RU2144945C1 - Aqueous surfactant composition - Google Patents

Abstract

FIELD: surfactants. SUBSTANCE: invention relates to surfactant compositions forming flocculated systems in water. Composition, in particular, contains gel-forming surfactant, water, and flocculant in amount sufficient to form flocculated, unstable and viscous gel-like composition. The latter also contains stabilizer capable of forming micelles in aqueous phase, which represents compound including C₆-C₂₅-alkyl, alkenyl, or alkylaryl group attached with its one end to the end of at least one hydrophilic group having molecular weight higher than 300. Stabilizer may also include polymer composed of more than four hydrophilic monomers. Indicated compound is selected, in particular, from the group consisting of polyglycosides and alkylthiolopolycaboxylates. EFFECT: enabled high surfactant and/or electrolyte level. 14 cl, 4 tbl, 26 ex

Description

 This invention relates to concentrated water-based surfactant compositions containing high levels of surfactant and / or electrolyte, which under normal conditions should produce either a product with an undesirable high viscosity or a product that separates into two or more phases when standing, or shows signs of excessive flocculation of a surfactant.

 Liquid detergents for laundries have several advantages compared to powder detergents, which leads to their more significant demand in the market for detergents for laundries. The need to suspend moderately soluble builders, such as sodium tripolyphosphate, or insoluble builders, such as zeolite, in the aqueous surfactant fluid has led to the development of structured surfactants. They are pseudoplastic compositions in which the structurant is a surfactant or lyotropic mesophase structurant / water.

 The introduction of compact powders containing higher concentrations of the active ingredient than traditional powders causes a tendency to move to liquids. There is a market need for more concentrated liquids to satisfy this trend, and in particular concentrated aqueous surfactant compositions containing dissolved or suspended structure-forming salts. The introduction of high levels of surfactant and / or dissolved electrolyte can accelerate the flocculation of the structured surfactant, leading to high viscosities and / or instability.

 The problem of suspending water-insoluble or sparingly soluble pesticides in a liquid medium is another new approach to avoid the use of solvents that pollute the environment. Structured surfactant systems are one such approach. Flocculation of systems, along with the crystalline growth of suspended solids, however, imposes serious limitations on the development of suitable products.

 Dyes and pigments that are insoluble or sparingly soluble in water must also be suspended in flowing liquid concentrates to avoid the manipulation of fine powders in the preparation of solutions for dye baths or printing inks.

 Attempts to suspend dyes and pigments in structured surfactants are difficult because of the tendency of the structure of the surfactant to flocculate or break down in the presence of polyelectrolytes, which are usually added to pigments before grinding and which act as grinding aids.

 Cosmetic, toilet, and pharmaceutical formulations also often require the preparation of stable suspensions of dispersed solids or liquids in a fluid aqueous medium that require a high concentration of electrolyte, surfactant, or both, or incorporation of a polyelectrolyte.

 Hydrocarbon-based drilling fluids are used for the lubrication of drill bits and for transporting destroyed rock from the bit to the surface. It has been found that structured surfactants provide the required rheology and suspending ability for the rock. Such solutions require tolerance to very high concentrations of electrolyte, for example, when a borehole penetrates a salt dome. They usually contain weighting agents such as barite, calcite or hematite to facilitate penetration to great depths. However, at the final stage of drilling, they are often replaced with open-cut solutions that contain soluble weighting agents such as calcium chloride or bromide. These dissolved alkaline earth metal electrolytes are highly flocculating with respect to most surfactant structures.

The ability to concentrate liquid detergent or other systems of surfactants is immediately limited by the tendency of most surfactants to form viscous mesophases at concentrations above 30 wt.%, Based on the weight of water and surfactant. Mesophases or liquid crystalline phases are phases that have a degree of order less than the order in a solid, but greater than the order in a classical liquid, for example, an order in one or two, but not three dimensions. Up to about 30%, many surfactants form micellar solutions (L ₁ phase) in which the surfactant is dispersed in water in the form of micelles, which are aggregates of surfactant molecules that are too small to be see in an optical microscope.

 Micellar solutions look and behave in most cases like true solutions. At about 30%, many detergent surfactants form the M phase, which is a liquid crystal with hexagonal symmetry and is usually a stationary wax-like substance. Such products are non-flowing and obviously cannot be used as liquid detergents. At higher concentrations, for example, above about 50% by weight, usually above a certain concentration range lying above 60% and below 80%, a more mobile phase, the G phase, is formed.

 G-phases are non-Newtonian (shear thinning) normally flowing phases, but usually have viscosity, flow characteristics and turbidity, an opalescent look, which makes them unattractive to consumers and unsuitable for direct use as, for example, detergents in laundries. Early attempts to suspend solids in typical G phases were unsuccessful, giving non-flowing products. However, low viscosity mobile G phases, with a relatively large d-distance, which are capable of suspending solids with the formation of fluid suspensions, have been reported.

At even higher concentrations, for example, above about 70 or 80%, most surfactants form hydrated solids. Some, especially non-ionic surfactants form a liquid phase containing water droplets (L ₂ phase) dispersed in micellar size.

It was found that L ₂ phases are unsuitable for use as liquid detergents, since they cannot be rapidly dispersed in water, and they tend to form gels. They cannot suspend solids. Other phases that can be observed include a viscous isotropic (V) phase, which is not mobile and has a glassy appearance.

 The various phases can be recognized by their appearance, rheology, textures in a polarizing microscope, using electron microscopy and X-ray diffraction or neutron scattering.

Definitions
The following terms require explanation or definition regarding the various phases discussed in this description: The "optically isotropic" phases of surfactants generally do not tend to rotate the plane of polarization of light with a polarized plane. If a drop of a sample is placed between two plates of a material with an optically polarizing plane, the polarization planes of which are at right angles, and the light is directed onto one plate, then the samples of optically isotropic surfactants will not appear brighter than their surroundings when they look through another record. Optically anisotropic materials appear to be significantly brighter. Optically anisotropic mesophases usually show characteristic textures when viewed through a microscope between crossed polaroids, while optically isotropic phases show a dark, without characteristic features, continuous field.

"Newtonian fluids" have a viscosity that remains constant at various shear rates. In the case of this description, liquids are considered Newtonian if the viscosity does not change significantly at shear rates of up to 1000 sec ^-1 .

L ₁ phases are mobile, optically isotropic and usually Newtonian liquids that do not show texture in a polarizing microscope. Electron microscopy can resolve the texture of such phases only at very high magnifications, and X-ray diffraction or neutron scattering usually gives only one wide peak, typical of each structure, at very small angles. The viscosity of the L ₁ phase is usually low, but can increase significantly as the concentration approaches the upper phase boundary.

L ₁ phases are single, thermodynamically stable phases and can be considered as aqueous solutions in which dissolved molecules aggregate into spherical, rod-shaped or disc-shaped micelles, which typically have a diameter of about 4 to 10 nm.

где n есть порядок пика."Lamellar" phases are phases that include multiple surfactant bilayers arranged in parallel and separated by a liquid medium. They include both solid phases and a typical form of a liquid crystal G phase. G-phases are usually fluid, non-Newtonian, anisotropic products. They usually look viscous, opalescent substances with a characteristic "blurred" appearance during flow. They form characteristic textures in a polarizing microscope, and samples destroyed by freezing have a lamellar appearance in an electron microscope. X-ray diffraction or neutron scattering likewise exhibits a lamellar structure with a main peak typically between 4 and 10 nm, usually from 5 to 6 nm. Peaks of a higher order, if any, appear on the second or higher layer lines Q of the value of the main peak. Q is the instantaneous transport vector and, in the case of lamellar phases, refers to the repeating distance d in the equation

where n is the order of the peak.

G-phases, however, can exist in several different forms, including domains with parallel layers that form a block of typical G-phases described above, and spherulites formed by a series of concentric spheroidal shells, each of which is a surfactant bilayer . As used herein, the term “lamellar” refers to compositions that are at least partially a form of the first type. Opaque compositions, at least predominantly of the latter type, in which the continuous phase is a substantially isotropic solution containing dispersed spherulites, are referred to herein as “spherulitic”. Spherulites usually have a diameter of 0.1 to 50 microns and thus differ significantly from micelles. Unlike micellar solutions, spherulitic compositions are mainly heterogeneous systems comprising at least two phases. They are anisotropic and non-Newtonian. Being tightly packed and stable, spherulites have good suspending properties of solids. Compositions in which the continuous phase comprises non-spherulitic bilayers typically contain some spherulites and they are usually (semi) transparent in the absence of a dispersed solid or other phase and are referred to herein as “G-phase compositions”. G phases are sometimes referred to in the literature as L _α phases.

M-phases are usually non-mobile, anisotropic products that resemble waxes. They give characteristic textures in a polarizing microscope and give a hexagonal structure in the diffraction pattern obtained using X-ray and neutron diffraction methods, which includes the main peak, usually at values corresponding to a repeating distance between 4 and 10 nm, and sometimes peaks of a higher order, first of which is at a Q value that is 3 ^{0.5 of} the Q value for the main peak, and the next peak has twice the Q value of the main peak. M-phases are sometimes referred to in the literature as H-phases.

L ₂ phases are an inversion of L ₁ phases containing micellar solutions of water in a continuous liquid surfactant medium. Like L ₁ phases, they are isotropic and are non-Newtonian systems.

Viscous isotropic or “V1” phases are usually non-mobile, non-Newtonian, optically isotropic and usually transparent, at least when they are pure. The V1 phases have a diffraction pattern characteristic of cubic symmetry, according to X-ray diffraction or neutron scattering data, with the main peak and peaks of higher order at 2 ^0.5 and 3 ^0.5 values of Q of the main peak.

It is reported that one such cubic liquid crystal phase is immediately formed from the micellar phase at room temperature as soon as the concentration of the surfactant is increased. It is believed that such a V1 phase, sometimes referred to as an L ₁ phase, can occur when micelles (probably spherical) are packed in a cubic lattice. At room temperature, a further increase in the concentration of the surfactant usually leads to the hexagonal phase (M ₁ ), followed by the lamellar phase (G). I ₁ phases, if any, are usually observed only in a very narrow range of concentrations, usually immediately above those concentrations at which an L ₁ phase is formed. The position of such V1 phases in the phase diagram indicates that the phase is constructed from small dense aggregates of surfactant in an aqueous medium.

The inverted form of the I ₁ phase (I ₂ phase) is reportedly likely to be between the reversed hexagonal (M ₂ ) and L ₂ phases.

It consists of a continuous surfactant medium containing aqueous micelles in a cubic lattice. An alternative form of the V1 phase, called the V ₁ phase, is observed at concentrations corresponding to the concentrations between the M and G phases, and may contain a bi-continuous system. It can exhibit even higher viscosity than I ₁ . The reversed phase, the V ₂ phase, between the G and M ₂ phases, is also postulated.

 Some other mesophases, including nematic ones, which contain thread-like structures, are observed or meant.

As used herein, the term “structured surfactant” refers to flowable, liquid, non-Newtonian compositions that have the ability to physically suspend solid particles due to the presence of a surfactant mesophase or solid phase that can be dispersed within the solvent phase. The latter usually represents the phase of an aqueous electrolyte. The surfactant phase is usually present as compacted spherulites dispersed in the aqueous phase. Alternatively, a fluid mobile lamellar phase or bi-continuous mesh inclusions of an aqueous or lamellar phase may be present. The hexagonal phases are usually not mobile enough to form the basis of a structured surfactant, but may, as an exception, be present. It is noted that the cubic phases are not sufficiently mobile. L ₁ or L ₂ phases are not structured per se and have insufficient suspending properties, but may be present, for example, as a continuous liquid phase in which a lamellar or spherulite phase is dispersed, or as a dispersed phase, for example, dispersed in a continuous lamellar or isotropic phase.

Structured surfactants differ from microemulsions, which are thermodynamically stable systems. A microemulsion is basically a micellar solution (L ₁ phase) in which a hydrophobic material is encapsulated in micelles.

 Structured surfactants also differ from colloidal systems, which are kinetically stable. In colloidal systems, the particles of the dispersed phase are small enough (for example, less than 1 μm) to be exposed to Brownian motion. This dispersion is maintained by constant mixing of the internal phase. In contrast, apparently structured surfactants are mechanically stable, with particles immobilized within the structure of the surfactant. While the system is at rest, no movement of suspended particles can be noticed, but the shear stresses associated with the casting process are sufficient to destroy the structure and make the product moveable.

Unless otherwise noted, viscosity data are viscosity measured on a Brookfield viscometer, spindle 4, speed 100 rpm, 20 ^° C. It corresponds to a shear rate of approximately 21 sec ^-1 . This is an indicator of the flow of non-Newtonian fluids.

