FR2744131A1 - System containing a non-ionic surfactant and an alkali metal silicate - Google Patents

Abstract

A system in aqueous dispersion or granular form containing at least one liquid, waxy or pasty nonionic surfactant (I) and an alkali metal silicate, is made by (1) dispersing the (I) in a concentrated aqueous solution of an alkali metal silicate as continuous liquid phase, using at least one non-ionic or anionic surfactant (II) which is compatible with the concentrated alkali metal silicate solution and capable of dispersing the (I) in the concentrated alkali metal silicate solution, and (2) optionally drying the resulting dispersion to form a solid shell of alkali metal silicate surrounding droplets or particles of the (I).

Description

SYSTEM BASED ON NON-IONIC SURFACTANT AGENT AND SIUCATE
ALKALINE METAL, IN THE FORM OF A DISPERSION OR PELLETS AND
ITS USE IN DETERGENCE
The present invention relates to a system based on at least one liquid, waxy or pasty nonionic surfactant and an alkali metal silicate, said system being in the form of a stable dispersion or granules. This system can be used as a constituent of liquid or powder detergent compositions.

The invention also relates to powdered or liquid detergent compositions based on said system.

 It is known to transform organic materials, especially surfactants, liquid under normal conditions of temperature and pressure, into powdery products by adsorption and / or absorption on a solid support, generally mineral more or less porous.

The two-component product obtained has the disadvantage of being only very slightly concentrated in organic matter, the support taking up a considerable amount of space.

This is due to the fact that the support products are not very porous and therefore poorly adsorbent.

Thus, the two-component nonionic surfactants / sodium carbonate, nonionic surfactants / sodium sulphate or nonionic surfactants / sodium silicate powder mixtures contain at most 30% of their weight of organic matter considered.

 The use of more porous supports such as precipitated 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.

These carriers, however, have the disadvantage of being insoluble in water, which can cause problems in the intended use.

 Another solution consists in using a cross-linked absorbent organic polymer (absorbent cross-linked polyacrylate, etc.) or a hydrocolloid (starch, guar, etc.); however, it is more expensive and may also have disadvantages in terms of denaturing interactions between the support and the organic material.

 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 phase dispersed by droplets or particles of agent. nonionic liquid surfactant, waxy or pasty, dispersions which, by simple drying, transform into granules by encapsulation of the droplets or particles of nonionic surfactant in a rigid shell of alkali metal silicate.

This solid form has the advantage of leading to a soluble product, easy availability, storage stable, which may contain high levels of nonionic surfactant and can provide 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 granules, has detergent and builder properties. ), which give it the ability to be used as a constituent of liquid or solid detergent compositions, especially for washing machines.

According to the invention, it is a system (S), in the form of a dispersion or granules, based on at least one liquid, waxy or pasty nonionic surfactant and a alkali metal silicate, characterized in that it is obtainable
- by dispersing in a concentrated aqueous solution of an alkali metal silicate as a continuous liquid phase, at least one nonionic surfactant (NIA) liquid, pasty or waxy immiscible or poorly miscible with said solution 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 agent (s) (s) Nonionic surfactant (s) liquid (s), pasty or waxy (NIA) in said concentrated solution of alkali metal silicate,
and optionally drying the formed dispersion, until a rigid shell of alkali metal silicate is obtained encapsulating said droplets or particles of nonionic surfactant (s) which are liquid, pasty or waxy (NIA).

 The term liquid nonionic surfactant (NIA), pasty or waxy immiscible or poorly miscible with an aqueous solution of alkali metal silicate, any nonionic surfactant is present as such in liquid form, pasty or waxy under 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, s' hydrate (by solvation of the hydrophilic portion) or hydrolyze more than 10% of its weight in said concentrated silicate solution.

 Among the nonionic surfactants (NIA) liquid, pasty or waxy, there may be mentioned alkoxylated nonionic surfactants.

