EP1019474B1 - Process for preparation of a system containing a non-ionic surfactant and an alkali metal silicate - Google Patents

Abstract

A system in the form of an aqueous dispersion or granules containing at least one liquid, waxy or pasty non-ionic surfactant and an alkali metal silicate. The system is prepared using a concentrated aqueous alkali metal silicate solution as the continuous liquid phase optionally containing glycerol, in which is dispersed at least one liquid, pasty or waxy non-ionic surfactant that is non-miscible or poorly compatible with said concentrated alkali metal silicate solution, and at least one non-ionic or anionic surfactant that is compatible with said concentrated alkali metal silicate solution and capable of causing the dispersion of said liquid, pasty or waxy non-ionic surfactant(s) in said concentrated alkali metal silicate solution. The resulting dispersion is optionally dried to produce a rigid alkali metal silicate shell encapsulating droplets or particles of the liquid, pasty or waxy non-ionic surfactant(s). The system may optionally further contain at least one other detergent builder and may be used as a component of a detergent composition, particularly for use in washing machines, or as the detergent composition itself.

Description

The subject of the present invention is a process for the preparation of a system based on at least one liquid, waxy or pasty nonionic surfactant and on an alkali metal silicate, said system being in the form of a dispersion stable aqueous or granular. This system can be used as a liquid or powder detergent composition or as a constituent of liquid or powder detergent compositions.

It is known to transform organic materials, in particular surfactants, liquids under normal temperature and pressure conditions, into pulverulent products by adsorption and / or absorption on a solid support, generally a more or less porous mineral.
The two-component product obtained has the drawback of being only very little concentrated in organic matter, the support taking up considerable space.
This is due to the fact that the support products are not very porous and therefore not very adsorbent.
Thus, the two-component mixtures of nonionic surfactants / sodium carbonate, nonionic surfactants / sodium sulfate or nonionic surfactants / powdered sodium silicate contain at best 30% of their weight of organic matter considered.

The use of more porous supports such as precipitation silicas, clays, sodium silicoaluminates, magnesium or calcium silicates, crystalline or amorphous aluminosilicates such as zeolites, makes it possible to obtain more concentrated mixtures of organic matter. , which can contain up to 65% of their weight of organic matter.
However, these supports have the disadvantage of being insoluble in water, which can cause problems in the intended use.

Another solution consists in using a crosslinked absorbent organic polymer (absorbent crosslinked polyacrylate, etc.) or a hydrocolloid (starch, guar, etc.); it is however more expensive and can also have drawbacks in terms of denaturing interactions between the support and the organic matter.

The Applicant has found a means for preparing stable dispersions of nonionic surfactants, the continuous phase of which consists of a concentrated aqueous solution of alkali metal silicate and the dispersed phase of droplets or particles of non-ionic surfactant. -liquid, waxy or pasty ionics, dispersions which, by simple drying, transform into granules by encapsulation of droplets or particles of nonionic surfactant in a rigid shell of alkali metal silicate.
This placing in solid form has the advantage of leading to a soluble product, of easy availability, stable in storage, which can contain high contents of nonionic surfactant and which can ensure a controlled release of said surfactant.

The system formed by the nonionic surfactant and the alkali metal silicate, whether in the form of an aqueous dispersion or of granules, has detergent and detergency builder properties, which give it the capacity to be used as a constituent of liquid or solid detergent compositions, household or industrial, in particular for washing machines.

• mise en dispersion
  • . dans une solution aqueuse concentrée d'un silicate de métal alcalin présentant un rapport molaire SiO₂ / M₂O allant de 1,5 à 4, comme phase liquide continue,
  • . d'au moins un agent tensioactif non-ionique (NIA) liquide, pâteux ou cireux non miscible ou faiblement miscible avec ladite solution aqueuse concentrée de silicate de métal alcalin,
  • . à l'aide d'au moins un agent tensioactif non-ionique ou anionique (TAS) compatible avec ladite solution concentrée de silicate de métal alcalin et susceptible de mettre en dispersion le ou les agent(s) tensioactif(s) non-ionique(s) liquide(s), pâteux ou cireux (NIA) dans ladite solution concentrée de silicate de métal alcalin,
• et éventuellement séchage de la dispersion formée, jusqu'à l'obtention d'une coquille rigide de silicate de métal alcalin encapsulant lesdites gouttelettes ou particules d'agent(s) tensioactif(s) non-ionique(s) liquides, pâteux ou cireux (NIA).

According to the invention, it is a process for the preparation of a system, in the form of an aqueous dispersion or of granules, based on at least one liquid, waxy or pasty nonionic surfactant and d '' an alkali metal silicate, by

• dispersal
  • . in a concentrated aqueous solution of an alkali metal silicate having a SiO ₂ / M ₂ O molar ratio ranging from 1.5 to 4, as a continuous liquid phase,
  • . at least one nonionic surfactant (NIA) liquid, pasty or waxy immiscible or slightly miscible with said concentrated aqueous solution of alkali metal silicate,
  • . using at least one nonionic or anionic surfactant (TAS) compatible with said concentrated solution of alkali metal silicate and capable of dispersing the nonionic surfactant (s) ( s) liquid (s), pasty or waxy (NIA) in said concentrated solution of alkali metal silicate,
• and optionally drying the dispersion formed, until a rigid shell of alkali metal silicate encapsulating said droplets or particles of liquid, pasty or waxy non-ionic surfactant (s) is obtained. (NIA).

The term “nonionic surfactant (NIA) liquid, pasty or waxy immiscible or slightly miscible with an aqueous solution of alkali metal silicate is understood to mean any nonionic surfactant in its liquid, pasty or waxy form as it is. normal conditions of temperature and pressure (generally temperature of the order of -10 to 45 ° C and pressure of the order of 0.8 to 1.2 bar) and not likely to dissolve, to hydrate (by solvation of the hydrophilic part) or hydrolyze to more than 10% of its weight in said concentrated silicate solution.

• les alkylphénols polyoxyalkylénés (polyéthoxyéthylénés, polyoxypropylénés, polyoxybutylénés) dont le substituant alkyle est en C₆-C₁₂ et contenant de 5 à 25 motifs oxyalkylènes ; à titre d'exemple, on peut citer les TRITON X-45, X-114, X-100 ou X-102 commercialisés par Rohm & Haas Cy, les IGEPAL NP2 à NP17 de RHONE-POULENG ;
• les alcools aliphatiques en C₈-C₂₂ polyoxyalkylénés contenant de 1 à 25 motifs oxyalkylènes (oxyéthylène, oxypropylène) ; à titre d'exemple, on peut citer les TERGITOL 15-S-9, TERGITOL 24-L-6 NMW commercialisés par Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 commercialisés par Shell Chemical Cy., KYRO EOB commercialisé par The Procter & Gamble Cy, les SYNPERONIC A3 à A9 de ICI, les RHODASURF IT, DB et B de RHONE-POULENC ;
• les hydrocarbures terpéniques alcoxylés tels que les α- ou β- pinènes éthoxylés et/ou propoxylés, contenant de 1 à 30 motifs oxyéthylène et/ou oxypropylène ;
• les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec le propylène glycol, l'éthylène glycol, de masse moléculaire en poids de l'ordre de 2000 à 10000, tels les PLURONIC commercialisés par BASF ;
• les produits résultant de la condensation de l'oxyde d'éthylène ou de l'oxyde de propylène avec l'éthylènediamine, tels les TETRONIC commercialisés par BASF ;
• les acides gras éthoxylés et/ou propoxylés en C₈-C₁₈ contenant de 5 à 25 motifs éthoxylés et/ou propoxylés ;
• les amides gras éthoxylés contenant de 5 à 30 motifs ;
• les amines éthoxylées contenant de 5 à 30 motifs éthoxylés ;
• les amidoamines alcoxylées contenant de 1 à 50, de préférence de 1 à 25, tout particulièrement de 2 à 20 motifs oxyalkylène (oxyéthylène de préférence) ;

Among the nonionic surfactants (NIA) which are liquid, pasty or waxy, there may be mentioned in particular alkoxylated nonionic surfactants.
Mention may in particular be made of those usually used in the field of detergents for washing clothes, such as

• polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C ₆ -C ₁₂ and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy, the IGEPAL NP2 to NP17 from RHONE-POULENG;
• polyoxyalkylenated C ₈ -C ₂₂ aliphatic alcohols containing from 1 to 25 oxyalkylene units (oxyethylene, oxypropylene); by way of example, mention may be made of TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical Cy., KYRO EOB marketed by The Procter & Gamble Cy, SYNPERONIC A3 to A9 from ICI, RHODASURF IT, DB and B from RHONE-POULENC;
• alkoxylated terpene hydrocarbons such as ethoxylated and / or propoxylated α- or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units;
• the products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, of molecular weight by weight of the order of 2000 to 10000, such as the Pluronic sold by BASF ;
• products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as TETRONIC sold by BASF;
• C ₈ -C ₁₈ ethoxylated and / or propoxylated fatty acids containing from 5 to 25 ethoxylated and / or propoxylated units;
• ethoxylated fatty amides containing from 5 to 30 units;
• ethoxylated amines containing from 5 to 30 ethoxylated units;
• alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20 oxyalkylene units (preferably oxyethylene);

Among the concentrated solutions of alkali metal silicate, there may be mentioned aqueous solutions of alkali metal silicate with a SiO ₂ / M ₂ O molar ratio which can range from 1.5 to 4, preferably from 2 to 3.5 and containing on the order of 35 to 50% of active material, M representing sodium or potassium; Mention may very particularly be made of commercial solutions of sodium silicate with a ratio of around 2 containing around 45 to 50% of active material, as well as those of sodium silicate with a ratio of around 3 containing of the order of 35 to 40% of active material. The small amounts of free water present in these concentrated silicate solutions are not sufficient to dissolve, hydrate (solvate) or hydrolyze the non-ionic surfactant (s) (NIA).