Technical problem
It is often required to disperse solids or liquids in an aqueous medium with an excess of their solubility in it. Such dispersions should be perfectly fluid and remain uniformly dispersed after prolonged standing.

 Surfactants have been found to have several advantages as suspending agents compared to more conventional dispersing agents such as colloids, microemulsions or the use of thickeners or mineral builders.

 Examples of systems that use structured surfactants include laundry detergents containing solid builders, hard surface cleaners containing abrasive particles, toilet accessories, dyes and pigment suspensions, pesticide suspensions, drilling fluids and lubricants.

 Water-based structured surfactant compositions, such as liquid laundry detergents, toilet accessories, and suspending media for pesticides, dyes, and other solids, often require a high surfactant and / or electrolyte content.

 The surfactant is usually present in the form of spherulites. Spherulites have a noticeable tendency to flocculation, especially at high concentrations of electrolyte. This tendency may cause instability and / or excessively high viscosity.

 Similar effects are noted in cases of other systems of structured surfactants. The purpose of this invention is to reduce flocculation and / or viscosity, and / or to increase the stability of such viscous, flocculated and / or unstable structured surfactants.

A particular type of surfactant that often creates instability problems or causes flocculation is a group containing tissue conditioners. They usually have two C ₁₅ to C ₂₅ alkyl or alkenyl groups (usually solid fat groups) and are usually cationic or amphoteric.

 A particular problem is to obtain high levels of the builder in a composition containing an effective combination of surfactants for washing synthetic fabrics. It has been found that high levels of a solid builder, such as potassium tripolyphosphate or zeolite, lead to unacceptably high viscosities.

 The problems of stability of surfactants or flocculation are not always limited to compositions containing excessive levels of electrolyte. They also arise when attempts are made to incorporate soluble polymers into structured surfactant systems. Such polymers are required, for example, as suspending agents for the soil, additives for grinding, film-forming agents for paintings or enamels, or in order to prevent the growth of crystals in pesticidal suspensions.

 Another problem with detergents with a zeolite builder is that they are less effective in soil removal than detergents based on polyphosphate. In EP-A-0419264, it is noted that the effectiveness of zeolites as structurants can be greatly enhanced by the presence of certain aminoforsphinates, which are usually obtained in oligomeric form, as a co-builder. Unfortunately, it was found that it is impossible to incorporate significant amounts of aminophosphinates in liquid detergents built on zeolite without causing phase separation.

State of the art
Structured surfactants in detergents are described in a number of publications, including GB 2123846, GB 2153380, EP-A-0452106 and EP-A-0530708.

 The following descriptions also apply to structured surfactants (see end of description).

 although in most cases, the structures that would have to be present in the described formulations are not stable enough to support solids in suspension.

 Structured surfactants in pesticidal formulations are described in EP-A-0388239.

 Structured surfactants in drilling fluids and other functional fluids are described in EP-A-0430602.

 Structured surfactants in suspensions of dyes and pigments are described in EP-A-0472089.

 EP-0301883 describes the use of certain polymers as viscosity lowering agents in liquid detergents. The polymers described in the above publication, however, are not effective enough. As a result of this, a number of patents have been published relating to more specialized polymers designed to provide a higher lowering of viscosity (see, for example, EP-A-0346993, EP-A-0346994, EP-A-0346995, EP-A-0415698 , EP-A-0458599, GB 2237813, WO 91/05844, WO 91/05845, WO 91/06622, WO 91/06623, WO 91/08280, WO 91/0881, WO 91/09102, WO 91/09107, WO 91/09108, WO 91/09109 and WO 91/09932). It is indicated that some of these polymers are deflocculants, while others cause osmotic shrinkage of spherulites. These polymers are relatively expensive products, and they make a relatively small contribution to the washing efficiency of the formulation. They usually have a comb-like structure with a hydrophilic polymer backbone carrying many hydrophobic side chains, or vice versa.

Invention
Applicant has found that certain surfactants that form micelles and which are soluble in the aqueous electrolyte phase of a structured surfactant up to at least 1% by weight are highly effective in deflocculating flocculated spherulitic or other surfactant systems by lowering the viscosity of overly viscous systems and / or stabilizing unstable structured surfactant formulations. Moreover, they contribute to surface activity and sometimes also influence formulation.

The stabilizers and / or deflocculants for use according to the invention are surfactants having a C _5-25 hydrophobic group, such as an alkyl, alkenyl or alkylphenyl group, especially a C _6-20 alkyl, alkenyl or alkylphenyl group, and a hydrophilic group that represents a polymer of a hydrophilic monomer, or, especially, a monomer with hydrophilic functional substituents, or a chain within which hydrophilic substituents are introduced and which is connected at one end to said hydrophobic group. The specified hydrophilic group preferably has an average weight of more than 300 AU, more often more than 500, preferably higher than 900 and especially more than 1000 AU.

 The hydrophilic group is usually a polymer containing more than 4, for example, from about six to eight monomer units, depending on the size of the monomer and the period of identity of the structure of the surfactant. Compounds that form micelles in the aqueous phase of a system to be deflocculated, which have a hydrophobic group of at least five carbon atoms bonded at one end to one end of at least one hydrophilic group having a mass of at least 300 ae and / or containing more than four hydrophilic monomer units, and which is compatible with the surfactant to be deflocculated, is referred to herein as “said stabilizers”. The choice of surfactants to act as said stabilizers depends on the nature and concentration of the electrolyte phase and the surfactant that it is desired to deflocculate.

 The stabilizer must be compatible with the phase of the surfactant to be deflocculated. Therefore, anionic stabilizers cannot be used together with cationic surfactants and vice versa. Structured surfactants are usually anionic and / or non-ionic, sometimes self-photographic, usually included as a minor ingredient. For such systems, anionic or nonionic stabilizers are preferred. For cationic structured systems, cationic or nonionic stabilizers are preferred.

 The following discussion is based on the assumption that the surfactant is initially anionic and / or nonionic unless otherwise indicated.

 A common type of electrolyte, in particular for laundry detergents, is the polyvalent anionic type, such as sodium or potassium tripolyphosphate, or potassium or sodium citrate, which are commonly used because of their solubility and structure-forming ability when high concentrations of electrolyte are required.

 In solutions containing high concentrations (e.g., more than 15% w / w) of sodium citrate or a solution of another polyvalent anionic electrolyte, a preferred example of said stabilizers is a polyelectrolyte interrupted by alkanol or alkyl thiol, such as polyacrylate, polymethacrylate or polycrotonate.

 Water-soluble polyacrylates with an alcohol or mercaptan chain stop are known to be used in the manufacture of coatings, adhesive paper and non-woven textile materials (e.g. JP 04081405, JP 01038405 and JP 62085089) and in the manufacture of latexes (e.g. JP 62280203 and DE 1947384). Calcium salts of such polymers are also described in JP 01310730 for use as dispersants for carbon black or iron oxide in water.

Applicant has discovered that a polycarboxylate or other polyelectrolyte having more than 4 hydrophilic monomer units whose units terminate with a C _6-25 aliphatic alcohol, thiol or amine or a C _6-25 aliphatic carboxylate, phosphate, phosphonate, phosphinate or phosphite ester group (hereinafter called "said polyelectrolyte stabilizer"), is more effective than the polymers previously proposed for deflocculation, lowering the viscosity of liquid detergents or stabilizing liquid detergents that contain electrolytes with polyvalent anions. These polyelectrolyte stabilizers also increase the effect of liquid detergent.

Another type of polyelectrolyte used as said stabilizer in electrolytes with polyvalent anions is the polycarboxylate alkyl ester obtained by the addition of unsaturated carboxylic acids such as itaconic, maleic or fumaric acid, or their salts to a compound having a C _8-25 alkyl group and polyoxyethylene a chain such as a polyethoxylated alcohol, for example using a free radical initiator. The product usually has one or preferably more ethoxy groups or one or preferably more than 1,2-dicarboxy ethyl groups.

 Such polycarboxylate alkyl esters are described, for example, in EP 0129328 and in Pat. Great Britain N 9314277.6.

 Another example of these stabilizers is an alkyl coated polysulfomaleate.

 Another example of these stabilizers, which is effective in a polyvalent anionic electrolyte, is an alkyl polyglycoside having a relatively high degree of polymerization. We found that alkyl polyglycosides are also extremely effective in providing lower viscosity and improved stability of concentrated aqueous systems of structured surfactants, along with enhanced action.

 Another example of these stabilizers, which is used in a multivalent anionic electrolyte, is glycolipid or a sugar ester. Monosaccharide esters are not effective, and disaccharide esters, such as sucrose and maltose esters, find very limited use, but higher oligosaccharide esters, such as maltopentaose paltate, have an effect. Esters with more than 4 glycoside groups are preferred. The effect of glycolipids on aggregated liposomes is noted in J. Colloid and Interface Sci., Vol. 152, N 2, Sept. 1992.

 Applicant has found that alkyl ethoxylates are usually not sufficiently soluble at high concentrations of a multivalent anionic type electrolyte to function as said stabilizer in such systems.

It has been found, for example, that C ₁₂ to C _{14 of} fifty moles of ethoxylate forms micelles in 15% w / w aqueous sodium citrate, but not in 20%. The stabilizing activity of ethoxylate is a consequence of the difference in solubility.

 The second type of electrolyte is the multivalent cationic type, such as calcium chloride, and is required, for example, as a soluble weighting agent in drilling fluids. Polycarboxylates are usually not sufficiently soluble in order to function as said stabilizer in the presence of high concentrations of a multivalent cation. Polysulfonates such as alkyl polyvinyl sulfonates or alkyl poly (2-acrylamido-2-methyl propane sulfonates) are preferred, and alkyl polyethoxylates, for example, containing more than 6, for example, more than 20 ethyleneoxy units, are also effective.

 The third type of electrolyte includes monovalent cations and anions, for example, sodium chloride, at a high concentration. Polyelectrolytes are less soluble in such systems, but higher polyethoxylates, such as alkyl 7 to 80 moles, polyethoxylates function well as said stabilizer.

 Another example of an electrolyte that can cause serious flocculation problems even at relatively low concentrations is a standard polyelectrolyte such as naphthalene sulfonate formaldehyde copolymer, carboxymethyl cellulose, or uncoated polyacrylate, or polymaleate. Such (usually) micelle-non-forming polymers are often required in structured surfactant systems. For example, pigment suspensions require grinding to a very fine particle size, and polyelectrolytes are often added in small amounts as grinding aid additives, which leads to serious flocculation problems of the structured surfactant.

 Applicant has found that alcohol ethoxylates are generally highly effective in deflocculating such systems and also systems in which instability or high viscosity is due to the presence of other types of soluble polymer.

 In addition, the applicant has found that, in the presence of said stabilizer, relatively high levels of aminophosphinates can be incorporated into the liquid surfactant compositions without substantially increasing instability.

In addition, the applicant has found that when deflocculants, such as said stabilizers, are gradually added to unstable or viscous compositions, the viscosity first decreases until a stable liquid product is formed. If a deflocculant is still added, then the viscosity rises to a maximum before falling again, and the further addition of a deflocculant results in a translucent, highly mobile G-phase composition with good suspending properties. Further addition leads to a transparent L ₁ phase, obviously unstructured. This product is potentially valuable as a clear detergent or shampoo for use where the ability to suspend a solid is not required.

 The Applicant has found that high levels of a builder and a high washing effect for synthetic fabrics can be achieved by incorporating relatively high levels of nonionic surfactants together with water-soluble builders such as potassium polyphosphate or potassium tripolyphosphate, especially in combination with a suspending builder such as sodium tripolyphosphate.

For such systems that require high concentrations of electrolyte and a high content of non-ionic surfactant, especially a non-ionic surfactant such as polyethoxylate, the Applicant has determined that a new type of heterogenized structured surfactant systems will form, which are usually very viscous. The new system contains an isotropic phase, which the applicant believes is a surfactant phase enriched in an L ₂ phase dispersed in a continuous phase, which may or may include an isotropic phase, which the applicant believes is L ₁ - phase, or in some cases is an anisotropic phase, such as a lamellar phase. Alternatively, in some cases, the dispersed phase may comprise an L ₁ phase in a continuous lamellar phase. In addition, the applicant does not exclude the formation of dispersions of L ₁ in the L ₂ phase.

 The Applicant has found that such new structured surfactant systems can be stabilized with said stabilizers to form systems useful for suspending solids.

SUMMARY OF THE INVENTION
According to one embodiment of the invention, the invention provides the use of a stabilizer containing a hydrocarbon-soluble hydrophobic group bonded at one end to one end of at least one hydrophilic group, which is a polymer chain of more than four hydrophilic monomer groups and / or which has a mass of more than 300 au to reduce or prevent flocculation of systems containing a flocculated surfactant compatible with said stabilizer and a liquid medium that is capable of flocculating said surfactant and in which said stabilizer is able to exist as a micellar solution.

