BG60382B1 - Liquid detergent compositions - Google Patents

Abstract

Liquid detergent compositions are suitable for washing. They are mobile, stable in storage under adverse weather conditions having high pH and resistant to slipping forces. They contain water, electrolyte, active ingredient and, preferably, a structural element. The composition include space-filling aggregates of surfactant containing spherolites, by nature co-continuous with water mycelium solution.

Description

The invention relates to novel, water-based liquid detergent compositions containing predominantly effective amounts of a detergent building block.

BACKGROUND OF THE INVENTION

It is known that the prior art in the field of liquid detergents is extremely wide. However, for the purpose of this invention, numerous data and reports on liquid detergents intended for use with a lower degree of contamination may be overlooked. The content of the building block known so far is much lower than necessary.

Recent state-of-the-art summaries in this area include JAOCS / April 1981 / P356A "Heavy Duty Laundry Detergents", which provides an overview of typical commercially available liquid formulations, and "Recent Changes in Laundry Detergents" by Rutkowski, published in 1981. by Marcel Dekker Inc. in the Surfactant Science Series.

Three of the main approaches to the problem of formulating fully "constructed" (structured) liquid detergents are: emulsifying a surfactant in an aqueous solution of a building block; suspending a solid building block in an aqueous solution or emulsion of a surfactant and suspending a solid building block in a gel having a multilayer surfactant base.

Examples of the first method are those cited in Sources' [1 to 7]. In each of these patents, an aqueous solution of a water-soluble building block is concentrated sufficiently to evacuate the surfactant (usually a liquid non-ionic type), which is dispersed in the aqueous medium as colloidal droplets using various emulsifiers. In each case, the system is a clear emulsion, usually containing relatively little building block. Due to the high cost of the soluble building blocks used, the emulsions become more expensive.

Examples of the second method are given in sources * [84-19]. The formulations described in these patents are either unstable on storage, or temperature unstable, or unstable by shear forces. Recently, commercial products have been marketed in Australia and Europe, following the examples of two of these patents. In particular, a certain commercial success is enjoyed by the composition described in AU 522 983, which is however sensitive to shear forces. Most of these formulations require expensive additives that are not functional ingredients.

The third method is described in EP 0086614. The compositions described have a bulk of a multilayer, solid or liquid crystalline surfactant. Such compositions may have viscosities higher than are required for known purposes.

Another method is to suspend a solid building block in an anhydrous liquid, non-ionic surfactant described in GB 1600981. These systems are expensive, limit the choice of surfactant, and the rinsing results are unsatisfactory. The content of the building block is high relative to the total composition but low to the active ingredients.

Several patents describe emulsions in which the building block is in the dispersed phase of an emulsion rather than a suspension. US 4057506 describes the preparation of clear emulsions of sodium tripolyphosphate, and US 4107067 lists inverse emulsions in which an aqueous solution of the building block is dispersed in a liquid crystalline surfactant system.

Also, a number of patents can be cited relating to hard surface cleaners, in which an abrasive is usually suspended in an aqueous surfactant solution [25, 26, 27, 28, 29]. However, the low surfactant content, the lack of a building block and the availability of high concentrations of abrasives generally preclude the possibility of these patents being useful in the formulation of laundry detergents.

Another publication that may be of interest is AU 507431, which describes suspensions of a building block in an aqueous surfactant stabilized with sodium carboxymethylcellulose or clay as a thickener. However, the concentrations of functional ingredients, and in particular of the building block in the formulations mentioned, are not sufficient for a perfectly acceptable commercial product and stability is not adequate to provide the required shelf life.

US 3039971 describes a detergent paste in which the building element is contained in a solution.

FR 2283951 describes suspensions of zeolite building blocks in non-ionic surfactant systems. The compositions are more dense pastes than moving liquids.

US 3346504 and US 3346873 describe the solubilization of sultains by hydrotropes, which are referred to therein as electrolytes.

The effect of silicates on liquid detergents is described in [34].

Each of the above-cited patents is selected from a very wide range of prior art. They do not exhaust all the information in this field known to those skilled in the art.

The terms in quotation marks used in the description and claims should have the meanings indicated below unless otherwise stated or the text suggests otherwise.

The term "building block" is sometimes used loosely in the field of detergents and means any substance that is not surfactant and which, included in the detergent formulation, increases the cleaning effect of the composition. Usually the meaning of the term is limited to the typical "building blocks" which are useful primarily as a means of preventing the adverse leaching effects of calcium and magnesium ions, for example by chelation, complexation, precipitation or absorption of ions, and second, as a source of alkalinity and buffering. The term "building block" is used in the description in a more limited sense and refers to additives that greatly enhance the effects of calcium. It includes sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts such as sodium or potassium orthophosphate, pyrophosphates, metaphosphates or tetraphosphate, as well as phosphonates such as acetodiphosphonates, amino-trimethylenothenosulfonate. The term includes alkali metal carbonates, zeolites and such organic binding / blocking agents as salts of nitrilotriacetic acid, citric acid and ethylenediaminetetraacetic acid, polymeric polycarboxylic acids such as polyacrylates and maleic anhydride copolymers.

There is no doubt that the term "building block" is used herein to include water-soluble alkali metal silicates, such as sodium silicate, but excluding additives such as carboxymethylcellulose or polyvinylpyrrolidone, the function of which is primarily to suspend contamination or re-deposition.

"Electrolyte" is used herein to mean those water-soluble ionic compounds (at 0 ° C) that dissociate at least partially into aqueous solution. Ions are obtained, and the concentrations they contain tend to reduce the total solubility (including micellar concentration) of surfactants in such solutions by the "salting" effect. The term includes water-soluble dissociable, inorganic salts, for example alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, perborates and polyphosphates, as well as some water-soluble organic salts that desolubilize or "saline" surfactants. It does not include salts of cationic compounds that form water-insoluble precipitates with the surfactants contained, or which are poorly soluble in the composition, such as calcium chloride or sodium sulfate.

Indication of the content or concentration of the electrolyte refers to the total amount of dissolved electrolyte, including each dissolved element, if the latter is also an electrolyte but excludes any suspended solids.

"Hydrotrop" means any water-soluble compound that tends to increase the solubility of surfactants in an aqueous solution. Typical hydrotropes include urea and the alkali metal or ammonium salts of lower alkylbenzenesulfonic acids, such as sodium toluenesulfonate and sodium xylenesulfonate.

The content of active ingredients may sometimes depend on whether a compound is an electrolyte or a hydrotrop. Sodium chloride is usually considered to be a typical electrolyte, but with respect to sultain it has the properties of hydrotrope. Therefore, "electrolyte" and "hydrotrop" as used herein should be explained in the context of the special active ingredients as well.

"Soap" as used herein means at least a moderately water-soluble salt of natural or synthetic aliphatic monocarboxylic acid, which salt has surface-active properties. The term includes sodium, potassium, lithium, ammonium and alkanolamine salts of natural and synthetic C _{8 22} fatty acids, including stearic, palmitic, oleic, linoleic, castoric, behenic and dodecanoic acids, resin acids and branched-chain monocarboxylic acids.

"Ordinary auxiliary ingredients" are those ingredients other than water, active ingredients, building blocks and electrolytes that can be incorporated into laundry detergent compositions mainly in quantitative ratios up to 5% and which are compatible in the corresponding formulation with a flowable, chemically stable non-precipitating composition . The term includes anti-deposit agents, dispersing agents, antifoams, perfumes, dyes, optical brighteners, hydrotropes, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, sulphide inhibitors, moisturizers, enzymes, stabilizers and their stabilizers and others. similar.

"Functional ingredients" as used herein means ingredients that are required to provide a beneficial effect in a laundry bath, and includes ingredients that contribute to increasing the laundry efficiency of the composition, e.g., surfactants, building blocks, bleaching agents, optical bleaches, buffers, enzymes and anti-retardants as well as anti-corrosion agents and antifoams but exclude water, solvents, dyes, perfumes, hydrotropes, sodium chloride, sodium sulfate, solubilizer and stabilizers, the sole function of which is to confer stability, flowability or other desirable characteristic of a concentrated formulation.

"Useful weight" means the percentage of functional ingredients relative to the total weight of the composition.

"Active ingredients" means surfactants.

The term "centrifugation" is to be understood as referring to centrifugation at 25 ° C for 17 hours at 800 times the normal gravitational force (gravity) / unless otherwise stated.

All indications of “high G centrifugation” (G-gravity) mean centrifugation at 20,000 G and a temperature of 25 ° C. High G centrifugation is carried out for 5 min unless otherwise stated.

The term "separable phase" is used herein to refer to components or mixtures thereof in a liquid detergent composition, each of which can be separated from the composition by centrifugation, forming a separate layer. The instructions for the composition of the "separable phases" refer to the compositions of the phases separated by centrifugation. Unless otherwise stated in the context, guidance on the composition of the composition applies to the non-centrifuged composition. The separable phase itself may consist of two or more thermodynamically distinct phases that cannot be separated from each other by centrifugation, such as in a stable emulsion or flocculent precipitate.

The term "dispersed" is used herein to describe a phase that is discontinuously distributed as discrete particles or droplets in at least one other phase.

"Co-continuous" means two or more interpenetrating phases, each of which extends continuously or as a continuous network over a total volume, or is formed by separate or dispersed interacting elements. A continuous base mass is formed, with a tendency to maintain the position of each element of it when the system is at rest. "Mutually dispersed" describes two or more phases that are co-continuous, or one or more of which are dispersed in the other or in the other phases.

"Solid phases" are substances which are contained in a solid formulation at ambient temperature and include any crystallization or hydrated water, unless otherwise stated in the context. According to the instructions, solids include microcrystalline and cryptocrystalline solids, i. E. those whose crystals are not directly observed by optical microscopy, but whose presence can only be assumed. "Solid layer" means a hard, paste-like or non-flowable jelly-like layer formed by centrifugation.

"Total water content" refers to water contained as a liquid predominantly in the aqueous phase, together with any other water in the composition, for example crystallization or hydrated or dissolved, or water contained in any other form, in any is mainly a non-aqueous phase. "Dry weight" refers to the residual weight after drying to a constant weight at 140 ° C.

The term "formulation" means the combination of ingredients that make up the dry weight of a composition. Thus, a number of compositions may be exemplified by the same formulation, but with a different percentage of dry weight.

"Stable" means that no layer containing more than 2% of the total volume is separated from the total mass of the composition for three months at room temperature and normal drawing.

"Sliding test" means a test in which a sample passes through a straight 40 mm tube having an internal radius of 0.25 mm at a pressure of 3,450 kN / m ² . The slip test shall be carried out on all the measurements described here as follows: a sample is introduced into a 500 ml high pressure vessel by suction through a wide-bore tube. The wide-bore pipe is replaced with a 0.25-mm pipe and a pressure of 3.450 kN / m ² is applied to the high pressure vessel until the vessel is empty. The 0.25 mm radius tube is then replaced with a wide bore pipe so that the cycle can be repeated. In the above method is usually a shear rate of approximately 127,000 sec ^1.

"Stable at slip" means stable after 3 passes through the slip test, and "slip stable" means unstable after undergoing 3 or less slip tests or at a lower slip rate.

"Non-slip-resistant" means a non-sustained loss of stability or a significant increase in viscosity after exposure to moderate slip. The slip sensitivity is determined by the Contraves 'Rheomat 30 viscometer, measuring system 2, at 25 ° C, with the slip increasing linearly from 0 to 280 seconds.' ¹ for 1 min / '' scroll down '' and then decrease linearly to 0 sec. 'for 1 min / top-down sliding' /. A composition is rated as non-slip when it is stable after the cycle and if the viscosity is at 150 s. ' ¹ when sliding from top to bottom is greater by not more than 10% of that when sliding from bottom to top.

"Thermostable" means that no layer containing more than 5% by volume of the composition is removed from the bulk of the composition for 24 hours by heating by immersing a 20 g sample in a water bath maintained at 90 ° C for at 110 min, followed by immediate immersion in a water bath maintained at 100 ° C for 10 min.

The "pH" of the detergent compositions herein refers to the pH as measured with a Rui Unicam 401 glass / calomel composite electrode.

