IE904724A1

IE904724A1 - Pellets containing active principles protected against degradation in the rumen of ruminants

Info

Publication number: IE904724A1
Application number: IE472490A
Authority: IE
Inventors: Claude Annonier; Pierre Autant; Hugues Porte; Jacques Ruel
Original assignee: Rhone Poulenc Nutrition Animal
Priority date: 1989-12-28
Filing date: 1990-12-28
Publication date: 1991-07-17
Also published as: HUT60902A; AU643722B2; FR2656772B1; CZ280981B6; MX173330B; JPH04218342A; NZ236685A; DK0437388T3; DE69101490D1; EP0437388B1; EP0437388A1; CN1053186A; MX23971A; KR910014045A; ZA91171B; AU6845090A; CA2033234A1; ES2062697T3; KR0143766B1; CA2033234C

Abstract

The present invention relates to novel compositions, in the form of pellets, used for the dietary and/or medicinal supplementation of ruminants, containing active substances protected against degradation in the rumen and one or more solubilisable, cross-linkable or meltable binders and, if appropriate, a separation agent and/or a filler.

Description

The present invention relates to pellets containing active principles which are protected against degradation by enzymes in the rumen of ruminants, a process for their preparation and animal feeds containing them.

Pellet is understood to mean a nutrient granule for animals obtained either by extrusion of a feed mixture through a die or by another technique. They take the form of sticks, preferably cylindrical, possessing, in particular, average sizes of 4 to 20 mm in length and 4 to 10 mm in diameter. Such pellets are widely used, since they are easy to handle and administer and are not dust-forming.

It is known that it is difficult to prepare pellets suitable for use in animal feed containing compounds useful to nutrition and/or therapy which cannot undergo pelletization on account of the sensitivity of the compounds to temperature, pressure and shearing.

Conventional pelletizing machines are machines which shape a feed mixture by forcing the mixture through a die in the presence of steam. This mixture is passed through a perforated plate (the die) by means of a press, which forces the mass to be extruded through the holes in the plate. On emerging from the die, the cylinders obtained are cut by a mechanical means or spontaneously. During the forced passage through the die, products having low thermal resistance or mechanical strength undergo degradation due both to the pressure exerted and to heat caused both by friction and by the addition of steam which promotes - 2 cohesion of the various floury ingredients of the base feeds.

EP-A-231,817 describes a process for preparing agglomerated feeds based on vitamins or on compounds essential to human or animal health. It was known in the prior art that, when these compounds undergo a temperature rise during passage through pelletizing machines, they are at least partially destroyed. In effect, compounds having low thermal resistance or mechanical strength are often mixed, in order to shape them, with molasses, and undergo the action of steam in order to effect their cohesion. The simultaneous action of steam and pressure destroys them. Patent Application EP 231,817 enabled the problem of manufacture of these agglomerated feeds to be solved by spraying a solution or suspension of the vitamin or vitamins or the drug, and optionally a fat, onto a base core. This process permits only a coating of the base substance with the vitamin, with or without a fat. The said process is easy to carry out using pulverulent or liquid products such as vitamins or drugs. These products are thus easy to use in the form of a solution or suspension. However this process is not readily adaptable to the formation of agglomerated nutrient granules in which the material sensitive to heat and/or compression takes the form of granules of average diameter approximately 0.3 to 5 mm.

FR-A-2,338,653, also discloses a process for preparing feedstuffs, onto which is sprayed an enzyme - 3 suspension, preferably of proteases, in a liquid or molten fat. This process provides the same teaching as the European application referred to above, and enables only pellets on which the temperature-sensitive substance is deposited at the periphery by a spraying phenomenon to be obtained.

It is inconceivable that granules of protected active principles could be sprayed onto pellets of nutrient material. Neither can these granules be introduced into pelletizing machines, since the coating undergoes attack by phenomena such as abrasion, shearing, temperature rise, the addition of steam and pressure, which bring about an at least partial degradation of the coating and hence an instability of the active principles in the rumen on ingestion by the animal.

Heretofore it therefore appeared impossible to make additives suitable for use in animal feeds for ruminants containing granular protected active principles other than by dispersing the granules in the feed, which creates problems of homogeneity, concentration and distribution.

The present invention therefore seeks to provide additives comprising granular protected active principles in the form of pellets which are directly assimilable by animals and which disintegrate in the rumen of ruminants.