According to a second embodiment of the invention, our invention provides the use of a compound that forms micelles in aqueous solutions of 18% by weight of potassium citrate and which contains a C ₆ to C ₂₅ aliphatic or alkaryl hydrophobic group, one end of which is associated with one end of at least one hydrophilic group having a mass of more than 300 ae and / or including more than four hydrophilic monomer units to lower the viscosity of viscous systems of structured surfactants and / or to convert stable surfactant systems into stable structured or micellar surfactant systems, where these systems contain at least 10% by weight, based on the total weight of the system, of a dissolved, desolubilizing surfactant electrolyte having a multivalent anion .

The present invention provides, as a third embodiment of the invention, the use of a C _5-25 alkyl, alkenyl or alkaryl polycarboxylate ester, C ₅ to C ₂₅ alkyl, alkenyl or alkaryl polyglycoside or a previously defined polyelectrolyte stabilizer to stabilize or reduce the viscosity of an aqueous anionic, a nonionic and / or amphoteric surfactant-containing composition comprising a dissolved electrolyte having a multivalent anion.

 According to a fourth embodiment of the invention, the present invention provides an aqueous surfactant composition comprising: at least one surfactant that is capable of forming a flocculating system per se and / or in the presence of a flocculant; an aqueous continuous phase containing enough flocculant when required to form a flocculated system with said surfactant; and a stabilizer, which is a compound capable of forming micelles in said aqueous phase, and said stabilizer has a hydrophobic group with at least five carbon atoms bonded at one end to one end of at least one hydrophilic group with a mass of more than 300 ae, and / or including at least five hydrophilic monomer units, and which is present in an amount sufficient to inhibit flocculation of the system.

According to a fifth embodiment, the present invention provides an aqueous structured surfactant composition comprising substantially: water, at least one structure-forming surfactant; the proportion of the dissolved flocculating surfactant agent, based on the weight of water, sufficient to form with the indicated structure-forming surfactant and water, (i) flocculating, (ii) unstable and / or (iii) viscous structured surfactant composition ; and at least one stabilizer, which is a micelle-forming compound that contains a C ₅ to C ₂₀ alkyl group attached to one end of the hydrophilic group, said hydrophilic group having a mass of more than 300 ae and / or comprising a polymer with more than four hydrophilic monomer units, so that the specified stabilizer is able to form micelles in an aqueous solution containing the specified electrolyte in the specified proportion, and the specified stabilizer is present in an amount sufficient to ensure (i) a less flocculated, (ii) a more stable and / or (iii) a less viscous structured surfactant composition, respectively.

According to a sixth embodiment, the invention provides an aqueous structured surfactant composition comprising: water, at least one structure-forming surfactant; the proportion of dissolved, desolubilizing surfactant electrolyte, based on the weight of said composition, is sufficient to form flocculated, (i) unstable and / or (iii) viscous structured surfactant composition with said water and surfactant ; and a stabilizer containing a micelle-forming compound that contains a C ₅ to C ₂₅ alkyl, alkenyl or alkaryl group bonded at one end to one end of at least one hydrophilic group, said hydrophilic group having a mass of more than 300 ae and / or includes a polymer with at least four hydrophilic monomer units, so that said stabilizer is capable of forming micelles in an aqueous solution containing said electrolyte in a specified proportion, said stabilizer being present sufficient to provide (i) a less flocculated, (ii) a more stable and / or (iii) a less viscous structured surfactant composition, respectively.

 According to a seventh embodiment, the present invention provides a water-based spherulitic composition containing at least 10% by weight, based on the weight of the composition, surfactant and at least 10% by weight, based on the weight the specified composition, a dissolved electrolyte, facilitating the formation in the absence of the specified stabilizer or (i) a composition that is separated when standing in two or more parts, or (ii) a stable composition having a viscosity, as defined above, of more than 0.8 PA • s , and q residually said stabilizer in order to (i) reduce or prevent said separation and / or (ii) reduce said viscosity, respectively.

According to an eighth embodiment, the present invention provides a stable, flowable, spherulitic structured surfactant composition comprising: water; enough surfactant to form a structure in the presence of an electrolyte; at least 10% by weight of a dissolved, desolubilizing surfactant salt having a multivalent anion, wherein the concentration of said salt in said water is sufficient to form with said water and said surfactant (i) unstable and / or (ii) flocculated, spherulitic composition of a structured surfactant; and a stabilizer having a C _5-20 alkyl group linked at one end to one end of at least one hydrophilic group having a mass of more than 300 ae and a plurality of hydroxyl, carboxylate, sulfonate, phosphonate, sulfate or phosphate groups, such that the stabilizer is soluble in an aqueous solution of the specified salt at the specified concentration. moreover, the stabilizer is present in an amount sufficient to provide (i) a more stable and / or (ii) less viscous spherulitic composition, respectively.

According to a ninth embodiment, the present invention provides an aqueous structured surfactant composition comprising: water; enough surfactant to form a structure in the presence of an electrolyte; a dissolved multivalent metal salt that desolubilizes said surfactant, the concentration of said salt in said water being sufficient to form, with said surfactant, (i) an unstable and / or (ii) flocculated, spherulitic system having a viscosity of more than 0, 8 Pa • s; and a stabilizer containing a compound that includes a C _5-20 alkyl group and a hydrophilic group having a mass of more than 300 au and provided with a plurality of ethoxylate, sulfonate, phosphonate, sulfate and phosphate groups, said stabilizer forming micelles in an aqueous solution of said salt of a multivalent metal at the indicated concentration, and this specified stabilizer is present in an amount sufficient to provide (i) a stable and / or (ii) less viscous spherulite composition, respectively.

According to a tenth embodiment, the present invention provides an aqueous structured surfactant composition comprising: water, a surfactant sufficient to form a structure in the presence of an electrolyte; at least 10% by weight of an alkali metal or ammonium salt of a monovalent anion, and this salt desolubilizes said surfactant, and the concentration of said salt is sufficient to form with said surfactant (i) an unstable spherulite system and / or (ii ) a flocculated system having a viscosity of more than 0.8 Pa • s; and C _6-20 alkyl, alkenyl or aralkyl alkoxylate having at least 8 or preferably 25 to 75 ethyleneoxy groups and optionally up to ten propyleneoxy groups per molecule, in an amount sufficient to form (i) a stable spherulite composition and / or (ii) a less viscous spherulitic composition, respectively.

According to an eleventh embodiment, the invention provides a tissue conditioning composition comprising: water; a cationic fabric conditioner having two C _15-25 alkyl or alkenyl groups; enough flocculant to form a viscous, flocculated and / or unstable system with the specified tissue conditioner and water; and enough stabilizer having a C ₅ to C ₂₅ hydrophobic group bonded at one end to one end of at least a nonionic or cationic hydrophilic group having a mass higher than 300 ae and / or containing at least five hydrophilic monomer units, and said stabilizer is capable of forming micelles in the presence of said water and said flocculant in order to lower the viscosity and / or degree of flocculation of said composition and / or stabilize said composition.

 According to a twelfth embodiment, the present invention provides a surfactant composition comprising: water; structure-forming surfactant; a sufficiently soluble electrolyte, if required, to form a structured surfactant system; sufficiently dissolved, non-micelle-forming polymer to flocculate, increase the viscosity of said structured surfactant system and / or destabilize said structured surfactant system, and said stabilizer enough to reduce flocculation and / or viscosity of said composition and / or stabilize specified composition.

According to a thirteenth embodiment, the present invention provides a surfactant composition suitable for use in a suspension of a solid, such as a pigment or pesticide, and comprising: water; structure-forming surfactant; any soluble surfactant desolubilizer that may be required to form a structure with said surfactant water; enough non-micelle-forming polyelectrolyte (for example, an additive for grinding) for flocculation of this structure; optionally suspended solids; and a stabilizer containing a micelle-forming compound having a C ₅ to C ₂₅ alkyl group attached at one end to one end of at least one hydrophilic group, and said hydrophilic group has a mass of more than 300 ae and / or is a polymer with more than four hydrophilic monomer units in an amount sufficient to form a less flocculated structured surfactant composition.

According to a fourteenth embodiment, the present invention provides a liquid detergent composition comprising: water; structure-forming surfactant; enough dissolved electrolyte, if required, to form a structured surfactant system with said surfactant and water; suspended zeolite builder; aminophosphinate of the formula:
RR'NCR ' ₂ PO (OH) CR' ₂ NRR '(I)
or polymers or oligomers with a repeating unit of the formula:
[-PO (OH) CR ' ₂ NR (R''NR) _n CR' ₂ -] (II)
where each of the R groups, which may be the same or different, is optionally substituted alkyl, cycloalkyl, alkenyl, aryl, aralkyl, alkaryl or alkoxyalkyl group of 1-20 carbon atoms, each of which may be optionally substituted one or more times, and each of the R ′ groups, which may be the same or different, is hydrogen or an R group as defined hereinabove, R ″ is a divalent alkylene, cycloalkylene, alkarylene, alkylene group arbitrarily interrupted by oxygen atoms, or an arylene group, and n is 0 or integer h layer is from 1 to 10, and polymers or oligomers; wherein said aminophosphinate is present in an amount sufficient to increase viscosity, flocculate, or destabilize said system; and sufficient specified stabilizer to lower the viscosity and / or degree of flocculation and / or to stabilize this composition.

According to a fifteenth embodiment, the present invention provides a G-phase composition comprising water, a surfactant and, optionally, a dissolved electrolyte
and / or suspended solids, and adapted, in the absence of a deflocculant, to form a mesophase-containing composition that divides into two or more parts upon standing and / or exhibits a viscosity, as described above, of more than 0.8 Pascal seconds, and is sufficient a deflocculant, such as said stabilizer, to form a stable G-phase composition and / or low viscosity G-phase, respectively.

According to a sixteenth embodiment, the present invention provides a clear, liquid, micellar solution containing water, a surfactant and, optionally, a dissolved electrolyte adapted in the absence of a deflocculant to form a composition containing a mesophase and a deflocculant such as said stabilizer is sufficient , to form a clear, L ₁ micellar solution.

 According to a seventeenth embodiment, the invention provides a structured surfactant composition comprising: water; a structure-forming surfactant comprising at least 30% by weight, based on the total content of the surfactant, a non-ionic surfactant; and enough water-soluble electrolyte to form a structured dispersion of an isotropic, liquid surfactant phase or a liquid surfactant / water phase in an anisotropic (e.g., lamellar) continuous phase.

It is preferred that the isotropic liquid surfactant / water phase is an L ₂ phase.

According to an eighteenth embodiment, the invention provides a structured surfactant composition comprising: water; a structure-forming surfactant comprising at least 30% by weight of a non-ionic surfactant; and enough water-soluble electrolyte to form a structured dispersion of an isotropic, liquid surfactant phase or a surfactant / water liquid phase (e.g., L ₂ phase) in an isotropic aqueous (e.g., L ₁ ) phase.

 Preferably, the new phases in accordance with said seventeenth and eighteenth embodiments of the invention are stabilized by the presence of said stabilizer.

Water environment
Some surfactants, especially surfactants that are highly soluble in oil, such as isopropylamine alkylbenzenesulfonates, are able to form flocculated, structured systems in water, even in the absence of electrolyte. In such cases, the aquatic environment may consist mainly of water. However, most surfactants flocculate only in the presence of dissolved electrolyte, and in particular in highly concentrated electrolyte solutions.

 The compositions of this invention therefore typically contain high levels of dissolved electrolyte desolubilizing a surfactant. Typically, the dissolved electrolyte is present in concentrations higher than 10%, for example, higher than 14%, in particular more than 15% by weight, based on the weight of the composition, up to saturation. For example, sufficiently soluble electrolytes may be present at concentrations between 16 and 40%. Electrolyte solids may be present above saturation, with the excess forming part of the suspended solid.

An electrolyte can be one of four main types:
(I) Salts of multivalent anions: - Of these, potassium pyrophosphate, potassium tripolyphosphate and sodium or potassium citrate are preferred.

 Such electrolytes are generally preferred when using detergents, pesticide compositions, and dye bath compositions.

 (II) Salts of polyvalent cations: - They are usually alkaline earth metal salts, especially halides. Preferred salts are calcium chloride and calcium bromide. Other salts include zinc halides, barium chloride and calcium nitrate. These electrolytes are preferred for use in drilling fluids as soluble weighting agents. Such salts, in particular, are used in formation and sealant solutions in which suspended solid weighting agents may be disadvantageous. They are also widely used in fabric conditioners.

