ES2335493T3 - PELLS AND PROCEDURE FOR MANUFACTURING. - Google Patents

Abstract

Pella in which in a matrix containing hemicellulose as a film-forming agent, it is encapsulated without forming a core and in a homogeneous discrete distribution at least one oily active component, sensitive to oxidation and / or slightly volatile, being discretely arranged in the matrix the capsules in which the component (s) are / are included; and the pellet has a particle size of at least 100 µm.

Description

Pellets and manufacturing procedure.

The invention relates to pellets containing at least one oil component, which seen by itself represents an active component or at least one active component of this type.

As a general rule, oily components and / or assets of this type are often sensitive to oxidation or slightly volatile, such that over more periods or less large the proportion of active components of this type it is reduced or these components lose their effect.

For this reason it is necessary to protect these components.

The invention can be used with the most diverse Applications. Thus, correspondingly choosing components suitable active the pellets according to the invention can be used as food for humans and animals, as a way of administration of pharmaceutical products, for additives in cleaning products, such as phytosanitary agents and many more stuff.

According to the current state of the art it is known emulsify oily components, which may additionally contain also active components, to immediately use a Emulsion of this type. However, this is only possible during a limited period since the long-term stability of the Emulsions of this type are not unlimited and, in addition, often do not They can use preservatives.

For this reason emulsions are processed to Turn them into powders. This is done, as described in the EP 0 598 920 B1, by spray drying a emulsion. According to the teaching that can be deduced therefrom, prepares an emulsion with an oil phase and as an emulsifier a Very specific soy hemicellulose that is soluble in water. TO from this emulsion, a spray drying is prepared powder in the form of microcapsules, may contain microcapsules in addition to the oil phase also other active components or additional active components.

However, such a powder that is formed by the corresponding microcapsules reaches a load limited, therefore has a reduced percentage of corresponding active component since the outer shell must be thick and thick enough to prevent an influence by part of the environmental humidity or volatilization of active components from the microcapsules.

In addition, due to the procedure during powder preparation by spray drying cannot avoid an undesirable negative influence on the components for mainly thermal causes, such that at least Its effectiveness is reduced.

However, these circumstances affect also to the solution described in EP 1 214 892 A1. Do not However, here it is also disadvantageous that the corresponding active component is exclusively an oily component or a oil component additionally with another active component that encapsulate around an inert nucleus, such that the portion of active components contained in the capsules of this type is reduced in relation to the total mass.

Powders prepared to date from emulsions also have a limited mechanical strength, such so that during transport and storage there is a considerable friction shrinkage or even the breakage of the capsules and, consequently, to volatilization or unwanted influences of the components.

Powders prepared by drying by spray have only a limited creep capacity of so that only with great efforts can one achieve precise dosage.

Yes to improve the properties before indicated the dust particles must be coated with a wrap  external protective (coating), due to its large surfaces a very large amount of coating material is required. Thus, to form denser coatings is required mass ratios between powder and coating material of up to 1: 1, which leads to higher preparation costs and to a reduction in the percentage of active component with respect to mass volume

From EP 1 252 831 A2 known particles for tobacco products with which to smoke must get a certain tone and flavor that are equivalent to natural substances

Therefore, the object of the invention is facilitate oxidation sensitive active components and also slightly volatile, alone or additionally, in the form of oils and / or active components additionally contained in such oils with a greater concentration and stable in the long term for subsequent administration, application or additional processing.

This objective is achieved according to the invention with pellets having the characteristics of claim 1. The pellets according to the invention can be manufactured with a method according to claim 23. Refinements and Advantageous configurations of the invention can be achieved with the characteristics contained in the claims subordinates

Facing the state's known solutions current technique, the pellets according to the invention are characterized because they contain the corresponding components assets in high concentration and yet protected from safe way.

For this, the active components are encapsulated with a homogeneous discrete distribution in a matrix which contains hemicellulose as a film forming agent. The Different pellets do not contain inert nuclei. They present in all the cases a particle size of at least 100 µm, preferably at least 300 µm.

The high percentage of active components contents in the pellets of this type can be obtained in particular by the manufacturing process likewise according to the invention, on which they will be made below more detailed explanations.

The hemicellulose to be used according to invention as a film-forming polysaccharide should be contained at least 0.5% by mass. Do not However, the percentage of this film forming agent can choose also greater and ascend up to 60% in mass. The agent film maker especially guarantees that a component, if necessary also several components, included in the matrix in the form of capsules arranged discreetly.