The operation of dispersing the surfactant (s) (NIA) in the said concentrated solution of alkali metal silicate can be carried out using any nonionic or anionic surfactant compatible with the concentrated solution of alkali metal silicate, that is to say capable of dissolving or of hydrating (solvating) giving a homogeneous isotropic phase with the concentrated solution of alkali metal silicate. This operation can be carried out in particular using at least one nonionic or anionic surfactant (TAS), the hydrophilic part of which contains one or more saccharide unit (s).
Said saccharide units generally contain from 5 to 6 carbon atoms. These can be derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, lyxose and / or ribose.

• les alkylpolyglycosides pouvant être obtenus par condensation (par exemple par catalyse acide) du glucose avec des alcools gras primaires (US-A-3 598 865 ; US-A-4 565 647 ; EP-A-132 043 ; EP-A-132 046 ...) présentant un groupe alkyle en C₄-C₂₀, de préférence en C₈-C₁₈, ainsi qu'un nombre moyen de motifs glucose de l'ordre 0,5 à 3, de préférence de l'ordre de 1,1 à 1,8 par mole d'alkylpolyglycoside (APG) ; on peut mentionner notamment ceux présentant
  • . un groupe alkyle en C₈-C₁₄ et en moyenne 1,4 motif glucose par mole
  • . un groupe alkyle en C₁₂-C₁₄ et en moyenne 1,4 motif glucose par mole
  • . un groupe alkyle en C₈-C₁₄ et en moyenne 1,5 motif glucose par mole
  • . un groupe alkyle en C₈-C₁₀ et en moyenne 1,6 motif glucose par mole commercialisés respectivement sous les dénominations GLUCOPON 600 EC®, GLUCOPON 600 CSUP®, GLUCOPON 650 EC®, GLUCOPON 225 CSUP®, par HENKEL;
• les dérivés des acides galacturonique, glucuronique, D-mannuronique, L-iduronique et guluronique présentant une chaîne hydrocarbonée comportant de 6 à 24 atomes de carbone, de préférence de 8 à 16 atomes de carbone, ainsi que leurs sels de métal alcalin (EP-A-532 370) ;
• les glucosamides tel que le lauryl-N-méthylglucosamide ;
• les sophorolipides, tels que ceux sous forme acide ou lactone, dérivés de l'acide 17-hydroxyoctadécénique ;

Among the nonionic or anionic surfactants (TAS) whose hydrophilic part has a saccharide structure containing from 5 to 6 carbon atoms, one can mention:

• alkylpolyglycosides obtainable by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-132,043; EP-A-132 046 ...) having a C ₄ -C ₂₀ , preferably C ₈ -C ₁₈ alkyl group, as well as an average number of glucose units of the order of 0.5 to 3, preferably of the order 1.1 to 1.8 per mole of alkylpolyglycoside (APG); we can mention in particular those presenting
  • . a C ₈ -C ₁₄ alkyl group and on average 1.4 glucose units per mole
  • . a C ₁₂ -C ₁₄ alkyl group and on average 1.4 glucose units per mole
  • . a C ₈ -C ₁₄ alkyl group and on average 1.5 glucose units per mole
  • . a C ₈ -C ₁₀ alkyl group and on average 1.6 glucose units per mole sold respectively under the names GLUCOPON 600 EC®, GLUCOPON 600 CSUP®, GLUCOPON 650 EC®, GLUCOPON 225 CSUP®, by HENKEL;
• derivatives of galacturonic, glucuronic, D-mannuronic, L-iduronic and guluronic acids having a hydrocarbon chain containing from 6 to 24 carbon atoms, preferably from 8 to 16 carbon atoms, as well as their alkali metal salts (EP- A-532 370);
• glucosamides such as lauryl-N-methylglucosamide;
• sophorolipids, such as those in acid or lactone form, derived from 17-hydroxyoctadecenic acid;

• la teneur en agent(s) tensioactif(s) non-ionique(s) (NIA) représente de l'ordre de 5 à 60 % en poids, de préférence de l'ordre de 5 à 55% en poids, tout particulièrement de l'ordre de 5 à 45% en poids du taux de matière sèche de ladite dispersion
• la teneur en solution concentrée de silicate de métal alcalin, exprimée en sec, représente de l'ordre de 20 à 70% en poids, de préférence de l'ordre de 30 à 60% en poids du taux de matière sèche de ladite dispersion
• la teneur en agent(s) tensioactif(s) non-ionique(s) ou anionique(s) (TAS), exprimée en sec, représente de l'ordre de 5 à 40% en poids, de préférence de l'ordre de 10 à 30% en poids du taux de matière sèche de ladite émulsion ou dispersion, le taux de matière sèche de ladite dispersion étant de l'ordre de 30 à 90%, de préférence de l'ordre de 40 à 80% en poids.

The respective amounts of nonionic surfactant (s) (NIA), concentrated solution of alkali metal silicate and nonionic or anionic surfactant (s) (s) (TAS) implemented for the realization of the system of the invention, are such that

• the content of nonionic surfactant (s) (NIA) represents of the order of 5 to 60% by weight, preferably of the order of 5 to 55% by weight, very particularly of around 5 to 45% by weight of the dry matter content of said dispersion
• the content of concentrated solution of alkali metal silicate, expressed as dry, represents of the order of 20 to 70% by weight, preferably of the order of 30 to 60% by weight of the dry matter content of said dispersion
• the content of nonionic or anionic surfactant (s) (TAS), expressed as dry matter, represents of the order of 5 to 40% by weight, preferably of the order of 10 to 30% by weight of the dry matter content of said emulsion or dispersion, the dry matter content of said dispersion being of the order of 30 to 90%, preferably of the order of 40 to 80% by weight.

The operation of dispersing the surfactant (s) (NIA) in said concentrated solution of alkali metal silicate using at least one nonionic or anionic surfactant (TAS) can be carried out according to all the methods of preparation of dispersions known to those skilled in the art.

A dispersion can be prepared by using high shear colloid mills, such as MENTON GAULIN®, MICROFLUIDIZER® (MICROFLUIDICS) etc ...

It is however preferable to prepare a dispersion according to methods using moderate stirring means.

Thus, a first well-suited method is direct phase emulsification, consisting in preparing a mixture of concentrated solution of alkali metal silicate and non-ionic or anionic surfactant (TAS), then in introducing therein the non-ionic surfactant. -ionic (NIA) in liquid form (melted if necessary), with stirring.

Another method is emulsification by phase inversion, consisting in introducing dropwise, with stirring, into the nonionic surfactant (NIA) in liquid form (molten if necessary), a mixture of concentrated solution of alkali metal silicate. and nonionic or anionic surfactant (TAS).

The operation of dispersing by emulsification of the nonionic surfactant (NIA) in the concentrated solution of alkali metal silicate using the nonionic or anionic surfactant (TAS) is carried out at a temperature at which said nonionic surfactant (NIA) is liquid. Surface active agent droplets non-ionic (NIA) obtained during this operation can have diameters of the order of 0.5 to 10 μm, preferably of the order of 0.7 to 5 μm.

The possible operation of drying the dispersion to obtain granules is carried out under conditions such that the continuous liquid matrix of alkali metal silicate is transformed by elimination of water into a continuous solid film coating the droplets or the particles d 'nonionic surfactant (NIA); the quantity of water remaining corresponding to a weight ratio of water remaining in the silicate / silicate in the dry range of the order of 5/95 to 25/75.
This operation can be carried out by any known means. Preferably, rapid drying of the dispersion is carried out.
Suitable for drying by freeze-drying (freezing followed by sublimation), and especially spray drying.
This latter mode of drying can be carried out in any known spray drying apparatus, such as atomization towers associating a spraying of the dispersion by a nozzle or a turbine with a stream of hot air, under conditions such as the temperature of the product during drying does not exceed 105 ° C.

