EP3717615B1 - Compressed solid composition for non-oral use - Google Patents

Description

The present invention relates to a new binding and/or disintegrating agent for obtaining a compressed solid composition for non-oral use, as well as a process for preparing said compressed solid composition.

The compressed solid compositions can be in several forms, generally conditioned by the intended use in order to obtain particular properties and to ensure optimum hold. For certain applications, it is indeed important that a compressed solid composition has good integrity before use as well as the possibility of rapid disintegration during use, in particular in contact with a liquid. These properties are generally ensured by binding agents and/or disintegrating agents.

The use of binding agents makes it possible to bring the mechanical strength of the compressed solid compositions, also called agglomerates, to a level sufficient to avoid the problems of formation of fine particles during their handling or their implementation. The advantages of using a binding agent are generally observed for all known compression or agglomeration techniques such as, for example, pressure-compaction, pelletization, granulation, nodulization, extrusion or even atomization. As for them, the disintegrating agents allow the compressed solid compositions which contain them to disintegrate on contact with a liquid, and in particular on contact with water.

Finally, certain agents are qualified as binders and disintegrants because they make it possible to obtain a sufficient level of mechanical resistance in a dry environment while also offering the possibility of disintegration during contact with a liquid.

In general, many binders are known to those skilled in the art. Mention may be made, by way of example, of polyvinyl alcohols and their derivatives, celluloses and their derivatives, lignosulphonates, starches and their derivatives, alkali silicates, cement, clays and finally molasses by combining the latter with lime.

Polyvinyl alcohols and their derivatives, celluloses and their derivatives, starches and starches modified by physical and/or chemical means, have good binding properties and make it possible to obtain agglomerates which satisfy the requirements of agglomeration techniques but do not meet not necessarily to economic requirements. Indeed, the necessary doses of use do not generally make it possible to obtain agglomerates or compressed solid compositions under satisfactory economic conditions.

Lignosulphonates have the disadvantage of being aggressive due to their pH and their composition with respect to the agglomeration means used. In addition, during combustion or during steaming operations necessary during compression processes, lignosulphonates can lead to the release of harmful vapors rich in sulfuric acid. It follows that lignosulphonates are a non-negligible cause of atmospheric pollution and corrosion. As part of the development of greener products with a reduced environmental impact, lignosulfonates should therefore be avoided.

Clays are low cost products with binding properties but their field of application is restricted. In addition, it is often necessary to combine them with other binders. Mention may be made, by way of example, of starches and derivatives.

As for alkaline silicates, they are delicate to handle and their prolonged use requires frequent cleaning of the installations in which they are used.

The types of binding agents used in the compositions vary according to the final application. For example, in the field of tablets and solid compositions for detergent use, the binders used are generally synthetic binders.

For example, the document EP 1 048 716 discloses a laundry composition in the form of a tablet comprising in particular clay and a surfactant. The tablet is in the form of a compressed mass of particles held together by a binder having a dispersing effect on the clay that is less significant than polyethylene glycol 6000 (PEG 6000). Specifically, the binder is a chemical binder selected from polyethylene glycol having a molecular weight of less than 1500, amine oxide and polyvinylpyrrolidone.

The document WO 2005/068603 describes tablets with improved breaking strength as well as a process for making them. The method includes a step of providing a binder having a shear modulus value G of 10 to 100 GPa, a phase angle value δ of at least 7 degrees, and a boiling point of at least 45°C at atmospheric pressure. The method then comprises a step of heating the binder above its boiling point followed by a step of applying said heated binder to a powder comprising a premix of detergent compounds so as to form a detergent composition. The last step of the process consists in transforming the detergent composition into a tablet. The binder used is chosen from the group consisting of anionic surfactants, non-anionic surfactants, polymeric materials, polyols, saccharic acids, carbohydrate alcohols, sugar esters, fatty acids, acid esters fatty acids, fatty acid amines and mixtures thereof.

The document EP 0 467 739 proposes a process for the manufacture of agglomerates, using a binder system which provides good mechanical and chemical properties of resistance to the agglomerates as well as good properties suitable for the combustion of the agglomerates when it comes to fuels. The method according to D8 uses for the agglomeration by compression and heating of powders, granules, based on carbonaceous materials, in particular fuels such as coal, anthracite, coke, or based on ores or other minerals, a binder system comprising at least one binder chosen from molasses, and at least one molasses hardening catalyst chosen from organic or inorganic ammonium salts.

Besides the fact that they are generally of synthetic origin, another disadvantage of the binding agents available stems from their main advantage. Indeed, these agents make it possible to obtain aggregates by ensuring such cohesion that it is generally not possible to disintegrate them by contact with a liquid such as water.

Thus, there is a need to have new binding agents for the manufacture of compressed solid compositions for non-oral use, said binding agents being able to replace the synthetic binding agents conventionally used and also making it possible to act as disintegrating agents in contact with a liquid, especially water.

It is therefore to the credit of the Applicant to have found that this objective could be achieved surprisingly, and against all expectations, by means of fermented molasses, whereas the latter was until now considered as a fermentation residue n having the sole interest of being valued in the field of agriculture and animal husbandry as spreading fertilizer or animal feed.

A first object of the invention relates to a compressed solid composition for non-oral use comprising fermented molasses as binding and/or disintegrating agent, said fermented molasses having a viscosity of 500 to 5000 mPa.s

In general, molasses is a substance known to those skilled in the art. It is a by-product of the manufacture of sugar from beets and cane in sugar factories, or brown sugars in refineries. The process of manufacturing sugar, whether it is made from cane or beet, results after the crystallization stage in obtaining sugar on the one hand and molasses on the other. In general, it is commonly accepted that sugar processes generate around 35 to 40 kilos of molasses per tonne of beet and 30 to 35 kilos of molasses per tonne of cane. At the French national level alone, the annual production amounts to several tens of thousands of tons.