Water soluble hemicellulose can be obtained, for example, from soybean or rapeseed seeds and is harmless from the physiological and environmental points of view.

It could also be provided in a quality almost equal to that of pure natural products, such as e.g. the gum arabic, and with a practically constant cost, that is, regardless of the atmospheric conditions that influence on the prices of the natural materials that form films.

There is also an acceptance by the consumers that is clearly superior to that of jellies also used routinely for this purpose.

Hydrates cannot be used for the matrix water soluble carbon. These can be selected among starches  or cellulose components.

To form the matrix different ones can be used starches, resulting in this regard particularly indicated the malt starch, but also cereal starch. They can used alone or also in combination with each other.

As a cellulose component for formation the cellulose is particularly suitable for cellulose microcrystalline (CMC).

The mass percentage of starch can keep up to a maximum of 90% by mass.

However, it is also possible to make pellets according to the invention with water soluble carbohydrates. From in this way, pellets can be manufactured by a continuous process of spray granulation in which the carbohydrates of these types are contained in the matrix and soluble polysaccharides in water they act as a film forming agent.

With water soluble carbohydrates you it can influence within wide limits on the size that can Reach the balls. In this way a size of particle of the pellets of this type in the interval included between 200 µm and 1,500 µm. A component can be encapsulated active with more than 15% by mass.

Carbohydrates appropriate for this are different oligosaccharides with different chain lengths. Particularly suitable in this regard are dextrins and Very particularly appropriate are maltose dextrins.

In addition to the organic components mentioned, a matrix can also be formed by inorganic components or Contain components of this type.

Appropriate inorganic substances are by example kaolin, CaCO 3, CaS, silicates, clay, bentonite, diatomaceous earth or aluminum oxide, which can also be used in the form of a mixture.

Inorganic components must also be largely insoluble in water.

In addition, mono-, di- or trisaccharides, being able to also keep here different mass percentages, which can be above 50% in mass.

In addition to neutral oily components, that is, those that do not exert any active action, can be used also oily components with active effect for the manufacture of pellets according to the invention. The percentage of these components It should preferably amount to at least 15% by mass. Han in this regard, particularly advantageous various fruit oils, but also oil extracts from fruit. In this way the oily components can be formed, for example, by orange and / or lemon oil. Aromatic note of taste and smell of these oily components can already get the desired active effect by itself, although also with additional active components.

However, as active components additional synthetic or natural dyes can also be used.  For this purpose, for example, carotin can be used, preferably beta-carotene, cantaxanthin or astaxanthin, which in addition to the coloring effect it also has additional effects known.

But also, as active components they can also use vitamins, preferably fat soluble vitamins such as eg vitamin A acetate, being possible also a combination of these vitamins with carotene.

But in addition to vitamins, as components other pharmaceutically active substances can also be used active. Other possible active components are diverse insecticides / biocides.

For the following applications of the pellets according to the invention in cleaning agents, but if necessary also in cosmetics, different substances can be used aromatic with the corresponding note of pleasant smell and given the additionally with surfactants.

For food substances can be used aromatic with taste and / or smell.

But as an active component they can be used also unsaturated fatty acids such as fatty acids polyunsaturated alpha-omega.

The active components contained additionally in the capsules in addition to the oil component, not They must be necessarily soluble in oil. Can be contents also in the form of dispersion, such as small crystals in an oily component. There is thus the possibility of dispersing in Microcrystalline form in an oily component unstable vitamins, as for example vitamin K (MSBC), and encapsulate them so corresponding in the pellets with the oily component.

The percentage of volume occupied by capsules immersed in the matrix should be maintained above 10%, preferably above 20%. But there is also the possibility of adjusting the volume percentage beyond those values and correspondingly raise the percentage of active component, that is to say of its load, in the pellas

The percentage of water in the finished pellets should be kept less than 10% by mass.

Unlike powders manufactured in accordance to the current state of the art by spray drying, the pellets according to the invention are obtained by combining the preparation of an emulsion with a direct formation of the pellets or a Extrusion performed below.

For the preparation of the emulsion a starch, an oily component, water soluble hemicellulose as film and water forming agent.

The emulsion that is obtained can be additionally incorporate, for example, starch to increase the viscosity and adjust a pasty consistency.

In this state it can be done in a way preferably an extrusion, then being able to remove from the corresponding extruder the pellets still slightly damp. If necessary, the pellets can be mechanically reviewed, so Preferred can be rounded.