Said optional drying operation can also be carried out in the open air in a thin layer in an oven.

• 5 à 60% de leur poids, de préférence 5 à 55% de leur poids, tout particulièrement 5 à 45% de leur poids d'agent(s) tensioactif(s) non-ionique(s) (NIA)
• 20 à 70% de leur poids, de préférence 30 à 60% de leur poids de silicate de métal alcalin exprimé en sec
• 5 à 40% de leur poids, de préférence 10 à 30% de leur poids d'agent(s) tensioactif(s) non-ionique(s) ou anionique(s) (TAS) exprimé en sec
• et de l'eau selon un rapport eau/silicate sec de l'ordre de 5/95 à 25/75.

The granules thus obtained comprise of the order of

• 5 to 60% of their weight, preferably 5 to 55% of their weight, very particularly 5 to 45% of their weight of nonionic surfactant (NIA)
• 20 to 70% of their weight, preferably 30 to 60% of their weight of alkali metal silicate expressed as dry
• 5 to 40% of their weight, preferably 10 to 30% of their weight of non-ionic or anionic surfactant (s) expressed as dry matter
• and water according to a dry water / silicate ratio of the order of 5/95 to 25/75.

According to a particular and improved embodiment of the invention, said system (S) is in the form of an aqueous dispersion additionally containing glycerol.
The presence of glycerol makes it possible in particular to improve the stability on hot storage (40 ° C.) of said system in dispersion.
The amount of glycerol that may be present is of the order of 3 to 20% by weight, preferably of the order of 4 to 20% by weight, very particularly of the order of 6 to 14% by weight relative to the total weight of said dispersion.
Said system (S) in the form of a dispersion, can be obtained by carrying out the dispersing operation according to the methods described above, in particular of emulsification in direct phase or by phase inversion, after prior introduction of the glycerol. in the concentrated aqueous solution of alkali metal silicate.

The system (S) forming the subject of the invention, whether it is in the form of an aqueous dispersion or of granules, can be used in household or industrial detergents, as a constituent of a detergent composition, for washing laundry in particular.
The term “constituent” is understood here to mean both a simple component for a detergent composition and the complete detergent composition proper.

When it is in the form of granules, said system (S) may be a simple component of a detergent powder composition or alone constitute a detergent powder composition.

• les polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexamétaphosphates) de métaux alcalins, d'ammonium ou d'alcanolamines
• les tetraborates ou les précurseurs de borates
• les carbonates (bicarbonates, sesquicarbonates) alcalins ou alcalino-terreux
• les silicates lamellaires décrits dans US-A-4 664 839
• les cogranulés de silicates hydratés de métaux alcalins et de carbonates de métaux alcalins (sodium ou de potassium) riches en atomes de silicium sous forme Q2 ou Q3, décrits dans EP-A-488 868, pour les compositions détergentes en poudre
• les aluminosilicates cristallins ou amorphes de métaux alcalins (sodium, potassium) ou d'ammonium, tels que les zéolithes A, P, X,
• les polyphosphonates hydrosolubles (éthane 1-hydroxy-1, 1-diphosphonates, sels de méthylène diphosphonates,)
• les sels hydrosolubles de polymères ou copolymères carboxyliques tels que les sels hydrosolubles d'acides polycarboxyliques de masse moléculaire de l'ordre de 2000 à à 100 000, obtenus par polymérisation ou copolymérisation d'acides carboxyliques éthyléniquement insaturés tels que acide acrylique, acide ou anhydride maléique, acide fumarique, acide itaconique, acide mésaconique, acide citraconique, acide méthylènemalonique, et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 à 10 000 (US-A-3 308 067), les copolymères d'acide acrylique et d'anhydride maléique de masse moléculaire de l'ordre de 5 000 à 75 000 (EP-A-66 915)
• les éthers polycarboxylates (acide oxydisuccinique et ses sels, tartrate monosuccinic acide et ses sels, tartrate disuccinic acide et ses sels
• les éthers hydroxypolycarboxylates
• l'acide citrique et ses sels, l'acide mellitique, l'acide succinique et leurs sels
• les sels d'acides polyacétiques (éthylènediaminetetraacétates, nitritotriacétates, N-(2 hydroxyéthyl)-nitrilodiacétates)
• les acides alkyl C5-C20 succiniques et leurs sels( 2-dodécénylsuccinates, lauryl succinates,)
• les esters polyacétals carboxyliques
• l'acide polyaspartique, l'acide polyglutamique et leurs sels
• les polyimides dérivés de la polycondensation de l'acide aspartique et/ou de l'acide glutamique
• les dérivés polycarboxyméthylés de l'acide glutamique [comme l'acide N,N-bis(carboxyméthyl)glutamique et ses sels, de sodium notamment] ou d'autres acides aminés
• les aminophosphonates tels que les nitrilotris(méthylène phosphonates)
• les composés aromatiques polyfonctionnels tels que les dihydroxydisulfobenzènes des agents tensioactifs anioniques, en quantité de l'ordre de 1 à 50%, tels que
• les alkylesters sulfonates de formule R-CH(SO₃M)-COOR', où R représente un radical alkyle en C₈-₂₀, de préférence en C₁₀-C₁₆, R' un radical alkyle en C₁-C₆, de préférence en C₁-C₃ et M un cation alcalin (sodium, potassium, lithium), ammonium substitué ou non substitué (méthyl-, diméthyl-, triméthyl-, tetraméthylammonium, diméthylpiperidinium, ) ou dérivé d'une alcanolamine (monoéthanolamine, diéthanolamine, triéthanolamine,) ;
• les alkylsulfates de formule ROSO₃M, où R représente un radical alkyle ou hydroxyalkyle en C₁₀-C₂₄, de préférence en C₁₂-C₂₀ et tout particulièrement en C₁₂-C₁₈, M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant en moyenne de 0,5 à 6 motifs, de préférence de 0,5 à 3 motifs OE et/ou OP ;
• les alkylamides sulfates de formule RCONHR'OSO₃M où R représente un radical alkyle en C₂-C₂₂, de préférence en C₆-C₂₀, R' un radical alkyle en C₂-C₃. M représentant un atome d'hydrogène ou un cation de même définition que ci-dessus, ainsi que leurs dérivés éthoxylénés (OE) et/ou propoxylénés (OP), présentant en moyenne de 0,5 à 60 motifs OE et/ou OP ;
• les sels d'acides gras saturés ou insaturés en C₈-C₂₄, de préférence en C₁₄-C₂₀, les alkylbenzènesulfonates en C₉-C₂₀, les alkylsulfonates primaires ou secondaires en C₈-C₂₂, les alkylglycérol sulfonates, les acides polycarboxyliques sulfonés décrits dans GB-A-1 082 179, les sulfonates de paraffine, les N-acyl N-alkyltaurates, les alkylphosphates, les iséthionates, les alkylsuccinamates les alkylsulfosuccinates, les monoesters ou diesters de sulfosuccinates, les N-acyl sarcosinates, les sulfates d'alkylglycosides, les polyéthoxycarboxylates, le cation ayant la même définition que ci-dessus.

des agents anti-salissures, en quantités de l'ordre de 0,01-10%, de préférence de l'ordre de 0,1 à 5%, et tout particulièrement de l'ordre de 0,2-3% en poids, agents tels que