In terms of composition, the dry matter content of molasses varies little and is commonly between 70% and 76%. Molasses has very low, or even zero, crude cellulose and fat content.

As a co-product of sugar manufacturing, molasses contains significant amounts of sugars. The total sugar content is substantially the same, whatever the origin of the molasses, generally between 58% and 70% of the dry mass (DM), but presents some differences depending on the industrial process applied to beet molasses.

On the other hand, depending on the origin of the molasses, beet or cane, if the sugar content is similar, the composition of these total sugars is quite different. Thus, in beet molasses, almost all the sugars are in the form of sucrose, whereas in cane molasses, sucrose represents only about 2/3 of the total sugars, or 30% to 40% of the raw product.

Molasses is a very viscous substance which represents a disadvantage for its transport and storage. On the other hand, this high viscosity constitutes an advantage for animal feed and it is generally used to feed ruminants and horses, mixed with straw or other cellulosic foods such as bran, or as a binder in rations. complete, see again to promote the ingestion of unpalatable foods. Indeed, thanks to the presence of sugars, amino acids and salts, molasses constitutes a food whose flavor and smell stimulate the appetite and promote the digestion of animals.

As an alternative to animal feed, molasses is also used by manufacturers for the production of so-called “noble” products via fermentation processes. Indeed, through the fermentation mechanisms available to certain micro-organisms, molasses makes it possible to obtain baker's yeast, ethyl alcohol, citric and glutamic acids, lysine or even antibiotics, and also generates liquid fermentation residues which correspond to fermented molasses.

Until now, fermented molasses was considered as a fermentation residue with only the interest of being valued in the field of agriculture and animal husbandry as spreading fertilizer or animal feed. . Indeed, the chemical composition of fermented molasses, despite a depletion of compounds due to fermentation, still makes them attractive in ruminant feed as much for their energy intake as for their nitrogen value.

It is therefore to the Applicant's credit, by proposing a compressed solid composition for non-oral use comprising fermented molasses as a binding and/or disintegrating agent, to have brought to light a new way of recovering fermented molasses by thus going against what was conventionally implemented for their use.

For the purposes of the present invention, the term “compressed solid composition” means any composition that can be obtained by compression methods known to those skilled in the art, such as, for example, pressure-compaction, pelletization, granulation, nodulization, extrusion or atomization. The compressed solid composition according to the invention can therefore also be considered as an agglomerate.

The compressed solid composition according to the invention can be in a multitude of compressed forms, said forms being conventionally adapted by those skilled in the art depending on the desired application. Thus, the compressed solid composition can be in the form of a single-layer or multi-layer tablet, a roller, a tablet, a granule, a pellet or even a lozenge. Preferably, the compressed solid composition is in the form of a single-layer or multi-layer tablet.

By non-oral use, it is meant within the meaning of the present invention that the compressed solid composition is not intended to be ingested by an animal or a human being and therefore cannot in particular support its diet.

For the purposes of clarification, the terms “tablets”, “compressed”, “compacted” or even “agglomerated” are indeed considered to be synonyms within the meaning of the present invention and can be used interchangeably.

Fermented molasses is a co-product of molasses obtained after fermentation of the latter by bacteria, yeasts or fungi, said fermentation making it possible to obtain so-called "noble" products such as baker's yeast, ethyl alcohol or even molasses. citric and glutamic acid. Preferably, the fermented molasses is obtained via the fermentation of molasses by yeasts.

According to the invention, the fermented molasses can equally well be obtained from beet molasses, cane molasses, or from a mixture of beet molasses and cane molasses. For example, the mixture may contain up to 60% fermented beet molasses, up to 70% fermented beet molasses, up to 80% fermented beet molasses, up to 90% fermented beet molasses , or even up to 95% fermented beet molasses. Advantageously, when the fermented molasses is a mixture of fermented beet and cane molasses, said mixture contains 90% fermented beet molasses.

Initially, the fermented molasses contains more than 90% water but the latter is advantageously concentrated in order to reduce the quantity of water and to obtain higher levels of dry matter.

Thus, the dry matter content of the fermented molasses, or of the mixture of beet molasses and cane molasses according to the invention can be from 50% to 80%. Preferably, the dry matter content of the fermented molasses is from 55% to 75%, and very particularly from 55% to 65%, such as for example around 60%.

• azote des acides aminés totaux : 25 % à 50 % de l'azote total
• azote de bétaïne : 0 % à 40 % de l'azote total
• azote ammoniacal : 2 % à 3 % de l'azote total

Conventionally, since it is intended or was used as a fertilizer or in animal feed, fermented molasses is also defined by its distribution of nitrogenous materials and by its aminogram. The fermented molasses according to the invention can thus have a distribution of nitrogenous materials as follows:

• nitrogen of total amino acids: 25% to 50% of total nitrogen
• betaine nitrogen: 0% to 40% of total nitrogen
• ammoniacal nitrogen: 2% to 3% of total nitrogen

• Acide aspartique : 6 - 8
• Thréonine : 0,5 - 3
• Serine acide glutamique : 115 - 130
• Proline : 3 - 4
• Glycine : 4 - 5
• Alanine : 2,5 - 3,5
• Valine : 2,5 - 3,5
• Méthionine et cystéine : 0,5 - 3
• Isoleucine : 1,5 - 2,5
• Tyrosine : 2 - 3,5
• Leucine : 3 - 4,5
• Phénylalanine : 1 - 2
• Lysine : 0,5 - 2,5
• Histidine : 0,5 - 2
• Arginine : 0,2 - 1