"Conductivity" refers to the specific electrical conductivity measured at 25 ° C and at a frequency of 50 kHz. These results are determined by a bridge for measuring the resistance of the "Radiometer" SDMZ.

"First conductivity minimum" refers to the conductivity diagram of an increase in the concentration of dissolved electrolyte in a liquid detergent composition containing a certain amount of the active ingredients and water in which the conductivity, usually initially raised to a maximum value, is reduced to minimum value and then it rises again. The term means the concentration of an electrolyte corresponding to this minimum value, or the lowest concentration of a dissolved electrolyte corresponding to one of a number of such minima.

All percentages, unless otherwise indicated, are by weight relative to the total weight of the composition.

The instructions here for “Viscosity apply, unless otherwise stated, to the viscosity measured with a viscometer with a beaker and pendulum at 25 ° C after 2 min, using a flat-bottomed beaker with an inside diameter of 20 mm and height 92 mm and pendulum with a diameter of 13.7 mm and 44 mm with conical ends with a horizontal angle of 45 ° C and an axis with a diameter of 4 m. The pendulum edge is at a distance of 23 mm from the base of the cup. This viscometer corresponds to the Contraves “Rheomat 30” viscometer, which uses a C measurement system.

The term "flowing" as used in the specification means having a viscosity lower than 2 Pa at a slip rate of 136 sec. ¹ .

"Viscosity decrease" means the difference between the viscosity of a sliding dilution composition measured at 21 seconds. ¹ , and the viscosity measured at 136 sec. ¹ .

"Flow rates" as indicated herein are determined with a Gyor RML Series II rheometer at 25 ° C.

Phase "L" means a clear, liquid, optically isotropic, micellar surfactant solution in water, phase L occurs at concentrations higher than the critical micellar concentration at which the molecules of the surfactant are taken to be agglomerated as spherical, flattened / disc / or oblong / rod-shaped micelles are formed.

A "double layer" comprises a layer of a surfactant two molecules in thickness, formed by two adjacent parallel layers, each consisting of molecules of a surfactant arranged so that the hydrophobic parts of the molecules are located inside the "double layer", and the hydrophilic parts are located on its outer surfaces. Double layer also means interconnected layers having a thickness of less than two molecules. The interconnected layer can be considered as a "double layer" in which the two layers are interpenetrated, creating the possibility of overlapping / overlapping / at least to some extent between the hydrophobic parts of the molecules of the two layers.

"Spherolite" means a spherical or spheroidal body in the size of 0.1 to 50. Spherulites sometimes have irregular shapes - oblong, flattened, pear-shaped or gyrus-like. "Bubble" means spherulite which contains a liquid phase bound by a "double layer". "Complex bubble" means a bubble that contains one or more smaller bubbles.

"Multilayer phase" means a hydrated solid or liquid crystalline phase in which multiple "double layers" are arranged in a practically parallel order, separated by aqueous layers or aqueous solution, and in which a sufficiently regular interspace distance of the lattice from 25 to 70 is sufficient, so that it can be easily detected by neutron diffraction when contained as an essential part of the composition. As used herein, the term excludes concentric complex bubbles.

The "G" phase refers to a liquid crystalline multilayer phase of the type known in the literature as the "pure" phase or the "multilayer" phase. Usually for any given surfactant or mixture of surfactants' G '' - the phase exists in a narrow concentration range. Pure 'G' phases can usually be determined by examining a sample under a polarization microscope between cross polarizers. Characteristic structures are observed in accordance with the classic Rosevir report [35] or [36].

"Spherical G-phase" means complex bubbles formed by concentrically substantially layers of a surfactant "double layer" alternating with an aqueous phase with an intermediate "G" phase. Usually, the traditional 'G' 'phases contain a small portion of the spherical' G '' phase.

"Alkaline" means an aqueous liquid phase containing an electrolyte which is separated from or interdispersed with a second liquid phase containing a greater amount of active ingredient and less electrolyte than the alkaline phase.

"Multilayer composition" means a composition in which the majority of the surfactant is contained as a multilayer phase, or in which the major sediment inhibiting factor is a multilayer phase. "Spherulite composition" means a composition in which most of the surfactant is contained as spherulite or which is stabilized against precipitation mainly by the spherulite phase of the surfactant.

Liquid detergents have so far been used mainly for light-duty applications such as dishwashing. In the market for heavy-duty detergents (intended for higher levels of contamination), for example laundry detergents, powders predominate due to the difficulty of incorporating an effective amount of surfactant, in particular a building block, into a stable liquid formulation. In theory, such liquids should be cheaper than powdered detergents, since they do not require drying and in many cases the sulfate filler commonly used in powdered detergents is replaced with water. It also creates greater convenience and faster dissolution in washing water than dust. Attempts to create functional ingredient solutions have been relatively unsuccessful commercially. One reason for this lack of success is that commonly used effective building blocks, such as sodium tripolyphosphate, are insufficiently soluble in aqueous formulations. In addition, due to the effects of salting, as the amount of dissolved building material increases, there is a tendency to decrease the amount of the surfactant that can be dissolved, and vice versa. Potassium pyrophosphate building blocks are used as alternatives to the sodium salts, together with the amine salts of the active ingredients, which are more soluble but have not been found to have effective value.

Liquid detergents containing a large amount of surfactant are marketed for laundry, but they are unsuitable for hard water areas and have only limited success, mainly related to markets where the use of effective building blocks is legally restricted and dust competition is accordingly more small.

Another method is to attempt to suspend the excess of the building block as a solid in a liquid micellar solution, or an emulsion of the surfactant. The problem, however, is to stabilize the system to keep the building block in suspension and prevent sedimentation. Many, relatively complex formulations have been proposed in the literature, including the use of expensive potassium salts instead of the cheaper sodium salts and solubilizers such as hydrotropes, dispersants or solvents, all of which prevented the potential cost savings from being realized. Even with such intrinsic additives, it is considered necessary to use low concentrations of a solid building block that provides limited washing efficiency. This method is based on known assumptions: that the active ingredient should be in solution as much as possible; that the amount of active ingredient should be relatively high; that the amount of suspended solids should be reduced to a minimum in order to avoid difficulties for the suspension against precipitation; that special thickeners or stabilizers are important to prevent sedimentation, and that electrolytes that would desolubilize the surfactant must be abandoned or retained to a very low degree.

A more important feature of this field so far is its empirical character. An acceptable general theory for separating the stability of some formulations and the instability of others has not been proposed. Therefore, there is no way to predict which formulations will be stable, and there is no common method for creating a new stable liquid detergent. There is no universally applicable teaching in this area, and even in the specific examples of most patents so far, liquid detergents have been formulated for several weeks. Relatively few exceptions were apparently discovered by chance and extrapolation was not possible.

Products of this type have been introduced into industrial production in Europe and Australia, but they have some serious drawbacks. They have relatively weak washing properties due either to the low weight ratio of the building block and the active ingredient or to low alkalinity. They have also shown evidence of undesirable sensitivity to mechanical and / or thermal stress, for example when slipping or storing under severe climatic conditions. Thus some formulations are separated by sliding, others become extremely viscous, most of them are separated after storage at 0 ° or 40 ° C. However, this area does not indicate how to address these shortcomings.

In addition to formulations that are industrially developed, many formulations have been proposed in the literature that are not suitable for practical industrial use. Such formulations are typically unstable or insufficiently stable to be stored normally without settling, or are too expensive to manufacture for industrial development.

Compositions have recently been proposed in which the active ingredients form a multilayer phase network separated from the aqueous phase by centrifugation, providing a gel structure capable of supporting suspended particles of a solid building block. The gel structure is obtained by adding enough electrolyte to salt the active ingredient to form an aqueous phase of alkali and a separable multilayer phase, keeping the solids content higher than the stability limit and lower than the maximum flowability / mobility /. The amount of electrolyte required depends on the hydrophilicity and melting point of the surfactant, as well as on whether any solubilizing additives such as hydrotropes or solvents are contained. Said gel formulations are superior to known commercial liquid formulations of useful weight and efficiency. In fact, the best of multilayer gel formulations eliminate contaminants more effectively than the best laundry powders.

The multilayer compositions disclosed so far have a mobility that is lower than optimal.

A new group of compositions comprising electrolyte, active ingredients and water, which are capable of suspending solids (particles) as building blocks, has been found to produce stable compositions combining improved washing / washing properties and satisfactory mobility. The stability of our new formulations is due to the previously unpublished spherulitic structure. A common method for the preparation of stable, rolling compositions with improved washing properties has also been found in comparison with a number of different attic ingredients.

Preferred embodiments of the present invention have the following advantages over the commercially available products known to date: high payload; a favorable ratio of the constituent to the surfactant; improved stability and washing properties, reduced value due to the use of cheaper ingredients and easy preparation. Other advantages include increased mobility, high pH and / or alkalinity; stability at high and / or low storage temperatures and satisfactory slip behavior.

When the active ingredients, dissolved electrolyte and water are in known quantitative ratios, depending on the particular active ingredients and electrolytes selected, a stable spherulitic composition capable of suspending solids as a building block is obtained. A method of obtaining such compositions, identifying them by various physicomechanical characteristics, as well as optimizing the quantitative ratios of the active ingredients and the electrolyte has been found, with a view to resisting shear stress and changes in storage temperature at high pH or alkalinity, and which are very mobile.

Unlike the multilayer compositions described in the prior art, the new compositions are found to be stabilized with the help of a surfactant contained in a spherulite rather than a multilayer phase.

TECHNICAL NATURE

OF THE INVENTION.

The invention provides above all a stable, flowable, liquid detergent composition consisting of active ingredients, an electrolyte and water capable of suspending solids (particles). The quantitative ratio of the electrolyte is sufficient to give a thermostable, non-slip, non-layered composition.

According to a second aspect of the invention there is provided a stable, flowable, liquid detergent composition capable of suspending solids (particles) and consisting of water, an active ingredient and an electrolyte in which the quantitative ratio of the electrolyte is sufficient to produce spatially filling spherulite flocculated a sludge that is thermostable and non-slip.

According to a third aspect, the invention relates to a stable, flowable, liquid detergent composition capable of suspending solids (particles) and consisting of water, an active ingredient and sufficient electrolyte to form a stable dispersion phase containing at least a portion of the active ingredients corresponding to of the trough (drop) in the conductivity diagram with respect to the electrolyte concentration, which contains the first minimum of conductivity, in which the amount of the corresponding electrolyte provides thermal stability and insensitivity sliding ness.

In each of the above options, the electrolyte concentration is sufficient to produce a slip-stable composition.

The composition according to any of the embodiments should contain suspended solids such as building blocks and / or abrasives. The suspended solids may be insoluble in the aqueous liquid medium already contained in amounts corresponding to saturation or encapsulated in a material that prevents them from dissolving in the medium.

According to a fourth aspect of the invention, there is provided a stable, flowable, liquid detergent composition comprising water, active ingredients, electrolyte and suspended solids, in which the composition is an electrolyte amount sufficient to produce a slip-resistant spherulite composition with a flow limit of 1 to 13 din. cm ² .

Preferably, the yield strength of the composition is greater than 1.5, greater than 2, most preferably greater than 2.5, for example above 3, but less than 10 din cm ² . Preferably, the viscosity at 136 sec is less than 1.5, preferably lower than 1, for example 0.2 to 0.6 Pa / sec.

According to a fifth aspect of the invention there is provided a stable, flowable, liquid detergent composition consisting of water, active ingredients of from 5 to 25% by weight, an electrolyte and a suspended solid element, the total weight ratio of the component and the active ingredient being 1 , 4: 1 to 4: 1, the electrolyte being sufficient to produce a stable, non-layered composition.

The composition may further comprise conventional auxiliary ingredients. Preferably, the active ingredients are from 10 to 20% by weight, preferably from 10 to 14% by weight, with the total weight ratio of the building block and the active ingredient being from 1.5: 1 to 3: 1, for example 1 , 9: 1 to 2.5: 1.

According to a sixth aspect of the invention there is provided a stable, flowable, liquid detergent composition consisting of water, active ingredients of from 5 to 25% by weight, an electrolyte and a suspended solid building block, with a useful weight of at least 35% by weight. The quantitative ratio of the electrolyte in the composition is sufficient to obtain a slip-resistant, spherulite composition.