• les dérivés cellulosiques tels que les hydroxyéthers de cellulose, la méthylcellulose, l'éthylcellulose, l'hydroxypropyl méthylcellulose, l'hydroxybutyl méthylcellulose
• les polyvinylesters greffés sur des troncs polyalkylènes tels que les polyvinylacétates greffés sur des troncs polyoxyéthylènes (EP-A-219 048)
• les alcools polyvinyliques
• les copolymères polyesters à base de motifs éthylène téréphtalate et/ou propylène téréphtalate et polyoxyéthylène téréphtalate, avec un rapport molaire (nombre de motifs) ethylène téréphtalate et/ou propylène téréphtalate / (nombre de motifs) polyoxyéthylène téréphtalate de l'ordre de 1/10 à 10/1, de préférence de l'ordre de 1/1 à 9/1, les polyoxyéthylène téréphtalates présentant des unités polyoxyéthylène ayant un poids moléculaire de l'ordre de 300 à 5000, de préférence de l'ordre de 600 à 5000 (US-A-3 959 230, US-A-3 893 929, US-A-4 116 896, US-A-4 702 857, US-A-4 770 666) ;
• les oligomères polyesters sulfonés obtenus par sulfonation d'un oligomère dérivé de l'alcool allylique éthoxylé, du diméthyltéréphtalate et du 1,2 propylène diol, présentant de 1 à 4 groupes sulfonés (US-A-4 968 451)
• les copolymères polyesters à base de motifs propylène téréphtalate et polyoxyéthylène téréphtalate et terminés par des motifs éthyles, méthyles (US-A-4 711 730) ou des oligomères polyesters terminés par des groupes alkylpolyéthoxy (US-A-4 702 857) ou des groupes anioniques sulfopolyéthoxy (US-A-4 721 580), sulfoaroyles (US-A-4 877 896)
• les polyesters sulfonés de masse moléculaire en nombre inférieure à 20 000, obtenus à partir d'un diester de l'acide téréphtalique, d'un diester de l'acide sulfoisophtalique et d'un diol (FR-A-2 720 400)
• les polyesters-polyuréthanes obtenus par réaction d'un polyester de masse moléculaire en nombre de 300-4000 obtenu à partir d'acide adipique et/ou d'acide téréphtalique et/ou d'acide sulfoisophtalique et d'un diol, sur un prépolymère à groupements isocyanates terminaux obtenus à partir d'un polyoxyéthylène glycol de masse moléculaire de 600-4000 et d'un diisocyanate (FR-A-2 334 698)

des agents antiredéposition, en quantités d'environ 0,01-10% en poids pour une composition détergente en poudre, d'environ 0,01-5% en poids pour une composition détergente liquide, agents tels que

• les monoamines ou polyamines éthoxylées, les polymères d'amines éthoxylées (US-A-4 597 898, EP-A-11 984)
• la carboxyméthylcellulose
• les oligomères polyesters sulfonés obtenus par condensation de l'acide isophtalique, du sulfosuccinate de diméthyle et de diéthylène glycol (FR-A-2 236 926)
• les polyvinylpyrollidones

des agents de blanchiment, en quantité d'environ 0,1-20%, de préférence 1-10% du poids de ladite composition détergente en poudre, tels que

• les perborates tels que le perborate de sodium monohydraté ou tétrahydraté
• les composés peroxygénés tels que le carbonate de sodium peroxyhydraté, le pyrophosphate peroxyhydraté, l'urée peroxyhydratée, le peroxyde de sodium, le persulfate de sodium
• les acides percarboxyliques et leurs sels (appelés "percarbonates") tels que le monoperoxyphtalate de magnésium hexahydraté, le métachloroperbenzoate de magnésium, l'acide 4-nonylamino-4-oxoperoxybutyrique, l'acide 6-nonylamino-6-oxoperoxycaproique, l'acide diperoxydodécanedioique, le nonylamide de l'acide peroxysuccinique, l'acide décyldiperoxysuccinique.

de préférence associés à un activateur de blanchiment générant in situ dans le milieu lessiviel, un peroxyacide carboxylique ; parmi ces activateurs, on peut mentionner, la tetraacétyléthylène diamine, la tetraacétyl méthylène diamine, le tetraacétyl glycoluryl, le p-acétoxybenzène sulfonate de sodium, le pentaacétyl glucose, l'octaacétyl lactose,
des agents de fluorescence , en quantité d'environ 0,05-1,2% en poids, agents tels que les dérivés de stilbène, pyrazoline, coumarine, acide fumarique, acide cinnamique, azoles, méthinecyanines, thiophènes,
des agents suppresseurs de mousses, en quantités pouvant aller jusqu'à 5% en poids, agents tels que

• les acides gras monocarboxyliques en C₁₀-C₂₄ ou leurs sels alcalins, d'ammonium ou d'alcanolamines, les triglycérides d'acides gras
• les hydrocarbures saturés ou insaturés aliphatiques, alicycliques, aromatiques ou hétérocycliques, tels que les paraffines, les cires
• les N-alkylaminotriazines
• les monostéarylphosphates, les monostéaryl alcool phosphates
• les huiles ou résines polyorganosiloxanes éventuellement combinées avec des particules de silice

des agents adoucissants, en quantités d'environ 0,5-10% en poids, agents tels que les argiles
des enzymes en quantité pouvant aller jusqu'à 5 mg en poids, de préférence de l'ordre de 0,05-3mg d'enzyme active /g de composition détergente, enzymes telles que les protéases, amylases, lipases, cellulases, peroxydases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868)
et d'autres additifs tels que

• des alcools (méthanol, éthanol, propanol, isopropanol, propanediol, éthylène glycol, glycérine)
• des agents tampons
• des parfums
• des pigments

When said system (S) in the form of granules is a simple component of a powdered detergent composition, it can be added in post-addition to the other components of said composition, and in an amount corresponding to that desired by the manufacturer. This amount, expressed as a nonionic surfactant (NIA), is generally of the order of 5 to 25 parts by weight per 100 parts of final composition.
Among the other components which may be present in the powder detergent compositions, there may be mentioned
mineral or organic detergency builders , in an amount such that the total amount of detergency builders is in the range of 5 to 50% by weight of said composition, detergency builders such as

• polyphosphates (tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates) of alkali metals, ammonium or alkanolamines
• tetraborates or borate precursors
• alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates)
• the lamellar silicates described in US-A-4,664,839
• the cogranules of hydrated alkali metal silicates and of alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868, for powdered detergent compositions
• crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X,
• water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, methylene salts diphosphonates,)
• the water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids of molecular weight of the order of 2000 to to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates of molecular weight l '' from 2,000 to 10,000 (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular weight of about 5,000 to 75,000 (EP-A-66,915)
• polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts
• hydroxypolycarboxylate ethers
• citric acid and its salts, mellitic acid, succinic acid and their salts
• the salts of polyacetic acids (ethylenediaminetetraacetates, nitritotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates)
• succinic C5-C20 alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates,)
• polyacetal carboxylic esters
• polyaspartic acid, polyglutamic acid and their salts
• polyimides derived from the polycondensation of aspartic acid and / or glutamic acid
• polycarboxymethylated derivatives of glutamic acid [such as N, N-bis (carboxymethyl) glutamic acid and its salts, especially of sodium] or other amino acids
• aminophosphonates such as nitrilotris (methylene phosphonates)
• polyfunctional aromatic compounds such as the dihydroxydisulfobenzenes of anionic surfactants , in an amount of the order of 1 to 50%, such as
• the alkyl esters sulfonates of formula R-CH (SO ₃ M) -COOR ', where R represents a C ₈ -C ₂₀ , preferably C ₁₀ -C ₁₆ alkyl radical, R' a C ₁ -C ₆ alkyl radical, preferably in C ₁ -C ₃ and M an alkaline cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium,) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine,);
• the alkyl sulphates of formula ROSO ₃ M, where R represents a C ₁₀ -C ₂₄ , preferably C ₁₂ -C _20, and especially C ₁₂ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation with the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 OE and / or OP units;
• the alkylamides sulfates of formula RCONHR'OSO ₃ M where R represents an alkyl radical in C ₂ -C ₂₂ , preferably in C ₆ -C ₂₀ , R 'an alkyl radical in C ₂ -C ₃ . M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 OE and / or OP units;
• the salts of C ₈ -C ₂₄ , preferably C ₁₄ -C ₂₀ saturated or unsaturated fatty acids, C ₉ -C ₂₀ alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates , alkyl glycoside sulfates, polyethoxycarboxylates, the cation having the same definition as above.

anti-fouling agents , in amounts of the order of 0.01-10%, preferably of the order of 0.1 to 5%, and very particularly of the order of 0.2-3% by weight , agents such as

• cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose
• polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048)
• polyvinyl alcohols
• polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio (number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666);
• sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1,2 propylene diol, having from 1 to 4 sulfonated groups (US Pat. No. 4,968,451)
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl, methyl units (US-A-4,711,730) or polyester oligomers terminated with alkylpolyethoxy groups (US-A-4,702,857) or sulfopolyethoxy anionic groups (US-A-4,721,580), sulfoaroyl (US-A-4,877,896)
• sulfonated polyesters with a molecular mass of less than 20,000, obtained from a diester of terephthalic acid, a diester of sulfoisophthalic acid and a diol (FR-A-2 720 400)
• polyesters-polyurethanes obtained by reaction of a polyester with a molecular mass of 300-4000 in number obtained from adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and a diisocyanate (FR-A-2 334 698)

anti-redeposition agents , in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as

• ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-11,984)
• carboxymethylcellulose
• the sulfonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulfosuccinate and of diethylene glycol (FR-A-2 236 926)
• polyvinylpyrollidones

bleaching agents, in an amount of about 0.1-20%, preferably 1-10% of the weight of said powdered detergent composition, such as