It can also be followed by a subsequent drying to further reduce the water content and there is the possibility of providing each of the pellets with a coating protector, which preferably creates moisture protection and that if necessary it can also prevent the pellets from sticking each other.

It has been surprisingly that a emulsion in which an oily component is distributed at least as a fine dispersion and with water soluble hemicellulose as film forming agent, for example. the adition of additional starches that increase viscosity, during a extrusion includes in the matrix the capsules containing the oil component and if necessary other active components, without destroy them You can also get a homogeneous distribution, that is very uniform, of the small capsules inside the matrix of each of the pellas. According to the number and therefore the percentage of capsules included in the matrix can be adjusted a greater or lesser load, that is, a corresponding percentage of active components, which can be maintained up to 20% by mass and also taller.

When extruding nozzles can be used relatively thin so that after extrusion the pellets may present orthogonally to extrusion diameters in the range of about 1 mm.

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Of course they can also be achieved sections of major pellets and if necessary also located somewhat by under 1 mm.

In extrusion you can work with a reduced temperature, especially against spray drying, in such a way that it also influences less negative on the active components used. They produce less evaporation losses.

In extrusion you can work with relatively low pressures. This also achieves a careful treatment of the encapsulated active components and ensures that the active components are protected against unwanted external influences and that they can be safely kept included within the matrix of the
pellas

The starch and / or the cellulose component used essentially for the formation of the matrix is harmless from the physiological and environmental point of view and it is also in Its mostly smell and neutral taste.

The pellets manufactured according to the invention they also have a good mechanical stability, such so that a reduction in wear can be achieved.

The following will describe in more detail the invention by way of examples.

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Example 1

(Comparative)

For the preparation of an emulsion they were mixed intensely 10 kg of modified starch (Hicap) with 30 kg of water, 8 kg of orange oil and 2 kg of malt starch. Then homogenization was carried out at approximately 20,000 kPa in a homogenizer of the company Niro. The emulsion thus prepared is gave it a doughy consistency by adding 12 kg of starch powder of cereal and mixing it next. The mass obtained from this mode is then extruded with a low pressure extruder Fuji-Paudal. A pella section of 1.2 was adjusted mm with the corresponding extrusion nozzles.

The pellets obtained in this way were rounded then and then dried in a fluidized bed until that a percentage of water of approximately 4%.

The loss of orange oil as a component asset stood at 8%, such that the mass percentage of orange oil in the finished pellets could keep above 18% by mass.

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Example 2

For the preparation of an emulsion they were mixed intensely 6 kg of hemicellulose as a film forming agent based on soybeans, 6 kg of malt starch, 30 kg of water and 36 kg of orange oil. This previous emulsion was homogenized to then also approximately at 20,000 kPa in a homogenizer of the company Niro.

To this homogenized emulsion were added to continued 6 kg of malt starch and 9 kg of cereal starch and mixed in such a way that a pasty consistency was adjusted That could be extruded. Then it was also extruded in the way already explained in example 1.

After drying the water content was placed also approximately 4% by mass and the 54% orange oil percentage by mass, having to review Only a 2% loss of orange oil.

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Example 3

(Comparative)

16 kg of starch were mixed thoroughly modified (Hicap 100), 27.2 kg of water and 6.86 kg of vitamin A acetate oil at a temperature of 60 ° C and then with a subsequent homogenization was obtained as in the examples a Emulsion finished. 2.5 kg of starch was added to this emulsion of malt and 7.6 kg of cereal starch and then performed again an extrusion with subsequent rounding and drying until a water content of approximately 4% by mass.

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Example 4

For the preparation of an emulsion 6 kg of hemicellulose based on soybeans were mixed intensely,
12 kg of malt starch and 30 kg of water with 36 kg of non-anionic acid at temperatures between 0 and 5 ° C and then also homogenized.

The pasty consistency was adjusted by adding 9 kg of cereal starch and then returned to subsequent rounding and drying up to Water percentage of approximately 4% by mass.

The non-anionic acid was encapsulated with security in the pellets and no loss could be noted.

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Example 5

125 g of starch were mixed as a powder of malt in powder form with 125 g of hemicellulose based on soybeans This powder mixture dissolved and mixed in 1,900 g of demineralized water. To this solution 1,350 g of an oil with a high percentage of fatty acid esters polyunsaturated and mixed vigorously. The oil had an index of iodine of 170. This previously emulsified mixture was homogenized with a two-stage homogenizer from Niro at pressures of 20,000 and 22,000 kPa and more emulsified.