According to a seventh aspect of the invention, a stable, flowable, liquid detergent composition comprising water, active ingredients of 5 to 25% by weight, an electrolyte and a suspended solid element is provided, with a total weight ratio of the ingredient and active ingredients of 1.5 : 1 to 4: 1 and the quantitative ratio of electrolyte is sufficient to obtain a spherulite composition resistant to storage at 40 ° C. It is preferable that the quantitative ratio of the electrolyte is sufficient to provide a thermostable composition.

According to an eighth aspect, the invention provides a stable, flowable, liquid detergent composition consisting of water, active ingredients of 5 to 20% by weight, electrolyte and suspended solid constituent, the total weight ratio of the constituent and the active ingredient being 1: 1 to 4: 1 and a quantitative ratio of the electrolyte is sufficient to give a heat-stable, non-slip composition which, by centrifugation, is separated into an aqueous layer containing more than 50% by weight of the active ingredients and a solid layer.

According to a ninth aspect of the invention, there is provided a stable, flowable, liquid detergent composition consisting of water, dissolved electrolyte and active ingredients of 8 to 14% by weight, together with a suspended solid constituent and, optionally, ordinary auxiliary ingredients. In centrifugation, the composition is divided into a solid layer and a single liquid layer with a yield strength greater than 1.5 dcm * ² .

According to a tenth aspect of the invention there is provided a composition consisting predominantly of water, active ingredients and an electrolyte capable of suspending particulate matter, the active ingredients being able to form a stable composition at the first minimum of conductivity and the amount of electrolyte contained is sufficient for provide a composition with a yield strength greater than

1.5 din cm ' ² , and a viscosity measured at 136 sec * ¹ less than 0.28 Pa / sec.

According to an eleventh aspect of the invention there is provided a flowable, stable detergent composition based on water, consisting of water, an electrolyte, an active ingredient and a building block and comprising a first, predominantly aqueous, liquid separable phase containing at least a portion of the electrolyte in solution and 50 up to 80% of the total weight of the active ingredients, at least one dispersed solid release phase comprising at least part of the constituent as a solid.

It is preferred that the aqueous release phase contains at least 40 to 60% of the total water content.

According to a twelfth aspect of the invention, a flowable, stable water-based detergent composition with a weight greater than 35% by weight and a pH greater than 9 comprising water, dissolved electrolyte, active ingredients of at least 5 is provided % by weight and a building block of at least 16% by weight. The electrolyte is in sufficient quantity to produce a slip-stable composition but insufficient to allow the active ingredients to form a substantial part of the layered phase.

According to a thirteenth aspect of the invention, a liquid water-based detergent composition is provided which contains sufficiently active ingredients to form a spatially-filled flocculated precipitate of surfactant-containing aqueous sparlites and an amount of electrolyte not less than that , corresponding to the formation of the layered phase, and sufficient to produce a non-slip composition.

According to a fourteenth aspect of the invention there is provided a flowable, stable detergent composition consisting of water, an electrolyte, an active ingredient and a building block, which is separated by centrifuging at least two layers: an aqueous layer containing a dissolved electrolyte of at least 10% by weight . of the total water content, and from 80 to 50% by weight. of the total active ingredient content, and a solid layer containing at least a portion of the building block.

In another embodiment, the invention provides a stable, spherulite composition consisting of active ingredients, electrolyte and water, which, after centrifugation at 20,000 G for 90 minutes, does not give a separate clear aqueous phase.

The invention provides stable, flowable, liquid detergent compositions consisting of water, active ingredients, and electrolyte, all of which have some of the following characteristics: include a spherulite phase, an alkaline phase or a Δ-phase, and preferably co-continuous with alkali- or with Cphase; they are basically layered; include a flocculated sludge system that is predominantly space-filling; include a flocculated sludge system formed of particles containing the active ingredients, which are predominantly spherulites, containing a surfactant and usually with concentric surfactant wraps alternating with an aqueous, e.g., lugaphase, and with a recurring distance of 60 to 100 A, preferably from 70 to 90 A; include spherulites with a diameter of 0.5 to 5 μ, predominantly 0.6 to 5 μ, which have a Maltese cross structure (cross with wedge-shaped shoulder - BC) when observed at appropriate magnifications between cross polarizers; they are diluted by sliding; they have a viscosity decrease of more than 0.35, usually greater than 0.4, often greater than 0.45 Pa / sec, but preferably less than 2 Pa / sec, for example 0.475 to 1.5, especially 0.48 up to 1.1 PA / sec; have a high payload of functional ingredients, typically over 20% by weight. for example, 25 to 75%, more commonly over 30%, predominantly over 35% and preferably over 40% by weight; they are characterized by a high ratio of the building block to the active ingredient, for example higher than 1: 1, for example 1.2: 1 to 4: 1, preferably 1.4: 1 to 4: 1, and most preferably 1, 5: 1 to 3.5: 1; they contain active ingredients of more than 5 and preferably more than 8% by weight of the composition; they contain active ingredients of less than 25-20%, typically less than 15%, preferably less than 14.5%, most preferably less than 14%, for example 10 to 13.5% by weight of the composition; they form, on spin, a single aqueous layer and a solid layer, wherein the aqueous layer generally has a flow limit of at least 1, preferably at least

1.5 din cm ² , for example 2 to 10 din cm ² , and a viscosity generally lower than 1.5 Pa / s at 136 sec. '; the weight amount of the active ingredient in the predominantly aqueous layer formed after centrifugation, based on the total content of the active ingredient in the composition, is greater than 50-55%, for example above 60% but less than 85-90%, for example, less than 80%, such as 75 to 65%; after centrifugation at high G for 90 min, no clear lye layer was observed; the pH of the composition is greater than 8.5, preferably 9 to 13, for example 9.5 to 12; diluting the composition with water to 0.5% dry weight gives a washing solution with a pH higher than 9.7 - 10, for example from 10.9 to 11.1; alkalinity is sufficient, with at least 0.8-1 ml of N / 10 HCLce reducing the pH of 100 ml of washing solution at 0.5% dry weight to 9, for example 4.7 to 8.6 ml; at least one predominantly aqueous liquid phase contains sufficient electrolyte to provide a concentration of at least 0.3 to 0.5, more preferably at least 1.2, for example 2.0 to 4.5 grams. ions per liter total content of alkali metal and / or ammonium cations; the electrolyte concentration is higher than that corresponding to the first conductivity minimum in the conductivity diagram relative to the electrolyte concentration; the conductivity is not more than 2 mS higher than the conductivity at the first conductivity minimum; the electrolyte concentration is lower than that which causes the formation of a substantial amount of the layered phase; the electrolyte concentration is higher than the minimum that provides a stable composition and that which provides a stable composition for sliding; the composition is non-slip and thermostable. The composition is stable at 40 ° C, its conductivity is reduced by 15 mlSm / cm; the compositions contain at least 15-20% by weight of the composition. a building block comprising at least sodium tripolyphosphate and consisting of an alkali metal silicate and / or carbonate, preferably sodium silicate and / or sodium carbonate; the viscosity of the composition at a slip rate of 136 'is between 0.1 and 2 Pa / sec, preferably between 0.2 and 1 Pa / sec, for example 0.3 to 0.6 Pa / sec; the composition has a yield strength of at least 1 - 2, preferably less than 20 - 30, most preferably 10 dynes / cm ² ; the phase containing the building block consists of solids with a maximum particle size smaller than the limit at which the particles tend to precipitate; the composition is stable by sliding: the active ingredients include at least two components, one of which is a non-ethoxylated anionic surfactant and the other is a surfactant that forms stable foams, for example, ether sulfate, alkanolamide or amino oxide.

When the concentration of the dissolved electrolyte in the corresponding aqueous mixture of surfactants is increased from zero, the composition typically undergoes a series of readily detectable steps as follows: Step I.

Initially, the conductivity increases to a maximum during which the viscosity step increases and in the initially clear, optically isotropic phase L, spherulites are formed which can be seen under a microscope and have so-called. Maltese cross structure, usually associated with spherulitic G-phases, when observed between cross / crosslinks / polarizers. However, neutron diffraction does not show data for the G phase or any other liquid crystalline phase and corresponds to a practically micellar composition.

The compositions of step 1 are clear and stable but do not have the ability to suspend solids.

Stage II.

As the electrolyte concentration increases, the conductivity decreases and the composition darkens. Low G centrifugation separates the composition into a clear aqueous phase and an opaque "emulsion phase," increasing the volume ratio of the last phase as the electrolyte concentration increases. Under the microscope, spherulites are observed to increase in number, their size decreases and agglomerate into free flocculated sludges separated by optically isotropic regions, which sludge becomes more dense with increasing electrolyte concentration.

The results of the neutron diffraction studies correspond to reduced micellar concentrations and an increasing proportion of larger bodies, but not to the presence of a significant amount of G phase. Stage II formulations are cloudy and unstable and rapidly precipitate.

Stage III.

The conductivity decreases to a minimum and then begins to increase. The distances between the spherulite flocculas are lost and the spherulites form a space-filling sediment that extends through the liquid phase. During high G centrifugation, no aqueous phase is released, even when it lasts for 90 minutes. A flow limit increasing to a maximum is observed and the composition is diluted by gliding with a marked decrease in viscosity.

Neutron diffraction does not produce a multilayer phase. Nuclear magnetic resonance shows no significant content of the G phase and reveals a low concentration of mycelium surfactant. Electron microscopy shows that at least part of the spherulites are complex bubbles with a concentric shell arrangement or overlapping partial shells, which are possibly further distances than in the normal G phase.

The compositions of step III are stable and capable of suspending particulate matter to form a stable suspension. The invention discloses such stage III formulations.

Stage IV.

The additional addition of dissolved electrolyte causes a progressive decrease in the size of the spherulites and an intensification of the brightness of the Maltese cross structure.

Spherulites cease to be space-filling and form separate floccules separated by optically isotropic regions. The yield strength and the pressure drop decrease and the conductivity increases to the maximum or begins to equalize. Neutron diffraction results in a significant amount of G phases. At high G centrifugation, clear turbidity was separated from the cloudy layer. The composition is unstable, tends to precipitate, and is unable to suspend solids.

Stage V.

A layered composition of the type described in GB 0086614 is formed. The viscosity is relatively high when the water content is adjusted to the extent necessary to obtain a stable composition.

The foregoing sequence is typical of the interactions of electrolytes with a wide variety of aqueous mixtures of surfactants. When the composition already contains a small amount of dissolved electrolyte, as in a complex detergent containing suspended tripolyphosphate, or when the initial surfactant mixture is not completely soluble in water, the first step may not be observed. Also, when the solubility of the electrolyte is limited, such as in the case of sodium tripolyphosphate or sodium carbonate, the additional addition of an electrolyte above its saturation limit will not result in a further composition in the sequence.

Preferred compositions of the present invention are in the third step of the above sequence. Between the third and second and fourth steps there are, respectively, intermediate compositions which are not sufficiently stable. Such compositions form a flocculated precipitate of surface-active spherulites, which are not completely space-filling, as shown by the fact that centrifugation at high G for 90 min results in the formation of a clear aqueous layer, or else the spherulites in them can be irreversibly destroyed. Although they may be stable when kept at ambient temperature, such compositions are often unstable when exposed to various types of voltage, such as high shear stress, elevated or lowered temperatures, or changes in pH. Their ability to suspend crushed solids is often limited. Many of the known prior art compositions are not sufficiently stable.

Formulations which are unstable in " boundary " areas can be modified in accordance with the technology of the present patent by adjusting the content of the electrolyte and / or active ingredient so that they are more closely aligned with the stable regions of the Stage III.

In centrifugation, the compositions of step III according to the present invention are generally separated into an aqueous layer containing an electrolyte of 90 to 50% by weight. of the total content of the active ingredients, typically 80-50%, more often 75-55% of the total content of the active ingredients, and at least one other layer containing preferably from 15 to 50% by weight. of the total active ingredient content together with a substantial portion of the constituent. The viscosities of the compositions of the invention at a slip rate of 136 sec-1 are typically between 0.1 and 2, preferably

0.2 and 1.5, for example 0.25 and 0.6 Pa / sec, and the viscosity reduction is between 0.4 and 2, for example 0.45 to 1.5 Pa / sec.

