relative to the weight of the entire lipid matrix, and very advantageously between 10 and 20%.

According to preferred embodiments, the lipid matrix is of substantially spherical shape and thus the core is of substantially spherical shape and of diameter between 10 and 1000 mhi and preferably between 200 and 400 mhi.

The lipid matrix can advantageously comprise vitamins.

Preferably, this lipid matrix has a high content of omega 6 and omega 3, in particular of DHA and EPA types.

The lipid matrix advantageously comprises at least 1% by weight of omega 3 types of DHA and EPA relative to the weight of the lipid matrix. It also preferably comprises less than 30% by weight of omega 3 types of DHA and EPA and very preferably less than 10% by weight relative to the weight of the lipid matrix. According to an advantageous embodiment, the lipid phase comprises a mineral filler.

The mineral filler is advantageously chosen from the group of phyllosilicates, such as clays, talcs and micas.

Preferably, the phyllosilicate is a smectite. Smectites have the advantage, by virtue of their lamellar structure with a greater spacing between the lamellae than the other phyllosilicates, of being able to be swollen by small hydrophobic molecules which will exfoliate the clay platelets and thus facilitate their dispersion in the lipid matrix. Micas and talcs can also be exfoliated in this way, but the energy that would be required to disperse the lamellar leaflets in the lipid matrix would be much higher. According to an advantageous embodiment, the content of the mineral filler in the lipid matrix is between 0.5 and 35% by weight and preferably less than 15% by weight relative to the weight of the lipid matrix.

The presence of this mineral filler in the lipid matrix has several important advantages. First, the load helps control the buoyancy of objects when used in aquaculture. It also strengthens the resistance of objects to the action of oxygen by greatly reducing its diffusion kinetics in the nucleus of objects and acts as a barrier to limit the escape of small molecules of nutrients and active substances. Finally, the very high developed surface of the smectite sheets makes it possible to microstructure the lipid matrix at the nanometric scale, which makes it possible to compartmentalize and to play on the digestibility kinetics of the lipid matrix.

The third element of this first product 10 is a gelled protein phase 11 surrounding the lipid matrix 18, and thus surrounding the core 12. This protein phase comprises proteins. This phase is advantageously prepared from proteins dissolved in a gelled aqueous phase.

The presence of this protein phase has the advantage of providing the target animal, in addition to the active substances, with the amino acids necessary for its growth, and of promoting the baitiness of the food.

The protein phase 11 as shown in Figure 1 surrounds a single core 12 with a substantially spherical geometry. However, depending on the method used to disperse the nuclei 12 in the protein phase 11, the same object 10 may include several nuclei 12 dispersed in the protein phase 11. Consequently, the external geometry of the objects and of this protein phase is very variable. (see figure 12).

Preferably, the protein phase comprises negatively charged and gelable polysaccharides, such as alginates, pectin, xanthan, gellan gum, etc.

The negatively charged polysaccharides can be functionalized with a carboxylic, sulphonate, alcoholate or phosphate function, alone or combined with positive charges (such as hyaluronic acid). The physicochemical conditions will be adjusted so as to have an excess of negative charges favoring the gelation conditions. Advantageously, the gelled protein phase is crosslinked by the action of a gelling agent released with a delay time which can be a metal which can complex with the carboxylic functions of the polysaccharides or an inorganic or organic oligomer with a charge opposite to the charge of the target polysaccharide.

Modulating the crosslinking delay time between 15 min and several hours makes it possible to promote mass mixing of the ingredients without caking of the gel, and thus to shape the food or food supplement.

The gelling agent may contain cations of calcium, zinc, magnesium or transition metals and a source of acidic protons (such as pyrophosphate or deltagluconolactone) hydrolyzable in water, allowing the release of the ionic form. Preferably, the gelled protein phase comprises a content of gellable polysaccharides of between 0.5 and 4.5% by weight and preferably less than 2% by weight relative to the weight of the gelled protein phase during the preparation of this protein phase. , that is to say before the final drying phase of the product.

At 5% alginate in a food ration, the literature describes a degradation in the efficiency of digestion because the polysaccharides trap nutrients. Above 5%, polysaccharides play a laxative role by trapping more water and associated nutrients.

Preferably, the gelled protein phase comprises a protein content of less than 30% by weight relative to the weight of the gelled protein phase during the preparation of this protein phase. Beyond this, the gelation of the protein phase becomes difficult, because the proteins block the reactive sites of the polysaccharides.

Advantageously, the proteins of the protein phase comprise proteins of size less than 30 kDa. The digestion of these proteins can thus be done more quickly, because there are fewer bonds to cut to bring the peptide fragments to a size that can be assimilated by the digestive tract.