 (III) - Salts of monovalent cations with monovalent anions: - These include alkali metal or ammonium halides such as potassium chloride, sodium chloride, potassium iodide, sodium bromide or ammonium bromide, or alkali metal or ammonium nitrate. It has been found that sodium chloride is especially useful for drilling fluids when drilling through saline formations.

 (IV) Polyelectrolytes: - These include non-forming micelles, polyelectrolytes, such as uncoated polyacrylate, polymaleate or another polycarboxylate, lignin sulfonate or naphthalene sulfonate formaldehyde copolymer. Such polyelectrolytes, in particular, have a high flocculating effect on structured surfactants, even at low concentrations. They can be deflocculated using the indicated polyelectrolyte stabilizer or alkyl polyethoxylates, or alkyl polyglycosides.

 Typically, the higher the amount of surfactant present depending on its solubility, the less electrolyte is required in order to form a structure capable of supporting solid materials and / or causing flocculation of the structured surfactant. Usually we prefer to choose electrolytes that contribute to the composition, and this is consistent with the above about using the cheapest electrolytes from an economic point of view.

 The proportion of the added electrolyte in this case is determined by the amount required in order to cause an adequate effect (for example, in terms of the washing action in the case of detergents). The specified stabilizer is used to obtain the desired viscosity and stability.

 However, the concentration of the electrolyte may depend, among other things, on the type of structure, the viscosity required, and also the cost and performance considerations. Usually, it is preferable for us to form spherulite systems, for example, such as those described in Applicant's applications GB-A-2, 153 380 and EP-A-0530708, in order to obtain a satisfactory balance between mobility and the payload of suspended solids. Such structures cannot usually be obtained bypassing the presence of certain amounts of polyelectrolyte.

 In addition to cost, the choice of electrolyte depends on the intended use of the suspension. Laundry products preferably contain a builder in the form of soluble salts. The composition may contain auxiliary or synergistic substances as an electrolyte or part of it. The selected electrolyte must also be compatible with the substance to be suspended. Electrolytes commonly used in this invention include alkali metal, alkaline earth metal, ammonium or amine salts, including chlorides, bromides, iodides, fluorides, orthophosphates, condensed phosphates such as potassium pyrophosphate or sodium tripolyphosphate. Phosphonates such as salts of acetodiphosphonic acid or amino tris (methylene phosphonates), ethylene deamine tetrakis (methylene phosphonates) and diethylene triamine pentakis (methylene phosphonates), sulfates, bicarbonates, carbonates, borates, nitrates, chlorates, chromates, formates, acetates, oxalates citrates, lactates, tartrates, silicates, hypochlorites, and, if necessary, maintain pH, for example, to improve the stability of a suspended solid or dispersible liquid or to reduce toxicity, acids or bases such as hydrochloric, sulfuric, phosphoric or acetic acid, or sodium, potassium, ammonium or calcium hydroxides, or alkaline silicates.

Avoid electrolytes that form insoluble precipitates with surfactants or that can contribute to the formation of large crystals, for example, more than 1 mm when standing. So, for example, sodium sulfate concentrations are higher or close to its saturated concentration in the composition at 20 ^o C are undesirable. Therefore, the applicant prefers compositions that do not contain sodium sulfate above its saturated concentration at 20 ^o C, in particular, compositions containing sodium sulfate below its saturated concentration at 15 ^o C.

 Because of the cost, where possible, the applicant prefers to use sodium salts as electrolytes, although it is often desirable to incorporate potassium salts into the electrolyte in order to obtain lower viscosity or higher electrolyte concentrations. Lithium and calcium salts have been tested successfully, but it is unlikely to be used in commercial formulations. Calcium salts, such as calcium chloride or calcium bromide, are used in drilling fluid systems in which their relatively high density is an advantage to provide weighting of the drilling fluid. Other bases, such organic bases, can be used, for example, lower alkyl amines and alkanolamines, including monoethanolamine, triethanolamine and isopropylamine.

 In addition to or instead of dissolved electrolyte in an aqueous medium, the presence of dissolved amounts of a flocculating polymer or a destabilizing non-electrolyte polymer in an amount capable of flocculating and / or destabilizing a surfactant is possible. Examples of such polymers are polyvinyl alcohol or polyethylene glycol.

Stabilizer
The Applicant believes that said stabilizer acts, at least initially, as a flocculation inhibitor. The applicant has found, in particular, a noticeable benefit from the addition of a stabilizer to surfactant systems that rapidly flocculate.

 In the absence of said stabilizer, it is often difficult to obtain a composition having a suitable combination of rheological properties and a washing action. Either this composition is too viscous to easily pour and sticks to the cup, or it is unstable and is divided into two or more layers. The difficulty increases when the total concentration of the surfactant and / or builder increases. The commercial demand for more concentrated liquid detergents has created a specific problem for formulation compilers, which was resolved using the specified stabilizer.

Preferably, the concentration of the surfactant and / or electrolyte is controlled so as to provide a composition which, when said stabilizer is added, does not sediment when standing for three months at ambient temperature, and preferably also at 0 ^° C or 40 ^° C or most preferably at both temperatures. It is also preferable to adjust the concentration so as to ensure shear stability of the composition, and it is desirable that the composition does not significantly increase viscosity after holding under normal shear. Sometimes you can choose the concentration of a surfactant and an electrolyte so as to obtain the above characteristics in the absence of the specified stabilizer, but at high viscosity. The specified stabilizer is then added in order to lower the viscosity.

 For the applicant, it is preferable that the compositions of this invention include the specified stabilizer in the range between 0.005 and 20%, preferably 0.01 to 5% by weight, in particular 0.05 to 2%, based on the weight of the composition.

 In those cases where the electrolyte has a multivalent anion, for example citrate or pyrophosphate, and the surfactant is anionic or nonionic, it is preferable for us that the hydrophilic part of the stabilizer has a lot of carboxy and / or hydroxy groups, for example, in particular an alkyl ester of a polycarboxylate, alkyl polyglycoside, alkyl polyglyclamide and / or said polyelectrolyte stabilizer.

 In cases where the electrolyte contains a multivalent cation, it is preferable for the applicant to use stabilizers with many ethoxylate, hydroxyl, sulfonate, phosphonate, sulfate or phosphate groups, such as higher alkyl polyethoxylate, polyvinyl alcohol, alkyl polyglycoside, alkyl polyvinyl sulfonate (alkyl, polyvinyl sulfonate, 2, alkyl poly 2-acrylamidomethyl propane sulfonate), sulfated alkyl polyvinyl alcohol, polysulfonated alkyl polystyrene, alkyl polyvinyl phosphonate, alkyl polyvinyl phosphate or poly (vinyl sulfonated) lkil polialkiloksilat.

 In cases where the electrolyte is an alkali metal halide or similar monovalent system, we prefer the use of alkyl ethoxylate having preferably more than 7, in particular more than 10, usually more than 20, for example from 25 to 75, in particular from 30 to 60, most preferably from 40 to 55 ethoxy groups.

 The compositions of this invention may contain one or more of these stabilizers.

The stabilizers used according to this invention are characterized in that the surfactants have a hydrophilic part and a hydrophobic part. The hydrophobic moiety typically contains a C _5-25 alkyl or alkenyl group, preferably a C ₆ to C ₂₅ , such as a C _8-20 alkyl or alkenyl group, for example a straight chain group. Alternatively, the hydrophobic moiety may contain an aryl, alkaryl, cycloalkyl, branched chain alkyl, alkyl polypropyleneoxy or alkyl poly butyleneoxy group. In some cases, it is possible or preferred to use an amyl group as a hydrophobic moiety. The hydrophilic moiety is required to be relatively large and preferably provided with many hydrophilic functional groups, such as hydroxyl or carboxylate groups or sulfonate.

 The required size of the hydrophilic part is indicated by the fact that alkyl glycosides with one or two glycosidic residues or ethoxylates with three ethoxylate residues are usually ineffective, while they with three, four, five, six and seven or more glycosidic residues gradually become more effective. Similarly, it appears that ethoxylates with five, six, seven or eight ethoxylate residues gradually become more effective in those aqueous media in which they are soluble. Therefore, alkyl polyglycosides with a degree of polymerization greater than about 1.2, preferably more than 1.3, which have a wide distribution and therefore contain significant amounts of higher glycosides, are useful, and the efficiency increases with increasing degree of polymerization. However, alkyl polyglycoside fractions, consisting mainly of diglycoside, for example, maltosides, triglycoside or even tetraglycoside, have been found to be less effective than mixtures containing small amounts of higher oligomers. A fraction consisting mainly of pentaglycoside, however, is very effective and comparable to the optimal examples of the indicated polyelectrolyte stabilizer in concentrated solutions of sodium citrate. As it was found, alkyl polyglycosides with two residues have a slight deflocculating effect in systems containing very high concentrations of electrolyte, for example 40%. The action increases with an increase in the degree of polymerization, more than four, for example, seven glycosidic residues, for full efficiency, depending on the concentration of the electrolyte. A higher degree of polymerization requires a lower concentration. This may be a function of the influence of the electrolyte concentration on the intermellar distance of the spherulite, which, in turn, determines how much stabilizer is retained by the spherulite surface.

 Alkyl ether polycarboxylates with one to three ethylene oxide residues and, on average, from 2 to 3 carboxy groups per molecule, are relatively ineffective, while carboxylates with more than three, in particular more than eight ethylene oxide residues or more than 4, especially more than 8 carboxy groups, usually more effective. For example, eleven moles of ethoxylate with 10 or more carboxy groups is very effective in citrate solution.

 Glucose esters are usually ineffective, but some effect is observed in concentrated electrolyte solutions with maltose esters. Oligosaccharide esters, such as maltopentose or a higher oligosaccharide, for example, partially hydrolyzed starch esters, are used.

 In systems such as 25% potassium chloride, higher ethoxylates, such as 7 to 80 moles, for example, 20 to 50 moles of ethoxylates, are very effective, but lower ethoxylates, such as 3 moles of ethoxylate, are relatively ineffective.

 In general, it seems that the effectiveness of polymeric surfactants depends more on the amount of higher (for example, having a hydrophobic group with a mass of more than 1000 ae, or polymers higher than tetramers) components, than on the average degree of polymerization of the hydrophilic part of the surfactant substances.

 One way to determine whether a particular compound has the required solubility is to measure its solubility in a concentrated aqueous electrolyte solution, the electrolyte present in the composition, or the electrolyte that is equivalent in chemical characteristics, is preferred.

 Stabilizers that are effective typically form micelles in a solution of electrolyte and any other flocculant present in the formulation in water in the same relative proportions as in the composition. Applicant has discovered micelle formation by shaking a suitable amount of a promising stabilizer (for example, 3% by weight based on the weight of the test solution) with an aqueous solution of the test electrolyte and an oil soluble dye. The mixture can be separated (for example, by centrifugation) to form a clear aqueous layer and a colored aqueous layer is observed. If the aqueous layer is colorless, then the formation of micelles is negligible. If staining is developed, this indicates the presence of micelles, and as established, the candidate should be a good stabilizer for systems containing similar concentrations of the same electrolyte.

 For example, in the case of liquid detergents based on citrate or similar systems in which the electrolyte consists at least predominantly of compounds with multivalent anions, potassium citrate, such as a solution containing 15% by weight to saturate potassium citrate, is suitable from 16% to 18%. The solubility of the stabilizer in the test solution is usually at least 1%, preferably at least 2%, more preferably at least 3%, most preferably at least 5% by weight. For example, the test can be based on the addition of a sufficiently concentrated, for example, higher than 30%, aqueous stabilizer solution to a solution of 18% potassium citrate in water in order to obtain 1 or 5% by weight of the stabilizer in the final solution or to obtain evidence of micelle formation with using the dye test described above.

 Not wanting to limit himself to any theory, the applicant believes that the hydrophobic part of the stabilizer is included in the outer spherulite bilayer, and the hydrophilic part is large enough to protrude beyond the surface of the spherulite, preventing flocculation, provided that it is sufficiently soluble in the surrounding aqueous medium .

 A distinctive feature of the stabilizer of this invention is mainly the end-to-end orientation of the hydrophobic and hydrophilic parts. This usually provides a substantially linear structure typical of a classical surfactant with a (usually) substantially linear hydrophilic polymer group blocked at one end by a hydrophobic group. This contrasts with a comb-like structure that was accented in the prior art for deflocculation, where hydrophilic chains have many hydrophobic side chains or vice versa. The applicant believes that the surface-active stabilizers of this invention lead to more effective deflocculation, and also contribute to the total surface activity of the composition. The applicant still does not exclude surfactants in which the hydrophilic part of the branching, for example, polysaccharide ethers, but the applicant also does not exclude branched hydrophobic groups, such as secondary or branched chain alkyl groups, and does not exclude compounds with more than one hydrophilic group, as in the case of an example of ethoxylated diethanolamides. However, the desired structure has one hydrophobic group linked at only one end to one or more hydrophilic groups in an end-to-end orientation.