Most of the emulsion oil drops obtained in this way had a particle size of
1.4 µm.

It was then added to the emulsion, which it had a mass of 2,380 g, a mixture of 1,289 g of a starch of corn (Cerestar) and 1,289 g of microcrystalline cellulose as well as An additional 496 g of water and mixed with each other. In this way a pasty consistency could be achieved with a percentage of 36% mass moisture.

This pasty dough was extruded with an extruder Fuji-Paudal with reduced pressure, presenting the extrusion nozzles with a diameter of 0.8 mm.

Then the pellets were dried extruded in a fluidized bed up to a percentage of water from 3% by mass.

The dried pellets had a content of 25% mass oil, which was controlled in atmospheric conditions over a period of four weeks at room temperature and bare storage. After these four weeks you was able to determine an iodine index of 162. This indicated that virtually no oxidation was recorded in the preparation and the subsequent storage. The percentage of free fat could determined below 0.1% by mass.

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Example 6

350 g of hemicellulose were mixed in the form of Powder based on soybeans with 700 g of malt starch and dissolved in 2,450 g of water. 1,500 g were added to this solution of orange oil and intense mixing was carried out. Be kept the mixture at a temperature below 10 ° C.

The previously emulsified mixture was homogenized with a two-stage homogenizer Niro at pressures of 20,000 and 22,000 kPa The highest percentage of oil drops contained in The emulsion had a particle size of 0.8 µm.

950 g was added to 3,950 g of this emulsion of microcrystalline cellulose (Vivapur) and 100 g of wheat starch, mixing in such a way that a doughy consistency was achieved with a moisture percentage of 39% by mass. Then you they carried out an extrusion and then spheronization and a drying in a fluidized bed.

The dried pellets were stored at 40 ° C and a 35% relative air humidity, uncovered and under the air influence At the beginning and end of storage it determined the percentage of cis- and translimonene epoxide, carveola and carvona. The measured values obtained are shown in the table 1 next.

TABLE 1

one

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Example 7

(Comparative)

Extrudable dough with dough consistency which had been obtained according to example 3 was added with a mass of 10 kg to a granulator of the company Glatt and additionally added 1 kg of Cerestar corn starch.

The granulation was carried out by space of five minutes and the granulate obtained in this way took a Spheronizer also from the company Glatt. The pellas spheronized were then dried in a fluidized bed until a moisture percentage of 3% by mass is reached.

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Example 8

0.5 kg of cellulose was mixed here based on soybeans with 2 kg dextrin maltose and dissolved slowly in 12.5 kg of demineralized water.

7.5 kg of maltose was added to this mixture dextrin of the same quality together with 3 kg of oil polyunsaturated, which can be obtained in C. N. Schmidt, B. V. Amsterdam, the Netherlands, and showing an iodine index of 170, and they were processed with a high speed mixer until 22.5 kg prior emulsion. This previous emulsion was homogenized with a two stage high pressure homogenizer at a pressure of 25,000 to 27,500 Ka.

This mixture was taken to a fluidized bed of a WFA 225 direct pelletizing device manufactured by the Glatt GmbH. The products obtained in this way are observed in an air atmosphere storage for a 4-week period, increasing the percentage of hexanal as oxidation product.

The individual pellets had a size of particle in the range between 250 and 355 µm.

But in the same way it is possible to manufacture with the same formulation pellets with a particle size in the range between 800 and 1,118 µm.

All pellets manufactured in this way they had a percentage of oil content greater than 23% by mass and a portion of hexanal? 0.5 mg / kg with respect to the oil.

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Example 8a

With the same formulation as in example 8, manufactured pellets according to the invention in which the orange oil Instead of 3 kg of unsaturated oil, they added 2 kg of orange oil that presented a percentage of 63% limonene. This mixture was homogenized the same as in the case from example 8.

The mixture obtained in this way was processed in a fluidized bed of a WSA 225 direct pellet forming equipment of the company Glatt GmbH. The pellets obtained in this way had essentially a particle size between 800 and 1,100 µm and a Limonene percentage of 19% by mass. Oil loss orange during direct pellet formation amounted to less than 5% and no limonene oxidation was observed during the process of pelletization and drying.

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Example 9

125 g of hemicellulose powder based on soybeans mixed with 125 g of malt starch they were dissolved in 1,250 g of demineralized water.

To this solution was added 1,250 g of acid arachidonic and mixed intensely.