Advantageously, the content of the protein phase in all of the finished products is between 5 and 75% by weight relative to the total weight of the assembly.

According to an advantageous embodiment, the protein phase additionally comprises a dispersed mineral filler, such as silica, phyllosilicates, metal oxides, etc.

This mineral filler, for example clay, has the advantage of making it possible to modulate the buoyancy of the objects. It also constitutes a barrier which opposes the diffusion into objects of oxygen. Indeed, the very high developed surface of the smectite sheets makes it possible to microstructure the protein matrix at the nanometric scale which makes it possible to compartmentalize and play on the digestibility kinetics of the protein matrix. Microstructure obtained by the interactions between the positively charged clay sheets on the sides and negatively on the largest surface with the alginate or the proteins of the protein phase.

Advantageously, the mineral filler is a phyllosilicate and very advantageously a smectite.

Advantageously, the protein phase comprises an osmotic agent.

A preferred choice may be sorbitol with a content of less than 5% by weight relative to the weight of the aqueous solution so as not to make the final product indigestible. A content of between 0.8 and 1.5% by weight of sorbitol is optimal. Guérande salt can also be used advantageously, which also makes it possible to provide useful mineral salts. According to another advantageous characteristic, the whole of the protein phase 11 and of the core 12 is of any shape with a greater dimension of between 500 mhi and 5 mm (see Figure 12).

The size of the objects according to the invention can easily be adapted to the intended target, to be compatible with the supply capacities of the latter.

The subject of the invention is also a food with a total protein content of between 20 and 70% by weight relative to the weight of the entire finished product. This content is obtained after the last optional step of drying the product. Proteins are mainly provided by the protein phase. In particular, from 80% to 100% by weight, advantageously from 90% to 100% by weight, of the proteins in the food are provided by the protein phase.

Another subject of the invention is a food supplement with a total protein content of between 10 and 20% by weight relative to the weight of the whole of the finished product. This content is obtained after the last optional step of drying the product. Proteins are mainly provided by the protein phase. In particular, from 80% to 100% by weight, advantageously from 90% to 100% by weight, of the proteins of the food supplement are provided by the protein phase. The proteins of the protein phase are predigested, at least in part, in the stomach of the animal, but the gelation of this protein phase coupled with the coating constitutes a physical barrier to the release of these predigested proteins in the stomach. It is interesting to limit such a release of predigested proteins in the stomach because their metabolization in the stomach would be used to create digestion and motor energy by causing ammonia-type releases resulting from this catabolization, instead of being metabolized in the intestines of animals, where their absorption is most efficient for the growth of these animals.

The fourth element of this first product 10 is to include a coating 14 around the protein phase 11.

This coating may comprise n layers of biocompatible materials, in particular biopolymers, with an alternating stack of positive and negative electrostatic charges which form coacervates structured in a stack of layers, and n is at least equal to 1.

This coating system has the advantage of facilitating the modulation of the thickness of the coating layer and the wide choice of biopolymers makes it possible to modulate the mesh of biopolymers on the surface, which will then be stiffened by more or less cross-links. strong of this mesh. n is an integer n is advantageously less than or equal to 15 and preferably between 2 and 10.

This variable number of layers is suitable for obtaining a good compromise between quality of encapsulation and controlled release into the digestive tract while allowing easy implementation.

The outer layer of this coating is preferably made of a positively charged polymer because this has antibacterial properties and thus improves the preservation of the food or food supplement.

Advantageously, the biocompatible materials are charged biopolymers.

The biopolymers of the coating can be chosen from the group of positively charged polysaccharides, such as polypeptides, chitosan, chitin derivatives, gums used as amine functionalized texturing agent such as functionalized guar gum, their combinations and negatively charged polysaccharides such as polypeptides, pectin, gum arabic, xanthan, alginates, carrageenans, cellulose derivatives ... as well as their combinations.

Advantageously, the coating comprises crosslinking agents, in particular by metal complexation or chemical bridging which can be chosen from the group of charged transition metals and multicharged anions such as polyphosphates including trisodium tetraphosphate (TSTP) Na3P4O10.

Advantageously, the core and / or the protein phase comprises (s) a charged polymer, or proteins with surface charges or cationic, anionic or zwitterionic surfactants.

It is also possible to specifically add biopolymers charged to the core and / or the protein phase to generate these charges. They will be chosen from anionic or cationic biopolymers mentioned above, but can also combine charges as in hyaluronic acid.

This makes it possible to modulate the residual or free charges by adjusting the pH conditions of the medium or by adjusting the stoichiometric balance of the complexation systems in the protein phase.