Concerning the aminogram of the proteins of the fermented molasses according to the invention, the average amino acid contents may be as presented below, the ranges of the contents being given in g/kg of dry matter:

• Aspartic acid: 6 - 8
• Threonine: 0.5 - 3
• Serine glutamic acid: 115 - 130
• Proline: 3 - 4
• Glycine: 4 - 5
• Alanine: 2.5 - 3.5
• Value: 2.5 - 3.5
• Methionine and cysteine: 0.5 - 3
• Isoleucine: 1.5 - 2.5
• Tyrosine: 2 - 3.5
• Leucine: 3 - 4.5
• Phenylalanine: 1 - 2
• Lysine: 0.5 - 2.5
• Histidine: 0.5 - 2
• Arginine: 0.2 - 1

As a co-product of fermentation, fermented molasses has a low sugar content. By the expression “low sugar content”, is meant a fermented molasses comprising less than 5%, less than 4%, less than 3%, less than 2%, and very particularly, less than 1% by weight of sugars per relative to the total mass of the dry extract. Preferably, the fermented molasses according to the invention is free of sugars.

The fermented molasses according to the invention, also qualified as raw fermented molasses, can undergo one or more chemical or physico-chemical treatments. For example, fermented molasses can undergo depotassification or demineralization. Such treatments can modify the nitrogen content of the fermented molasses. A depotassification treatment consists for example of acidification of the raw fermented molasses with a solution of H ₂ SO ₄ , followed by neutralization with ammonia.

Treatments that can be applied to fermented molasses vary qualitatively and quantitatively the mineral content. Thus, a raw fermented molasses can have a raw ash content of 14% to 22% by weight relative to the raw product and a rate of potassium from 5% to 18% by weight relative to the crude product. On the other hand, in the case of depotassified or demineralized fermented molasses, the raw ash content varies from 5% to 14% by weight relative to the raw product and the potassium content is generally less than 4% by weight relative to the raw product. .

Due to a high ash content, raw fermented molasses has a density that can vary from 1.10 to 1.50. Preferably, the specific gravity of the fermented molasses is 1.20 to 1.40, and most preferably 1.25 to 1.35.

The fermented molasses according to the invention has a viscosity of 500 mPa.s to 5000 mPa.s, preferably of 1000 mPa.s to 4000 mPa.s, and a slightly acidic pH of 5 to 6.

The compressed solid composition in accordance with the invention thus comprises raw or demineralized fermented molasses as binding and/or disintegrating agent.

Said fermented molasses is present within the compressed solid composition in effective proportions. By effective proportions is meant those which are sufficient to obtain the desired effect, namely the obtaining of a compressed solid composition which can in particular be transported, handled and/or stored without substantial damage and which can disintegrate upon contact with a liquid such as water.

Advantageously, the quantities used of raw or demineralized fermented molasses within the compressed solid composition according to the invention can be from 0.1% to 15% by weight, preferably from 0.5% to 5% by weight, and even more preferably from 0.5% to 1.5% by weight relative to the total weight of the compressed solid composition.

The binding properties thus brought to light of the fermented molasses make it possible to obtain a compressed solid composition having sufficient mechanical strength in order to avoid the problems of formation of fine particles during their handling. Advantageously, the fermented molasses also acts as a disintegrating agent allowing the compressed solid composition to disintegrate on contact with a liquid, and in particular on contact with water.

By means of the compressed solid compositions according to the invention, the inventors have thus identified a new way of upgrading fermented molasses but also an alternative to the use of synthetic or non-conventional binding agents used to obtain the compositions solid. By way of example, mention will in particular be made of polyethylene glycol, polyvinylpyrrolidone, ethoxylated fatty alcohols, starch, hydroxyethylcellulose, gelatin or even microcrystalline cellulose.

Thus, the compressed solid composition comprising the fermented molasses according to the invention may be free of polyethylene glycol and/or polyvinylpyrrolidone and/or ethoxylated fatty alcohols and/or starch and/or hydroxyethylcellulose and/or gelatin and/or microcrystalline cellulose.

According to a particular embodiment, the fermented molasses can be adjuvanted in order in particular to present particular physical properties. Thus, the molasses can be adjuvanted with a compound chosen from the group comprising cellulose derivatives such as carboxymethylcellulose, hemicelluloses, lignins, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, derivatives starches such as wheat, maize, cassava, tapioca, potato, rice starch, dextrins and other modified starches, dextrans, sugar derivatives such as glucose, fructose, lactose, sucrose, sucrose, sorbitol, glycerol, natural gums such as diutan, gelan, xanthan, carrageenan, pectins, alginates, chitosan, gum arabic, tragacanth, carob, acacia, agar agar, guar, production by-products such as beet pulp, chicory pulp, dried or undried apple marc, sugar cane bagasse, citrus pulp, fruit juice waste, gum production waste, starch waste, derived from minerals, smectites, bentonites and other clays derived from silica, lime, magnesia and other of the same family as well as the mixture of several of these compounds. Preferably, the fermented molasses is adjuvanted with carboxymethylcellulose. The amounts of compounds for adjuvanting the fermented molasses can be comprised from 0.1% to 2%, preferentially from 0.1% to 1%, more preferably from 0.1% to 0.5%. The percentages being expressed in dry weight relative to the total dry weight of the fermented molasses with adjuvant.

The compressed solid composition may also include one or more additives. The additives can be chosen from additives known to those skilled in the art such as, for example, effervescent agents, detergent agents, sequestering agents, tableting additives, bleaching agents, polymers, surfactants, flow agents , stabilizing agents, anti-foaming agents, coloring agents or else lubricating agents.