The previously emulsified mixture was homogenized in two stages at pressures of 20,000 kPa and 35,000 kPa. The particles individual oil emulsion had essentially a size of 0.8 µm.

Next, 645 g of this emulsion is mixed with 2,000 g of kaolin (GTY Clay) and 600 g of cellulose microcrystalline and achieved a doughy consistency suitable for extrusion with a percentage of water of 28% by mass.

Then the dough was extruded and a spheronization and drying in the fluidized bed until it is reached a percentage of water of 3% by mass.

The percentage of encapsulated arachidonic acid It was 8.5% by mass.

In a storage at air at temperature environment could not detect losses or an impairment of acid arachidonic

Claims (28)

1. Pella in which in a matrix containing hemicellulose as a film forming agent is encapsulated without form a nucleus and in a homogeneous discrete distribution at least an oily active component, sensitive to oxidation and / or slightly volatile, being arranged discreetly in the matrix the capsules in which it is / are included component (s); and the pellet has a particle size of at least 100 µm.

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2. Pella according to claim 1, characterized in that it contains hemicellulose as a water-soluble polysaccharide and film former in at least 0.5% by mass.

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3. Pella according to claim 1 or 2, characterized in that it contains the oily component sensitive to oxidation in at least 15% by mass.

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4. Pella according to one of the claims previous characterized in that it has a particle size of at least 300 µm.

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5. Pella according to one of the claims previous characterized in that the matrix contains at least one carbohydrate not soluble in water.

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6. Pella according to claim 5, characterized in that the non-water soluble carbohydrate is a starch and / or a cellulose component.

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7. Pella according to claim 6, characterized in that the non-water soluble carbohydrate is a cereal starch, microcrystalline cellulose, malt starch or a mixture thereof.

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8. Pella according to one of the claims previous characterized in that the matrix contains mono-, di- or trisaccharides.

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9. Pella according to one of the claims previous characterized in that the matrix contains an inorganic component that is not soluble in water.

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10. Pella according to one of the claims previous characterized in that the inorganic component is kaolin, CaCO 3, CaS, a silicate, aluminum oxide, clay, bentonite or diatomaceous earth.

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11. Pella according to one of the claims previous characterized in that the matrix contains at least one water soluble carbohydrate.

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12. Pella according to claim 11. characterized in that at least one water soluble carbohydrate is selected from the group of dextrins and maltose dextrins.

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13. Pella according to claim 11 or 12, characterized in that the particle size of the pellets is in the range of 200 to 1,500 µm.

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14. Pella according to one of the claims previous characterized in that the oil component is an oil of aromatic fruit or fruit oil extract of this type.

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15. Pella according to one of the claims previous characterized in that the active component is a dye.

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16. Pella according to one of the claims previous characterized in that the active component is an aromatic substance.

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17. Pella according to one of the claims previous wherein the active component is an unsaturated fatty acid.

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18. Pella according to one of the claims previous characterized in that the active component is a pharmaceutical active ingredient or contains a pharmaceutical active ingredient.

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19. Pella according to one of the claims previous characterized in that the active component is an insecticide / biocide.

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20. Pella according to one of the claims previous characterized in that the active component can be dissolved or dispersed in an oily component.

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21. Pella according to one of the claims previous characterized in that the capsules occupy a volume of at least 10% in the pellet.

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22. Pella according to one of the claims previous characterized in that the water content is less than 10% by mass.

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23. Procedure for the manufacture of pellets in which at least one oil component alone or with one component Additional asset is contained in a matrix, coreless and in shape encapsulated, and individual capsules in which it is (n) content (s) the component (s) and are arranged with a discrete and homogeneous distribution;

in which it prepares an aqueous emulsion that in addition to at least one component Oily contains hemicellulose as a polysaccharide forming film and water soluble, in which the oily component is content in finely distributed form,

to this emulsion a substance or mixture of forming substances of matrix to adjust a pasty consistency and from it it They make the pellets.

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24. Method according to claim 2. 3, characterized in that the pellets are manufactured by extrusion or direct formation of pellets. 25. Procedure according to one of the claims 23 or 24, characterized in that the emulsion is prepared in two stages, with high pressure homogenization being carried out in the second stage.

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26. Procedure according to one of the claims 23 to 25, characterized in that after extrusion a rounding of the pellets is carried out.

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27. Procedure according to one of the claims 23 to 26, characterized in that the pellets are subsequently dried.

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28. Procedure according to one of the claims 23 to 27, characterized in that the pellets are provided with a protective coating.