We have now devised additives, suitable for use in animal feeds which are in the form of pellets - 4 comprising a granular protected active principle. Such pellets may be obtained by mixing the granules with a binding agent and forming the pellets. The pellets may for example be formed by moulding or by extrusion, typically at a temperature of less than 100°C and in the absence of steam Accordingly the present invention provides pellets comprising a granular active principle protected against degradation in the rumen and a soluble crosslinkable or meltable binding agent. Optionally the pellets further comprise a disintegrating agent and/or filler.

The invention also provides a process for the preparation of such pellets which process comprises mixing granular active principle protected against degradation in the rumen, and soluble, crosslinkable or meltable binding agents, and forming pellets from the mixture.

As a further feature the invention provides animal feeds comprising such pellets.

The active principle in the pellets of the present invention may be an essential amino acid, a salt derivative or analogue thereof, such as methionine or lysine or a salt derivative or analogue thereof, a vitamin, a medicinal principle such as an antibiotic or other nutritional or medicinal additive.

Some amino acids are essential in the feeding of ruminants since they are present only in limited amounts in the daily nutritional intake. This applies, in particular, to methionine and lysine. These amino acids when - 5 administered orally to ruminants, are destroyed in the rumen by the action of the digestive enzymes and microorganisms present in this organ. For these compounds to be utilizable by the animal and beneficial thereto, it >s necessary to protect them with a substance enabling them to pass through the rumen without damage but capable of disintegration in or after the abomasum, so as to release the active substance in the intestine and thereby enable it to pass into the body.

This protection of the active principle, such as methionine or lysine, may be achieved by using granules of the active principle, coated with a composition comprising a combination of a substance sensitive to pH variations, selected, in particular, from synthetic basic copolymers, with hydrophobic substances which may be selected, for example, from fatty acids or their derivatives and hydrophobic polymers. Such compositions are described, for example, in French Patents FR 78/23,966 (2,401,620), FR 78/23,968 (2,401,621) or FR 81/18,954 (2,514,261).

Among the main groups of coating agents, copolymers of vinylpyridine and styrene with a hydrophobic substance, preferably stearic acid and/or a non-watersoluble polymer, for example ethylcellulose, may be mentioned by way of examples.

Alternatively the active principle may be protected using a coating agent sensitive to enzymatic digestion in the conditions of the abomasum or intestine, - 6 such as chitosan and/or zein, combined with a hydrophobic substance, preferably stearic acid, and optionally a nonwater-soluble polymer, preferably ethylcellulose.

The granules of protected active principles typically take the form of substantially spherical particles having an average diameter of between 0.3 and 5 mm, and preferably approximately 2 mm.

The binding agents which are usable in the present invention are preferably selected from feed materials permitting liguid/solid conversion, so that a definite shape resembling that of the feed pellet may be imparted thereto and set.

Two classes of binding agents may in particular be used: soluble binding agents used in a solvent or dispersant medium from which the solvent or dispersant medium may be removed e.g. by drying, to produce solid pellets and meltable binding agents which may be used molten and allowed to solidify to produce pellets.

Among binding agents used in a solvent or dispersant medium, there may be mentioned: - the class of hydrocolloids such as, in particular, water-soluble derivatives of cellulose, such as: carboxymethylcellulose, hydroxypropylcellulose, hydroxyethylcellulose, - 7 hydroxymethyIce1lulose, the class of natural or synthetic polysaccharides such as: gum arabic, gum tragacanth, carrageenates, dextrins, starch, xanthan gum, alginates, - sugars, molasses and vinasses, lignosulphonates, grain flours or seaweed meal, the class of crystallizable inorganic compounds such as lime, plaster, sodium silicate, calcium carbonate and silica, gelatins, - tanned proteins, polyvalent cation salts of natural or synthetic polyacids, drying oils and mastics obtained by the combination of a drying oil and a filler.

Some of the above binding agents are crosslinkable for example, hydrocolloids such as alginate, gelatin, xanthum gum, cellulose derivatives, other polysaccharides, molasses and vinasses. Crosslinkable binding agents may be used with crosslinking agents selected, for example, an aldehydes if the crosslinkable binding agent is a for protein, a salt or oxides of di- or trivalent metals if the crosslinkable binding agent is an alginate, xanthan gum, molasses, vinasses or some other curing agent suited to the - 8 binding agent used and well known to those skilled in the art.

Among binding agents capable of being melted, there may be mentioned, by way of examples: fatty acids and alcohols, hydrogenated vegetable and animal fats, - glycerol esters, paraffin waxes, - natural or synthetic waxes, synthetic polymers such as polyethylene glycols, polyvinyl acetate, etc.

Among all the binding agents, it is preferable to use molasses, vinasses, fatty acids, hydrogenated vegetable or animal fats, plaster and paraffin waxes.

