DK166030B - LIQUID DETERGENT COMPOSITION - Google Patents

Description

DK 166030 B

The present invention relates to a new, stable pourable liquid detergent composition comprising water, surfactant, dissolved electrolyte salt which acts to desolubilize the surfactant, and suspended particles of a solid builder.

Except where the contrary is stated, or the context otherwise contradicts it, the following terms in quotation marks, wherever they are used in the present description with claims, have the meanings given below.

The term "builder" is sometimes used vaguely within the detergent field to include any non-surfactant whose presence in a detergent composition enhances the purification effect of the preparation. However, it is more common for the term to be limited to such typical builders, which are primarily used as a means of preventing or counteracting the negative effects of washing due to calcium and magnesium ions, e.g. by chelating, sequestering, precipitating or absorbing the ions, and secondly as an alkalinity or buffering source. The term "builder" is used herein in the more limited sense and refers to additives that substantially mitigate the effects of calcium. It includes sodium or potassium tripolyphosphate and other phosphate and condensed phosphate salts, such as sodium or potassium orthophosphates, pyrophosphates, metaphosphates or tetraphosphates, and phosphonates such as acetodiphosphonates, aminotronisethylene phosphonates and ethylenediaminetrametramethyl. enphosphonater. It also includes alkali metal carbonates, zeolites and such organic sequestrants as salts of nitrilotriacetic acid, citric acid and ethylenediamine tetraacetic acid, polymeric polycarboxylic acids such as polyacrylates and maleic anhydride based copolymers.

For the avoidance of doubt, "builder" is used herein as comprising water-soluble alkali metal silicates such as sodium silicate, but not additives such as carboxymethyl cellulose or polyvinylpyrrolidone, the function of which is 0

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2 is mainly dirt suspending or as anti-repellant.

"Electrolyte" is used herein to denote water-soluble ionic compounds having a solubility 5 in water at 0 ° C expressed as anhydrous compound of at least 5 which dissociates at least partially in aqueous solution to provide ions and which at the concentrations present tend to lower the total solubility (including micellar concentration) 10 of surfactants in such solutions by a "salting out" effect. It includes water-soluble dissociable inorganic salts, such as e.g. alkali metal or ammonium chlorides, nitrates, phosphates, carbonates, silicates, sulfates, perborates and polyphosphates, and also certain water-soluble organic salts which insolubilize or "salt out" surfactants. It does not include salts of cations which form water-insoluble precipitates with surfactants present.

References herein to electrolyte content or concentration refer to total dissolved electrolyte, including any dissolved builder if such builder is also electrolyte but excludes any suspended solids.

"Hydrotrope" means any water-soluble compound which tends to increase the solubility of surfactants in aqueous solution. Typical hydrotropes include the urea and the alkali metal or ammonium salts of the lower alkylbenzenesulfonic acids such as sodium toluene sulfonate and sodium xylene sulfonate.

30 Whether a particular compound is an electrolyte or a hydrotrope can sometimes depend on the active ingredients present. Sodium chloride is generally regarded as a typical electrolyte, but in relation to sultainer it behaves like a hydrotrope. The "electrolyte" and "hydrotrope" as used herein must therefore be interpreted in the context of the particular active ingredients.

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As used herein, "soap" means an at least heavily water-soluble salt of a natural or synthetic aliphatic monocarboxylic acid, which salt has surfactant properties. The term includes sodium, potassium, lithium, ammonium and alkanolamine salts of natural or synthetic C C fed fatty acids including stearic acid, palmitic acid, oleic acid, linoleic acid, ricinoleic acid, behenic acid and dodecanoic acid, resin acids and branched monocarboxylic acids.

1Q The "usual minor constituents" include non-water constituents, active constituents, builders and electrolytes which can be included in textile detergents, typically in proportions of up to 5%, which are compatible in that composition with a pourable, chemically stable, non-sedimenting agent. The term includes anti-repellents, dispersants, antifoams, perfumes, dyes, optical brighteners, solvents, buffers, bleaches, corrosion inhibitors, antioxidants, preservatives, fluff inhibitors, wetting agents, enzymes and their stabilizers, and the like. As used herein, "functional constituents" means ingredients required to provide a beneficial effect in the washing liquid, and include constituents which contribute to the washing efficiency of the agent, e.g.

surfactants, builders, bleaches, optical brighteners, alkaline buffers, enzymes and anti-repellents, and also anti-corrosion and anti-foaming agents, but excludes water, solvents, dyes, perfumes, hydrotropes, sodium chloride, sodium sulfate, solubilizers, solubilizers, solubilizers, whose sole function is to impart stability, fluidity or other desirable properties in a concentrated preparation. "Utility value" means the percentage of functional constituents based on the total weight of the agent. "Active constituents" means surfactants.

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All reference herein to "centrifugation", unless otherwise stated, refers to centrifugation at 25 ° C for 17 hours at 800 x G.

Any mention herein of "centrifugation at high G" 5 means centrifugation at 20,000 G at 25 ° C. Unless otherwise stated, centrifugation is performed at high G for 5 minutes.

The term "separable phase" as used herein refers to components or mixtures of components of a pourable detergent, each separable from the agent, to form a defined layer by centrifugation. Unless otherwise indicated in the context, all references to the composition of separable phases are references to the composition of the phases separated by centrifugation, and references to an agent structure refer to the non-centrifuged agent. A single separable phase may comprise two or more thermodynamically delimited phases which cannot be separated except after centrifugation such as, e.g. a stable emulsion or lint.

"Dispersed" herein describes a phase which is discontinuously distributed as separate particles or droplets at least in one other phase. "Co-continuous" describes two or more interpenetrating phases, each extending continuously or as a continuous network through a common volume or formed by distinct or dispersed elements cooperating to form a continuous matrix seeking maintaining the position of each element relative to the matrix when the system is. resting. "Interlaced" describes two or more phases that are either co-continuous or one or more dispersed in one or the other.

Mention of "solid phases" means substances which are actually present in the solid-state agent at ambient temperature, and optionally include crystallization or hydration water, unless otherwise provided.

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0 goes out of context. References to solids include references to microcrystalline and cryptocrystalline solids, i.e. solids whose crystals are not directly observed by optical microscopy but whose presence can be joined. A "solid layer" is a solid, doughy or non-pourable gelatinous layer formed by centrifugation.

"Total water" refers to water occurring as liquid water in a predominantly aqueous phase together with any other water in the agent, e.g. crystallization or hydration water or water dissolved or otherwise occurring in any predominantly non-aqueous phase. "Dry weight" refers to residual weight after drying to constant weight at 140 ° C.

The term "preparation" is used herein to denote the combination of ingredients which constitute a medium dry weight. Thus, the same preparation can be exemplified by a number of agents which differ in terms of percent dry weight.

"Stable" means that no layer containing more than 2% of the total volume is separated from the main mass of the agent within 3 months at room temperature under normal gravity.

The "displacement sample" is a sample in which the test 25 sample is passed through a straight 40 mm tube with an inner radius of 0.25 mm under a pressure of 35 kg / cm overpressure. The shear test is performed for all of the measurements described herein by aspirating a test sample into a 500 ml pressure vessel through a wide-opening tube, replacing the 30-wide tube with a 0.25 mm radius tube and applying a nitrogen pressure of 35 kg / cm overpressure in the pressure vessel until it is empty. The 0.25 mm tube is then replaced with the tube with the wide opening so that the cycle can be repeated. As a rule, by the above method, a shear rate of approx. 127,000 sec 0

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6 "Shear stable" means stable after 3 passing shear tests, "" shear unstable "means unstable after undergoing 3 or fewer shear tests or at lower shear rates.

"Shear insensitive" means that no stability loss or significant viscosity increase occurs after exposure to moderate shear. Shear sensitivity is determined by 10 Contraves1 "Rheomat 30" viscometer, cone and plate measuring system 2, at 25 ° C, the displacement being linearly increased from 0 to 280 sec. ^ in 1 minute ("upsweep") and immediately linearly reduced to ΰ sec in "in 1 minute (" downsweep "). An agent is rated 15 as non-shear sensitive if it is stable after the cycle and if the viscosity at 150 sec after the downsweep is no more than 10% greater than after the upsweep.

"Temperature stable" means that no layer containing more than 5% by volume is separated from the main mass of the agent within 24 hours after being heated by immersing a sample of 20 g in a water bath maintained at 90 ° C 110 minutes, followed by immediate immersion in a water bath maintained at 100 ° C for 10 minutes.

Detergent "pH" means pH measured with a Pye "Unicam 401" combined glass / calomel electrode.

"Conductivity" is specific conductivity measured at 25 ° C at a frequency of 50 kHz. The indicated results are measured on a "CDM3 Radiometer" wiring bridge using a "CDC314" flow and pipette cell.

"First conductivity minimum" refers to the graphical representation of conductivity deposited as a function of increasing dissolved electrolyte concentration in a liquid detergent containing a fixed proportion of active ingredients relative to water, the conductivity which in

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0 • 7 level has first risen to a maximum value, decreases to a minimum value and then rises again. The term denotes the electrolyte concentration corresponding to this minimum value or the lowest concentration of dissolved e-electrolyte corresponding to one of several such minimum values.

All percentages, unless otherwise stated, are by weight based on the total weight of the agent.

All references to "viscosity" are, unless otherwise stated, viscosity measured on a bowl-and-solder viscometer at 25 ° C after flowing for two minutes, using a 20 mm internal diameter flat bottom bowl. mm, 92 mm long and a solder with a diameter of 13.7 mm, 44 mm long with tapered ends with a horizontal angle of 45 ° and a spindle with a diameter of 4 mm. The solder tip is 23 mm from the bottom of the bowl. This corresponds to Contrave's "Rheomat 30" viscometer with measuring system C.

"Pourable" means, as used herein, having a viscosity of less than 2 Pascal seconds at a shear rate of 136 sec. "Viscosity drop" means the difference between the viscosity of a diluted agent measured at 21 sec. And the viscosity. measured at 136 sec. "Flow voltages" referred to herein are measured on a "RML Series II Deer Rheometer" at 25 ° C.