The stabilizer preferably has a critical micellar concentration (as weight% by weight in water at 25 ^° C.) of less than 0.5, more preferably less than 0.4, in particular less than 0.35, more preferably less than 0, 3. The applicant, in particular, prefers stabilizers having a critical micellar concentration of greater than 1 • 10 ^-5 .

Preferably, the stabilizer provides a surface tension of from 20 to 50 mN m ^-1 , for example, from 28 to 38 mN m ^-1 .

 The stabilizer must be chemically compatible with the surfactant to be deflocculated. Typically, anionic stabilizers are not suitable for use as deflocculants of cationic surfactant structures, and cationic stabilizers cannot be used to deflocculate anionic surfactant structures. However, non-ionic stabilizers are compatible with both anionic and cationic types of surfactants.

The specified stabilizer is usually a compound of General formula RXA, where R is a C _5-25 alkyl, alkaryl or alkenyl group. X is O, CO ₂ , S, NR ¹ , PO ₄ R ¹ or PO ₃ R ¹ , where R ¹ is hydrogen or an alkyl group, such as a C ₁ to C ₄ alkyl or A group, and A is a hydrophilic group, for example containing a chain of more than 4 monomer units linked at one end to X and this chain is hydrophilic enough to give the stabilizer the ability to form micellar solutions (especially solutions containing more than 5% by weight, based on the total weight of the solution), in an aqueous solution of an electrolyte present in the system to be deflocculated at its concentration in the relative system But its content in water. Products that are only partially soluble in the electrolyte solution may be used. Any insoluble fraction will contribute to the total surface activity, while the soluble fraction will additionally act as the specified stabilizer. And it can be, for example, a polyelectrolyte group or a polyglycoside group, a polyvinyl alcohol group or a polyvinylpyrrolidone group or a polyethoxylate having at least six monomeric groups.

Polyelectrolyte Stabilizers
These polyelectrolyte stabilizers are preferably represented by formula (I):
(I) RX- [CZ ₂ -CZ ₂ ] _n H
where R and X have the same meaning as previously, at least one Z represents a COOM carboxylate group, where M is H or a metal or base, such that the polymer is soluble in water, any other Z is H or C ₁ to a C ₄ alkyl group, n = 1 to 100, preferably from 5 to 50, most preferably from 10 to 30. The alkyl or alkenyl group R preferably has from 8 to 24, more preferably from 10 to 20, especially from 12 to 18 carbon atoms. R may be a straight or branched chain primary alkyl or alkenyl group, such as cocoyl, lauryl, cetyl, stearyl, patmityl, hexadecyl, talloyl, oleyl, decyl, linoleyl, dodecyl, or linolenyl group. R alternatively may be a C _6-18 alkyl phenyl group.

 The ratio of the hydrophobic part to the hydrophilic part in the stabilizers (I) should preferably be sufficient to ensure the solubility of the polymer in a saturated solution of sodium carbonate.

Said polyelectrolyte stabilizers are therefore preferably linear, water-soluble, end-blocked polyacrylates, polymaleates, polymethacrylates or polycrotonates containing a hydrophobic part (R) and a hydrophilic part [CZ ₂ -CZ ₂ ]. Copolymers, for example acrylate / maleate copolymers, may be used.

 The monomer units of acrylic or maleic acid may be present in the form of a neutralized salt, or in the form of an acid form, or a mixture of both. Preferably, the monomer units of acrylic acid are neutralized with sodium. Alternatively, they can be neutralized with sodium. Alternatively, they can be neutralized with potassium, lithium, ammonium, calcium or an organic base.

 The hydrophobic and hydrophilic parts of said polyelectrolyte stabilizer are preferably bonded by a sulfur atom, i.e. the polymer is preferably blocked by thiol.

 For surfactants represented by formula (I), it is preferred that the weight average of such surfactants is greater than 250 au, preferably greater than 500 and most preferably greater than 1000 au.

 Typically, said polyelectrolyte stabilizer is present in aqueous surfactant compositions as provided by this invention at a level between 0.01 and 5% by weight, preferably at levels between 0.05 and 3% by weight, for example 0.1 and 2% by weight, based on the total weight of the composition.

Typically, said polyelectrolyte stabilizers (I) are prepared according to the following method:
A hydrophilic monomer, for example acrylic acid, and a chain terminating agent, for example, hexadecane thiol, are reacted together in a suitable ratio, preferably from 90:10 to 50:50, for example, from 70:30 to 80:20, in the presence of a solvent, for example acetone, and a free radical initiator, for example, azobisisobutyronitrile, until the polymerization reaction is completed, for example, by refluxing for about 2 hours. Upon completion of the reaction, the solvent is distilled off, for example, by rotary evaporation, and the obtained polymer product is neutralized by adding a base, for example, NaOH solution, obtaining (I).

Alkyl ether polycarboxylates
Alternatively, said stabilizer may be a polycarboxylate polyalkoxylate of general formula (I):
(I): R (R ¹ ) _x [R ² (R ³ ) _z H] _y R ⁴ ,
in which R is straight chain or branched alkyl, alkaryl or alkenyl or a straight or branched chain alkyl or alkenyl carboxyl group having in each case 6 to 25 carbon atoms, each R ¹ is OCH ₂ CH ₂ or OCH (CH ₃ ) CH ₂ group, each R ² is OC ₂ H ₃ or OC ₃ H ₅ group, each R ³ is C (R ⁵ ) ₂ C (R ⁵ ) ₂ group, where from 1 to 4, preferably 2, R ⁵ groups on the R ³ group are CO ₂ A groups, with each other R ⁵ group being a C ₁ -C ₂ alkyl, hydroxyalkyl or carboxyalkyl group or, preferably, H, R ⁴ is OH, SO ₄ B, SO ₃ B, OR, sulfosuccinyl, OCH ₂ CO ₂ B or R ₂ ⁶ NR ⁷ , R ⁶ is a C ₁ -C ₄ alkyl or hydroxyalkyl group, R ⁷ is a C ₁ -C ₂₀ alkyl group, a benzyl group CH ₂ CO ₂ B, or —O group or PO ₄ B ₂ , B is a cation capable of forming water-soluble salts of said carboxylic acid, such as a metal, alkaline or alkaline earth, each z is in the range from 1 to 5, preferably 1, y is at least , 1, and (x + y) has an average value of from 1 to 50, where R ¹ and R ² groups can be randomly or in any order along the polyalkoxylate chain.

 For example, it is preferable to use an alkyl ester of a polycarboxylate such as is prepared by adding at least one, preferably more than two, for example, three to thirty moles of an unsaturated carboxylic acid or its salts, such as itaconic acid, fumaric acid or preferably maleic acid , to an alkyl polyethoxylate, such as a polyethoxylated alcohol or a fatty acid, for example using a free radical initiator. For example, an aqueous solution of a polyethoxy compound, such as polyethoxylated alcohol, and a sodium salt of an unsaturated acid, such as sodium maleate, can be heated in the presence of a peroxide compound, such as dibenzoyl peroxide. Other carboxylic acids may be used, such as acrylic, itaconic, aconitic, angelic, methacrylic, fumaric and tiglinic.

 Preferably, such polycarboxylates have a “backbone” comprising 2 to 50, more preferably 3 to 40, for example 5 to 30, especially 8 to 20 ethyleneoxy groups, and a plurality of side chains, each of which includes, for example, 1 , 2-dicarboxy ethyl, 1,2,3,4-tetracarboxy butyl or the higher telomeric derivative of a carboxylic acid. Preferably, said polycarboxylate alkyl ester has at least four, more preferably at least six, for example eight to fifty carboxyl groups.

Alkyl Polyglycosides
Alternatively, said stabilizer may be an alkyl polyglycoside. Alkyl polyglycosides are products obtained by the alkylation reduction of sugars, such as fructose or, preferably, glucose, usually by reacting with a fatty alcohol in the presence of a sulfonic acid catalyst or by transesterifying a lower alkyl polyglycoside such as methyl, ethyl, propyl or butyl polyglycoside, C _6-25 alcohol. The applicant, however, does not exclude the use of amyl polyglycosides. The degree of polymerization of the glycoside residue depends on the proportion of alcohol and reaction conditions, but is usually from 1.2 to 10. For the present invention, the applicant prefers alkyl polyglycosides having a degree of polymerization higher than 1.3, more preferably higher than 1.5, especially higher than 1.7, for example from 2 to 20. The applicant, in particular, prefers alkyl polyglycosides containing a significant amount of a substance with more than four units.

Polyalkoxylates
Alkyl polyalkoxylates, such as C ₈ to C ₂₀ alkyl polyethoxylates, or mixed ethoxylate / propoxylates can be used as stabilizers, especially in dilute polyelectrolytes or concentrated salts of alkali or alkaline earth metals of monovalent anions, for example halides or nitrates. In addition to alkoxylated alcohols, other polyalkoxylates having a C _6-20 alkyl group can be used, such as ethoxylated carboxylic acids, ethoxylated fatty amines, alkyl glyceryl ethoxylates, alkyl sorbitan ethoxylates, ethoxylated alkyl phosphates or ethoxylated mono or diethanolamides. Alkoxylates having more than six, for example, more than seven, in particular more than eight ethyleneoxy groups, are generally preferred. In particular, ethoxylates having from ten to sixty, for example from twelve to fifty ethyleneoxy groups, are preferred. Propyleneoxy groups, if present, are usually part of a hydrophobic group, for example, in an alkyl propyleneoxy group. However, propyleneoxy groups can also occur with ethyleneoxy groups in the hydrophilic part of the stabilizer (for example, in the random copolymer), provided that they do not reduce its solubility in the aqueous phase of the system to be deflocculated.

 This typically requires that propyleneoxy groups comprise less than 50% of the total alkylene group in the hydrophilic portion of the stabilizer, for example, less than 30%, usually less than 20%. It is generally preferred that the hydrophilic moiety of the molecule contains less than 8 propyleneoxy groups, for example, less than four.

Other stabilizers
Alternatively, said stabilizer may be alkyl or alkyl thiol coated with polyvinyl alcohol or polyvinylpyrrolidone. Alternatively, an alcohol or carboxylic acid can react with epihalohydrin to form an alkyl polyepihalohydrin, and the product is hydrolyzed, for example, with non-aqueous alkali. Glycolipids (sugar esters) and, in particular, di- or oligosaccharide esters such as sucrose stearate or maltopentose palmitate are also used as said stabilizers as well as alkyl polysulfomaleates. Other potential stabilizers used include alkyl ether carboxylates, alkyl ether sulfates, alkyl ether phosphates, alkyl polyvinyl sulfonates, alkyl poly (2-acrylamido-2-methylpropane sulfonates) and quaternized alkyl amido polyalkyleneamines, such as quaternized alkylamido penta ethylene hexamine.

The introduction of the specified stabilizer
Said stabilizer is usually more effective in preventing flocculation than in deflocculation of an already flocculated composition. However, when a stabilizer is added to the surfactant prior to electrolyte, sometimes a significant subsequent change in viscosity during storage is observed. Therefore, it is preferable to add at least most of the specified stabilizer after the electrolyte. It is usually desirable to add at least a small proportion of the stabilizer first, in order to maintain sufficient mobility before mixing the ingredients, but the amount added first must be kept to the minimum required to obtain a miscible system. However, it is preferable to add the remainder of the electrolyte immediately after adding the electrolyte.

Viscosity
The concentrated, water-based, structured or mesophase-containing surfactant compositions provided by this invention, in the absence of said stabilizer, are usually unstable, highly viscous or non-mobile and are unsuitable for use as, for example, detergent compositions or solids suspending solids . Viscosities higher than 4 Pa • s, measured with a Brookfield RVT viscometer, spindle 5, 100 rpm at 20 ^o C, are not rare for some of these compositions, others are separated when standing on a relatively fluid aqueous layer and a relatively viscous layer containing a significant amount of surfactant, together, sometimes with other layers, depending on what additional ingredients are present.

The aqueous structured surfactant compositions of this invention preferably have a viscosity at a shear rate of 21 s ⁻¹ or under the viscometric conditions described above not higher than 2 Pa • s, preferably not higher than 1.6 Pa • s. Surfactant compositions exhibiting a viscosity of no higher than 1.4 Pa • s are particularly preferred. Typically, we seek to obtain compositions with a viscosity of less than 1.2 Pa • s, in particular less than 1 Pa • s, for example, less than 0.8 Pa • s.

 The surfactant compositions of this invention, in practice, usually have a viscosity, determined under the conditions described above, of more than 0.3 Pa • s, for example, more than 0.5 Pa • s.