As examples of stabilizers, there may be mentioned esters of parahydroxybenzoic acid such as methylparaben and propylparaben, alcohols such as chlorobutanol, benzyl alcohol and phenylethyl alcohol, phenols such as phenol and cresol, sulphite salts such as sodium bisulphite and sodium sulphite, salts of edetic acid such as sodium edetate and tetrasodium edetate, and hydrogenated oils, sesame, chondroitin-sodium sulfate, dibutylhydroxytoluene, adipic acid, ascorbic acid, stearic L-ascorbate esters, sodium L-ascorbate, L-aspartic acid, sodium L-aspartate, sodium acetyltryptophan, acetanilide, aprotinin solution, l aminoethylsulfonic acid, aminoacetic acid, DL-alanine, L-alanine, benzalkonium chloride, sorbic acid.

By way of example of lubricating agents, mention may be made of stearic acids such as stearic acid, calcium stearate and magnesium stearate, waxes such as white beeswax and carnauba wax, sulphates such as sodium sulfate, silicic acid compounds such as magnesium silicate and light silicic anhydride, lauryl sulfates such as sodium lauryl sulfate, cocoa butter, carmellose calcium, carmellose sodium, callopeptide, hydrated silicon dioxide, hydrated amorphous silicon oxide, dry aluminum hydroxide gel, glycerin, light liquid paraffin, hydrogenated oil, synthetic aluminum silicate, sesame, wheat starch, talc, macrogols, phosphoric acid.

As an example of a detergent agent, mention may be made of polyacrylates, acrylic/maleic copolymers, monomeric polycarbonates such as citrates, gluconates, oxydisuccinate, mono-di- and tri-succinate glycerols, carboxymethyloxysuccinates, carboxymethyloxymalonates, dipicolinates , and hydroxyethyliminodiacetates.

According to a particular embodiment, the compressed solid composition may also comprise at least one active ingredient, at least one filler and optionally at least one additive which may be chosen from effervescent agents, detergent agents, sequestering agents, tableting additives , bleaching agents, polymers, surfactants, flow agents, stabilizing agents, anti-foaming agents, coloring agents or else lubricating agents. According to this particular embodiment, the compressed solid composition can be in the form of a tablet and finds an application in the field of washing and/or household, agricultural and industrial cleaning. By way of example of household washing and/or cleaning, mention may be made of washing in a machine, such as in particular washing in a dishwasher.

According to a particular embodiment, the compressed solid composition for non-oral use according to the invention has a friability of between 5% and 15%, preferably between 5% and 11%, and most particularly between 6% and 8% .

According to a particular embodiment, the compressed solid composition for non-oral use according to the invention has a hardness of between 50 N and 90 N, preferably between 60 N and 80 N, and very particularly between 70 N and 75 N .

According to a particular embodiment, the compressed solid composition for non-oral use according to the invention has a dust level (dust area) of less than 3, preferably less than 2.5, and very particularly less than 2.

According to another particular embodiment, the compressed solid composition for non-oral use in accordance with the invention can be packaged in sachets in order to keep it protected from humidity and to provide additional protection for handling and /or transport and/or storage. Advantageously, the sachet is a biodegradable and/or water-soluble sachet.

According to another particular embodiment, the compressed solid composition comprising fermented molasses as binding and/or disintegrating agent is in the form of an effervescent toilet cleaning tablet, dishwasher tablets, calcium hypochlorite for swimming pools, granulated fertilizer.

As examples of compressed solid composition which may be in the form of multilayer tablets, and in particular of multilayer dishwasher tablets, mention will be made of the composition given in the table below:

Another object of the invention relates to the use of fermented molasses as a binding and/or disintegrating agent for the manufacture of a compressed solid composition for non-oral use.

Fermented molasses is as previously defined. The use of fermented molasses as a binding and/or disintegrating agent within a compressed solid composition is doubly advantageous. On the one hand, the use according to the invention makes it possible to propose a new way of upgrading molasses which was hitherto only intended for spreading or for animal feed. On the other hand, the use according to the invention allows the substitution of the synthetic binding agents conventionally used and thus to obtain compressed solid compositions that are more respectful of the environment.

The quantities of fermented molasses used within the compressed solid composition can be from 0.1% to 15% by weight, preferably from 0.5% to 5% by weight, and even more preferably from 0.5% to 1.5% by weight relative to the total weight of the compressed solid composition.

The compressed solid composition may be as defined above and may be in the form of a single-layer or multi-layer tablet, a pebble, a tablet, a granule, a pellet or even a tablet. Preferably, the compressed solid composition is in the form of a single-layer or multi-layer tablet.

Another object of the invention relates to a binding and/or disintegrating composition comprising at least fermented molasses as binding agent.

The fermented molasses in accordance with the invention can also be used as such within a binding and/or disintegrating composition containing one or more other constituents of any kind, including binding or capable, for example, to increase the mechanical strength of the final product, in particular an agglomerate, or to minimize the phenomena of crumbling which may be suffered by said agglomerate during its handling or its storage. Fermented molasses is as previously defined.

According to a particular embodiment, the binder composition according to the invention can also comprise a hardening agent, that is to say capable of further improving the binding power.

According to a particular embodiment, the fermented molasses can be adjuvanted in order in particular to present particular physical properties. Thus, the molasses can be adjuvanted with a compound chosen from the group comprising cellulose derivatives such as carboxymethylcellulose, lignins, hemicelluloses, ethyl cellulose, methyl cellulose, hydroxypropyl cellulose, hydroxypropyl methylcellulose, derivatives starches such as wheat, maize, cassava, tapioca, potato, rice starch, dextrins and other modified starches, dextrans, sugar derivatives such as glucose, fructose, lactose, sucrose, sucrose, sorbitol, glycerol, natural gums such as diutan, gelan, xanthan, carrageenan, pectins, alginates, chitosan, gum arabic, tragacanth, carob, acacia, agar agar, guar, production by-products such as beet pulp, chicory pulp, dried or undried apple marc, sugar cane bagasse, citrus pulp, fruit juice waste, gum production waste, starch waste, erives of minerals, smectites, bentonites and other clays derived from silica, lime, magnesia and other of the same family as well as the mixture of several of these compounds.