"L" phase means a clear liquid optical isotropic micellar surfactant solution in water which occurs at concentrations above the critical micellar concentration and where the surfactant molecules are believed to aggregate to form spherical oblate (slice) or prolate ( rod) micelles.

"Annex" includes layers of surfactant which are approx. two molecules thick formed from two adjacent parallel layers, each comprising ten-sided molecules arranged such that the hydrophobic moieties of the molecules are located in the center of the annex, and the

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0 8 hydrophilic parts are located on its outer surfaces.

"Attachments" are used herein to include interlaced finger layers which are less than two molecules thick. An interlaced finger layer can be considered as an appendage where the two layers are interposed, allowing some degree of overlap between the hydrophobic moieties of the two-layer molecules.

"Spherulite" means a spherical or elliptical body having dimensions from 0.1 to 50 µm. Spherulites 10 can sometimes be mistaken for elongated, oblate, bulbous or hourglass shaped. "Vesicle" means a spherulite containing a liquid phase bound by an appendix. "Multi-vesicle" means a vesicle containing one or more smaller vesicles.

"Lamellar phase" means a hydrated solid or liquid crystal phase, with several annexes arranged in substantially parallel rows, separated by layers of water or an aqueous solution with a sufficiently regular lattice spaced from 25 to 70 to 20 can be detected by neutron diffraction when it appears as a substantial proportion of an agent. As used herein, it excludes concentric multi-vesicles.

The "G" phase refers to a liquid crystal lamellar phase of the type also known in the literature as the "pure" or "lamellar" phase. The "G" phase for any given surfactant or surfactant mixture generally occurs within a narrow concentration range. As a rule, pure G phases can be identified by examining a sample under a polarizing microscope between crossed polarizers. Characteristic structures are observed according to Rosevear, JAOCS bed 31, page 628 (1954) or in J. Colloid and Interfacial Science, vol. 30, No. 4, page 500 (1969).

"Spherical G phase" means multivesicles formed from essentially concentric shells of ten

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0 side attachments alternating with aqueous phase with a G phase in between. Typically, common G-phases may contain a smaller proportion of spherical G-phases.

"Lud" means an aqueous liquid phase containing electrolyte, which phase is separated from or interlaced with another liquid phase containing more active substance and less electrolyte than the liquor phase.

"Laminate composition" means a composition wherein the predominant portion of surfactant occurs as a 10 lamellar phase or where a lamellar phase is the major factor preventing sedimentation. "Spherulitic composition" means a composition wherein a predominant amount of surfactant is present as spherulite or is substantially stabilized against sedimentation by a spherulitic surfactant phase.

Liquid detergents have so far in the main proceedings been used for easier cleaning such as washing up. The market for heavy detergents, e.g. for textile washing, has been dominated by powders because it is difficult to obtain an effective amount of surfactant in especially builder in stable liquid preparation. Such liquids should theoretically be cheaper than washing powders, because the need to dry would be avoided and the sulphate fiber, which is usually used in washing powders, could be replaced with water. They also offer such reliefs as easier handling and faster dissolution in washing water than the powder does. The attempts that have been made to obtain solutions of the functional constituents ^ have not, in economic terms, been particularly successful.

30 One of the reasons for the lack of success has been that the most commonly used and cost-effective builders, e.g. sodium tripolyphosphate, is not sufficiently soluble in aqueous compositions. Further, increasing the amount of dissolved builder, due to the salting effects, tends to lower the amount of dissolvable surfactant and vice versa. Potassium o 10

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pyrophosphate builders, together with amine salts of the more soluble active ingredients, have been tried as alternatives to the sodium salts, but have not proved to be cost effective.

5 Liquid detergents without builder containing the high surfactant levels are marketed for textile washing, but are unsuitable for hard water areas and have had only limited success, mainly limited to markets where the use of effective builders is subject to legal restrictions and competition from powders are similarly smaller.

Another option is to try to suspend the excess builder as a solid in a liquid micellar solution or emulsion of surfactant. However, the problem has been to stabilize the system so that the builder is kept suspended and to prevent sedimentation. The literature has suggested numerous, relatively mind-boggling preparations, including the use of costly potassium salts in place of the cheaper sodium salts and the use of solubilizers such as hydrotropes, dispersants, or solvents, all of which have prevented the realization of a possible cost reduction. Even with such irrelevant additives, it was considered necessary to use relatively low concentrations of solid builder, which gives limited washing efficiency. This solution was subject to certain assumptions: that the active ingredient should be dissolved as far as possible, that the amount of active ingredient should be relatively large, that the amount of suspended solids should be as small as possible to avoid difficulties in stabilizing the suspension. against sedimentation, that special thickening agents or stabilizers were important in preventing sedimentation, and that electrolytes which would insolubilize the tensile should be avoided or kept at very low levels.

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An important feature of the prior art has been its empirical nature. No acceptable theory has been put forward that accounts for the stability of some compositions and the instability of others. Thus, there is no method for predicting which compositions will be stable and no general procedure for designing a new stable liquid detergent. The prior art contains no universally applicable teachings, and even the specific examples in most prior patents of liquid detergents provide compositions that are separated within a few weeks. The relatively few exceptions have apparently been discovered by accident, and extrapolation has been impossible.

Products of this type have been on the market in Europe and Australia, but have suffered from some serious disadvantages. In particular, the individual compositions have been found to be sensitive to relatively small variations in the preparation and preparation procedure.

Deviation from a particular composition, which is optimized within fairly narrow limits, results in the rule of instability and shortened shelf life. Those skilled in the art have therefore had to confine themselves to particular constituents and proportions which have not included many of the most effective combinations of surfactants and builders and 25 minor constituents for textile washing, and have had to resort to special manufacturing methods.

The products have had relatively poor washing properties, either due to low builder / active ingredient weight ratios or due to low alkalinity. They have also shown signs of undesirable sensitivity to mechanical and / or thermal influences, e.g.

eg by displacement or storage under extreme climatic temperature conditions.

Thus, some compositions differentiate after 35 shear stress, others become excessively viscous, most differ after storage at either 0 or 0 12

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clay 40 ° C. The prior art has not disclosed how these deficiencies should be overcome.

In addition to the compositions which have been developed industrially, many compositions have been proposed in the literature which are not suitable for practical commercial exploitation. As a rule, such compositions are unstable or not sufficiently stable to withstand normal storage without sedimentation or are too costly to produce in relation to their washing efficiency to be considered an industrial development.

Recently, a number of compositions have been proposed in which the active ingredients form a network of a lamellar phase separable from the aqueous phase by centrifugation, providing a gel structure capable of supporting suspended particles in a solid builder. Gel structures are obtained by adding sufficient electrolyte to salt out the active ingredient to form an aqueous lute phase and a separable lamellar phase, and by holding the solids content above a threshold for stability and below a ceiling for pourability. .

The amount of electrolyte needed depends on the hydrophilicity and melting point of the surfactant and whether solubilizing additives such as hydrotropes or solvents are present. The above gel compositions tend to have higher utility and a higher builder / active ingredient ratio and to be more cost effective than the known liquid compositions on the market. In fact, the best of the above-mentioned lamellar gel compositions are more cost-effective dirt-removing agents than the best textile detergents.

However, the previously known lamellar compositions have had a mobility lower than the optimum for this purpose.

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It has now been found that a new group of compositions comprising electrolyte, active ingredients and water is capable of suspending solids such as builders to form stable compositions, where better washability is combined with satisfactory mobility. It is believed that the stability of the new compositions is due to a previously unsphered spherulitic structure, and a general method has been found for the production of stable, mobile compositions 1Q with superior washability from a wide variety of active ingredients.

Preferred embodiments of the invention have at least some of the following advantages over the products so far marketed: high efficiency, higher builder / surfactant ratio, improved stability, lower cost due to the use of cheaper ingredients and easier manufacture, high mobility, better washability, high pH and / or alkalinity, good stability at high and / or low storage temperatures, and 20 satisfactory shear properties.

It has been found that when active constituents dissolved in electrolyte and water are present in certain proportions which depend on the particular active constituents and electrolytes selected, a stable spherulitic composition capable of being obtained is obtained. to suspend solid particles such as builder. In addition, it has been found how such compositions are obtained and how they can be identified by a variety of physical characteristics. Furthermore, 30 have been found to optimize the proportions of active constituents and electrolyte so as to obtain compositions that are stable to shear stresses and to normal temperature variations likely to occur during storage in a wide variety of climatic conditions. and against high pH or alkalinity and are highly mobile. Unlike the composite

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In the prior art relating to lamellar compositions, the new compositions appear to be stabilized by surfactant present in spherulitic rather than a lamellar phase.

The prior art for liquid washing agents is extremely extensive. However, in relation to the present invention, the numerous references to lighter liquid detergents and clear liquid textile detergents with or without builder will not be taken into account, where all ingredients are present in solution. The builder level is substantially lower than desired.

Recent general summaries of the state of the art include JOACS (April 1981) P356A, "Heavy 15 Duty Laundry Detergents", which provides an overview of the typical liquid preparations on the market, and "Recent Changes in Laundry Detergents" by Rutkowski, published in 1981 by Marcel Dekker, Inc. in the Surfactant Science Series.

There are three main ways to solve the problem of preparing full builder liquid detergents, namely emulsifying a surfactant in an aqueous builder solution, suspending a solid builder in an aqueous solution or emulsion of surfactant, and suspending solid builder in a gel with a lamellar surfactant matrix.

The first solution is described in e.g.

United States Patent Nos. 3,235,505., 3,346,503, Nos. 3,351,557, 3,509,059, 3,574,122 and 3,328,309, and Cana-30 Patent Nos. 917,031. In all of these patents, an aqueous solution of a water-soluble builder is sufficiently concentrated to desalinate the surfactant (usually a liquid nonionic type) and this is dispersed in the aqueous medium as colloidal droplets by various emulsifiers. In all cases, the system is a clear emulsion, which usually contains • 15

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0 relatively low builder levels and which are undesirably expensive due to the cost of using soluble builders.