Mention may in particular be made of those usually used in the field of detergents for washing clothes, such as
polyoxyalkylenated alkylphenols (polyethoxyethylenated, polyoxypropylenated,
polyoxybutylenes) whose alkyl substituent is C6-C12 and containing from 5 to 25 oxyalkylene units; by way of example, mention may be made of TRITON X95, X-114, X-
100 or X-102 marketed by Rohm & Haas Cy, the IGEPAL NP2 to NP17 of
Rhone-Poulenc;
polyoxyalkylenated C 8 -C 22 aliphatic alcohols containing from 1 to 25 units
oxyalkylenes (oxyethylene, oxypropylene); for example, we can mention the
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, ICI SYMPERONIC A3 to A9, RHODASURF IT, DB and B from
Rhone-Poulenc;
alkoxylated terpenic hydrocarbons, such as ethoxylated α- or pinenes;
and / or propoxylated, containing from 1 to 30 oxyethylene and / or oxypropylene units
- the products resulting from the condensation of ethylene oxide or
Propylene with Propylene Glycol, Ethylene Glycol, Molecular Weight
weight in the order of 2000 to 10000, such as PLURONIC marketed by BASF;
- the products resulting from the condensation of ethylene oxide or
propylene with ethylenediamine, such as TETRONIC marketed by BASF;
ethoxylated and / or propoxylated C8-C18 fatty acids containing from 5 to 25 units
ethoxylated and / or propoxylated
ethoxylated fatty amides containing from 5 to 30 ethoxylated units
ethoxylated amines containing from 5 to 30 ethoxylated units
alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, all
particularly from 2 to 20 oxyalkylene units (preferably oxyethylene)
Among the concentrated solutions of alkali metal silicate, mention may be made of aqueous solutions of alkali metal silicate with an SiO 2 / M2O molar ratio ranging from 1.5 to 4, preferably from 2 to 3.5, and containing approximately from 35 to 50% of active ingredient, M representing sodium or potassium; mention may be made especially commercial solutions of sodium silicate with a ratio of about 2 containing about 45 to 50% of active ingredient, as well as those of sodium silicate with a ratio of about 3 containing of the order of 35 to 40% active ingredient.

The small amounts of free water present in these concentrated silicate solutions are not sufficient to dissolve, hydrate (solvate) or hydrolyze the nonionic surfactant (s) (NIA).

 The operation of dispersing the agent (s) surfactant (s) (NIA) in said concentrated solution of alkali metal silicate can be carried out using any nonionic surfactant or anionic compatible with the concentrated solution of alkali metal silicate, that is to say able to dissolve or hydrate (solvate) to give an isotropic homogeneous 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) whose hydrophilic part 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, albos, idose, arabinose, xylose, lyxose and / or ribose.

Among the nonionic or anionic surfactants (TAS) whose hydrophilic part has a saccharide structure containing from 5 to 6 carbon atoms, mention may be made of:
the alkylpolyglycosides which can be obtained 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 an alkyl group
C4-C20, preferably C8-C18, and an average number of glucose units of
the order 0.5 to 3, preferably of the order of 1.1 to 1.8 per mole of alkylpolyglycoside
(APG); we can mention in particular those presenting
a Cg-C14 alkyl group and an average of 1.4 glucose units per mole
a C12-C14 alkyl group and an average of 1.4 glucose units per mole
a Cg-C14 alkyl group and an average of 1.5 glucose units per mole
a Cg-C10 alkyl group and an average of 1.6 glucose units per mole
marketed under the names GLUCOPON 600 EC),
GLUCOPON 600 CSUP, GLUCOPON 650 EC, GLUCOPON 225 CSUP), by
Henkel.

derivatives of galacturonic acid, glucuronic acid, D-mannuronic acid, L
iduronic and guluronic ... with a hydrocarbon chain containing 6
to 24 carbon atoms, preferably 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 the acid
17-hydroxyoctadécénique
The respective amounts of nonionic surfactant (s) (NIA), concentrated alkali metal silicate solution and nonionic surfactant (s) or anionic (s) (TAS) implemented for the realization of the system of the invention, are such that
the content of nonionic surfactant (s) (NIA) represents from about 10 to 60% by weight, preferably from about 15 to 55% by weight of the dry matter content of said dispersion
the content of concentrated solution of alkali metal silicate, expressed in dry matter, is of the order of 10 to 70% by weight, preferably of the order of 20 to 60% by weight, of the solids content of said dispersion;
the content of non-ionic surfactant (s) or anionic surfactant (s) (TAS), expressed in dry matter, represents from about 5 to 40% by weight, preferably from order of 10 to 30% by weight of the solids content of said emulsion or dispersion, the solids content of said dispersion being of the order of 30 to 90%, preferably of the order of 40 to 80% in weight.