1. 1) fourniture d'une matière active, d'une charge et éventuellement d'au moins un additif choisi parmi les agents effervescents, les agents détergents, les agents séquestrants, les additifs de pastillages, agents de blanchiment, les polymères, les surfactants, les agents d'écoulement, les agents stabilisants, les agents anti-moussant, les agents colorants ou encore les agents lubrifiants.
2. 2) incorporation de mélasse fermentée aux composés fournis à l'étape précédente afin d'obtenir un mélange,
3. 3) compactage dudit mélange afin d'obtenir ladite composition solide comprimée.

Another object of the invention relates to a process for the manufacture of a compressed solid composition for non-oral use comprising the following steps:

1. 1) supply of an active ingredient, a filler and optionally at least one additive chosen from effervescent agents, detergent agents, sequestering agents, tablet additives, bleaching agents, polymers, surfactants, flow agents, stabilizers, anti-foaming agents, coloring agents or else lubricating agents.
2. 2) incorporation of fermented molasses to the compounds provided in the previous step in order to obtain a mixture,
3. 3) compacting said mixture in order to obtain said compressed solid composition.

The first step of the process therefore consists in providing an active ingredient, a filler and optionally at least one additive chosen from effervescent agents, detergent agents, sequestering agents, tablet additives, bleaching agents, polymers, surfactants, flow agents, stabilizers, anti-foaming agents, coloring agents or else lubricating agents. The active material and the filler are chosen by a person skilled in the art according to the application sought for the compressed solid composition.

The fermented molasses is then incorporated according to a second step to the compounds supplied according to the first step of the process so as to obtain a mixture. Fermented molasses is as defined above, namely in particular the co-product obtained by fermentation of molasses. The quantities of molasses to be incorporated according to this step can be comprised from 0.1% to 15% by weight, preferentially from 0.5% to 5% by weight, and even more preferentially from 0.5% to 1.5% by weight. weight relative to the total weight of the mixture.

The incorporation step can be carried out by techniques known to those skilled in the art which result in obtaining a mixture. Thus, the incorporation step can for example be obtained by spraying.

Finally, the third step of the process according to the invention consists of a compacting step which can be carried out according to the techniques known to those skilled in the art, resulting in the compression or the agglomeration of the mixture prepared in the previous step. Thus, the compacting step can for example be carried out by pressure-compaction on a rotary press, by pelletization, by granulation, by nodulization, by extrusion or even by atomization. By way of example, the step of compaction by pressure-compaction can be implemented by means of a rotary press. The compacting step thus makes it possible to obtain a compressed solid composition which can take several forms, such as for example a single-layer or multi-layer tablet, a pebble, a tablet, a granule, a pellet or a pellet.

The method according to the invention may also comprise a drying step after the incorporation and/or compacting step.

The invention will be better understood with the help of the examples which follow, which are intended to be purely illustrative and in no way limit the scope of the protection.

EXAMPLES

• Test de Friabilité : Ce test consiste à mesurer la perte de masse de la composition solide comprimée après rotations dans un tambour à 25 rotations/min pendant 2 minutes. Ce test est mis en œuvre par l'intermédiaire de la machine FT2 distribuée par SOTAX. La friabilité est déterminée selon la formule ci-dessous : $$\mathrm{F}\left(\%\right)=\left[\left(\mathrm{m}1-\mathrm{m}2\right)/\left(\mathrm{m}1\right)\right]\times 100$$
  
  dans laquelle ml correspond à la masse de la composition avant les rotations, et m2 à la masse de la composition après rotations.
• Délitement : Ce test consiste à mesurer le temps de désintégration de la composition solide comprimée dans un milieu liquide. Le test est mis en œuvre par un appareillage effectuant des mouvements de va-et-vient en pleine immersion. Pour ce faire, la composition solide comprimée est placée dans un panier et subit 60 va-et-vient par minute dans un bêcher rempli avec une eau chauffée à 30°C ± 1°C.
• Le premier va-et-vient correspond à T₀ et lorsqu'il n'y a plus de résidu de composition solide comprimée dans le panier, le temps écoulé depuis T₀ correspond au temps de délitement. La valeur du temps de délitement est donnée en minute, et correspond à la moyenne de 5 mesures.
• Dureté : La dureté est calculée par l'intermédiaire d'une machine de traction Synergie 100 (MTS) et du logiciel Test works 4 et correspond à la force nécessaire pour casser la composition solide comprimée. La dureté est exprimée en Newton (N) et correspond à la moyenne de 5 mesures.
• Taux de poussière : La mesure est réalisée par l'intermédiaire de la machine DustMon L et du logiciel DustMon L software selon les recommandations du fabriquant. La mesure consiste à évaluer la concentration de poussière d'une masse de composition solide comprimée lors de sa chute au moment de son passage devant un faisceau laser. La valeur est donnée en aire de poussière (en anglais « dust area »).
• Taux de matières sèches : Méthode de Karl Fisher

In the following examples, the mechanical properties were measured with the following methods:

• Friability test: This test consists in measuring the loss of mass of the solid composition compressed after rotations in a drum at 25 rotations/min for 2 minutes. This test is implemented through the FT2 machine distributed by SOTAX. The friability is determined according to the formula below: $$\mathrm{F}\left(\%\right)=\left[\left(\mathrm{m}1-\mathrm{m}2\right)/\left(\mathrm{m}1\right)\right]\times 100$$
  
  in which ml corresponds to the mass of the composition before the rotations, and m2 to the mass of the composition after the rotations.
• Disintegration: This test consists of measuring the disintegration time of the solid composition compressed in a liquid medium. The test is implemented by an apparatus carrying out back and forth movements in full immersion. To do this, the compressed solid composition is placed in a basket and undergoes 60 back and forth motions per minute in a beaker filled with water heated to 30°C ± 1°C.
• The first back and forth corresponds to T ₀ and when there is no longer any residue of compressed solid composition in the basket, the time elapsed since T ₀ corresponds to the disintegration time. The value of the disintegration time is given in minutes, and corresponds to the average of 5 measurements.
• Hardness: The hardness is calculated using a Synergie 100 tensile machine (MTS) and the Test Works 4 software and corresponds to the force required to break the compressed solid composition. Hardness is expressed in Newtons (N) and corresponds to the average of 5 measurements.
• Dust rate: The measurement is carried out using the DustMon L machine and the DustMon L software according to the manufacturer's recommendations. The measurement consists of evaluating the dust concentration of a mass of solid composition compressed during its fall as it passes in front of a laser beam. The value is given in dust area.
• Dry matter content: Karl Fisher method

EXAMPLE 1: Preparation of a compressed solid composition for non-oral use comprising fermented molasses as binding and/or disintegrating agent.

For this example, the compressed solid composition is in the form of a multilayer tablet composed of a first layer, an intermediate layer and a third layer.

A mixture of fermented beet and cane molasses is used. The mixture contains approximately 90% fermented beet molasses and approximately 10% fermented cane molasses. Fermented molasses has a dry matter content of 60%. This fermented molasses is then added with carboxymethylcellulose in an amount (sec/sec) of 0.2%.

The adjuvanted fermented molasses is mixed in an amount (dry/dry) with other compounds to obtain the first and third layer of the tablet. The compositions of all the layers of the tablet are listed below:

Each composition is then compacted one on top of the other by means of a rotary press so as to obtain a solid composition compressed in the form of a multilayer tablet.

The mechanical properties of said tablet were measured according to the protocols described above and the results are presented in Table 1 below: TABLE 1 Multi-layer tablet Friability (%) 7.1 Disintegration (min) 10 Hardness (N) 71 Dust rate 1.7

The compressed solid composition according to the invention has good mechanical properties and can thus be easily handled and transported without breaking or generating large amounts of fines. It also has a disintegration time compatible with applications in the field of cleaning for which disintegration times of less than 12 min (on the basis of the protocol described above) are generally sought.

COMPARATIVE EXAMPLE 1: Preparation of a compressed solid composition for non-oral use comprising polyethylene glycol (PEG) as binding and/or disintegrating agent.

In order to compare the properties obtained and to demonstrate the advantage of compressed solid compositions comprising fermented molasses as binding and/or disintegrating agent, a second multilayer tablet was prepared.

Polyethylene glycol is mixed in an amount (dry/dry) with other compounds to obtain the first and third layer of the tablet. The compositions of all the layers of the tablet are listed below:

Each composition is then compacted according to the same protocol as Example 1 by means of a rotary press so as to obtain a solid composition compressed in the form of a multilayer tablet.

The mechanical properties of said tablet were measured according to the same protocols as Example 1 and the results are presented in Table 2 below: TABLE 2 Comparative Multi-Layer Tablet Friability (%) 3 Disintegration (min) 8 Hardness (N) 75 Dust rate 2

The mechanical properties obtained with so-called “conventional” compressed solid compositions based on PEG are thus comparable with the compressed solid compositions according to the invention based on fermented molasses as binding and/or disintegrating agent.

Thus, as this comparison demonstrates, the use of fermented molasses according to the invention as a binder and/or disintegrant also happens to be a good alternative to the chemical binders conventionally used while allowing a new way of upgrading a product. hitherto only intended for spreading or animal feed.

EXAMPLE 2 Demonstration of the binding effect of fermented molasses according to the invention.

The objective of this example is to demonstrate the good binding properties of the fermented molasses according to the invention.

A- Products used:

• Carbon black: ^ENSACO® (Imerys company); Particle size: Dv10 = 3.15 µm Dv50 = 11.8 µm; Dv90 = 33.7 µm.
• Binder solution 1: fermented cane molasses with a dry matter content of 60%.
• Binder solution 2: mixture containing 90% fermented beet molasses, 10% fermented cane molasses and having a dry matter content of 60%.
• Binder solution 3 (control): Bretax C (lignosulfonate, Burgo Company). Bretax C is a known binder on the market.

Each of the binder solutions is used to be sprayed on the carbon black and allow its granulation.

B- Dry granulation

The carbon black is placed in the tank (5L) of the pilot shear mixer within which the stirring member is set in rotation.

For each binder solution, a mass quantity of 5% by weight relative to the weight of the carbon black is sprayed inside the tank using a bi-fluid nozzle so as to allow the granulation of the carbon black.

• Vitesse linéaire: 14,1 m/s,
• Débit de pulvérisation : 5 g/min,
• Pression puisée : 0,1 bar.

The pilot mixer parameters are as follows:

• Linear speed: 14.1 m/s,
• Spray rate: 5 g/min,
• Pulsed pressure: 0.1 bar.

The various tests carried out are listed in Table 3 below: TABLE 3 Trials Mass of black carbon (g) Binder solution sprayed Mass of solution sprayed (g) Mixing time (s) 1 300 Binder solution 1 15.8 282 2 300 Binder solution 2 15.8 280 3 300 Binder solution 3 15.8 252

C- Particle size analysis:

For each of the tests, the carbon black granules obtained were analyzed by laser granulometry in order to analyze the effect of each binder solution.