Stage III formulations are non-slip resistant and are generally slip resistant. In contrast, high shear forces tend to make semi-stable boundary compositions unstable. Viscosity is often increased even by moderate shear strength and formulations can undergo rapid precipitation. This can create practical difficulties in production and bottling. The compositions of step III according to the invention, unlike many semi-stable compositions, are generally stable at high pH and stored at temperatures of about 40 ° C or less than 5 ° C. They are usually thermostable when heated to 100 ° C.

In neutron diffraction analysis, Stage III formulations do not usually show data for the (layered) phase, although some formulations close to the Stage IV boundary show data for insignificant amounts of G phase.

The above trends are explained by the assumption that as the electrolyte concentration increases, the surfactant progressively moves from the mycelium to the spherulite phase. The spherulites initially take the form of complex bubbles, in which multiple "double layers" are located, practically concentric, but at a wider and irregular distance than in the ordinary G phase.

There may be two aqueous phases, the C-phase and the alkaline phase, the latter may also be the C-phase containing less micelles and more electrolyte than the first. One of these phases, possibly alkaline, may form the inner phase of the bubbles.

As the electrolyte content increases and the amount of active ingredient decreases, there is a tendency to formulate compositions that are less viscous with equivalent stability and solids content. This reduces the quantitative ratio of the mycelial surfactant without significantly reducing the amount of spherulites. The lower soy content decreases the viscosity and the spherulite phase remains sufficient to maintain stability.

In the preferred stable composition according to the invention, the spherulites are sufficiently thickly compacted to form a coarse flocculated precipitate that is substantially space-filling, i. E. it extends over the entire volume of the fluid. The spherulites probably interact to form a weak three-dimensional bulk (matrix) strong enough to support suspended particles, but weak enough to break down and easily flow under the influence of shear forces and recover when they remove. The size of the spherulites correlates with stability, with formulations with large spherulites of 5μ and greater being less stable than those in which the majority of the surfactant is in spherulites of size 0.5 to 5 μ.

As the electrolyte content increases, the spherulites become smaller and more compact, tending to smaller and more uniform spheres of G-phase. As a result, G-phase spherulites are no longer space-filling and the composition tends to precipitate.

The compositions according to the invention may preferably contain surfactants of at least 5%, less than 30% and typically less than 25% by weight. It is preferable for the surfactant to comprise from 5 to 20% by weight of the composition, for example 8 to 15% by weight, typically 10 to 14.5%, especially less than 14, often even less, preferably by 13%.

The concentration of the active ingredients may be a critical factor in the preparation of the compositions of the invention.

Below a certain minimum of concentration that is different depending on the particular active system, the composition cannot be stabilized by the addition of more electrolyte, but the maximum is also important for avoiding unstable and / or extremely viscous compositions.

Semi-stable spherulite compositions in the prior art often contain relatively high amounts of active ingredients. This results in a relatively high viscosity of the aqueous suspending medium, which in turn greatly limits the amount of the building block that can be suspended at any given acceptable viscosity limit. Thus, the overall ratio of the building block to the active ingredient is low compared to the powders, resulting in poor washing performance.

It is unclear to a large extent how the active ingredients in such formulations could be reduced without completely destabilizing the systems. It has been found that if the electrolyte concentration is increased sufficiently, the concentration of the active ingredient can be reduced significantly to obtain aqueous media with equivalent or even higher stability and thus lower viscosity. Such environments can suspend large quantities of a building block without losing their mobility, and from the resulting large increases in the ratio of the building block to the active ingredient, equivalent substantial increases in value are achieved.

It is easier to obtain spherulite floccules from mixed surfactants than from single surfactants. Thus, mixtures of one or more non-ethoxylated anionic surfactants such as alkylbenzenesulfonate and / or alkyl sulfate with one or more co-surfactants which form stable foams, such as alkyl ether sulfates and / or alkanolamides or aminoacids, are suitable taken individually. Additionally, minor amounts of ethoxylated non-ionic surfactants or amphoteric surfactants or cationic tissue softeners may be contained.

The surfactant mixture may consist, for example, of one or more at least moderately water-soluble sulfonic or mono-esterified sulfuric acid salts, for example alkylbenzenesulfonate, alkylsulfate, alkylsulphate, olefin sulfonate, alkanesulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonyl alkylethanolamide sulfate, alkylethanolamidetersulfate or? -sulfomatic acid or its esters, each of which has at least one alkyl or alkenyl group of 8 to 22, more commonly 10 to 20 aliphatic carbon atoms. The corresponding alkyl or alkenyl groups are preferably straight chain primary groups, but may optionally be secondary or branched chain groups. The term "ether" herein refers to a polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene-oxypropylene or mixed glyceryloxyethylene or glyceryloxypropylene group containing oxyalkylene groups of from 1 to 20 carbon atoms. For example sulphonated or sulphated surfactant may be sodium dodecyl benzene sulphonate, potassium heksadetsilbenzolsulfonat, sodium dodetsildimetilbenzolsulfonat, sodium lauryl sulphate, sodium tallow sulphate, potassium oleyl sulphate, ammonium lauryl or monoetanolamintsetilsulfat ethoxylated with 10 moles of ethylene oxide.

Other anionic surfactants useful in the present invention are paraffin sulfonates, olefin sulfonates, fatty alkyl sulfosuccinates, fatty alkyl sulphosuccinates, acetylsarcositates, acetylates, acetates, acetates, acetates, acetates, acetates, acetates, acetates, acetates Anionic phosphate esters may also be used. In each case, the anionic surfactant contains at least one aliphatic hydrocarbon chain of 8 to 22, preferably 10 to 22, carbon atoms and, in the case of ethers, one or more glyceryl and / or ethyleneoxy and / or propylene oxy groups of 20 carbon atoms.

Preferred anionic surfactants are sodium salts. Other salts of commercial interest are the salts of potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanolamine and alkylamines containing up to 7 aliphatic carbon atoms.

The mixture of surfactants may optionally contain or, less preferably, consist of non-ionic surfactants. The nonionic surfactant may be eg _{10 J2} alkanolamide mono- or di-lower alkanolamine, such as coconut monoethanolamide. Other non-ionic surfactants which are optionally contained are ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkylamides, ethoxylated alkylphenols, ethoxylated esters of glycerol, ethoxylated esters of phosphoric acid esters of phosphoric acid the ethoxylated and propoxylated analogs of all the aforementioned ethoxylated non-ionic substances, all of which have an alkyl or alkenyl group having 8 to 22 carbon atoms and ethylene oxide and / or propyleneoxy groups of up to 20 carbon atoms, or any other nonionic surfactant which has hitherto been incorporated in powder or liquid detergent compositions eg amine oxides. The latter generally have at least one C ₂₂ , preferably C _{1 (V 2 O} , alkyl or alkenyl group and up to two lower (for example, C ₄ , preferably C, ₂ ) alkyl groups.

Preferred active ingredients or mixtures of the invention are, for example, those having a hydrophilic-lipophilic balance (CLB) greater than 7, preferably higher than 8-10, most preferably higher than 12, but below 18, better than 16 and best below 15.

Some of the detergents of the invention may contain cationic surfactants, and in particular cationic fabric softeners and / or bactericides, typically as a minimum part of the total active substance. The cationic fabric softeners of relevance according to the invention are quaternary amines with two long chain alkyl or alkenyl groups (eg C _{12 22} usually C ₁₆ ) or two short chain alkyl groups (eg C, ₄ ) or one group with a short chain and one benzyl group. These include imidazoline and quaternized imidazolines with two long chain alkyl or alkenyl groups, and amidoamines and quaternized amidoamines having two long chain alkyl or alkenyl groups. Typically, all quaternized softeners are salts of anions that impart a degree of water solubility, such as formate, acetate, lactate, tartrate, chloride, metosulfate, ethosulfate, sulfate or nitrate. Compositions of the invention which have the character of tissue softeners may contain bleaching clays.

The compositions of the invention may also contain an amphoteric surfactant, which can typically be incorporated into surfactants containing a cationic tissue softener, as well as a minor component to the active ingredients, in any of the other detergent types described above.

Amphoteric surfactants are betaine, sulfobetaine, and phosphobetaine, which are prepared by reacting a suitable tertiary azotine compound containing a long chain alkyl or alkenyl group with a suitable reagent such as chloroacetic acid or propansulfone. Examples of suitable tertiary nitrogen-containing compounds are: tertiary amines having one or two long-chain alkyl or alkenyl groups, optionally a benzyl group, and any other short-chain alkyl group; imadosoline having one or two long chain alkyl or alkenyl groups and amidoamines having one or two long chain alkyl or alkenyl groups.

The specific types of surfactants described above are an example of conventional surfactants that are suitable for use according to the invention. Any surfactant capable of performing a useful function in the washing solution may be included. A more complete description of the main types of surfactants that are commercially available is given in [38].

The electrolyte is required to interact with the surfactant to form a space-filling spherulitic system. However, it is preferred that the electrolyte concentration is not sufficient to significantly accumulate planar "double layers" and to form non-spherical multilayer phases. In such multilayer phases, unstable or unstable compositions can only be obtained by sliding, unless the payload is high enough to form a stable multilayer phase structure. However, the relatively stable bulk, characterized by the latter compositions, generally results in an undesirably high viscosity.

Insufficient amount of electrolyte results in unstable or slip sensitive or thermosetting systems and / or systems that have an undesirable high viscosity. Therefore, the amount of electrolyte must be selected according to the nature of the surfactant and the amount of any hydrotrope contained in order to obtain the compositions of the present invention.

The optimal amount of electrolyte can usually be determined by progressively adding the electrolyte to an aqueous, micellar solution of the active ingredients (typically about 15 to 20% by weight of the active substances) and observing one or more characteristic properties of the system such as turbidity, conductivity, flow limit, appearance under polarization microscope, or high G centrifugation behavior

When detecting properties characteristic of stage III as described above, for example when the composition is turbid at or near the first conductivity minimum, flocculated sediment of spherulites which do not show clear isotropic zones and a clear layer after centrifugation at high G, then the spherulite interval is determined.

The amount can be optimized at this interval by observing the amount required to avoid clear layer formation at high G centrifugation for 90 min and / or to obtain a thermostable and / or slip resistant composition . If the composition is intended for a commercial product whose viscosity is of paramount importance, the optimized composition may be progressively diluted until appropriate viscosity is achieved or signs of instability are obtained. In the latter case, the addition of the electrolyte may continue until a sufficiently stable composition is obtained.

The amount of the electrolyte is preferably higher than that at the First Conductivity Minimum in the Conductivity / Electrolyte concentration graph and corresponds to the amount required to provide a composition having a Yield Point greater than 1,5dina.sm ^'2.

The use of functional electrolytes such as carbonates, silicates, pyrophosphates, polyphosphates, nitrile acetates and citrates, all of which are building blocks, is preferred, but the effective concentration of some such electrolytes, such as carbonates, may be undesirably limited by their solubility. In such cases, it may be necessary to add a more soluble non-functional electrolyte. Sodium chloride and sodium nitrate have been found to be particularly effective in this regard.

The amount of electrolyte in at least one predominantly aqueous phase is often sufficient to provide a concentration of at least 0.3, preferably at least 1.2, for example 2.0 to 4.5 grams per liter of cations per liter. alkali metal, alkaline earth metal and / or ammonium cations.

The building block of the preferred compositions according to the invention is contained as separate solid crystallites suspended in the composition. The crystallite size is usually up to 60, for example from 1 to 50.

Formulations containing sodium tripolyphosphate as a building block or a large amount thereof, mixed with other building blocks, are preferred. show stability and mobility over a wider dry weight range than formulations with other building blocks. According to the invention there are compositions containing other building blocks such as potassium tripolyphosphate, carbonates, zeolites, nitrile triacetates, citrates, metaphosphates, pyrophosphates, phosphonates, EDTA and / or polycarboxylates, preferably in admixture with tripolyphosphate. Orthophosphates, mainly as minor constituents in admixture with tripolyphosphate, as well as alkali metal silicates and carbonates, may be present.