The physicochemical system is thus adjusted so as to obtain an excess of free amines resulting from the proteins of the protein phase which will be positively charged under conditions of pH lower than 9. This excess of positive charges is the necessary condition for depositing the protein. first layer of anionic biopolymer of the coating.

If necessary, if the physicochemical system of the protein layer rather exhibits an excess of negative charges, linked to the balance of the ingredients that constitute it, the coating will begin with a first layer of cationic biopolymers.

The coating of the protein phase and the core may also include a layer of reinforcing materials.

These reinforcing materials can be chosen from the group of clays, silicas and filled fibers, and their combinations.

These reinforcing materials have a predominance of negative electrostatic charges on their surfaces and are thus attracted by the positive surface charges of the coating. It is thus possible to place a reinforcing layer between two layers of cationic polysaccharides. Preferably, the reinforcing materials are a phyllosilicate and very preferably a smectite.

This coating 14 therefore consists of layers of biopolymers, advantageously of polysaccharides, charged alternately more and less. In the animal's stomach, the pH is acidic and it is the mesh of positively charged biopolymers that is most resistant to this acidic pH and that ensures the integrity of the coating.

The negatively charged layers of the coating are advantageously bridged by cations such as Ca ++. These bridges are dissolved in an acidic medium, so when we arrive in a neutral to basic medium (the intestines) we have a real liberation of all the layers of the coating. As soon as there is a breach in the coating, the enzymes of the bile will be able to penetrate to the nucleus and cause the release of lipids as well as their nutrients and active substances, leading very quickly also to the release of the particles of the aqueous phase as well as their nutrients and active substances. This coating therefore ensures the rapid release of all nutrients and active substances in the area of the intestines of monogastric animals, where their absorption during their journey is the most efficient possible.

This product is designed to provide nutritional balance in growing animals, which must cope with pathogens and stress in the breeding environment. This product is therefore recommended as food or as a food supplement in the juvenile stage of monogastric species with high mortality: such as in avian breeding, for example for chicks, or in aquaculture for fry. The flexibility of formulation and modulation of the properties also makes it an interesting product to accompany the finishing of pre-commercial animals.

Figure 2 shows a second product 20 achievable with the method according to one of the objects of the invention. This second product 20 is similar to the first product 10 but has a simplified structure: it does not include a protein phase between the core 12 and the coating 14. Like the product 10, it comprises a core 12 comprising an aqueous phase composed of aqueous particles. 16 dispersed in a lipid matrix 18 and a coating 14.

This second product is particularly interesting for providing specific nutrients or active substances. Figure 3 shows a third product 30 similar to the first product 10 of Figure 1.

This third product 30 additionally comprises, with respect to the first product 10, a coating or coating 34 of the lipid matrix 18 placed between this lipid matrix 18 and the protein phase 11.

Like the coating 14 of the product 10, this coating 34 comprises n layers of biocompatible materials, with an alternating stack of positive and negative electrostatic charges forming coacervates structured in a stack of layers, n being at least equal to 1. Preferably, the number of layers n is between 2 and 10. n is an integer. The biocompatible materials are as described above for coating 14.

This addition of the coating 34 makes it possible, if necessary, to delay the release of the active components from the internal phase of the core. The outer layer of this coating 34 is preferably made of a positively charged polymer because this has antibacterial properties and thus improves the preservation of the food or food supplement.

This third architecture makes it possible to meet even later release requirements in the digestive tract from the nucleus, such as the release of prebiotics or probiotics which must remain intact until the terminal phase of the digestive tract. Figure 5 shows the different steps of a manufacturing process of the first product 10 according to one of the objects of the invention.

The core (s) of the first product 10 are prepared from a double water-in-oil-in-water emulsion followed by filtration or decantation. Then this nucleus is completed by a protein phase which will be shaped to the size and the target geometry. A coating is then carried out 14. The last optional step in preparing the products is drying to bring the moisture content of the products to a value of less than 10% by weight, relative to the total weight of the product. This drying is carried out at low temperature, preferably below 50 ° C, for example between 18 ° C and 40 ° C.

Step (a) consists in preparing an aqueous phase by dispersing the necessary water-soluble active substances in water and adding the gelling reagents. These reagents are as described above for the gelled aqueous phase, and can be a polysaccharide, a calcium salt, in particular calcium sulfate or calcium carbonate, in the presence of pyrophosphate or deltagluconolactone.

Step (a ’) consists of preparing a gelled protein phase by dispersing proteins in water with gelling reagents, optionally an osmotic agent and optionally mineral fillers such as phyllosilicates. in step (b), the aqueous phase from step (a) is injected into a vegetable or animal oil to obtain a first emulsion of aqueous particles in the oil.