• perborates such as sodium perborate monohydrate or tetrahydrate
• peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate
• percarboxylic acids and their salts (called "percarbonates") such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide peroxysuccinic acid, decyldiperoxysuccinic acid.

preferably combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose,
fluorescent agents , in an amount of about 0.05-1.2% by weight, agents such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes,
foam suppressants , in amounts up to 5% by weight, agents such as

• C ₁₀ -C ₂₄ monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides
• aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons, such as paraffins, waxes
• N-alkylaminotriazines
• monostearylphosphates, monostearyl alcohol phosphates
• polyorganosiloxane oils or resins optionally combined with silica particles

softening agents, in amounts of about 0.5-10% by weight, agents such as clays
enzymes in an amount up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as proteases, amylases, lipases, cellulases, peroxidases ( US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868)
and other additives such as

• alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin)
• buffering agents
• perfumes
• pigments

When said system (S) in the form of granules, constitutes in itself a detergent composition (SD) in powder, for washing machine in particular, it is preferable that the quantity of silicate of alkali metal expressed in dry, represents around from 30 to 70%, very particularly of the order of 40 to 60% of the weight of said system expressed in dry terms, and that of nonionic surfactant (NIA) represents of the order of 10 to 35%, very particularly of the order of 15 to 30% of the weight of said system expressed in sec.

When it is in the form of an aqueous dispersion, it is preferable that said system (S) constitutes the liquid detergent composition itself. He can then present as is (i.e. composed of its three basic constituents, alkali metal silicate, nonionic surfactant (NIA) and nonionic or anionic surfactant (TAS), water and optionally glycerol) or added other detergency components introduced during its preparation.

To constitute as such a liquid detergent composition (SD), for washing machines in particular, said system (S) in the form of an aqueous dispersion contains an amount of alkali metal silicate expressed as dry, of the order of 30 to 70 %, preferably of the order of 40 to 60% of the weight of said system expressed in dry terms, and an amount of nonionic surfactant (NIA) of the order of 5 to 35%, preferably of the order from 5 to 30% of the weight of said system expressed in sec.

Said system (S) in the form of an aqueous dispersion, added during its preparation of at least one detergency component can constitute a liquid detergent composition, for washing machines in particular.
The nature and the quantity of the components as well as the possible quantity of water introduced via these components are chosen so as not to destructure the liquid dispersion. It is preferable that the total amount of these components does not exceed 10% of the weight of the final detergent composition.

• 1) les additifs de détergence solubles ou dispersables mais non-hydrolysables dans la solution concentrée de silicate de métal alcalin, tels que
  • . les sels hydrosolubles de polymères ou copolymères carboxyliques tels que les sels hydrosolubles d'acides polycarboxyliques de masse moléculaire de l'ordre de 2000 à 100 000, obtenus par polymérisation ou copolymérisation d'acides carboxyliques éthyléniquement insaturés tels que acide acrylique, acide ou anhydride maléique, acide fumarique, acide itaconique, acide mésaconique, acide citraconique, acide méthylènemalonique, et tout particulièrement les polyacrylates de masse moléculaire de l'ordre de 2 000 à 10 000 (US-A-3 308 067), les copolymères d'acide acrylique et d'anhydride maléique de masse moléculaire de l'ordre de 5 000 à 75 000 (EP-A-66 915) ; il peuvent êre mis en oeuvre en quantité (exprimée en sec) de l'ordre de 0,5 à 6% du poids de composition détergente exprimé en sec
  • . les polypeptides tels que l'acide polyaspartique, l'acide polyglutamique et leurs sels, en quantité (exprimée en sec) de l'ordre de 0,5 à 6% du poids de composition détergente exprimé en sec
  • . les polyphosphonates hydrosolubles (éthane 1-hydroxy-1, 1-diphosphonates, sels de méthylène diphosphonates, ), en quantité (exprimée en sec) de l'ordre de 0,5 à 6% du poids de composition détergente exprimé en sec
  • . les sels d'acides polyacétiques (éthylènediaminetetraacétates, nitrilotriacétates, N-(2 hydroxyéthyl)-nitrilodiacétates), en quantité (exprimée en sec) de l'ordre de 0,5 à 6% du poids de composition détergente exprimé en sec
  • . les dérivés polycarboxyméthylés de l'acide glutamique [comme l'acide N,N-bis(carboxyméthyl)glutamique et ses sels, de sodium notamment] ou d'autres acides aminés, en quantité (exprimée en sec) de l'ordre de 0,5 à 6% du poids de composition détergente exprimé en sec
  • . les carbonates (bicarbonates, sesquicarbonates) alcalins, en quantité (exprimée en sec) de l'ordre de 1 à 10 % du poids de composition détergente exprimé en sec
  • . les azurants optiques tels que les dérivés de stilbène, pyrazoline, coumarine, acide fumarique, acide cinnamique, azoles, méthinecyanines, thiophènes, en quantité exprimée en sec de l'ordre de 0,1 à 0,5 % du poids de composition détergente exprimé en sec
  Ce type d'additifs peut être introduit au sein dudit système (S) par mélange préalable du ou des additif(s) avec la solution de silicate de métal alcalin, l'agent tensioactif non-ionique (NIA) étant ensuite mis en dispersion dans ledit mélange à l'aide de l'agent tensioactif (TAS).
• (2) les additifs de détergence solubles ou dispersables dans l'agent tensioactif non-ionique (NIA), comme notamment les enzymes telles que les protéases, amylases, lipases, cellulases, peroxydases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868), en quantité exprimée en sec de l'ordre de 0,1 à 0,5 % du poids de composition détergente exprimé en sec
  Ce type d'additif peut être introduit au sein dudit système par dispersion ou solubilisation dans l'agent tensioactif non-ionique (NIA) liquide, avant mise en dispersion dudit agent tensioactif non-ionique (NIA) dans la solution de silicate.
• 3) les additifs de détergence insolubles dans la solution de silicate et dans l'agent tensioactif non-ionique (NIA) liquide, comme notamment les agents suppresseurs de mousse tels que
  • . les hydrocarbures saturés ou insaturés aliphatiques, alicycliques, aromatiques ou hétérocycliques, tels que les paraffines, les cires
  • . les monostéarylphosphates, les monostéaryl alcool phosphates
  • . les huiles ou résines polyorganosiloxanes éventuellement combinées avec des particules de silice
  en quantité exprimée en sec de l'ordre de 0,1 à 0,5 % du poids de composition détergente exprimé en sec
  Ce type d'additif peut être introduit au sein du système (S) par mise en dispersion dans la solution de silicate par l'intermédiaire de l'agent tensioactif (TAS), puis addition de l'agent tensioactif non-ionique (NIA). Le système formé est ici une codispersion.

The mode of introduction of said additive (s) within said system (S) in the form of a dispersion, depends on the behavior of said additive (s) with respect to the concentrated solution of silicate and of nonionic surfactant (NIA).
Among the additives, there may be mentioned in particular:

• 1) soluble or dispersible but non-hydrolyzable detergency additives in the concentrated solution of alkali metal silicate, such as
  • . the water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids with a molecular weight of about 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride , fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and more particularly polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular weight of the order of 5,000 to 75,000 (EP-A-66,915); they can be used in an amount (expressed in dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry
  • . polypeptides such as polyaspartic acid, polyglutamic acid and their salts, in an amount (expressed in dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry
  • . water-soluble polyphosphonates (1-hydroxy-1-ethane, 1-diphosphonates, methylene salts diphosphonates,), in an amount (expressed in dry) of the order of 0.5 to 6% by weight of detergent composition expressed in dry
  • . the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates), in quantity (expressed as dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry
  • . polycarboxymethylated derivatives of glutamic acid [such as N, N-bis (carboxymethyl) glutamic acid and its salts, sodium in particular] or other amino acids, in quantity (expressed as dry) of the order of 0 , 5 to 6% of the weight of detergent composition expressed in dry
  • . alkali carbonates (bicarbonates, sesquicarbonates), in quantity (expressed in dry) of the order of 1 to 10% of the weight of detergent composition expressed in dry
  • . optical brighteners such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes, in dry quantity of the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
  This type of additive can be introduced into said system (S) by prior mixing of the additive (s) with the alkali metal silicate solution, the nonionic surfactant (NIA) then being dispersed in said mixture using the surfactant (TAS).
• (2) detergency additives soluble or dispersible in the nonionic surfactant (NIA), such as in particular enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139, US-A -4 101 457, US-A-4 507 219, US-A-4 261 868), in quantity expressed as dry of the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
  This type of additive can be introduced into said system by dispersion or solubilization in the liquid nonionic surfactant (NIA), before dispersing said nonionic surfactant (NIA) in the silicate solution.
• 3) detergency additives insoluble in the silicate solution and in the liquid nonionic surfactant (NIA), such as in particular foam suppressants such as
  • . aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons, such as paraffins, waxes
  • . monostearylphosphates, monostearyl alcohol phosphates
  • . polyorganosiloxane oils or resins optionally combined with silica particles
  in quantity expressed as dry on the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
  This type of additive can be introduced into the system (S) by dispersing it in the silicate solution via the surfactant (TAS), then adding the nonionic surfactant (NIA). . The system formed here is a codispersion.