Silicates and carbonates are especially preferred because they perform important functions. They provide the desired free alkalinity for saponification of grease in the dirt, have the effect of being building blocks, and silicates inhibit the corrosion of aluminum surfaces in washing machines. In addition, they are effective as the electrolytes needed to form a spherulitic system.

When silicate is used to prepare the compositions, it generally has a Na ₂ O: SiO ₂ ratio of 1: 1 to 1: 2 or 1: 1.5 to 1: 1.8. It is possible to use any ratio of Na ₂ O (or other base) and SiO ₂ , or even silicic acid, to provide silica in the composition as well as any additional alkalinity required by the addition of another base such as sodium carbonate or hydroxide . Silicates are not required for formulations not intended for use in washing machines, provided that there is an alternative source of alkalinity.

Compositions in which the constituent is completely contained in a solution, for example sodium nitrile triacetate, sodium citrate, sodium silicate or mixtures thereof, are not excluded.

The building block typically represents at least 15% by weight, even at least 20%. It is preferred that the ratio of the building block to the surfactant is higher than 1: 1, preferably 1.2: 1 to 4: 1.

For economic reasons, it is generally preferred that the cations present are predominantly sodium. For example, the preferred building block is sodium tripolyphosphate, the preferred anionic surfactants are the sodium salts of sulfated or sulfonated anionic surfactants, and any backfill (for pollution), such as carboxymethyl cellulose, or carboxylate, or carboxy preferably contained as sodium salt. Sodium chloride, sodium nitrate or other soluble inorganic sodium salts may be added to increase the electrolyte concentration. Calcium is usually only contained when the active ingredients consist of surfactants such as olefin sulfonates or non-ionogens that are compatible with its presence. Magnesium salts may be present and they are compatible with calcium surfactants.

The choice of salts of potassium, ammonium, lower amines, alkanolamines or mixed cations is also possible. However, formulations containing such cations in large quantities are not expected to be more effective than traditional laundry powders.

The compositions of the invention are preferably alkaline, since it is desirable to buffer with an alkaline buffer to ensure a pH of the composition (measured with a glass calomel electrode) higher than 8.5, preferably above 9, most preferably more than 9.2, for example 9.5 to 12, especially 10 to 11. It is preferred that the compositions according to the invention provide a pH higher than 9.7, for example higher than 10, especially 10.5 to 11.5 in the laundry bath containing the composition diluted to 0.5% dry weight. It is desirable that they have sufficient free alkalinity to require at least 0.4 ml, preferably at least 0.8 ml, at most 1 to 12 ml, for example 3 to 10 ml, usually 4 to 9 ml of N / 10HC1 for lowering at a pH of 100 ml of a dilute solution of the composition containing 0.5% dry matter up to 9, although higher alkalinity compositions may also be acceptable commercially. In practice, generally lower alkalis are less acceptable, although they are not excluded from the scope of the invention.

The alkaline buffer is preferably sodium tripolyphosphate, and the alkalinity is preferably provided, at least in part, by sodium carbonate. Among other preferred alkaline buffers is sodium silicate.

Until now, liquid detergent compositions typically contained high concentrations of hydrotropes and / or organic water-miscible hydroxyl solvents such as methanol, ethanol, isopropanol, glycol, glycerin, polyethylene glycol and polypropylene glycol. However, they are expensive and do not have functional ingredients. In certain circumstances, they may increase their flowability or allow the surfactant to form a more easily spherulite phase. Therefore, they do not completely exclude from all the compositions according to the invention, but it is preferable to limit their contents to the minimum necessary to provide a spherulitic composition with sufficient flowability. It may sometimes be necessary to adjust the solvents as components of flavoring agents or of other conventional auxiliary ingredients.

The dry weight of the composition affects stability and flowability. The optimum dry weight may be significantly different for the different formulations and may be selected to provide the required viscosity. In general, it has not been established that it is possible to guarantee stable formulations at less than about 35% by weight. dry weight, although some formulations can be obtained in a stable form at less than 30% dry weight and sometimes as little as 25% dry weight. It is not excluded that stable compositions can be obtained at as low a dry weight as up to 20%.

For any given formulation according to the invention, dry weight limits within which the composition is both stable and flowable can be determined. Typically, precipitation occurs below these limits, and above them the composition is unstable or too viscous. Acceptable limits can be routinely determined for any given formulation by preparing the slurry with the minimum amount of water required to maintain the mixable composition, diluting a number of samples to progressively increasing dilutions, and monitoring the samples for appropriate period for signs of precipitation. For some formulations, the acceptable dry weight ranges can be extended from 30-35 to 6070% by weight, and in others they can be much narrower, for example from 40 to 45% by weight.

If the above methods cannot determine the boundaries for a stable flowable composition, the formulation should be modified according to the methods presented here, for example by adding more sodium carbonate solution, sodium silicate or other electrolyte if the composition exhibits stage-specific properties. I or II, or by reducing the electrolyte content or adding hydrotrop, if the composition exhibits properties inherent in stage IV or V. Alternatively, if difficulties are encountered in establishing a stable spherulitic system by simple alteration of the electrolyte content, the active ingredients may be modified by the addition of a foam stabilizing surfactant such as alkyl ether sulfate, alkanolamide or amine oxide if the composition tends to form step IV or V, or by addition of alkylsulfonate benzobenzalbenzal inherent in stage I or II.

The compositions of the invention can in many cases be readily prepared by mixing the ingredients together. However, they are not destabilized or thickened by high shear forces.

The order and conditions for mixing ingredients are sometimes important in order to obtain a stable structured mixture according to the invention.

The compositions of the invention may be prepared with any suitable active ingredient as follows. First, a clear aqueous "L" solution of the active ingredients is obtained at a suitable concentration, for example 15 to 30% by weight. of the active substance, if necessary, upon heating, and the electrolyte is dissolved in L ₍ solution or a concentrated electrolyte solution is added (preferably functional electrolyte) until the mixture is opaque. Then a sample of the mixture is centrifuged at 20,000 G for 20 minutes. 5 min. If a clear aqueous phase is obtained, more electrolyte is added to the mixture, while centrifugation at high G no longer indicates the formation of a single, substantially clear aqueous phase, and then the weight ratio of the active ingredient is noted. m and the dissolved electrolyte.

A composition can then be prepared that contains all the desired ingredients and has a predetermined weight ratio of the active ingredient to the electrolyte at the desired dry weight percentage (typically 40 to 50%). The formation of a clear aqueous alkaline phase after centrifugation at high G indicates that a multilayer phase or a non-space-spherical “G” phase is obtained. The amount of electrolyte is then reduced until clear phase formation is observed during high G centrifugation. In order to determine the optimum mobility / stability characteristics, samples of the latter formulation are prepared at different dry weights.

If difficulties are encountered in determining the appropriate ratio of active substance to electrolyte in the first step of the above procedure, the process may be repeated using a more soluble electrolyte, such as a non-functional electrolyte such as sodium chloride or sodium nitrate. Alternatively, the active system can be modified by the addition of surfactants that have a beneficial effect on the formation of stable dispersions according to the invention, for example, ethersulfates, amine oxides or alkanolamides, if properties of step IV or V, or a non-oxidized anionic substance are observed if the Stage I or II properties are easier to obtain.

Mixing is carried out at ambient temperature, when the dispersion is normal, and some ingredients, such as non-ionic surfactants such as coconut myoethanolamide, require gentle heating, for example, at 40 ° C, to obtain a normal dispersion. This degree of heating can usually be achieved by the heat of hydration of sodium tripolyphosphate. In order to provide sufficient heating, it is preferable to add the tripolyphosphate in an anhydrous form containing a sufficient amount of temperature-enhancing modification, commonly referred to as "phase I". The above procedure is just one of several methods that can be used with success for all or most of the compositions according to the invention. Some formulations are more sensitive than others to the order and temperature of mixing.

Considering the different types of formulations according to the invention, strongly foaming sulfate or sulfonate type formulations and slightly foaming formulations are distinguished.

Highly foaming formulations are typically based on mixtures of one or more non-ethoxylated surfactants, preferably sulfate or sulfonated surfactants, with one or more co-surfactants that form a stable foam, such as ethoxylated anionic or surface anionic active substances fatty alkanolamide. The first component of the active ingredients, i. non-ethoxylated anionic surfactant may for example be a _{C] 0} alkyl sulphate and / or C _{| 014} alkyl benzene sulphonate. The second component, or surfactant, may be straight chain or branched chain sodium C _{10 20} , alkyl ether sulfate or alkyl phenol ether sulfate, aminetersulfate, alkanolamidesethersulfate or fatty acid or sulfate. Alternatively or additionally, the second component may consist of amine oxide or fatty alkylamide. The total weight ratio of the non-oxidized anionic and co-surfactant may be from 5: 1 to 1: 3, preferably 4: 1 to 1: 2, for example 3: 1 to 1: 1. Small amounts (eg up to 1% by weight of the compositions / soap) may be contained to facilitate the rinsing of the tissue. Non-ionic ethoxylates of up to 20% by weight may be contained in minimal amounts. of the total active ingredient content, preferably less than 15% by weight, usually less than 10% by weight.

Sodium alkylsulfate or alkylbenzenesulfonate can be completely or partially substituted by other sulfonated non-ethoxylated surfactants, including fatty alkylphosphates, or by paraffin sulfonates The alkyl ether sulfate may be completely or partially substituted by other ether sulfates, such as alkyl phenyl ether sulfates, fatty acylmonoethanolamideethersulfates or mixtures thereof.

According to a particular embodiment, the invention provides a stable, flowable, non-slip-resistant spherulitic composition consisting of: water; from 12 to 40% by weight active ingredient based on the dry weight of the composition and from 20 to 80% by weight. a dry element based on the dry weight of the composition contained at least partially as a suspended solid and partly as at least a portion of the respective dissolved electrolyte in a total weight ratio of the active ingredient: active ingredients from 1.3: 1 to 4: 1 in this composition said active ingredients consist of: (A) - 30 to 80% by weight are non-alkoxylated anionic sulfated or sulfonated surfactant and (E) - 20 to 70% by weight. of the total surfactant content are at least one foam stabilizing surfactant which is a co-surfactant such as alkoxylated anionic surfactant, alkanolamide or amine oxide.

The above composition may optionally contain an additional soap of up to 6% relative to the dry weight of the composition. It is preferred nealkoksiliranoto sulphated or sulphonated anionic surfactant consists essentially of alkyl sulphate or alkyl benzene sulphonate, preferably sodium alkyl benzene sulphonate, for example, C _{10 14} alkyl benzene sulphonate.

The anionic surfactant may alternatively consist of a mixture of alkylbenzenesulfonate and / or alkylsulfate with alkyl ether sulfate and / or alkylphenol ether sulfate in weight ratios, for example from 1: 3 to 5: 1, typically 1: 2 to 1: 1, to 3: 1, for example 2: 1. In the latter case, the total anionic surfactant content is preferably from 12 to 40%, for example 15 to 30% of the dry weight of the compositions.

Low-foaming compositions of the invention can be prepared using suitable foam inhibitors. The choice of foam inhibitor is important because some commercially available foam inhibitors may lose their storage efficacy in the compositions of the invention, while others are effective only at high enough concentrations to affect the viscosity or stability of the composition. Mixtures of organopolysiloxane and colloidal silica have been found to be particularly effective.

According to another specific embodiment, the invention provides a stable, flowable, liquid detergent water based composition comprising: 12 to 40% of the active ingredients based on the dry weight of the composition, which include from 30 to 90% nonalkoxylated sulfated and / or sulfonated anionic surfactants a substance based on the dry weight of the active ingredients and the rest is alkyl ether sulfate and / or alkanolamide or amine oxide; an aqueous phase containing sufficient electrolyte in solution to form a space-filling flocculated spherulite precipitate, which includes part of said active ingredients and is inter-dispersed with the corresponding aqueous phase; suspended particles of the building block; an effective amount of at least one foam inhibitor and, optionally, conventional auxiliary ingredients.