The second solution is disclosed in English Patents Nos. 858,893, 948,617, 943,271, 1,468,181, 1,506,427, 2,028,365, European Patent No. 38,101, Australian Patent No. 522,983, U.S. Patent No. 4,018. 720, 3,232,878, 3,075,922 and 2,920,045. The compositions described in these patents 10 are either not stable or are not temperature stable or shear stable. Products on the market corresponding to two of these patents have recently come on sale in Australia and Europe. In particular, a composition similar to Australian Patent Specification No. 522,983 has achieved some sales success, but has been shown to be sensitive to displacement.

The third solution is described in European Patent No. 0086,614. The compositions described have a matrix of lamellar, solid or liquid crystal surfactant. Such compositions may have viscosities that are higher than desirable for certain applications.

One solution is to suspend solid builder in an anhydrous liquid nonionic surfactant, see e.g.

25 Belgian Patent No. 1,600,981. Such systems are expensive, limited in surfactant selection and provide unsatisfactory rinsing properties.

The builder level, although high relative to the overall composition, is low relative to the active ingredients, and therefore the cost efficiency is very low.

Several patents describe emulsions in which the builder is present in the dispersed phase in an emulsion rather than in suspension. U.S. Patent No. 4,057,506 discloses the preparation of clear sodium tripolyphosphate emulsions, and U.S. Patent No. 4,107,067 discloses inverted emulsions wherein an aqueous builder solution is

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0 16 dispersed in a liquid crystal surfactant system.

Many patents may also be mentioned which deal with hard surface cleaners where a abrasive is usually suspended in an aqueous ten-sided solution, e.g. English Patent No. 2,031,455, United States Patent Nos. 3,281,367, 3,813,349, 3,956,158 and 4,302,347. However, the low surfactant levels, the lack of builder and the presence of high abrasive concentrations generally exclude these agents from being of any use in the preparation of textile detergents.

Other publications that may be of interest are: Australian Patent No. 507,431, which describes builder suspensions in aqueous surfactant stabilized with sodium carboxymethyl cellulose or clay as a thickener. However, the level of functional constituents and especially of the builder in the exemplified preparations is not sufficient for a fully acceptable commodity and the stability is insufficient to provide a usable storage life.

U.S. Patent 3,039,971 discloses a cleaning paste containing builder in solution.

French Patent No. 2,283,951 describes suspensions of zeolite builders in nonionic surfactant systems, but the compositions are rigid pastes. for mobile liquids.

US Patent Nos. 3,346,504 and Nos.

3,346,873 discloses solubilization of sultaines with hydrotropes, which in these writings is referred to as "electrolytes".

A.C.S. Symposium Series No. 194, "Silicates in Detergents" describes the effect of silicates on liquid detergents.

It will be seen that each of the above-mentioned patents is selected from the very extensive prior art and the relevant aspects are elucidated by means of

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17, using the knowledge of the present invention as a guide in the selection and highlighting. Those of ordinary skill in the art would not necessarily have chosen these patents as particularly significant or these aspects as being of particular interest or relevance at the time of the first claimed priority of the invention and without prior knowledge of the present invention.

Therefore, the above review does not constitute an overall picture of the knowledge of one of ordinary skill in the art.

The invention relates to a stable, pourable, liquid detergent composition comprising water, surfactant, dissolved electrolyte salt which acts to desolubilize the surfactant, and suspended solids builder particles, thereby total builder weight ratio, including any dissolved builder, and surfactant is greater than 1.5: 1 and in which composition the weight ratio of the surfactant to the water is such that when said salt is continuously dissolved in the surfactant, the curve of the electrical conductivity of the solution enters the aqueous micelle solution in which said weight ratio prevails; through a minimum range containing a minimum electrical conductivity at which the solution is stable and unclear, which detergent composition is peculiar to the fact that said salt, when any dissolved builder is included, is dissolved in the composition in a total amount corresponding to that said minimum range, which quantity is selected from the minimum and maximum amounts at which the composition is stable for at least 3 months, both at room temperature and at a temperature of 5 ° C, e.g. at 0 ° C, and preferably also at 40 ° C.

Preferably, the flow limit of the composition is above 1.5, especially above 2, and more preferably above 2.5, e.g. Preferably, the viscosity at 136 sec-1 is less than 1.5, especially less than 1, e.g. 0.2-0.6 pascal seconds.

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The composition may additionally contain the usual minor constituents. Preferably, the active ingredients occur in a proportion of 10-20, especially 10-14 wt%, and the total weight ratio of builder to active ingredient is from 1.5: 1 to 3: 1, e.g. 1.9: 1 to 2.5: 1.

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In more detail, according to the invention, stable, pourable liquid washing compositions, comprising water, active ingredients and electrolyte are provided, and all the compositions exhibit at least some, but not necessarily all, of the following characteristics:

They comprise a spherulitic phase interrupted by a lute or L 2 phase and preferably co-continuous with the lute or L 2 phase, they are substantially non-lamellar, they comprise a lint system which is preferably spacer-filled, comprises a lint system formed by particles comprising the active ingredients, which are preferably surfactant-containing spherulites, as a rule, with concentric shells of surfactant alternating with an aqueous, e.g. lute phase and with a repetition distance of 60-100, 20o preferably 70-90, often 75-85, e.g. 80 Å, they comprise spherulites of 0.5 to 5 µm, preferably 0.6-5 µm in diameter, which have a so-called Maltese cross structure when viewed at appropriate magnification between crossed polarizers; they are diluted - r. by displacement; they have a viscosity drop of more than 0.35, usually more than 0.4, often over 0.45 Pascal seconds, but preferably less than 2 Pascal seconds, e.g. 0.475-1.5, especially 0.48-1.1 Pascal seconds; they have a high utility weight of functional constituents, typically more than 20% by weight, e.g. 25-75, more preferably at least 30, preferably at least 35 and especially at least 40% by weight; they contain a high relationship between builder and active ingredient, e.g. higher than 1: 1, preferably 1.2: 1 to 4: 1, more often 1.4: 1 to 4: 1, especially 1.5: 1 to 3.5: 1; they contain more than .5, and preferably more than 35% by weight of the active ingredient composition; they contain less than 25, preferably less than 20, in reg 0

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19 below 15, more often below 14.5 and especially less than 14%, e.g. 10-13.5% by weight of active ingredients calculated on the composition; they form a single aqueous layer and a solid layer by centrifugation, the aqueous layer generally having a flow limit of at least 1, preferably at least -2 -2 1.5 dynes cm, e.g. 2-10 dyn cm and usually a viscosity of less than 1.5 Pascal seconds at 136 sec. the weight ratio of active ingredient in the predominantly aqueous layer formed after centrifugation based on total active ingredient in the composition is greater than 50, preferably above 55, e.g. above 60% but less than 90, preferably less than 85, e.g. less than 80%, such as 75-65%; no clear coating is observed by centrifugation at high G for 90 minutes; the pH of the composition is above 8.5, preferably 9-13, e.g. 9.5 to 12; the composition provides a wash liquid by diluting with water to 0.5% dry weight with a pH above 9.7, preferably above 10, e.g. from 10.9 to 11.1; the alkalinity is sufficient to require at least 0.8 ml of N / 10 HCl to reduce the pH of 20 loo ml of wash liquid at 0.5% dry weight to 0, preferably 1 ml, e.g. 4.7-8.6 ml; the at least one predominantly aqueous liquid phase contains sufficient electrolyte to provide a concentration of at least 0.3, preferably at least 0.5, especially at least 1.2, e.g. 2.0-25 4.5 g ions per liters of total eel potassium metal and / or ammonium cations; the electrolyte concentration is greater than that corresponding to the first conductivity minimum on the graphical conductivity versus electrolyte concentration; the conductivity is not more than 30 mSS greater than the conductivity at the first conductivity minimum; the electrolyte concentration is below that which results in the formation of a substantial proportion of the lamellar phase; the electrolyte concentration is above the minimum which provides a stable, and preferably above the minimum, which provides a shear stable composition; together- 0

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20 composition is shear insensitive} composition is temperature stable} composition is stable at 40 ° C; the compositions contain at least 15, preferably 5, more than 20% by weight of the builder; 136 ^ 1Q is between 0.1 and 2 Pascal seconds, preferably between 0.2 and 1 Pascal seconds, e.g. The 0.3-0.6 Pascal seconds} composition has a flow limit of preferably at least 1, more often at least 1.5, e.g. at least 2, preferably less than 30, e.g. less than 20, especially less than 15, generally less than 10 dynes / cm; a phase containing builder comprises solid particles with a maximum particle size below the limit at which the particles tend to sediment} the composition is shear stable} the active ingredients comprise at least 2 components, one of which is unethoxylated anionic surfactant, and the other a surfactant which forms a stable foam, such as an ether sulfate, alkanolamide or amine oxide.

As the concentration of dissolved electrolyte in a suitable aqueous surfactant mixture is progressively increased from 0, the composition generally undergoes a number of easily recognizable stages as follows:

Stage I: First, the conductivity rises to a maximum during which the viscosity rises, and the initially clear, optically isotropic L 2 phase begins to show signs of spherulite formation. These are visible under a microscope and exhibit the so-called "Maltese cross" structure, which is usually associated with spherulistic "G" phases when viewed between crossed polarizers. However, neutron diffraction shows no evidence of a "G" phase or any other liquid crystal phase and is consistent with a predominantly micellar s mammal composition.

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Stage I compositions are generally clear and stable, but have no ability to suspend solid particles.

Stage II? In the second stage, the conductivity decreases with increasing electrolyte concentration and the composition becomes unclear. High G centrifugation separates the composition into a clear aqueous phase and a cloudy "emission phase" as the volume fraction of the latter phase increases with increasing electrolyte concentration. Under microscope spherulites are observed in ever-increasing numbers and smaller sizes, and they accumulate into loose lobes separated by optically isotropic regions, and these lobes become filled as the electrolyte concentration increases.