Additives may be introduced into the pellets such as fillers which enable the pellet to be provided with the desired qualities of density, mechanical strength and disintegrating agents to provide rapid disintegration of the pellets.

By way of useful additives for the preparation of the pellets according to the invention, there may be mentioned: as fillers - inorganic additives such as: silica, silicates, talc, clays, calcium carbonates, phosphates. as disintegrating agents - additives derived from natural products such as: grain flours, residues of the - 9 cereals and wood industries, ground feed cakes, various brewery and fermentation residues, cellulose vegetable fibres, Other usable additives include polysaccharides and sugars.

The binding agent, supplemented where appropriate with additives, preferably represents 40 to 95 % of the mass of the pellets. The content of inorganic or natural additives represents from 0 to 80% by weight relative to the binding agent.

The mixing of the binding agent and the protected product may be carried out for example at the same time as the shaping or beforehand. The shaping may be carried out by means of a die or a mould.

The nature of the binding agent, the pouring temperature and the quantity of additives will be adjusted by those skilled in the art to obtain the desired appetency, density, shape, size, mechanical strength, solubility and ability to disintegrate in the rumen in the pellets of the present invention.

The pellets preferably take the form of sticks, preferably cylindrical, possessing, in particular, average sizes of 4 to 20 mm in length and 4 to 10 mm in diameter.

The pellets according to the invention possess the following features which make them useful for incorporation in animal feed for ruminants: 1/ They are miscible in all proportions with the - 10 granulated feeds generally distributed to animals as a supplement to the basic feed ration. That is to say, they can withstand without unmixing the different steps of handling to which granulated feeds are subjected, and become integrated in the feed distribution system. 2/ Loss of protection of the protected active principles is limited therein during shaping. 3/ They disintegrate rapidly in the rumen and, on mastication during rumination, avoid a loss of protection of the active principles included. The protected active principles can then continue their passage freely. 4/ Their capacity for miscibility with traditional granulated feeds depends essentially on the shape and density of the products produced, and presents no problems for those skilled in the art.

The extent of protection which characterizes the protected principles is equal to 100 minus the extent of release observed in vitro by measurement of the release of the active principles after 24 h in 1,000 ml of pH 6 buffer with stirring at 300 rpm at 40°C. The extent of release represents the percentage proportion of active principles released during the test. The size of the test sample is dependent on the nature of the active principle and its content. For the amino acids mentioned as examples, the test is carried out on approximately 6 g of equivalent.

The extent of protection should naturally be as high as possible. - 11 The disintegration of the pellets in the rumen, which permits release of the protected active principles, is assessed by incubation in the rumen of fistulated cattle by means of sachets made of nylon fabric with a mesh aperture of 350 microns. The disintegration time should be as short as possible, and especially less than 48 h.

The present invention will be now be illustrated further by the following Examples: EXAMPLES The protected active principles used for the examples are granules approximately 2 mm in diameter composed of: Type A protected active principle: Particles of lysine monohydrochloride and methionine in the proportion by weight 75:25, containing approximately 12 % of a binding agent consisting of a mixture of stearic acid containing 5 % w/w of 2vinylpyridine-co-styrene copolymer, protected against degradation in the rumen by a coating layer representing 16 % by weight of the protected product, this layer being composed of a mixture of 30 % of 2-vinylpyridine-co-styrene copolymer, 60 % of talc and 10 % of stearic acid.

The extent of protection of the type A granules is %.

Type B protected active principle: Particles of lysine monohydrochloride and - 12 methionine in the proportion by weight 75:25, containing approximately 12 % of a binding agent consisting of a mixture of stearic acid containing 5 % w/w of 2vinylpyridine-co-styrene copolymer, protected against degradation in the rumen by a coating layer representing 12 % by weight of the protected product, this layer being composed of a mixture of 20 % of 2-vinylpyridine-co-styrene copolymer and 80 % of stearic acid.

The extent of protection of the type B granules is %.

The type A and B products used for the feeding of ruminants are described in Patents US 4,181,708 and EP 260,186.

EXAMPLE-! % by weight of type A granules are introduced into a mixture of flours intended for the feeding of livestock, and made into the form of a granulated feed in a KAHL rotary die press after steam treatment in accordance with the traditional method of preparation of granulated feeds. The product obtained takes the form of extruded cylinders 5 mm in diameter and approximately 15 mm in length.

The residual extent of protection of the amino acids used for the example is 0 * in the granulated feed after passage through the press.