According to another specific embodiment, the invention provides a flowable, stable detergent composition with a weight of from 30 to 50%, which consists essentially of from 12 to 40% by weight. active ingredients based on the dry weight of the composition, at least 30% by weight. a building block based on the dry weight of the composition at a ratio of the building block to the active ingredient greater than

1.1 to 1, said active ingredient consisting mainly of alkylbenzenesulfonate having 8 to 18 aliphatic carbon atoms and alkyl-ethanolamide selected from C _{10) S} alkylmonoethanolamides and diethanolamides, with a weight ratio of alkylbenzenesulfonate 1.5 and ethanol benzenesulfonate 1.5: ethanol : 1, and the building block is selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrile triacetate, sodium silicate and mixtures thereof such that the amount of dissolved building block is sufficient to provide a flow rate greater than 1 , 5 din. Cm ' ² .

In a particularly preferred embodiment of the invention, the stable, liquid detergent composition consists of the following components:

A is a mixture of (1) sodium alkylbenzenesulfonate with 10 to 18, preferably 10 to 14 aliphatic carbon atoms, c) and / or sodium alkyl ethersulfate having an alkyl group with an average of 8 to 18, preferably 10 to 14 carbon atoms and from 1 to 20 ethyleneoxy and / or propyleneoxy, preferably from 2 to 10, for example from 3 to 5, the ratio (i): (ii) being between 10: 1 and 1:10, especially 10: 1.5 to 10: 5, for example 10: 2 to 10: 4;

B is a building block selected from sodium tripolyphosphate, zeolite, sodium nitrile triacetate and mixtures thereof, at a weight ratio of B: A from 1.1: 1 to 4: 1, preferably 1.2: 1 to 3.5: 1, e.g. 2: 1 to 3: 1;

B is an electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof at a concentration of 2 to 20% by weight, preferably 3 to 18% by weight, especially 7 to 15% by weight. of the composition; the composition having a weight of 30 to 50% by weight, preferably 35 to 50% by weight, for example 38 to 45% by weight. and said composition preferably contains minimal but effective amounts of anti-deposition agents, preferably sodium carboxymethylcellulose, perfume (coloring agent), colorant and optical brightener.

The sodium cation in the above composition may optionally be substituted in whole or in part by potassium, lithium or ammonium. Sodium tripolyphosphate preferably comprises 40 to 95% of the total weight of the building block, for example 45 to 80%. If the composition is intended for automatic washing, it is preferable to contain at least one foam inhibitor.

The described compositions may optionally contain minimal amounts of alkanolamide such as coconut monoethanolamide or diethanolamide or ethoxylated non-ionic surfactant, for example, up to 15% of the total amount of active ingredients, preferably less than 10%.

The compositions of the invention may contain conventional auxiliary ingredients. The main ones are anti-scouring agents, dispersants, optical brighteners and whitening agents.

In the preparation of detergents, the most commonly used backscatter is sodium carboxymethylcellulose (NKMC), which can be contained in the compositions of the invention, for example, in effective amounts in accordance with the desired viscosity and stability. Generally speaking, NCMC is effective at concentrations of about 1%, and it is preferable not to exceed this concentration, since larger amounts of NCMC can greatly increase the viscosity of a liquid composition and also have an effect on stability.

Among the alternative anti-deposition and / or stain remover / contaminants / are potassium, ammonium and other soluble salts of NKMC, phosphonates, methylcellulose, polyvinylpyrrolidone, carboxymethyl starch and similar polyelectrolytes, all of which may be used in place of the NKMC.

Optical bleaches are optional but preferred ingredients of the compositions. Unlike some formulations of the prior art, the stability of the compositions according to the invention is not dependent on optical brighteners and therefore any optical brighteners of effective value may be selected or not included in the compositions at all. Any fluorescent dyes recommended so far for use as optical brighteners in liquid detergents, as well as many dyes commonly suitable for powder detergents, may be used. Optical bleaches may be present in conventional quantities.

Optical brightener concentrations between 0.05 and 0.5%, for example 0.075 to 0.3%, typically 0.1 to 0.2%, are usually sufficient. Lower concentrations may be used, but they are unlikely to be effective while higher concentrations, although not excluded, are unlikely to be of effective value and may in some cases cause problems with respect to of compatibility.

Typical examples of optical brighteners that can be used in the invention are: ethoxylated 1,2- (benzimidazolyl) ethylene; 2-styryl naphthyl [1,2d] oxazole; 1,2-bis (5methyl-2-benzoxazolyl) ethylene; disodium-4,4-bis (6-methylethanolamine-3-anilino-1,3,5-triazin-2-yl) -2,2-styrene benzonate; N - (2-hydroxyethyl-4,4-bis) benzimidazolyl / stilbene; 4,4bis [4-bis (2-hydroxyethyl) -amino-6/3 ”sulfonyl / amino-1,3,5” -triazin-2ylamino] -2,2-stilbendisulfonate tetranate; disodium-

4- [6-sulfonaphtho [1 ', 2]] triazol-2-yl] -2-stybenzulfonate; disodium 4,4-bis [4- (2 '' hydroxyethoxy) -6-amino-N ', 3,5-triazin-2ylamino] 2,2-stilbendisulfonate; 4-methyl-7-dimethylaminocoumarin and alkoxylated 4,4-bis (benzimidazolyl) stilbene.

Liquid detergents according to the invention may optionally include bleaching agents that are chemically stable and compatible. Encapsulated bleaching agents may form part of the suspended solid. The action of the peroxy-whitening agents in the compositions according to the invention can be enhanced by the presence of bleach activators such as tetraacetylethylenediamine in effective amounts. Also, photoactive bleaches such as zinc or aluminum sulfonated phthalocyanine may be present

Laundry detergents traditionally contain perfumes (fragrances) and colorants in an amount of up to 1-2%. They may also be contained in the composition according to the invention.

The flavoring agent needs to be carefully selected as the solvents present can modify the active ingredients.

Optionally, proteolytic and amylolytic enzymes may be incorporated in conventional amounts together with stabilizers and enzyme carriers. Encapsulated enzymes may be suspended in the composition.

Other auxiliary ingredients include foam removers, bases, buffers, germicides such as formaldehyde, color enhancers such as vinyl latex emulsion, inert abrasives such as silica and anti-corrosion agents such as benzotriazole.

The compositions of the invention are suitable for laundry purposes, and the invention provides a method for washing clothes that are mixed in a laundry bath containing any composition of the invention. Particularly useful for use in automatic washing machines are the low-foaming compositions described herein. The compositions can also be used for washing dishes or for cleaning hard surfaces, with low foaming products being particularly suitable for use in dishwashers. These objectives constitute another aspect of the invention.

The compositions of the invention are typically used for washing clothes in boiling water or for washing at moderate or low temperatures, for example 50 to 80 ° C, in particular 55 to 68 ° C, or 20 to 50 ° C, especially 30 to 40 ° S. The compositions may be added to the washing water at concentrations between 0.05 and 3% dry weight relative to the washing water, preferably 0.1 to 2%, more often 0.3 to 1%, for example 0.4 to 0,8%.

The invention is illustrated by the examples given in the following tables.

The formulations of the examples are stable and flowable. They are resistant to storage at 40 ° C and non-slip. They are thermostable and, with the exception of example 83, are also stable at slip.

Example No.

1 2 3 4 5 6 Sodium C ₁₀ _ ₁₄ linear alkyl benzene sulphonate 10 10 10 10 9.3 10 Coconut diethanolamide 5 5 5 5 2.3 2.5 Sodium carbonate 5 5 5 5 4.6 5 Sodium tripolyphosphate 25 25 18 27 16.7 18 Zeolite A. - - 9 - 9.3 10 Sodium carboxymethylcellulose 1.0 1.0 Sodium C _n alkyl sulfate 3 moles of ethylene oxide (EO) 2.3 2.5 Optical bleach 0.15 0.15 0.15 0.15 - 0.15 C _{) 2 lg} alcohol per 8 mole EC 1.8 Mixed mono- and di-C _161B - 0.5 - - 0.5 - alkyl phosphate A non-ionic foam inhibitor 2.0

Example No.

7 8 9 10 11 12 Sodium C ₁₀ . ₁₄ linear alkylbenzenesulfonate 10 9.2 9.3 9.5 9.3 10 Coconut monoethanolamide 5 4.6 4.2 4.2 4.2 5 Sodium carbonate 5 4.6 5.2 4,8 5.2 5 Sodium tripolyphosphate 25 23.5 19,0 18,1 18.5 18 Zeolite A. - - 9.0 0.6 8.8 10 Sodium carboxymethyl- lulose 1.0 - - - - 0.5 Optical bleach 0.15 0.14 0.14 0.14 0.14 0.15 Mixed mono- and di-C _{] b (|} - 0.5 0.5 0.5 0.5 - alkyl phosphate Non - ionogenic inhibitor of foam - 2.6 - 2.2 - - Silicone antifoam - - - - - 1.10

Example N °

13 14 15 16 17 18 19 Sodium C, _{O u} linear alkyl benzene sulphonate 10 10 9.2 10 10 8.7 9.0 Sodium C ₂₁₈ alkyl sulfate of 3 moles of EC 5 5 3.7 5 5 3.9 4.0 Sodium carbonate 5 5 4.6 5 5 4,8 5 Sodium tripolyphosphate 25 25 23.1 18,0 18,0 18,4 19,0 Zeolite A. - - - 10 10 11.6 11,0 Sodium carboxymethylcellulose 1.0 1.0 1.0 1.0 With ₁₂₁₈ alcohol of 8 mole EC 2.0 1.9 2.0 Phosphoric acid mono- and di- _C1818 alkyl ester 1.0 0.5 Optical bleach 0.15 0.15 0.14 0.15 0.15 0.14 0.15 Silicone antifoam - - - - - - 0.5 Non - ionogenic inhibitor of foam 1.9

Example No. 20 21 Sodium C _{10- m} linear alkylbenzene- sodium sulfonate with _{12 u} alkyl sulfate 9,1 9,4 3 moles of EC 4,8 4.0 Sodium carbonate 5.0 4.6 Sodium tripolyphosphate 18.5 19,0 Zeolite A. 9.0 10,0 With ₁₂₁₈ alcohol of 8 mole EC 2.0 A mixed mono- and di-C ₁₆₁₈ alkyl phosphor ester acid 0.5 0.5 Optical bleach 0.15 0.15

Example No.

22 23 24 Sodium C _{] 0} . _{| 4} linear alkylbenzenesulfonate- a phonate 9.2 7.8 8.3 Sodium C ₁₂₁₈ alkyl sulfate 3 moles of EC 9.2 7.8 4,1 Sodium carbonate 4.6 3.9 4.2 Sodium tripolyphosphate 6,9 5.9 15.0 Sodium nitrile triacetate 13,8 11.7 8.3 With ₁₂₁₈ alcohol of 8 mole EC - 1.7 - Coconut diethanolamide 1.8 1.6 -

25 Example No. 26 Sodium C _{| 0 | 4} linear alkylbenzene- sulfonate 9 8.6 Coconut monoethanolamide - 1.4 Sodium carbonate 5 - Sodium tripolyphosphate 19 25.3 Zeolite A. 5 - Sodium carboxymethyl- cellulose - 1.4 Niterated with C ₁₂₁₈ alkyl sulfate 4 2.3 3 moles of EC Optical bleach 0.15 0.13 Sodium silicate / SiO ₂ : Na ₂ 0,1,6: 1 / 5 5.8 Silicone antipentile 1

27 Example No. 28 Sodium C _{1 (M4} 10 8.8 linear alkylbenzenesulfonate Coconut monoethanolamide - 1.5 Sodium carbonate 5 5.8 Sodium tripolyphosphate 27 25.6 Optical bleach - 0.14 C _{12- (4-} Alkediethyl amine- amine oxide 5 2.3 Silicone antifoam 1 -

Example No.