 The operation of dispersing the agent (s) surfactant (s) (NIA) in said concentrated solution of alkali metal silicate with at least one nonionic or anionic surfactant (TAS) can be carried out according to all 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 M.CROFLUIDIZER (MICROFLUIDICS) etc.

 However, it is preferable to prepare a dispersion according to methods employing moderate stirring means.

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

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

 The operation of emulsifying dispersion of the nonionic surfactant (NIA) in the concentrated solution of alkali metal silicate using non-ionic surfactant or anionic surfactant (TAS) is carried out at a temperature at which said nonionic surfactant (NIA) is liquid. The droplets of nonionic surfactant (NIA) obtained during this operation may have diameters of the order of 0.5 to 10 μm, preferably of the order of 0.7 to 511m.

 The eventual drying operation of the dispersion to obtain granules is carried out under conditions such that the continuous liquid matrix of alkali metal silicate is converted by elimination of water into a continuous solid film coating the droplets or particles of nonionic surfactant (NIA); the quantity of water remaining corresponding to a weight ratio of water remaining in the silicatelsilicate in the order of 15/85 to 25/75.

This operation can be performed by any known means. Preferably, a rapid drying of the dispersion is used.

Drying by lyophilization (freezing followed by sublimation), and especially spray drying, are suitable.

This latter mode of drying can be carried out in any known apparatus for spray drying, such as atomization towers associating a spray of the dispersion by a nozzle or a turbine with a stream of hot air, under conditions such that the temperature of the product during drying does not exceed 1 05 C.

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

The granules thus obtained comprise of the order of
- 10 to 60% of their weight, preferably 15 to 55% of their weight of agent (s) surfactant (s) non-ionic (s) (NIA)
- 10 to 70% of their weight, preferably 20 to 60% of their weight of alkali metal silicate expressed in sec
5 to 40% of their weight, preferably 10 to 30% of their weight of surfactant (s) surfactant (s) nonionic (s) or anionic (s) (TAS) expressed in sec
the water / dry silicate ratio being of the order of 15/85 to 25/75
The system (S) which is the subject of the invention, whether in the form of a dispersion or of granules, can be used as a constituent of a detergent composition, especially for washing machines. Here, the term "constituents both a single component for detergent formulation, and the complete detergent formulation itself.

 The present invention therefore also relates to the use of the system (S) forming the subject of the invention as a constituent of a detergent composition, as well as the detergent compositions comprising or consisting of said system (S).

 When it is in the form of granules, said system (S) may be added post-addition to the other components of a powdered detergent composition, in an amount corresponding to that desired by the manufacturer. This amount, expressed as nonionic surfactant (NIA), is generally of the order of 5 to 25 parts by weight per 100 parts of final composition.