The detergent composition formed by said system (S) in the form of an aqueous dispersion, either as it is or added during its preparation with at least one detergency compound, can be used both for the main washing of laundry and as a stain remover before washing.
The term “stain remover before washing” (“prespotter”) means a product which, deposited before washing, without prior dilution, on the soiled area of the laundry, allows better removal of the soil during the main wash.

The following examples are given without limitation.

Example 1

• 40 parties en poids de SYNPERONIC A7, alcool linéaire en C₁₂-C₁₄ éthoxylé à 7 moles d'oxyde d'éthylène
  • . 40 parties en poids (exprimé en sec) de solution de silicate de sodium de rapport SiO₂/Na₂O de 2, à 45% d'extrait sec
• 20 parties en poids (exprimé en sec) de GLUCOPON 600 CSP (solution d'alkylpolyglucoside à 50% d'extrait sec) par :
  • . introduction dans réacteur de 2 litres, muni d'un agitateur à cadre, du GLUCOPON 600 CSP dans la solution aqueuse de silicate de sodium,
  • . chauffage à 60°C pendant 10 minutes sous agitation à une vitesse de 200 tours/min
  • . ajout goutte à goutte sous agitation à 1000 tours/min, du SYNPERIONIC A7
  • . maintien au repos du mélange obtenu pendant 48 heures environ
  • . passage dudit mélange dans un microfluidiseur à 500bar
  • . et maintien au repos pendant 24 heures environ.

L'émulsion obtenue est stable ; elle présente un diamètre homogène de goutte inférieur au micromètre et une viscosité inférieure à celle de la solution de silicate de départ.
L'émulsion est séchée en couche mince de 1cm sur lame de verre à l'étuve à 60°C. pendant 24 heures.
Le produit obtenu contient 4% en poids d'eau ; il est broyable et s'écoule librement, bien qu'il contienne plus de 50% de tensioactif non-ionique.An aqueous emulsion containing

• 40 parts by weight of SYNPERONIC A7, linear alcohol C ₁₂ -C ₁₄ ethoxylated with 7 moles of ethylene oxide
  • . 40 parts by weight (expressed as dry) of sodium silicate solution with an SiO ₂ / Na ₂ O ratio of 2, 45% dry extract
• 20 parts by weight (expressed in sec) of GLUCOPON 600 CSP (alkylpolyglucoside solution at 50% dry extract) by:
  • . introduction into a 2 liter reactor, fitted with a frame stirrer, of GLUCOPON 600 CSP into the aqueous sodium silicate solution,
  • . heating at 60 ° C for 10 minutes with stirring at a speed of 200 rpm
  • . addition dropwise with stirring at 1000 rpm of SYNPERIONIC A7
  • . keeping the mixture obtained at rest for approximately 48 hours
  • . passage of said mixture in a microfluidizer at 500bar
  • . and stay at rest for about 24 hours.

The emulsion obtained is stable; it has a homogeneous drop diameter less than a micrometer and a viscosity lower than that of the starting silicate solution.
The emulsion is dried in a thin layer of 1 cm on a glass slide in an oven at 60 ° C. for 24 hours.
The product obtained contains 4% by weight of water; it is grindable and flows freely, although it contains more than 50% of nonionic surfactant.

Example 2

• introduction successive dans un réacteur de 2 litres maintenu à 40°C sous agitation continue à 200 tours /minute à l'aide d'un agitateur à cadre
  • . de la solution de silicate
  • . des azurants optiques
  et agitation pendant 5 minutes
• addition du GLUCOPON 600 CSP
• addition d'un mélange préalablement préparé à 30°C de SYNPERONIC A7 et d'enzyme
• puis introduction de l'anti-mousse

L'ensemble est homogénéisé à 1000 tours/minute en évitant l'introduction d'air.
Le pouvoir détergent et antiredéposition de la formulation détergente ci-dessus est testé comme suit.The following liquid detergent formulation formulation components parts by weight sodium silicate solution with an SiO ₂ / Na ₂ O ratio of 2, 45% dry extract 79.3 TINOPAL SOP + TINOPAL DMSX (optical brighteners) 0.2 GLUCOPON 600 CSP, 50% dry extract 10 SYNPERONIC A7 10 SAVINASE 32 KNUP (NOVO protease) 0.3 RHODORSIL 20476 defoamer 0.2 (i.e. 15 parts by weight, expressed as dry matter, of surfactants per 100 parts by weight of detergent formulation)
is prepared by:

• successive introduction into a 2 liter reactor maintained at 40 ° C with continuous stirring at 200 revolutions / minute using a frame stirrer
  • . silicate solution
  • . optical brighteners
  and shaking for 5 minutes
• addition of GLUCOPON 600 CSP
• addition of a mixture previously prepared at 30 ° C of SYNPERONIC A7 and of enzyme
• then introduction of the anti-foam

The whole is homogenized at 1000 revolutions / minute avoiding the introduction of air.
The detergent and anti-deposition power of the above detergent formulation is tested as follows.

PRINCIPLE

The test simulates a simplified machine wash, using a tergotometer. It consists of washing, at 40 ° C in water with a hardness of 30 ° TH, test pieces of soiled fabrics in a standard and uniform manner, with the formulation to be tested. The washing lasts thirty minutes and the detergency is evaluated by measuring the whiteness of the pieces of fabric, before and after washing, using a colorimeter. In addition, white, unsoiled control fabrics are incorporated, which make it possible to evaluate the redeposition of soiling by measuring the reflectances before and after washing.

APPARATUS AND MATERIAL Material:

• Tergotometer: "U.S. TESTING Co Inc" HOBOKEN N.J. Model 7243.
• Glazing machine for ironing fabric samples after washing.
• Color measuring device "Dr Lange LUCI 100".

Fabrics

Standard fabrics are manufactured by the CFT (Center For Test materials) or by the company "Test Fabric". They have the following characteristics: Standard soiled fabrics (Soil) number of pieces per test - Dirty cotton CS-2 CFT (cocoa) 2 - Dirty cotton CS-1 CFT (blood) 2 - Dirty cotton K 10D CFT (sebum) 2 - Dirty polyester K 30D CFT (sebum) 2 - Dirty cotton AS-2 CFT (mineral oil and soot) 2 - Cotton polyester EMPA 104 CFT (mineral oil and ink) 2 - Polyester Test Fabric (soot) 2 Standard white fabrics - Cotton CN 1 white, not soiled, of CFT 5 - Cotton polyester PCN 1, white, no dirty, CFT 5 or, for each test, a total of 24 pieces of tissue.

OPERATING MODE Detergency test

The tergotometer is a device made up of 4 2-liter stainless steel pots on which are fitted stirrers which are adjusted to 50 cycles per minute (100 back and forth). The pots are placed in a water tank regulated at 40 ° C.

In each pot we put 1 liter of water containing 8.2g of formulation to be tested.
When the water is at temperature, the pots are introduced into the thermostatically controlled bath, simultaneously stirring and a stopwatch.
At the end of washing (30 minutes) the baths are recovered (250 cc) for pH control.
The fabrics are rinsed three times with tap water, then wrung by hand and dried flat individually between two sheets of white absorbent paper.
The fabrics are again placed between two sheets of clean absorbent paper, and ironed in the freezer at a temperature close to 110 ° C.

Measuring headers

The measurements are carried out with the "LUCI 100" colorimeter before and after washing according to the "L", "a", "b" system (scale from black to white, from green to red, and from blue to yellow) to measure the detergent power of the surfactants tested (increase the whiteness of the pieces of soiled tissue).

Detergency calculation

The value "DE" (detergency) is calculated for each type of fabric by taking the geometric sum of the color differences DL, Da and Db before and after washing on soiled fabrics. :
Is $${\text{detergency DE = (DL}}^{\text{2}}{\text{Da +}}^{\text{2}}{\text{Db +}}^{\text{2}}{\text{)}}^{\text{1/2}}$$

Anti-deposition power

The anti-redeposition power of the tested products is demonstrated using standard white soiled cotton CN1 and polyester / cotton PCN1 fabrics, the color of which is measured before and after washing. Redeposition is the difference in reflectance between the initial white fabric and the white fabric that has been washed in the presence of soiled fabrics.