29 30 31 32 33 34 35 Sodium C ₁₀ _ ₁₄ linear alkyl benzene sulphonate 10 9 10 10 10 9.5 9.5 Sodium C ₁₂ alkyl sulfate of 3 moles of EC 5 4 2.5 2.5 Coconut monoethanolamide - - 5 5 - - - With ₁₂₁₄ alcohol of 8 mole EC 2 Zeolite A. 22 17 24.5 17 30 22 22 Sodium carbonate 10 15 7.5 - - 10 - Sodium tripolyphosphate - - - 15 2.5 - - Sodium nitrilotriacetate - - - - - - 10

36 37 Example No. 38 Sodium C _{1 (M4} linear alkylbenzenesulfonate 10 7.4 8.2

Sodium C ₁₂ - alkylsulfate

3 moles of EC - 1.9 - Coconut monoethanolamide 5 1,2 4,1 Zeolite A. 17 24,8 26,4 Sodium tripolyphosphate 15 - - Sodium silicate / Si0 ₂ : Na ₂ 0, 1,6: 1 / - 11.6 8.2

39 Example No. 40 41 42 43 44 45 Sodium C _{1 (M4} linear alkylbenzenesulfonate 5.0 6.5 7.0 6,1 10.9 5.2 8.0 Coconut diethanolamide 4.0 4,8 3.5 3.8 3.0 7.0 6.0 Sodium carbonate 5.0 4.0 4.4 3.8 5.0 4.3 4,8 Sodium tripolyphosphate 25,0 20,2 21.9 19,9 24.7 21.7 18,1 Zeolite A. 8.0 - - - - - 8.6 Sodium carboxymethylcellulose 1.0 0.8 0.9 0.8 1.0 - - 2-Tal-1-methyl-1- (thal amidoethyl) imidazolinylmethyl sulfate 0.75 0.6 2.0 1.1 0.75 0.65 0.75 Optical bleach 0.15 0.12 0.13 0.11 0.15 0.13 0.14 Mixed mono- and di-C 1-6 alkyl phosphate 0.5 0.43 0.5 Silicone antifoam - 1.0 1.0 1.0 1.0 - -

Example No.

47 48

Sodium C ₁ -C ₄ linear alkylbenzenesulfonate

a phonate 8.8 10,0 10,0 Coconut monoethanolamide 3.5 4.0 4.0 Sodium carbonate 4.4 - - Sodium tripolyphosphate 16.7 19,0 19,0 Zeolite A. 7.9 9.0 9.0 Sodium silicate / Si0 ₂ : Na ₂ 0, '1: 1, ** 1,6: 1 / - 5.0 * 5.0 ** Optical bleach 0.13 0.15 0.15 Mixed mono- and di-C,. ,, 14-18 alkyl phosphate 0.44 0.5 0.5

Example No.

49 50 51 52 Sodium C _1u _ ₁₄ linear alkyl benzene sulphonate 9.5 10,0 10,0 10,0 Coconut monoethanolamide 4.2 4.0 - - Sodium carbonate - - 5.0 5.0

Sodium tripolyphosphate 18,1 19,0 25,0 25,0 Zeolite A. 8.6 9.0 - - Sodium carboxymethyl- cellulose - - 1.0 1.0 Coconut diethanolamide - - 5.0 5.0 Optical bleach 0.14 0.15 0.15 0.15 Mixed mono- and di-C _{16 (|} alkyl phosphate 0.5 0.5 - - Trisodium sulfosuccinate - - 1.0 - Sodium ethylenediaminetet- Rakis / methenphosphonate / - - - 0.5 Trisodium orthophosphate 2.9 5.0 - -

53 54 Example No. 55 56 57 58 Sodium C _{1 <M4} linear alkylbenzenesulfonate 10.6 10.6 10.6 10.6 10.6 10.6 Coconut monoethanolamide 2.5 1.7 2.5 2.5 1.7 1.7 Sodium carbonate - 4.6 - - 4.6 4.6 Sodium silicate / Si0 ₂ : Na ₂ 0,1,6: 1 / 6.4 - 6.4 6.4 - - Sodium tripolyphosphate 13.7 14.9 13.7 13.7 14.9 14.9 Zeolite A. 9.0 10,0 9.0 9.0 10,0 10,0 Sodium carboxymethyl- cellulose 1.0 1.0 - 1.0 1.0 - Sodium C ₁₂₁₄ alkyl-3 mol. ethoxysulfate 0.7 1,2 0.7 0.7 1,2 1,2 Optical bleach 0.14 0.14 0.14 0.14 0.14 0.14 Silicone antifoam 1.0 1.0 - - - -

59 60 Example No. 65 61 62 63 64 Sodium C10-14 linear alkylbenzenesulfonate 9.3 9.3 9.5 9,4 8.9 9.2 9.2 Coconut diethanolamide 3.5 3.5 2.4 2.75 5.2 3.5 3.5 Sodium carbonate 5.8 5.8 5.9 5.9 5,6 5.8 5.8 Sodium tripolyphosphate 29.0 18.6 29.7 29.5 27.8 28,9 28,8 Zeolite A. - 11,0 - - - - - Sodium carboxymethyl- cellulose - - - - - 0.1 0.1 Optical bleach 0.14 0.14 0.14 0.14 0.14 0.14 0.14

66 67 68 Example No. 69 70 Oleic acid - - 8,5 8.3 9,1 Sodium hydroxide - - 0,91 0.88 0.97 Sodium xylsulfonate - - 0,5 0.5 0.5

Sodium C _{1 (I4} linear

alkylbenzenesulfonate 9,1 7.9 - - - Coconut diethanolamide 3.4 1.8 3.2 3.0 3.3 Sodium carbonate 5.7 5.8 4.2 4.9 2.4 Sodium tripolyphosphate 17.7 17.3 14,0 13.6 14,8 Zeolite A. 11.4 11.6 9,4 9,1 9.9 Sodium carboxymethyl- cellulose 0.14 0.15 1.6 1.5 1.7 Sodium C ₁₂₁₈ alkyl sulphate 3 moles of EC - 2.0 - - - Optical bleach 0.14 0.14 0.15 0.15 0.16 Mixed mono- and di-C _{| 618} alkyl phosphate 0.47 0.48 1.6 1.5 1.7 Non - ionogenic inhibitor of foam 0.95 1.0 - - - With _{1218 -} alcohol to 8 mall EC - - 3.0 2.9 3.1

72 Example No. 73 Oleic acid 6,8 6,1 Sodium hydroxide Sodium C _{10 14} linear 0.7 0.65 alkyl benzenesulfonate 2.85 2.2 Coconut diethanolamide 3.65 3.7 Sodium tripolyphosphate 29.2 29,8 Sodium chloride 1.7 2.0 Example no 74

Sodium C ₁₄ linear alkylbenzene- sulfonate 7.8 Sodium C _{12 lg} alkyl at 3 the mall EC 2.6 Sodium tripolyphosphate 23.4 Sodium carboxymethyl- cellulose 1.0 Optical bleach 0.15 Perfume / fragrance substance /, colorant, water as needed

Example No.

75 76 77 78 79 80 81 Sodium C _{1 (1-4} linear alkylbenzenesulfonate 8.4 7.0 7.0 6.0 9.0 14.2 9.6 Sodium C _121b alkyl sulfate of 3 moles of EC 2.8 3.0 3.0 3.0 2.7 1.9 0.6

C _{l2 | g} alcohol of 8 mol

EC 1.9 - - - - - - Coconut diethanolamine - - - 2.0 0.9 - - Coconut monoethanolamine - - - - - - 2.3 Methyl Sodium Tal sulfonic acid ester - - - - - - Mixed mono- and di-C _{| 6 | g} alkyl phosphate - - - - - - - Sodium carbonate 4.6 5.0 5.0 7.5 6,8 6.6 - Sodium silicate / SiO ₂ : Na ₂ 0,1,6: 1 / 2.3 5.0 5.0 5.0 4.5 2.8 5,6 Sodium chloride 0.9 - - - - - - Sodium tripolyphosphate 17.7 21.5 18,0 8.0 9.0 17,0 21.0 Zeolite A. 4.6 - 4.0 12,0 9.0 - - Sodium carboxymethyl- cellulose - - - - - - 0.9 Optical bleach 0.14 0.15 0.15 0.15 0.15 0.14 0.14 Silicone antifoam 0.46 - 1.0 - - - 0.9

82 83 Example No. 84 Sodium C _{1) M4} linear alkyl benzenesulfonate 7.4 5.0 9.0 Sodium C _{12) g} alkyl sulfate 3 moles of EC - - 4.0 With ₁₂ alcohols of 8 mole EC - - - Coconut diethanolamine - - - Coconut monoethanolamine 3.7 3.4 - Sodium tallow methyl ester of sulfonic acid - 3.4 - Mixed mono- and di-C _{16 | g} alkyl phosphate - 0.4 - Sodium carbonate 6,9 4.2 7.5 Sodium silicate / SiO ₂ : Na ₂ 0,1,6: 1 / - - - Sodium chloride - - - Sodium tripolyphosphate 20,2 15.9 25,0 Zeolite A. - 7,6 - Sodium carboxymethyl- cellulose 0.9 - - Optical bleach 0.14 0.13 0.15 Silicone antifoam 0.9 - 1.0

The figures show variations in conductivity, yield strength and viscosity according to changes in the concentration of the electrolyte and the active ingredient.

Figure 1 is a diagram showing the conductivity of an aqueous 20.6% solution of active ingredients consisting of 2 parts by weight. sodium dodecylbenzenesulfonate and 1 parts by weight sodium With _{12 g of} alkyl sulfate x 3 moles of EO, at different concentrations of added sodium silicate with a molar ratio of Na ₂ O: SiO ₂ 1: 1.6. The numbers on the horizontal axis express the amount of silica in the composition, expressed as wt.% Solids.

In the interval between 0 and 7%, the added silica solution results in a clear, optically isotropic composition typical of step 1 described above. Between the points indicated by "A" and "B" a are obtained stage II compositions which are cloudy, unstable and contain a non-space-filled flocculent precipitate of spherulites. Between "B" and "C" are the formulations of step III according to the invention. They are turbid, stable compositions that contain mainly spatially filled flocculent sludge from spherulites, have a flow limit and form only one liquid phase after centrifugation at high G. After "G", step IV compositions are obtained containing space-free flocculent sludge. spherical G phase that are unstable. As will be seen, the stable formulations of stage III are obtained at the trough of the conductivity curve around the first conductivity minimum.

Figure 2 shows the effect of the addition of sodium nitrate to the same aqueous system of the active substance. After point “C”, step IV undergoes a second maximum of conductivity, followed by a second minimum of conductivity corresponding to the formation of a layered composition according to step V, at approximately “D”.

Figure 3 shows the variations in viscosity, conductivity and yield strength when sodium carbonate is added to the same active substance system.

The left axis shows the viscosity at 136 seconds. ' ¹ in Pa / sec, the numbers in brackets refer to the conductivity in milli cm cm ¹ ; the right-hand scale refers to the yield point in cm ² ; the horizontal axis represents the total percentage of sodium carbonate contained, expressed as dry weight of sodium carbonate, based on the total weight of the composition.

In the case of sodium carbonate, a minimum in the conductivity curve (dashed line) is not observed. The reason for this is that the solubility limit of sodium carbonate is reached, so further addition of carbonate results in its suspension and does not increase the dissolved electrolyte concentration. Therefore, stage IV cannot be observed. The sharp increase in the yield point (right peak) coincides with the occurrence of stage III at point “B”. This is typical of the compositions according to the invention.

Figure 4 shows the effect of changing the relative quantitative ratios of sodium dodecylbenzenesulfonate and coconut monoethanolamide in a composition containing sodium dodecylbenzenesulfonate, sodium tripolyphosphate, sodium carbonate and water at a ratio of 0.2: 0.5: 0.1: The horizontal scale represents the weight ratio of coconut monoethanolamide and sodium dodecylbenzenesulfonate. The vertical scale represents the conductivity in millis cm cm ' ¹ (circles) and also the viscosity in Pa / sec X10 (triangles).

Figure 5 shows a similar ratio in which coconut monoethanolamide is replaced by sodium C _{12 (} alkylsulfate x 3 moles of ethylene oxide. The horizontal scale is the weight ratio of ether sulfate and alkylbenzenesulfonate.

Figures 4 and 5 show how compositions according to the invention can be prepared by modifying the active ingredients.