15 Neutron diffraction studies agree with reduced micellar concentrations and an increasing proportion of larger bodies, but not with the presence of any significant proportion of "G" phase. The stage II compositions are unclear and unstable and settle rapidly.

20 Stage III. Conductivity drops to a minimum and then begins to increase. The gaps between the spherululite lobes disappear and the spherulites form a gap-filling lump that extends throughout the liquid phase. Centrifugation at high G does not separate an aqueous phase, even when continued for 90 minutes. A flow limit which increases to a maximum is observed and the composition is diluted by shear with a pronounced viscosity drop.

Neutron diffraction gives no indication of any substantial part of the lamellar phase. Nuclear magnetic resonance also shows no sign of any significant content of "G" phase and suggests a low concentration of micellar surfactant. Electromicroscopy shows that at least some of the spherulites are multivesicles with a mainly concentric arrangement of shells or overlapping partial shells, possibly at greater intervals than in a normal G phase.

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The compositions of stage III are stable and capable of suspending solid particles to form a stable suspension, and such compositions of stage III are the subject of the invention.

5 Stage IV. Further addition of dissolved electrolyte causes a progressive reduction in the size of the spherical litters and a reinforcement of the "Maltese cross" structure. The spherulites cease to be gap-filling, forming distinct lichen masses separated by 10 optically isotropic regions. Flow limit and viscosity drop decrease, and conductivity increases to a maximum or begins to level. Neutron diffraction shows signs of significant "G" phases. High G centrifugation separates a clear lye phase from a cloudy layer. The composition is unstable, tends to sediment, and is unable to suspend solid particles.

Stage V. A lamellar composition of the type described in European Patent No. 0086614 is formed. When the water content is adjusted to the extent required to obtain a stable composition, the viscosity is relatively high.

The preceding sequence is typical of the interaction of electrolytes with a wide variety of aqueous surfactant mixtures. When the composition already contains some dissolved electrolyte, as in a detergent with builder containing suspended tripolyphosphate, or when the initial surfactant mixture is not completely soluble in water, the first stage may not be observed. Similarly, when the solubility of the electrolyte is limited, e.g. in the case of sodium tripolyphosphate or sodium carbonate, addition of additional electrolyte above its saturation limit will not advance the composition in the sequence.

The preferred compositions of the invention are within the third stage of the above sequence.

Between respectively. the third stage and the second and fourth 0 • 23

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intermediate compositions occur which are semi-stable. Such compositions provide a lint mass of surfactant ferulite which is not completely spacer-filled, as evidenced by the fact that high G centrifugation for 90 minutes results in the formation of a clear aqueous layer or that the spherulites are capable of irreversibly bursting. Such compositions, although stable when left at ambient temperature, are often unstable when subjected to various kinds of stresses, such as high shear stress, elevated or lowered temperatures, or pH changes. Their ability to suspend finely divided solids is often limited. A number of the known compositions are within these semi-stable regions.

It has been found that, as a rule, compositions within these semi-stable boundary regions can be modified in accordance with the teachings of the present patent by adjusting the electrolyte content so that it is more in line with the stable regions of stage III. .

As a rule, by centrifugation, stage III compositions according to the invention are separated into an aqueous layer containing electrolyte and 90-50% by weight of the total active ingredients, usually 80-50, especially 75-55%, e.g. 70-55% of the total active ingredient, and at least one other layer, which preferably contains from 15 to 50% by weight of the total active ingredient together with a substantial proportion of the builder. The viscosities of the present compositions at a shear rate of 136 sec are typically between 0.1 and 2, preferably 0.2 and 1.5, e.g. 0.25 and 0.6 Pascal seconds, and a viscosity drop is usually between 0.4 and 2, e.g. 0.45 and 1.5 Pascal seconds.

35 0

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24

Stage III compositions are non-shear sensitive and usually shear stable. In contrast, high shear forces tend to make the composition within the semi-stable boundary line unstable. The viscosity is often greatly enhanced by even moderate shear, and they can often undergo rapid sedimentation. This can present practical difficulties during preparation and filling. The stage III composition of the invention is generally stable to high pH and when stored at temperatures around 40 ° C or below 5 ° C, in contrast to many semi-stable compositions. They are typically temperature stable when heated to 100 ° C.

Stage III compositions, as a rule, show no sign of a lamellar phase in neutron diffraction analysis, although some compositions near the boundary of stage IV may show evidence of smaller amounts of "G" phase.

It is believed that the above properties can be most easily explained from the assumption that the surfactant is progressively transferred from the micellar to a spherulitic phase with increasing electrolyte concentration. Initially, the ferulites are believed to take the form of possible bicycles, where a plurality of appendices are arranged mainly concentrically, but at a wider and more irregular range than in a regular "G" phase.

It is possible that there are two aqueous phases, one L 2 - and one lye phase, the latter of which may also be an L 2 phase containing fewer micelles and more electrolyte than the former. One of these phases, possibly the lute phase, can form the inner phase of the vesicles.

It has been found that increasing the electrolyte listening content and reducing the proportion of active ingredient tend to yield compositions which are less viscous in relation to equivalent stability and solid utility weight.

35 It is believed that this reduces the proportion of micellar surfactant without significantly reducing the amount of spherulite. 0 25

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ter. The lower micellar content reduces the viscosity while the spherulite phase remains sufficient to maintain stability.

It is believed that in the preferred stable composition of the invention, the spherulites are sufficiently tightly packed to form an aggregate liner mass which is mostly spacer-expanding, ie. it extends through the volume of the liquid. The spherulites probably cooperate to form a weak three-dimensional matrix 10 sufficiently strong to support suspended particles but weak enough to decompose and flow easily under the influence of shear forces and to form again when these forces are removed. The size of the spherulites seems to be related to stability; Thus, compositions with large spherulites of 5 ^, u and more are less stable than compositions where the majority of the surfactant is present as spherulites of 0.5-5 ^, u.

As the electrolyte content increases, the spherulites become smaller and perhaps more compact as they tend to the smaller and more regular spheres in the "C" phase. As a result, the "G" phase sphere roulette is no longer spacer-filled, and the composition tends to settle.

The compositions of the invention preferably contain at least 5 but less than 30 and generally less than 25% by weight of surfactants. Particularly preferred is the surfactant 5-20% by weight of the composition, e.g.

8-15% by weight, usually 10-14.5, especially less than 14 and often less than 13%.

The concentration of active ingredients may be a critical factor in the preparation of the compositions of the invention. Below a certain minimum which varies according to the particular active system, the composition cannot be stabilized by adding more electrolyte, but maximum is also important to avoid viscous compositions.

0

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26

The known semi-stable spherulitic compositions have often contained relatively large amounts of active ingredients. This has resulted in relatively high viscosity of the aqueous suspension medium, which in turn has severely limited the amount of builder which can be suspended for any given acceptable viscosity limit. Thus, the ratio of total builder to active ingredient has been low compared to powders with consequent poor washing properties.

10 It was not at all foreseeable that the active ingredients in such compositions could be reduced without the systems being totally stabilized. Surprisingly, it has been found that if the electrolyte concentration is raised sufficiently, the concentration of active ingredient can be substantially reduced, giving aqueous media of similar or even greater stability and yet with lower viscosity. Such media can suspend larger volumes of builder without losing their appropriate mobility, and the resulting large forgo increases in builder-active ingredient ratio provide an equally significant increase in dietary efficiency.

As a rule, it is considerably easier to produce spherulitic lye from mixed surfactants than single surfactants. Thus, mixtures of one or more non-ethoxylated surfactants, such as alkylbenzene sulfonate and / or alkyl sulfate, and one or more co-surfactants which form stable foams such as alkylene sulfates and / or alkanolamides or amine oxides are generally more suitable than a any surfactant 30 alone.

In addition, small amounts of ethoxylated nonionic surfactants or amphoteric surfactants or cationic fabric softeners may be present.

The surfactant mixture can e.g. include a number or more in the least heavily water-soluble salts of sulfonated or mono-esterified sulfuric acid, e.g. et al.

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Alkylbenzene sulphate, alkyl ether sulphate, olefin sulphonate, alkanesulphonate, alkylphenol sulphate, alkylphenol ether sulphate, alkylethanolamide sulphate, alkylethane-olamide ether sulphate or α-sulpho fatty acid or each of its 5 usually 10-20 aliphatic carbon atoms.

These alkyl or alkenyl groups are preferably straight chain primary groups, but may optionally be secondary or branched groups. The term "ether" above re-10. ferric to polyoxyethylene, polyoxypropylene, glyceryl and mixed polyoxyethylene oxypropylene or mixed glyceryloxyethylene or glyceryl oxypropylene groups which usually contain 1-20 oxyalkylene groups. Thus, the sulphonated or sulphated surfactant may be sodium dodecylbenzenesulfonate, potassium hexadecylbenzenesulfonate, sodium dodecyldimethylbenzenesulfonate, sodium laurylsulphate, sodium laurylsulphate, potassium oleosulfate, ammonium sulphate, ammonium sulphate,

Other anionic surfactants useful in the present invention include paraffin sulphonates, olefin sulphonates, fatty alkyl sulphosuccinates, fatty alkyl ether sulphosuccinates, fatty alkyl sulphosuccinates, fatty alkyl ethersulphosuccinamates, islets, acyl arsosates, acylsarcosines, and alkyl ether carboxylates. Anionic phosphate esters can also be used. In any case, the anionic surfactant usually contains at least one aliphatic hydrocarbon chain having from 8 to 22, preferably 10 to 20 carbon atoms, and in the case of ethers one or more glyceryl and / or up to 20 ethylene oxy and / or propylene oxy groups.

Preferred anionic surfactants are sodium salts. Other salts having an industrial interest include those of potassium, lithium, calcium, magnesium, ammonium, monoethanolamine, diethanolamine, triethanol.

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28 minutes and alkylamines containing up to seven aliphatic carbon atoms.