Then, in step (c), this first emulsion is left to stand or is heated moderately, to less than 100 ° C and ideally to less than 60 ° C, for example from 40 ° C to 60 ° C, to complete the gelation reactions of aqueous particles and obtain robust gelled aqueous particles dispersed in oil (step (c)).

The first emulsion from step (c) is then added to a mixture of at least one animal or vegetable oil and at least one liquid wax prepared beforehand. The oil + wax mixture advantageously comprises from 1 to 50% by weight of wax relative to the total weight of the mixture, more advantageously from 5 to 15% by weight of wax. For the crystallizable wax (s) used to be liquid, the temperature of the mixture is higher than the melting point of the waxes (step (d)).

In step (e), the whole of the first emulsion and the mixture of at least one oil and at least one liquid wax, resulting from step (c), are introduced into an aqueous solution with stirring to obtain a second emulsion; this second emulsion comprises the gelled aqueous particles of the first emulsion dispersed in a lipid matrix which is itself in the form of particles dispersed in the aqueous solution. This second emulsion from step (e) is cooled in step (f) to a temperature below the solidification temperature of the crystallizable waxes present to stabilize the lipid particles.

It remains in step (g) to isolate the nuclei or lipid particles from the products by filtration or decantation, removing the aqueous phase.

After step (g), the lipid particles resulting from step (g) are dispersed in the protein phase during gelling, prepared in step (a ′). Homogenization is carried out with the minimum of shearing, the shear obtained for example by stirring by hand (step (h)). The dispersion is then, for example, introduced into a cold extruder to shape the product through a die at the outlet of the die, one continuous cutting G extradate with a rotary blade to the target size and sets are obtained consisting of cores coated with a protein phase ready to be coated.

This addition of the protein phase can also be carried out in a fluidized bed or in spheronization. The chosen processes, extrusion, fluidized bed, spheronization, are implemented at low temperature, below 50 ° C (step (h)), for example ranging from 18 ° C to 50 ° C.

Note: the gelation kinetics of the protein phase are adjusted to allow all the operations of step (h) to be carried out. Gelation is only completed at the end of step (h) after a standing time allowing the layer to solidify.

It should be noted that due to their method of manufacture by preparing emulsions, the aqueous phases 16 and the lipid particles 18 have a relatively spherical geometry. On the other hand, the assemblies made up of the protein phase 11 surrounding the lipid phase 18 of the products 20 which are obtained by cutting an extradate from a die can take any shape.

Finally, in step (i) the coating is formed of the assemblies made up of the protein phase 11 surrounding the lipid phase 18 obtained from step (h) by immersions in an aqueous bath in which solutions of materials will be provided alternately. cationic and anionic biocompatible.

After the coating of step (i), the products are advantageously dried by air flow at low temperature below 50 ° C and preferably between 18 and 40 ° C to bring the humidity level to a lower value. at 10% by weight, relative to the total weight of the product. This increases the shelf life of the products. This last step (j) is optional.

Figure 4 illustrates this formation of the coating of the assemblies consisting of the protein phase 11 surrounding the lipid phase 18 from step (g) by successive additions of biopolymers, preferably polysaccharides, positively and negatively charged.

Note: The representation of the protein phase in Figure 4 has been modified from that of the other figures for clarity.

Note: the whole is shown here in the form of a particle but it can have any shape On the left of FIG. 4, we see the assembly consisting of a core 12 of the first product 10 surrounded by a protein phase 11. This protein layer comprises free surface charges, preferably positive.

This assembly is coated by the addition of an aqueous solution of negatively charged biopolymers 52, for example polysaccharides.

Through electrostatic interactions, the negatively charged biopolymer will coat the surface of the assembly to form a negative layer of coacervate.

An aqueous solution of positively charged biopolymer 54 is then added to the dispersion with the charged particles now negatively on the surface. This will then spontaneously cover the layer previously placed.

The operation is repeated by alternating the aqueous solutions of more and less loaded biopolymers until a coating 14 is obtained comprising the desired number n of layers. Usually n is between 2 and 10.

Advantageously, in step (e), the continuous aqueous solution in which the second emulsion is produced (emulsion of lipids with wax) comprises at least one osmotic agent and at least one surfactant.

The osmotic agent can be chosen from the group of sugars, salts, water-soluble polymers, preferably with a molecular mass of less than 150 kg / mole, and combinations thereof.