• . coton CN1
• . Terry coton 12A

The measurement of the incrustation inhibiting effect is measured after 6 washes at 60 ° C. in hard water at 40 ° TH, in the absence of soiled fabrics on the following unsoiled test pieces:

• . cotton CN1
• . Terry cotton 12A

The mineral incrustation is calculated from the ash rate (in% relative to the total weight of the cotton) of the fabrics washed, dried and burned at 950 ° C for 3 hours.

The results obtained appear in Table 1 and are compared with those obtained with the same amount (8.2 g / l) of a compact liquid commercial detergent containing 50% of its weight of surfactants.

It is noted that the detergent power of the formulation of the invention is significantly higher than that of the commercial detergent, although the level of surfactants of the formulation of the invention (15%) is much lower than that ( 50%) of commercial laundry.

Example 3

• 12 parties en poids de SYNPERONIC A7, alcool linéaire en C₁₂-C₁₄ éthoxylé à 7 moles d'oxyde d'éthylène
• 6 parties en poids (exprimé en sec) de GLUCOPON 600 CSP (solution d'alkylpolyglucoside à 50% d'extrait sec)
  • . une solution de silicate de sodium de rapport SiO₂/Na₂O de 2, à 45% d'extrait sec selon les quantités données au tableau 2
• du glycérol selon les quantités données au tableau 2
  par :
  • . introduction dans un réacteur de 2 litres, muni d'un agitateur à cadre, du GLUCOPON 600 CSP dans un mélange préalable du glycérol et de la solution aqueuse de silicate de sodium,
  • . chauffage à 60°C pendant 10 minutes sous agitation à une vitesse de 200 tours/min
  • . ajout goutte à goutte sous agitation à 1000 tours/min, du SYNPERONIC A7
  • . maintien au repos du mélange obtenu pendant 48 heures environ
  • . passage dudit mélange dans un microfluidiseur à 500 bar
  • . et maintien au repos pendant 24 heures environ.

La stabilité des émulsions est observée après 1 jour, 3 jours, 5 jours et 20 jours de stockage en flacons fermés, en étuve à 40°C.
Les résultats figurent au tableau 2.
On constate que :

• . l'émulsion ne contenant pas de glycérol (3a) ou 1% (3b) de glycérol présente un déphasage de 60% après 5 jours
• . les émulsions contenant 4% (3c) ou 19% (3d) en poids de glycérol ne présentent pas encore de déphasage après 20 jours.

Aqueous emulsions containing

• 12 parts by weight of SYNPERONIC A7, linear alcohol C ₁₂ -C ₁₄ ethoxylated with 7 moles of ethylene oxide
• 6 parts by weight (expressed in dry) of GLUCOPON 600 CSP (alkylpolyglucoside solution at 50% dry extract)
  • . a sodium silicate solution with an SiO ₂ / Na ₂ O ratio of 2, 45% dry extract according to the quantities given in Table 2
• glycerol according to the quantities given in table 2
  through :
  • . introduction into a 2 liter reactor, fitted with a frame stirrer, of GLUCOPON 600 CSP in a preliminary mixture of glycerol and aqueous sodium silicate solution,
  • . heating at 60 ° C for 10 minutes with stirring at a speed of 200 rpm
  • . addition dropwise with stirring at 1000 rpm of SYNPERONIC A7
  • . keeping the mixture obtained at rest for approximately 48 hours
  • . passage of said mixture in a microfluidizer at 500 bar
  • . and stay at rest for about 24 hours.

The stability of the emulsions is observed after 1 day, 3 days, 5 days and 20 days of storage in closed bottles, in an oven at 40 ° C.
The results are shown in Table 2.
We observe that :

• . the emulsion containing no glycerol (3a) or 1% (3b) of glycerol has a phase shift of 60% after 5 days
• . emulsions containing 4% (3c) or 19% (3d) by weight of glycerol do not yet show a phase shift after 20 days.

Example 4

• introduction dans un réacteur de 2 litres maintenu à 40°C sous agitation continue à 200 tours /minute à l'aide d'un agitateur à cadre, de la solution de silicate contenant le glycérol
• addition du GLUCOPON 600 CSP
• addition d'un mélange préalablement préparé à 30°C de SYNPERONIC A7 et d'enzyme
• puis introduction de l'anti-mousse

L'ensemble est homogénéisé à 1000 tours/minute en évitant l'introduction d'air.The following liquid detergent formulation formulation components parts by weight sodium silicate solution with an SiO ₂ / Na ₂ O ratio of 2, 45% dry extract 75.5 glycerol 4 GLUCOPON 600 CSP, 50% dry extract 10 SYNPERONIC A7 10 SAVINASE 32 KNUP (NOVO protease) 0.3 RHODORSIL 20476 defoamer 0.2 (i.e. 15 parts by weight, expressed as dry matter, of surfactants per 100 parts by weight of detergent formulation)
is prepared by:

• introduction into a 2 liter reactor maintained at 40 ° C with continuous stirring at 200 revolutions / minute using a frame stirrer, the silicate solution containing glycerol
• addition of GLUCOPON 600 CSP
• addition of a mixture previously prepared at 30 ° C of SYNPERONIC A7 and of enzyme
• then introduction of the anti-foam

The whole is homogenized at 1000 revolutions / minute avoiding the introduction of air.

The detergent power according to the test described in Example 2 is given in Table 1
It is found that the presence of glycerol also makes it possible to improve the washing performance.

Examples 5a and 5b

Two detergent powder compositions are prepared, one consisting of 100% of granules prepared in Example 1, the other consisting of 80% of said granules and 20% of other additives mentioned in Table 3.

The detergent and anti-scaling power of these two compositions is compared to that of a commercial powder detergent, containing more than 35 constituents, including a complex detergency builder system based on zeolite, sodium carbonate and polymers. , a surfactant system (18%) composed of 4 different products, an enzymatic system and an activated bleaching system.

The detergent power is measured in a Tergotometer according to the method described in Example 2, with the following modifications:
- wash time: 20 minutes (instead of 30 minutes)
- 5g / l of composition to be tested (instead of 8.2g / l)
on the following soiling Standard soiled fabrics (Soil) number of pieces per test - BC-3 CFT cotton (tea) 2 - Dirty cotton CS-3 CFT (wine) 2 - EMPA SUNAK cotton (oxidizable soiling) 2 - Polyester Test Fabric (soot) 2 - Dirty cotton K 10D CFT (sebum) 2 - Dirty cotton / polyester K 20D CFT (sebum) 2 - Dirty polyester K 30D CFT (sebum) 2 - Dirty cotton AS-2 CFT (mineral oil and soot) 2 - Dirty cotton CS-2 CFT (cocoa) 2 - Dirty cotton CS-1 CFT (blood) 2

The encrustation inhibiting effect is measured as in Example 2.
The results obtained are shown in Table 3

Example 6 Stain remover before washing "" prespotter ")

As in Example 3, an aqueous emulsion containing components of the emulsion parts by weight sodium silicate solution with an SiO ₂ / Na ₂ O ratio of 2, 45% dry extract 80 glycerol 4 GLUCOPON 600 CSP, 50% dry extract 8 SYNPERONIC A7 8

The stain-removing power of this emulsion (stain-removing agent before washing) is tested as follows.

PRINCIPLE

The agent to be tested is deposited in a concentrated state on the soiled tissue and spread locally using a spatula.
A contact time of 5 minutes between the textile and the product is respected, before proceeding to the actual washing using a detergent in a household washing machine of AEG brand, cycle 40 ° C.