In association with said granular system (S) may be present in the powder detergent compositions of other additives, such as: mineral or organlouges detergents builders (1), in an amount such that the total amount of detergency builder is of the order 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
- cogranulates of hydrated silicates of alkali metals and metal carbonates
alkali (sodium or potassium) rich in silicon atoms in Q2 form or
Q3, described in EP-A-488 868, for detergent powder 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, salts
methylene diphosphonates, ...)
the water-soluble salts of carboxylic polymers or copolymers such as salts
water-soluble polycarboxylic acids with a molecular mass of around
to 100,000, obtained by polymerization or copolymerization of carboxylic acids
ethylenically unsaturated such as acrylic acid, maleic acid or anhydride,
fumaric acid, itaconic acid, mesaconic acid, citraconic acid, acid
methylenemalonique, and especially polyacrylates mass
molecular weight of about 2,000 to 10,000 (US-A-3,308,067), the acid copolymers
acrylic acid and maleic anhydride with a molecular mass of about
75000 (EP-A-66 915)
polycarboxylate ethers (oxydisuccinic acid and its salts, tartrate
monosuccinic acid and its salts, disuccinic acid tartrate and its salts
the hydroxypolycarboxylate ethers
- Citric acid and its salts, mellitic acid, succinic acid and their salts
salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, S
(2 hydroxyethyl) nitrilodiacetates)
- C5-C20 alkyl succinic 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 acid
glutamic
polycarboxymethyl derivatives of glutamic acid [such as N, N
bis (carboxymethyl) glutamic acid and its salts, in particular sodium] or other
amino acids
aminophosphonates such as nitriotris (methylene phosphonates)
polyfunctional aromatic compounds such as dihydroxydisulfobenzenes of anionic surfactants, in an amount of the order of 1 to 50%, such as
the alkyl ester sulfonates of formula R-CH (SO 3 M) -COOR ', where R represents a
C8-C20 alkyl, preferably C10-C16 alkyl, R 'is C1-C6 alkyl,
preferably C1 -C3 and M an alkaline cation (sodium, potassium, lithium),
substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-,
tetramethylammonium, dimethylpiperidinium, ...) or an alkanolamine derivative
(monoethanolamine, diethanolamine, triethanolamine, ...)
alkylsulfates of formula ROSO3M, where R represents an alkyl radical or
C1-C24 hydroxyalkyl, preferably C1-C20 hydroxyalkyl, and most preferably
C12-C181 M representing a hydrogen atom or a cation of the same definition
above, as well as their ethoxylenated (EO) and / or propoxylenated (OP) derivatives,
with an average of 0.5 to 6 units, preferably 0.5 to 3 EO units and / or
OP ;;
the alkylamide sulphates of formula RCONHR'OSO3M where R represents a radical
C2-C22 alkyl, preferably C6-C20 alkyl, R 'is a C2-C3 alkyl radical, M
representing a hydrogen atom or a cation of the same definition as above,
as well as their ethoxylenated (EO) and / or propoxylenated (OP) derivatives,
average of 0.5 to 60 EO and / or OP units;
saturated or unsaturated C 8 -C 24 and preferably C 14 -C 20 fatty acid salts,
C8-C20 alkylbenzenesulfonates, primary or secondary alkylsulfonates
Cg-C22, 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-acyls
sarcosinates, alkylglycoside sulfates, polyethoxycarboxylates, cation
having the same definition as above.

anti-fouling agents, in amounts of the order of 0.01-10%, preferably of the order
from 0.1 to 5%, and especially of the order of 0.2-3% by weight, agents such as
cellulosic 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
polyesters based on ethylene terephthalate and propylene units
terephthalate and polyoxyethylene terephthalate, with a molar ratio (number of
patterns) 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, 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-A4 702 857,
US-A-4,770,666);
the sulphonated polyester oligomers obtained by sulphonation of a derived oligomer
ethoxylated allyl alcohol, dimethylterephthalate and 1,2-propylene diol,
having 1 to 4 sulfonated groups (US-A-4,968,451)
the polyester copolymers based on propylene terephthalate units and
polyoxyethylene terephthalate and terminated with ethyl, methyl units (US-A4
711,730) or polyester oligomers terminated with alkylpolyethoxy groups.
(US-A4 702 857) or sulfopolyethoxy anionic groups (US Pat. No. A4,721,580),
sulfoaroyles (US-A4 877 896)
sulphonated polyesters with a number of molecular masses of less than 20 000,
obtained from a diester of terephthalic acid, an acid diester
sulfoisophthalic and a diol (FR-A-2,720,400)
polyesters-polyurethanes obtained by reaction of a mass polyester
Molecular number 300-4000 obtained from adipic acid and / or acid
tereptalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with
terminal isocyanate groups obtained from a polyoxyethylene glycol of
molecular mass of 600-4000 and a diisocyanate (FR-A-2,334,698), anbredéposltlon agents, in amounts of about 0.01-10% by weight for a
detergent powder composition, of about 0.01-5% by weight for a composition
liquid detergent, agents such as
ethoxylated monoamines or polyamines, polymers of ethoxylated amines
(US-A-4 597 898, EP-A-1 984)
- carboxymethylcellulose
the sulphonated polyester oligomers obtained by condensation of the acid
isophthalic acid, dimethyl sulfosuccinate and diethylene glycol
(FR-A-2,236,926)
the polyvinylpyrollidones of the 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, metachloroperbenzoate
Magnesium, 4-Nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-acid
oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide acid
peroxysuccinic acid, decyldiperoxysuccinic acid.