The surfactant mixture may optionally contain or, which is less preferred, consist of non-5-ionic surfactants. The nonionic surfactant may e.g. be a C 1-6 alkanolamide of a mono- or di-lower alkanolamine such as coconut monoethanolamide. Other nonionic surfactants that may be present include ethoxylated alcohols, ethoxylated carboxylic acids, ethoxylated amines, ethoxylated alkyl olamides, ethoxylated alkyl phenols, ethoxylated phosphate esters, and the propoxylated or ethoxylated and propoxylated analogs of all the aforementioned ethoxyls. ionic compounds, all having a C 8 -22 alkyl or 15 alkenyl group and up to 20 ethylene oxy and / or propylene oxy groups, or any other non-ionic surfactant heretofore incorporated in powdered or liquid washing compositions , eg. amine oxides. The latter typically has at least one, 20 C

The preferred active ingredients or mixtures for the compositions of the invention are e.g.

25 having HLB greater than 7, preferably greater than 8, particularly preferably greater than 10, and more preferably greater than 12 and preferably less than 18, particularly preferably less than 16, and more preferably less than 15.

Some of our detergents may contain cationic surfactants and especially cationic fabric softeners and / or bactericides, usually as a minor proportion of the total active material. Cationic fabric softeners of value in the compositions of the invention comprise quaternary amines with two long chain 35 (e.g., 2-22-22 "C 1-6 alkyl- or alkene-0

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29 nyl groups and either two short chain (e.g. C 1-4) alkyl groups or a short chain and a benzyl group. They also include imidazoline and quaternized imidazolines having two long chain alkyl or alkenyl groups, and 5 amidoamines and quaternized amidoamines having two long chain alkyl or alkenyl groups. The quaternized plasticizers are generally salts, of anions that give a certain measure of water solubility, such as formate, acetate, lactate, tartrate, chloride, methosulphate, ethosulphate, sulphate or nitrate. The compositions of the invention having textile plasticizer character may contain smectitler species.

Compositions of the invention may also contain amphoteric surfactant, which may typically be included in surfactants with cationic fabric softener, but may also be included, as a rule, as a minor component of the active ingredients of any other of the aforementioned detergent types.

Amphoteric surfactants include betaines, sulphobetaines and phosphobetaines formed by reacting an appropriate tertiary nitrogen compound with a long chain alkyl or alkenyl group with an appropriate reagent such as chloroacetic acid or propane sultone. Examples of suitable tertiary nitrogen containing compounds include: tertiary amines having one or two long chain alkyl or alkenyl groups, optionally a benzyl group or any other short chain alkyl group substituent, imidazoline with one or two long chain alkyl or alkenyl groups and amidoamines with one or two long-chain alkyl or alkenyl groups.

Those skilled in the detergent will appreciate that the particular surfactant types described above are only examples of the more common surfactants useful in the invention. Any surfactant that may be useful in the washing liquid may be included. A more detailed description of the main types of

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30

ISLAND

surfactants available on the market can be found in the current edition of "MaChutcheon's Emulsifiers & Detergents", published by the MaCuthcheon division of the Manufacturing Confectioners Publishing Company.

Electrolyte is essential for interaction with the surfactant to form a spherulitic system. Preferably, however, the E-electrolyte concentration is not sufficient to allow substantial stacking of any planar attachments to form non-spherical interlayer phases. Such lamellar phases can provide unstable or shear unstable compositions unless the utility weight is sufficiently high for the lamellar phase to form a stable structure according to European Patent Specification No. 86614. The relatively strong matrix characterizing the latter compositions , however, usually results in undesirably high viscosity.

It has been found possible for a suitable surfactant system of suitable concentration to stabilize the system of the invention by including in the composition an appropriate amount of electrolyte.

Insufficient electrolyte results in unstable or shear or temperature sensitive systems and / or in systems of undesirably high viscosity. Therefore, the electrolyte proportion must be selected depending on the nature of the surfactant 25 and the amount of hydrotrope present if present to obtain compositions according to the invention.

The optimum electrolyte content can usually be determined by making progressive additions to an aqueous micellar solution of the active ingredients (usually about 15-20% by weight of active ingredients) and observing one or more of several characteristic features of systems such as turbidity, conductivity, flow limit, appearance under polarizing microscope, or high G centrifugation behavior.

When the characteristics characteristic of stage III as previously described are demonstrated, e.g. one

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31 0 cloudy composition at or near a first conductivity minimum, with a fluff mass of spherulites showing no clear isotropic ranges and no clear layer by centrifugation at high G, 5 spherulite interval has been identified.

The proportion can be optimized within this range by observing the amount required so as not to get a clear layer at high G centrifugation for 90 minutes.

If the composition is intended for a market where low viscosity is more important than e.g. low shelf life, the optimized composition can be progressively diluted until an appropriate viscosity is reached or instability is observed. If the latter occurs, additional additions of electrolyte can be made until a sufficiently stable composition is obtained.

The amount of electrolyte is preferably greater than that at the first conductivity minimum in the graphical conductivity / electrolyte concentration and corresponds to the amount required to obtain a composition with a flow limit of over 1.5 dynes cm.

It is preferred to use functional electrolytes such as carbonates, silicates, pyrophosphates, polyphosphates, nitriloacetates and citrates, all of which are builders, but effective concentration of some of these electrolytes, e.g. carbonates, may be undesirably limited by their solubility. In this case, it may be necessary to add a more soluble non - functional electrolyte. Sodium chloride and sodium nitrate have proven particularly effective in this regard.

Often, in the at least one predominantly aqueous phase, the electrolyte fraction is sufficient to give a concentration of at least 0.3, preferably at least 1.2, e.g. 2.0-4.5 g ions per liters of alkali metal, alkaline earth metal and / or ammonium cations.

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The builder of the preferred compositions according to the invention is generally believed to occur, at least in part, as separate solid crystals suspended in the composition. The crystallites usually have a size of up to 60, e.g. L-50 ^, u.

It has been found that preparations containing sodium tripolyphosphate as a builder or at least a predominant proportion of sodium tripolyphosphate mixed with other builders exhibit stability and mobility over a greater range of dry weight than similar preparations with other builders. Such preparations are therefore preferred. However, the invention also relates to compositions comprising other builders such as potassium tripolyphosphate, carbonates, zeolites, nitrilotriacetates, citrates, metaphosphates, pyrophosphates, phosphonates, EDTA and / or polycarboxylates, optionally but preferably mixed with tripolyphosphate * Orthophosphates may appear as minor constituents mixed with tripolyphosphate, as well as alkali metal silicates and carbonates.

Silicates and carbonates are particularly preferred because they fulfill several valuable functions. They provide the free alkalinity desirable for hydrolyzing fats in the soil, they have an effect as builders, and in the case of silicates, they inhibit the corrosion of aluminum surfaces in washing machines.

In addition, they are effective as electrolytes necessary for the formation of a spherulitic system.

When silicate is used to prepare 30 compositions of the invention, this generally has a Na 2 O / SiO 2 ratio of 1: 1 to 1: 2, or 1: 1.5 to 1: 1.8. However, it should be noted that any ratio of Na 2 O (or other base) to SiO 2 or even silicic acid can be used to provide the silicate in the composition, and any additional necessary alkalinity is obtained by adding an O

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33 other base, such as sodium carbonate or hydroxide. Preparations not to be used in washing machines do not require silicates, provided that an alternative source of alkalinity exists.

The composition of the invention does not preclude the builder from appearing almost completely in solution, e.g. sodium nitrilotriacetate, sodium citrate, sodium silicate or mixtures thereof.

The builder usually constitutes at least 15% by weight of the 10 compositions, preferably at least 20%. It is preferred that the builder-surfactant ratio is above 1: 1, preferably 1.2: 1 to 4: 1.

For economic reasons, it is generally preferred that the occurring cations consist, at least overweight, of sodium. Thus, the preferred builder is sodium tripolyphosphate, the preferred anionic surfactants, and optionally anti-gene deposits, e.g. carboxymethyl cellulose or alkali, e.g. silicate or carbonate is also preferably present as sodium salts. Sodium chloride, sodium nitrate or other soluble inorganic sodium salts may be added to increase the electrolyte concentration. Calcium usually occurs only when the active ingredients comprise surfactants, such as olefin sulphonates or non-ionic compounds which tolerate its presence. Magnesium salts can be found and are more compatible with surfactants than calcium.

Alternatively, although not so preferred, salts of potassium, ammonium, lower 30 amines, alkanolamines or mixed cations may be selected. However, compositions containing high proportions of such cations are unlikely to be cost-effective in comparison with conventional textile washing powders.

The compositions of the invention are preferably alkaline in that they are desirably buffered with an alkaline buffer so that the pH of the composition, measured at

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34 o a glass calomel electrode, is above 8.5, preferably above 9, especially above 9.2, e.g. 9.5-12, especially 10-11. In particular, it is preferred that the composition be adapted so as to obtain a pH greater than 9.7, e.g. above 10.5, especially 10.5-11.5, in a wash liquid containing the composition diluted to 0.5% dry weight. Desirably, they have sufficient free alkalinity to require at least 0.4 ml, preferably at least 0.8 ml, especially 1-12 ml, e.g.

3-10 ml, usually 4-9 ml of 10N HCl to reduce the pH in 100 ml of diluted solution of the composition, containing 0.5% dry weight, to 9, although higher alkalinity compositions may also be commercially acceptable.

As a rule, lower alkalinities are less acceptable commercially, but not excluded from the scope of the invention.

The alkaline buffer is preferably sodium tripolyphosphate and the alkalinity is preferably obtained at least in part by means of sodium carbonate. Other preferred alkaline buffers include sodium silicate.

Thus far, liquid washing compositions have generally contained substantial concentrations of hydrops and / or organic water-miscible hydroxyl solvents such as methanol, ethanol, isopropanol, glycol, glycerol, polyethylene glycol and polypropylene glycol. However, they are expensive and do not constitute functional constituents. They may, under certain circumstances, promote slope or allow a surfactant to form a spherulitic phase more easily. Therefore, they cannot be completely excluded from all compositions of the invention, but it is preferred that their occurrence be limited to the minimum required to ensure a spherulitic composition with appropriate pourability. If not required, it is preferred that they do not occur. Solvents can sometimes be adapted as 35 constituents in perfumes or other conventional minor constituents.