DETAILS

10x10cm standard soil test tubes prepared by specialized laboratories are used, namely Standard soiled fabrics (Soil) - Dirty cotton K 10D CFT (sebum) - Dirty cotton / polyester K 20D CFT (sebum) - Dirty polyester K 30D CFT (sebum) - Dirty cotton AS-2 CFT (mineral oil and soot) - Polyester / Cotton EMPA 104 from St Gall (soot)

These 5 test pieces are sewn flat on a cotton towel of 60x40cm.
15 g of agent to be evaluated are placed on the soiled test pieces and spread out in an approximate circle of 3 cm in diameter.
After 5 minutes of contact time, the test pieces (on their towel holder) are introduced into an AEG household washing machine, accompanied by a load of 3 kg of linen consisting of clean sponge towels.
A washing cycle is then carried out at 40 ° C., with 100 g of commercial brand ARIEL standard detergent.
After washing, the test pieces are visually examined to assess the additional detergent effect due to the local presence of a stain-removing agent.
Clearer areas, located at the agent's depot, allow this effect to be seen.
(We could also have performed trichromatic laboratory measurements to quantify the additional detergent effect)

The aqueous emulsion tested as a stain removing agent before washing is compared with a commercial product rich in surfactants, of the following composition: anionic surfactant 15% nonionic surfactant 5% pearly base 1% water 19%

The performance of the emulsion tested is visually superior to that of the commercial product, especially on sebum-based soiling, although it is less concentrated in surfactant. Table 1 liquid formulation Trade from example 2 from example 4 detergents CS2 19.45 14.98 16,11 CS1 31.82 39.28 39,16 K10D 14.96 13.6 12.82 AS2 17.37 17.98 23.17 EMPA104 12,02 17.74 22,80 TF polyester (soot) 26.41 20.95 21,60 K30D 11.22 16.8 17,60 cumulative detergency 133.3 141.3 153.3 antiredeposition CN1 -1.74 -2.3 PCN1 -1.14 -2.1 inlay CN1 0.16 0.42 12A 0.88 0.63 emulsion example 3a 3b 3c 3d SYNPERONIC A7 12 12 12 12 GLUCOPON 600 CSP (50% dry extract) 12 12 12 12 glycerol 0 1 4 19 sodium silicate solution (45% dry extract 76 75 72 56 phase shift% after 1 day 30 25 0 0 3 days 50 40 0 0 5 days 60 60 0 0 20 days 65 65 0 0 examples Solid detergent composition 5a 5b comparative components granules of example 1 100 80 whitening system perborate monohydrate 15 DAT 4 enzyme system protease (savinase) 0.5 amylase (termamyl) 0.5 commercial composition 100 detergents BC3 5.2 8.3 6.3 CS3 11.6 15.6 14.5 sunak 12.5 18.6 18.0 TF 29.3 25.6 18.5 K10D 13.2 12.9 13.6 K20D 18.8 17.8 14.5 K30D 19.6 16.1 16.0 AS2 24.9 22.2 26.8 CS2 10.9 15.8 24.9 CS1 17 21.8 20.6 cumulative detergency 163 174.7 173.7 inlay CN1 0.23 0.17 0.35 12A 0.83 0.56 0.81

Claims (16)

1. Process for preparing a system, in the form of an aqueous dispersion or granules, based on at least one liquid, waxy or pasty nonionic surfactant and on an alkali metal silicate, by

   - dispersing

   · in a concentrated aqueous solution of an alkali metal silicate with an SiO₂/M₂O molar ratio ranging from 1.5 to 4, as continuous liquid phase,

   · at least one liquid, pasty or waxy nonionic surfactant (NIS), which is immiscible or sparingly miscible with the said concentrated aqueous alkali metal silicate solution,

   · using at least one nonionic or anionic surfactant (SA) that is compatible with the said concentrated alkali metal silicate solution and capable of dispersing the liquid, pasty or waxy nonionic surfactant(s) (NIS) in the said concentrated alkali metal silicate solution,

   - and optionally drying the dispersion formed, until a rigid shell of alkali metal silicate encapsulating the said droplets or particles of liquid, pasty or waxy nonionic surfactant(s) (NIS) is obtained.
2. Process according to Claim 1, characterized in that the nonionic surfactant is an alkoxylated nonionic surfactant chosen from

   - polyoxyalkylenated (polyoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols in which the alkyl substituent is C₆-C₁₂ and containing from 5 to 25 oxyalkylene units

   - polyoxyalkylenated C₈-C₂₂ aliphatic alcohols containing from 1 to 25 oxyalkylene (oxyethylene or oxypropylene) units

   - ethoxylated and/or propoxylated α- or β-pinenes containing from 1 to 30 oxyethylene and/or oxypropylene units

   - products resulting from the condensation of ethylene oxide or of propylene oxide with propylene glycol or ethylene glycol, with a weight-average molecular mass of about from 2000 to 10 000

   - products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine

   - C₈-C₁₈ ethoxylated and/or propoxylated fatty acids containing from 5 to 25 ethoxylated and/or propoxylated units

   - ethoxylated fatty amides containing from 5 to 30 ethoxylated units

   - ethoxylated amines containing from 5 to 30 ethoxylated units

   - alkoxylated amido amines containing from 1 to 50, preferably from 1 to 25 and most particularly from 2 to 20 oxyalkylene units.
3. Process according to Claim 1 or 2, characterized in that the aqueous alkali metal silicate solution has an SiO₂/M₂O molar ratio ranging from 2 to 3.5 and contains from 35% to 50% of active material, M representing sodium or potassium.
4. Process according to any one of Claims 1 to 3, characterized in that the hydrophilic portion of the nonionic or anionic surfactant (NIS) has one or more saccharide unit(s) containing 5 or 6 carbon atoms.
5. Process according to Claim 4, characterized in that the nonionic or anionic surfactant (NIS) is chosen from

   - alkylpolyglycosides

   - galacturonic, glucuronic, D-mannuronic, L-iduronic and guluronic acid derivatives, with a hydrocarbon-based chain containing from 6 to 24 carbon atoms and preferably from 8 to 16 carbon atoms, and also the alkali metal salts thereof

   - glucosamides

   - sophorolipids.
6. Process according to any one of Claims 1 to 5, characterized in that the dispersing operation is performed by using respective amounts of nonionic surfactant(s) (NIS), of concentrated alkali metal silicate solution and of nonionic or anionic surfactant(s) (SA) such that

   - the content of nonionic surfactant(s) (NIS) represents from 5% to 60% by weight, preferably from 5% to 55% by weight and most particularly from 5% to 45% by weight of the solids content of the said dispersion

   - the content of concentrated alkali metal silicate solution, expressed on a dry basis, represents from 20% to 70% by weight and preferably from 30% to 60% by weight of the solids content of the said dispersion

   - the content of nonionic or anionic surfactant(s) (NIS), expressed on a dry basis, represents from 5% to 40% by weight and preferably from 10% to 30% by weight of the solids content of the said emulsion or dispersion,

   the solids content of the said dispersion being from 30% to 90% and preferably from 40% to 80% by weight.
7. Process for preparing a system in the form of granules according to any one of Claims 1 to 6, characterized in that the drying operation is performed until the amount of water remaining corresponds to a weight ratio: water remaining in the silicate/dry silicate, of from 5/95 to 25/75.
8. Process for preparing a system in the form of a dispersion according to Claim 6, characterized in that the dispersing operation is also performed in the presence of glycerol.
9. Process for preparing a system in the form of a dispersion according to Claim 8, characterized in that the amount of glycerol represents from 3% to 20%, preferably from 4% to 20% and most particularly from 6% to 14% of the total weight of the said dispersion.
10. Process for preparing a system in the form of a dispersion according to any one of Claims 6, 8 or 9, characterized in that the content of nonionic surfactant(s) (NIS) represents from 5% to 35% by weight and preferably from 5% to 30% by weight of the solids content of the said dispersion, and the content of concentrated alkali metal silicate solution, expressed on a dry basis, represents from 30% to 70% by weight and preferably from 40% to 60% by weight of the solids content of the said dispersion.
11. Process for preparing a system in the form of granules according to Claim 7, characterized in that the content of nonionic surfactant(s) (NIS) represents from 10% to 35% by weight and preferably from 15% to 30% by weight of the said system expressed on a dry basis, and the content of alkali metal silicate, expressed on a dry basis, represents from 30% to 70% by weight and preferably from 40% to 60% by weight of the said system expressed on a dry basis.
12. Process for preparing a system in the form of a dispersion according to any one of Claims 1 to 6, 8 or 9, characterized in that the dispersing operation is also performed in the presence of at least one detergent additive chosen from

    - detergent additives that are soluble or dispersible but non-hydrolysable in the concentrated alkali metal silicate solution

    - detergent additives that are soluble or dispersible in the nonionic surfactant (NIS)

    - detergent additives that are insoluble in the silicate solution and in the liquid nonionic surfactant (NIS)

    in an amount, expressed on a dry basis, not exceeding 10% of the weight of the said system thus supplemented with additive.
13. Process for preparing the system forming the subject of any one of Claims 1 to 12, characterized in that the said system is intended to be used as a constituent of a detergent composition, especially for a washing machine.
14. Process for preparing the system in the form of a dispersion forming the subject of Claim 10, characterized in that the said system is intended to be used as a liquid detergent composition, especially for a washing machine.
15. Process for preparing the system in the form of granules according to any one of Claims 1 to 7, characterized in that the said system is intended to be used as a constituent of a solid detergent composition, especially for a washing machine, in an amount, expressed as nonionic surfactant (NIS), of from 5 to 25 parts by weight per 100 parts of detergent composition.
16. Process for preparing the system in the form of a dispersion forming the subject of Claim 11, characterized in that the said system is intended to be used as a solid detergent composition, especially for a washing machine.