preferably associated with a bleach activator generating in situ in the medium
detergent, a carboxylic peroxyacid; among these activators, we can mention,
tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl
glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose,
Octaacetyl lactose, ...

fluorescers, in an amount of about 0.05-1.2% by weight, agents such as
derivatives of stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid,
azoles, methinecyanines, thiophenes, ...

suds suppressing agents, in amounts of up to 5% by weight,
agents such as
- C10-C24 monocarboxylic fatty acids or their alkaline, ammonium salts
or alkanolamines, triglycerides of fatty acids
- saturated or unsaturated aliphatic, alicyclic, aromatic or
heterocyclic, such as paraffins, waxes
- N-alkylaminotriazines
- monostearylphosphates, monostearyl alcohol phosphates
polyorganosiloxane oils or resins optionally combined with
silica particles of the softening agents, in amounts of about 0.5-10% by weight, agents such as
clays of the enzymes in an amount of up to 5 mg by weight, preferably of the order
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-A4 101 457, US-A4 507 219, US-A-4 261 868) and other addltlfs such as
alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol,
glycerin)
- buffering agents
- perfumes
- pigments
When it is in the form of granules, said system (S) can constitute in itself a detergent composition (SD) powder, for washing machines in particular, when the amount of alkali silicate silicate expressed in dry, represents 30 to 70%, preferably of the order of 40 to 60% of the weight of said system expressed in dry, and that of nonionic surfactant (NIA) represents of the order of 10 to 35%, preferably of the order of 15 to 30% of the weight of said system expressed in sec.

 When it is in the form of a liquid dispersion, it is preferable that said system (S), as such or added other detergency components introduced during its preparation, constitutes the liquid detergent composition itself.

 To form as such a liquid detergent composition (SD), especially for a washing machine, said system (S) in the form of a liquid dispersion contains an amount of alkali metal silicate expressed in dry, of the order of 30 to 70 %, preferably of the order of 40 to 60% of the weight of said system expressed in sec, and an amount of nonionic surfactant (NIA) of the order of 10 to 35%, preferably from 15 to 30% of the weight of said system expressed in sec.

 Said system (S) in the form of a liquid dispersion, added during its preparation of at least one detergency component can constitute a liquid detergent composition, especially for washing machines.

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 preferred that the total amount of these components does not exceed 10% of the weight of the final detergent composition.

 The mode of introduction of said additive (s) into said system (S) in the form of a dispersion is a function of the behavior of said additive (s) with respect to the concentrated solution of silicate and of the nonionic surfactant (NIA).

Among the additives, mention may be made in particular of:
- 1) soluble or dispersible but non-hydroilysable detergent additives in the concentrated solution of alkali metal silicate, such as water-soluble salts of carboxylic polymers or copolymers such as water-soluble salts of polycarboxylic acids of molecular weight of the order from 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 most particularly the molecular weight polyacrylates in the range of 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 about 75,000 (EP-A-66 915); they may be used in an amount (expressed in dry matter) of the order of 0.5 to 6% of the weight of detergent composition expressed in sec, polypeptides such as polyaspartic acid, polyglutamic acid and their salts, in quantity (expressed in dry matter) of the order of 0.5 to 6% by weight of detergent composition expressed in dry form the water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.), in quantity (expressed in dry matter) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates, N (2 hydroxyethyl) -nitrilodiacetates), in quantity (expressed in dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in sec
the polycarboxymethyl derivatives of glutamic acid [such as N, Nbis (carboxymethyl) glutamic acid and its salts, in particular sodium salts] or other amino acids, in quantity (expressed in dry matter) of the order of 0.5 at 6% of the weight of the detergent composition expressed in dry form the alkali carbonates (bicarbonates, sesquicarbonates), in an amount (expressed in dry matter) of the order of 1 to 10% of the weight of detergent composition, expressed in dry form, optical brighteners such as derivatives of stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanines, thiophenes, in an amount expressed in dry matter of the order of 0.1 to 0.5% by weight of detergent composition expressed as dry matter
This type of additive may be introduced into said system (S) by premixing the additive (s) with the alkali metal silicate solution, the nonionic surfactant (NIA) being subsequently dispersed. in said mixture using the surfactant (TAS).