EXAMPLE .2 % of type B granules are introduced into a - 13 mixture of flours intended for the feeding of livestock, and made into the form of a granulated feed in a KAHL rotary die press after steam treatment in accordance with the traditional method of preparation of granulated feeds. The product obtained takes the form of extruded cylinders 5 mm in diameter and approximately 15 mm in length.

The residual extent of protection of the amino acids used for the example is 0 % in the granulated feed after passage through the press.

Examples 1 and 2 show that making this type of product into the form of a granulated feed by traditional methods leads to a substantial total degradation of their protection against degradation in the rumen, and consequently to loss of their efficacy for the feeding of ruminants.

EXAMPLE 3 Granules containing active principles protected against degradation in the rumen, and miscible in all proportions with the traditional granulated feed, are obtained in the following manner: Granules of type A protected active principle are introduced into the cavities of a mould. The cavities are frustoconical in shape, 20 mm in height and 8 mm and 10 mm in diameter at the ends.

A molten binding agent is injected under pressure into the porous structure of the particulate bed thus produced in each cavity. - 14 The finished product is recovered by releasing from the mould after solidification of the binding agent on cooling.

The binding agent used for the example possesses the following composition: stearic acid 33.33 % palmitic acid 22.22 % calcium carbonate 22.22 % fermentation residue 22.22 % (reference EUROLYSINE PL 73) The extent of protection and the amino acid titre in the final product are given in Table I.

EXAMPLE 4 Granules containing type A active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by the moulding technique described in Example 3, with the use of a molten binding agent composed of: stearic acid 30 % palmitic acid 20 % glyceryl monostearate 50 % The extent of protection and the amino acid titre in the final product are given in Table I.

EXAMPLE 5 Granules containing type A active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are - 15 obtained by the moulding technique described in Example 3, with the use of a molten binding agent composed of: stearic acid 16.67 % palmitic acid 11.11 % glyceryl monostearate 27.78 % calcium carbonate 44.44 % The extent of protection and the amino acid titre in the final product are given in Table I.

EXAMPLE 6 Granules containing type A active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by mixing type A granules with a binding agent composed of: plaster 22.73 % calcium carbonate 45.45 % water 31.82 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after drying in an oven.

The extent of protection and the amino acid titre in the final product are given in Table I.

EXAMPUL 2 Granules containing type A active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by mixing type A granules with a binding agent - 16 composed of: plaster 25.32 % microcrystalline cellulose 18.99 % water 55.70 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support, the particles being recovered after drying in an oven.

EXAMPLE 8 Granules containing type B active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by mixing type B granules with a binding agent composed of: plaster 29.41 % calcium carbonate 58.82 % water 41.18 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after drying in an oven.

EXAMPLE 9 Granules containing type B active principles protected against degradation in the rumen, miscible in all - 17 proportions with the traditional granulated feed, are obtained by mixing type B granules with a binding agent composed of: plaster 25.32 % microcrystalline cellulose 18.99 % water 55.57 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after drying in an oven.

EXAMPLE IQ Granules containing type A active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by mixing type A granules with a binding agent composed of: beet molasses 76.92 % calcium oxide 23.08 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after spontaneous curing.

EXAMPLE 11 Granules containing type A active principles protected against degradation in the rumen, miscible in all - 18 proportions with the traditional granulated feed, are obtained by mixing type A granules with a binding agent composed of: molasses 71.43 % gelatin 14.29 % water 14.29 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after gelling.

E_WffU 12 Granules containing type B active principles protected against degradation in the rumen, miscible in all proportions with the traditional granulated feed, are obtained by mixing type B granules with a binding agent composed of: molasses 71.43 % gelatin 14.29 % water 14.29 % The mixture is made into the form of particles measuring approximately 20 mm by 10 mm, by pouring onto a non-adhesive support and recovery after gelling.

Table I summarises the extent of protection observed for the protected active principles used in the - 19 examples, after making into the form of pellets according to the invention.

It also shows that the judicious choice of the composition of the binding agent enables the rate of disintegration of the said granules in the rumen to be adjusted.

It is understood that the method of making into the form of pellets by agglomeration in the presence of a binding agent, described in the present invention, may be applied to an extremely wide range of active principles protected against degradation in the rumen, by matching the physicochemical features of the binding agent to the nature of their protection. The pH of the binding agent, the temperature at which it is used and its compatibility or its solvent power with respect to the composition protecting the protected active principle in question should be taken especially into consideration.