A preferred choice may be sorbitol with a content of less than 5% by weight relative to the weight of the continuous aqueous solution so as not to make the final product indigestible. A content of between 0.8 and 1.5% by weight of sorbitol is optimal. Guérande salt can also be used advantageously, which also makes it possible to provide useful mineral salts. The presence of an osmotic agent has the advantage of setting up an osmotic barrier which prevents the passage of the active substances present in the aqueous phase of the first emulsion which also contains an osmotic agent, of the same nature or different from that of the first emulsion. external continuous phase, advantageously from those described above; this internal aqueous phase being itself dispersed in the lipid phase. The osmotic agent makes it possible to guarantee a balance of osmotic pressures. This avoids a pumping effect of nutrients through the lipid wall. The protein phase 11 also comprises an osmotic agent, of the same nature or different from that of the external continuous phase, advantageously from those described above. This reinforces the effectiveness of the osmotic barrier.

Very advantageously, the surfactant is chosen from the group of phospholipids, polymers such as carboxymethylcellulose (CMC), hyaluronic acid, polylysines, proteins such as casein or hydrolysates of plant or animal proteins, surfactants, and their combinations.

FIG. 5 also presents an additional and optional step (a ”) in which a dispersion of a mineral phase such as clays is carried out in at least part of the mixture of at least one oil and at least one liquid wax d. animal or vegetable oils and liquid waxes used in step (d). As previously indicated, these clays are preferably phyllosilicates and very preferably smectites. To facilitate the exfoliation of the clay layers in this lipid medium, the dispersion is carried out in the presence of a surfactant, which preferably has a cationic polar head.

It is advantageously possible to use lecithin, betaine, polylisin, as well as their combinations.

FIG. 5 also shows another additional and optional step (c ') in which, after having obtained the first emulsion of aqueous particles in oil (step (b)), it is subjected to high shear such as rotor / stator to homogenize and reduce the size of these aqueous particles before their complete gelation. This shear is preferably between 2000 and 20,000 s-1.

The manufacture of the second product 20 is similar to that of product 10, it suffices to carry out a coating directly after obtaining the lipid particles in step (g). Figure 6 shows the additional steps for the preparation of the third product. After step (g) which makes it possible to obtain the lipid particles 18 by filtration or decantation, a coating 34 of these lipid particles 18 is formed by successive additions of solutions of biopolymers, advantageously of polysaccharides, positively and negatively charged (step ( g ')). The last addition is preferably that of a positively charged biopolymer.

Then, the coated lipid particles thus obtained following step (g ′) are dispersed in a protein phase, and the whole is shaped by cold extrusion. The addition particles in the protein phase can also be produced by deposition in a fluidized bed or by spheronization. Cylinders or geometries (depending on the die used) of the protein phase are obtained in which the lipid particles are found dispersed. These extrudates must then be cut, for example with a rotary blade, to obtain the sets of cores 32 coated with the coating 34 dispersed in a protein phase 11 of the third products (step (h)).

It remains to carry out the coating 14 to obtain these third products 30. This coating is carried out as previously described.

A final optional drying step can then be carried out as previously described under a flow of air at low temperature, preferably below 50 ° C, for example between 18 and 40 ° C, until a lower humidity level is obtained. at 10% by weight, relative to the total weight of the product.

Preparation of a food supplement

An example of the preparation of a food supplement of the first product is now described.

Preparation of the gelled internal aqueous phase This preparation comprises the following steps:

We fill a beaker with water. Then the hydrophilic nutrients to be encapsulated are added. These nutrient inputs represent around 30% by weight relative to the weight of the water put into the beaker. The solution is then mixed in a high shear rotor-stator mixer of the Silverson Mixer type, L5M-A for 1 min at 1000 rpm (revolutions per minute). Then 3.5% by weight of sodium alginate is added to the previous solution. Mix with the high shear mixer for 5 min at 2000 rpm. After complete dispersion of the above alginate, 0.5% by weight of pyrophosphate and 1.75% by weight of calcium sulfate are added simultaneously. The mixture is rapidly homogenized in a rotor-stator mixer at 2000 rpm, then all of this aqueous phase is poured into a volume of cod liver oil serving as dispersion medium. The ratio of the volume of oil to the volume of the aqueous phase is less than 3.4. The whole is strongly mixed with the high shear mixer at 2000 rpm to reduce the size of the water drops in the oil before the aqueous phase gels. Allowed to stand for 15 min for the aqueous phase particles to solidify. FIG. 7 shows the size distribution of the gelled aqueous particles obtained. The average size of the aqueous phase particles obtained with the shear rate at 2000 rpm is 161 µm. The average size can be reduced by increasing the shear rate of the solution, or by changing the viscosity of the alginate solution. By reducing the concentration of alginate in the solution from 3.5% by weight to 2% by weight, a decrease in viscosity of more than a factor of 10 was obtained. The shearing is then more efficient and the average size of the particles. decreases.