(2) detergency additives that are soluble or dispersible in the nonionic surfactant (NIA), such as enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139, US-A-4,101,457, US-A-4,507,219,
US-A4 261 868), in an amount expressed in seconds of the order of 0.1 to 0.5% by weight of detergent composition expressed as dry matter.
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 solution of silicate.

3) detergency additives insoluble in the silicate solution and in the liquid nonionic surfactant (NIA), such as, in particular, suds suppressing agents such as saturated or unsaturated aliphatic, alicyclic, aromatic or heterocyclic hydrocarbons; , such as paraffins, waxes, monostearylphosphates, monostearyl alcohol phosphates, polyorganosiloxane oils or resins optionally combined with silica particles in amounts expressed in dry form of the order of 0.1 to 0.5% by weight of detergent composition expressed in sec
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. ionic (NIA) .The system formed here is a codispersion.

 The following examples are given in a non-limiting manner.

Example 1
An aqueous emulsion containing
40 parts by weight of SYNPERONIC A7, C12-C14 linear alcohol ethoxylated with 7 moles of ethylene oxide
40 parts by weight of sodium silicate solution with an SiO 2 / Na 2 O ratio of 2 to 45% solids
20 parts by weight in dry weight of GLUCOPON 600 CSP (alkyl polyglucoside) at 50% solids content by introduction into a 2-liter reactor equipped with a frame stirrer, GLUCOPON 600
CSP in the aqueous sodium silicate solution, heating at 60 ° C. for 10 minutes with stirring at a speed of 200 rpm, added dropwise with stirring at 1000 rpm, SYNPERIONIC A7 keeping at rest the mixture obtained during About 48 hours passing said mixture in a microfluidizer at 500bar and keeping at rest for about 24 hours.

The emulsion obtained is stable; it has a homogeneous drop diameter of less than one micrometer and a lower viscosity than that of the starting silicate solution.

The emulsion is dried in a 1 cm thin layer on a glass slide in an oven at 60 ° C for 24 hours.

The product obtained is grindable and flows freely, although it contains more than 50% of nonionic surfactant.

Example 2
The following liquid detergent formulation
components of the formulation parts by weight sodium silicate solution with SiO2 / Na2O ratio of 2, 77.3 to 45% dry extract NORASOL LMW 4500 polyacrylate, at 50% solids content 2
TINOPAL SUP + TINOPAL DMSX (optical brighteners) 0.2
GLUCOPON 600 CSP, 50% dry extract 10
SYMPERONIC A7 10
SAVINASE 32 KNUP (NOVO protease) 0.3 antifoam RHODORSIL 20476 0.2 (ie 15 parts by weight, expressed in dry form, 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 rpm using a frame stirrer
silicate solution
of the polyacrylate solution
optical brighteners and stirring for 5 minutes - addition of GLUCOPON 600 CSP - addition of a previously prepared mixture at 30 ° C of SYMPERONIC A7 and enzyme - then introduction of antifoam
The whole is homogenized at 1000 rpm avoiding the introduction of air.

The detergency and antiredeposition power of the above detergent formulation is tested as follows.

PRINCIPLE
The test simulates a simplified machine wash, using a tergotometer. It consists in washing, at 40 ° C in water of hardness 30 "TH, samples of fabric soiled 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 cloth, before and after washing, using a colorimeter. In addition, white non-soiled control fabrics are incorporated, which make it possible to evaluate the redeposition of soil by measuring the reflectances before and after washing.

EQUIPMENT AND EQUIPMENT
Material: - Tergotometer: "US TESTING Co Inc." HOBOKEN NJ Model 7243.

- Glaze to iron fabric samples after washing.

- Color Measuring Device "Dr Lange LUCI 100".

Fabrics
Standard fabrics are manufactured by CFT (Center For Test Materials) or by the company "Test Fabric". They have the following characteristics:
Standard soiled fabrics (soiling) number of pieces per test
- CS-2 CFT cocoa (cocoa) 2
- Dirty cotton CS-1 CFT (blood) 2
- Cotton soil K 10D CFT (mineral oil and sebum) 2
- Poyester sali K 30D CFT (sebum) 2
- Asiatic cotton AS-2 CFT (mineral oil and soot) 2
- EMPA 104 CFT cotton polyester (mineral oil and ink) 2
- Polyester Test Fabric (soot) 2
Standard white fabrics - CN 1 cotton, white, unsalted, CFT 5 - PCN 1 cotton, white, unsalted, CFT 5 or, for each test, a total of 24 pieces of fabric.