EXAMPLE 13 Granules containing type B active principles protected against degradation in the rumen, miscible in all proportions with traditional granulated feed are obtained by mixing type B granules with a binding agent composed of: Clay 50% Soya Flour 12.5% Aqueous solution (4%) of CMC* 37.5% The mixture is made into the form of particles measuring approximately 8 mm in diameter by extrusion - 20 through a die. The extrudate thus obtained is dried in a ventilated oven and reduced to particles of about 20 mm in length.

The extent of protection and the protected amino acid titre in the final product are given in Table 2.

EXAMPLE 14 Granules containing type B active principles protected against degradation in the rumen, miscable in all proportions with traditional granulated feed are obtained by mixing granules of type B with a binding agent composed of: Dolomite 59.7% Soya Flour 14.9% Aqueous solution (4%) of CMC* 25.4% The mixture is made into the form of particles of about 8 mm in diameter in extrusion through a die. The extrudate thus obtained is dried in a ventilated oven and reduced to particles of about 20 mm in length.

Example No Level of B in agglomerated final product % by weight Extent of disintegration in the rumen after 6H 24H 48H % by weight Extent of protection of active principle in the final product % by weight 13 37.5 100 99 14 37.5 100 89 CMC: sodium salt of carboxymethylcellulose Η Η H mhoooomoui^u Example No. ra>>0303>>>>> Nature of the active principle protected oouiowwvouiuiw Level of A or B in the agglomerated final product % by weight Η Η Η H H o o o o o o o o o o Η H * OOO H HI-» Ο Η Ο Ο O O Ul O O O Extent of disintegration of the final product in the rumen after 6 h 24 h 48 h % by weight OOCOOVOOVOOOSOOO uaHUUl'fiO'WMU Extent of protection of the active principle in the final product % Characteristics of the products produced:

Claims

1. WE CLAIM:

1. Pellets comprising a granular active principle protected against degradation in the rumen and a soluble, crosslinkable or metable binding agent. 5

2. Pellets according to claim 1 which further comprise a disintegrating agent and/or a filler.

3. Pellets according to claim 1 or 2, in which the active principle is a vitamin, amino acid or drug.

4. Pellets according to claim l, 2 or 3 in 10 which the active principle is protected against degradation in the rumen by a pH-sensitive copolymer, a natural product or an enzymatically degradable product.

5. Pellets according to claim 4, in which the active principle is protected by a pH-sensitive 15 copolymer based on vinylpyridine and on styrene in combination with a hydrophobic substance.

6. Pellets according to claim 4, in which the active principle is protected by a natural product or an enzymatically degradable product selected from zein or 20 chitosan.

7. Pellets according to any one of the preceding claims, in which the protected active principle is in the form of granules of average diameter 0.3 to 5 mm.

8. Pellets according to any one of the 25 preceding claims which comprise a crosslinkable binding agent which is a hydrocolloid which is an alginate, xanthun gum, gelatin, cellulose derivative, other polysaccharide, - 24 molasses or vinasses.

9. Pellets according to any one of the preceding claims which comprise as a crosslinking agent an aldehyde and a crosslinkable binding agent which is a 5 protein or a salt or oxide of a di- or trivalent metal and a crosslinkable binding agent which is an alginate, xanthan gum, molasses or vinasses.

10. Pellets according to any one of the preceding claims which comprise a meltable binding agent 10 which is a fatty acid, fatty alcohol, glycerol ester, polyethylene glycol, paraffin wax, natural or synthetic wax or a hydrogenated animal or vegetable fat.

11. Pellets according to any one of the preceding claims in which the binding agent is molasses, 15 vinasses, a fatty acid, a hydrogenated vegetable or animal fat, plaster or a paraffin wax.

12. Pellets according to any one of claims 2 to 11 which comprises a disintegrating agent which is a grain flour, ground feed cake, brewery or fermentation 20 residue, cereal or wood by-product or cellulose fibres. - 25

13. Pellets according to claim 1 which are substantially hereinbefore described in any one of Examples 3 to 14.

14. A process for the preparation of pellets 5 as claimed in claim 1 which process comprises mixing granular active principle protected against degradation in the rumen, and a soluble, crosslinkable or meltable binding agent, and forming pellets from the mixture.

15. A process according to claim 11 in which 10 the pellets are formed by molding or by extruding the mixture at a temperature of less then 100°C and in the absence of steam.

16. A process according to claim 14 which is substantially as hereinbefore described in any one of 15 Examples 3 to 14.

17. Pellets according to any one of claims 1 to 13 when prepared by a process according to any one of claims 14 to 16.

18. An animal feed comprising, as a

19. 20 nutritional or medicinal supplement, pellets according to any one of claims 1 to 13 or 17.