• Mastersizer 3000 (Société Malvern)
• Accessoire Aero S.

Device used for measurement:

• Mastersizer 3000 (Malvern Company)
• Aero S accessory.

• Voie sèche,
• Pression : 0,5 bars,
• Temps de mesure du blanc : 30 secondes,
• Temps de mesure : 60 secondes.

Operational Parameters:

• Dry way,
• Pressure: 0.5 bar,
• Blank measurement time: 30 seconds,
• Measurement time: 60 seconds.

D - Results of particle size analyses:

TABLE 4 Particle size parameter Dv10 (µm) Dv50 (µm) Dv90 (µm) Raw ENSACO ^® carbon black 3.15 11.8 33.7 Trial 1 3.87 15.5 44.9 Trial 2 4.03 16.3 71.8 Trial 3 3.73 15.5 43.2

In comparison with a binder control solution, the results demonstrate that the fermented molasses according to the invention makes it possible to obtain a binding effect on the carbon black which is just as effective (test 1 vs. test 3), or even more effective (test 2 vs. test 3).

This example thus demonstrates the very good binding properties of the fermented molasses according to the invention and the fact that the latter can be advantageously used in compressed solid compositions as a binding agent.

EXAMPLE 3 Demonstration of the binding and disintegrating effect of fermented molasses according to the invention.

Fermented molasses is used in this example to granulate fermented cane molasses powder. The products used are listed below:

A - Products used:

• Fermented cane molasses powder with a dry matter content of 97%.
• Fermented molasses 1: fermented cane molasses with a dry matter content of 60%.
• Fermented molasses 2: mixture of fermented beet and cane molasses. The mixture contains approximately 90% fermented beet molasses and approximately 10% fermented cane molasses. Fermented molasses has a dry matter content of 60%. This fermented molasses is then added with carboxymethylcellulose in an amount (sec/sec) of 0.2%.

Fermented molasses 1 and 2 are used as a binding and/or disintegrating composition on fermented cane molasses powder. The fermented molasses are implemented in order to granulate the powder and thus obtain compressed solid compositions. The granules obtained were then analyzed.

B - Particle size analysis:

Apparatus used for laser particle size measurement: Mastersizer 3000 (Malvern Company) as above.

• Dv10= 18,1 µm,
• Dv50 = 77,5 µm,
• Dv90 = 234 µm,
• largeur de distribution (span) = 2,788.

Fermented cane molasses powder has been analyzed by laser granulometry and has the characteristics below:

• Dv10= 18.1 µm,
• Dv50 = 77.5 µm,
• Dv90 = 234 µm,
• distribution width (span) = 2.788.

C - Tests carried out Trial 1:

For this test, the granulation is carried out on a wet granulator (model VG-25, GLATT Company) and according to the conditions below: TABLE 5 Compressed air pressure (bar) 1.5 Masterflex L/S pump setting Hose 18 4mL/min Mixer (rpm) 500 Crusher (rpm) 1000 Double jacket cryostat °C 15

1501.4 g of fermented cane molasses powder is placed within the granulator. The granulation is then carried out with 10% by weight of a liquid solution of molasses 1 relative to the weight of powder. The amount of powdered solution is 150 g and the ratio of powdered molasses 1 liquid solution/raw cane fermented molasses powder is 10%.

Analysis of the granules obtained:

• Dv10 = 62,4 µm,
• Dv50= 166 µm,
• Dv90 = 629 µm,
• largeur de distribution (span) = 3,442.

The granules obtained were analyzed under the same conditions as the fermented cane molasses powder and have the characteristics below:

• Dv10 = 62.4 µm,
• Dv50= 166 µm,
• Dv90 = 629 µm,
• distribution width (span) = 3.442.

In comparison with the powder, these particle size values that the fermented molasses has a binding effect and makes it possible to obtain solid compositions compressed in the form of granules.

Trial 2:

For this test, the granulator is the same as that of test 1 and the operating conditions are the same with the exception of the setting of the mixer which is set to 600 U/min.

1500 g of fermented cane molasses powder is placed in the granulator and the granulation is carried out with 5% of a liquid solution of molasses 2. The quantity of sprayed solution is 75 g and the ratio of sprayed solution/powder of raw cane molasses is 5%.

Analysis of the granules obtained :

• Dv10 = 55,4 µm,
• Dv50 = 127 µm,
• Dv90 = 305 µm,
• largeur de distribution (span) = 1,965.

The granules obtained were analyzed under the same conditions as fermented cane molasses powder and has the characteristics below:

• Dv10 = 55.4 µm,
• Dv50 = 127 µm,
• Dv90 = 305 µm,
• distribution width (span) = 1.965.

In comparison with the powder, these particle size values that the fermented molasses has a binding effect and makes it possible to obtain solid compositions compressed in the form of granules. The distribution width is here less than the powder, reflecting a more centered distribution of the particle size of the granules.

B - Wettability test

• Disposer 100 mL d'eau distillée à 20°C dans un bêcher de 400 mL,
• Prendre 10 g de l'échantillon et le déposer à la surface de l'eau tout en lançant le chronomètre,
• Arrêter le chronomètre lorsque l'échantillon est entièrement mouillé.

The wettability of the granules obtained in tests 1 and 2 is compared with that of fermented cane molasses powder according to the following protocol:

• Place 100 mL of distilled water at 20°C in a 400 mL beaker,
• Take 10 g of the sample and place it on the surface of the water while starting the stopwatch,
• Stop the stopwatch when the sample is completely wet.