OPERATIVE MODE
Detergency test
The tergotometer is a device consisting of 4 pots of 2 liters stainless steel on which are fitted agitators that are set at 50 cycles per minute (100 round trips). The pots are placed in a water tank regulated at 40 ° C.

 In each pot is placed 1 liter of water containing 8.29 of test formulation.

When the water is at temperature, the pots are introduced into the thermostatic bath by simultaneously triggering the 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 dewatered by hand and individually dried individually between two sheets of absorbent white paper.

The tissues are again put between two sheets of clean absorbent paper, and ironed in the ice at a temperature of 110 ° C.

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

Calculation of detergency
The value "DE" (detergency) is calculated for each type of fabric by geometric sum of the color differences DL, Da and Db before and after washing on the soiled fabrics:
Is
DE detergency = (DL2 + Da2 + Db2) 112 Pouvolr antiredenosition
The anti-redeposition properties of the tested products are evidenced by the use of standard non-soaked white cotton CNI 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 tissue and the washed white tissue in the presence of soiled tissue.

The measurement of the scale inhibitor effect is measured after 6 washes at 60 "C in 40" hard water TH, in the absence of soiled fabrics on the following unsalted test pieces:
CNI cotton
Terrez cotton 1 2A
Mineral incrustation is calculated from the ash content (in% based on the total weight of the cotton) of the washed, dried and burnt fabrics at 950 ° C for 3 hours.

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

It is found that the detergency 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 significantly lower than that (50%) of the commercial laundry.

Table 1

<tb><SEP> formulation <SEP> liquid
<tb><SEP> of <SEP> commerce <SEP> of <SEP> example <SEP> 2
<tb> Detergence <SEP>
<tb> CS2 <SEP> 19.45 <SEP> 14.98
<tb> CS1 <SEP> 31.82 <SEP> 39.28
<tb> K10D <SEP> 14.96 <SEP> 13.6
<tb> AS2 <SEP> 17.37 <SEP> 17.98
<tb> EMPA104 <SEP> 12.02 <SEP> 17.74
<tb> TF <SEP> polyester <SEP> 26.41 <SEP> 20.95
<tb> K30D <SEP> 11.22 <SEP> 16.8
<tb> cumulative <SEP> detergency <SEP> 133.3 <SEP> 141.3
<tb> Antiredeposition
<tb> CNi <SEP> -1.74 <SEP> -2.3
<tb> PCN1 <SEP> -1.14 <SEP> -2.1 <SEP>
<tb> Inlay
<tb> CNi <SEP> 0.16 <SEP> 0.42
<tb> 12A <SEP> 0.88 <SEP> 0.63
<Tb>

Claims (13)