 Ideally, for detergent products preferred by the consumer, the viscosity of the compositions of this invention, determined by the above method, is in the range between 0.7 and 1.2 Pa · s, in order to satisfy the required flow characteristics.

Surface-active substance
The compositions of this invention typically contain a sufficient amount of surfactant to form a structured system. For some surfactants, it can be up to 2% by weight, but more often it needs at least 3%, more often at least 4%, usually more than 5% by weight.

 The detergent compositions of the present invention preferably contain at least 10% by weight of the total surfactant, based on the total weight of the composition, most preferably at least 20%, in particular more than 25%, for example, more than thirty%. In practice, it is unlikely that the concentration of surfactant is more than 80% based on the weight of the composition. The specified stabilizer is part of a total surfactant.

 The amount of surfactant present in the composition is preferably greater than the minimum possible in the presence of a sufficient amount of electrolyte desolubilizing the surfactant to form a stable, solid-suspending, structured surfactant system.

 The surfactant may include an anionic, cationic, nonionic, amphoteric and / or zwitterionic form or mixtures thereof.

The anionic surfactant may contain C _10-20 alkyl benzenesulfonate or alkyl ether sulfate, which is preferably a product obtained by ethoxylation of a natural fatty or synthetic C _10-20 alcohol, for example, C _12-14 alcohol with from 1 to 20, preferably from 2 to 10, for example, from 3 to 4 ethyleneoxy groups, distilling off the unreacted alcohol, reacting the ethoxylated product with a sulfonating agent, and neutralizing the resulting alkyl sulfuric acid ester base. The term also includes alkyl glyceryl sulfates and a random or block copolymer of alkyl ethoxy / propoxy sulfates.

The anionic surfactant may also contain, for example, C _10-20 , for example C _12-18 alkyl sulfate.

The surfactant may preferably include C _8-20 , for example, C _10-18 aliphatic soap. Soap may have a saturated or unsaturated, unbranched or branched chain. Preferred examples include dodecanoates, myristates, stearates, oleates, linoleates, linolenates and palmitates, and coconut and tall soaps. In cases where foam control is a significant factor, we particularly prefer to include soaps, such as ethanolamine soaps and especially monoethanolamine soaps, which have been found to be generally well stored in the cold and have good detergent properties.

 According to another embodiment of the invention, the soap and / or carboxylic acid is preferably present in a total weight ratio, based on the total weight of the surfactant, at least 20%, more preferably from 20 to 75%, most preferably from 25 to 50%, for example from 29 to 40%. The surfactant may include other anionic surfactants such as olefin sulfonates, paraffin sulfonates, taurides, isethionates, ether sulfonates, ether carboxylates, aliphatic ester sulfonates, for example, alkyl glyceryl sulfonates, sulfosuccinates or sulfosuccinamates. Preferably, other anionic surfactants are present in a total proportion of less than 45% by weight, based on the total weight of surfactants, more preferably less than 40%, most preferably less than 30%, for example, less than 20% . The cation of any anionic surfactant is usually sodium, but can alternatively be potassium, lithium, calcium, magnesium, ammonium or alkyl ammonium having up to 6 aliphatic carbon atoms, including isopropylammonium, monoethanolammonium, diethanolammonium and triethanolammonium.

 Ammonium and ethanolammonium salts are usually more stable than sodium salts. Mixtures of the above cations can be used.

The surfactant preferably contains one or preferably more non-ionic surfactants. They preferably include alkoxylated C _8-20 , preferably C _12-18 alcohols. Alkoxylates may be ethoxylates, propoxylates or mixed ethoxylated / propoxylated alcohols. Particularly preferred are ethoxylates with from 2 to 20, in particular with from 2.5 to 15 ethyleneoxy groups.

 The alcohol may be fatty alcohol or synthetic, for example, branched chain alcohol. Preferably, the nonionic component has an HLB of from 6 to 16.5, in particular from 7 to 16, for example, from 8 to 15.5. Mixtures of two or more nonionic surfactants having a weight average HLB in accordance with the above values are preferred.

Other ethoxylated and / or propoxylated surfactants that may be present include C _6-16 alkyl phenol alkoxylates, alkoxylated fatty acids, alkoxylated amines, alkoxylated alkanolamides and alkoxylated alkyl sorbitan and / or glyceryl esters.

 Other non-ionic surfactants that may be present include amine oxides, fatty alkanolamides such as coconut diethanolamide and alkylaminoethyl fructosides and glucosides.

 The weight proportion of non-ionic surfactant is preferably at least 2% and usually less than 40%, more typically less than 30%, for example, from 3 to 25%, especially from 5 to 20%, based on total weight of surfactant. However, compositions are included in which the non-ionic surfactant is contained in an amount of from 40 to 100% of the total weight of the surfactant, and they may be preferred for some applications.

 The surfactant may or may include major or minor amounts of amphoteric and / or cationic surfactants, for example betaines, imidazolines, amido amines, quaternized ammonium surfactants and especially cationic fabric conditioners having two long chain alkyl groups, such as tall groups. Examples of fabric conditioners that can be deflocculated according to our invention are dithalloyl dimethyl ammonium salt, dithalloyl methyl benzylammonium salts, dithalloyl imidazolines, dithalloyl amidoamines and quaternized dithalloyl imidazolines and amidoamines.

 The fabric conditioner anion may be, for example, or may include methosulfate, chloride, sulfate, acetate, lactate, tartrate, citrate or formate. Preferably, the compositions of our invention do not contain substantial amounts of both anionic and cationic surfactants.

Aminophosphinates
A specific feature of this invention is its use to stabilize structured liquid detergent compositions containing suspended zeolite and an aminophosphinate co-builder.

The co-structurant may contain compounds that have the formula:
RR'NCR ' ₂ PO (OH) CR' ₂ NRR '(I)
or polymers or oligomers with a repeating unit of the formula
[-PO (OH) CR ' ₂ NR (R''NR) _n CR' ₂ -] (II)
where each of R groups, which may be the same or different, is optionally substituted alkyl, cycloalkyl, alkenyl, aryl, aralkyl, alkaryl or alkoxyalkyl group with 1-20 carbon atoms, each of which may be optionally substituted once or more than once, and each of the R 'groups, which may be the same or different, is hydrogen or an R group as previously defined, R''is a divalent alkylene, cycloalkylene, alkarylene, alkylene group arbitrarily interrupted by oxygen atoms, or an arylene group a, and n is 0 or an integer from 1 to 10, and their polymers or oligomers. All functional groups resident in R, R ′ or R ″ must not be permanently decomposed in the presence of a carbonyl compound or hypophosphorous acid or inorganic acid.

 The co-structurant may be a polymeric or oligomeric aminophosphinate with repeating units of formula (II) or a compound of formula (I) in which R contains at least one phosphorus or sulfur atom. It can be obtained from lysine, 1-amino sorbitol, 4-amino butyric acid or 6-amino caproic acid.

 Polymeric or oligomeric phosphinates can have a mass corresponding to at least 2 units of formula (II), or up to 1000, for example 200, for example, they can have masses up to 244 ae or up to 100000 ae or more, such as 500000 ae.

The phosphinates may be in the form of free acids or in the form of at least partially neutralized salts thereof. The cations are preferably alkali metal ions, preferably sodium or alternatively potassium or lithium, but there may be other monovalent, divalent or trivalent cations, such as ammonium and organically substituted ammonium (including quaternized ammonium), such as triethyl or triethanolammonium, quaternized phosphonium, such as tetrakis hydroxymethyl phosphonium, cations of alkaline earth metals such as calcium and magnesium, or other metal ions such as aluminum. Preferably, the salts or partial salts are water soluble, for example, with a solubility in water at 20 ^° C. of at least 10 g / l, in particular at least 100 g / l.

 R 'groups are preferably all hydrogen atoms. Alternatively, they may independently be alkyl, for example methyl or ethyl, aryl, for example phenyl or tolyl, cycloalkyl, aralkyl, for example benzyl, alkoxyalkyl, for example alkoxyhexyl, or these groups may be optionally substituted at least once or, at least twice, such as substituted alkyl, for example, haloalkyl, carboxyalkyl or phosphonoalkyl, substituted aryl, for example, hydroxyphenyl or nitrophenyl.

 Preferably, the R groups are substituted alkyl, for example ethyl or methyl, or aryl, for example phenyl or tolyl groups, or heterocycles, such as thiazole or triazole groups, and especially at least one and preferably all were groups which carry one or more functional groups capable of coordinating with metal ions, such as carbonyl, carboxyl, amino, imino, amido, phosphonic acid, hydroxyl, sulfonic acid, arsenate, their inorganic and organic esters, for example sulfate or phosphate, and salts thereof. Phosphinates can carry a number of different R groups, as is the case when more than one amine is added to the reaction mixture from which they are isolated.

Preferred phosphinates for use as co-builders are phosphinates in which at least one of the R groups carries at least one carboxylic acid substituent, for example, —C ₆ H ₄ COOH, but especially a carboxyalkyl group, containing from 2 to 12 carbon atoms, for example, —CH ₂ COOH when the phosphinate is synthesized using glycine, —CH (COOH) CH ₂ COOH when the phosphinate is synthesized using aspartic acid or —CH (COOH) CH ₂ CH ₂ COOH when phosphinate is synthesized using glutamic acid.

 Phosphinates can be optically active, for example, as in the case of examples in which at least one of the R, R ′ or R ″ groups is chiral, or when two R ′ groups on one or more carbon atoms in (I) or (ii) are not identical. The arrangement of substituents around each chiral center can be of any configuration. If desired, the racemic mixture can be resolved into optical isomers by methods known per se. Phosphinates can be prepared by reacting hypophosphorous acid with an amine in the presence of a carbonyl compound, which is either a ketone or an aldehyde, or a mixture thereof, and an inorganic acid. Hypophosphorous acid may be added to the reaction as an acid or as a salt thereof, for example sodium hypophosphite. The reaction is accompanied by the release of water.

 The preparation of a co-structurant is described in more detail in EP-0419264. The level of co-structurant in structured liquid surfactants is usually limited to less than about 2% by weight or lower, its tendency to destabilize the structured surfactant. When using the specified stabilizer, it is possible to include significantly larger amounts of co-structurant, for example, up to 10%, preferably from 2 to 8%, for example, from 3 to 6% by weight, based on the total weight of the composition.

 The formulations thus include: structured surfactants, for example, from 5 to 50% by weight; enough dissolved electrolyte, when required, to form a structure (preferably spherulitic); suspended zeolites, for example, from 10 to 40% by weight; the amount of aminophosphinate co-structurant sufficient to cause flocculation or instability of the structured surfactant (for example, from 3 to 8% by weight); and said stabilizer is sufficient to reduce flocculation or stabilize the composition (for example, from 0.01 to 3% by weight).

Suspended solids
A major advantage of the preferred compositions of this invention is their ability to form non-sedimentary fluid suspensions for suspended solids.

 Optionally, the composition may contain up to, for example, 80% by weight, based on the weight of the composition, suspended solids, more often up to 30%, for example, from 10 to 25%. This amount will depend on the nature and intended use of the composition.

 For example, insoluble builders such as zeolite, or moderately soluble builders such as sodium tripolyphosphate, which can be suspended in a structured surfactant environment, are often required in detergent compositions.

 The surfactant systems of this invention can also be used to suspend: abrasives, such as talc, silica, calcite or coarse zeolite, to prepare hard surface cleaners; or pesticides to produce water dispersible, capable of flowing compositions containing water-insoluble pesticides, without the danger of toxic dust or solvents polluting the environment. They are useful in preparing suspensions of pigments, dyes, pharmaceuticals, biocides, or as drilling fluids containing suspended shale and / or weighting agents such as sodium chloride, calcite, barite, galena or haematite.

 They can be used to suspend peeling, including talc, clay, polymer balls, sawdust, silicon dioxide, seeds, peanut or dicalcium phosphate, perlizers such as mica, glycerol mono- or distearate or ethylene glycol mono- or distearate, natural oils such as coconut oil, evening primrose oil, peanut oil, meadow foam, apricot oil, avocado oil, peach oil or jojoba oil, synthetic oils such as silicone oils, vitamins, anti-dandruff, ta such as zinc omadin, and selenium disulfide, proteins, emollients such as linolin or isopropyl myristate, waxes and sun protection agents such as titanium dioxide and zinc oxide.