Preparation of the crystallizable lipid phase Preparation of a first beaker of molten wax

In a first beaker, add a given mass of beeswax or sodium stearate, and a mass of sunflower oil 15% greater than the mass of beeswax or sodium stearate. The sum of the two ingredients represents 25.5% by weight of the total mass of the lipid phase prepared. Then the first beaker is placed in a water bath preheated to 75 ° C until the wax has completely melted (wax melting temperature 60 to 63 ° C).

Preparation of a second beaker of clay exfoliated in oil In a second beaker are added 100 units of weight of rapeseed oil, 30 units of weight of linseed oil, 1.24 units of weight of betaine, 1.24 weight units of soya lecithin, 50 weight units of montmorillonite pre-impregnated with 10% by weight of water relative to the weight of montmorillonite. The whole is mixed with the high shear mixer for 30 min at 2000 rpm. The mixture is completed with specific contributions such as vitamins A, E, D, K etc ... for less than 0.2 units of weight. The exfoliated clay preparation represents about 30% by weight based on the total mass of the prepared lipid phase. The quality of the exfoliation of montmorillonite in oil can be assessed by light microscopy by observing the homogeneity of the dispersion, with the reduction of macroscopic aggregates of several hundred µm.

Combining the prepared lipid phases in a third beaker

In a third beaker, kept in a water bath at 70 ° C, the prepared oil phases are combined in the following proportions:

44% by weight of the dispersion of aqueous particles gelled in a lipid matrix of cod liver oil prepared above; 31% by weight of the mixture of the second beaker (rapeseed and linseed oils, exfoliated montmorillonite, etc.); and

25% by weight of the mixture of liquid waxes and sunflower oil prepared previously. Homogenized with a high shear mixer for 2 min at 1000 rpm. An oil phase is obtained which is ready to be dispersed to form the enriched lipid particles.

Preparation of the external aqueous phase

In a jacketed reactor, equipped with a stirrer and a temperature control, an aqueous solution is prepared according to the following composition: water for a volume equivalent to 2.5 times the volume of lipid phase to disperse;

1% by weight relative to the mass of the aqueous solution of osmotic agent (sorbitol or sodium chloride); and

0.4% by weight relative to the mass of the aqueous solution of casein (surfactant, which can be substituted by animal or plant proteins).

Homogenize until the ingredients are completely dissolved, and the solution is brought to 65 ° C.

Manufacture of lipid particles

With a stirrer capable of dispersing solids, the aqueous phase is stirred continuously at 450 rpm while maintaining the temperature at 65 ° C. Then, all of the lipid phase prepared above and maintained at 70 ° C. is quickly poured into the external aqueous phase. The dispersion is allowed to stabilize until it reaches about 62 ° C, the stirring is reduced to 400 rpm, the mixture is cooled with the jacket of the reactor to reach 60 ° C, the stirring is reduced to 350 rpm, the mixing is accelerated. cooling by adding ice-cold water to rapidly reach 45 ° C., the lipid particles are allowed to cool to room temperature via the jacket of the reactor while maintaining stirring at 150 rpm. When the dispersion is below 25 ° C, the solidified lipid particles are filtered through a sieve.

The lipid particles thus obtained are characterized in size using a Malvem Mastersizer 3000 particle size analyzer with a liquid dispersion by hydro EV, with the software of the size determination apparatus (Fraunhôfer's equation). The measurements were carried out on 3 manufacturing tests: the three tests give the same average size of the lipid particles of 330 μm (FIG. 8). Figure 9 shows the change in the iodine number measured according to standard NF EN ISO 3961 (September 2013), during aging in the open air of the lipid particles. Line L1 gives the reference iodine number obtained from the formulation of the particles. Lines L2 and L3 give the upper and lower 95% confidence limits and line L4 the evolution of the measured iodine number of the lipid particles. This line L4 shows that all the measurements after the first are within the interval between the high and low confidence limits and this makes it possible to confirm the storage stability of the particles thanks in particular to the increase in the mean path of the particles. oxygen molecules imposed by the presence of clay. Thus during storage, no significant variation is observed in the number of unsaturations (double bonds resulting from omega 3-6 and 9) provided by the oils used for the formulation.

Figure 10 shows an image of a lipid particle obtained under a scanning electron microscope.