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35

The dry weight of the composition affects stability and pourability. The optimum dry weight can vary considerably from one type of preparation to another and can be selected to obtain the required viscosity.

In general, it has not been possible to guarantee stable compositions under a dry weight of approx. 35% by weight, but some types of preparation can be obtained in stable form below 30% dry weight, and sometimes as low as 25% dry weight.

The possibility of producing stable compositions with 10 dry weight as low as 20% cannot be ruled out.

For any given preparation according to the invention, a range of dry weight can be identified within which the composition is both stable and pourable. As a rule, sedimentation occurs during this interval, and over the interval the preparation is viscous. The acceptable range can be routinely determined for any given preparation by preparing suspensions using the minimum water necessary to maintain a stirred composition, dilute a number of samples progressively to stronger dilutions, and observe the samples for evidence of sedimentation over an appropriate period of time. For some preparations, an acceptable dry weight range may range from 30 or 35 to 60 or even 70% by weight, otherwise it may be much narrower, e.g. 40-45% by weight.

If a stable pourable interval cannot be determined by the above methods, the preparation should be modified according to the information given here, e.g. by the addition of more sodium carbonate, sodium silicate solution or other electrolyte if the composition exhibits the properties of stage I or II, or by reducing the electrolyte content or adding hydrotrope if the composition exhibits the properties of stage IV or V.

35 If difficulties arise in finding a stable spherulitic system by simply changing the electrode.

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Alternatively, the active ingredients may be modified by adding a foam-stabilizing surfactant such as alkyl ether sulfate, alkanolamide or amine oxide if the composition tends to form stage IV 5 or V, or by adding alkyl benzene sulfonate or alkyl sulfate whose stage I or II prevails. .

In many cases, the compositions of the invention can be readily prepared by normal stirring of the ingredients together. It is a characteristic of the preferred compositions that they are not stabilized or thickened when subjected to high shear forces.

The order and conditions of mixing of the components are sometimes important to produce a stable structured mixture according to the invention.

The compositions of the invention can usually be obtained for any suitable active ingredients by first preparing a clear aqueous L 2 solution of the active ingredients at a suitable concentration (e.g., 15-30% by weight of active ingredients) under heating conditions. Solution, if necessary, and dissolving electrolyte in the L 2 solution to add concentrated electrolyte solution (preferably functional electrolyte) until the mixture becomes cloudy. Then, a sample of the mixture is centrifuged at 20,000 G for 5 minutes. If a clear aqueous phase can be observed, more electrolyte is added to the mixture until high-G centrifugation no longer shows signs of a separate, mostly clear aqueous phase. The weight ratio of active ingredients to dissolved electrolyte is then noted.

A composition containing all the desired constituents and having a weight ratio of active constituents to electrolyte as already determined can then be prepared at the desired percentage dry weight (usually 40-50%). The formation of a clear aqueous liquid phase at high G centrifugation suggests the presence of lamellar phase and the amount of electrolyte is then reduced, 0

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37 until no clear phase is observed at high G centrifugation. Samples of the latter preparation at different dry weight percentages can be prepared to determine the optimum mobility / stability characteristics.

If difficulties arise in determining a suitably active constituent / electrolyte ratio in the first stage of the above procedure, this can be repeated using a more soluble electrolyte, e.g. a non-functional electrolyte such as sodium chloride or sodium nitrate. Alternatively, the active ingredient system may be modified by the addition of surfactants favoring stable dispersions of the invention, e.g. ether sulfates, amine oxides or alkanolamides if properties of stage IV or V are observed, or a non-ethoxylated anionic surfactant if the properties of stage I or II are more easily obtained.

As a rule, the mixture is carried out at ambient temperature when it matches appropriate dispersion; certain components, e.g. nonionic surfactants such as coconut demoethanolamide require gentle heating, e.g. 40 ° C for appropriate dispersion.

This degree of heating can usually be obtained by the heat generated by hydration of sodium tripolyphosphate. In order to ensure sufficient heating, it is preferred to add the tripolyphosphate in anhydrous form and containing a sufficiently high proportion of the high temperature rise modification, which is usually called "phase I". The above procedure is only one of several methods that can be successfully used for all or most of the compositions of the invention. Some preparations are more sensitive to the mixing order and temperature than others.

In a more detailed review of the different types of preparation according to the invention, 0 is distinguished

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38 especially between high foaming preparations of the sulphate or sulphonate type and low foaming preparations.

High foaming preparations can usually be based on mixtures of one or more non-ethoxylated anionic surfactants, preferably a sulphate or sulphonated surfactant, with one or more co-surfactants forming a stable foam such as an ethoxy -leaded anionic surfactant, an amine oxide or a fatty canola amide. The first component of the active constituents, viz. the non-ethoxylated anionic surfactant, e.g. be a C1-6 alkyl alkyl sulphate and / or cyo 14 alkyl benzene sulphonate. The other component or co-surfactant may be a straight or branched sodium-C10 -20 alkyl, C1-10 mole of ether sulfate or an alkyl phenol ether sulfate, amine ether sulfate, alkanolamide ether sulfate or fatty acid ether sulfate. Alternatively or additionally, the second component may comprise an amine oxide or fatty alkyl amide. The entire weight ratio of non-ethoxylated anionic compound / co-surfactant is usually from 5: 1 to 1: 3, preferably 4: 1 to 1: 2, e.g. 3: 1 to 1: 1.

Small amounts (eg, up to 1% by weight of the compositions) of soap may be present to aid in rinsing the fabrics. Ethoxylates can be present in smaller proportions, usually up to 20% by weight of the total active ingredients, preferably below 15, usually less than 10%.

The sodium alkyl sulphate or alkyl benzene sulphonate may be completely or partially replaced in the above compositions by other sulphonated, non-ethoxylated 3 sulphosuccinamater. The alkyl thersulphate may be wholly or partially replaced by 35 other ether sulphates such as alkyl phenyl ether sulphates, fatty acyl monoethanolamide ether sulphates or mixtures thereof.

0

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39

According to a particular embodiment, the invention provides a stable, pourable, spherulitic composition comprising: water, from 12 to 40% dry weight active ingredients based on the dry weight of the composition and 5 from 20 to 80% dry weight builder based on the dry weight of the composition, at least partially present as suspended solids and partly as at least a portion of the dissolved electrolyte, wherein the active ingredients consist of (a) from 30 to 80% by weight thereof of a non-alkoxylated anionic sulphated or sulphonated surfactant, and (b) from 20 to 70% by weight of total surfactant of at least one foam stabilizing surfactant co-surfactant, such as an alkoxylated anionic surfactant, an alkanoamide or an amine oxide.

Optionally, the above composition may further contain up to 6% dry weight of the composition of soap. Preferably, the non-alkoxylated sulphated or sulphonated anionic surfactant consists essentially of alkyl sulphate or alkyl benzene sulphonate, e.g. C ^ Q _ ^ - alkylbenzensulphonat.

Alternatively, the anionic surfactant may comprise a mixture of alkylbenzene sulfonate and / or alkyl sulfate with alkyl ether sulfate and / or alkyl phenol ether sulfate in weight ratios of e.g. 1: 3 to 5: 1, in the rule 1: 2 to 4: 1, preferably 1: 1 to 3: 1, e.g. 2: 1.

Low-foaming compositions of the invention can be prepared by suitable foam inhibitors. Selection of foam inhibitor requires some care because some foam inhibitors on the market may lose their effectiveness in storage in compositions of the invention, while others are only effective at concentrations so high as to affect the composition's viscosity or stability. It has been found that mixtures of organopolysiloxane and colloidal silica are particularly effective.

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The invention relates to yet another particular embodiment, a stable, pourable, liquid, water-based washing composition comprising: from 12 to 40%, based on. dry weight active ingredients comprising from 30-90% based on the dry weight of the active ingredients of non-alkoxylated sulphated and / or sulphonated anionic surfactant and the residue alkyl ether sulphate and / or an alkanol amide or amine oxide, an aqueous phase containing sufficient electrolyte in solution to form an interspace-filling spherulitic lime mass comprising the active ingredients and the aqueous phase, suspended builder particles, an effective amount of at least one foam inhibitor, and optionally the usual minor components.

In yet another embodiment of the invention there is provided a pourable, stable washing composition having a useful weight of 30-50% consisting mainly of 12-40% dry weight, based on the dry weight of the composition, active ingredients, at least 30% builder based on the dry weight of the composition. , a builder-active ingredient ratio of greater than 1.1: 1, the active ingredients mainly consisting of alkylbenzene sulfonate having 8-18 aliphatic carbon atoms and an alkyl ethanolamide selected from C 1-6 alkylmonoethanolamides 25 and diethanolamides having a weight ratio of alkylbenzenesulfonate to ethanolamide of from 1.5: 1 to 4: 1, the builder being selected from sodium tripolyphosphate, sodium carbonate, zeolite, sodium nitrilotriacetate, sodium silicate and mixtures thereof, so that the amount of dissolved builder is sufficient to give a flow limit of -2 more than 1.5 dyn cm

A particularly preferred embodiment of the invention is a pourable, stable, liquid washing composition consisting essentially of:

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41 (A) a mixture of (i) a sodium alkylbenzene sulfonate having 10-18, preferably 10-14 aliphatic carbon atoms, with (ii) a sodium alkyl ether sulfate having an alkyl group having an average of 8 to 18, preferably 5-10-14 carbon atoms and from 1-20, preferably 2-10, f.

for example, 3-5 ethyleneoxy and / or propyleneoxy groups, in a ratio of (i) to (ii) between 10: 1 and 1:10, especially 10: 1.5 to 10: 5, e.g. . 10: 2 to 10: 4, (B) a builder selected from sodium tripolyphosphate, 10 zeolite, sodium nitrilotriacetate and mixtures thereof in a weight ratio of B to A of 1.1: 1 to 4: 1, preferably 1.2: 1 to 3.5: 1, e.g. 2: 1 to 3: 1, and (C) an electrolyte selected from sodium carbonate, sodium silicate, sodium nitrate, sodium chloride and mixtures thereof at a concentration of 2 to 20 wt%, preferably 3-18 wt%, especially 7-15 wt% of the composition, the composition having a useful weight of 30-50 wt%, preferably 35-50 wt%, e.g. 38-45% by weight, and the composition preferably contains smaller but effective amounts of antigen repellents, preferably sodium carboxymethyl cellulose, perfume, dyes and optical brightener.