Structure formers
It is preferred that the detergent compositions of the present invention contain dissolved builders and / or suspended particles of solid builders in order to provide a completely liquid detergent. A “builder” is used herein to mean a compound that promotes the detergent action of a surfactant by improving the action of dissolved calcium and / or magnesium. Typically, builders also help maintain the alkalinity of the aqueous solution. Typical builders include separators and complexing agents such as sodium tripolyphosphate, potassium pyrophosphate, trisodium phosphate, sodium ethylenediamine tetraacetate, sodium citrate or sodium nitrile triacetate, ion exchangers such as zeolites, and precipitants such as sodium or potassium carbonate and such other alkalis like sodium silicate. The specified stabilizer also contributes to the overall structure-forming. Preferred builders are zeolite and sodium tripolyphosphate. The builder is usually present in concentrations up to 50% by weight of the composition, for example, from 15 to 30%.

pH
The pH of the composition for use in laundries is preferably alkaline, as measured after dilution with water to obtain a solution containing 1% by weight of the composition, for example, from 7 to 12, more preferably from 8 to 12, most preferably from 9 to 11.

Hydrotropes
The compositions of the present invention may optionally contain a small amount of hydrotropes, such as sodium xylene sulfonate, sodium toluene sulfonate or sodium cumene sulfonate, for example in concentrations up to 5% by weight, based on the total weight of the composition, preferably not more than 2%, for example from 0.1 to 1%. Hydrotropes tend to destroy the structure of the surfactant and therefore it is important not to use excessive amounts of it. They are mainly useful for lowering the viscosity of the formulation, but if they are too high, they make the composition unstable.

Solvents
In addition to water, the composition may contain solvents. However, like hypotropes, solvents tend to destroy the structure of the surfactant. In addition, again, like hydrotropes, they increase the cost of the formulation without significantly improving the washing action. In addition, they undesirably affect the environment, and the invention has a certain value in the preparation of solvent-free compositions. Therefore, it is preferred that they contain less than 6%, more preferably less than 5%, most preferably less than 3%, in particular less than 2%, even better less than 1%, for example, less than 0.5% by weight solvents such as water-miscible alcohols or glycols, based on the total weight of the composition.

 Preferably, the compositions are substantially solvent free, although it is sometimes desirable to have small amounts of glycerol and propylene glycol. Concentrations up to about 3% by weight, for example, from 1 to 2% by weight, ethanol is sometimes required to improve flavor. Such concentrations are often compatible without causing system destabilization.

Polymers
The compositions of this invention may contain various polymers. In particular, useful amounts of polyelectrolytes, such as unblocked polyacrylates or polymaleates, can be included. Such polymers may be useful because they tend to lower viscosity and because they have an effect on detergent design and may have anti-corrosion or anti-burn activity. Unfortunately, they also tend to destroy the structure of surfactants and cannot normally be incorporated into significant amounts of structured surfactants without causing system destabilization. Applicant has also found that relatively high levels of polyelectrolytes can be added to structured detergents in combination with said stabilizer without causing destabilization of the structure. This can provide stable products of even lower viscosity than can be achieved using only the specified stabilizer.

 Some examples of polymers that can be incorporated into the receptor are anti-redeposition agents, such as sodium carboxymethyl cellulose, anti-foaming agents, such as silicone anti-foaming agents, enzyme stabilizers, such as polyvinyl alcohols and polyvinyl pyrrolidone, dispersants, such as lignin sulfonates and encapsulate like rubbers and resins. Applicant has found that grinding additives, such as sodium dimethylnaphthalene sulfonate / formaldehyde condensates, are useful when a solid dispersible in a composition requires grinding, as is the case with dye or pesticide formulations. The amount of polymer added depends on the purpose for which it is used. In some cases, it can be only 0.01% by weight or even less. More often it is in the range from 0.1 to 10%, in particular from 0.2 to 5%, for example, from 0.5 to 2% by weight.

Other detergents
The solids-suspending detergent compositions of this invention may contain conventional detergent additives, such as anti-redeposition agents, typically sodium carboxymethyl cellulose, optical brighteners, sequestrants, anti-foaming agents, enzymes, enzyme stabilizers, preservatives, dyes, pigments, perfumes, fabric conditioners, for example emollients or bentonites, silencers, bleach activators and / or chemically compatible bleaches. It has been found that peroxide bleaches, such as sodium perborate, especially bleaches that are protected, for example, by encapsulation, are more stable from degradation in the formulations of this invention than conventional liquid detergents. In general, all conventional detergent additives that are capable of dispersing in a detergent composition in the form of solid particles or liquid droplets, above their solubility in this detergent, and which do not chemically interact in it, can be suspended in the composition.

Applications
In addition to creating new detergents for laundries, fabric conditioners and cleansing creams, the stabilized structured surfactants of this invention can be used as toiletries, including shampoos, liquid soaps, creams, lotions, balms, ointments, antiseptics, and skin care products teeth and hemostatic agents.

 They provide the necessary suspending media for dye and pigment concentrators, and printing inks, pesticide concentrators and drilling fluids. In the presence of dense dissolved electrolytes, such as calcium bromide, they are especially useful for hydrocarbon-based sealing fluids used to fill the gap between the pipe and the inner wall of the well, to protect the former from mechanical stress and formation fluids in oil wells, or as a lubricant - coolants or greases.

New phases
Compositions containing a G phase according to this invention are highly mobile and are used as solid suspending systems. They are preferably obtained using the specified stabilizer, but can alternatively be obtained using other deflocculants, such as the polymers described in EP, 0346995, GB 2287813 and WO 9106622.

Similarly, stabilized and new L ₁ systems of the present invention can be obtained with other deflocculants than said stabilizer. They are not used as suspending media, but meet the requirements for clear liquid detergents and shampoos at high levels of surfactant and electrolyte.

The Applicant has found, in particular, that when compositions containing relatively high proportions of a nonionic surfactant are formulated at very high concentrations of a water-soluble electrolyte, such as potassium pyrophosphate, a previously unpublished structural phase is obtained containing an isotropic dispersed phase comprising particles typically having diameter of from 1 to 50 microns, which we believe to consist of a micellar phase, probably, L ₂ inverse micellar phase or in some instances possibly anhydrous zhidkog surfactant, and a continuous phase which is typically either an isotropic phase probably L ₁ or aqueous electrolyte, or a mobile mesophase such as a dilute anisotropic phase which the applicant believes may be lamellar G-phase. The Applicant has found that the gradual addition of a sufficiently soluble electrolyte to a composition containing relatively high proportions of a nonionic surfactant first causes the formation of a typical spherulite composition, while the electrical conductivity passes through the peak and then drops to a minimum, after which it increases sharply to second maximum. Near the minimum, a noticeable change in the dispersed phase occurs, changing from small densely packed, anisotropic spherulites to larger, more isotropic droplets farther apart from each other in a predominantly isotropic or weakly anisotropic continuous phase. The optimum for solid suspending systems is within the first trough of conductivity closer to the conductivity minimum.

 Typically, the proposed new structured system contains from 15% to 100% based on the total weight of the surfactant, more usually at least 30%, for example, from 40% to 90%, especially from 50 to 80% non-ionic surfactant an active substance, such as alcohol ethoxylate or alkyl phenol ethoxylate, along with anionic surfactants such as alkyl benzene sulfonate, alkyl sulfate or alkyl ethoxy sulfate. The composition contains high levels, for example at least 15%, in particular more than 18%, more preferably over 20% by weight of a soluble electrolyte such as potassium pyrophosphate and / or potassium citrate. New structured compositions usually tend to flocculate and require the presence of the specified stabilizer in order to be fluid.

 The invention is further illustrated by the following examples. The thiol polyacrylate surfactant used as the stabilizer in the following examples is prepared by reacting hexadecantiol and acrylic acid in a 24:76 weight ratio in the presence of 0.005 parts by weight of azobisdiisobutyronitrile in a 55 wt.% Solution in acetone of both reagents in based on the total weight of the solution. The mixture was refluxed for one hour, the acetone was distilled off, and the residue was dissolved in 17% by weight aqueous sodium hydroxide solution to obtain a 35% by weight surfactant solution. The product is soluble in an 18% potassium citrate solution of more than 5%. It is also soluble in 25% potassium citrate and at least up to 1% soluble in a 35% potassium chloride solution.

Example 1
The liquid detergent composition for washing includes, wt.%:
Sodium alkylbenzenesulfonate - 8
Triethanolamine alkyl sulfate - 2
3 moles of fatty alcohol ethoxylate - 11
Sodium Tripolyphosphate - 20
Potassium Pyrophosphate - 20
Silicone antifoam - 0.33
Sodium phosphonate, sequestrant - 1
Optical Brightener - 0.05
Fragrance - 0.8
Water - Residue
The composition is prepared with various concentrations of a thiol polyacrylate stabilizer and the viscosity is measured on a Brookfield RVT Brookfield viscometer spindle 4 at 100 rpm and at 20 ^o C. These results are presented in table 1.

The product includes isotropic droplets, which are likely the L ₂ phase in the continuous phase, which is isotropic.

Example 2
A series of aqueous surfactant compositions are prepared, shown in Table 2. Sodium citrate is gradually added to each up to 16.3% by weight (measured as monohydrate). Each composition passes through a homogeneous and stable, but viscous, region at a certain concentration of citrate, but undergoes flocculation and separation as soon as the maximum concentration of citrate is reached. In each case, the addition of 2% by weight 27% by weight of an aqueous solution of the previously indicated thiol polyacrylate stabilizer with stirring results in a homogeneous deflocculated mobile fluid, which, according to microscopic examination, is spherulitic.

Example 3
The compositions illustrated in Table 3 are all stable, mobile, spherulitic fluids. In the absence of the specified stabilizer, they are viscous, flocculated pastes, which, when standing, are separated into a curled mass and a transparent layer at the bottom, which occupies approximately 10% by volume.

 All components are expressed as 100% solids.

Example 4
Alkaline detergent for washing for special use; for example, in hospitals, and adapted for automatic dosing, receive according to the following formula, wt.%:
Sodium hydroxy - 6.8
9 moles of nonylphenyl ethoxylate - 13.4
Sodium C _12-14 linear alkylbenzenesulfonate - 14.0
Sodium diethylene triamine pentakis (methylene phosphonate) - 7.0
Anti-redeposition agent - 7.0
Optical Brightener - 0.05
Thiol Polyacrylate - 0.4
In the absence of a thiol polyacrylate stabilizer, the product has a high viscosity and tends to separate into a fluid liquid phase located above the curled lump. The addition of a stabilizer results in a mobile, stable spherulite composition; the gradual addition of excess thiol polyacrylate causes an increase in viscosity to a maximum. However, the addition of a total of 3% thiol of a polyacrylate surfactant results in a fluid, mobile (semi) transparent G phase with good suspending properties for a solid. Further addition of the stabilizer leads to the formation of a transparent, optically isotopic, Newtonian, micellar solution.

Example 5
A highly concentrated liquid laundry detergent is obtained by mixing together the components in the given order (see table 4).

The product is an opaque, stable, mobile spherulitic composition having a viscosity of 0.65 Pa • s at 21 sec ^-1 .

Example 6
Get liquid laundry formulations (see table. 5).

Example 7
Get a concentrated suspension of the dye, having a formulation,% by weight:
Yellow dye ("Terasil Gelb) - 35
Linear sodium C _12-14 alkylbenzenesulfonate - 6.5
Sodium alkyl ethoxysulfate - 3.25
Potassium chloride - 2
Sodium Dimethyl Naphthalenesulfonate
Formaldehyde Condensate - 6
26% aqueous solution of thiol acrylate stabilizer - 5
Water - 42.25
The composition is mobile, stable and dispersible in water. In the absence of a stabilizer, the composition is viscous and highly flocculated.

Example 8
Get a concentrated suspension of the dye, having a formulation,% by weight:
Yellow dye ("Nerasil Gelb") - 35
95% active isopropylamine linear C _12-14 alkylbenzenesulfate - 5
30% aqueous solution of thiol polyacrylate stabilizer - 5
40% aqueous sodium dimethylnaphthalenesulfonate - 6
Formaldehyde Condensate - 6
Water - 49
The composition is mobile, stable and rapidly dispersible in water. In the absence of a stabilizer, the composition flocculates with the separation of a surfactant, followed by sedimentation of the dispersed dye.

Example 9
Get a degreasing agent for metals having a composition, wt.%:
9 moles of nonyl phenyl ethoxylate - 8.2
3 moles of ethoxylate C _12-14 - 10.3
30% aqueous solution of thioacrylate - 1.5
40% aqueous solution of sodium ethylhexyl sulfate - 6.8
Sodium Tripolyphosphate - 24.0
15% aqueous solution of sodium orthophosphate - 47.9
25% aqueous solution of sodium hydroxide - 1.3
The composition is mobile and stable. In the absence of a stabilizer, it is viscous and is separated when standing.

Example 10
Formulate two drilling fluids containing in wt.% (See table. 6).