Figure 6 shows the change in conductivity in milliscm cm ^-1 with the addition of sodium nitrate in various quantitative proportions to a detergent composition containing a suspended constituent and containing the following components by weight: Sodium dodecylbenzenesulfonate 9, Sodium C ₁₂ alkyl alkylsu x 3 moles EC 4, Silicone antifoam 1, Perfume / fragrance / 0,6, C _61H mixed mono- and dialkyl _phosphate 0,5, Optical bleach 0,15, Sodium tripolyphosphate 19, Zeolite A 12.

On this curve, stage I was not observed due to the already dissolved tripolyphosphate. Conductivity drops from a maximum at “A” to the beginning of stage III at “B”.

Figure 7 shows the yield strength for the same system, in cm ² .

Figure 8 shows the viscosity at 136 cm ^-1 (lower curve), 21 cm ^-1 (upper curve) and its decrease (mean curve) in Pa / sec X 10.

Figure 9 shows the change in conductivity with a change in the quantitative ratios of sodium silicate in 20.6% wt. aqueous sodium dodecylbenzenesulfonate solution in admixture with coconut monoethanolamide at a weight ratio of 10: 4.

Again, stage I is not observed here, but in this case, because the active ingredients are not completely soluble in water at room temperature. Thus, in the absence of electrolyte, the composition is cloudy and unstable.

Figures 10 and 11 are copies of microscopic images in a transmitted Pt / C beam, freezing crack formation at magnifications of X78,000 and X150,000 / lin /, respectively.

Both images taken with a transmission electron microscope at Lancaster University present a sample with the following composition in% by weight: sodium dodecylbenzenesulfonate 11,8, sodium C ₁₂ 'alkylsulfate x 3 mol EC 5,2, sodium silicate / Na ₂ O : SiO ₂ 1.6.1 / 17.4 and water for balance.

The micrograph shows spherulites with diameters between 0, 2 and 1 μ, which are reported to be complex bubbles with concentric structure and repeated spatial distance (including the thickness of one surfactant shell and one adjacent aqueous layer) of 80 ± A.

Claims (59)

Claims 1. Liquid detergent composition comprising water, a surfactant, a building block and an electrolyte, characterized in that the surfactant is in such a weight ratio with water that when in aqueous micellar solution of the surfactant, it solubilizes solubility gradually the surfactant, the electrical conductivity of the solution goes through the first minimum, in which the mixture is stable and cloudy, with the total weight of the building block relative to the surface the active substance is at least 1.5: 1 and the amount of dissolved electrolyte relative to the total amount of the composition, including the dispersed building block, corresponds to the amount determined by the area around the minimum of the curve reflecting the conductivity / concentration dependence of the electrolyte in the composition and includes the concentration at said first conductivity minimum such that the amount of electrolyte is in the range between the minimum and maximum of the quantities at which such stability of the composition is ensured that upon storage a layer containing a maximum of 2% of the total volume of the composition may be separated at room temperature as well as at temperatures of 5 ° C for 3 months. Composition according to claim 1, characterized in that the amount of electrolyte is between the minimum and maximum of such quantities that, when stored for a period of 3 months at both room temperature and at 0 ° C, separate a layer containing a maximum of 2% by volume of the total composition. Composition according to Claims 1 and 2, characterized in that the amount of electrolyte is between the minimum and maximum of such quantities that, at storage of the composition for 3 months, both at room temperature and at temperatures below 5 ° C and at 40 ° C, a layer containing up to 2% of the total volume of the composition may be separated. Composition according to claims 1 to 3, characterized in that the amount of electrolyte is higher than the maximum of such quantities in which the composition is slip sensitive. 5. Composition according to claims 1 to 4, characterized in that the amount of electrolyte is in the range at which the drop viscosity of the composition is greater than 0.4 Pa / sec. Composition according to claim 5, characterized in that the droplet viscosity is between 0.4 and 2 Pa / sec; A composition according to claims 5 and 6, characterized in that the drop viscosity of the composition is greater than 0.45 Pa / s. Composition according to claim 7, characterized in that the droplet viscosity is between 0.475 and 1.5 Pa / sec. Composition according to claim 8, characterized in that the droplet viscosity is between 0.48 and 1.1 Pa / s. Composition according to claims 1 to 9, characterized in that the viscosity is between 0.1 and 2 Pa / sec at a shear rate of 136 sec ¹ . Composition according to claim 10, characterized in that the viscosity is between 0.2 and 1 Pa / s at a shear rate of 136 sec *. Composition according to claim 11, characterized in that the viscosity is between 0.3 and 0.6 Pa / s at a shear rate of 136 sec ' ¹ . A composition according to claims 1 to 12, characterized in that the amount of electrolyte is between the minimum and maximum of the amounts in which no clear aqueous layer is released after centrifugation of the composition at 20,000 G for 5 min at 25 ° C. Composition according to claims 1 to 13, characterized in that the amount of electrolyte is between the minimum and maximum of the amounts in which no clear aqueous layer is released after centrifugation of the composition at 20,000 G for 90 minutes at 25 ° C. A composition according to claims 1 to 14, characterized in that the amount of electrolyte is sufficient to provide stability of the composition when slip. A composition according to claims 1 to 15, characterized in that the amount of electrolyte is sufficient to make the composition insensitive to slip. Composition according to claims 1 to 16, characterized in that the amount of electrolyte is sufficient to ensure the temperature stability of the composition. A composition according to claims 1 to 17, characterized in that it contains from 5 to less than 30% by weight. surfactant, by weight of the composition. A composition according to claims 1 to 18, characterized in that the electrolyte consists of at least one alkali metal or ammonium salt selected from the group of carbonates, silicates, tripolyphosphates, orthophosphates, pyrophosphates, nitrilotriacetates, citrates, chlorides and nitrates. A composition according to claim 19, characterized in that it contains at least 5% by weight. relative to the total composition, a surfactant selected from linear alkylbenzenesulfonates and mixtures thereof with at least one surfactant selected from the group of anionic, non-ionic, cationic, zwitterionic or amphoteric surfactants. A composition according to claims 1 to 20, characterized in that it is an aqueous composition in which solids are suspended. A composition according to claim 21, characterized in that the solids comprise a particle-shaped building block. The composition of claim 21, wherein the solids comprise an abrasive. 24. The composition according to claims 1 to 20, characterized in that the electrolyte contains a water-soluble building block that is in excess of the composition in terms of its solubility at room temperature, and therefore the composition contains suspended solids. particles of this building block. A composition according to claims 1 to 24, characterized in that it has a weight of from 25 to 75% by weight. A composition according to claims 1 to 25, characterized in that at a temperature of 25 ° C there is a flow point greater than 1.5x10 ' ⁵ and a viscosity lower than 0.28 Pa / s, measured at a shear rate of 136 sec ¹ . A composition according to claims 1 to 26, characterized in that it has a flow point of 1.5x10 ' ⁵ to less than 30x10' ⁵ N cm ² at a temperature of 25 ° C. A composition according to claims 1 to 27, characterized in that it has a drop viscosity of 0.45 to 2 Pa / s. The composition of claims 1 to 28, characterized in that it has a weight of at least 35% by weight. A composition according to claims 1 to 29, characterized in that the weight ratio of the constituent to the surfactant is 1.5: 1 to 3.5: 1. A composition according to claims 1 to 30, characterized in that it contains 10 to 13.5% of the surfactant relative to the total weight of the composition. A composition according to claims 1 to 31, characterized in that, after centrifugation for 17 hours at 800 G, it is separated into a layer of solid and an aqueous layer with a point of flow greater than 2x10 ' ⁵ N cm' ² at 25 ° C. The composition of claims 1 to 32, characterized in that after centrifugation for 17 hours at 25 ° C at 800 G, it is separated into a layer of solid and an aqueous layer with a viscosity of less than 1.5 Pa / s, measured at a sliding rate 136 sec ¹ . A composition according to claims 1 to 33, characterized in that it has a pH value of 9 to 13. A composition according to claims 1 to 34, characterized in that it contains sufficient alkaline substances such that in order to reduce the pH to 100 ml of the aqueous solution of this composition, it is diluted to a content of 0.5% by weight. dry matter, up to a pH of 9 requires at least 0.8 ml of 10N HCL. A composition according to claims 1 to 35, characterized in that at a dilution of up to 0.5% by weight. dry matter to reduce the pH of 100 ml of aqueous solution to 9 is required 4.7 to 8.6 ml of 10N HCL. A composition as claimed in claims 1 to 36, characterized in that the amount of electrolyte is such as to provide at a temperature of 25 ° C and at 50 kHz a conductivity which is at most 2 millicm cm 2 'higher than that corresponding to the first minimum of conductivity. A composition according to claims 1 to 37, characterized in that at 25 ° C and 50 kHz there is a conductivity of less than 15 milliscm per cm. A composition according to claims 1 to 38, characterized in that the surfactant comprises a mixture of (a) non-alkoxylated sulfated or sulfonated anionic surfactants and (B) alkoxylated anionic surfactants and / or non-ionogenic substances. The composition of claim 39, wherein component (A) contains alkylbenzenesulfonate having 8 to 22 aliphatic carbon atoms. A composition according to claims 39 and 40, characterized in that component (A) comprises olefin sulfonate, alkanesulfonate, alkylphenolsulfate, sulfocarboxylic acid and / or sulfocarboxylic acid ester having from 8 to 22 carbon atoms in the alkali group. A composition according to claims 39 to 41, characterized in that component (B) contains alkylethylenoxy sulfate with a C _{g 22} alkyl group and up to 20 ethylene oxy groups. A composition according to claims 39 to 42, characterized in that component (B) contains ethoxylated alcohol of 8 to 22 carbon atoms, carboxylic acid, amine, alkylamide or glyceryl ester having in each of the above cases up to 20 ethylene oxy groups. A composition according to claims 39 to 43, characterized in that component (B) contains alkyl monoethanolamide of 8 to 22 carbon atoms or diethanolamide. A composition according to claims 39 to 44, characterized in that component (B) contains mono-C, _21- alkyl-di (C [ ₄ alkyl) amino oxide. A composition according to claims 39 to 45, characterized in that the weight ratio of component (A) to (B) is from 5: 1 to 1: 3. The composition of claim 46, wherein the weight ratio of component (A) to (B) is from 4: 1 to 1: 2. The composition of claim 47, wherein the weight ratio of component (A) to (B) is from 3: 1 to 1: 1. A composition according to claims 1 to 48, characterized in that it contains a foaming agent. A composition according to claims 1 to 48, characterized in that it contains a foam inhibitor. A composition according to claim 50, wherein the foam inhibitor comprises an organopolysiloxane component. A composition according to claims 1 to 51, characterized in that it contains suspended particles of sodium tripolyphosphate and / or zeolite. 53. A stable, water-insoluble detergent composition according to claims 1 to 53, characterized in that it contains from 12 to 40% by weight of the surfactant dry substance containing from 30 to 90% by weight of the non-alkoxylated dry substance a sulfated and / or sulfonated anionic surfactant and the residue is an alkyl ether sulfate and / or a non-ionic surfactant; an aqueous phase containing sufficient electrolyte in the solution to form a spatially filling spherulite flocculated structure that encompasses the surfactant and is interdispersed with the aqueous phase; suspended particles of the building block; an effective amount of at least one foam inhibitor and, optionally, other excipients commonly used in detergent and detergent formulations other than water, surfactants, building blocks and electrolytes. Composition according to claims 1 to 53, characterized in that it contains bleaching agents and / or enzymes encapsulated in the suspension. The composition of claims 1 to 54, characterized in that most of the surfactants are in the form of spherulites with a diameter of 0.1 to 5 microns. 56. A composition according to claim 55, wherein the greater weight amount of the surfactant is in the form of spherulites with a diameter of 0.2 to 5 microns. The composition of claim 56, wherein the greater weight amount of the surfactant is in the form of spherulites with a diameter of 0.2 to 1 micron. Composition according to claims 1 to 57, characterized in that it contains spherulites with a diameter of 0.1 to 50 microns, which are multilayered bubbles of concentric structure and with a mean distance between the individual layers of 6 to 10 nm. 59. The composition of claim 58, wherein the average distance between the individual layers is from 7 to 9 nm.