The sodium cation in the above composition may or may not be replaced in whole or in part by potassium, lithium or ammonium. Preferably, the sodium tripolyphosphate represents 40-95% of the builder's total weight, e.g. 45-80%. Preferably, the composition contains at least one foam inhibitor, if necessary, for machine washing.

The above compositions may optionally contain minor proportions of alkanolamide such as coconut monoethanolamide or diethanolamide or ethoxylated nonionic surfactant.

The compositions of the invention may contain the usual minor constituents. Most important of these are anti-repellents, dispersants, op-agents

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42 clearing agents and bleaching agents.

The most commonly used antigenic agent in the preparation of detergents is sodium carboxymethyl cellulose (SCMC), which can be found in the compositions of the invention, e.g. in effective amounts consistent with the desired viscosity and stability. In general, SCMC is effective at concentrations of approx. 1%, and it is preferred not to exceed the normal effective concentrations since SCMC can greatly increase the viscosity of a liquid composition and also affect its stability.

Alternative anti-gene deposition and / or soil release agents include potassium, ammonium and other soluble CMC salts, phosphonates, methyl cellulose, polyvinylpyrrolidone, carboxymethyl starch and similar polyol electrolytes, all of which can be used in place of SCMC.

Optical clarifiers (OBAs) are optional but preferred ingredients in the compositions of the invention. Contrary to some known preparations, the compositions of the invention do not depend on OBAs for stability, and thus, any suitable and cost-effective OBA can be freely chosen or completely omitted. It has been found that any of the fluorescent dyes hitherto recommended for use as OBAs in liquid detergents can be used, as are many dyes usually suitable for use in detergent powders. OBA can occur in normal quantities. Typical 0BA concentrations between 0.05 and 0.5% are sufficient, e.g. 0.075-0.3%, especially 0.1-0.2%. Lower concentrations may be used but are unlikely to be effective, while higher concentrations, although their use cannot be excluded, are unlikely to prove cost-effective and may in some cases give rise to compatibility problems.

o 43

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Typical examples of OBAs which can be used in the present invention include: ethoxylated 1,2- (benzimidazolyl) ethylene, 2-styrylnaphth [1,2-d] oxazole, 1,2-bis (5'- methyl 2-benzoxazolyl) ethylene, disodium 5 -4,4'-bis (6-methylethanolamine-3-anilino-1,3,5-triazine-2 "-yl) -2,2'-stilbenzulfonate, N - (2-hydroxyethyl-4.41-bis (benzimidazolyl) stilbene, tetrasodium-4,4'-bis [4 "- bis (2" -hydroxyethyl) -amino-6 "(3" -sulphophenyl) amino -1 ", 3", 5 "-triazine-2" -ylamino] -2,2'-stilbene disulphonate, disodium 4- (6 "-sulphonaphtho [11,2'-d] triazol-2-yl ) -2- -Stylbenzulfonate, disodium-4,41-bis- [4 "- (2" -hydroxy-ethoxy) -6 "-amino-1", 3 ", 5" -triazine-2 "-yl-amino ] -2,2-stilbene disulphonate, 4-methyl-7-dimethylaminocoumarin and alkoxylated 4,4'-bis (benzimidazolyl) stilbene.

Bleaching agents may optionally be incorporated into liquid detergents according to the invention, provided chemical stability and compatibility are provided. Encapsulated bleaches may form part of the suspended solids. The effect of peroxy bleaches in the compositions of the invention may be enhanced by the presence of bleach activators such as tetraacetylethylenediamine in effective amounts. Photoactive drugs such as zinc or aluminum sulphonated phthalocyanine may also be present.

Perfumes and dyes are generally found in textile detergents in amounts of up to 1 or 2% and can also be found in the compositions of the invention. Care must sometimes be taken in selecting a suitable perfume because the solvents present can modify the properties of the active ingredients.

Proteolytic and amylolytic enzymes may be e-valently present in conventional amounts, optionally together with enzyme stabilizers and carriers. Encapsulated enzymes can be suspended in the composition.

44

DK 166030 B

0

Other minor constituents include foaming agents, alkalis, buffers, germicides such as formaldehyde, clarifiers such as vinyl latex emulsion, inactive abrasives such as silica, and anti-corrosion agents such as benzotriazole.

The compositions of the invention are generally suitable for use in textile washing, and the invention comprises a method of textile washing by keeping the fabrics moving in a wash liquid containing any composition of the invention as described herein. Low-foaming compositions described herein are especially intended for use in washing machines. The compositions can also be used for dishwashing or for cleaning hard surfaces, the low-foaming products being particularly suitable for use in dishwashers. These applications are a further aspect of the invention.

The compositions of the invention can generally be used for textile washing in boiling water 20 or for washing at medium or low temperatures, respectively. eg. 50-80, especially 55-68 ° C, or 20-50, especially 30-40 ° C.

As a rule, the compositions can be added to the wash water at concentrations of between 0.05 and 3% dry weight based on the wash water, preferably 0.1-2, especially 0.3-1, f.

25, for example, 0.4-0.8%.

The invention will now be elucidated with the aid of examples set forth in the following tables.

30 35 o 45

DK 166030 B

examples

The examples are stable and pourable compositions. They are stable when stored at 40 ° C and are not shear sensitive. They are temperature stable and with the exception of Example 83 shear stable.

Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6

Sodium C ,. . .-line-10-14 10 ore-alkylbenzene sulfonate 10 10 10 10 10 10

Coconut diethanol amide 5 5 5 5 2.3 2.5

Sodium carbonate 5 5 5 5 4.6 5 15 Sodium tripolyphosphate 25 25 18 27 16.7 18 "Zeolite A" - - 9 - 9.3 10

Sodium Carboxy Methyl Cellulose 1.0 1.0 - 20 Sodium K 2,2 O 2 alkyl 3 moles ethoxysulfate - - - - 2.3 2.5

Optical clarifier. 0.15 0.15 0.15 0.15 - 0.15 Cg alcohol 8 moles of ethaxylate - 1.8 Mixed mono- and di-

Cig-ig alkyl alkyl phosphate - 0.5 - - 0.5

Non-ionic Foam Inhibitor - 2.0 - 30 35

DK 166030B

46

CN

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tf © O tf tf N tf O) Η H Æ H

2 Æ Æ S S = 2 O CQ tf H cn

DK 166030 B

47 rH 1/1

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. »S <- '' cn σ \ * 3 * ld σ \ i — il I lool

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H 0 rH -U O H-> ft ri Sr -H

h il li «xl Q) co σ 'w S tj 6 i ft i x: -p ft S 0 o ® S 3 N * rH CO ϋ C> 1> t Η rd

H 3 rH rH C rH KO I. ft C ^ CD

1 01 13 0 0 O .G OH

0 rj (N (QJl) CU ^ o π M rh

SS S>, P -Η = P * O * <B «Η M

ONUX <«M <(0rHX) isH r-i ΠΪ -rj

1 C I 0 O -P O G C Π3 X φ C

Pci) 6x: ££ H-> S | rH-Pi CO

C ^ i ^ CC-HC co>, O C0 Μ0 · Η

• H · Η cu -Η -Η Η -ri Η X Ό rH M CD O I

ij ^ C CShOSh I O C ICD-iH-HO)

Ij ^ + JH + J + JO-P CN X3 COί CO -P -P H Ad

CrHCdOrtirtiN ^ Η -P rH rH CD ft -H Al

Z C 2 g 3 2 = ZUOPSOOOWH

0

DK 166030 B

48

Ex. Ex. 21

Sodium C ^ Q _ linear alkylbenzene sulfonate 9.1 9.4

Sodium C12 _ alkyl alkyl 3 moles of ethoxysulphate 4.8 4.0

Sodium carbonate 5.0 4.6

Sodium Tripolyphosphate 18.5 19.0 "Zeolite A" 9.0 10.0

C₂₂i8 alcohol 8 moles of ethoxylate 2.0 Mixed mono- and di-C ^ g__ alkylphosphate ester 0.5 0.5

Optical Clarifier 0.15 0.15 15 Ex. 22 Ex. 23 Ex. 24

Sodium C ^ Q _ linear alkylbenzene sulfonate 9.2 7.8 8.3

Sodium C ^₂_1g alkyl 3 moles ethoxysulfate 9.2 7.8 4.1 Sodium carbonate 4.6 3.9 4.2

Sodium tripolyphosphate 6.9 5.9 15.0

Sodium nitrilo triacetate 13.8 11.7 8.3 C₂ii ““ alcohol 8 moles of ethoxylate - 1.7

Coconut diethanolamide 1.8 1.6 25

Ex. 25_Eks. 26

Sodium C ^ g _ - linear alkyl benzene sulfonate 9 8.6

Coconut monoethanolamide - 1.4 30 Sodium carbonate 5

Sodium Tripolyphosphate 19 25.3 "Zeolite A" 5

Sodium carboxymethyl cellulose - 1,4

Sodium C ^₂₂gg alkyl 3 moles of ethoxysulfate 4 2.3

Optical Clarifier 0.15 0.13

Sodium silicate (SiO 2: Na 2 O 1.6: 1) 5.8

Silicone foaming agent 1 0

DK 166030B

49

Ex. 27 Ex. 28

Sodium C ^ g _ ^ linear alkylbenzene sulfonate 8.8

Coconut monoethanolamide - 1.5 5 Sodium carbonate 5 5.8

Sodium Tripolyphosphate 27 25.6

Optical Clarifier - 0.14

C2-2144 alkyldimethylamine amine oxide 2.3

Silicone foaming agent 1 10 15 20 25 30 35

DK 166030 B

50

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m m m m

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44 w i t h in a in S »» s.