Sample A is highly flocculated, giving a viscoelastic fluid that instantly forms a gel upon shear with stirring at 300 rpm. Prior to shear, A has an initial yield strength of 0.1 N and a viscosity at 21 sec ^{−1 of} 0.5 Pa • s. Viscosity decreases with increasing shear to a substantially constant viscosity of 0.17 Pa • s. In contrast, sample B, containing a stabilizer, is a stable, fluid having an initial yield point of 0.1 N and a viscosity at 25 sec ^-1 of 0.55 Pa • s, which increases with increasing shear to a constant value of 0.09 Pa • with .

After stirring at 300 rpm for 15 minutes, the product has an initial yield strength of 0.17 N, a viscosity at 21 sec ^-1 0.38 Pa • s, falling to a constant value of 0.087 Pa • s, at high shear rates. The composition is suitable for use as a drilling fluid, a buffer fluid, a drilling fluid or a sealing fluid.

Example 11
Get the drilling fluid formulation as follows, wt.%:
3 moles of ethoxysulfate Calcium C _12-14 - 6.7
Calcium Oxide - 0.8
H ₂ O - 51.8
Silicone antifoam - 0.4
Calcium Chloride Dihydrate - 34.0
C _12-14 alkylbenzene sulfonic acid - 3.9
Poly AMPS Stabilizer ^* - 3.0
^* The stabilizer is a polymer of 2-acrylamido-2-methylpropanesulfonic acid having a degree of polymerization of 12.

The product is stable and has an initial yield strength of 0.17 N, a viscosity at 21 sec ^-1 1.7 Pa • s and a constant viscosity of 0.13 Pa • s. After 15 minutes at 300 rpm, the initial yield strength was 0.3 N and the viscosity at 21 sec ^-1 was 1.0 Pa • s, dropping to a constant value of 0.9 Pa • s with increasing shear.

Example 12
The following concentrated surfactant system is obtained in an potassium chloride electrolyte and deflocculated by adding twenty moles of ethoxylate alcohol,%:
Linear sodium C _12-14 alkylbenzenesulfate - 12
Sodium alkyl ethoxysulfate - 6
Potassium chloride - 18
C _16-18 alcohol (20E0) ethoxylate - 0.5
Water - 63.5
The composition is mobile and stable, giving a viscosity (shear rate of 21 sec ^-1 ) 0.35 Pa • s. In the absence of a stabilizer - ethoxylate alcohol, it is viscous and is separated when standing.

Example 13
The deflocculating effect of the stabilizer and the viscosity of the deflocculated system are controlled by concentration of the added destabilizer. The minimum amount of stabilizer required for deflocculation depends on the structure of the deflocculant and the composition of the deflocculated system. In the event that deflocculation occurred, with an increase in the concentration of the destabilizer, the viscosity of the system passes through a minimum, then increases to a maximum.

Example 14
It is believed that for each row of flocculated surfactants, there is a sharp difference based on the size of the head group between those groups that have a head group large enough to deflocculate and those that have minimal deflocculating effect (see table 7, eight).

 This is illustrated by the following surfactant system, which can deflocculate with an alkyl polyglycoside. X is the minimum weight percentage of alkyl polyglycoside required for deflocculation.

Monoethanolamine C _12-14 alkylbenzenesulfonate - 30
C _12-14 alkyl 8 moles of ethoxylate - 10
Potassium Citrate Monohydrate - 15
Alkyl polyglycoside - x%
Water is the balance
The degree of polymerization (SP) of an alkyl polyglycoside can be defined as the average number of repeating glycosidic units per alkyl polyglycoside molecule, and can be determined using GLC or GPC methods.

 Therefore, the effect of the size of the head group of a deflocculant on deflocculation can be illustrated by observing the effect of SP alkyl polyglycoside on deflocculation. In the above system, x is the minimum amount of APG (APG) required to cause flocculation (see table 9).

Example 15
Example 14 is repeated using the region of higher DP of alkylpolyglycosides in order to determine which components of the alkylpolyglycoside products are most responsible for flocculation.

 Tab. 10 represents a specific distribution of glycosidic oligomers for each of the tested alkylpolyglycoside products. In this surfactant system, effective deflocculation is observed for oligomers with a degree of polymerization of greater than or equal to seven. At lower degrees of polymerization, only weak flocculation takes place.

Example 16
The reason for the relationship between the size of the head group and the deflocculating effect, apparently, partially follows from the relationship between the size of the head group and the inter-lamellar distance of spherulites.

 It has been found that a shorter distance requires a smaller head group for deflocculation. This is illustrated in table. eleven.

 The interplanar spacing (according to X-ray diffraction data) decreases significantly with increasing electrolyte content (see Table 12).

Example 17
The following ingredients are mixed in the prescribed manner,% weight / weight solids:
Water - residue 100%
C _12-14 alkyl 1.32 cn glycoside (added as 70% solution) - 1.00
Optical Brightener (TINOPAL CBS / X) - 0.15
Calcium Acetate - 0.20
Potassium hydroxide (added as a 50% solution) - 1.64
Monoethanolamine - 2.87
Palm Fruit Fatty Acid - 4.00
Trical potassium citrate monohydrate - 11.50
Sodium C _12-14 alkyl benzenesulfonate - 19.00
Antifoam - 0.05
Zeolite - 18.0
Fragrance - 1.30
C _12-14 alcohol 3 moles of ethoxylate - 7.00
Borax - 2.00
Antifoam - 0.05
Enzyme (SAVINASE 16.OL EX) - 0.40
Bacteriostat (PROXEL GXL) - 0.05
Dye - 0.002
C _12-14 alkyl 1.32 cn glycoside (as 70% solution) - 1.00
"TINOPAL""SAVINASE" and "PROXEL" are registered trademarks.

The composition is a mobile, stable, opaque, spherulitic liquid having the following characteristics:
pH (concentrated) - 9.5
pH (1% solution) - 9.0
Viscosity (Brookfield RVT spindle 4100 rpm) - 1.0 Pa • s
Density - 1.25 s cm ^-1
In the absence of alkyl polyglycoside, the product flocculates rapidly. The slight thickening observed at the end of the movement is corrected by adding an alkyl polyglycoside at the end.

Example 18. The following ingredients are mixed in a given order,% weight / weight The remainder of the substances:
Water - balance up to 100%
Optical Brightening Agent (TINOPAL CBS / X) - 0.1
Disodium Ethylenediamine Tetracetate - 0.55
Calcium Chloride Dihydrate - 0.20
Dye - 0.025
Sodium hydroxide - 5.92
Monoethanolamine - 5.20
Citric Acid - 9.47
Thiol polyacrylate stabilizer - 0.0625
Linear alkylbenzenesulfonic acid - 12.0
Sodium Metaborate - 4.0
Thiol polyacrylate stabilizer - 0.1875
Enzyme - 1.40
The product is a stable, mobile, spherulitic fluid. In the absence of a stabilizer, the product slowly flocculates.

Examples 19-21
Mix the ingredients in the given order (see table. 13).

 The product is a flowable, opaque, solid-free, stable liquid. In the absence of a stabilizer, the product is stationary.

Examples 22 and 23
The following ingredients are mixed in the given order (see table. 14).

 The product in each case is a mobile liquid. When the same composition is obtained without a stabilizer, a highly viscous, curdled product is obtained.

Example 24
The following composition is stable and capable of flowing in the absence of aminophosphinate. Aminophosphinate is prepared according to the method described in Example 1 of EP-A-0419264. The washing action of the product is much lower than the washing action of a detergent based on tripolyphosphate. The addition of aminophosphinate significantly increases the detergent effect, but a concentration higher than 2% by weight causes slow flocculation with separation into a flowing fluid and a viscous, curdled mass. Adding the specified stabilizer makes it possible to raise the level of aminophosphinate to 5.75% by weight without adversely affecting the stability or viscosity of the product. The composition includes the following components, wt.% Based on the weight of the composition:
Optical Brightener - 0.13
Calcium Acetate - 0.09
C _12-14 alcohol 3 moles of ethoxylate - 2.65
Silicone antifoam - 0.18
Triethanolamine - 2.08
Trical potassium citrate monohydrate - 12.17
Zeolite powder - 21.24
Sodium diethylene triamine pentakis (methylene phosphonate) - 0.66
Sodium C _10-18 Fatty Acid - 4.25
Linear sodium C _12-14 alkylbenzenesulfonate - 2.78
Sodium C _12-14 alkyl 3 moles of ethoxysulfate - 4.35
Potassium Carbonate - 1.77
Enzymes - 0.8
Fragrance - 0.35
Aminophosphinate - 5.75
Thiol polyacrylate stabilizer - 0.25
Water - the rest
Examples 25 and 26
The following fabric conditioner formulations are prepared (see table 15). In the absence of an alkyl ethoxylate stabilizer, they are viscous and unstable, which quickly separate upon standing. The inclusion of ethoxylate has proven effective in obtaining a stable, flowable composition.

 Anionic surfactants, such as thiol polyacrylates, have been found to be ineffective.

Claims (14)

1. An aqueous composition of a surfactant forming a flocculated system in water, containing at least one structure-forming surfactant, water, a flocculating agent in an amount sufficient to form flocculated surfactant with said structure-forming surfactant, and water (i) (ii) an unstable and / or (iii) viscous structured composition and a stabilizer capable of forming micelles in the aqueous phase in an amount sufficient to provide (i) less flocculated (ii) a more stable and / or (iii) a less viscous structured surfactant composition, respectively, characterized in that said stabilizer is a compound comprising a C ₆ - C ₂₅ alkyl, alkenyl or alkaryl group linked at one end to one end at least one hydrophilic group, said hydrophilic group having a mass of more than 300 ae and / or comprising a polymer with more than four hydrophilic monomeric units and said compound being selected from the group Luciano polikglikozidy and alkiltiopolikarboksilaty.  2. The composition according to p. 1, characterized in that it further comprises solid particles suspended with it.  3. The composition according to claim 1 or 2, characterized in that the specified surfactant is present as a spherulite phase.  4. The composition according to claim 1 or 2, characterized in that the specified surfactant is present as a lamellar phase.  5. The composition according to claim 1 or 2, characterized in that the structure-forming surfactant includes a non-ionic surfactant in an amount of 30% of the total weight of the surfactant and a water-soluble electrolyte in an amount sufficient to form a structured dispersion " isotropic surfactant / aqueous phase in the continuous lamellar phase. 6. The composition according to p. 5, characterized in that said dispersion "isotropic surfactant / aqueous phase" is an L ₂ phase. 7. The composition according to p. 6, characterized in that said dispersion "surfactant / aqueous phase" includes L ₁ phase. 8. A composition according to any one of the preceding paragraphs, characterized in that the stabilizer contains a hydrophilic polymer group comprising from six to eighty monomeric units selected from the group consisting of acrylate, methacrylate, maleate and crotonate, and attached at one end to C ₆ - C ₂₅ -alkyl, alkenyl or alkarylthiol group. 9. The composition of claim 8, characterized in that the polymer group ends at one end of C ₈ - C ₂₀ -alkyl - or alenylthiol.  10. The composition according to p. 9, characterized in that the stabilizer is a polyacrylate with an end alkylthiol group. 11. A composition according to any one of claims 1 to 7, characterized in that said stabilizer comprises a C ₈ -C ₂₀ alkyl, alkenyl or alkaryl polyglucoside containing enough material with more than four glycoside residues effective to reduce viscosity, and / or the degree of flocculation, and / or to stabilize the specified composition. 12. The composition according to claim 11, characterized in that the specified C ₈ - C ₂₀ -alkylpolyglucoside includes an effective amount of an alkylpolyglycoside with 6 to 12 glycosidic residues.  13. The composition according to any one of the preceding paragraphs, characterized in that it comprises water from 20 to 60 wt.% Based on the total weight of the composition of surfactants, and these surfactants include from 0 to 80 wt.% Based on the total weight of the surfactant of the anionic surfactant and from 20 to 100% based on the total weight of the surfactant of the nonionic surfactant; from 8 to 50 wt.% based on the weight of the composition of dissolved potassium salts selected from the group comprising tripolyphosphate, pyrophosphate and citrate, and the total concentration of dissolved electrolyte is sufficient with the specified surfactant and water to provide a viscous, flocculated, and / or an unstable spherulitic system and / or flocculated dispersion of an isotropic liquid surface-active phase in an isotropic or anisotropic aqueous continuous phase; and a stabilizer in an amount sufficient to reduce the viscosity and / or degree of flocculation and / or stabilization of the composition.  14. The composition according to p. 13, characterized in that it contains up to 35 wt.% Based on the weight of the composition of the suspended solid component. Priority on points:
04/05/94 according to claims 1 to 7;
05/06/94 according to claims 8-14.

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