Outer protein layer - preparation of the protein layer covering the lipid particles

Preparation of the protein matrix containing the lipid particles:

In a planetary mixer type kneader, we introduce:

100 parts by weight of the protein formulation corresponding to the nutrient requirements of the target species;

33 parts by weight of sodium alginate;

8.3 parts by weight of pyrophosphate;

33 parts by weight of calcium sulfate;

1 part by weight of sorbitol (osmotic agent) nutritional additives according to the nutritional target (amount less than 2 parts by weight). After homogenization of the solids, a volume of water is added, the mass of which corresponds to 600 parts by weight, and the mixture is vigorously homogenized with a planetary kneader type mixer for 10 min.

A mass of lipid particles corresponding to 630 parts by weight is introduced. Note: it is necessary to take into account the residual humidity of the lipid particles which can vary from 2 to 50% by weight. Then it is homogenized while limiting the shearing until a homogeneous paste is obtained. This dough is then introduced into a cold single-screw extruder to shape the dough through a die with the target diameter of the size. food supplement. The extrudate is continuously cut by a rotating blade to the target size of the food supplement.

The protein particles are allowed to stand for two hours to obtain their solidification. The solidification kinetics of the food were characterized using the ARES-G2 rheometer from T A-instrument, with the 40 mm ² cone / plane mobile. A 5 ° rotary shear was applied at a frequency of 1 Hz, and the change in force over time was measured.

Figure 11 shows a curve for monitoring the rheological behavior of the protein layer in the case of a protein phase obtained with 2% by weight of alginate and 15% by weight of protein relative to the total weight of the protein phase. This figure 11 gives the evolution as a function of time of the measured modules G ’and G”.

A destructuring of the polyelectrolyte / protein gel is observed at short observation times, with a decrease in the shear force G ’, marking several levels. Then a resumption of force beyond 3800 seconds, reflecting the emergence of a percolating crosslinking domain between the two shear plates. This crosslinking seems to saturate at 8300 seconds, then there is a detachment probably related to the separation of the solidified sample from the wall of the cone / plane.

We deduce that the mixture can be worked for about an hour without risking destroying the gelling mechanism, and with two consecutive hours of rest we reach the maximum level of rigidity of the food supplement. The protein particles thus obtained can be stored in a cool place (4 ° C), or used for the coating step by depositing a layer of biopolymer layer-by-layer, in English "Layer by Layer".

Figure 12 shows an example of protein particles obtained after gelation of a size of the order of a millimeter.

Preparation of the release modulation coating by a biopolymer deposited layer by layer (in English "layer by layer")

Coating layer by layer

The procedure is described for 100 g of lipid particles dispersed in 300 g of water supplemented with 1% sorbitol.

A stirring device is used which promotes good homogenization, without inducing excessive shearing of the solution (double-finned mobile). We prepare :

2000 ml of a first aqueous solution of chitosan at 0.1% by weight relative to the weight of the aqueous solution (with 0.05% by weight of acetic acid);

2000 ml of a second 0.1% by weight aqueous sodium alginate solution;

200 ml of a third 2% by weight aqueous solution of calcium chloride; and 200 ml of a fourth 0.5 wt% aqueous solution of trisodium tetraphosphate (TSTP).

The additions are started with the 0.1% by weight sodium alginate solution; stirred for 1 to 2 min between each addition. The chitosan solution is then added.

The procedure followed and the proportions of each addition are as follows (all% are% by weight):

+ 20 ml of 0.1% sodium alginate solution;

+ 20 ml of 0.1% chitosan solution;

+ 60 ml of 0.1% sodium alginate solution;

+ 20 ml of 0.5% trisodium tetraphosphate (TSTP) solution;

+10 ml of 0.1% chitosan solution;

+ 10 ml of 2% calcium chloride solution;

+ 4.25 g of montmorillonite;

+ 100 ml of 0.1% chitosan solution;

+ 80 ml of 0.1% sodium alginate solution;

+ 20 ml of 0.1% chitosan solution; and + 20 ml of 2% calcium chloride solution.

Stirred for 15 min at 370 rpm. This procedure results in a seven-layer coating, the first of which is anionic sodium alginate layer and the last is cationic chitosan. In the middle of the coating, there is a layer of smectite (montmorillonite) sheets. These operations could be repeated up to seven times in the laboratory. Characterizations:

The lipid particles remain dispersed in solution, the non-flocculation is monitored with the naked eye as the charged biopolymers are added.

Conductometric monitoring of the conductance of the solutions makes it possible to monitor the deposition of the charged biopolymers. As a reference, the change in the conductivity of a pure water solution is measured, to which metered additions of 0.1% chitosan solution (curve Cl) are made, then independently of the metered additions of 0.1% sodium alginate (curve C2), and finally the combination of the two (curve C3). Figure 13 shows the results obtained.