 1) System, in the form of a dispersion or granules, based on at least one liquid, waxy or pasty nonionic surfactant and an alkali metal silicate, characterized in that it is likely to be obtained  - by dispersing. in a concentrated aqueous solution of an alkali metal silicate as a continuous liquid phase, at least one non-ionic surfactant (NIA) liquid, pasty or waxy immiscible or poorly 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 surfactant (s) (s) ) non-ionic (s) liquid (s), pasty or waxy (NIA) in said concentrated solution of alkali metal silicate,  and optionally drying the formed dispersion, until a rigid shell of alkali metal silicate is obtained encapsulating said droplets or particles of nonionic surfactant (s) which are liquid, pasty or waxy (NIA).  2) System according to claim 1, characterized in that the nonionic surfactant is an alkoxylated nonionic surfactant chosen from  polyoxyalkylenated alkylphenols (polyethoxyethylenated, polyoxypropylenated,  polyoxybutylenes) whose alkyl substituent is C6-C12 and contains from 5 to 25  oxyalkylenic units  polyoxyalkylenated C 8 -C 22 aliphatic alcohols containing from 1 to 25 units  oxyalkylenes (oxyethylene, oxypropylene)  ethoxylated and / or propoxylated α-or pinenes containing from 1 to 30 units  oxyethylene and / or oxypropylene  - the products resulting from the condensation of ethylene oxide or  Propylene with Propylene Glycol, Ethylene Glycol, Molecular Weight  weight in the range of 2000 to 10000  - the products resulting from the condensation of ethylene oxide or  propylene with ethylenediamine  ethoxylated and / or propoxylated C8-C18 fatty acids containing from 5 to 25 units  ethoxylated and / or propoxylated  ethoxylated fatty amides containing from 5 to 30 ethoxylated units  ethoxylated amines containing from 5 to 30 ethoxylated units  alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, all  particularly from 2 to 20 oxyalkylene units  3) System according to claim 1) or 2), characterized in that the aqueous solution of alkali metal silicate has an SiO2 / M2O molar ratio ranging from 1.5 to 4, preferably from 2 to 3.5, and contains the order of 35 to 50% of active material, M representing sodium or potassium.  4) System according to any one of claims 1) to 3), characterized in that the hydrophilic part of the nonionic surfactant or anionic surfactant (TAS) has one or more saccharide unit (s) ) containing from 5 to 6 carbon atoms.  5) System according to claim 4, characterized in that the nonionic surfactant or anionic surfactant (TAS) is chosen from  alkylpolyglycosides  derivatives of galacturonic acid, glucuronic acid, D-mannuronic acid, L  iduronic and guluronic, having a hydrocarbon chain having from 6 to  24 carbon atoms, preferably 8 to 16 carbon atoms, as well as their  alkali metal salts  - glucosamides  - sophorolipids  6) System according to any one of claims 1) to 5), characterized in that the dispersing operation is performed by implementation of respective amounts of agent (s) surfactant (s) not ionic solution (s) (NIA), concentrated solution of alkali metal silicate and nonionic surfactant (s) or anionic (s) (TAS) such as  the content of nonionic surfactant (s) (NIA) represents from about 10 to 60% by weight, preferably from about 15 to 55% by weight of the dry matter content of said dispersion  the content of concentrated solution of alkali metal silicate, expressed in dry matter, is of the order of 10 to 70% by weight, preferably of the order of 20 to 60% by weight, of the solids content of said dispersion;  the content of non-ionic surfactant (s) or anionic surfactant (s) (TAS), expressed in dry matter, represents from about 5 to 40% by weight, preferably from order of 10 to 30% by weight of the solids content of said emulsion or dispersion, the solids content of said dispersion being of the order of 30 to 90%, preferably of the order of 40 to 80% in weight.  7) System in granular form, according to any one of claims 1) to 6), characterized in that the drying operation is carried out until the remaining amount of water corresponds to a weight ratio water remaining in the silicate / dry silicate of the order of 15/85 to 25/75.  8) System in the form of a dispersion according to claim 6), characterized in that the content of surfactant (s) surfactant (s) non-ionic (s) (NIA) is of the order of 10 to 35 % by weight, preferably of the order of 15 to 30% by weight of the dry matter content of said dispersion and that in concentrated solution of alkali metal silicate, expressed in dry, of the order of 30 to 70% by weight weight, preferably of the order of 40 to 60% by weight of the solids content of said dispersion.  9) System in the form of granules according to claim 7), characterized in that the content of surfactant (s) surfactant (s) non-ionic (s) (NIA) is of the order of 10 to 35% by weight, preferably of the order of 15 to 30% by weight of said system expressed in dry, and that of alkali metal silicate, expressed in dry, of the order of 30 to 70% by weight, preferably of 40 to 60% by weight of said system expressed in sec.  10) System in the form of a dispersion, according to any one of claims 1) to 6), characterized in that it further comprises at least one detergency additive, chosen from  the soluble or dispersible but non-hydrolysable detergency additives in the concentrated solution of alkali metal silicate  the detergent additives soluble or dispersible in the nonionic surfactant (NIA)  the detergency additives insoluble in the silicate solution and in the liquid nonionic surfactant (NIA) in an amount, expressed in dry matter, not exceeding 10% of the weight of said system thus additive.  11) Use of the system according to any one of claims 1) to 10) as a constituent of detergent compositions, particularly for washing machines.  12) A detergent composition comprising or consisting of the system of claims 1) to 10).  13) solid detergent composition according to claim 12, comprising the system subject of any one of claims 1) to 7), in granular form, in quantity, expressed as nonionic surfactant (NIA) , of the order of 5 to 25 parts by weight per 100 parts of detergent composition.