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h cd cdooo 43-P η ιβ d xl ^ I -p I 43 £ 3 -Pdil 1143 1¾ ^ cd C0 -PldH Id i> t O »tf 00 44> i +! HJ3H + J (D430 £ 3 Η H Η H <D Hid

10 I id O -P 43 0 0 -H 110 O O

0 43 cn 43 £ 3 0) 0 43 di P O CN S3 ft-H

HdiHdjO "H44 = P-H-P HH0 = * HH

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id φ id 4J o 0 h n id id id id id n id id S43S (dw «o = a a s a a a = a a

DK 166030 B

51 in m m * 'S' O O OO Η ΙΟ Γ-- H m * »*» *

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ffi η λ H + iÆdii ε <u g cl,> 1 w +1 2 z! "C te to .c 1 <y ts t5 cn h <—io Ι-i η ε" dhox! Tu 1 c ε tn hi +1 c +> Οι ε Η -H 10 oc M4 (ti (ti Π5> 1 > 1 tH> - * Cr * + J ghd, dghx; J =: oc I c «α I0 + J00 Ο-ΡΝΗΟΛΑί 0 .G Φ Λ &

Η O Η O · Η = O 8 Ό (d Q Μ <W

η η Ό id λΙ ni I -ΗΗε Oni 1 3 Ti ο -Ο υπε ^ ί οι

εω · & ΕΗ -'- ιε> · Η + joiC

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S £! «S S = SCMQiOcQ I W

52

DK 166030 B

0

Ex. 46 Ex. 47 Ex. 48

Sodium C ^ Q _ linear alkylbenzene sulfonate 8.8 10.0 10.0

Coconut monoethanolamide 3.5 4.0 4.0 5 Sodium carbonate 4.4

Sodium Tripolyphosphate 16.7 19.0 19.0 "Zeolite A" 7.9 9.0 9.0

Sodium Silicate (SiO.:Na_0) * 1: 1, 1.6: 1 - 5.0 5.0 ** Ί0 Optical Clarifier 0.13 0.15 0.15

Mixed mono- and di-C, cΛ-lb-lo alkyl phosphate 0.44 0.5 0.5 Ex. 49 Ex. 50 Ex. 51 Ex. 52

Sodium C alk ^ _ - linear alkylbenzene sulfonate 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 clarifier 0.14 0.15 0.15 0.15

Mixed mono- and di- -C1-6-alkylphosphate 0.5 0.5

Trisodium sulphosucciant - - 1.0

Sodium ethylenediamine-tetrachis (methenophosphonate) -. - - 0.5

Trisodium Orthophosphate 2.9 5.0 35

DK 166030B

53 oo 10 in • 'tf vo tf m r * ·· vo σι o cm h cm m oo co cm h # ^ k, ^ s.> S **> * »· KKKV · ** **

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DK 166030B

54

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Ο'Ζ'Ζ'ΖΆ '&' Ζ'Ζ - SSOOCQ I HO

55

DK 166030 B

0

Ex. 72 Ex. 73

Oleic acid 6.8 6.1

Sodium hydroxide 0.7 0.65

Sodium C ^ 0_14ær linear alkylbenzene sulfonate 2.85 2.2 5 Coconut diethanolamide 3.65 3.7

Sodium tripolyphosphate 29.2 29.8

Sodium chloride 1.7 2.0

Ex. 74 10 Sodium C ^ _ line linear alkylbenzene sulfonate 7.8

Sodium C ^₂_ g ~ alkyl 3 moles of ethoxysulfate 2.6

Sodium tripolyphosphate 23.4

Sodium carbonate 5.0

Sodium Carboxymethyl Cellulose 1.0 Optical Clarifier 0.15

Perfume, dye, water up to 100 20 25 30 35

DK 166030B

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DK 166030B

57 0

The drawing shows variations in conductivity, flow limit and viscosity depending on variations in e-electrolyte concentration and in active ingredients.

FIG. Figure 1 is a graph showing the conductivity of an aqueous 20.6% solution of active ingredients consisting of 2 parts by weight of sodium dodecylbenzenesulfonate and 1 part of sodium C1-6 alkyl 3 moles of ethoxysulfate; depending on different concentration of sodium silicate, NaOiSiO4, molar ratio 1.6: 1. The numbers on the horizontal axis refer to the amount of silicate in the composition expressed as weight percent solids.

Between 0 and 7% added silicate solution gives a mainly clear, optically isotropic composition typical of stage I as described above. Between the 15 points labeled "A" and "B", Stage II compositions are obtained which are unclear, unstable and include non-space-expanding spherulite lichen masses. Between "B" and "C", compositions are obtained in stage III according to the invention.

These are vague, stable compositions containing mainly spacer-filling spherulite lye masses and have a flow limit and exhibit only a single liquid phase at high G centrifugation. In addition to "C", compositions are obtained in stage IV containing non-spacer-extending spherical G-phase fluids and which are not stable. Stable compositions appear to be in stage. III is obtained in the conductivity recess around the first conductivity minimum. .

FIG. Figure 2 shows the effect of adding sodium nitrate to the same aqueous active system. In addition to the 30 point "C" in stage IV, another conductivity is passed - maximum, followed by another conductivity minimum corresponding to the formation of a lamellar composition according to stage V approximately at "D".

FIG. 3 shows variations in viscosity, conductivity and flow limit when sodium carbonate is added to the same active system.

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DK 166030 B

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The axis on the left shows viscosity at 136 sec. ^ in Pascal seconds, the numbers in brackets refer to the conductivity in the milliseconds cm scale on the right hand refers to the flow limit in dyn cm, the horizontal axis 5 represents the total percentage of sodium carbonate present, expressed as dry weight sodium carbonate based on the total weight of the composition.

In the case of sodium carbonate, no minimum is observed in the conductivity curve (dashed line).

This shows that the solubility limit of sodium carbonate has been reached, so that additional carbonate additions are suspended and do not increase the dissolved electrolyte concentration. Therefore, no stage IV can be observed.

The steep rise in flow limit (tip to the right) coincides with the beginning of stage III at point "B".

This is typical of the compositions of the present invention.

FIG. 4 shows the effect of varying the ratios of sodium dodecylbenzene sulfonate to coconut monoethanolamide in a composition containing active ingredients, sodium tripolyphosphate, sodium carbonate and water in a ratio of 0.2: 0.5: 0.1: 1.0. The horizontal scale represents the weight ratio of coconut monoethanolamide to sodium dodecylbenzene sulfonate.

25 The vertical scale represents the conductivity in millimeters cm 1 (circles) and likewise viscosity in Pascal seconds x 10 (triangles).

FIG. Figure 5 shows a similar ratio in which the active ingredients are a mixture of sodium dodecylbenzene sulfonate and sodium C ^ .. ·] 3 3 3 3 mol 3 mole of ethoxysulfate. The horizontal scale is the weight ratio of ether sulfate to alkylbenzene sulfonate.

FIG. 4 and 5 illustrate how it is possible to prepare compositions according to the invention by modifying the active ingredients and not changing the concentration of active ingredients and electrolyte.

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FIG. 6 shows the variation in conductivity in milli-Siemens cm when sodium nitrate in various amounts is added to a washing composition containing suspended builder and having the composition: 5% by weight

Sodium dodecylbenzenesulfonate 9

Sodium C12_1g-alkyl 3 moles of ethoxysulfate 4 10 Silicone frothing agent 1

Parfurne 0.6

Cig ^ g mixed mono. and dialkyl phosphate 0.5

Optical Clarifier 0.15 15 Sodium Tripolyphosphate 19 "Zeolite A" 12 Due to the already dissolved tripolyphosphate, no stage I of this 20 curve is observed. Conductivity drops from a maximum at "A", until stage III occurs at "B".

FIG. 7 shows the flow limit for the same sewing - 2 stem in dyn cm, and fig. 8 shows the viscosity at 136 cm 2 (bottom curve), 21 cm 2 (upper curve), and the viscosity drop (middle curve) in Pascal seconds x 10.

FIG. 9 illustrates the change in conductivity depending on varying amounts of sodium silicate in a 20.6% by weight aqueous sodium dodecylbenzenesulfonate solution mixed with coconut monoethanolamide in a weight ratio of 10: 4.

Here, too, no stage I is observed because the active ingredients are not completely soluble in water at room temperature. Thus, the composition is cloudy and unstable without the presence of electrolyte.

FIG. 10 and 11 are transmission micrographs of

Pt / C replica after freezing refraction in magnifications respectively.

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DK 166030 B

0 45,000 and 110,000 times (lin).

The micrographs produced at Lancaster University transmission electron microscope both reproduce a sample with the composition: 5% by weight

Sodium dodecylbenzene sulfonate 11.8

Sodium C ^₂_ g alkyl 3 moles ethoxysulfate 5.2 Sodium silicate (Na₂O: SiO₂ = 1.6: 1) 17.4

Water the rest 10

The micrograph shows spherulites of between 0.2 and 1 µ u in diameter, showing signs of being multicycle with a concentric structure, with a repeated gap (including the thickness of a surfactant shell and an aqueous layer adjacent to it). at 80Å.

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Claims (1)

DK 166030 B Stable, pourable, liquid detergent composition comprising water, surfactant, dissolved electrolyte salt which acts to desolubilize the surfactant, and suspended particles of solid builder, thereby total builder weight ratio, including any dissolved builder, and surfactant. is greater than 1.5: 1, and in which composition the weight ratio of the surfactant to the water is such that when said salt is continuously dissolved in the surfactant, the curve of the electrical conductivity of the solution goes into the aqueous micelle solution in which said weight ratio prevails , through a minimum range containing a minimum of electrical conductivity at which the solution is stable and cloudy, characterized in that said salt, when any dissolved builder is included, dissolves in the composition in a total amount corresponding to said minimum range , which quantity is selected between the minimum and maximum quantities at which composition it is stable for at least 3 20 months, both at room temperature and at a temperature of 5 ° C, e.g. at 0 ° C, and preferably also at 40 ° C.