We thus characterize the increase in the conductivity of the solution during the addition of chitosan and sodium alginate, with a greater conductivity for the alginate. The combination of the two reagents results in a slower sawtooth increase in conductivity compared to that of anionic and cationic polymers alone, because the charges largely neutralize each other, and the radius of gyration of the coacervates becomes greater (conductivity apparent lower).

Figure 14 shows the change in the conductivity of a solution of lipid particles during metered additions of charged biopolymers. This figure 14 shows that the addition of anionic and cationic biopolymers does not induce an increase in the conductivity of the solution, on the contrary, it decreases. It is the signature of the condensation of anionic and cationic biopolymers at the surface of the particles, leading to the decrease in the overall conductivity of the solution, because the large lipid particles contribute little to the conductivity, and the salts in solution (agent osmotic) are trapped in the interface during condensation, and no longer contribute to the conductivity of the solution.

The foods and food supplements which constitute some of the objects of the invention are therefore products of modular architecture which make it possible to encapsulate various nutrients and active substances and to release them into the digestive system of the target animals.

Stabilization thanks to the coating materials allows it to resist the acidic environment of the stomach while allowing rapid disintegration in a subsequent basic medium which ensures a very rapid and effective release of all the nutrients and active substances where they are the most effective.

The modular architecture of the core makes it possible to incorporate in the aqueous internal phase of the order of twenty different water-soluble active substances, in the first product, this incorporation takes place in particles with a diameter of the order of 20 to 100 μm; in the internal lipid phase, it is also possible to incorporate around twenty different liposoluble active substances in a matrix with a diameter of around 400 μm or less. The manufacturing process is also very respectful of these nutrients and active substances.

The products objects of the invention are thus with their modular architecture of very flexible use and by varying the manufacturing conditions, it is possible to vary the respective dimensions of the particles and the cores as well as the nature and the quantity of the active substances and nutrients to fine tune them to all target animals.

Claims

1. Process for the preparation of a food or a food supplement (10, 20, 30) in the form of modular stack objects allowing a controlled release of nutritive and / or physiologically active substances for monogastric animals, comprising a core ( 12, 32) with an aqueous phase (16) with water-soluble active substances and a lipid phase (18) with liposoluble active components, said aqueous phase (16) being dispersed in said lipid phase (18), and a coating ( 14) of the nucleus, comprising the following steps:

(e) introducing all of said first emulsion and said mixture of at least one oil and at least one liquid wax into an aqueous solution with stirring to obtain a second emulsion, said second emulsion comprising gelled aqueous particles dispersed in a lipid matrix, said lipid matrix itself being in the form of particles dispersed in said aqueous solution;

2. Preparation process according to claim 1, wherein after obtaining the first emulsion of water-in-oil particles in step (b), said first emulsion is subjected to high shear, preferably between 2000. and 20,000 s-1, for reducing the size of the aqueous particles in the oil before gelation of said particles of the aqueous phase (step (b ').

3. Preparation process according to one of claims 1 and 2, comprising a final step (j) of drying the products under a flow of air at a temperature below 50 ° C, preferably between 18 and 40 ° C.

4. Preparation process according to any one of the preceding claims, wherein said at least one wax is a crystallizable wax with a melting point of less than 90 degrees Celsius and preferably less than 65 degrees Celsius.

5. Preparation process according to any one of the preceding claims, wherein said gelling reagents comprise an anionic polysaccharide such as an alginate, a calcium salt and pyrophosphate.

6. Preparation process according to claim 5, in which the calcium salt is chosen from the group of calcium sulphate, carbonate and stearate.

7. Preparation process according to any one of the preceding claims, in which all of the aqueous solutions used comprise a controlled amount of osmotic agent.

8. Preparation process according to claim 7, wherein said osmotic agent is chosen from the group of sugars, salts, water-soluble polymers, preferably of molecular weight less than 150 kg / mole, and combinations thereof.

9. Preparation process according to any one of the preceding claims, in which, after having obtained said lipid particles in step (f) and before forming the coating in step (g), said lipid particles are dispersed. in a protein phase (step (f)).

10. Preparation process according to any one of the preceding claims, in which, before injecting said first emulsion into a mixture of oils and liquid waxes, a precise dose is brought into said mixture of oils and liquid waxes. of said liposoluble active substances.

11. Preparation process according to one of the preceding claims, wherein, before injecting said first emulsion into a mixture of at least one oil and at least one liquid wax, said mixture is dispersed in at least an oil and at least one liquid wax a clay phase exfoliated in a lipid medium.

12. Preparation process according to claim 11, wherein the exfoliation of a clay phase in a lipid medium is carried out in the presence of a surfactant, said surfactant having the characteristic of having a cationic polar head.

13. The preparation process according to claim 12, wherein said surfactant is lecithin.