The results are shown below in Table 6: TABLE 6 Duration (s) Fermented cane molasses powder 115 Granules of trial 1 8 Trial 2 pellets 5

The duration here expresses the time necessary for the different samples to reach the passage of the air/water interface.

The results show that the granules obtained exhibit a significant decrease in wettability. The fermented molasses according to the invention makes it possible to improve this parameter and thus to demonstrate the good binding properties.

C - Disintegration test

• Prélever 10g de l'échantillon à tester et le tamiser de manière à récupérer la fraction tamisée 180-125 µm.
• Prendre le tamis comprenant la fraction tamisée 180-125 µm et le disposer au-dessus d'un bécher de 2 L,
• Ajouter de 400 mL d'eau distillée à 20°C afin que le tamis trempe à la surface,
• Agiter à environ 300 tours/min.

The disintegration test is carried out on the granules obtained in the previous tests 1 and 2 in order to highlight the disintegrating effect of the fermented molasses. The test is carried out according to the following protocol:

• Take 10g of the sample to be tested and sieve it so as to recover the 180-125 µm sieved fraction.
• Take the sieve comprising the 180-125 µm sieved fraction and place it above a 2 L beaker,
• Add 400 mL of distilled water at 20°C so that the sieve soaks on the surface,
• Shake at about 300 rpm.

The evolution of the weight of the whole is monitored over time from the addition of the first mL of distilled water. This makes it possible to translate the reduction in the weight of the sample as a function of time.

The results are presented in Table 7 below: TABLE 7 Time(s) Fermented cane molasses powder Granules of trial 1 Trial 2 pellets 10 3.1 1.4 20 2.7 30 -0.5 1.2 50 0.3 60 -5.2 -1.7 -1.2 90 -8.4 -2.2 -3.1 120 -9.2 -2.9 -5.8 150 -10.5 -4.5 -6.7 180 -10.6 -5.2 -7.4 210 End of test (0g) -5.9 -8.2 270 -6.6 -9.2 330 -7.4 End of test (0g) 390 -7.9 450 -8.5 510 End of test (0g)

The positive values at the start of the test reflect the water absorption of the granules. Over time, the results show that under the action of water the granules obtained from the fermented molasses according to the invention can completely disintegrate, thus demonstrating the disintegrating effect of said fermented molasses.

In conclusion, this example thus demonstrates the binding and disintegrating properties of the fermented molasses according to the invention. Indeed, its implementation makes it possible to obtain solid compositions compressed in the form of granules, said granules then being able to disintegrate under the action of water.

Claims (16)

1. Compressed solid composition for non-oral use characterised in that it comprises fermented molasses as binder and/or disintegrating agent, said fermented molasses having a viscosity of 500 to 5000 mPa.s.
2. Compressed solid composition for non-oral use according to claim 1, characterised in that the fermented molasses is obtained by fermentation of beet molasses, cane molasses or a mixture of beet and cane molasses.
3. Compressed solid composition for non-oral use according to claims 1 or 2, characterised in that the fermented molasses has a dry matter content between 50% and 80%.
4. Compressed solid composition for non-oral use according to one of claims 1 to 3, characterised in that the fermented molasses comprises less than 5%, and preferably less than 1% by weight sugars relative to the total mass of the dry extract.
5. Compressed solid composition for non-oral use according to one of claims 1 to 4, characterised in that the fermented molasses is adjuvanted with carboxymethylcellulose.
6. Compressed solid composition for non-oral use according to claim 5, characterised in that the quantity (dry/dry) of carboxymethylcellulose is 0.1% to 2%, preferably 0.1% to 1%, more preferably 0.1% to 0.5%.
7. Compressed solid composition for non-oral use according to one of claims 1 to 6, characterised in that it comprises an active substance, a filler and optionally at least one additive chosen from effervescent agents, detergent agents, sequestering agents, tablet additives, bleaching agents, polymers, surfactants, flow agents, stabilisers, anti-foaming agents, colouring agents and lubricants.
8. Compressed solid composition for non-oral use according to one of claims 1 to 7, characterised in that it is in the form of a single-layer or multilayer tablet, a lozenge, a pill, a granule, a pellet or a pastille.
9. Compressed solid composition for non-oral use according to one of claims 1 to 8, characterised in that it is devoid of polyethylene glycol and/or microcrystalline cellulose and/or polyvinylpyrrolidone and/or starch, and/or hydroxyethylcellulose and/or gelatin.
10. Use of a compressed solid composition for non-oral use according to one of claims 1 to 9, for washing in a dishwasher.
11. Use of fermented molasses as a binder and/or disintegrating agent for manufacturing a compressed solid composition for non-oral use.
12. Use according to claim 11, characterised in that the fermented molasses is present in the compressed solid composition for non-oral use in a quantity by weight of 0.1% to 15% relative to the total weight of the composition.
13. Binder and/or disintegrating agent characterised in that it comprises at least fermented molasses as binder, said fermented molasses having a viscosity of 500 to 5000 mPa.s.
14. Method for manufacturing a compressed solid composition for non-oral use comprising the following steps:

    - providing an active substance, a filler and optionally at least one additive chosen from effervescent agents, detergent agents, sequestering agents, tablet additives, bleaching agents, polymers, surfactants, flow agents, stabilisers, anti-foaming agents, colouring agents or lubricants.

    - incorporating fermented molasses with the compounds provided in the preceding step in order to obtain a mixture,

    - compacting the mixture in order to obtain said compressed solid composition.
15. Manufacturing method according to claim 14, characterised in that the incorporation is carried out by spraying.
16. Manufacturing method according to claim 14 or 15, characterised in that the compacting step is carried out on a rotary press.